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Article

On the Importance of H-Bonding Interactions in the Enclathration of Boric Acids in Na(I) Polymers: Experimental and Theoretical Studies

by
Trishnajyoti Baishya
1,
Kamal K. Dutta
1,
Antonio Frontera
2,*,
Rosa M. Gomila
2,
Miquel Barceló-Oliver
2 and
Manjit K. Bhattacharyya
1,*
1
Department of Chemistry, Cotton University, Guwahati 781001, Assam, India
2
Departament de Química, Universitat de les Illes Balears, Crta de Valldemossa km 7.7, 07122 Palma de Mallorca, Spain
*
Authors to whom correspondence should be addressed.
Crystals 2023, 13(6), 895; https://doi.org/10.3390/cryst13060895
Submission received: 30 April 2023 / Revised: 20 May 2023 / Accepted: 25 May 2023 / Published: 30 May 2023
(This article belongs to the Special Issue Different Kinds of Hydrogen Bonds in Crystal Structures)
Browse Figures
Versions Notes

Abstract

:
Two Na(I) coordination polymers, namely, {Na(BA)2(μ-H2O)2}n{adp}n (1) and {[Na2(μ-BA)(μ-fum)(μ-H2O)4](BA)}n (2) (where, BA = boric acid, adp = adipic acid, fum = fumarate),were prepared and characterized using elemental analysis, TGA, FT-IR, and single-crystal X-ray diffraction techniques. Various unconventional supramolecular interactions, i.e., CH∙∙∙HC and parallel CO∙∙∙CO interactions, stabilize the layered assembly of compound 1. Interesting dual enclathration of BA molecules within the supramolecular host cavities formed by O-H∙∙∙O and C-H∙∙∙C interactions stabilizes the crystal structure of compound 2. The H-bonding interactions in 1 and 2 were further studied theoretically using the quantum theory of atoms in molecules (QTAIM) and the noncovalent interaction plot (NCI Plot) computational tools. The energy of the H-bonds was estimated using the potential energy density at the bond critical points. Theoretical calculations confirmed the presence of O-H∙∙∙O H-bonding interactions in both compounds, forming structure-guiding R 2 2 ( 8 ) synthons relevant for the stability of the compounds.

1. Introduction

Coordination polymers represent the supramolecular architecture of metal ions and organic moieties that extends in association with covalent bonding, as well as supramolecular contacts [1,2,3]. In the current research era, the design and synthesis of coordination polymers involving supramolecular interactions has attracted immense attention owing to their interesting physical, chemical properties, and potential applications [4,5]. Although coordination polymers involving transition metals bridged by organic ligands have been well explored [6,7], examples of polymers with s-block elements such as sodium are still scarce in the literature. The strategic synthesis of coordination polymers of such elements is still challenging, which may be due to various factors such as varying coordination number, size of the binding partners, and electrostatic interactions between the ligands and the metal ions [8].
The design of boron-based compounds has received a great deal of interest because of their potential utilities as boron-containing drugs and materials for medical diagnostics [9,10]. Boron compounds can be used as modulators for the bioactivity of biomolecules, in boron capture neutron therapy (BNCT) for drug delivery, and in molecular modeling of drug design [11,12]. Boric acid has been effectively utilized as a building block to construct a variety of compounds with interesting structural topologies [13,14]. Cebula et al. recently highlighted the importance of supramolecular assemblies of boron-mediated anionic clusters and their applications in biological fields [15]. In an organic crystal of 4-pyridinylboronic acid, B∙∙∙Cl σ-hole triel bonding interactions were observed, established using various computational tools [16].
To understand the role of noncovalent contacts in self-assembly processes, innumerable efforts have been undertaken due to their potential applications in a wide range of fields such as catalysis, crystal engineering, pharmaceutical design, molecular biology, and molecular recognition [17,18,19]. Although supramolecular interactions are weaker than covalent bonds, their large numbers and cumulative effects make them potential candidates in the design of crystal structures [20,21]. H-bonding interactions can be considered as the most common which play crucial roles in molecular self-assembly processes [22], as well as in the stabilization of biomolecules such as -DNA and proteins (Figure 1) [23]. In the stabilization of metal–organic compounds, the dipolar interactions between carbonyl groups (CO∙∙∙CO) are also equally important in the stability of the crystal structures [24].
The saturated aliphatic dicarboxylate moieties, as important flexible bridging ligands, can adopt conformational and coordination versatilities owing to their single-bonded carbon chains, which can be considered for the development of interesting metal–organic compounds [25,26]. The dicarboxylate anions can exhibit multiple coordination motifs such as uni-bidentate, bis-monodentate, bis-bidentate, tridentate, and tetradentate etc., thereby interconnecting metal centers to form polynuclear complexes [27,28]. Saturated dicarboxylic acids also serve as suitable H-bonding acceptors [29,30], resulting in the development of bridging metal–organic compounds with various desired self-assembled architectures [31,32]. As a consequence, adipic acid has evolved as a potential bridging ligand to form interesting coordination polymers with potential applications [33,34,35]. The dicarboxylate groups of fumarate anion (an unsaturated dicarboxylate) also have the ability to coordinate with the metal centers in multidentate fashion [36]. As a result, metal fumarate complexes have been explored with interesting structural topologies [37]. In recent times, a few boric acid-mediated metal–organic compounds have also been reported with desired applications [15,38].
In order to visualize the role of supramolecular interactions in polymeric complexes, we report herein the synthesis and crystal structures of two Na(I) polymers, namely, {Na(BA)2(μ-H2O)2}n{adp}n (1) and {[Na2(μ-BA)(μ-fum)(μ-H2O)4](BA)}n (2) (where, BA = boric acid, adp = adipic acid, fum = fumarate), along with their characterization using FT-IR spectroscopy, TGA, and elemental analysis. The presence of various noncovalent interactions such as C-H∙∙∙H-C and parallel CO∙∙∙CO interactions stabilizes the 2D architecture of compound 1. Fascinating dual enclathration of guest BA molecules within the supramolecular host cavities formed by O-H∙∙∙O hydrogen-bonding and noncovalent C-H∙∙∙H-C interactions provides rigidity to the crystal structure of compound 2. To explore the energetic features and the characteristics of H-bonding interactions, we use QTAIM and NCI plot computational tools. The strength of the H-bonding interactions is investigated using the potential energy density in QTAIM, revealing the importance of R 2 2 ( 8 ) synthons in the crystal structures.

2. Experimental

2.1. Materials and Methods

The chemicals used in the present study, namely, sodium hydroxide, boric acid, adipic acid, and fumaric acid, were purchased from commercial sources and used as received. We prepared the disodium salt of fumaric acid using standard laboratory methods. A Perkin Elmer 2400 Series II CHNS/O analyzer was used to carry out the elemental analysis of the compounds. KBr phase FT-IR spectra were recorded using a Bruker Alpha Infrared spectrophotometer (resolution = 4 cm−1; number of scans = 16), in the wavenumber range 4000–500 cm−1. Thermogravimetric studies were carried out under the flow of N2 gas using a Mettler Toledo TGA/DSC1 STARe system at a heating rate of 10 °C·min−1. The TGA curves were recorded in the temperature range 25–1000 °C with 2 μg resolution.

2.2. Syntheses

2.2.1. Synthesis of {Na(BA)2(μ-H2O)2}n{adp}n (1)

Compound 1 was synthesized via the reaction of sodium hydroxide (0.040 g, 1.0 mmol) and boric acid (0.124 g, 2.0 mmol) in 10 mL of deionized water. The reaction mixture was mechanically stirred at room temperature for about 2 h. Then, adipic acid (1 mmol, 0.146 g) was slowly added, and the resulting solution was mechanically stirred for another hour (Scheme 1). The resulting solution was kept unperturbed in cooling conditions (2–4 °C) for crystallization, from which block-shaped colorless single crystals were obtained after a few days. Yield: 0.282 g (86.02%). Analysis calculated for C6H19B2NaO12:C, 21.98%; H, 5.84%; found: C, 21.82%; H, 5.75%. IR (KBr pellet, cm−1): 3401 (br), 3228 (sh), 3055 (s), 2963 (m), 2876 (m), 2860 (sh), 2579 (m), 1984 (m), 1922 (sh), 1697 (s), 1601 (s), 1506 (s), 1410 (s), 1288 (m), 1225 (s),1163 (w), 1090 (m), 998 (w), 944 (m), 850 (s), 780 (w), 717 (s), 646 (sh), 537 (m) (s, strong; m, medium; w, weak; br, broad; sh, shoulder).

2.2.2. Synthesis of {[Na2(μ-BA)(μ-fum)(μ-H2O)4](BA)}n (2)

For the synthesis of compound 2, a mixture of sodium hydroxide (0.08 g, 2.0 mmol) and boric acid (0.124 g, 2.0 mmol) was mechanically stirred at room temperature for about 2 h in 10 mL of deionized water. Then, Na2-fum (0.160 g, 1.0 mmol) was added slowly, and the resulting solution was mechanically stirred for another hour (Scheme 1). The resulting solution was kept unperturbed in cooling conditions below 4 °C, from which block-shaped colorless single crystals were obtained after a few days. Yield: 0.295 g (82.86%). Analysis calculated for C4H16B2Na2O14: C, 13.49%; H, 4.50%; found: C, 13.41%; H, 4.39%. IR (KBr pellet, cm−1): 3447 (br), 3283 (sh), 2494 (s), 2140 (m), 2070 (w), 1690 (s), 1600 (s), 1427 (s), 1374 (s), 1265 (s), 1187 (s), 975 (s), 842 (m), 812 (m), 795 (m), 764 (m), 685 (s), 592 (sh) (s, strong; m, medium; w, weak; br, broad; sh, shoulder).

2.3. Crystallographic Data Collection and Refinement

Single-crystal XRD data of the compounds were recorded using a Bruker D8 Venture diffractometer with a Photon III 14 detector, using an Incoatec high-brilliance IμS DIAMOND Cu tube. The Bruker APEX4 program was used for the data reduction and cell refinements [39]. Scaling and merging of the datasets of the wavelength were carried out using SADABS [39]. Crystal structures of the compounds were solved using the direct method and refined using the full-matrix least-squares technique with SHELXL-2018/3 [40] inWinGX [41] software. The non-hydrogen atoms of the crystal structures were refined with anisotropic thermal parameters using full-matrix least-squares calculations on F2. Hydrogen atoms were inserted at calculated positions and refined as riders. Diamond 3.2 software was used to draw the compounds [42]. Crystallographic data of the compounds are presented in Table 1.
CCDC 2213579 and 2213580 contain the supplementary crystallographic data for the compounds 1 and 2 respectively. These data can be obtained free of charge at http://www.ccdc.cam.ac.uk or from the Cambridge Crystallographic Data Center (12 Union Road, Cambridge CB2 1EZ, UK; Fax: (+44) 1223-336-033; or E-mail: [email protected]).

2.4. Theoretical Methods

The single-point calculations were carried out using the Turbomole 7.7 program [43] and the PBE0-D3/def2-TZVP [44,45,46] level of theory. The crystallographic coordinates were used to evaluate the interactions in compounds 1 and 2 since we were interested in studying the H-bonding interactions in the solid state. Since the structures were polymeric, finite models extracted from the solid-state structures were selected to study the formation of the H-bonding interactions. The Bader’s “Atoms in molecules” theory (QTAIM) [47] and noncovalent interaction plot (NCI Plot) [48] were used to study the interactions discussed herein using the Multiwfn program [49] and represented using the VMD visualization software [50]. For the calculation of the H-bond energies, we used the equation proposed by Espinosa et al. (E = ½Vr) [51].

3. Results

3.1. Synthesis and General Aspects

{Na(BA)2(μ-H2O)2}n{adp}n (1) was synthesized via a reaction involving NaOH, BA, and adp in 1:2:1 ratio at room temperature in deionized water. Similarly, {[Na2(μ-BA)(μ-fum)(μ-H2O)4](BA)}n (2) was prepared by reacting NaOH, BA, and Na2-fum in 2:2:1 ratio at room temperature in deionized water. Compounds 1 and 2 were soluble in water, as well as common organic solvents. The crystal structure of compound 2 was already reported by Ozer et al. [52] (Table S1). However, we synthesized the compound by employing a comparatively simple synthetic pathway at room temperature. We also explored the detailed structural characteristics of the compound, which revealed the unusual dual enclathration of BA moieties in the supramolecular host cavity of the compound (vide infra). Moreover, the energetic features of the H-bonding interactions were investigated in the crystal structure using computational tools (vide infra).

3.2. Crystal Structure Analysis

The molecular structure of compound 1 is depicted in Figure 2. Table S2 contains the bond lengths and bond angles around the Na(I) centers. The compound crystallized in the triclinic P 1 ¯ space group. Compound 1 comprises two 1D polymeric chains. The first one possesses Na(I) centers bridged by two water molecules. Two BA molecules are also coordinated with the Na(I) centers. Thus, each Na(I) center is hexacoordinated with two O atoms from the BA molecules (O2B and O2B’) and four Oatoms from the bridged water molecules (O1W, O1W, O1W’, and O1W’’). The coordination geometry around each Na(I) center is ideal octahedron, where the axial positions are filled by two bridged water molecules, whereas the equatorial sites are occupied by the other bridged water molecules and the two Oatoms of BA moieties. Moreover, the second 1D polymeric chain holds adp molecules bridged by the hydrogen atom of adp (H3A). X-ray crystallographic analysis indicates that the 1D polymeric chain of Na(I) centers possesses a crystallographic inversion center at the midpoint of two neighboring Na(I) centers. The 1D polymeric chain of adp also possesses crystallographic inversion at the midpoint of the C–C bond of adp.
The 1D polymeric chain of compound 1 consisting of the Na(I) centers is stabilized by noncovalent intramolecular O-H∙∙∙O hydrogen-bonding interactions (Figure S1 see Supplementary materials). The O4B atoms of the coordinated boric acid molecules are involved in O-H∙∙∙O hydrogen-bonding interactions with the bridged water molecule O1W, with O1W-H1WB∙∙∙O4B having a distance of 2.09 Å.
The 1D polymeric chains of the compound 1 also propagate along the ab plane to stabilize the layered assembly aided by CH∙∙∙HC and parallel CO∙∙∙CO interactions (Figure S2). H atoms (H4AA, H4AB, H5AA, and H5AB) of the adp molecules are involved in CH∙∙∙HC bonding interactions, with H4AA∙∙∙H4AB and H5AA∙∙∙H5AB separations of 2.40 and 2.34 Å respectively. There are unusual parallel CO∙∙∙CO interactions among the carbonyl groups of adp molecules having a Cg1(defined by centroid of C2A and O1A)∙∙∙Cg2(defined by centroid of C2A and O1A)separation of 3.77 Å.
The 1D polymeric chains of Na(I) centers of the compound propagate along the crystallographic ab plane and form the layered assembly stabilized by O-H∙∙∙O hydrogen-bonding interactions (Figure 3). O-H∙∙∙O interactions are observed between O2B and O3B atoms of coordinated boric acid molecules (O2B-H2B∙∙∙O3B = 1.95 Å).
Both the polymeric chains of adp moieties and Na(I) centers are interconnected along the bc plane to stabilize the layered assembly (Figure 4b) aided by C-H∙∙∙O and O-H∙∙∙O interactions. The –CH (C4AH4A) moiety of adp is involved in C-H∙∙∙O hydrogen-bonding interactions with O4B atom of coordinated BA of the Na(I) centers, having a C4A-H4A∙∙∙O4B distance of 2.74 Å. The supramolecular ring motif formed is represented using Etter’s graph set notation, i.e.,   R 2 2 ( 8 ) [53].
Moreover, the O1A and O3A atoms of adp moieties are involved in O-H∙∙∙O hydrogen-bonding interactions with coordinated BA moieties of the Na(I) centers, having O3B-H3B∙∙∙O1A and O4B-H4B∙∙∙O3A distances of 1.89 and 2.06 Å, respectively (Figure 4a). These interactions were further studied theoretically (vide infra).
Figure 5 depicts the molecular structure of compound 2. Tables S3 and S4 contains bond lengths and bond angles around Na(I) centers. Compound 2 crystallized in the orthorhombic Pnma space group. The crystal structure of compound 2 consists of a 1D polymeric chain and one uncoordinated BA moiety (Figure 5). The polymeric chain possesses two crystallographically unique Na(I) centers (Na1 and Na2) having a similar coordination environment with minor differences in bond lengths and bond angles. Two neighboring Na(I) centers are bridged by two water molecules, along with one BA and one fum moiety. Na1 centers are hexacoordinated with four bridged water molecules (O1W, O1W′, O2W, and O2W′), the O1 atom from the bridged fum, and the O2A atom from the bridged BA molecule.
However, Na2 centers are also hexacoordinated with four bridged water molecules (O1W, O1W′, O2W, and O2W′), the O8 atom from bridged fum, and the O3A atom from the bridged BA molecule. The coordination geometry around each Na1 center is distorted octahedron, where the axial sites are filled up by O1 and O2A, while equatorial sites are filled by the four bridged water molecules. The O1W, O1W′, O2W, and O2W′ atoms deviate from the mean equatorial plane with a rms deviation of 0.0304 Å. Similarly, for Na2 centers, axial sites are filled by O8 and O3A, whereas the equatorial positions are filled by four bridged water molecules. The structural properties such as bond lengths and bond angles of the compound are found to be slightly different from those of the previously reported compound (Tables S3 and S4).
Analysis of the crystal packing of compound 2 revealed that O7 and O8 atoms of bridged fum are involved in intramolecular O-H∙∙∙O interactions with bridged BA moieties, having O4A-H4A∙∙∙O7 and O2A-H2A∙∙∙O8 distances of 1.71 and 1.80 Å, respectively (Figure 6). The uncoordinated BA moiety is involved in intermolecular O-H∙∙∙O interactions with the O1 and O3 atoms of bridged fum, having O3B-H3B∙∙∙O3 and O2B-H2B∙∙∙O1 distances of 1.75 and 1.77 Å, respectively. Moreover, uncoordinated and bridged BA moieties are also involved in O-H∙∙∙O interactions (O3A-H3A∙∙∙O2B = 1.86 Å, O4B-H4B∙∙∙O4A = 1.81 Å) (Figure 6). The H-bonded ring motif formed in compound 2 is represented by Etter’s graph set notation, i.e.,   R 2 2 ( 8 ) [53]. These R 2 2 ( 8 ) synthons were further studied theoretically (vide infra).
Unusual dual enclathration of lattice boric acid moieties within the supramolecular host cavity aided by O-H∙∙∙O and C-H∙∙∙C interactions (Figure 7a) stabilize the layered assembly of the compound. The O7 atom of bridging fum and the O2W molecule areinvolved in O-H∙∙∙O interactions (O2W-H2WB∙∙∙O7 = 2.08 Å). Noncovalent C-H∙∙∙C contacts are observed between -C5H5 moieties and C4 atoms of fum of two neighboring 1D polymeric chains, having a C5-H5∙∙∙C4 distance of 3.88 Å [C(sp2)–C(sp2), C5∙∙∙C4 = 3.95 Å]. Moreover, enclathration of two BA moieties takes place with the help of O-H∙∙∙O interactions involving the O1 and O3 atoms of bridging fum, as well as the O3A and O4A atoms of bridging BA (O2B-H2B∙∙∙O1 = 1.77 Å, O3B-H3B∙∙∙O3 = 1.75 Å, O3A-H3A∙∙∙O2B = 1.87 Å, and O4B-H4B∙∙∙O4A = 1.82 Å). In addition, O3B and O4B atoms of enclathrated boric acids are also involved in O-H∙∙∙O interactions with bridging O1W and O2W molecules, having O2W-H2WA∙∙∙O3B and O1W-H1WB∙∙∙O4B distances of 1.92 and 2.22 Å, respectively (Table 2).
Interestingly, dual enclathration of uncoordinated BA molecules within the supramolecular host cavities forms the 2D architecture of 2 along the ac plane (Figure 7b). Such dual enclathration of BA moieties within supramolecular host cavities is rare.

3.3. FT-IR Spectroscopy

The FT-IR spectra of compounds 1 and 2 (KBr phase) were recorded in the region 4000–500 cm−1 (Figure 8). The comparatively broad absorption peaks in both compounds at around 3401 and 3447 cm−1 can be attributed to O–H stretching vibrations of water molecules [54,55]. FT-IR spectra exhibited peaks due to ρr (H2O) (712 cm−1) and ρw (H2O) (645 cm−1), which indicates the presence of coordinated water molecules [55]. For 1, strong absorption bands at 1601 and 1410 cm−1 are due to the asymmetric and symmetric stretching vibrations of the carboxylate moieties of adp [56]. Peaks at 2963 and 2876 cm−1 in 1 are due to the asymmetric and symmetric C–H stretching vibrations of–CH2 moieties of adp [57,58]. Peaks for C–C stretching of the adpcan be observed at 1225 (asymmetric) and 1090 (symmetric) cm−1 in 1 [59]. Δν = νassym − νsym of fum (greater than 200 cm−1) can be attributed to the monodentate coordination of the carboxylate groups to the Na(I) centers in compound 2 [60]. The medium-intensity peaks at 812 and 795 cm−1 in compound 2 are due to the OCO bending vibrations of fum [60]. The sharp peak at 1710 cm−1 in 1 indicates that the carboxylate group of adp does not undergo deprotonation, whereas its absence in 2 supports the deprotonation of carboxylate moieties [61].

3.4. Thermogravimetric Analysis

TG analysis of the compounds was carried out in the temperature range 25–1000 °C under N2 atmosphere at aheating rate of 10 °C/min (Figure 9). For compound 1, in the temperature range 50–100 °C, two coordinated water molecules were decomposed (observed = 11.56%; calculate = 10.98%) [62]. In the temperature range 101–270 °C, one coordinated BA molecule was decomposed with the observed weight loss of 17.04% (calculated = 18.86%) [63]. The observed weight loss of 62.24% (calculated = 62.76%) in the temperature range 271–930 °C can be attributed to the loss of one coordinate BA molecule and one coordinated adp moiety [63,64]. For compound 2, four coordinated water molecules were decomposed between 51 and 180 °C (observed = 19.80%, calculated = 20.24%) [62]. In the temperature range 181–326 °C, two BA moieties and one fum moieties were lost (observed = 66.20%, calculated = 67.36%) [63,65].

3.5. Theoretical Study

The theoretical study was devoted to the analysis of the H-bonding interactions observed involving boric acid, both as a donor and as an acceptor, that are relevant to the stability of the solid state of the compounds. The polymeric nature of the complexes complicated the theoretical analysis. Therefore, we used finite models of the compounds and took advantage of the QTAIM method that allows the quantification of the H-bonds using the potential energy density values at the bond critical points (CPs). To do so, the Vr values at the bond critical points that characterize each synthon and the equation E = ½Vr were used. As a representative fragment of compound 1, we used the model represented in Figure 10a, composed of a central Na atom coordinated to four water molecules and two monodentate boric acids and two sets of H-bridged adipate dimers. Such a model included the most relevant H-bonds observed in compound 1. The QTAIM analysis combined with the NCI plot analysis is shown in Figure 10a, where each H-bond is characterized by a bond critical point (CP, red sphere) and a bond path connecting the H-atoms to the O-atoms. Moreover, green (weak) and blue (strong) RDG isosurfaces also characterize the H-bonds. One important synthon corresponds to the supramolecular R 2 2 ( 8 ) ring, where the BA forms two strong H-bonds with one fum. The formation energy of this synthon is −11.7 kcal/mol due the contribution of both OH···OH-bonds, where the boric acid acts as a double H-bond donor. The equatorial water molecules participate in two H-bonds, one intramolecular with the BA and the other one intermolecular with the adp. The intermolecular one is stronger (−4.6 kcal/mol), likely due to the anionic nature of the H-bond acceptor.
The oligomeric model used for compound 2 is shown in Figure 10b, composed of a total of six hexacoordinated sodium atoms, three coordinated BAs, two free BAs, and three bidentate fum ligands. It is interesting to highlight the formation of three different   R 2 2 ( 8 ) synthons in the solid state, which have very large interaction energies. One of the synthons is generated by the interaction of the coordinated and non-coordinated BAs, with a formation energy of −17.8 kcal/mol. The other two R 2 2 ( 8 ) synthons correspond to the interaction of the non-coordinated and coordinated BAs with the fumarate ligands. Both synthons exhibit very strong formation energies due to the anionic nature of the H-bond donor and the strong acidity of the H-bond donor atoms. In fact, the strongest synthon (−25.4 kcal/mol) corresponds to the coordinated BA, where the acidity of these OH groups is enhanced by the coordination to the sodium cation.

4. Conclusions

Two Na(I) polymeric compounds were synthesized and characterized using single-crystal X-ray diffraction, FT-IR, and TG analyses. Compound 1 comprises two polymeric chains: one water-bridged polymeric Na(I) chain and another chain formed by adp molecules with bridging hydrogen atoms. Compound 2 contains a polymeric Na(I) chain bridged by BA and fum moieties. The coordination environment around the Na(I) atoms in both polymers is octahedral. Unconventional supramolecular contacts, namely, C-H∙∙∙H-C and parallel CO∙∙∙CO interactions, stabilize the layered assembly of compound 1. Interesting dual enclathration of BA molecules within the supramolecular hosts formed by O-H∙∙∙O and C-H∙∙∙H-C interactions stabilizes the crystal structure of compound 2. The structure-directing H-bonded noncovalent interactions in the crystal structures were further studied theoretically using the combined QTAIM/NCI plot method, and the energies were estimated using the Vr energy predictor. It is demonstrated that the formation of a strong structure directing H-bonded   R 2 2 ( 8 ) synthons in the compounds is relevant for the layered assemblies of the compounds.

Supplementary Materials

The following supporting information can be downloaded at https://www.mdpi.com/article/10.3390/cryst13060895/s1: Table S1: Comparison of crystal parameters of compound 2 with the already reported compound; Table S2: Selected bond lengths (Å) and bond angles (°) of Na(I) centers in compound 1; Tables S3 and S4: Selected bond lengths (Å) and bond angles (°), respectively, of Na(I) centers in compound 2 and the previously reported compound (CCDC 1455138); Figure S1: The 1D polymeric chain of compound 1 stabilized by intramolecular O-H∙∙∙O hydrogen bonding interactions; Figure S2: Layered assembly of compound 1 involving polymeric chain of adp moieties assisted by unusual CH∙∙∙HC and parallel CO∙∙∙CO interactions along the crystallographic ab plane.

Author Contributions

Conceptualization, A.F. and M.K.B.; methodology, A.F. and M.K.B.; software, A.F. and R.M.G.; formal analysis, A.F.; investigation, T.B., K.K.D. and R.M.G.; data curation, M.B.-O.; writing—original draft preparation, T.B., K.K.D. and M.K.B.; writing—review and editing, M.K.B.; visualization, A.F.; supervision, M.K.B.; project administration, A.F. and M.K.B.; funding acquisition, A.F. and M.K.B. All authors have read and agreed to the published version of the manuscript.

Funding

Financial support from ASTEC, DST, the Government of Assam (grant number ASTEC/S&T/192(177)/2020-2021/43), and the Government of Spain, MICIU/AEI (projects No. EQC2018-004265-P and PID2020-115637GB-I00) is gratefully acknowledged. The authors thank IIT-Guwahati for TG data.

Data Availability Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

References

  1. Engel, E.R.; Scott, J.L. Advances in the Green Chemistry of Coordination Polymer Materials. Green Chem. 2020, 22, 3693–3715. [Google Scholar] [CrossRef]
  2. Biradha, K.; Ramanan, A.; Vittal, J.J. Coordination Polymers versus Metal–Organic Frameworks. Cryst. Growth Des. 2009, 9, 2969–2970. [Google Scholar] [CrossRef]
  3. Ghosh, A.K.; Hazra, A.; Mondal, A.; Banerjee, P. Weak Interactions: The Architect behind the Structural Diversity of Coordination Polymer. Inorg. Chim. Acta 2019, 488, 86–119. [Google Scholar] [CrossRef]
  4. Bureekaew, S.; Shimomura, S.; Kitagawa, S. Chemistry and Application of Flexible Porous Coordination Polymers. Sci. Technol. Adv. Mater. 2008, 9, 14108. [Google Scholar] [CrossRef] [PubMed]
  5. Scaeteanu, G.V.; Maxim, C.; Badea, M.; Olar, R. Zinc(II) Carboxylate Coordination Polymers with Versatile Applications. Molecules 2023, 28, 1132. [Google Scholar] [CrossRef]
  6. Ou, Y.C.; Zhong, R.M.; Wu, J.Z. Recent Advances in Structures and Applications of Coordination Polymers Based on Cyclohexanepolycarboxylate Ligands. Dalton Trans. 2022, 51, 2992–3003. [Google Scholar] [CrossRef] [PubMed]
  7. Ding, B.; Solomon, M.B.; Leong, C.F.; D’Alessandro, D.M. Redox-Active Ligands: Recent Advances towards Their Incorporation into Coordination Polymers and Metal-Organic Frameworks. Coord. Chem. Rev. 2021, 439, 213891. [Google Scholar] [CrossRef]
  8. Fromm, K.M. Coordination Polymer Networks with S-Block Metal Ions. Coord. Chem. Rev. 2008, 252, 856–885. [Google Scholar] [CrossRef]
  9. Das, B.C.; Chokkalingam, P.; Masilamani, P.; Shukla, S.; Das, S. Stimuli-Responsive Boron-Based Materials in Drug Delivery. Int. J. Mol. Sci. 2023, 24, 2757. [Google Scholar] [CrossRef]
  10. Córdova-Chávez, R.I.; Carrasco-Ruiz, M.F.; Rodríguez-Vera, D.; Pérez-Capistran, T.; Tamay-Cach, F.; Scorei, I.R.; Abad-García, A.; Soriano-Ursúa, M.A. Boron-Containing Compounds for Prevention, Diagnosis, and Treatment of Human Metabolic Disorders. Biol. Trace Elem. Res. 2023, 201, 2222–2239. [Google Scholar]
  11. Ji, L.; Zhou, H. Recent developments in the synthesis of bioactive boron-containing compounds. Tetrahedron Lett. 2021, 82, 153411–153426. [Google Scholar] [CrossRef]
  12. Ali, F.; Hosmane, N.S.; Zhu, Y. Boron Chemistry for Medical Applications. Molecules 2020, 25, 828. [Google Scholar] [CrossRef] [PubMed]
  13. Lopalco, A.; Lopedota, A.A.; Laquintana, V.; Denora, N.; Stella, V.J. Boric Acid, a Lewis Acid with Unique and Unusual Properties: Formulation Implications. J. Pharm. Sci. 2020, 109, 2375–2386. [Google Scholar] [CrossRef] [PubMed]
  14. Tan, W.; Chen, T.; Liu, W.; Ye, F.; Zhao, S. Design and fabrication of boric acid functionalized hierarchical porous metal-organic frameworks for specific removal of cis-diol-containing compounds from aqueous solution. Appl. Surface Sci. 2021, 535, 147714. [Google Scholar] [CrossRef]
  15. Cebula, J.; Fink, K.; Boratyński, J.; Goszczyński, T.M. Supramolecular chemistry of anionic boron clusters and its applications in biology. Coord. Chem. Rev. 2023, 477, 214940. [Google Scholar] [CrossRef]
  16. Alkorta, I.; Elguero, J.; Frontera, A. Not only hydrogen bonds: Other noncovalent interactions. Crystals 2020, 10, 180. [Google Scholar] [CrossRef]
  17. Bhattacharyya, M.K.; Saha, U.; Dutta, D.; Frontera, A.; Verma, A.K.; Sharma, P.; Das, A. Unconventional DNA-Relevant π-Stacked Hydrogen Bonded Arrays Involving Supramolecular Guest Benzoate Dimers and Cooperative Anion–π/π–π/π–Anion Contacts in Coordination Compounds of Co(II) and Zn(II) Phenanthroline: Experimental and Theoretical Studies. New J. Chem. 2020, 44, 4504–4518. [Google Scholar] [CrossRef]
  18. Desiraju, G.R. Chemistry beyond the Molecule. Nature 2001, 412, 397–400. [Google Scholar] [CrossRef]
  19. Crabtree, R.H. Hypervalency, Secondary Bonding and Hydrogen Bonding: Siblings under the Skin. Chem. Soc. Rev. 2017, 46, 1720–1729. [Google Scholar] [CrossRef]
  20. Karas, L.J.; Wu, C.-H.; Das, R.; Wu, J.I.-C. Hydrogen Bond Design Principles. WIREs Comput. Mol. Sci. 2020, 10, e1477. [Google Scholar] [CrossRef]
  21. Mahmudov, K.T.; Kopylovich, M.N.; da Silva, M.F.C.G.; Pombeiro, A.J.L. Non-Covalent Interactions in the Synthesis of Coordination Compounds: Recent Advances. Coord. Chem. Rev. 2017, 345, 54–72. [Google Scholar] [CrossRef]
  22. Desiraju, G.R.; Steiner, T. The Weak Hydrogen Bond: In Structural Chemistry and Biology; Oxford University Press: Oxford, UK, 2001. [Google Scholar]
  23. Gutiérrez-Flores, J.; Ramos, E.; Mendoza, C.I.; Hernández-Lemus, E. Electronic Properties of DNA: Description of Weak Interactions in TATA-Box-like Chains. Biophys. Chem. 2018, 233, 26–35. [Google Scholar] [CrossRef]
  24. Allen, F.H.; Baalham, C.A.; Lommerse, J.P.M.; Raithby, P.R. Carbonyl–Carbonyl Interactions Can Be Competitive with Hydrogen Bonds. Acta Crystallogr. 1998, 54, 320–329. [Google Scholar] [CrossRef]
  25. Contejean, Z.I.; LaDuca, R.L. Nitroaromatic-Detecting Zinc and Cadmium Coordination Polymers with Methyl-Substituted Aliphatic Dicarboxylate and 4,4′-Dipyridylamine Ligands and Diverse Topologies. J. Solid State Chem. 2018, 266, 44–53. [Google Scholar] [CrossRef]
  26. White, C.L.; LaDuca, R.L. Nickel Adipate Coordination Polymers with Isomeric Dipyridylamide Ligands: Topological Disorder and Divergent Magnetic Properties. CrystEngComm. 2016, 18, 6789–6797. [Google Scholar] [CrossRef]
  27. Ignatyev, I.; Kondratenko, Y.; Fundamensky, V.; Kochina, T. Synthesis and Characterization of Cobalt(II) Complexes with Triethanolamine and Succinate and/or Nitrate Anions. Transit. Met. Chem. 2018, 43, 127–136. [Google Scholar] [CrossRef]
  28. Forlin, E.; Lanza, A.; Nicola, C.D.; Monari, M.; Gazzano, M.; Nestola, F.; Pettinari, C.; Pandolfo, L. 1D and 3D Coordination Polymers Based on the Cu3(Μ3-OH)(μ-Pz)3 and Cu(Hpz)3 SBUs Connected by the Flexible Glutarate Dianion. Inorg. Chim. Acta 2018, 470, 385–392. [Google Scholar] [CrossRef]
  29. Biswas, C.; Jana, A.D.; Drew, M.G.B.; Mostafa, G.; Ghosh, A. Segregated Self-Assembly and Pillaring Action of Aliphatic Dicarboxylic Acids in the Super Structure of Cu–Picolinate Complexes. Polyhedron 2009, 28, 653–660. [Google Scholar] [CrossRef]
  30. Kathalikkattil, A.C.; Damodaran, S.; Bisht, K.K.; Suresh, E. Hydrogen Bonded Binary Molecular Adducts Derived from Exobidentate N-Donor Ligand with Dicarboxylic Acids: Acid⋯imidazole Hydrogen-Bonding Interactions in Neutral and Ionic Heterosynthons. J. Mol. Struct. 2011, 985, 361–370. [Google Scholar] [CrossRef]
  31. Dutta, B.; Maity, S.; Ghosh, S.; Sinha, C.; Mir, M.H. An Acetylenedicarboxylato-Bridged Mn(Ii)-Based 1D Coordination Polymer: Electrochemical CO2 Reduction and Magnetic Properties. New J. Chem. 2019, 43, 5167–5172. [Google Scholar] [CrossRef]
  32. Arici, M.; Erer, H.; Karaçam, S.; Yeşilel, O.Z.J. Coordination polymers based on 3,3-dimethylglutarate and 1,4-bis ((1H-imidazol-1-yl) methyl) benzene: Hydrothermal synthesis and characterizations. J. Solid State Chem. 2019, 277, 811–818. [Google Scholar] [CrossRef]
  33. Chandra, A.; Dutta, B.; Pal, K.; Jana, K.; Sinha, C. Designing of an Adipic Acid Bridged Zn(II) Coordination Polymer: Synthesis and Biological Study. J. Mol. Struct. 2021, 1243, 130923. [Google Scholar] [CrossRef]
  34. Zhang, J.W.; Xu, S.; Liu, S.N.; Hu, J.; Qiao, Y.X.; Liu, B.Q. Two Series of Substituent-Group-Directed Adipate-Based Lanthanide Coordination Polymers: Syntheses, Structures, Photoluminescence, and Magnetism. Eur. J. Inorg. Chem. 2020, 2020, 1233–1241. [Google Scholar] [CrossRef]
  35. Song, Y.; Yan, Y.; Zhang, H.; Wang, X. Synthesis and Structural Characterization of a Novel 2D Supramolecular Lead Coordination Polymer with Phenanthroline Derivate and Adipic Acid. Main Group Met. Chem. 2021, 44, 239–242. [Google Scholar] [CrossRef]
  36. Zhang, G.; Yang, G.; Ma, J.S. Hydrothermal Syntheses and Characterization of Novel 3D Open-Framework and 2D Grid Lanthanide Fumarates:  Ln2(Fum)3(H2fum)(H2O)2 (Ln = Ce or Nd), [Sm2(Fum)3(H2O)4](H2O)3, and [Yb2(Fum)3(H2O)4](H2O)2. Cryst. Growth Des. 2006, 6, 933–939. [Google Scholar] [CrossRef]
  37. Gogoi, A.; Das, A.; Frontera, A.; Verma, A.K.; Bhattacharyya, M.K. Energetically Significant Unconventional π-π Contacts Involving Fumarate in a Novel Coordination Polymer of Zn(II): In-Vitro Anticancer Evaluation and Theoretical Studies. Inorg. Chim. Acta 2019, 493, 1–13. [Google Scholar] [CrossRef]
  38. Ozer, D.; Köse, D.A.; Şahin, O.; Oztas, N.A. Synthesis and Characterization of Boric Acid Mediated Metal-Organic Frameworks Based on Trimesic Acid and Terephthalic Acid. J. Mol. Struct. 2017, 1141, 261–267. [Google Scholar] [CrossRef]
  39. APEX3, SAINT, SADABS and XP; Bruker AXS Inc.: Madison, WI, USA, 2015.
  40. Sheldrick, G.M. Crystal Structure Refinement with SHELXL. Acta Crystallogr. Sect. A Found. Crystallogr. 2008, 64, 112–122. [Google Scholar] [CrossRef]
  41. Farrugia, L.J. WinGX and ORTEP for Windows: An update. J. Appl. Crystallogr. 1999, 32, 837–838. [Google Scholar] [CrossRef]
  42. Brandenburg, K. Diamond 3.1f; Crystal Impact GbR: Bonn, Germany, 2008. [Google Scholar]
  43. Ahlrichs, R.; Bär, M.; Häser, M.; Horn, H.; Kölmel, C. Electronic Structure Calculations on Workstation Computers: The Program System Turbomole. Chem. Phys. Lett. 1989, 162, 165–169. [Google Scholar] [CrossRef]
  44. Adamo, C.; Barone, V. Toward Reliable Density Functional Methods without Adjustable Parameters: The PBE0 Model. J. Chem. Phys. 1999, 110, 6158–6170. [Google Scholar] [CrossRef]
  45. Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A Consistent and Accurate ab initio Parametrization of Density Functional Dispersion Correction (DFT-D) for the 94 Elements H-Pu. J. Chem. Phys. 2010, 132, 154104–154119. [Google Scholar] [CrossRef] [PubMed]
  46. Weigend, F. Accurate Coulomb-Fitting Basis Sets for H to Rn. Phys. Chem. Chem. Phys. 2006, 8, 1057–1065. [Google Scholar] [CrossRef] [PubMed]
  47. Bader, R.F.W. Atoms in Molecules. Chem. Rev. 1991, 91, 893–928. [Google Scholar] [CrossRef]
  48. Johnson, E.R.; Keinan, S.; Mori-Sánchez, P.; Contreras-García, J.; Cohen, A.J.; Yang, W. Revealing Noncovalent Interactions. J. Am. Chem. Soc. 2010, 132, 6498–6506. [Google Scholar] [CrossRef] [PubMed]
  49. Lu, T.; Chen, F. Multiwfn: A Multifunctional Wavefunction Analyzer. J. Comput. Chem. 2012, 33, 580–592. [Google Scholar] [CrossRef]
  50. Humphrey, J.W.; Dalke, A.; Schulten, K. VMD: Visual molecular dynamics. J. Mol. Graph. 1996, 14, 33–38. [Google Scholar] [CrossRef]
  51. Espinosa, E.; Molins, E.; Lecomte, C. Hydrogen Bond Strengths Revealed by Topological Analyses of Experimentally Observed Electron Densities. Chem. Phys. Lett. 1998, 285, 170–173. [Google Scholar] [CrossRef]
  52. Ozer, D.; Köse, D.A.; Sahin, O.; Oztas, N.A. Study of Structural, Surface and Hydrogen Storage Properties of Boric Acid Mediated Metal (Sodium)-Organic Frameworks. J. Mol. Struct. 2018, 1157, 159–164. [Google Scholar] [CrossRef]
  53. Etter, M.C. Encoding and decoding hydrogen-bond patterns of organic compounds. Acc. Chem. Res. 1990, 23, 120–126. [Google Scholar] [CrossRef]
  54. Nashre-ul-Islam, S.M.; Dutta, D.; Guha, A.K.; Bhattacharyya, M.K. An Unusual Werner Type Clathrate of Mn(II) Benzoate Involving Energetically Significant Weak CH⋯C Contacts: A Combined Experimental and Theoretical Study. J. Mol. Struct. 2019, 1175, 130–138. [Google Scholar] [CrossRef]
  55. Manna, S.C.; Mistri, S.; Jana, A.D. A Rare Supramolecular Assembly Involving Ion Pairs of Coordination Complexes with a Host–Guest Relationship: Synthesis, Crystal Structure, Photoluminescence and Thermal Study. CrystEngComm 2012, 14, 7415–7422. [Google Scholar] [CrossRef]
  56. Nath, H.; Dutta, D.; Sharma, P.; Frontera, A.; Verma, A.K.; Barceló-Oliver, M.; Devi, M.; Bhattacharyya, M.K. Adipato Bridged Novel Hexanuclear Cu(II) and Polymeric Co(II) Coordination Compounds Involving Cooperative Supramolecular Assemblies and Encapsulated Guest Water Clusters in a Square Grid Host: Antiproliferative Evaluation and Theoretical Studies. Dalton Trans. 2020, 49, 9863–9881. [Google Scholar] [CrossRef] [PubMed]
  57. Tan, X.-F.; Zhou, J.; Zou, H.-H.; Xiao, H.-P.; Tang, Q.; Jiang, T.; Zhang, X. Synthesis, Crystal Structures and Properties of a Series of Lanthanide Adipates [Ln2(Ad)3(H2O)4] (Ln = Y3+, Ho3+, Er3+, Tm3+). J. Clust. Sci. 2016, 27, 2025–2033. [Google Scholar] [CrossRef]
  58. Jumanath, E.C.; Pradyumnan, P.P. Thermal Degradation and Spectroscopic Studies of Single-Crystalline Organometallic Calcium Adipate Monohydrate. J. Therm. Anal. Calorim. 2020, 140, 567–575. [Google Scholar] [CrossRef]
  59. Jumanath, E.C.; Pradyumnan, P.P. Growth, Characterization and Dielectric Proprty Studies of Zinc Adipate Dihydrate Crystals. AIP Conf. Proc. 2019, 2082, 1–5. [Google Scholar]
  60. Deacon, G.B.; Phillips, R.J. Relationships between the Carbon-Oxygen Stretching Frequencies of Carboxylato Complexes and the Type of Carboxylate Coordination. Coord. Chem. Rev. 1980, 33, 227–250. [Google Scholar] [CrossRef]
  61. Nakamoto, K. Infrared and Raman Spectra of Inorganic and Coordination Compounds, Part B: Applications in Coordination, Organometallic, and Bioinorganic Chemistry; John Wiley & Sons: Hoboken, NJ, USA, 2009. [Google Scholar]
  62. Bora, S.J.; Das, B.K. Synthesis, structure and properties of a fumarate bridged Ni (II) coordination polymer. J. Mol. Struct. 2011, 999, 83–88. [Google Scholar] [CrossRef]
  63. Hernández, M.F.; Suárez, G.; Cipollone, M.; Conconi, M.S.; Aglietti, E.F.; Rendtorff, N.M. Formation, Microstructure and Properties of Aluminum Borate Ceramics Obtained from Alumina and Boric Acid. Ceram. Int. 2017, 43, 2188–2195. [Google Scholar] [CrossRef]
  64. Wang, C.G.; Xing, Y.H.; Li, Z.P.; Li, J.; Zeng, X.Q.; Ge, M.F.; Niu, S.Y. A Series of Three-Dimensional Lanthanide-Rigid-Flexible Frameworks: Synthesis, Structure, and Luminescent Properties of Coordination Polymers with 2,5-Pyridine Dicarboxylic Acid and Adipic Acid. Cryst. Growth Des. 2009, 9, 1525–1530. [Google Scholar] [CrossRef]
  65. Téllez-López, A.; Sánchez-Mendieta, V.; Jaramillo-García, J.; Rosales-Vázquez, L.D.; García-Orozco, I.; Morales-Luckie, R.A.; Escudero, R.; Morales-Leal, F. Modification of the Structure and Magnetic Properties of Fumarato-Bridged Mn Coordination Polymers through Different Dimethyl-2,2′-Bipyridine Co-Ligands. Transit. Met. Chem. 2016, 41, 879–887. [Google Scholar] [CrossRef]
Crystals 13 00895 g001 550
Figure 1. DNA double-helical structure stabilized by HB interactions and π-stacking.
Figure 1. DNA double-helical structure stabilized by HB interactions and π-stacking.
Crystals 13 00895 g001
Crystals 13 00895 sch001 550
Scheme 1. Synthesis of compounds 1 and 2.
Scheme 1. Synthesis of compounds 1 and 2.
Crystals 13 00895 sch001
Crystals 13 00895 g002 550
Figure 2. Molecular structure of the polymeric complex 1.
Figure 2. Molecular structure of the polymeric complex 1.
Crystals 13 00895 g002
Crystals 13 00895 g003 550
Figure 3. Layered assembly of compound 1 involving the polymeric chains of Na(I) centers assisted by O-H∙∙∙O hydrogen-bonding interactions along the crystallographic ab plane.
Figure 3. Layered assembly of compound 1 involving the polymeric chains of Na(I) centers assisted by O-H∙∙∙O hydrogen-bonding interactions along the crystallographic ab plane.
Crystals 13 00895 g003
Crystals 13 00895 g004 550
Figure 4. (a) Partial view of the layered assembly of compound 1 stabilized by O-H∙∙∙O hydrogen-bonding interactions. (b) Layered assembly of compound 1 involving both the polymeric chains of adp and Na(I) centers along the crystallographic bc plane.
Figure 4. (a) Partial view of the layered assembly of compound 1 stabilized by O-H∙∙∙O hydrogen-bonding interactions. (b) Layered assembly of compound 1 involving both the polymeric chains of adp and Na(I) centers along the crystallographic bc plane.
Crystals 13 00895 g004
Crystals 13 00895 g005 550
Figure 5. Molecular structure of polymeric complex 2.
Figure 5. Molecular structure of polymeric complex 2.
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Crystals 13 00895 g006 550
Figure 6. The 1D polymeric chain of compound 2 involving intramolecular and intermolecular O-H∙∙∙O hydrogen-bonding interactions.
Figure 6. The 1D polymeric chain of compound 2 involving intramolecular and intermolecular O-H∙∙∙O hydrogen-bonding interactions.
Crystals 13 00895 g006
Crystals 13 00895 g007 550
Figure 7. (a) Dual enclathration of lattice BA molecules in the supramolecular host cavity formed of 2. (b) The 2D architecture of 2 along the crystallographic ac plane aided by dual enclathration of lattice BA molecules within the supramolecular host cavity.
Figure 7. (a) Dual enclathration of lattice BA molecules in the supramolecular host cavity formed of 2. (b) The 2D architecture of 2 along the crystallographic ac plane aided by dual enclathration of lattice BA molecules within the supramolecular host cavity.
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Crystals 13 00895 g008 550
Figure 8. FT-IR spectra of compounds 1 and 2.
Figure 8. FT-IR spectra of compounds 1 and 2.
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Crystals 13 00895 g009 550
Figure 9. Thermogravimetric curves of the compounds 1 and 2.
Figure 9. Thermogravimetric curves of the compounds 1 and 2.
Crystals 13 00895 g009
Crystals 13 00895 g010 550
Figure 10. QTAIM (bond CPs in red and bond paths as orange lines) and NCI plot analysis (RDG = 0.6, ρcut-off = 0.04, color range −0.04 a.u. ≤ (signλ2)ρ ≤ 0.04 a.u.).
Figure 10. QTAIM (bond CPs in red and bond paths as orange lines) and NCI plot analysis (RDG = 0.6, ρcut-off = 0.04, color range −0.04 a.u. ≤ (signλ2)ρ ≤ 0.04 a.u.).
Crystals 13 00895 g010
Table
Table 1. Crystallographic data and structure refinement details for compounds 1 and 2.
Table 1. Crystallographic data and structure refinement details for compounds 1 and 2.
Crystal Parameters12
Empirical formulaC6H19B2NaO12C4H16B2Na2O14
Formula weight327.82355.77
Temperature (K)100.0294.0
Wavelength (Å)1.541781.54178
Crystal systemTriclinicOrthorhombic
Space groupP 1 ¯ Pnma
a (Å)3.7723 (4)14.0708 (12)
b (Å)8.6376 (9)6.7995 (6)
c (Å)10.9248 (12)14.9868 (12)
α (°)87.123 (4)90
β (°)84.622 (4)90
γ (°)82.919 (4)90
Volume (Å3)351.43 (7)1433.9 (2)
Z14
Calculated density (g/cm3)1.5491.648
Absorption coefficient (mm−1)1.5431.950
F(000)172.0736.0
Crystal size (mm3)0.26 × 0.24 × 0.150.39 × 0.26 × 0.21
θ range for data collection (°)8.134 to 137.1248.62 to 136.55
Index ranges−4 ≤ h ≤ 4,
−10 ≤ k ≤ 10,
−13 ≤ l ≤ 13		−16 ≤ h ≤ 16,
−8 ≤ k ≤ 7,
−18 ≤ l ≤ 18
Reflections collected748415,582
Unique data (Rint)12761421
Refinement methodFull-matrix least squares on F2Full-matrix least-squares on F2
Data/restraints/parameters1276/0/1181421/0/161
Goodness-of-fit on F21.0741.065
Final Rindices [I > 2σ (I)] R1/wR20.0422/0.11520.0228/0.0616
Rindices (all data) R1/wR20.0427/0.11610.0229/0.0617
Largest diff. peak and hole (e·Å−3)0.31 and −0.240.25 and −0.19
Table
Table 2. Selected hydrogen bond distances (Å) and angles (°) for compounds 1 and 2.
Table 2. Selected hydrogen bond distances (Å) and angles (°) for compounds 1 and 2.
D–H∙∙∙Ad(D–H)d(D∙∙∙A)d(H∙∙∙A)<(DHA)
Compound 1
O1W-H1WB∙∙∙O4B#10.862.912.09159.4
O2B-H2B∙∙∙O3B#30.822.7691.95175
C4A-H4AB∙∙∙O3A0.993.022.64103.1
C4A-H4AA∙∙∙O4B0.993.7262.74175.1
O3B-H3B∙∙∙O1A#20.772.6581.89175
O4B-H4B∙∙∙O3A#20.832.8912.06176.5
Compound 2
O4A-H4A∙∙∙O7#60.892.61.71178
O2A-H2A∙∙∙O8#60.872.6651.8174
O2W-H2WB∙∙∙O7#40.832.9022.08168.9
O2B-H2B∙∙∙O10.882.6461.77178
O3B-H3B∙∙∙O30.92.6381.75172
O3A-H3A∙∙∙O2B#70.812.6771.87177
O4B-H4B∙∙∙O4A#60.872.6821.82176
O2W-H2WA∙∙∙O3B#50.862.7771.92175.3
O1W-H1WB∙∙∙O4B#50.83.0162.22169.1
#1 1 + X, +Y, +Z; #2 −1 + X, 1 + Y, +Z; #3 1 − X, 1 − Y, 1 − Z; #4 1 − X, − 1/2 + Y, 1 − Z; #5 1/2 − X, 1 − Y, −1/2 + Z; #6 −1/2 + X, 3/2 − Y, 1/2 − Z; #7 1/2 + X, 3/2 − Y, 1/2 − Z.
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Baishya, T.; Dutta, K.K.; Frontera, A.; Gomila, R.M.; Barceló-Oliver, M.; Bhattacharyya, M.K. On the Importance of H-Bonding Interactions in the Enclathration of Boric Acids in Na(I) Polymers: Experimental and Theoretical Studies. Crystals 2023, 13, 895. https://doi.org/10.3390/cryst13060895

AMA Style

Baishya T, Dutta KK, Frontera A, Gomila RM, Barceló-Oliver M, Bhattacharyya MK. On the Importance of H-Bonding Interactions in the Enclathration of Boric Acids in Na(I) Polymers: Experimental and Theoretical Studies. Crystals. 2023; 13(6):895. https://doi.org/10.3390/cryst13060895

Chicago/Turabian Style

Baishya, Trishnajyoti, Kamal K. Dutta, Antonio Frontera, Rosa M. Gomila, Miquel Barceló-Oliver, and Manjit K. Bhattacharyya. 2023. "On the Importance of H-Bonding Interactions in the Enclathration of Boric Acids in Na(I) Polymers: Experimental and Theoretical Studies" Crystals 13, no. 6: 895. https://doi.org/10.3390/cryst13060895

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