Diaqua­(5-carb­oxy­benzene-1,3-di­carboxyl­ato-κO 1)(4,4′-dimethyl-2,2′-bipyridine-κ2 N,N′)zinc

Chong-Zhen Mei; Kai-Hui Li; Wen-Wen Shan

doi:10.1107/S1600536811019519

. 2011 May 28;67(Pt 6):m804. doi: 10.1107/S1600536811019519

Diaqua(5-carboxybenzene-1,3-dicarboxylato-κO ¹)(4,4′-dimethyl-2,2′-bipyridine-κ² N,N′)zinc

Chong-Zhen Mei ^a, Kai-Hui Li ^a, Wen-Wen Shan ^a,^*

PMCID: PMC3120513 PMID: 21754680

Abstract

In the title compound, [Zn(C₉H₄O₆)(C₁₂H₁₂N₂)(H₂O)₂], the Zn^II atom is five-coordinated by two N atoms from a 4,4′-dimethyl-2,2′-bipyridine ligand, one O atom from a 5-carboxybenzene-1,3-dicarboxylate ligand and two water molecules in a distorted trigonal–bipyramidal geometry. The complex molecules are linked by intermolecular O—H⋯O hydrogen bonds and partly overlapping π–π interactions [centroid–centroid distance = 4.017 (2) Å] into a three-dimensional supramolecular network.

Related literature

For background to the network topologies and applications of coordination polymers, see: Maspoch et al. (2007 ▶); Ockwig et al. (2005 ▶); Zang et al. (2006 ▶). For O—H⋯O hydrogen bonds, see: Desiraju et al. (2004 ▶). For π–π interactions, see: Zang et al. (2010 ▶).

Experimental

Crystal data

[Zn(C₉H₄O₆)(C₁₂H₁₂N₂)(H₂O)₂]
M _r = 493.76
Triclinic,
a = 9.1938 (9) Å
b = 10.7978 (8) Å
c = 11.5842 (7) Å
α = 85.238 (6)°
β = 72.960 (7)°
γ = 69.760 (8)°
V = 1031.40 (16) Å³
Z = 2
Mo Kα radiation
μ = 1.24 mm⁻¹
T = 296 K
0.21 × 0.20 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.780, T _max = 0.798
7701 measured reflections
3607 independent reflections
3246 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.089
S = 1.05
3607 reflections
292 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811019519/hy2433sup1.cif

e-67-0m804-sup1.cif^{(21.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811019519/hy2433Isup2.hkl

e-67-0m804-Isup2.hkl^{(176.8KB, 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
O5—H5A⋯O6ⁱ	0.82	1.79	2.603 (2)	171
O1W—H1WA⋯O1ⁱⁱ	0.84	1.81	2.635 (2)	165
O1W—H1WB⋯O2ⁱⁱⁱ	0.84	1.75	2.593 (2)	171
O2W—H2WA⋯O2^iv	0.85	1.86	2.688 (2)	166
O2W—H2WB⋯O4^v	0.84	1.79	2.633 (2)	176

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

Acknowledgments

This work was supported financially by the Natural Science Foundation of Henan Province (No. 2010 A140009) and the International Technology Cooperation Project of Science and Technology Department of Henan Province of China (No. 104300510044).

supplementary crystallographic information

Comment

Supramolecular coordination assemblies have received much attention not only for their variety of architectures but also for the potential applications as functional materials (Maspoch et al., 2007; Ockwig et al., 2005). A great number of multidentate organic ligands such as organic aromatic polycarboxylate ligands and N-donor building blocks have been successfully employed in the generation of many interesting systems (Zang et al., 2006). To further explore the influence of multicarboxylate and N-donor ligands on the properties and construction of coordination compounds, we undertake the synthetic and structural studies on a Zn(II) complex based on benzene-1,3,5-tricarboxylic acid (H₃btc) and 4,4'-dimethyl-2,2'-bipyridine (dmbpy), Zn(Hbtc)(bmbpy)(H₂O)₂.

As shown in Fig. 1, the asymmetric unit consists of one Zn^II atom, one Hbtc ligand, one dmbpy ligand and two coordinated water molecules. The Hbtc ligand occurs in a form with an intact COOH group. The metal ion is coordinated by one O atom from the Hbtc ligand, two O atoms of water molecules and two N atoms from the chelating dmbpy ligand, completing a distorted trigonal bipyramidal geometry. N1, O1W and O2W comprise the equatorial plane, while O3 and N2 occupy the axial positions. A pair of symmetry-related complex molecules are associated together through O1W—H1WA···O1ⁱ hydrogen bonds (Table 1) [symmetry code: (i) 1-x, 1-y, 1-z], forming a dimeric unit, in which π–π stacking interaction occurs with a centroid–centroid distance of 4.017 (2)Å between two face-to-face aromatic rings (phenyl ring and pyridine ring bearing the N1 atom). Adjacent dimeric units are connected by O2W—H2WA···O2ⁱⁱ hydrogen bonds [symmetry code: (ii) -x, 1-y, 1-z], resulting in a one-dimensional supramolecular chain running along the a-axis (Fig. 2). As depicted in Fig. 3, the chains are extended to a two-dimensional supramolecular structure through O1W—H1WB···O2ⁱⁱⁱ and O2W—H2WB···O4^iv hydrogen bonds [symmetry codes: (iii) x, 1+y, z; (iv) -x, 2-y, 1-z]. The hydroxyl group and the uncoordinated O atom of the intact COOH group serve as donor and accepter, respectively. Neighboring such carboxylic groups are linked together through O5—H5A···O6^v hydrogen bonds [symmetry code: (v) -1-x, 1-y, 2-z]. Thus, the layers are interconnected into a three-dimensional supramolecular structure (Fig. 4).

Experimental

The title compound was synthesized hydrothermally in a Teflon-lined stainless steel container by heating a mixture of benzene-1,3,5-tricarboxylic acid (0.011 g, 0.05 mmol), 4,4'-dimethyl-2,2'-bipyridine (0.009 g, 0.05 mmol), Zn(NO₃)₂.6H₂O (0.015 g, 0.05 mmol) and NaOH (0.004 g, 0.1 mmol) in 7 ml of distilled water at 120°C for 3 d, and then cooled to room temperature. Colorless block crystals of the title compound were obtained in 68% yield based on zinc.