Structural Invariance of a Zn<sup>II</sup> Coordination Polymer with 5-Aminoisophthalic Acid under Different Synthetic Conditions

A same coordination polymer [Zn(aip)(DMSO)] (aip: 5-aminoisophthalate and DMSO: dimethylsulfoxide) was synthesized using the same reactants (ZnSO₄, aip and H₂O/DMSO) but in different conditions, in which the stoichiometry (1:1-4:1 metal:ligand ratio), temperature (70 and 100 °C) and synthetic method (liquid-liquid diffusion, solvothermal and conventional with stirring) varied. A liquid assisted mechanochemical approach using ZnO as Zn^II source instead ZnSO₄, but keeping DMSO as milling liquid, also resulted in the same compound. This new coordination polymer was investigated using single-crystal X-ray diffraction technique, revealing a two-dimensional honeycomb-type network formation. The crystal structure was compared with either similar or isostructural compounds reported in the literature. Our studies show that the synthetic method and other synthetic variables do not affect the formation of [Zn(aip)(DMSO)] coordination polymers and probe the high stability (thermodynamic and kinetic) and structural invariance of this structure.

Keywords:
coordination polymer; zinc aminoisophthalate; network stability; X-ray diffraction

Authorship

Iara M. L. Rosa ^** e-mail: cristalografia.landre@gmail.com; doriguetto@unifal-mg.edu.br

Laboratório de Cristalografia, Instituto de Química, Universidade Federal de Alfenas, 37130-000 Alfenas-MG, BrazilUniversidade Federal de AlfenasBrazilAlfenas, MG, BrazilLaboratório de Cristalografia, Instituto de Química, Universidade Federal de Alfenas, 37130-000 Alfenas-MG, Brazil

Ana C. Z. dos Santos

Luana A. R. Giusto

Carlos B. Pinheiro

Laboratório de Cristalografia, Departamento de Física, Universidade Federal de Minas Gerais, 30161-970 Belo Horizonte-MG, BrazilUniversidade Federal de Minas GeraisBrazilBelo Horizonte, MG, BrazilLaboratório de Cristalografia, Departamento de Física, Universidade Federal de Minas Gerais, 30161-970 Belo Horizonte-MG, Brazil

Antonio C. Doriguetto ^** e-mail: cristalografia.landre@gmail.com; doriguetto@unifal-mg.edu.br

* e-mail: cristalografia.landre@gmail.com; doriguetto@unifal-mg.edu.br

SCIMAGO INSTITUTIONS RANKINGS

Figures | Tables

Figures (9)
Tables (1)

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Scheme 1
Chemical structure of the 5-aminoisophthalic acid (H₂aip or aip in its deprotonated form).

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Figure 1
Representation of syntheses conducted in this work.

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Figure 2
PXRD patterns for products (a) 1a-1e and (b) 1f-1h. For identification purposes, the calculated powder pattern of 1 obtained from the single-crystal X-ray diffraction data is also shown. The black arrows in the 1f-1g PXRD patterns indicate Bragg peaks that do not match to crystal structure of 1. Reflexions marked with the Miller index (100), (002) and (101) in the 1h PXRD pattern indicate the presence of unreacted ZnO (ICDD crystal chart No. 36-1451). The X-ray diffraction pattern calculated from low-temperature crystal structure (150 K, see Table 1) is, as expected, slightly shifted (right direction) from the experimental ones performed at room temperature (298 K) for the products 1a-1h.

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Figure 3
Ellipsoid representation of compound 1 with atomic labeling: (a) the asymmetric unit, tetrahedral environment of the metal and (b) two-dimensional network. The hydrogen atoms were omitted for clarity.

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Figure 4
(a) Simplified view of the compound 1 showing the honeycomb-type network and (b) intermolecular hydrogen bonds (dashed lines) that connect layers A and B. The supramolecular synthons are highlighted and DMSO molecules are indicated with blue and green blue arrows (pointing upward and downward, respectively) to show the opposite directions to each layer.

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Figure 5
Shortest (d₁) and longest (d₂) interlayer distances for compound1.

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Figure 6
Effect of the torsion angle on the orientation of the ligand aip in the network for compound 1, the (a) CPO-8-L2 analogues and (b) CPO-8-L1 analogues (CSD code: OBODOA).³⁸38 Kuai, H.-W.; Cheng, X.-C.; Acta Crystallogr., Sect. E: Crystallogr. Commun. 2011, 67, m1835. The red and green arrows indicate orientations 1 and 2, respectively, of the aip molecule in the two-dimensional network.

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Figure 7
Intermolecular hydrogen bond (dashed line) between the N–H moiety of the imidazole molecule and the uncoordinated oxygen of the aip ligand, which directly affects the torsion angle of compound CPO-8-IMDZ.³⁸38 Kuai, H.-W.; Cheng, X.-C.; Acta Crystallogr., Sect. E: Crystallogr. Commun. 2011, 67, m1835.

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Figure 8
(a) Intramolecular hydrogen bond in 1 and the CPO-8-L2 analogues because of the non-coplanarity of the ligands with orientation 1 (red arrow), and (b) the absence of intramolecular hydrogen bond in the CPO-8-L1 analogues (CSD code: OBODOA).³⁸38 Kuai, H.-W.; Cheng, X.-C.; Acta Crystallogr., Sect. E: Crystallogr. Commun. 2011, 67, m1835.

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Table 1
Crystallographic data for compound 1

Scheme 1 Chemical structure of the 5-aminoisophthalic acid (H₂aip or aip in its deprotonated form).

Figure 1 Representation of syntheses conducted in this work.

Figure 2 PXRD patterns for products (a) 1a-1e and (b) 1f-1h. For identification purposes, the calculated powder pattern of 1 obtained from the single-crystal X-ray diffraction data is also shown. The black arrows in the 1f-1g PXRD patterns indicate Bragg peaks that do not match to crystal structure of 1. Reflexions marked with the Miller index (100), (002) and (101) in the 1h PXRD pattern indicate the presence of unreacted ZnO (ICDD crystal chart No. 36-1451). The X-ray diffraction pattern calculated from low-temperature crystal structure (150 K, see Table 1) is, as expected, slightly shifted (right direction) from the experimental ones performed at room temperature (298 K) for the products 1a-1h.

Figure 3 Ellipsoid representation of compound 1 with atomic labeling: (a) the asymmetric unit, tetrahedral environment of the metal and (b) two-dimensional network. The hydrogen atoms were omitted for clarity.

Figure 4 (a) Simplified view of the compound 1 showing the honeycomb-type network and (b) intermolecular hydrogen bonds (dashed lines) that connect layers A and B. The supramolecular synthons are highlighted and DMSO molecules are indicated with blue and green blue arrows (pointing upward and downward, respectively) to show the opposite directions to each layer.

Figure 5 Shortest (d₁) and longest (d₂) interlayer distances for compound1.

Figure 6 Effect of the torsion angle on the orientation of the ligand aip in the network for compound 1, the (a) CPO-8-L2 analogues and (b) CPO-8-L1 analogues (CSD code: OBODOA).³⁸38 Kuai, H.-W.; Cheng, X.-C.; Acta Crystallogr., Sect. E: Crystallogr. Commun. 2011, 67, m1835. The red and green arrows indicate orientations 1 and 2, respectively, of the aip molecule in the two-dimensional network.

Figure 7 Intermolecular hydrogen bond (dashed line) between the N–H moiety of the imidazole molecule and the uncoordinated oxygen of the aip ligand, which directly affects the torsion angle of compound CPO-8-IMDZ.³⁸38 Kuai, H.-W.; Cheng, X.-C.; Acta Crystallogr., Sect. E: Crystallogr. Commun. 2011, 67, m1835.

Figure 8 (a) Intramolecular hydrogen bond in 1 and the CPO-8-L2 analogues because of the non-coplanarity of the ligands with orientation 1 (red arrow), and (b) the absence of intramolecular hydrogen bond in the CPO-8-L1 analogues (CSD code: OBODOA).³⁸38 Kuai, H.-W.; Cheng, X.-C.; Acta Crystallogr., Sect. E: Crystallogr. Commun. 2011, 67, m1835.

Table 1 Crystallographic data for compound 1

Crystal data
Chemical formula	C₁₀H₁₁NO₅SZn
M_r	322.63
Crystal system, space group	monoclinic, P2_1/c
Temperature / K	150
a, b, c / Å	9.8569 (6), 7.6800 (4), 16.1298 (8)
β / degree	95.220 (5)
V / Å³	1215.98 (11)
Z	4
Radiation type	MoKα
µ / mm^-1	2.21
Crystal habit	plate
Crystal size / mm	0.28 × 0.20 × 0.12
Data collection
No. of measured, independent and observed [I > 2σ(I)] reflections	10560, 3009 and 2265
R_int	0.049
(sin θ/λ)_max / Å^-1	0.694
Refinement
R[F² > 2σ(F²)], wR(F²) and S	0.044, 0.098 and 1.07
No. of reflections	3009
No. of parameters	164
No. of restraints	0
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min / (e Å^-3)	0.98, -1.15

w = 1/[σ²(F_o²) + (0.0274P)² + 2.7606P], where P = (F_o² + 2F_c²)/3.

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