Tetra­aqua­bis­[1-(3-carb­oxy­phen­yl)-4,4′-bipyridin-1-ium-κN 1′]zinc bis­(4,5-carb­oxy­benzene-1,2-dicarboxyl­ate) 2.5-hydrate

Jie Zhang; Yi Tan; Zhiyong Fu

doi:10.1107/S1600536811045156

. 2011 Nov 5;67(Pt 12):m1701–m1702. doi: 10.1107/S1600536811045156

Tetraaquabis[1-(3-carboxyphenyl)-4,4′-bipyridin-1-ium-κN ^1′]zinc bis(4,5-carboxybenzene-1,2-dicarboxylate) 2.5-hydrate

Jie Zhang ^a, Yi Tan ^a, Zhiyong Fu ^a,^*

PMCID: PMC3238626 PMID: 22199517

Abstract

In the complex cation of the title compound, [Zn(C₁₇H₁₃N₂O₂)₂(H₂O)₄](C₁₀H₄O₈)₂·2.5H₂O, the Zn^II atom, lying on an inversion center, is coordinated by two N atoms from two N-(3-carboxyphenyl)-4,4′-bipyridin-1-ium ligands and four water molecules in a distorted octahedral geometry. The pyromellitate anion is double deprotonated. O—H⋯O and C—H⋯O hydrogen bonds connect the cations, anions and uncoordinated water molecules into a three-dimensional supramolecular network. One of the two lattice water molecules shows an occupancy of 0.25. An intramolecular O—H⋯O hydrogen bond is present in the anion.

Related literature

For background to the structures and applications of viologen compounds, see: Ebbesen et al. (1984 ▶); Jin et al. (2010 ▶); Sun et al. (2005 ▶); Xu et al. (2007 ▶).

Experimental

Crystal data

[Zn(C₁₇H₁₃N₂O₂)₂(H₂O)₄](C₁₀H₄O₈)₂·2.5H₂O
M _r = 1241.33
Monoclinic,
a = 7.5476 (2) Å
b = 19.5528 (4) Å
c = 19.2752 (4) Å
β = 110.431 (2)°
V = 2665.63 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.56 mm⁻¹
T = 298 K
0.43 × 0.41 × 0.37 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.781, T _max = 0.825
25451 measured reflections
4867 independent reflections
4250 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.078
S = 1.06
4867 reflections
429 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: SMART (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 datablock(s) global, I. DOI: 10.1107/S1600536811045156/hy2468sup1.cif

e-67-m1701-sup1.cif^{(31.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811045156/hy2468Isup2.hkl

e-67-m1701-Isup2.hkl^{(238.4KB, 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—H7⋯O12ⁱ	0.87 (2)	1.80 (3)	2.656 (3)	164 (3)
O3—H1⋯O11ⁱⁱ	0.85 (2)	1.88 (3)	2.732 (2)	175 (3)
O3—H2⋯O11ⁱⁱⁱ	0.81 (3)	2.03 (2)	2.820 (4)	163 (2)
O4—H3⋯O13ⁱⁱⁱ	0.84 (2)	1.84 (3)	2.677 (6)	175 (3)
O4—H4⋯O12^iv	0.90 (3)	1.79 (4)	2.694 (2)	177 (4)
O6—H9⋯O7	0.87 (3)	1.56 (3)	2.418 (2)	174 (3)
O9—H8⋯O8ⁱⁱⁱ	0.85 (3)	1.82 (3)	2.646 (3)	163 (4)
O13—H5⋯O10	0.92 (4)	1.90 (2)	2.813 (3)	174 (3)
O13—H6⋯O7ⁱⁱⁱ	0.87 (4)	1.86 (4)	2.723 (2)	169 (3)
O14—H11⋯O13	0.82 (2)	2.18 (2)	2.846 (2)	138 (2)
C7—H7A⋯O1^v	0.93	2.30	3.155 (2)	153
C8—H8A⋯O12^vi	0.93	2.52	3.302 (2)	142
C9—H9A⋯O2^vii	0.93	2.30	3.225 (2)	172
C10—H10A⋯O5^viii	0.93	2.15	3.060 (3)	167

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

Acknowledgments

The authors thank the NNSFC (grant Nos. 21053001 and 20701014), the Fundamental Research Funds for the Central Universities (2009ZM0030) and the SRP program of the SCUT for financial support. They also thank Professor Tong Chun Kuang (Analytical and Testing Center of SCUT) for the data collection.

supplementary crystallographic information

Comment

Viologens are quaternary salts derived from 4,4'-bipyridine (Ebbesen et al., 1984). Intensively interests have been focused on these compounds for their electron-transfer properties and enormous potential applications in electrochromic displays and optically switchable devices (Jin et al., 2010; Sun et al., 2005; Xu et al., 2007). Most of them are dimethyl-, diethyl-, dibetaine- and dibenzyl viologens. Here we report the synthesis and structure of a new viologen compound with N-3-carboxyphenyl substitution and double-deprotonated pyromellitate as compensation anions.

The asymmetric unit of the title compound contains one Zn^II atom lying on an inversion center, one N-(3-carboxyphenyl)-4,4'-bipyridinium ligand, one double-deprotonated pyromellitate anion, two coordinated water molecules and 1.25 uncooedinated water molecules (Fig. 1). The Zn^II atom is six-coordinated by two N atoms of the viologen ligands and four O atoms of water molecules. The Zn—N bond length is 2.1689 (14) Å and the Zn—O bond lengths are 2.0798 (13) and 2.1335 (14) Å. The bond angles vary from 88.98 (6) to 93.42 (5)°, indicating a distorted octahedral geometry. O—H···O and C—H···O hydrogen bonds (Table 1) connect the cations, anions and uncoordinated water molecules into a three-dimensional supramolecular network (Fig. 2).

Experimental

A mixture of N-(3-carboxyphenyl)-4,4'-bipyridinium chloride (0.2 mmol), ZnO(1 mmol), phosphoric acid (2 mmol), pyromellitic acid (0.2 mmol) and water (5 ml) was sealed in a 23 ml Teflon-lined bomb at 120°C for 72 h. Yellow block-shaped crystals were obtained.