Crystal structure of poly[tetraaqua-bis(μ4-3–1-(carboxylatomethyl)-1H-1,2,4-triazole-3-carboxylato)-κ4O:O′,O″,N)zinc(II)], C5H7N3O6Zn
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Fan Fan
Abstract
C5H7N3O6Zn, triclinic, P
The molecular structure is shown in the figure. Table 1 contains the crystallographic data and the list of the atoms including atomic coordinates and displacement parameters can be found in the cif-file attached to this article.
Data collection and handling.
| Crystal: | Colourless block |
| Size: | 0.23 × 0.20 × 0.18 mm |
| Wavelength: | MoKα radiation (0.71073 Å) |
| μ: | 3.00 mm−1 |
| Diffractometer, scan mode: | Bruker APEX-II, φ and ω scans |
| θmax, completeness: | 25.0°, 100 % |
| N(hkl)measured, N(hkl)unique, Rint: | 2104, 1439, 0.016 |
| Criterion for Iobs, N(hkl)gt: | Iobs > 2 σ(Iobs), 1,285 |
| N(param)refined: | 155 |
| Programs: | Bruker, 1 Shelx 2 |
1 Source of material
The mixture of Zn(NO3)2⋅6H2O (1 mmol, 297.5 mg), 1-(carboxymethyl)-1H-1,2,4-triazole-3-carboxylic acid (H2cta) (1 mmol, 171.0 mg), dimethylformamide (3 mL) and H2O (1 mL) were placed in a 25 mL Teflon-lined autoclave at 363 K for 72 h. After cooling to room temperature, colorless block crystals were obtained.
2 Experimental details
The OH– distances were restraint at 0.85(1) Å by DFIX commands. The H atoms bound to C atoms were placed in calculated positions and constrained to ride on their parent atoms, with d(C–H) = 0.93 Å (aromatic) and d(C–H) = 0.97 Å (methylene) with Uiso(H) = 1.2Ueq(C).
3 Discussion
The rational design and synthesis of coordination polymers have long been a key focus in research in the last decades. 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 In this context, organic ligands usually play an extremely important role in the construction of coordination polymers. Among the various organic ligands, triazole-based ligands are important class of organic ligands, which have nitrogen atoms in variable positions and strong metal-coordinating capabilities, are able to provide a variety of coordination sites. 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 As a triazole-based ligand, 1-(carboxymethyl)-1H-1,2,4-triazole-3-carboxylic acid (H2 cta) contains a triazole ring and two carboxylic acid groups, which endow the corresponding deprotonated anions with excellent coordination ability in the formation of coordination polymers. With the expansion of the research scope of coordination polymers based on H2 cta, a Zn(II) coordination polymer based on cta2− was synthesized, which can be potentially used as a fluorescence detector by fluorescence. 21 , 22 , 23
X-ray crystallographic analysis reveals that the title compound is isostructural with its analogous compound Mn(II) coordination polymer based on cta2−. 17 The asymmetric unit of the title structure contains two half Zn2+, one cta2− ligand and two coordinated water molecules (see the figure). The two Zn(II) cations exhibit similar coordination mode which exhibit distorted octahedral geometry. The six atoms that coordinate with Zn1 cation come from two carboxyl oxygen atoms and two nitrogen atoms of two symmetry related cta2− ligands and two symmetry related coordinated water oxygen atoms. Meanwhile, the Zn2 cation is coordinated by four carboxyl oxygen atoms from for symmetry related cta2− ligands and two symmetry related coordinated water oxygen atoms.
The Zn–O lengths (2.0474(19)–2.1733(19) Å) and Zn–N length (2.069(2) Å) are all in normal ranges. The cta2− ligands linked the Zn cations to form a two-dimensional structure. In the crystal packing, the adjacent networks are linked into three-dimensional frameworks by O–H⋯O and O–H⋯N hydrogen bonds from coordinated water molecules and carboxylate and triazole groups of cta2− ligands. Furthermore, intramolecular O–H⋯O hydrogen bonds from coordinated water molecules and carboxylate groups of cta2− ligands could further consolidate the whole structure.
Funding source: Hebei Public Security Police Vocational College
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Research funding: This work was financial supported by Hebei Public Security Police Vocational College.
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