catena-Poly[[diaqua­nickel(II)]-bis­(μ-2-{[5-(pyridin-4-yl)-1,3,4-oxadiazol-2-yl]sulfan­yl}acetato)]

Ru-Qin Gao; Chao-Hui Xia; Guo-Ting Li

doi:10.1107/S1600536812020259

. 2012 May 12;68(Pt 6):m763–m764. doi: 10.1107/S1600536812020259

catena-Poly[[diaquanickel(II)]-bis(μ-2-{[5-(pyridin-4-yl)-1,3,4-oxadiazol-2-yl]sulfanyl}acetato)]

Ru-Qin Gao ^a,^*, Chao-Hui Xia ^b, Guo-Ting Li ^a

PMCID: PMC3379099 PMID: 22719320

Abstract

In the title compound, [Ni(C₉H₆N₃O₃S)₂(H₂O)₂]_n, the Ni^II atom, located on an inversion center, is ligated in an octahedral geometry by two carboxylate O atoms from two 2-{[5-(pyridin-4-yl)-1,3,4-oxadiazol-2-yl]sulfanyl}acetate (L) ligands and two O atoms from water molecules in the equatorial plane, and two pyridine N atoms from other two L ligands at the apical sites. Two L ligands bridge pairs of metal atoms in an antiparallel manner, forming centrosymmetric dinuclear quasi-rectangular units which are linked into infinite double-stranded chains parallel to [100]. O—H⋯O hydrogen bonds between the coordinating water molecules and the carboxylate groups of the L ligand as well as interchain S⋯N interactions [2.726 (2)–3.363 (2) Å] lead to the formation of a layer structure parallel to (001).

Related literature

For coordination polymers of 1,3,4-oxadiazole-2-thione, see: Wu et al. (2010 ▶); Lundin et al. (2006 ▶); Wang et al. (2007) ▶. For coordination polymers of symmetric pyridyl-containing oxadiazole ligands, see: Ma et al. (2007 ▶); Du et al. (2006) ▶. For unsymmetric pyridyl-containing oxadiazole ligands, see: Wang & Li (2011 ▶).

Experimental

Crystal data

[Ni(C₉H₆N₃O₃S)₂(H₂O)₂]
M _r = 567.20
Monoclinic,
a = 11.8862 (18) Å
b = 5.6431 (9) Å
c = 15.500 (2) Å
β = 95.687 (2)°
V = 1034.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.20 mm⁻¹
T = 293 K
0.15 × 0.13 × 0.07 mm

Data collection

Siemens SMART CCD diffractometer
7195 measured reflections
1822 independent reflections
1488 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.068
S = 1.03
1822 reflections
166 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1994 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812020259/zj2075sup1.cif

e-68-0m763-sup1.cif^{(15.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812020259/zj2075Isup2.hkl

e-68-0m763-Isup2.hkl^{(89.7KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Ni1—O2	2.0702 (16)
Ni1—O4	2.0781 (18)
Ni1—N1ⁱ	2.1157 (19)

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Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O3	0.82 (1)	1.83 (1)	2.633 (3)	167 (3)
O4—H4B⋯O2ⁱⁱ	0.82 (1)	2.11 (2)	2.857 (3)	153 (3)

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Symmetry code: (ii) Inline graphic .

Acknowledgments

This work was supported by the Natural Science Foundation of China.

supplementary crystallographic information

Comment

There have been considerable interests in the coordination polymers of 1,3,4-oxadiazole-2-thione because of their intriguing architectures (Wu, et al., 2010) and potential applications as functional materials (Lundin, et al., 2006; Wang, et al., 2007). In particular, pyridyl-containing oxadiazole ligands, such as symmetric 5-phenyl-1,3,4-oxadiazole-2-thione (Ma, et al., 2007) and 5-(4-pyridyl)-1,3,4-oxadiazole-2-thione (Du, et al., 2006), have been extensively explored in the construction of porous coordination polymers. As our continuous work in this aspect (Wang & Li, 2011), we report that the reaction of NiCl₂.6H₂O and sodium(I) salt of 2-(5-(pyridin-4-yl)-1,3,4-oxadiazol-2-ylthio)acetic acid (HL) leads to a new complex [Ni(L)₂(H₂O)₂]_n (1) herein.

In (1) the Ni^II center is located at the inversion center ligated by two carboxylato O atoms from two deprotonated L and two O atoms from water molecules in the equatorial plane, and two pyridyl N atoms from other two deprotonated L at the apical sites. Thus the Ni^II ion is in a six-coordinated octahedral coordination geometry (Fig. 1). The bond distances of Ni—O and Ni—N range from 2.070 (2) to 2.116 (2) Å, while O—Ni—N angles range from 85.90 (7) to 94.10 (7) °, indicating a slight distortion from an ideal octahedron.

Complex (1) displays an extended infinite double-strand chain structure constructed of dinuclear quasi-rectangle units (Fig. 2). The dinuclear quasi-rectangle units are centrosymmetric and formed by two L anions antiparallelly bridging two metal centers in monodentate modes with two nickel atoms and two methylene carbon atoms of the L at the corners and the diagonal Ni···Ni distances of 11.886 (2) Å. As for L, the pyridyl group and the acetate group deviate from the center ring of oxadiazole-2-thione group, with the dihedral angels being 36.0 (7) and 88.5 (7) °, respectively. Notably, the conformation of L is apt to the dinuclear quasi-rectangle which is further stabilized by CH···π stacking interactions between antiparallel the pyridyl-1,3,4-oxadiazol groups of the L in the same rectangle unit with the distances of H_pyridyl to centroid of oxadiazol group being 3.320 (2) Å and 3.353 (2) Å. The chains of complex (1) are connected by O—H···O hydrogen bonds between the coordinated water molecules (as donors) and the carboxylate groups of L (as acceptors), leading to the formation of a two-dimensional network structure (Fig. 2, Table 3). Additionally, the interchain weak interactions between S and N of the oxadiazole-2-thione groups of L stabilize the layer structure (the distances of S···N being in a range of 2.726 (2) to 3.363 (2) Å).

Experimental

For the synthesis of sodium(I) salt of ligand 2-(5-(pyridin-4-yl)-1,3,4-oxadiazol-2-ylthio)acetic acid (HL), see: Wang & Li, (2011). The title compound (1).n(H₂O) was prepared according to the following process. A mixture of NaL (51.8 mg, 0.2 mmol), NiCl₂.6H₂O (23.8 mg, 0.1 mmol) and deionized water (20 ml) was stirred for 30 minutes and then filtered. The filtrate was allowed to evaporate at room temperature for three days, and then green needle crystals were obtain in 72% yield. Selected IR (cm^-1, KBr pellet): 3374(m), 3091(w), 2994(w), 1621(m), 1579(s), 1463(s), 1382(s), 1224(m), 1192(m), 1065(m), 958(w), 707(s), 586(w).