*3.1. Characterization of the Ni-BDC, Fe-BDC, and Fe2Ni-BDC Catalysts*

In this study, a BMOF based on the coupling effects between Ni2<sup>+</sup> and Fe2<sup>+</sup> ions (Fe2Ni-BDC) and the respective single-metal-ion MOFs (Ni-BDC and Fe-BDC) were obtained by direct synthesis with a clear solution containing nickel (II) nitrate hexahydrate and/or iron (III) chloride hexahydrate and terephthalic acid (H2BDC) in dimethylformamide (DMF) solvent. Evidence of the formation of a MOF with bimetallic nodes was confirmed by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, and nitrogen physisorption measurements.

The XRD patterns of the resulting Ni-BDC, Fe-BDC, and Fe2Ni-BDC samples are shown in Figure S3 (Supplementary Materials). The pure Ni-BDC powder exhibited a similar XRD pattern (Figure S3a) to the previously reported ones synthesized by a solvothermal method with main diffraction peaks at 2θ of 11◦ , 11.5◦ , 14◦ , 15◦ , 16.5◦ , 17,5◦ , 28◦ , and 29◦ [27,28,30–32]. As can be observed in Figure 1b, the XRD patterns of the Fe-BDC exhibited peaks at 2θ of approximately of 9.2◦ , 9.5◦ , 14.0◦ , 16.4◦ , and 18.7◦ , and this result was also similar to the simulated patterns of MIL-53(Fe) previously reported in the literature [27,33]. Furthermore, the simulated diffraction patterns for the Ni- and Fe-based system (see Figures S1 and S2, Supplementary Materials) were exhibited. In the pattern of the Fe2Ni-BDC samples (Figure S3c, Supplementary Materials), the XRD peaks emerged around 2θ of 7.4◦ , 8.8◦ , 9.2◦ , 9.8◦ , 16.7◦ , 18.7◦ , 17.8◦ , 20.0◦ , and 21.8◦ . It is clear that this result is also in line with those of the sample previously reported in the literature [25,26]. Besides this, no other diffraction peak combined with iron oxides, nickel oxides, or other diffraction peaks was found, proving the high purity of the samples. The XRD analytic results illustrate that the crystal structure of Fe2Ni-BDC was substantially affected by the existence of assorted metal ions (Ni2<sup>+</sup> and Fe3<sup>+</sup> ions), and Fe2Ni-BDC crystals could be formed by the combination of H2BDC with Ni2<sup>+</sup> and Fe3<sup>+</sup> ions [25,26]. The XRD patterns of the resulting Ni-BDC, Fe-BDC, and Fe2Ni-BDC samples are shown in Figure S3 (Supplementary Materials). The pure Ni-BDC powder exhibited a similar XRD pattern (Figure S3a) to the previously reported ones synthesized by a solvothermal method with main diffraction peaks at 2θ of 11°, 11.5°, 14°, 15°, 16.5°, 17,5°, 28°, and 29° [27,28,30–32]. As can be observed in Figure 1b, the XRD patterns of the Fe-BDC exhibited peaks at 2θ of approximately of 9.2°, 9.5°, 14.0°, 16.4°, and 18.7°, and this result was also similar to the simulated patterns of MIL-53(Fe) previously reported in the literature [27,33]. Furthermore, the simulated diffraction patterns for the Ni- and Fe-based system (see Figures S1 and S2, Supplementary Materials) were exhibited. In the pattern of the Fe2Ni-BDC samples (Figure S3c, Supplementary Materials), the XRD peaks emerged around 2θ of 7.4°, 8.8°, 9.2°, 9.8°, 16.7°, 18.7°, 17.8°, 20.0°, and 21.8°. It is clear that this result is also in line with those of the sample previously reported in the literature [25,26]. Besides this, no other diffraction peak combined with iron oxides, nickel oxides, or other diffraction peaks was found, proving the high purity of the samples. The XRD analytic results illustrate that the crystal structure of Fe2Ni-BDC was substantially affected by the existence of assorted metal ions (Ni2+ and Fe3+ ions), and Fe2Ni-BDC crystals could be formed by the combination of H2BDC with Ni2+ and Fe3+ ions [25,26].

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spectroscopy (FT-IR), Raman spectroscopy, and nitrogen physisorption measurements.

**Figure 1.** Raman spectroscopy of the Ni-1,4-Benzenedicarboxylic (Ni-BDC) (**a**), Fe-1,4- **Figure 1.** Raman spectroscopy of the Ni-1,4-Benzenedicarboxylic (Ni-BDC) (**a**), Fe-1,4-Benzenedicarboxylic (Fe-BDC) (**b**), and Fe2Ni-1,4-Benzenedicarboxylic (Fe2Ni-BDC) (**c**).

Benzenedicarboxylic (Fe-BDC) (**b**), and Fe2Ni-1,4-Benzenedicarboxylic (Fe2Ni-BDC) (**c**). The FT-IR spectra of Ni-BDC, Fe-BDC, and Fe2Ni-BDC are shown in Figure S4 (Supplementary Materials). The FT-IR spectra exhibited stretching vibration of the C=O bond at approximately 1680 cm−1, while υasym (OCO) and υsym (OCO) bonds displayed stretching vibration at around 1601 cm−1 and 1391 cm−1, respectively. Besides this, the FT-IR spectra displayed stretching vibration of the υ(C–O) and δ(C–H) bonds at 1017 cm−1 and 749 cm−1 (Figure S4A, Supplementary Materials). These results showed that the existence of the metal–ligand bond in the MOF structures. Particularly, the FT-IR spectrum of H2BDC displayed no band at 1700 cm−1. This result proves the absence of free H2BDC in the MOF structures [34,35]. The feature bands of H2O and DMF in the MOF materials were exhibited at 1657 cm−1 and 3387 cm−1 [25,26]. At lower frequencies, stretching vibration of the C–H bond, C=C bond, and –OCO function was observed at approximately 750 cm−1, 690 cm−1, and 660 cm−1, respectively, proving the existence of the vibrations of the organic linker BDC (Figure S4B, Supplementary Materials) [26]. Moreover, it is clear that the strong band at 547 cm−1 may be attributed The FT-IR spectra of Ni-BDC, Fe-BDC, and Fe2Ni-BDC are shown in Figure S4 (Supplementary Materials). The FT-IR spectra exhibited stretching vibration of the C=O bond at approximately 1680 cm−<sup>1</sup> , while υasym (OCO) and υsym (OCO) bonds displayed stretching vibration at around 1601 cm−<sup>1</sup> and 1391 cm−<sup>1</sup> , respectively. Besides this, the FT-IR spectra displayed stretching vibration of the υ(C–O) and δ(C–H) bonds at 1017 cm−<sup>1</sup> and 749 cm−<sup>1</sup> (Figure S4A, Supplementary Materials). These results showed that the existence of the metal–ligand bond in the MOF structures. Particularly, the FT-IR spectrum of H2BDC displayed no band at 1700 cm−<sup>1</sup> . This result proves the absence of free H2BDC in the MOF structures [34,35]. The feature bands of H2O and DMF in the MOF materials were exhibited at 1657 cm−<sup>1</sup> and 3387 cm−<sup>1</sup> [25,26]. At lower frequencies, stretching vibration of the C–H bond, C=C bond, and –OCO function was observed at approximately 750 cm−<sup>1</sup> , 690 cm−<sup>1</sup> , and 660 cm−<sup>1</sup> , respectively, proving the existence of the vibrations of the organic linker BDC (Figure S4B, Supplementary Materials) [26]. Moreover, it is clear that the strong band at 547 cm−<sup>1</sup> may be attributed to either NiO vibrations or FeO vibrations [36]. The weak range at about 720 cm−<sup>1</sup> is associated with

Fe2NiO vibration, which was also detected in the Fe2Ni-BDC sample [26]. This result reinforces the notion that Ni2<sup>+</sup> and Fe3<sup>+</sup> ions may combine with H2BDC to form Fe2Ni-BDC crystals.

The Raman spectroscopy results of Ni-BDC, Fe-BDC, and Fe2Ni-BDC are shown in Figure 1. Following previous studies, the symmetric oscillation modes and asymmetric oscillation of the COO– bond in the carboxylate group detected at approximately 1445 cm−<sup>1</sup> and 1501 cm−<sup>1</sup> may be the organic linker BDC in the metal–organic frameworks. The oscillation at around 1140 cm−<sup>1</sup> can be attributed to the C–C bond of the carboxylate group with a benzene ring. Besides this, vibration of the C–H bond was observed at around 865 cm−<sup>1</sup> and 630 cm−<sup>1</sup> [25]. As shown in Figure 1, the presence of BDC ligand was also discovered in the catalyst sample, and no Raman sign corresponding to NiO, FeO, or other impurities was detected on the pattern, which is consistent with the X-ray diffraction results.

Concurrent thermal analysis permits simultaneous measurement of both the weight and heat flow alteration of Ni-BDC, Fe-BDC, and Fe2Ni-BDC powder in relation to the temperature under an air atmosphere. The patterns show the differential scanning calorimetry (DSC) and thermogravimetry (TGA) curved of Ni-BDC, Fe-BDC, and Fe2Ni-BDC powder from room temperature to 800 ◦C under an air atmosphere (Figure 2). In the DSC curve of Ni-BDC, a powerful exothermic process occurred between 380 ◦C and 480 ◦C, manifesting as a peak temperature at 450.57 ◦C (Figure 2a). In the DSC curve of Fe-BDC, a robust exothermic process occurred between 260 ◦C and 340 ◦C, illustrating a peak temperature at 316.53 ◦C (Figure 2b). In the DSC curve of Fe2Ni-BDC, a strongly exothermic process took place from 320 ◦C to 490 ◦C, signified by a peak temperature at 437.99 ◦C (Figure 2c). The weight loss occurring at temperatures below 200 ◦C could be attributable to the vaporization of solvent (H2O or DMF) obstructed within the frame, while the weight loss occurring between 200 ◦<sup>C</sup> and 260 ◦C is the result of the strong combining of H2O or the frame of H2O. A sudden weight loss may be discerned between 280 and 480 ◦C, conforming to a strongly exothermic process in the DSC curve. Herein, elemental analysis, i.e., EDX mapping and ICP analysis, can aid the identification of the Ni/Fe ratio in the bimetallic Ni/Fe-BDC MOF. Based on the results obtained from EDX mapping, we found that the proximate percentages of Ni and Fe were 5.7% and 11.2%, respectively (Figure S5, Supplementary Materials) or 1:2 when calculated in a molar ratio. Similarly, ICP analysis also indicated that the molar (atomic) ratio between Ni and Fe was at approximately 1:2. Therefore, it matched well with the formula of NiFe2-BDC. *Processes* **2019**, *7*, x 5 of 14 to either NiO vibrations or FeO vibrations [36]. The weak range at about 720 cm−1 is associated with Fe2NiO vibration, which was also detected in the Fe2Ni-BDC sample [26]. This result reinforces the notion that Ni2+ and Fe3+ ions may combine with H2BDC to form Fe2Ni-BDC crystals.

**Figure 2.** TGA analysis of the Ni-1,4-Benzenedicarboxylic (Ni-BDC) (a), Fe-1,4-Benzenedicarboxylic (Fe-BDC) (b), and Fe2Ni-1,4-Benzenedicarboxylic (Fe2Ni-BDC) (c). **Figure 2.** TGA analysis of the Ni-1,4-Benzenedicarboxylic (Ni-BDC) (**a**), Fe-1,4-Benzenedicarboxylic (Fe-BDC) (**b**), and Fe2Ni-1,4-Benzenedicarboxylic (Fe2Ni-BDC) (**c**).

The Raman spectroscopy results of Ni-BDC, Fe-BDC, and Fe2Ni-BDC are shown in Figure 1. Following previous studies, the symmetric oscillation modes and asymmetric oscillation of the COO– bond in the carboxylate group detected at approximately 1445 cm−1 and 1501 cm−1 may be the organic linker BDC in the metal–organic frameworks. The oscillation at around 1140 cm−1 can be attributed to the C–C bond of the carboxylate group with a benzene ring. Besides this, vibration of the C–H bond was observed at around 865 cm−1 and 630 cm−1 [25]. As shown in Figure 1, the presence of BDC ligand was also discovered in the catalyst sample, and no Raman sign corresponding to NiO, FeO, or The morphology, size, and regularity of the Ni-BDC, Fe-BDC, and Fe2Ni-BDC samples were studied by SEM (Figure 3). The Ni-BDC sample includes stacked planar sheets with a size up to several micrometers (Figure 3a). The shape of pure Fe-BDC showed two types of particles: bigger, rod-like particles and other, smaller, pseudo-spherical particles (Figure 3b). The SEM pictures of the particles unveiled the creation of uniform micro-sized hexagonal rods (Figure 3c). Besides this, the Fe2Ni-BDC sample consists of stacked planar sheets and other smaller pseudo-spherical particles.

thermogravimetry (TGA) curved of Ni-BDC, Fe-BDC, and Fe2Ni-BDC powder from room temperature to 800 °C under an air atmosphere (Figure 2). In the DSC curve of Ni-BDC, a powerful exothermic process occurred between 380 °C and 480 °C, manifesting as a peak temperature at 450.57 °C (Figure 2a). In the DSC curve of Fe-BDC, a robust exothermic process occurred between 260 °C and 340 °C, illustrating a peak temperature at 316.53 °C (Figure 2b). In the DSC curve of Fe2Ni-BDC, a strongly exothermic process took place from 320 °C to 490 °C, signified by a peak temperature at 437.99 °C (Figure 2c). The weight loss occurring at temperatures below 200 °C could be attributable to the vaporization of solvent (H2O or DMF) obstructed within the frame, while the weight loss occurring between 200 °C and 260 °C is the result of the strong combining of H2O or the frame of H2O. A sudden weight loss may be discerned between 280 and 480 °C, conforming to a strongly exothermic process in the DSC curve. Herein, elemental analysis, i.e., EDX mapping and ICP analysis, can aid the identification of the Ni/Fe ratio in the bimetallic Ni/Fe-BDC MOF. Based on the results obtained from EDX mapping, we found that the proximate percentages of Ni and Fe were 5.7% and 11.2%, respectively (Figures S5, Supplementary Materials) or 1:2 when calculated in a molar ratio. Similarly, ICP analysis also indicated that the molar (atomic) ratio between Ni and Fe was at

The morphology, size, and regularity of the Ni-BDC, Fe-BDC, and Fe2Ni-BDC samples were studied by SEM (Figure 3). The Ni-BDC sample includes stacked planar sheets with a size up to several micrometers (Figure 3a). The shape of pure Fe-BDC showed two types of particles: bigger, rod-like particles and other, smaller, pseudo-spherical particles (Figure 3b). The SEM pictures of the

approximately 1:2. Therefore, it matched well with the formula of NiFe2-BDC.

other impurities was detected on the pattern, which is consistent with the X-ray diffraction results. Concurrent thermal analysis permits simultaneous measurement of both the weight and heat

Fe2Ni-BDC sample consists of stacked planar sheets and other smaller pseudo-spherical particles.

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particles unveiled the creation of uniform micro-sized hexagonal rods (Figure 3c). Besides this, the

**Figure 3.** SEM images of Ni-1,4-Benzenedicarboxylic (Ni-BDC) (a), Fe-1,4-Benzenedicarboxylic (Fe-BDC) (b), and Fe2Ni-1,4-Benzenedicarboxylic (Fe2Ni-BDC) (c). **Figure 3.** SEM images of Ni-1,4-Benzenedicarboxylic (Ni-BDC) (**a**), Fe-1,4-Benzenedicarboxylic (Fe-BDC) (**b**), and Fe2Ni-1,4-Benzenedicarboxylic (Fe2Ni-BDC) (**c**). **Figure 3.** SEM images of Ni-1,4-Benzenedicarboxylic (Ni-BDC) (a), Fe-1,4-Benzenedicarboxylic (Fe-BDC) (b), and Fe2Ni-1,4-Benzenedicarboxylic (Fe2Ni-BDC) (c).

The surface areas of the catalysts were confirmed by nitrogen adsorption–desorption isotherms derived from Brunauer–Emmett–Teller (BET). The isotherms of Ni-BDC, Fe-BDC, and Fe2Ni-BDC are presented in Figure 4. The BET surface areas of Fe-BDC and Fe2Ni-BDC were 158 m2/g and 247 m2/g, respectively. Meanwhile, the BET surface area of Ni-BDC was extremely low at around 2.28 m2/g, and it does not seem to be porous. The mesopore size distribution curves of specimens calculated using the Barrett–Joyner–Halenda (BJH) model are displayed in Figure 4. The pore volume and pore width of Ni-BDC, Fe-BDC, and Fe2Ni-BDC suggested average pore sizes of about 25 nm, 11 nm, and 13 nm, respectively. Based on the above results, including XRD, FT-IR, Raman, DSC, TGA, and BET, we conclude that an Fe2Ni-BDC bimetallic metal–organic framework was successfully synthesized by the solvothermal approach. The surface areas of the catalysts were confirmed by nitrogen adsorption–desorption isotherms derived from Brunauer–Emmett–Teller (BET). The isotherms of Ni-BDC, Fe-BDC, and Fe2Ni-BDC are presented in Figure 4. The BET surface areas of Fe-BDC and Fe2Ni-BDC were 158 m<sup>2</sup> /g and 247 m<sup>2</sup> /g, respectively. Meanwhile, the BET surface area of Ni-BDC was extremely low at around 2.28 m<sup>2</sup> /g, and it does not seem to be porous. The mesopore size distribution curves of specimens calculated using the Barrett–Joyner–Halenda (BJH) model are displayed in Figure 4. The pore volume and pore width of Ni-BDC, Fe-BDC, and Fe2Ni-BDC suggested average pore sizes of about 25 nm, 11 nm, and 13 nm, respectively. Based on the above results, including XRD, FT-IR, Raman, DSC, TGA, and BET, we conclude that an Fe2Ni-BDC bimetallic metal–organic framework was successfully synthesized by the solvothermal approach. The surface areas of the catalysts were confirmed by nitrogen adsorption–desorption isotherms derived from Brunauer–Emmett–Teller (BET). The isotherms of Ni-BDC, Fe-BDC, and Fe2Ni-BDC are presented in Figure 4. The BET surface areas of Fe-BDC and Fe2Ni-BDC were 158 m2/g and 247 m2/g, respectively. Meanwhile, the BET surface area of Ni-BDC was extremely low at around 2.28 m2/g, and it does not seem to be porous. The mesopore size distribution curves of specimens calculated using the Barrett–Joyner–Halenda (BJH) model are displayed in Figure 4. The pore volume and pore width of Ni-BDC, Fe-BDC, and Fe2Ni-BDC suggested average pore sizes of about 25 nm, 11 nm, and 13 nm, respectively. Based on the above results, including XRD, FT-IR, Raman, DSC, TGA, and BET, we conclude that an Fe2Ni-BDC bimetallic metal–organic framework was successfully synthesized by the solvothermal approach.

**Figure 4.** N<sup>2</sup> adsorption–desorption isotherms (left) and pore size distributions (right) of metal–organic framework (MOF) samples.

#### *3.2. The Synthesis of N-Pyridinyl Benzamide 3.2. The Synthesis of N-Pyridinyl Benzamide*

organic framework (MOF) samples.

Scheme 1 illustrates the amidation reaction between trans-β-nitrostyrene and 2-aminopyridine using catalysts Ni(NO3)2·6H2O, FeCl3·6H2O, Ni-BDC, Fe-BDC, and Fe2Ni-BDC. The performance of the reactions with different metal-centered catalysts demonstrated that Fe2Ni-BDC resulted in the best activity for this amidation process (Figure 5a, Table S1). Scheme 1 illustrates the amidation reaction between trans-β-nitrostyrene and 2-aminopyridine using catalysts Ni(NO3)2·6H2O, FeCl3·6H2O, Ni-BDC, Fe-BDC, and Fe2Ni-BDC. The performance of the reactions with different metal-centered catalysts demonstrated that Fe2Ni-BDC resulted in the best activity for this amidation process (Figure 5a, Table S1).

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**Scheme 1.** The amidation reaction between trans-β-nitrostyrene and 2-aminopyridine using Fe2Ni-BDC as a catalyst. **Scheme 1.** The amidation reaction between trans-β-nitrostyrene and 2-aminopyridine using Fe2Ni-BDC as a catalyst. *Processes* **2019**, *7*, x 8 of 14

**Figure 5.** The yield of N-pyridinyl benzamide vs. catalyst (**a**), temperature (**b**), catalyst amount (**c**), reaction molar ratio (**d**), solvents (**e**), and yield of N-pyridinyl benzamide under air, O2, N2, and air + 2,2,6,6-Tetramethyl-1-piperidinyloxy (TEMPO) (**f**). **Figure 5.** The yield of N-pyridinyl benzamide vs. catalyst (**a**), temperature (**b**), catalyst amount (**c**), reaction molar ratio (**d**), solvents (**e**), and yield of N-pyridinyl benzamide under air, O<sup>2</sup> , N<sup>2</sup> , and air + 2,2,6,6-Tetramethyl-1-piperidinyloxy (TEMPO) (**f**).

We also investigated the effect of the trans-β-nitrostyrene/2-aminopyridine molar ratio on the production of N-(pyridin-2-yl)-benzamide. The reaction was carried at 80 °C under air in DCM for 24 h in the presence of 10 mol % of catalyst. The survey data illustrated that the reactant molar ratio exerted a significant effect on the yield of product **3a**. The reaction utilizing the proportion of 1

The amidation reaction was performed at different temperatures from room temperature to 100 ◦C. The results (Figure 5b and Table S1) indicated that lower temperature led to a decline in product yield, and the reaction occurred when the mixture was heated. Also, when this reaction was carried out at 100 ◦C, a lower yield of product **3a** was observed, which could result from the decomposition of reactants and products, adversely affecting the reaction process. The yield of product **3a** reached its highest value when the reaction was carried out at 80 ◦C; therefore, 80 ◦C was chosen as the optimal reaction temperature for further studies.

Figure 5c shows the effect of catalyst amount (mol %) on the yield of product **3a**. These results revealed that the yield of **3a** reached a peak (82%) when using 10 mol % catalyst. This behavior necessitates the bimetallic framework for catalyzing the alteration. The use of BMOF catalyst for the reaction brought about a remarkable progression in the reaction yield. The reaction utilizing 5 mol % of catalyst might achieve around 47% yield, and this yield figure could be improved to 60% yield if 7.5 mol % catalyst is used. However, the use of more than 10 mol % catalyst seemed to be redundant because the yield of **3a** was not improved substantially above this concentration (Table S1).

We also investigated the effect of the trans-β-nitrostyrene/2-aminopyridine molar ratio on the production of N-(pyridin-2-yl)-benzamide. The reaction was carried at 80 ◦C under air in DCM for 24 h in the presence of 10 mol % of catalyst. The survey data illustrated that the reactant molar ratio exerted a significant effect on the yield of product **3a**. The reaction utilizing the proportion of 1 equivalent of **1a** achieved 82% yield in air. The excess **1a** reactant resulted in a reduced yield of **3a**. Indeed, as the yield of the product reached 56%, the molar proportion of reactants in the reaction approximated 2:1. However, the yield was decreased drastically to merely 35% when 3 equivalents of **1a** were used. It was clear that excess **2a** was preferred in the reaction. The yield of product **3a** reached approximately 78% after 24 h with a reactant molar proportion of either 1:2 or 1:3. However, the optimal yield of **3a** was attained at the reactant molar proportion of 1:1 (Figure 5d, Table S1).

Because the amidation reaction of **1a** and **2a** was carried out in the liquid phase, we needed to examine the effect of solvents on the catalytic activity. In the first report of the synthesis of N-(pyridin-2-yl)-benzamide derivatives from **1a** and **2a**, Zhengwang Chen et al. [16] implemented the reaction in various co-solvents and illustrated that co-solvent H2O/dioxane could improve the yield of products. The effect of solvents such as toluene, DMF, 1,4-dioxane, tetrahydrofuran (THF), chlorobenzene, DCM/H2O, dioxane/H2O, H2O, and dichloroethane on the yield of **3a** was investigated. As shown in Figure 5e and Table S1, DMF solvent was unsuitable for the reaction utilizing the bimetallic framework catalyst, with only 5% yield of **3a** after 24 h. The yields of product **3a** were higher in toluene and tetrahydrofuran—30% and 37% yields, respectively, after 24 h. The reactions controlled in dioxane, dioxane/H2O, H2O, and chlorobenzene produced **3a** in yields of 52%, 46%, 50%, and 57%, respectively. Higher yields of 75% and 72% were obtained for DCM/H2O and dichloroethane. Among the aforementioned solvents, DCM gave the best result with an 82% yield of **3a** after 24h (Figure 5e and Table S1).

As shown in Figure 5f, the production of **3a** was not detected when the reaction was conducted under N<sup>2</sup> gas, highlighting the essential role of O<sup>2</sup> in the reaction. Further investigation of the reaction with the bimetallic framework catalyst under O<sup>2</sup> illustrating the role of the Fe2Ni-BDC catalyst was not feasible. Besides this, the reaction that was carried out in the presence of 2,2,6,6-Tetramethyl-1-piperidinyloxy (TEMPO) revealed no obvious prevention of the reaction, allowing us to propose a probably easier radical path in this amidation reaction (Figure 5f, Table S1). After some surveys, we determined that the appropriate reaction conditions are as follows: *trans*-β-nitrostyrene (**1a**, 0.2 mmol), 2-aminopyridine (**2a**, 0.2 mmol), catalyst (10 mol %), and DCM (1 mL) at 80 ◦C for 24 h.

A leaching evaluation was employed to confirm whether the active sites going into solution from the solid catalyst could accelerate the creation of N-(pyridin-2-yl)-benzamide, as the leaching phenomenon could happen throughout the stages of the reaction. The reaction was performed at 80 ◦C in DCM solvent for 24 h, with reactants consisting of *trans*-1-nitro-phenylethylene and 2-pyridyl amine and with 10 mol % catalyst under air atmosphere. After the initial 4 h stage with 12% yield recorded, the catalyst was separated by centrifugation. Then, new reactants were added to the solution phase in a clean, pressurized vial with magnetic stirring and the temperature maintained at 80 ◦C for 24 h. It was observed that the formation of N-(pyridin-2-yl)-benzamide stopped after the catalyst was separated (Figure 6a). These figures indicate that the amidation of *trans*-1-nitro-phenylethylene with 2-aminopyridine to generate N-(pyridin-2-yl)-benzamide could be maintained only in the presence of the solid catalyst. *Processes* **2019**, *7*, x 10 of 14

**Figure 6.** Leaching test (**a**), catalyst reusability (**b**), XRD pattern (**c**), and FT-IR spectroscopy (**d**) of the **Figure 6.** Leaching test (**a**), catalyst reusability (**b**), XRD pattern (**c**), and FT-IR spectroscopy (**d**) of the fresh and recovered catalyst.

fresh and recovered catalyst. Another striking feature that differentiates heterogeneous catalysis from homogeneous catalysis is the capability of the catalyst to be recovered and recycled. The catalyst was appropriately surveyed for recyclability in the reaction over six successive runs. The reaction was performed under optimal conditions at 80 °C in an air atmosphere. Upon completion of the first run, the catalyst was separated, washed cautiously with DCM and DMF, and dried at 100 °C for 3 h. Afterward, the recovered catalyst was recycled in new experiments. After the experiments were conducted, these data demonstrated that the catalyst might be recycled numerous times in the reaction of 2-aminopyridine and *trans*-1 nitro-phenylethylene to create N-(pyridin-2-yl)-benzamide without significantly compromising the yield. The yield of N-(pyridin-2-yl)-benzamide noted in the sixth run was 77% (Figure 6b). Moreover, the whole catalyst might be withheld after the reaction process, as shown by XRD (Figure 6c) and FT-Another striking feature that differentiates heterogeneous catalysis from homogeneous catalysis is the capability of the catalyst to be recovered and recycled. The catalyst was appropriately surveyed for recyclability in the reaction over six successive runs. The reaction was performed under optimal conditions at 80 ◦C in an air atmosphere. Upon completion of the first run, the catalyst was separated, washed cautiously with DCM and DMF, and dried at 100 ◦C for 3 h. Afterward, the recovered catalyst was recycled in new experiments. After the experiments were conducted, these data demonstrated that the catalyst might be recycled numerous times in the reaction of 2-aminopyridine and *trans*-1-nitro-phenylethylene to create N-(pyridin-2-yl)-benzamide without significantly compromising the yield. The yield of N-(pyridin-2-yl)-benzamide noted in the sixth run was 77% (Figure 6b). Moreover, the whole catalyst might be withheld after the reaction process, as shown by XRD (Figure 6c) and FT-IR (Figure 6d) spectroscopy of the recovered BMOFs.

because the Fe3+ and Ni2+ ions in the BMOFs had many empty orbitals in the molecule. Intermediary **C** formed through successive dehydration of **B** and was reorganized to imine intermediary **D**. Following that, hydration of **E** brought about the intermediary **F**. After that, protonation of **F** took place by dehydration to provide the α-aminonitrile to intermediary **G**. Eventually, the target product

Based on the experimental results, a reasonable mechanism is suggested in Scheme 2. Initially,

IR (Figure 6d) spectroscopy of the recovered BMOFs.

S14 and Figure S15).

Based on the experimental results, a reasonable mechanism is suggested in Scheme 2. Initially, the intermediary **A** was created via the Michael addition of *trans*-β-nitrostyrene **1a** and 2-pyridine amines **2a** as a nucleophile. When the catalyst played the role of a Lewis acid, the intermediary **A** was able to form a bond covalent with the O molecule on the nitro group, permitting the Michael addition, because the Fe3<sup>+</sup> and Ni2<sup>+</sup> ions in the BMOFs had many empty orbitals in the molecule. Intermediary **C** formed through successive dehydration of **B** and was reorganized to imine intermediary **D**. Following that, hydration of **E** brought about the intermediary **F**. After that, protonation of **F** took place by dehydration to provide the α-aminonitrile to intermediary **G**. Eventually, the target product **3a** was formed via a nucleophilic addition and elimination process. Via this proposed mechanism, the catalyst with two active metal centers improved the reaction yield. Therefore, the catalysis activity of Fe2Ni-BDC was enhanced when compared with the catalysis activity of the single-metal centers of Ni-BDC and Fe-BDC. *Processes* **2019**, *7*, x 11 of 14 **3a** was formed via a nucleophilic addition and elimination process. Via this proposed mechanism, the catalyst with two active metal centers improved the reaction yield. Therefore, the catalysis activity of Fe2Ni-BDC was enhanced when compared with the catalysis activity of the single-metal centers of Ni-BDC and Fe-BDC.

**Scheme 2.** Proposed reaction mechanism. **Scheme 2.** Proposed reaction mechanism.

The study was subsequently extended to the synthesis of various N-(pyridin-2-yl)-benzamide derivatives. The reactions were conducted between derivatives of 2-aminopyridine and *trans*-βnitrostyrene in DCM solvent for 24 h under air atmosphere at 80 °C with 10 mol % of the catalyst. The products were purified by column chromatography, and isolated yields were noted. As shown in Table 2, N-(pyridin-2-yl)-benzamide was created with 82% yield (entry 1, Table 1, Figure S6 and Figure S7). The existence of a substituent on the pyridine ring in 2-aminopyridine reduced the yield slightly. The reaction performed between 4-methyl-2-aminopyridine and *trans*-β-nitrostyrene produced N-(4-methylpyridin-2-yl)benzamide with 78% yield (entry 2, Table 1, Figure S8 and Figure S9), while a 68% yield of N-(5-chloropyridin-2-yl)benzamide was obtained for a reaction between 5 cloro-2-aminopyridine and *trans*-β-nitrostyrene (entry 3, Table 1, Figure S10 and Figure S11). Besides The study was subsequently extended to the synthesis of various N-(pyridin-2-yl)-benzamide derivatives. The reactions were conducted between derivatives of 2-aminopyridine and *trans*-β-nitrostyrene in DCM solvent for 24 h under air atmosphere at 80 ◦C with 10 mol % of the catalyst. The products were purified by column chromatography, and isolated yields were noted. As shown in Table 1, N-(pyridin-2-yl)-benzamide was created with 82% yield (entry 1, Table 1, Figures S6 and S7). The existence of a substituent on the pyridine ring in 2-aminopyridine reduced the yield slightly. The reaction performed between 4-methyl-2-aminopyridine and *trans*-β-nitrostyrene produced N-(4-methylpyridin-2-yl)benzamide with 78% yield (entry 2, Table 1, Figures S8 and S9), while a 68% yield of N-(5-chloropyridin-2-yl)benzamide was obtained for a reaction between 5-cloro-2-aminopyridine and *trans*-β-nitrostyrene (entry 3, Table 1, Figures S10 and S11). Besides these,

**Table 1.** Synthesis of different N-(pyridin-2-yl)-benzamide derivatives utilizing Fe2Ni-BDC catalyst. **Entry Reactant 1 Reactant 2 Product Isolated Yields (%)**

these, the reaction conducted between 4-methyl-o-phenylenediamine and *trans*-β-nitrostyrene

the reaction conducted between 4-methyl-o-phenylenediamine and *trans*-β-nitrostyrene produced 5-methyl-2-phenyl-1*H*-benzo[*d*]imidazole with 63% yield (entry 4, Table 1, Figures S12 and S13). Finally, N-(pyridin-2-yl)-benzamide was still generated when the reaction was performed between benzoylformic acid and 2-aminopyridine with 74% yield (entry 5, Table 1, Figures S14 and S15).


**Table 1.** Synthesis of different N-(pyridin-2-yl)-benzamide derivatives utilizing Fe2Ni-BDC catalyst.

#### The bimetallic metal–organic framework Fe2Ni-BDC is a productive heterogeneous catalyst for The bimetallic metal–organic framework Fe2Ni-BDC is a productive heterogeneous catalyst for The bimetallic metal–organic framework Fe2Ni-BDC is a productive heterogeneous catalyst for The bimetallic metal–organic framework Fe2Ni-BDC is a productive heterogeneous catalyst for The bimetallic metal–organic framework Fe2Ni-BDC is a productive heterogeneous catalyst for The bimetallic metal–organic framework Fe2Ni-BDC is a productive heterogeneous catalyst for **4. Conclusions** The bimetallic metal–organic framework Fe2Ni-BDC is a productive heterogeneous catalyst for **4. Conclusions** The bimetallic metal–organic framework Fe2Ni-BDC is a productive heterogeneous catalyst for **Conclusions** The bimetallic metal–organic framework Fe2Ni-BDC is a heterogeneous catalyst for **4. Conclusions 4. Conclusions 4. Conclusions 4. Conclusions 4. Conclusions 4. Conclusions 4. Conclusions**

**4. Conclusions**

**4. Conclusions**

**4. Conclusions**

**4. Conclusions**

**4. Conclusions**

**4. Conclusions**

(pyridin-2-yl)benzamide.

(pyridin-2-yl)benzamide.

(pyridin-2-yl)benzamide.

(pyridin-2-yl)benzamide.

(pyridin-2-yl)benzamide.

(pyridin-2-yl)benzamide.

(pyridin-2-yl)benzamide.

(pyridin-2-yl)benzamide.

(pyridin-2-yl)benzamide.

(pyridin-2-yl)benzamide.

(pyridin-2-yl)benzamide.

(pyridin-2-yl)benzamide.

(pyridin-2-yl)benzamide.

(pyridin-2-yl)benzamide.

(pyridin-2-yl)benzamide.

number 2018.01.18/HĐ-KHCN.

number 2018.01.18/HĐ-KHCN.

number 2018.01.18/HĐ-KHCN.

number 2018.01.18/HĐ-KHCN.

number 2018.01.18/HĐ-KHCN.

number 2018.01.18/HĐ-KHCN.

number 2018.01.18/HĐ-KHCN.

number 2018.01.18/HĐ-KHCN.

number 2018.01.18/HĐ-KHCN.

number 2018.01.18/HĐ-KHCN.

number 2018.01.18/HĐ-KHCN.

number 2018.01.18/HĐ-KHCN.

number 2018.01.18/HĐ-KHCN.

number 2018.01.18/HĐ-KHCN.

number 2018.01.18/HĐ-KHCN.

editing, L.G.B., D-.V.N.V., T.V.N., S.-S.H. and S.T.D.

editing, L.G.B., D-.V.N.V., T.V.N., S.-S.H. and S.T.D.

editing, L.G.B., D-.V.N.V., T.V.N., S.-S.H. and S.T.D.

editing, L.G.B., D-.V.N.V., T.V.N., S.-S.H. and S.T.D.

editing, L.G.B., D-.V.N.V., T.V.N., S.-S.H. and S.T.D.

editing, L.G.B., D-.V.N.V., T.V.N., S.-S.H. and S.T.D.

editing, L.G.B., D-.V.N.V., T.V.N., S.-S.H. and S.T.D.

editing, L.G.B., D-.V.N.V., T.V.N., S.-S.H. and S.T.D.

editing, L.G.B., D-.V.N.V., T.V.N., S.-S.H. and S.T.D.

editing, L.G.B., D-.V.N.V., T.V.N., S.-S.H. and S.T.D.

editing, L.G.B., D-.V.N.V., T.V.N., S.-S.H. and S.T.D.

editing, L.G.B., D-.V.N.V., T.V.N., S.-S.H. and S.T.D.

editing, L.G.B., D-.V.N.V., T.V.N., S.-S.H. and S.T.D.

editing, L.G.B., D-.V.N.V., T.V.N., S.-S.H. and S.T.D.

editing, L.G.B., D-.V.N.V., T.V.N., S.-S.H. and S.T.D.

the amidation reaction between *trans*-1-nitro-phenylethylene and 2-aminopyridine to create N- (pyridin-2-yl)-benzamide under air. Fe2Ni-BDC showed higher productivity in the synthesis of N- (pyridin-2-yl)-benzamide than other metal–organic frameworks. The bimetallic metal–organic framework was surveyed as a heterogeneous catalyst for the amidation reaction. The catalyst was successfully recovered and reused for the reaction generating N-(pyridin-2-yl)-benzamide without a reduction in catalyst activity. To the best of our knowledge, the formation of N-(pyridin-2-yl) benzamide has not been previously achieved utilizing a heterogeneous catalyst. the amidation reaction between *trans*-1-nitro-phenylethylene and 2-aminopyridine to create N- (pyridin-2-yl)-benzamide under air. Fe2Ni-BDC showed higher productivity in the synthesis of N- (pyridin-2-yl)-benzamide than other metal–organic frameworks. The bimetallic metal–organic framework was surveyed as a heterogeneous catalyst for the amidation reaction. The catalyst was successfully recovered and reused for the reaction generating N-(pyridin-2-yl)-benzamide without a reduction in catalyst activity. To the best of our knowledge, the formation of N-(pyridin-2-yl) benzamide has not been previously achieved utilizing a heterogeneous catalyst. the amidation reaction between *trans*-1-nitro-phenylethylene and 2-aminopyridine to create N- (pyridin-2-yl)-benzamide under air. Fe2Ni-BDC showed higher productivity in the synthesis of N- (pyridin-2-yl)-benzamide than other metal–organic frameworks. The bimetallic metal–organic framework was surveyed as a heterogeneous catalyst for the amidation reaction. The catalyst was successfully recovered and reused for the reaction generating N-(pyridin-2-yl)-benzamide without a reduction in catalyst activity. To the best of our knowledge, the formation of N-(pyridin-2-yl) benzamide has not been previously achieved utilizing a heterogeneous catalyst. the amidation reaction between *trans*-1-nitro-phenylethylene and 2-aminopyridine to create N- (pyridin-2-yl)-benzamide under air. Fe2Ni-BDC showed higher productivity in the synthesis of N- (pyridin-2-yl)-benzamide than other metal–organic frameworks. The bimetallic metal–organic framework was surveyed as a heterogeneous catalyst for the amidation reaction. The catalyst was successfully recovered and reused for the reaction generating N-(pyridin-2-yl)-benzamide without a reduction in catalyst activity. To the best of our knowledge, the formation of N-(pyridin-2-yl) benzamide has not been previously achieved utilizing a heterogeneous catalyst. the amidation reaction between *trans*-1-nitro-phenylethylene and 2-aminopyridine to create N- (pyridin-2-yl)-benzamide under air. Fe2Ni-BDC showed higher productivity in the synthesis of N- (pyridin-2-yl)-benzamide than other metal–organic frameworks. The bimetallic metal–organic framework was surveyed as a heterogeneous catalyst for the amidation reaction. The catalyst was successfully recovered and reused for the reaction generating N-(pyridin-2-yl)-benzamide without a reduction in catalyst activity. To the best of our knowledge, the formation of N-(pyridin-2-yl) benzamide has not been previously achieved utilizing a heterogeneous catalyst. the amidation reaction between *trans*-1-nitro-phenylethylene and 2-aminopyridine to create N- (pyridin-2-yl)-benzamide under air. Fe2Ni-BDC showed higher productivity in the synthesis of N- (pyridin-2-yl)-benzamide than other metal–organic frameworks. The bimetallic metal–organic framework was surveyed as a heterogeneous catalyst for the amidation reaction. The catalyst was successfully recovered and reused for the reaction generating N-(pyridin-2-yl)-benzamide without a reduction in catalyst activity. To the best of our knowledge, the formation of N-(pyridin-2-yl) benzamide has not been previously achieved utilizing a heterogeneous catalyst. the amidation reaction between *trans*-1-nitro-phenylethylene and 2-aminopyridine to create N- (pyridin-2-yl)-benzamide under air. Fe2Ni-BDC showed higher productivity in the synthesis of N- (pyridin-2-yl)-benzamide than other metal–organic frameworks. The bimetallic metal–organic framework was surveyed as a heterogeneous catalyst for the amidation reaction. The catalyst was successfully recovered and reused for the reaction generating N-(pyridin-2-yl)-benzamide without a reduction in catalyst activity. To the best of our knowledge, the formation of N-(pyridin-2-yl) benzamide has not been previously achieved utilizing a heterogeneous catalyst. the amidation reaction between *trans*-1-nitro-phenylethylene and 2-aminopyridine to create N- (pyridin-2-yl)-benzamide under air. Fe2Ni-BDC showed higher productivity in the synthesis of N- (pyridin-2-yl)-benzamide than other metal–organic frameworks. The bimetallic metal–organic framework was surveyed as a heterogeneous catalyst for the amidation reaction. The catalyst was successfully recovered and reused for the reaction generating N-(pyridin-2-yl)-benzamide without a reduction in catalyst activity. To the best of our knowledge, the formation of N-(pyridin-2-yl) benzamide has not been previously achieved utilizing a heterogeneous catalyst. the amidation reaction between *trans*-1-nitro-phenylethylene and 2-aminopyridine to create N- (pyridin-2-yl)-benzamide under air. Fe2Ni-BDC showed higher in the synthesis of N- (pyridin-2-yl)-benzamide than other metal–organic frameworks. The bimetallic metal–organic framework was surveyed as a heterogeneous catalyst for the amidation reaction. The catalyst was successfully recovered and reused for the reaction generating N-(pyridin-2-yl)-benzamide without a reduction in catalyst activity. To the best of our knowledge, the formation of N-(pyridin-2-yl) benzamide has not been previously achieved utilizing a heterogeneous The bimetallic metal–organic framework Fe2Ni-BDC is a productive heterogeneous catalyst for the amidation reaction between *trans*-1-nitro-phenylethylene and 2-aminopyridine to create N- (pyridin-2-yl)-benzamide under air. Fe2Ni-BDC showed higher productivity in the synthesis of N- (pyridin-2-yl)-benzamide than other metal–organic frameworks. The bimetallic metal–organic framework was surveyed as a heterogeneous catalyst for the amidation reaction. The catalyst was successfully recovered and reused for the reaction generating N-(pyridin-2-yl)-benzamide without a reduction in catalyst activity. To the best of our knowledge, the formation of N-(pyridin-2-yl) benzamide has not been previously achieved utilizing a heterogeneous catalyst. The bimetallic metal–organic framework Fe2Ni-BDC is a productive heterogeneous catalyst for the amidation reaction between *trans*-1-nitro-phenylethylene and 2-aminopyridine to create N- (pyridin-2-yl)-benzamide under air. Fe2Ni-BDC showed higher productivity in the synthesis of N- (pyridin-2-yl)-benzamide than other metal–organic frameworks. The bimetallic metal–organic framework was surveyed as a heterogeneous catalyst for the amidation reaction. The catalyst was successfully recovered and reused for the reaction generating N-(pyridin-2-yl)-benzamide without a reduction in catalyst activity. To the best of our knowledge, the formation of N-(pyridin-2-yl) benzamide has not been previously achieved utilizing a heterogeneous catalyst. The bimetallic metal–organic framework Fe2Ni-BDC is a productive heterogeneous catalyst for the amidation reaction between *trans*-1-nitro-phenylethylene and 2-aminopyridine to create N- (pyridin-2-yl)-benzamide under air. Fe2Ni-BDC showed higher productivity in the synthesis of N- (pyridin-2-yl)-benzamide than other metal–organic frameworks. The bimetallic metal–organic framework was surveyed as a heterogeneous catalyst for the amidation reaction. The catalyst was successfully recovered and reused for the reaction generating N-(pyridin-2-yl)-benzamide without a reduction in catalyst activity. To the best of our knowledge, the formation of N-(pyridin-2-yl) benzamide has not been previously achieved utilizing a heterogeneous catalyst. The bimetallic metal–organic framework Fe2Ni-BDC is a productive heterogeneous catalyst for the amidation reaction between *trans*-1-nitro-phenylethylene and 2-aminopyridine to create N- (pyridin-2-yl)-benzamide under air. Fe2Ni-BDC showed higher productivity in the synthesis of N- (pyridin-2-yl)-benzamide than other metal–organic frameworks. The bimetallic metal–organic framework was surveyed as a heterogeneous catalyst for the amidation reaction. The catalyst was successfully recovered and reused for the reaction generating N-(pyridin-2-yl)-benzamide without a reduction in catalyst activity. To the best of our knowledge, the formation of N-(pyridin-2-yl) benzamide has not been previously achieved utilizing a heterogeneous catalyst. The bimetallic metal–organic framework Fe2Ni-BDC is a productive heterogeneous catalyst for the amidation reaction between *trans*-1-nitro-phenylethylene and 2-aminopyridine to create N- (pyridin-2-yl)-benzamide under air. Fe2Ni-BDC showed higher productivity in the synthesis of N- (pyridin-2-yl)-benzamide than other metal–organic frameworks. The bimetallic metal–organic framework was surveyed as a heterogeneous catalyst for the amidation reaction. The catalyst was successfully recovered and reused for the reaction generating N-(pyridin-2-yl)-benzamide without a reduction in catalyst activity. To the best of our knowledge, the formation of N-(pyridin-2-yl) benzamide has not been previously achieved utilizing a heterogeneous catalyst. The bimetallic metal–organic framework Fe2Ni-BDC is a productive heterogeneous catalyst for the amidation reaction between *trans*-1-nitro-phenylethylene and 2-aminopyridine to create N- (pyridin-2-yl)-benzamide under air. Fe2Ni-BDC showed higher productivity in the synthesis of N- (pyridin-2-yl)-benzamide than other metal–organic frameworks. The bimetallic metal–organic framework was surveyed as a heterogeneous catalyst for the amidation reaction. The catalyst was successfully recovered and reused for the reaction generating N-(pyridin-2-yl)-benzamide without a reduction in catalyst activity. To the best of our knowledge, the formation of N-(pyridin-2-yl) benzamide has not been previously achieved utilizing a heterogeneous catalyst. The bimetallic metal–organic framework Fe2Ni-BDC is a productive heterogeneous catalyst for the amidation reaction between *trans*-1-nitro-phenylethylene and 2-aminopyridine to create N-(pyridin-2-yl)-benzamide under air. Fe2Ni-BDC showed higher productivity in the synthesis of N-(pyridin-2-yl)-benzamide than other metal–organic frameworks. The bimetallic metal–organic framework was surveyed as a heterogeneous catalyst for the amidation reaction. The catalyst was successfully recovered and reused for the reaction generating N-(pyridin-2-yl)-benzamide without a reduction in catalyst activity. To the best of our knowledge, the formation of N-(pyridin-2-yl)-benzamide has not been previously achieved utilizing a heterogeneous catalyst.

**Supplementary Materials:** The following are available online at www.mdpi.com/xxx/s1: 1. General

**Supplementary Materials:** The following are available online at www.mdpi.com/xxx/s1: 1. General

**Supplementary Materials:** The following are available online at www.mdpi.com/xxx/s1: 1. General

**Supplementary Materials:** The following are available online at www.mdpi.com/xxx/s1: 1. General

**Supplementary Materials:** The following are available online at www.mdpi.com/xxx/s1: 1. General

**Supplementary Materials:** The following are available online at www.mdpi.com/xxx/s1: 1. General

**Supplementary Materials:** The following are available online at www.mdpi.com/xxx/s1: 1. General

**Supplementary Materials:** The following are available online at www.mdpi.com/xxx/s1: 1. General

**Supplementary Materials:** The following are available online at www.mdpi.com/xxx/s1: 1. General

**Supplementary Materials:** The following are available online at www.mdpi.com/xxx/s1: 1. General

**Supplementary Materials:** The following are available online at www.mdpi.com/xxx/s1: 1. General

of N-(4-methylpyridin-2-yl)benzamide. Figure S10: 1H-NMR spectra of 5-methyl-2-phenyl-1Hbenzo[d]imidazole. Figure S11: 13C-NMR spectra of 5-methyl-2-phenyl- 1H-benzo[d]imidazole. Figure S12: 1H-NMR spectra of N-(5-chloropyridin-2-yl)benzamide. Figure S13: 13C-NMR spectra of N-(5-chloropyridin-2-

yl)benzamide. Figure S8: 1H-NMR spectra of N-(4-methylpyridin-2-yl)benzamide. Figure S9: 13C-NMR spectra of N-(4-methylpyridin-2-yl)benzamide. Figure S10: 1H-NMR spectra of 5-methyl-2-phenyl-1Hbenzo[d]imidazole. Figure S11: 13C-NMR spectra of 5-methyl-2-phenyl- 1H-benzo[d]imidazole. Figure S12: 1H-

of N-(4-methylpyridin-2-yl)benzamide. Figure S10: 1H-NMR spectra of 5-methyl-2-phenyl-1Hbenzo[d]imidazole. Figure S11: 13C-NMR spectra of 5-methyl-2-phenyl- 1H-benzo[d]imidazole. Figure S12: 1H-NMR spectra of N-(5-chloropyridin-2-yl)benzamide. Figure S13: 13C-NMR spectra of N-(5-chloropyridin-2-

yl)benzamide. Figure S8: 1H-NMR spectra of N-(4-methylpyridin-2-yl)benzamide. Figure S9: 13C-NMR spectra of N-(4-methylpyridin-2-yl)benzamide. Figure S10: 1H-NMR spectra of 5-methyl-2-phenyl-1Hbenzo[d]imidazole. Figure S11: 13C-NMR spectra of 5-methyl-2-phenyl- 1H-benzo[d]imidazole. Figure S12: 1H-

of N-(4-methylpyridin-2-yl)benzamide. Figure S10: 1H-NMR spectra of 5-methyl-2-phenyl-1Hbenzo[d]imidazole. Figure S11: 13C-NMR spectra of 5-methyl-2-phenyl- 1H-benzo[d]imidazole. Figure S12: 1H-

of N-(4-methylpyridin-2-yl)benzamide. Figure S10: 1H-NMR spectra of 5-methyl-2-phenyl-1Hbenzo[d]imidazole. Figure S11: 13C-NMR spectra of 5-methyl-2-phenyl- 1H-benzo[d]imidazole. Figure S12: 1H-

of N-(4-methylpyridin-2-yl)benzamide. Figure S10: 1H-NMR spectra of 5-methyl-2-phenyl-1Hbenzo[d]imidazole. Figure S11: 13C-NMR spectra of 5-methyl-2-phenyl- 1H-benzo[d]imidazole. Figure S12: 1H-NMR spectra of N-(5-chloropyridin-2-yl)benzamide. Figure S13: 13C-NMR spectra of N-(5-chloropyridin-2-

of N-(4-methylpyridin-2-yl)benzamide. Figure S10: 1H-NMR spectra of 5-methyl-2-phenyl-1Hbenzo[d]imidazole. Figure S11: 13C-NMR spectra of 5-methyl-2-phenyl- 1H-benzo[d]imidazole. Figure S12: 1H-NMR spectra of N-(5-chloropyridin-2-yl)benzamide. Figure S13: 13C-NMR spectra of N-(5-chloropyridin-2-

of N-(4-methylpyridin-2-yl)benzamide. Figure S10: 1H-NMR spectra of 5-methyl-2-phenyl-1Hbenzo[d]imidazole. Figure S11: 13C-NMR spectra of 5-methyl-2-phenyl- 1H-benzo[d]imidazole. Figure S12: 1H-

of N-(4-methylpyridin-2-yl)benzamide. Figure S10: 1H-NMR spectra of 5-methyl-2-phenyl-1Hbenzo[d]imidazole. Figure S11: 13C-NMR spectra of 5-methyl-2-phenyl- 1H-benzo[d]imidazole. Figure S12: 1H-

of N-(4-methylpyridin-2-yl)benzamide.Figure S10: 1H-NMR spectra of 5-methyl-2-phenyl-1Hbenzo[d]imidazole. Figure S11: 13C-NMR spectra of 5-methyl-2-phenyl- 1H-benzo[d]imidazole. S12: 1H-

of N-(4-methylpyridin-2-yl)benzamide. Figure S10: 1H-NMR spectra of 5-methyl-2-phenyl-1Hbenzo[d]imidazole. Figure S11: 13C-NMR spectra of 5-methyl-2-phenyl- 1H-benzo[d]imidazole. Figure S12: 1H-NMR spectra of N-(5-chloropyridin-2-yl)benzamide. Figure S13: 13C-NMR spectra of N-(5-chloropyridin-2-

of N-(4-methylpyridin-2-yl)benzamide. Figure S10: 1H-NMR spectra of 5-methyl-2-phenyl-1Hbenzo[d]imidazole. Figure S11: 13C-NMR spectra of 5-methyl-2-phenyl- 1H-benzo[d]imidazole. Figure S12: 1H-NMR spectra of N-(5-chloropyridin-2-yl)benzamide. Figure S13: 13C-NMR spectra of N-(5-chloropyridin-2-

yl)benzamide. Figure S8: 1H-NMR spectra of N-(4-methylpyridin-2-yl)benzamide. Figure S9: 13C-NMR spectra of N-(4-methylpyridin-2-yl)benzamide. Figure S10: 1H-NMR spectra of 5-methyl-2-phenyl-1Hbenzo[d]imidazole. Figure S11: 13C-NMR spectra of 5-methyl-2-phenyl- 1H-benzo[d]imidazole. Figure S12: 1H-

of N-(4-methylpyridin-2-yl)benzamide. Figure S10: 1H-NMR spectra of 5-methyl-2-phenyl-1Hbenzo[d]imidazole. Figure S11: 13C-NMR spectra of 5-methyl-2-phenyl- 1H-benzo[d]imidazole. Figure S12: 1H-

**Author Contributions:** Data curation, O.K.T.N., V.H.N. and N.V.T.; Formal analysis, T.V.T. and S.T.D.; Methodology, T.V.T., V.H.N., N.V.T. and T.V.N.; Writing—original draft, O.K.T.N.; Writing—review and

**Author Contributions:** Data curation, O.K.T.N., V.H.N. and N.V.T.; Formal analysis, T.V.T. and S.T.D.; Methodology, T.V.T., V.H.N., N.V.T. and T.V.N.; Writing—original draft, O.K.T.N.; Writing—review and

yl)benzamide. Figure S14: 1H-NMR spectra of N-(pyridin-2-yl)benzamide. Figure S15: 13C-NMR spectra of N-

**Author Contributions:** Data curation, O.K.T.N., V.H.N. and N.V.T.; Formal analysis, T.V.T. and S.T.D.; Methodology, T.V.T., V.H.N., N.V.T. and T.V.N.; Writing—original draft, O.K.T.N.; Writing—review and

**Author Contributions:** Data curation, O.K.T.N., V.H.N. and N.V.T.; Formal analysis, T.V.T. and S.T.D.; Methodology, T.V.T., V.H.N., N.V.T. and T.V.N.; Writing—original draft, O.K.T.N.; Writing—review and

**Author Contributions:** Data curation, O.K.T.N., V.H.N. and N.V.T.; Formal analysis, T.V.T. and S.T.D.; Methodology, T.V.T., V.H.N., N.V.T. and T.V.N.; Writing—original draft, O.K.T.N.; Writing—review and

**Author Contributions:** Data curation, O.K.T.N., V.H.N. and N.V.T.; Formal analysis, T.V.T. and S.T.D.; Methodology, T.V.T., V.H.N., N.V.T. and T.V.N.; Writing—original draft, O.K.T.N.; Writing—review and

**Author Contributions:** Data curation, O.K.T.N., V.H.N. and N.V.T.; Formal analysis, T.V.T. and S.T.D.; Methodology, T.V.T., V.H.N., N.V.T. and T.V.N.; Writing—original draft, O.K.T.N.; Writing—review and

**Author Contributions:** Data curation, O.K.T.N., V.H.N. and N.V.T.; Formal analysis, T.V.T. and S.T.D.; Methodology, T.V.T., V.H.N., N.V.T. and T.V.N.; Writing—original draft, O.K.T.N.; Writing—review and

**Author Contributions:** Data curation, O.K.T.N., V.H.N. and N.V.T.; Formal analysis, T.V.T. and S.T.D.; Methodology, T.V.T., V.H.N., N.V.T. and T.V.N.; Writing—original draft, O.K.T.N.; Writing—review and

**Author Contributions:** Data curation, O.K.T.N., V.H.N. and N.V.T.; Formal analysis, T.V.T. and S.T.D.; Methodology, T.V.T., V.H.N., N.V.T. and T.V.N.; Writing—original draft, O.K.T.N.; Writing—review and

**Author Contributions:** Data curation, O.K.T.N., V.H.N. and N.V.T.; Formal analysis, T.V.T. and S.T.D.; Methodology, T.V.T., V.H.N., N.V.T. and T.V.N.; Writing—original draft, O.K.T.N.; Writing—review and

yl)benzamide. Figure S14: 1H-NMR spectra of N-(pyridin-2-yl)benzamide. Figure S15: 13C-NMR spectra of N-

**Author Contributions:** Data curation, O.K.T.N., V.H.N. and N.V.T.; Formal analysis, T.V.T. and S.T.D.; Methodology, T.V.T., V.H.N., N.V.T. and T.V.N.; Writing—original draft, O.K.T.N.; Writing—review and

**Author Contributions:** Data curation, O.K.T.N., V.H.N. and N.V.T.; Formal analysis, T.V.T. and S.T.D.; Methodology, T.V.T., V.H.N., N.V.T. and T.V.N.; Writing—original draft, O.K.T.N.; Writing—review and

yl)benzamide. Figure S14: 1H-NMR spectra of N-(pyridin-2-yl)benzamide. Figure S15: 13C-NMR spectra of N-

**Author Contributions:** Data curation, O.K.T.N., V.H.N. and N.V.T.; Formal analysis, T.V.T. and S.T.D.; Methodology, T.V.T., V.H.N., N.V.T. and T.V.N.; Writing—original draft, O.K.T.N.; Writing—review and

**Author Contributions:** Data curation, O.K.T.N., V.H.N. and N.V.T.; Formal analysis, T.V.T. and S.T.D.; Methodology, T.V.T., V.H.N., N.V.T. and T.V.N.; Writing—original draft, O.K.T.N.; Writing—review and

**Funding:** This research was funded by NTTU Foundation for Science and Technology Development under grant

**Funding:** This research was funded by NTTU Foundation for Science and Technology Development under grant

**Funding:** This research was funded by NTTU Foundation for Science and Technology Development under grant

**Funding:** This research was funded by NTTU Foundation for Science and Technology Development under grant

**Funding:** This research was funded by NTTU Foundation for Science and Technology Development under grant

**Funding:** This research was funded by NTTU Foundation for Science and Technology Development under grant

**Funding:** This research was funded by NTTU Foundation for Science and Technology Development under grant

**Funding:** This research was funded by NTTU Foundation for Science and Technology Development under grant

**Funding:** This research was funded by NTTU Foundation for Science and Technology Development under grant

**Funding:** This research was funded by NTTU Foundation for Science and Technology Development under grant

**Funding:** This research was funded by NTTU Foundation for Science and Technology Development under grant

**Funding:** This research was funded by NTTU Foundation for Science and Technology Development under grant

**Funding:** This research was funded by NTTU Foundation for Science and Technology Development under grant

**Funding:** This research was funded by NTTU Foundation for Science and Technology Development under grant

**Funding:** This research was funded by NTTU Foundation for Science and Technology Development under grant

experimental information. 2. General procedure for the synthesis of N-pyridyl benzamide. 3. General procedure of investigation for the synthesis of N-pyridinyl benzamide. 4. Characterization data for all products. Table S1: Optimization of reaction conditions. Figure S1: The presented simulated diffraction patterns for Ni-based was based on the corresponding check CIF file of Ni-BDC compare with experimental patterns. Figure S2: The presented simulated diffraction patterns for Fe-based was based on the corresponding check CIF file of MIL-53 (Fe) compare with experimental patterns. Figure S3: X-ray powder diffraction of Ni-BDC, Fe-BDC and Fe2Ni-BDC. Figure S4: FT-IR spectra of the Ni-BDC, Fe-BDC, and Fe2Ni-BDC. Figure S5: EDX mapping point of Fe2Ni-BDC. Figure S6: 1H-NMR spectra of N-(pyridin-2-yl)benzamide. Figure S7: 13C-NMR spectra of N-(pyridin-2 yl)benzamide. Figure S8: 1H-NMR spectra of N-(4-methylpyridin-2-yl)benzamide. Figure S9: 13C-NMR spectra experimental information. 2. General procedure for the synthesis of N-pyridyl benzamide. 3. General procedure of investigation for the synthesis of N-pyridinyl benzamide. 4. Characterization data for all products. Table S1: Optimization of reaction conditions. Figure S1: The presented simulated diffraction patterns for Ni-based was based on the corresponding check CIF file of Ni-BDC compare with experimental patterns. Figure S2: The presented simulated diffraction patterns for Fe-based was based on the corresponding check CIF file of MIL-53 (Fe) compare with experimental patterns. Figure S3: X-ray powder diffraction of Ni-BDC, Fe-BDC and Fe2Ni-BDC. Figure S4: FT-IR spectra of the Ni-BDC, Fe-BDC, and Fe2Ni-BDC. Figure S5: EDX mapping point of Fe2Ni-BDC. Figure S6: 1H-NMR spectra of N-(pyridin-2-yl)benzamide. Figure S7: 13C-NMR spectra of N-(pyridin-2 yl)benzamide. Figure S8: 1H-NMR spectra of N-(4-methylpyridin-2-yl)benzamide. Figure S9: 13C-NMR spectra experimental information. 2. General procedure for the synthesis of N-pyridyl benzamide. 3. General procedure of investigation for the synthesis of N-pyridinyl benzamide. 4. Characterization data for all products. Table S1: Optimization of reaction conditions. Figure S1: The presented simulated diffraction patterns for Ni-based was based on the corresponding check CIF file of Ni-BDC compare with experimental patterns. Figure S2: The presented simulated diffraction patterns for Fe-based was based on the corresponding check CIF file of MIL-53 (Fe) compare with experimental patterns. Figure S3: X-ray powder diffraction of Ni-BDC, Fe-BDC and Fe2Ni-BDC. Figure S4: FT-IR spectra of the Ni-BDC, Fe-BDC, and Fe2Ni-BDC. Figure S5: EDX mapping point of Fe2Ni-BDC. Figure S6: 1H-NMR spectra of N-(pyridin-2-yl)benzamide. Figure S7: 13C-NMR spectra of N-(pyridin-2 yl)benzamide. Figure S8: 1H-NMR spectra of N-(4-methylpyridin-2-yl)benzamide. Figure S9: 13C-NMR spectra experimental information. 2. General procedure for the synthesis of N-pyridyl benzamide. 3. General procedure of investigation for the synthesis of N-pyridinyl benzamide. 4. Characterization data for all products. Table S1: Optimization of reaction conditions. Figure S1: The presented simulated diffraction patterns for Ni-based was based on the corresponding check CIF file of Ni-BDC compare with experimental patterns. Figure S2: The presented simulated diffraction patterns for Fe-based was based on the corresponding check CIF file of MIL-53 (Fe) compare with experimental patterns. Figure S3: X-ray powder diffraction of Ni-BDC, Fe-BDC and Fe2Ni-BDC. Figure S4: FT-IR spectra of the Ni-BDC, Fe-BDC, and Fe2Ni-BDC. Figure S5: EDX mapping point of Fe2Ni-BDC. Figure S6: 1H-NMR spectra of N-(pyridin-2-yl)benzamide. Figure S7: 13C-NMR spectra of N-(pyridin-2 yl)benzamide. Figure S8: 1H-NMR spectra of N-(4-methylpyridin-2-yl)benzamide. Figure S9: 13C-NMR spectra experimental information. 2. General procedure for the synthesis of N-pyridyl benzamide. 3. General procedure of investigation for the synthesis of N-pyridinyl benzamide. 4. Characterization data for all products. Table S1: Optimization of reaction conditions. Figure S1: The presented simulated diffraction patterns for Ni-based was based on the corresponding check CIF file of Ni-BDC compare with experimental patterns. Figure S2: The presented simulated diffraction patterns for Fe-based was based on the corresponding check CIF file of MIL-53 (Fe) compare with experimental patterns. Figure S3: X-ray powder diffraction of Ni-BDC, Fe-BDC and Fe2Ni-BDC. Figure S4: FT-IR spectra of the Ni-BDC, Fe-BDC, and Fe2Ni-BDC. Figure S5: EDX mapping point of Fe2Ni-BDC. Figure S6: 1H-NMR spectra of N-(pyridin-2-yl)benzamide. Figure S7: 13C-NMR spectra of N-(pyridin-2 yl)benzamide. Figure S8: 1H-NMR spectra of N-(4-methylpyridin-2-yl)benzamide. Figure S9: 13C-NMR spectra experimental information. 2. General procedure for the synthesis of N-pyridyl benzamide. 3. General procedure of investigation for the synthesis of N-pyridinyl benzamide. 4. Characterization data for all products. Table S1: Optimization of reaction conditions. Figure S1: The presented simulated diffraction patterns for Ni-based was based on the corresponding check CIF file of Ni-BDC compare with experimental patterns. Figure S2: The presented simulated diffraction patterns for Fe-based was based on the corresponding check CIF file of MIL-53 (Fe) compare with experimental patterns. Figure S3: X-ray powder diffraction of Ni-BDC, Fe-BDC and Fe2Ni-BDC. Figure S4: FT-IR spectra of the Ni-BDC, Fe-BDC, and Fe2Ni-BDC. Figure S5: EDX mapping point of Fe2Ni-BDC. Figure S6: 1H-NMR spectra of N-(pyridin-2-yl)benzamide. Figure S7: 13C-NMR spectra of N-(pyridin-2 yl)benzamide. Figure S8: 1H-NMR spectra of N-(4-methylpyridin-2-yl)benzamide. Figure S9: 13C-NMR spectra experimental information. 2. General procedure for the synthesis of N-pyridyl benzamide. 3. General procedure of investigation for the synthesis of N-pyridinyl benzamide. 4. Characterization data for all products. Table S1: Optimization of reaction conditions. Figure S1: The presented simulated diffraction patterns for Ni-based was based on the corresponding check CIF file of Ni-BDC compare with experimental patterns. Figure S2: The presented simulated diffraction patterns for Fe-based was based on the corresponding check CIF file of MIL-53 (Fe) compare with experimental patterns. Figure S3: X-ray powder diffraction of Ni-BDC, Fe-BDC and Fe2Ni-BDC. Figure S4: FT-IR spectra of the Ni-BDC, Fe-BDC, and Fe2Ni-BDC. Figure S5: EDX mapping point of Fe2Ni-BDC. Figure S6: 1H-NMR spectra of N-(pyridin-2-yl)benzamide. Figure S7: 13C-NMR spectra of N-(pyridin-2 yl)benzamide. Figure S8: 1H-NMR spectra of N-(4-methylpyridin-2-yl)benzamide. Figure S9: 13C-NMR spectra experimental information. 2. General procedure for the synthesis of N-pyridyl benzamide. 3. General procedure of investigation for the synthesis of N-pyridinyl benzamide. 4. Characterization data for all products. Table S1: Optimization of reaction conditions. Figure S1: The presented simulated diffraction patterns for Ni-based was based on the corresponding check CIF file of Ni-BDC compare with experimental patterns. Figure S2: The presented simulated diffraction patterns for Fe-based was based on the corresponding check CIF file of MIL-53 (Fe) compare with experimental patterns. Figure S3: X-ray powder diffraction of Ni-BDC, Fe-BDC and Fe2Ni-BDC. Figure S4: FT-IR spectra of the Ni-BDC, Fe-BDC, and Fe2Ni-BDC. Figure S5: EDX mapping point of Fe2Ni-BDC. Figure S6: 1H-NMR spectra of N-(pyridin-2-yl)benzamide. Figure S7: 13C-NMR spectra of N-(pyridin-2 yl)benzamide. Figure S8: 1H-NMR spectra of N-(4-methylpyridin-2-yl)benzamide. Figure S9: 13C-NMR spectra experimental information. 2. General procedure for the synthesis of N-pyridyl benzamide. 3. General procedure of investigation for the synthesis of N-pyridinyl benzamide. 4. Characterization data for all products. Table S1: Optimization of reaction conditions. Figure S1: The presented simulated diffraction patterns for Ni-based was based on the corresponding check CIF file of Ni-BDC compare with experimental patterns. Figure S2: The presented simulated diffraction for Fe-based was based on the corresponding check CIF file MIL-53 (Fe) compare with experimental patterns. Figure S3: X-ray powder diffraction of Ni-BDC, Fe-BDC and Fe2Ni- Figure S4: FT-IR spectra of the Ni-BDC, Fe-BDC, and Fe2Ni-BDC. Figure S5: EDX mapping point Fe2Ni-BDC. Figure S6: 1H-NMR spectra of N-(pyridin-2-yl)benzamide. Figure S7: 13C-NMR spectra of N-(pyridin-2 yl)benzamide. Figure S8: 1H-NMR spectra of N-(4-methylpyridin-2-yl)benzamide. Figure S9: 13C-NMR spectra experimental information. 2. General procedure for the synthesis of N-pyridyl benzamide. 3. General procedure of investigation for the synthesis of N-pyridinyl benzamide. 4. Characterization data for all products. Table S1: Optimization of reaction conditions. Figure S1: The presented simulated diffraction patterns for Ni-based was based on the corresponding check CIF file of Ni-BDC compare with experimental patterns. Figure S2: The presented simulated diffraction patterns for Fe-based was based on the corresponding check CIF file of MIL-53 (Fe) compare with experimental patterns. Figure S3: X-ray powder diffraction of Ni-BDC, Fe-BDC and Fe2Ni-BDC. Figure S4: FT-IR spectra of the Ni-BDC, Fe-BDC, and Fe2Ni-BDC. Figure S5: EDX mapping point of Fe2Ni-BDC. Figure S6: 1H-NMR spectra of N-(pyridin-2-yl)benzamide. Figure S7: 13C-NMR spectra of N-(pyridin-2 yl)benzamide. Figure S8: 1H-NMR spectra of N-(4-methylpyridin-2-yl)benzamide. Figure S9: 13C-NMR spectra **Supplementary Materials:** The following are available online at www.mdpi.com/xxx/s1: 1. General experimental information. 2. General procedure for the synthesis of N-pyridyl benzamide. 3. General procedure of investigation for the synthesis of N-pyridinyl benzamide. 4. Characterization data for all products. Table S1: Optimization of reaction conditions. Figure S1: The presented simulated diffraction patterns for Ni-based was based on the corresponding check CIF file of Ni-BDC compare with experimental patterns. Figure S2: The presented simulated diffraction patterns for Fe-based was based on the corresponding check CIF file of MIL-53 (Fe) compare with experimental patterns. Figure S3: X-ray powder diffraction of Ni-BDC, Fe-BDC and Fe2Ni-BDC. Figure S4: FT-IR spectra of the Ni-BDC, Fe-BDC, and Fe2Ni-BDC. Figure S5: EDX mapping point of Fe2Ni-BDC. Figure S6: 1H-NMR spectra of N-(pyridin-2-yl)benzamide. Figure S7: 13C-NMR spectra of N-(pyridin-2 yl)benzamide. Figure S8: 1H-NMR spectra of N-(4-methylpyridin-2-yl)benzamide. Figure S9: 13C-NMR spectra experimental information. 2. General procedure for the synthesis of N-pyridyl benzamide. 3. General procedure of investigation for the synthesis of N-pyridinyl benzamide. 4. Characterization data for all products. Table S1: Optimization of reaction conditions. Figure S1: The presented simulated diffraction patterns for Ni-based was based on the corresponding check CIF file of Ni-BDC compare with experimental patterns. Figure S2: The presented simulated diffraction patterns for Fe-based was based on the corresponding check CIF file of MIL-53 (Fe) compare with experimental patterns. Figure S3: X-ray powder diffraction of Ni-BDC, Fe-BDC and Fe2Ni-BDC. Figure S4: FT-IR spectra of the Ni-BDC, Fe-BDC, and Fe2Ni-BDC. Figure S5: EDX mapping point of Fe2Ni-BDC. Figure S6: 1H-NMR spectra of N-(pyridin-2-yl)benzamide. Figure S7: 13C-NMR spectra of N-(pyridin-2 yl)benzamide. Figure S8: 1H-NMR spectra of N-(4-methylpyridin-2-yl)benzamide. Figure S9: 13C-NMR spectra **Supplementary Materials:** The following are available online at www.mdpi.com/xxx/s1: 1. General experimental information. 2. General procedure for the synthesis of N-pyridyl benzamide. 3. General procedure of investigation for the synthesis of N-pyridinyl benzamide. 4. Characterization data for all products. Table S1: Optimization of reaction conditions. Figure S1: The presented simulated diffraction patterns for Ni-based was based on the corresponding check CIF file of Ni-BDC compare with experimental patterns. Figure S2: The presented simulated diffraction patterns for Fe-based was based on the corresponding check CIF file of MIL-53 (Fe) compare with experimental patterns. Figure S3: X-ray powder diffraction of Ni-BDC, Fe-BDC and Fe2Ni-BDC. Figure S4: FT-IR spectra of the Ni-BDC, Fe-BDC, and Fe2Ni-BDC. Figure S5: EDX mapping point of Fe2Ni-BDC. Figure S6: 1H-NMR spectra of N-(pyridin-2-yl)benzamide. Figure S7: 13C-NMR spectra of N-(pyridin-2- **Supplementary Materials:** The following are available online at www.mdpi.com/xxx/s1: 1. General experimental information. 2. General procedure for the synthesis of N-pyridyl benzamide. 3. General procedure of investigation for the synthesis of N-pyridinyl benzamide. 4. Characterization data for all products. Table S1: Optimization of reaction conditions. Figure S1: The presented simulated diffraction patterns for Ni-based was based on the corresponding check CIF file of Ni-BDC compare with experimental patterns. Figure S2: The presented simulated diffraction patterns for Fe-based was based on the corresponding check CIF file of MIL-53 (Fe) compare with experimental patterns. Figure S3: X-ray powder diffraction of Ni-BDC, Fe-BDC and Fe2Ni-BDC. Figure S4: FT-IR spectra of the Ni-BDC, Fe-BDC, and Fe2Ni-BDC. Figure S5: EDX mapping point of Fe2Ni-BDC. Figure S6: 1H-NMR spectra of N-(pyridin-2-yl)benzamide. Figure S7: 13C-NMR spectra of N-(pyridin-2- **Supplementary Materials:** The following are available online at www.mdpi.com/xxx/s1: 1. General experimental information. 2. General procedure for the synthesis of N-pyridyl benzamide. 3. General procedure of investigation for the synthesis of N-pyridinyl benzamide. 4. Characterization data for all products. Table S1: Optimization of reaction conditions. Figure S1: The presented simulated diffraction patterns for Ni-based was based on the corresponding check CIF file of Ni-BDC compare with experimental patterns. Figure S2: The presented simulated diffraction patterns for Fe-based was based on the corresponding check CIF file of MIL-53 (Fe) compare with experimental patterns. Figure S3: X-ray powder diffraction of Ni-BDC, Fe-BDC and Fe2Ni-BDC. Figure S4: FT-IR spectra of the Ni-BDC, Fe-BDC, and Fe2Ni-BDC. Figure S5: EDX mapping point of Fe2Ni-BDC. Figure S6: 1H-NMR spectra of N-(pyridin-2-yl)benzamide. Figure S7: 13C-NMR spectra of N-(pyridin-2- **Supplementary Materials:** The following are available online at http://www.mdpi.com/2227-9717/7/11/789/s1: 1. General experimental information. 2. General procedure for the synthesis of N-pyridyl benzamide. 3. General procedure of investigation for the synthesis of N-pyridinyl benzamide. 4. Characterization data for all products. Table S1: Optimization of reaction conditions. Figure S1: The presented simulated diffraction patterns for Ni-based was based on the corresponding check CIF file of Ni-BDC compare with experimental patterns. Figure S2: The presented simulated diffraction patterns for Fe-based was based on the corresponding check CIF file of MIL-53 (Fe) compare with experimental patterns. Figure S3: X-ray powder diffraction of Ni-BDC, Fe-BDC and Fe2Ni-BDC. Figure S4: FT-IR spectra of the Ni-BDC, Fe-BDC, and Fe2Ni-BDC. Figure S5: EDX mapping point of Fe2Ni-BDC. Figure S6: <sup>1</sup>H-NMR spectra of N-(pyridin-2-yl)benzamide. Figure S7: <sup>13</sup>C-NMR spectra of N-(pyridin-2-yl)benzamide.

Figure S8: <sup>1</sup>H-NMR spectra of N-(4-methylpyridin-2-yl)benzamide. Figure S9: <sup>13</sup>C-NMR spectra of N-(4-methylpyridin-2-yl)benzamide. Figure S10: <sup>1</sup>H-NMR spectra of 5-methyl-2-phenyl-1H-benzo[d]imidazole. Figure S11: <sup>13</sup>C-NMR spectra of 5-methyl-2-phenyl- 1H-benzo[d]imidazole. Figure S12: <sup>1</sup>H-NMR spectra of N-(5-chloropyridin-2-yl)benzamide. Figure S13: <sup>13</sup>C-NMR spectra of N-(5-chloropyridin-2-yl)benzamide. Figure S14: 1H-NMR spectra of N-(pyridin-2-yl)benzamide. Figure S15: <sup>13</sup>C-NMR spectra of N-(pyridin-2-yl)benzamide.

**Author Contributions:** Data curation, O.K.T.N., V.H.N. and N.V.T.; Formal analysis, T.V.T. and S.T.D.; Methodology, T.V.T., V.H.N., N.V.T. and T.V.N.; Supervision, T.D.N.; Writing—original draft, O.K.T.N.; Writing—review and editing, L.G.B., D-.V.N.V., T.V.N., S.-S.H. and S.T.D.

**Funding:** This work was supported by the Vietnam National Foundation for Science and Technology Development (NAFOSTED) under grant number 104.01-2019.16.

**Conflicts of Interest:** The authors declare no conflict of interest.
