catena-Poly[[tetra­aqua­(μ-4,4′-bipyridine-κ2 N:N′)zinc(II)] fumarate tetra­hydrate]

Yong Tian; Ya-Pan Wu; Dong-Sheng Li; Hui Wang; Ji-Wu Wang

doi:10.1107/S1600536808009227

. 2008 Apr 16;64(Pt 5):m662–m663. doi: 10.1107/S1600536808009227

catena-Poly[[tetraaqua(μ-4,4′-bipyridine-κ² N:N′)zinc(II)] fumarate tetrahydrate]

Yong Tian ^a, Ya-Pan Wu ^b, Dong-Sheng Li ^a,^b,^*, Hui Wang ^a, Ji-Wu Wang ^b

PMCID: PMC2961133 PMID: 21202206

Abstract

In the title compound, {[Zn(C₁₀H₈N₂)(H₂O)₄](C₄H₂O₄)·4H₂O}_n, the Zn^II atom is coordinated by two N atoms from two μ-4,4′-bipyridine ligands and four water molecules in a distorted octahedral geometry. The coordination unit is extended through the Zn—N bond, leading to a one-dimensional cationic chain. A twofold rotation axis passes through the Zn atom and along the axis of the 4,4′-bipyridine ligand. Each uncoordinated water molecule acts as both hydrogen-bond donor and acceptor. A three-dimensional network is constructed through hydrogen bonds involving water molecules and fumarate dianions.

Related literature

For related literature, see: Lu et al. (2006 ▶); Moulton & Zaworotko (2001 ▶); Nordell et al. (2003 ▶); Wagner et al. (2002 ▶); Wen et al. (2005 ▶); Yaghi et al. (1997 ▶); Zaworotko (2001 ▶); Zhou et al. (2007 ▶).

Experimental

Crystal data

[Zn(C₁₀H₈N₂)(H₂O)₄](C₄H₂O₄)·4H₂O
M _r = 479.74
Monoclinic,
a = 17.094 (5) Å
b = 11.394 (3) Å
c = 13.082 (6) Å
β = 126.652 (2)°
V = 2044.3 (12) Å³
Z = 4
Mo Kα radiation
μ = 1.26 mm⁻¹
T = 293 (2) K
0.39 × 0.28 × 0.26 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.626, T _max = 0.712
7538 measured reflections
1907 independent reflections
1724 reflections with I > 2σ(I)
R _int = 0.051

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.112
S = 1.09
1907 reflections
134 parameters
H-atom parameters constrained
Δρ_max = 0.98 e Å⁻³
Δρ_min = −0.86 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808009227/hy2122sup1.cif

e-64-0m662-sup1.cif^{(16.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808009227/hy2122Isup2.hkl

e-64-0m662-Isup2.hkl^{(94KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Zn1—O2	2.0697 (18)
Zn1—N2ⁱ	2.133 (3)
Zn1—N1	2.146 (3)
Zn1—O1	2.186 (2)

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O2ⁱⁱ—Zn1—O2	179.01 (9)
O2—Zn1—N2ⁱ	89.50 (4)
O2—Zn1—N1	90.50 (4)
O2—Zn1—O1ⁱⁱ	91.97 (7)
O2—Zn1—O1	88.01 (7)
N2ⁱ—Zn1—O1	89.21 (4)
N1—Zn1—O1	90.79 (4)
O1ⁱⁱ—Zn1—O1	178.43 (8)

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1W⋯O3ⁱⁱⁱ	0.83	1.93	2.757 (2)	173
O1—H2W⋯O4^iv	0.83	2.01	2.835 (3)	172
O2—H3W⋯O3	0.83	1.91	2.732 (2)	172
O2—H4W⋯O6^v	0.82	1.83	2.623 (3)	162
O3—H5W⋯O5	0.83	1.88	2.707 (3)	173
O3—H6W⋯O4^iv	0.82	2.10	2.911 (3)	172
O4—H7W⋯O6^v	0.83	2.00	2.832 (3)	175
O4—H8W⋯O5	0.83	1.99	2.811 (3)	169

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

Acknowledgments

This work was supported by the Natural Science Research Foundation of Shaanxi Provincial Education Office of China (grant No. 06JK155), the Natural Science Foundation of Shaanxi Province of China (grant No. 2006B08) and the Sustentatio Program for New-Century Elitists of the Ministry of Education, China (NCET-06-0891).

supplementary crystallographic information

Comment

Coordination polymer networks represent a result of applying supramolecular concepts to the design of new functional solids and are well exemplified by compounds in which transition metal centers (nodes) are connected by linear bidentate organic ligands (spacer groups) such as 4,4'-bipyridine (Lu et al., 2006; Nordell et al., 2003; Wagner et al., 2002; Wen et al., 2005; Yaghi et al., 1997; Zhou et al., 2007). These supramolecular structures are of interest as they provide opportunity for generating open framework compounds with controllable cavity sizes and they therefore have the potential to exhibit porosity and/or encapsulate guest molecules (Moulton & Zaworotko, 2001; Zaworotko, 2001).

The title compound consists of one [Zn(C₁₀H₈N₂) (H₂O)₄]²⁺ cation, one fumarate dianion and four lattice water molecules (Fig. 1). Each Zn^II atom is six-coordinated in an octahedral geometry with four O atoms of four water molecules in the equatorial plane and two N atoms from two µ-4,4'-bipyridine ligands in the axial sites, resulting a one-dimensional cationic chain along the b-axis. The two pyridyl rings of 4,4'-bipyridine present a torsion angle of 10.0 (2)°.

Each lattice water molecule acts as both hydrogen-bond donor and acceptor. In the crystal structure, the cationic chains are arranged parallel to the bc plane with the fumarate dianions and lattice water molecules located between the sheets composed of the chains. A three-dimensional supramolecular network is formed by hydrogen-bonding interactions involving the water molecules and fumarate dianions (Fig. 2).

Experimental

A mixture of Zn(NO₃)₂.6H₂O (0.030 g, 0.1 mmol), 4,4'-bipyridine (0.016 g, 0.1 mmol), mercaptosuccinic acid (0.015 g, 0.1 mmol), NaOH (0.008 g, 0.2 mmol) and distilled water (10 ml) was sealed in a 25 ml Teflon-lined stainless autoclave and heated at 433 K for 72 h under autogenous pressure. After slowly cooling to room temperature, yellow block-like crystals of the title compound suitable for X-ray analysis were obtained from the reaction mixture by filtration.