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Article

Synthesis, Supramolecular Structural Investigations of Co(II) and Cu(II) Azido Complexes with Pyridine-Type Ligands

by
Mezna Saleh Altowyan
1,
Jörg H. Albering
2,
Assem Barakat
3,
Saied M. Soliman
4,* and
Morsy A. M. Abu-Youssef
4,*
1
Department of Chemistry, College of Science, Princess Nourah bint Abdulrahman University, P.O. Box 84428, Riyadh 11671, Saudi Arabia
2
Graz University of Technology, Mandellstr. 11/III, A-8010 Graz, Austria
3
Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia
4
Department of Chemistry, Faculty of Science, Alexandria University, P.O. Box 426, Ibrahimia, Alexandria 21321, Egypt
*
Authors to whom correspondence should be addressed.
Crystals 2023, 13(2), 346; https://doi.org/10.3390/cryst13020346
Submission received: 31 January 2023 / Revised: 12 February 2023 / Accepted: 15 February 2023 / Published: 17 February 2023
(This article belongs to the Special Issue New Advances in Transition Metal Complexes)
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Abstract

:
Two new Co(II) and Cu(II) azido complexes with 4-picoline (4-Pic) and pyridine-2-carboxaldoxime (HAld) were synthesized by self-assembly of the organic ligand and the M(II) nitrate in the presence of azide as a co-ligand. Their structures were determined to be [Co(4-Pic)4(H2O)(N3)]NO3*H2O*4-Pic (1) and [Cu(HAld)(Ald)(N3)] (2) using X-ray single crystal diffraction. In complex 1, the coordination geometry is a slightly distorted octahedron with a water molecule and azide ion located trans to one another. On the other hand, complex 2 has a distorted square pyramid CuN5 coordination sphere with N-atoms of the organic ligand as a basal plane and azide ion as apical. All types of intermolecular contacts and their contributions in the molecular packing were analyzed using Hirshfeld analysis. The intermolecular contacts, H…H (53.9%), O…H (14.1%), N…H (11.0%) and H…C (18.8%) in 1, and H…H (27.4%), N…H (27.7%), O…H (14.7%) and H…C (13.6%) in 2 have the largest contributions. Of all the contacts, the O…H, N…H and C…C interactions in 2 and the O…H, N…H and H…C in 1 are apparently shorter than the van der Waals radii sum of the interacting atoms. Atoms in molecules (AIM) topological parameters explained the lower symmetry of the coordinated azide in 1 than 2.

1. Introduction

Metal complexes have attracted the attention of researchers for their diverse and fascinating applications in different fields [1,2,3,4,5,6]. These compounds have interesting applications such as gas storage and separation of ions [7,8]. On the other hand, the coordination environment in metal complexes depends on many factors such as the nature of the metal ion, ligand and medium used [9,10]. Moreover, the presence of linker group such as azide has a great impact not only on the dimensionality of the resulting coordination compound but also on their functionality and applications [11,12,13,14,15,16,17,18,19,20,21].
The chemistry of azide containing compounds has attracted the attention of scientist due to the versatile applications of these compounds especially in the field of explosives. Some metal azides such as Pb(N3)2 and Cu(N3)2 are well known explosives [22,23]. Moreover, azide compounds are important as propellants in air bags [24]. Hence, these compounds could be considered as a good source of energy. Intuitively, the increase in N3− ion content in a compound has a vital role in obtaining better energy sources. Moreover, the azide binding mode in metal complexes is an important factor in achieving this purpose. Many azide binding modes have been reported in the literature, ranging from ionic, terminal and µ-1,1 (end-on) to µ-1,3 (end-to-end) bridging modes. The azide binding modes depend on a number of factors including the type and oxidation state of the metal ion and the nature of the auxiliary ligand. Moreover, these factors have an important role in upholding the stability of the azide containing compounds. Cobalt azide complexes are generally stable compounds [25,26,27]. As a result, these azide complexes could be considered as promising compounds for tunable heat energy release. Based on the literature, the [Co(NH3)5(N3)](N3)2 complex is the first well known azide complex [28].
On the other hand, nitrogen heterocycles such as pyridine compounds have great importance as ligands in coordination chemistry [29,30,31]. The introduction of the substituent has a pivotal role in changing the electronic, steric and conformational characteristics of the ligand which affect the ligand coordination ability [32,33,34,35,36,37,38,39]. In light of the fascinating structure and applications of azido complexes [40,41,42] with various N-heterocycles, our plan in the current work is to synthesize the Co(II) and Cu(II) azido complexes of 4-picoline (4-Pic) and pyridine-2-carboxaldoxime (HAld) (Figure 1). Combined experimental and theoretical studies were used to shed light on their structural aspects. In this regard, the structures obtained from the single crystal X-ray diffraction analyses were studied using Hirshfeld and DFT calculations.

2. Experiment

2.1. Physicochemical Characterizations

All details regarding chemicals and physicochemical characterizations are given in Supplementary data.

2.2. Synthesis of the Metal Complexes 1 and 2

2.2.1. Synthesis of [Co(4-Pic)4(H2O)(N3)]NO3*H2O*4-Pic; 1

A solution of Co(NO3)2.6H2O (0.2 mmole in 10 mL ethanol) was added to 10 mL ethanolic solution of 1.0 mmole 4-picoline (4-Pic), then 1 mL saturated aqueous solution of NaN3 was added dropwise with constant stirring for 10 min followed by filtration and the clear filtrate was left to slowly evaporate at rt. After one week, pink crystals of 1 were obtained.
[Co(4-Pic)4(H2O)(N3)]NO3*H2O*4-Pic; 1: Yield: 65%; Anal. Calcd. C30H39CoN9O5: C, 54.21; H, 5.91; N, 18.97; Co, 8.87%. Found: C, 54.09; H, 5.84; N, 18.83; Co, 8.96%.

2.2.2. Synthesis of [Cu(HAld)(Ald)(N3)]; 2

A solution of Cu(NO3)2.3H2O (0.2 mmole in 10 mL ethanol) was added to 10 mL ethanolic solution of 0.4 mmole pyridine-2-aldoxime (HAld), then 1 mL saturated aqueous solution of NaN3 was added dropwise with constant stirring for 10 min followed by filtration and the clear filtrate was left to slowly evaporate at rt. After 5 days, dark green crystals of 2 were obtained.
[Cu(HAld)(Ald)(N3)]; 2: Yield: 69%; Anal. Calcd. C12H11CuN7O2: C, 41.32; H, 3.18; N, 28.11; Cu, 18.22%. Found: C, 41.21; H, 3.11; N, 27.97; Cu, 18.10%.

2.3. X-ray Diffraction Analysis

The crystal structures of the two azide complexes were determined as described in the Supplementary Materials [43,44]. Crystal data are given in Table 1. It is worth noting that the crystals of complex 1 were extremely brittle and tended to decompose after a while on the diffractometer. The measurement was stopped before it was completed—due to crystal decomposition. Upon cooling, the material crumbled, ending up in a more or less polycrystalline lump. Thus, we decided to use the data measured at the best crystal in the sample and solve the structure based upon these data. Anyway even with the reduced dataset it was possible to determine the structure properly, without any deviations from the ideal shape of the displacement parameters or unusual interatomic distances.

3. Hirshfeld and DFT Calculations

The topology analyses including Hirshfeld calculations, construction of the different maps (dnorm, shape index (SI) and curvedness) and decomposition of the different intermolecular contacts were performed using Crystal Explorer 17.5 program [45,46,47]. DFT computational details are described in the Supplementary Materials [48,49,50,51,52].

4. Results and Discussion

4.1. X-ray Structure Description

4.1.1. Structure of [Co(4-Pic)4(H2O)(N3)]NO3*H2O*4-Pic; 1

This Co(II) complex crystallizes in the monoclinic crystal system and space group P21/c. The unit cell parameters are a = 11.3305(7) Å, b = 11.3887(15) Å, c = 25.9243(16) Å and β= 101.672(2)°, 101.672(2)°, V = 3276.1(5) A3, Z = 4. Compound 1 is a cationic complex in which the coordination sphere comprises a hexa-coordinated Co(II) ion (Figure 2). There are four Co-N interactions with the four 4-Pic ligand units as N-donor ligand via the heterocyclic nitrogen of the pyridine moiety. The Co-N lengths vary from 2.160(4) Å (Co1-N4) to 2.211(3) Å (Co1-N5). The angles of the trans bonds N4-Co1-N6 and N5-Co1-N7 are 178.48(10)° and 175.25(10)°, respectively, while the angles of the cis N-Co-N bonds range from 87.04(14)° (N6-Co1-N7) to 93.06(13)° (N4-Co1-N5). The coordination sphere of the Co(II) is completed by a terminally coordinated azide ion and a water molecule located trans to one another. The corresponding Co1-N1 and Co1-O1 bond lengths are 2.102(3) and 2.091(2) Å, respectively, while the O1-Co1-N1 is 178.79(16)° which is very close to the ideal value of 180° (Table 2). Hence the CoN5O coordination geometry is a slightly distorted octahedron. The outer sphere of 1 contains one nearby nitrate anion and two neutral molecules, which are the crystal water and a fifth free 4-Pic molecule.
The structure of complex 1 comprised numerous intra- and intermolecular hydrogen bonding interactions. Presentation of these hydrogen bond contacts is shown in Figure 3 while the hydrogen bond parameters are depicted in Table 3. It is clear that the nitrate counter anion in the outer sphere acts as a hydrogen bond acceptor which connects the crystal water and free 4-Pic molecules with the complex cationic part via the coordinated water as hydrogen bond donor. Moreover, the latter form a short and strong O1-H2A…O2 hydrogen bond with the crystal water as hydrogen bond acceptor. It is worth noting that there is no significant direct interaction between the complex cationic unit and the free 4-Pic molecule.
As shown in Figure 4, there is an alternating arrangement for the inner and outer spheres of the complex. In this packing structure the complex cationic units form nearly parallel layers along the bc plane, while a second layer of the crystal water, nitrate anion and the free 4-Pic molecule interpenetrate the layers of the cationic complex. The two layer structures are held together via a complicated set of weak and strong H…O bridges.

4.1.2. Structure of [Cu(HAld)(Ald)(N3)]; 2

This Cu(II) complex crystallizes in the monoclinic crystal system and space group P21/n. The unit cell parameters are a = 6.8277(2) Å, b = 10.2203(2) Å, c = 18.8056(6) Å and 94.700(2)°, V = 1307.86(6) A3, Z = 4. Compound 2 is a neutral complex in which the Cu(II) is penta-coordinated with the two HAld/Ald− organic ligand combination as bidentate NN-chelate, in addition to one terminally coordinated azide ion (Figure 5). In this structure, the HAld/Ald− organic ligand combination represents one deprotonated mononegative (Ald−) and one neutral (HAld) unit. Hence, the X-ray structure of this complex comprised electrically neutral monomers of the [Cu(HAld)(Ald)(N3)] complex. Selected bond lengths and angles for the coordination sphere are depicted in Table 4. The Cu-N(pyridine) lengths are generally longer than the Cu-N(oxime) in both ligand units. The Cu1-N1 (2.0341(9) Å) and Cu1-N2 (1.9967(9) Å) bonds in one unit are slightly longer than the corresponding Cu1-N3 (2.0480(9) Å) and Cu1-N4 (1.9946(9) Å) bonds in the other ligand unit. The last Cu1-N5 interaction with the azide ligand is the longest (2.2158(10) Å). Hence the structure of the coordination sphere is more like a distorted square pyramid where the N-atoms from the organic ligand units represent the base of the square while the N5 atom from the azide anion acts as apical. Based on Addison criterion [53], the largest angles N4-Cu1-N1 (β = 170.83°) and N2-Cu1-N3 (α = 156.74°) give a τ = ( β − α ) 60 value of 0.24 suggesting as a distorted square pyramid CuN5 coordination environment.
The analysis of the residual electron densities in the region of the oxygen atoms of the oxime ligands showed two approximately equal peaks for the protons of the N-O-H group. Therefore, a split position for this proton was added, the H1 and H2 positions. It is obvious that the neutral protonated ligand (HAld) and the deprotonated anion (Ald)− are statistically distributed 50:50 to the respective position. The fact that the displacement ellipsoids are more or less round leads to the assumption that this disorder has hardly any influence on the crystal structure and the interatomic distances and bond angles.
As can be seen from Figure 5, the two organic ligand units are located syn to one another and found stabilized by the intramolecular O-H…O hydrogen bridge shown as a turquoise dotted line in Figure 6A. In addition, the structure of 2 showed some intermolecular O…H and N…H hydrogen bridge contacts which connect the complex molecules to build the 3D supramolecular structure of this complex (Table 5). In this complex, all the intermolecular contacts belong to the weak C-H…O and C-H…N interactions where the oxime oxygen and the azide nitrogen are the hydrogen bond acceptor sites while the aromatic C-H bonds are the hydrogen bond donors. Presentation of the packing scheme along the a-axis is shown in Figure 6B.
An interesting feature of packing for the complex units in 2 is shown in Figure 7A. The molecules of complex 2 are connected via the C-H…N and C-H…O interactions along the ac plane. The aromatic ring systems are nearly parallel to one another, leading to some π-π stacking interactions which connect the complex units through the a-direction (Figure 7B). The shortest C…C contacts are C2…C10 (3.383 Å) and C3…C8 (3.325 Å).

4.2. Analysis of Molecular Packing

The results of the Hirshfeld calculations are important for accurately analyzing the molecular packing of crystalline compounds. Different maps such as dnorm, shape index and curvedness are important for deciding the important contacts (Figures S1 and S2 (Supplementary Materials)). The fingerprint plot was used to quantitatively estimate the different intermolecular contacts affecting the packing of this complex in the crystal. The dominant contacts are the H…H (53.9%), O…H (14.1%), N…H (11.0%) and H…C (18.8%) interactions (Figure 8). Not all these contacts showed the characteristics of strong interactions. The red spots in the dnorm map are related to the short distance O…H, N…H and H…C contacts. Moreover, the fingerprint plots of these contacts showed the characteristic spikes of strong intermolecular interactions (Figure 8).
There is extensive number of the polar O…H interactions which are shorter than the vdWs radii sum of the O and H atoms. Moreover, some significantly short N…H and H…C interactions were detected. List of the short contacts and the corresponding interaction distances are depicted in Table 6. The shortest interaction distances are 2.445, 2.676 and 1.682 Å, corresponding to N9…H1A, H3A…C25 and O2…H2A contacts, respectively.
In the neutral Cu(II) complex 2, the crystal stability is controlled by a large number of intermolecular contacts such as the H…H (27.4%), N…H (27.7%), O…H (14.7%), H…C (13.6%) which are considered the most dominant contacts in the crystal packing (Figure 9). Only the O…H, N…H and C…C interactions appeared as red regions in the dnorm map, indicating that these contacts are shorter than the vdW radii sum of the interacting atoms (Table 6). The N7…H11, O2…H3 and C3…C8 interactions are the shortest and the corresponding interaction distances are 2.406, 2.424 and 3.325 Å, respectively. Moreover, the SI map showed the characteristic red/blue triangles for the π-π interactions (Figure 9).

4.3. AIM Studies

The free N3− ion is symmetric as the two N-N bonds are equidistant. In contrast, the coordinated azide is asymmetric and the two N-N bonds are not equivalent [54,55]. In this regard, the atoms in molecules (AIM) calculations [51,56,57,58,59,60,61] were used to judge this behavior in the studied Co(II) and Cu(II) complexes. The calculated AIM topological parameters of the N-N bonds are presented in Table 7. From the first glance, the two N-N bonds of the coordinated azide are not equivalent. The difference in the N-N distances are 0.04 and 0.02 Å in complexes 1 and 2, respectively where the NA-NB bonds are generally longer than the NB-NC ones (Figure 10). Hence, the formation of the metal azide bond affects its symmetry.
The electron density (ρ(r)) at the bond critical point was used as a measure for the bond strength. The ρ(r) values of the NA-NB bonds are calculated to be 0.4847 and 0.4833 a.u. in complexes 1 and 2, respectively. The corresponding values for the NB-NC bonds are 0.5424 and 0.5105 a.u., respectively. These results are in agreement with the NA-NB bonds longer than the NB-NC ones in both complexes. Moreover, the results indicated that the degree of asymmetry is higher in the case of complex 1 than 2. On the other hand, the ρ(r) values at the N-N BCPs are higher than 0.1 a.u. and the ∇ 2 ρ(r) values are negative, indicating clear covalent interactions (Table 7).
Another application of the AIM parameters is to identify the nature and strength of the different M-N and M-O bonds in the studied systems (Table 8). The low electron density (ρ(r) < 0.10 au) values and positive H(r) as well as the positive ∇ 2 ρ(r) and V(r)/G(r) < 1 for the Co-N bonds with the organic ligand indicated mainly closed shell coordination interactions [62,63,64,65]. The same is true for the Co-O bond with the coordinated water molecule. The Co-N(azide) bond has more negative H(r) and slightly higher V(r)/G(r) than the Co-N(4-Pic). The slightly negative H(r) and V(r)/G(r) marginally higher than 1 for all Cu-N bonds in 2 revealed very few covalent characters. On the other hand, the high ρ(r) values are indicative on the bond strength. As can be seen from Table 8, shorter coordination interaction for a given bond has higher ρ(r) values at the BCP than the longer one.

4.4. Natural Charges

Decomposition of the charge distribution at the different ligand groups coordinated to the metal ion enabled us to assess the amount of electron density transferred from the ligand groups as Lewis base to the metal ion as Lewis acid. Natural charge calculations of complexes 1 and 2 were used to predict the amount of electron density transferred from the ligand groups to the donor atoms. A summary of natural charges at these fragments is presented in Table 9. The charges at the metal centers are +0.9623 and + 0.7655 for complexes 1 and 2, respectively instead of +2. Hence, there is 1.0377 e and 1.2345 e were transferred from the ligand groups to Co(II) and Cu(II), respectively. In case of the former, 0.5804 e was transferred from the four 4-Pic ligand units while the azide and water molecule transferred 0.2862 and 0.1278, respectively. In the case of the latter, 0.3354 e was transferred from the neutral HAld while the anionic Ald− and azide ions transferred 0.6198 e and 0.2973 e to the Cu(II) site, respectively.

5. Conclusions

The molecular and supramolecular structures of the monomeric complexes [Co(4-Pic)4(H2O)(N3)]NO3*H2O*4-Pic (1) and [Cu(HAld)(Ald)(N3)] (2) were presented. In complex 1, the CuN5O coordination geometry is a slightly distorted octahedron while the CuN5 coordination sphere in complex 2 has a square pyramidal configuration. In both complexes, the azide ion is terminally coordinated with the metal ion. For the organic ligands used in this work, the 4-picoline (4-Pic) is a monodentate ligand in 1 while the pyridine-2-carboxaldoxime (HAld) is a bidentate chelate in 2. The crystal packing is dominated by H…H, O…H, N…H and H…C interactions in 1 based on Hirshfeld analysis. For 2, the H…H, N…H, O…H and H…C are the most dominant contacts. The charges at the metal centers are calculated to be +0.9623 and +0.7655 for complexes 1 and 2. Moreover, AIM is used to identify the nature and strength of the M-N and M-O bonds. Selection of the prober organic ligand could have a great impact on extending the dimensionality of the metal complex. Hence, more functional ligands will be introduced in our future work for this task.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/cryst13020346/s1, X-ray single crystal diffraction measurement; Computational details; Figure S1 Hirshfeld surfaces of 1. Figure S2 Hirshfeld surfaces of 2.

Author Contributions

Conceptualization, J.H.A., S.M.S. and M.A.M.A.-Y.; methodology, J.H.A., M.S.A. and A.B.; software, S.M.S., J.H.A.; A.E-F., M.S.A. and A.B.; formal analysis, M.S.A. and J.H.A.; investigation, S.M.S., M.A.M.A.-Y. and J.H.A.; resources, J.H.A., M.S.A. and A.B.; writing—original draft preparation, J.H.A., S.M.S., M.A.M.A.-Y., M.S.A. and A.B.; writing— review and editing, J.H.A., S.M.S., M.A.M.A.-Y., M.S.A. and A.B.; supervision, S.M.S. and M.A.M.A.-Y.; project administration, J.H.A., A.B., S.M.S. and M.A.M.A.-Y. and funding acquisition, M.S.A., A.B. All authors have read and agreed to the published version of the manuscript.

Funding

Princess Nourah bint Abdulrahman University Researchers Supporting Project number (PNURSP2023R86), Princess Nourah bint Abdulrahman University, Riyadh, Saudi Arabia.

Data Availability Statement

Not applicable.

Acknowledgments

Princess Nourah bint Abdulrahman University Researchers Supporting Project number (PNURSP2023R86), Princess Nourah bint Abdulrahman University, Riyadh, Saudi Arabia.

Conflicts of Interest

The authors declare no conflict of interest.

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Crystals 13 00346 g001 550
Figure 1. Structure of 4-picoline (4-Pic) and pyridine-2-carboxaldoxime (HAld).
Figure 1. Structure of 4-picoline (4-Pic) and pyridine-2-carboxaldoxime (HAld).
Crystals 13 00346 g001
Crystals 13 00346 g002 550
Figure 2. X-ray structure of 1 drawn at 50% probability level for thermal ellipsoids. The labels of the aromatic and aliphatic protons are not depicted for better clarity.
Figure 2. X-ray structure of 1 drawn at 50% probability level for thermal ellipsoids. The labels of the aromatic and aliphatic protons are not depicted for better clarity.
Crystals 13 00346 g002
Crystals 13 00346 g003 550
Figure 3. H-bridge contacts (A) and H-bonding network (B) in 1.
Figure 3. H-bridge contacts (A) and H-bonding network (B) in 1.
Crystals 13 00346 g003
Crystals 13 00346 g004 550
Figure 4. Packing scheme of compound 1. The projections along [100] (A) and [010] (B) directions, respectively. Hydrogen atoms are omitted in both projections.
Figure 4. Packing scheme of compound 1. The projections along [100] (A) and [010] (B) directions, respectively. Hydrogen atoms are omitted in both projections.
Crystals 13 00346 g004
Crystals 13 00346 g005 550
Figure 5. X-ray structure of 2 drawn at 50% probability level for thermal ellipsoids. The labels of the protons, except split H1 and H2 atoms are not depicted for better clarity.
Figure 5. X-ray structure of 2 drawn at 50% probability level for thermal ellipsoids. The labels of the protons, except split H1 and H2 atoms are not depicted for better clarity.
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Crystals 13 00346 g006 550
Figure 6. Hydrogen bridge contacts (A) and packing view along a-axis (B) in 2.
Figure 6. Hydrogen bridge contacts (A) and packing view along a-axis (B) in 2.
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Crystals 13 00346 g007 550
Figure 7. Packing scheme of 2 along the monoclinic b-axis (A) and π-π stacking interactions extended through the a-direction (B). Hydrogen atoms are omitted in both projections.
Figure 7. Packing scheme of 2 along the monoclinic b-axis (A) and π-π stacking interactions extended through the a-direction (B). Hydrogen atoms are omitted in both projections.
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Crystals 13 00346 g008 550
Figure 8. Hirshfeld surfaces and pie chart showing the intermolecular interactions in 1. A–C in the dnorm map belong to the O…H, N…H and H…C contacts, respectively.
Figure 8. Hirshfeld surfaces and pie chart showing the intermolecular interactions in 1. A–C in the dnorm map belong to the O…H, N…H and H…C contacts, respectively.
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Crystals 13 00346 g009 550
Figure 9. Hirshfeld surfaces and pie chart showing the intermolecular interactions in 2. A–C in the dnorm map belong to the O…H, N…H and C…C contacts, respectively.
Figure 9. Hirshfeld surfaces and pie chart showing the intermolecular interactions in 2. A–C in the dnorm map belong to the O…H, N…H and C…C contacts, respectively.
Crystals 13 00346 g009
Crystals 13 00346 g010 550
Figure 10. The resonance structures of the terminally coordinated azide.
Figure 10. The resonance structures of the terminally coordinated azide.
Crystals 13 00346 g010
Table
Table 1. Crystal data of 1 and 2.
Table 1. Crystal data of 1 and 2.
Compound12
Empirical formulaC30H39CoN9O5C12H11CuN7O2
Fw 664.63348.82
T (K)293(2) K100(2) K
λ (Å)0.71073 Å0.71073 Å
cryst systMonoclinicMonoclinic
Space group P21/cP21/n
a (Å)11.3305(7)6.8277(2)
b (Å)11.3887(15)10.2203(2)
c (Å)25.9243(16)18.8056(6)
β (°)101.672(2)94.700(2)
V (Å3)3276.1(5)1307.86(6)
Z44
ρcalc (Mg/m3)1.347 Mg/m31.772 Mg/m3
μ (Mo Kα) (mm−1)0.576 mm−11.690 mm−1
F(000)1396708
θ-range2.180 to 26.341°2.173 to 32.498°
No. reflns.768528,102
Unique reflns.4249 [R(int) = 0.0414]4745 [R(int) = 0.0310]
Completeness to theta = 25.242°64.10%100.00%
GOOF (F2)1.0371.032
Final R indices [I > 2sigma(I)]R1 = 0.0392, wR2 = 0.0930R1 = 0.0229, wR2 = 0.0635
R indices (all data)R1 = 0.0754, wR2 = 0.1144R1 = 0.0264, wR2 = 0.0657
CCDC2,158,2052,158,206
Table
Table 2. Bond lengths (Å) and angles (°) of complex 1.
Table 2. Bond lengths (Å) and angles (°) of complex 1.
BondBond LengthBondBond Length
Co(1)-O(1) 2.091(2)Co(1)-N(6) 2.181(4)
Co(1)-N(1) 2.102(3)Co(1)-N(7) 2.198(3)
Co(1)-N(4) 2.160(4)Co(1)-N(5) 2.211(3)
BondsAngleBondsAngle
O(1)-Co(1)-N(1)178.79(16)N(1)-Co(1)-N(7)89.77(11)
O(1)-Co(1)-N(4)88.80(12)N(4)-Co(1)-N(7)91.54(14)
N(1)-Co(1)-N(4)90.50(15)N(6)-Co(1)-N(7)87.04(14)
O(1)-Co(1)-N(6)91.72(12)O(1)-Co(1)-N(5)89.67(9)
N(1)-Co(1)-N(6)88.96(15)N(1)-Co(1)-N(5)91.35(11)
N(4)-Co(1)-N(6)178.48(10)N(4)-Co(1)-N(5)93.06(13)
O(1)-Co(1)-N(7)89.27(9)N(6)-Co(1)-N(5)88.37(14)
O(5)-Co(1)-N(7)175.25(10)
Table
Table 3. Hydrogen bonds in complex 1.
Table 3. Hydrogen bonds in complex 1.
D-H…Ad(D-H)d(H…A)<DHAd(D…A)Symmetry Code
O1-H1A…O3 0.8532.568133.643.216
O1-H1A…O4 0.8531.909170.042.753
O1-H2A…O20.8071.859178.012.665[x + 1, y, z]
O2-H3A…N80.8191.973173.172.788
O2-H4A…O30.8661.953167.152.803[−x + 1, y − 1/2, −z + 1/2]
O2-H4A…O50.8662.611135.833.288[−x + 1, y − 1/2, −z + 1/2]
C7-H7…N1 0.932.483124.233.103
C10-H10…O5 0.932.513139.783.278[−x + 1, y − 1/2, −z + 1/2]
C11-H11…O1 0.932.496121.543.086
C17-H17…N1 0.932.468120.953.052
C25-H25…O3 0.932.658158.253.538[x − 1, y, z]
C28-H28…O4 0.932.584168.863.501
C29-H29…O5 0.932.586139.483.348[−x + 1, y − 1/2, −z + 1/2]
Table
Table 4. Bond lengths (Å) and angles (°) for complex 2.
Table 4. Bond lengths (Å) and angles (°) for complex 2.
BondBond LengthBondBond length
Cu(1)-N(4) 1.9946(9)Cu(1)-N(3) 2.0480(9)
Cu(1)-N(2) 1.9967(9)Cu(1)-N(5) 2.2158(10)
Cu(1)-N(1) 2.0341(9)
BondsAngleBondsAngle
N(4)-Cu(1)-N(2)90.94(4)N(1)-Cu(1)-N(3)106.57(4)
N(4)-Cu(1)-N(1)170.83(4)N(4)-Cu(1)-N(5)90.34(4)
N(2)-Cu(1)-N(1)80.57(4)N(2)-Cu(1)-N(5)101.56(4)
N(4)-Cu(1)-N(3)79.98(4)N(1)-Cu(1)-N(5)94.74(4)
N(2)-Cu(1)-N(3)156.74(4)N(3)-Cu(1)-N(5)99.88(4)
Table
Table 5. Hydrogen bonds in complex 2.
Table 5. Hydrogen bonds in complex 2.
D-Hd(D-H)d(H…A)<DHAd(D…A)Symmetry Code
O1-H1…O20.84(3)1.61(3)2.4431(13)174(4)
C3-H3…O20.952.543.3761(15)148−1/2 + x, 3/2 − y, 1/2 + z
C7-H7…N7 0.952.573.3751(15)1431 − x, 2 − y, −z
C9-H9…O10.952.353.2252(14)152x, 1 + y, z
C10-H10…N50.952.543.2872(15) 1361/2 − x, 1/2 + y, 1/2 − z
C11-H11…N70.952.513.2984(15)1411 − x, 2 − y, −z
C12-H12…N60.952.623.4037(15) 1401/2 − x, −1/2 + y, 1/2 − z
Table
Table 6. Short distance contacts in compounds 1 and 2.
Table 6. Short distance contacts in compounds 1 and 2.
ContactDistanceContactDistanceContactDistance
12
N3…H24B2.498O3…H252.517C3…C83.325
N3…H42.591O2…H2A1.682N7…H72.461
N9…H1A2.445O3…H4A1.839N7…H112.406
H13…C252.684O5…H4A2.529N7…H2B2.521
H3A…C252.676O5…H12C2.513N6…H122.519
H20…C92.749O5…H102.397N5…H102.442
O4…H1A1.781O5…H292.472O2…H32.424
O3…H1A2.482O4…H282.453O2…H42.531
O1…H92.236
Table
Table 7. The topological parameters of the azide N-N bonds.
Table 7. The topological parameters of the azide N-N bonds.
BonddN-NΔdρ(r), a.u ∇ 2 ρ(r) aV(r)/G(r) b
Complex 1
NA-NB1.189(6)0.040.4847−1.38462.884
NB-NC1.149(7) 0.5424−1.42162.670
Complex 2
NA-NB1.192(1)0.020.4833−1.23462.743
NB-NC1.172(1) 0.5105−1.22702.623
a Laplacian of electron density; b Ratio of potential to kinetic energy density.
Table
Table 8. The AIM parameters for compounds 1 and 2.
Table 8. The AIM parameters for compounds 1 and 2.
BondBond Lengthρ(r); a.u.H(r) a; a.u.V(r)/G(r) b ∇ 2 ρ(r) c
Complex 1
Co1-O12.091(2)0.04010.00230.9740.3519
Co1-N12.102(3)0.0616−0.00881.1040.3040
Co1-N42.159(4)0.04190.00080.9910.3589
Co1-N52.211(3)0.03600.00170.9750.2868
Co1-N62.181(4)0.03960.00080.9910.3380
Co1-N72.197(3)0.03770.00130.9820.2989
Complex 1
Cu1-N12.034(1)0.0553−0.00501.0410.4637
Cu1-N21.997(1)0.0588−0.00431.0320.5258
Cu1-N32.048(1)0.0552−0.00491.0420.4513
Cu1-N41.994(1)0.0798−0.01911.1750.3597
Cu1-N52.216(1)0.03810.00001.0000.2947
a Total energy density; b potential to kinetic energy density; c Laplacian of electron density.
Table
Table 9. The natural charges at metal center, ligand groups.
Table 9. The natural charges at metal center, ligand groups.
1 2
Co0.9623Cu0.7655
4-Pic0.5804HAld0.3354
H2O0.1278Ald−−0.7207
N3−−0.7138N3−−0.7207
NO3−−0.9567
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Altowyan, M.S.; Albering, J.H.; Barakat, A.; Soliman, S.M.; Abu-Youssef, M.A.M. Synthesis, Supramolecular Structural Investigations of Co(II) and Cu(II) Azido Complexes with Pyridine-Type Ligands. Crystals 2023, 13, 346. https://doi.org/10.3390/cryst13020346

AMA Style

Altowyan MS, Albering JH, Barakat A, Soliman SM, Abu-Youssef MAM. Synthesis, Supramolecular Structural Investigations of Co(II) and Cu(II) Azido Complexes with Pyridine-Type Ligands. Crystals. 2023; 13(2):346. https://doi.org/10.3390/cryst13020346

Chicago/Turabian Style

Altowyan, Mezna Saleh, Jörg H. Albering, Assem Barakat, Saied M. Soliman, and Morsy A. M. Abu-Youssef. 2023. "Synthesis, Supramolecular Structural Investigations of Co(II) and Cu(II) Azido Complexes with Pyridine-Type Ligands" Crystals 13, no. 2: 346. https://doi.org/10.3390/cryst13020346

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