catena-Poly[[[aqua­tris­(pyridine-κN)nickel(II)]-μ-2,3,5,6-tetra­chloro­benzene-1,4-dicarboxyl­ato-κ2 O 1:O 4] pyridine monosolvate]

Chang-Ge Zheng; Pei-Pei Zhang; Peng Zhang; Song Li

doi:10.1107/S1600536810045794

. 2010 Nov 20;66(Pt 12):m1618. doi: 10.1107/S1600536810045794

catena-Poly[[[aquatris(pyridine-κN)nickel(II)]-μ-2,3,5,6-tetrachlorobenzene-1,4-dicarboxylato-κ² O ¹:O ⁴] pyridine monosolvate]

Chang-Ge Zheng ^a,^*, Pei-Pei Zhang ^a, Peng Zhang ^a, Song Li ^a

PMCID: PMC3011545 PMID: 21589294

Abstract

The asymmetric unit of the title compound, {[Ni(C₈Cl₄O₄)(C₅H₅N)₃(H₂O)]·C₅H₅N}_n, contains two independent nickel(II) cations displaying a distorted octahedral coordination geometry provided by the N atoms of three pyridine molecules, the O atom of a water molecule, and O atoms of two monodentate μ₂-bridging tetrachloroterephthalate dianions. The metal atoms are linked by the dianions into zigzag chains running parallel to [11 Inline graphic ]. The crystal packing is stabilized by O—H⋯N and O—H⋯O hydrogen bonds.

Related literature

For the modelling of hydrogen adsorption in metal-organic frameworks, see: Mulder et al. (2005 ▶); Zheng et al. (2009 ▶). For related structures, see: Kim et al. (2003 ▶); Go et al. (2004 ▶); Wang et al. (2003 ▶); Li et al. (2003 ▶); Zheng et al. (2008 ▶).

Experimental

Crystal data

[Ni(C₈Cl₄O₄)(C₅H₅N)₃(H₂O)]·C₅H₅N
M _r = 1390.01
Triclinic,
a = 8.6148 (6) Å
b = 17.6879 (10) Å
c = 21.0617 (10) Å
α = 68.279 (5)°
β = 79.750 (6)°
γ = 84.853 (6)°
V = 2932.9 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.07 mm⁻¹
T = 293 K
0.26 × 0.21 × 0.10 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ▶) T _min = 0.688, T _max = 1.000
26508 measured reflections
11670 independent reflections
8092 reflections with I > 2σ(I)
R _int = 0.060

Refinement

R[F ² > 2σ(F ²)] = 0.076
wR(F ²) = 0.151
S = 1.07
11670 reflections
757 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810045794/rz2513sup1.cif

e-66-m1618-sup1.cif^{(42KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810045794/rz2513Isup2.hkl

e-66-m1618-Isup2.hkl^{(570.5KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9A⋯O2	0.85	2.02	2.751 (4)	143
O9—H9B⋯N7	0.85	1.89	2.699 (6)	159
O10—H10A⋯N8ⁱ	0.85	1.97	2.783 (6)	161
O10—H10B⋯O3ⁱⁱ	0.85	1.83	2.677 (4)	174

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

This work was supported by the Center of Analysis and Testing of Jiangnan University and the Research Institute of Element-Organic Chemistry of Suzhou University

supplementary crystallographic information

Comment

Transition metal complexes have attracted considerable interest, owning to their elegant framework topologies as well as their potential applications in gas sorption, catalysis and optoelectronic devices, and a considerable amount of research work has been done on this type of complexes. However, there are few reports on polyhalogenated benzene-1,4-dicarboxylic ligands, especially tetrachloroterephthalic acid. Computer calculations have suggested that halogens such as chlorine can enhance the adsorption of hydrogen molecules in metal organic frameworks (Mulder et al., 2005; Zheng et al., 2009), so the title compound was synthesized and its crystal structure is reported herein.

The asymmetric unit of the title compound (Fig. 1) consists two independent nickel(II) cations having distorted octahedral coordination geometry, where the equatorial plane is provided by the N atoms of three pyridine molecules and the O atom of a water molecule, and the axial positions are occupied by the O atoms of two monodentate µ₂-bridging tetrachloroterephthalate dianions. The bridging role of the dianions results in the formation of one-dimensional neutral zigzag chains running parallel to the [111] direction. The Ni—O bond lengths lie in the range 2.065 (3)–2.095 (3) Å, and agree well with the values reported in the literature for related compounds (Kim et al., 2003; Go et al., 2004). The Ni—N bond lengths lie in the range of 2.094 (4)–2.124 (4) Å, and are also comparable with those reported for the similar complexes (Wang et al., 2003; Li et al., 2003; Zheng et al., 2008). The crystal packing is stabilized by O—H···N and O—H···O hydrogen interactions (Table 1).

Experimental

All the reagents and solvents empolyed were commercially available. Tetrachloroterephthalic acid was purified by recrystallization. The title compound was synthesized by slow vapour diffusion at room temperature of pyridine (3 ml) in to a methanol solution (3 ml) containing a mixture of tetrachloroterephthalic acid (0.0304 g, 0.10 mmol) and NiCl₂.6H₂O (0.0476 g, 0.20 mmol) diluted with deionized water (2 ml). After ten days, green block-shaped crystals were obtained.The green block-shaped crystals were collected by filtration, washed with methanol (3 ml), and air dried to give the title complex (0.09 g, 65% yield). Elemental analysis (%) calcd. for C₅₆H₄₄Cl₈N₈Ni₂: C, 48.34%; H, 3.17%; N, 8.06%; Found: C,48.14%; H, 2.98%; N, 7.94%.