catena-Poly[[[tetra­aqua­zinc(II)]-μ-4,4′-bipyridine-κ2 N:N′] benzene-1,4-di­carboxyl­ate]

Ming-Bo Ruan; Jian-Cheng Deng; Zhi-Gang Li; Jing-Wei Xu

doi:10.1107/S1600536809019412

. 2009 Jun 6;65(Pt 7):m743. doi: 10.1107/S1600536809019412

catena-Poly[[[tetraaquazinc(II)]-μ-4,4′-bipyridine-κ² N:N′] benzene-1,4-dicarboxylate]

Ming-Bo Ruan ^a, Jian-Cheng Deng ^a,^*, Zhi-Gang Li ^b, Jing-Wei Xu ^c

PMCID: PMC2969229 PMID: 21582682

Abstract

In the title compound, {[Zn(C₁₀H₈N₂)(H₂O)₄](C₈H₄O₄)}_n, the Zn^II atoms, lying on a twofold rotation axis, are bridged by 4,4′-bipyridine ligands, resulting in a linear chain along the b axis. In the chain, the Zn^II atom adopts a slightly distorted octahedral coordination geometry involving four water molecules at the equatorial positions. The noncoordinated benzene-1,4-dicarboxylate anion, which is also located on a twofold rotation axis, bridges adjacent chains through O—H⋯O hydrogen bonds, forming a three-dimensional supramolecular network.

Related literature

For background information on hydrothermal reactions, see: Yaghi et al. (2003 ▶). For hydrogen-bond graph-set motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

[Zn(C₁₀H₈N₂)(H₂O)₄](C₈H₄O₄)
M _r = 457.75
Monoclinic,
a = 6.9861 (12) Å
b = 11.3436 (19) Å
c = 11.3219 (19) Å
β = 101.209 (3)°
V = 880.1 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.45 mm⁻¹
T = 186 K
0.21 × 0.18 × 0.12 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.751, T _max = 0.845
4812 measured reflections
1735 independent reflections
1465 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.108
S = 1.08
1735 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT-Plus (Bruker, 2003 ▶); data reduction: SAINT-Plus; 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: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809019412/is2415sup1.cif

e-65-0m743-sup1.cif^{(16.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809019412/is2415Isup2.hkl

e-65-0m743-Isup2.hkl^{(85.5KB, 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
O1—H1AA⋯O3ⁱ	0.87	1.89	2.753 (3)	169
O1—H1AB⋯O4ⁱⁱ	0.86	2.08	2.893 (3)	157
O2—H2AA⋯O4ⁱⁱⁱ	0.85	1.87	2.718 (3)	173
O2—H2AB⋯O3^iv	0.84	1.91	2.742 (3)	171

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

Acknowledgments

This work was supported by the Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, People’s Republic of China.

supplementary crystallographic information

Comment

Hydro(solvo)thermal reaction has shown a kind of promising technique for the preparation of complexes with novel structures and special properties (Yaghi et al., 2003). Here we report the structure of the title compound, (I), which contains one-dimensional cation chains and non-coordinated benzene-1,4-dicarboxylate as couteranions under solvothermal condition.

Compound, (I), as shown in Fig. 1, consists of one-dimensional [Zn(C₁₀H₈N₂)(H₂O)₄]_n cation chains and benzene-1,4-dicarboxylate anions. The Zn(II) atoms are in a slightly distorted octahedral geometry, where two N atoms from two 4,4'-bipyridine ligands occupy the axial positions, and the equatorial positions are completed by four water molecules. The compound crystallizes in a centrosymmetric space group, which defines twofold axes along both the one-dimensional chains and the benzene-1,4-dicarboxylate anions.

In the crystal structure, intermolecular O—H···O hydrogen bonds are present (Table 1 and Fig. 2) and the coordinated water molecules are linked with two benzene-1,4-dicarboxylate anions to form R₄⁴(12) and R₆⁴(16) hydrogen-bonding rings (Bernstein et al., 1995). In addition, there are strong π···π interactions between pyridine rings and phenyl rings at (x, y, z) and (1/2 - x,1 + y, 3/2 - z), with the shortest atom-to-center distance of 3.322 (4) Å. The two kinds of interactions lead to a three-dimensional supramolecular network (Fig. 2).

Experimental

Compound (I) was solvothermally prepared from a reaction mixture of Zn(BF₄)₂ (0.2 mmol), 4,4'-bipyridine (0.1 mmol), benzene-1,4-dicarboxylic acid (0.1 mmol), methanol (3 ml) and distilled water (8 ml) in a molar ratio of 2:1:740:4444; the pH value was adjusted to 4.8 with trimethylamine and acetic acid. The mixture was stirred for 20 min at room temperature and then sealed in a Teflon-lined stainless steel autoclave with a 23 ml capacity at 423 K for 72 h. After cooling to room temperature, colourless block-shaped crystals were obtained; these were washed with deionized water, filtered, and dried in air (yield 48% based on Zn).