catena-Poly[[[diaqua­(1,10-phenanthroline-κ2 N,N′)zinc]-μ-4,4′-bipyridine-κ2 N:N′] dinitrate 4,4′-bipyridine hemisolvate monohydrate]

Shan Xu; Yong-Cheng Dai; Qi-Ming Qiu; Qiong-Hua Jin; Cun-Lin Zhang

doi:10.1107/S1600536812036318

. 2012 Aug 31;68(Pt 9):m1222–m1223. doi: 10.1107/S1600536812036318

catena-Poly[[[diaqua(1,10-phenanthroline-κ² N,N′)zinc]-μ-4,4′-bipyridine-κ² N:N′] dinitrate 4,4′-bipyridine hemisolvate monohydrate]

Shan Xu ^a, Yong-Cheng Dai ^a, Qi-Ming Qiu ^a, Qiong-Hua Jin ^a,^*, Cun-Lin Zhang ^b

PMCID: PMC3435629 PMID: 22969502

Abstract

In the title compound, [Zn(C₁₀H₈N₂)(C₁₂H₈N₂)(H₂O)₂](NO₃)₂·0.5C₁₀H₈N₂·H₂O, the Zn^II atom is coordinated in a distorted octahedral geometry by two N atoms from two 4,4′-bipyridine (4,4′-bipy) ligands, two N atoms from a chelating 1,10-phenanthroline ligand and two O atoms from two mutually cis water molecules. The 4,4′-bipy ligands bridge the Zn^II atoms into a chain structure along [100]. The uncoordinated 4,4′-bipy molecule lies on an inversion center. O—H⋯O and O—H⋯N hydrogen bonds connect the cationic chains, the nitrate anions, the uncoordinated 4,4′-bipy molecules and the water molecules into tow-dimensional networks.

Related literature

For background to metal complexes of 1,10-phenanthroline and its derivatives in biological systems, see: Rama Krishna et al. (2000 ▶); Sastri et al. (2003 ▶). For related structures, see: Bai et al. (2009 ▶); Blake et al. (1998 ▶); Boag et al. (1999 ▶); Carlucci et al. (1997 ▶); Chen et al. (2006 ▶); Du & Li (2007 ▶); Ma et al. (2006 ▶); Xiong et al. (1999 ▶); Zhang et al. (2009 ▶); Zhang & Janiak (2001 ▶).

Experimental

Crystal data

[Zn(C₁₀H₈N₂)(C₁₂H₈N₂)(H₂O)₂](NO₃)₂·0.5C₁₀H₈N₂·H₂O
M _r = 657.94
Monoclinic,
a = 11.3910 (11) Å
b = 13.0561 (13) Å
c = 19.8509 (18) Å
β = 103.487 (1)°
V = 2870.9 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.92 mm⁻¹
T = 298 K
0.35 × 0.31 × 0.18 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.739, T _max = 0.852
14110 measured reflections
5072 independent reflections
3309 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.132
S = 1.03
5072 reflections
397 parameters
H-atom parameters constrained
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.42 e Å⁻³

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

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812036318/hy2580sup1.cif

e-68-m1222-sup1.cif^{(26.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812036318/hy2580Isup2.hkl

e-68-m1222-Isup2.hkl^{(248.4KB, 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
O7—H7C⋯O1ⁱ	0.85	1.89	2.737 (5)	180
O7—H7D⋯O6ⁱⁱ	0.85	1.93	2.782 (5)	180
O8—H8C⋯N5	0.85	1.89	2.724 (5)	169
O8—H8D⋯O3ⁱ	0.85	1.90	2.744 (6)	169
O9—H9C⋯O2ⁱⁱⁱ	0.85	2.24	3.091 (7)	176
O9—H9D⋯O4^iv	0.85	2.27	3.114 (8)	176

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

Acknowledgments

This work was supported by the National Natural Science Foundation of China (grant No. 21171119), the National Keystone Basic Research Program (973 Program) under grant Nos. 2007CB310408 and 2006CB302901, and the Committee of Education of the Beijing Foundation of China (grant No. KM201210028020).

supplementary crystallographic information

Comment

1,10-Phenanthroline (phen) is a versatile ligand capable of forming highly stable complexes with transition metal ions (Bai et al., 2009; Blake et al., 1998; Chen et al., 2006; Du & Li, 2007; Ma et al., 2006; Zhang et al., 2009; Zhang & Janiak, 2001). Metal complexes of 1,10-phenanthroline and its derivatives are interesting because they play an important role in biological systems, for example, some can recognize DNA and some can induce apoptosis in human cancer cells (Rama Krishna et al., 2000; Sastri et al., 2003). 4,4'-Bipyridine (4,4'-bipy) can act as a Lewis base. It can also be cocrystallized with hydrogen donors such as alcohols or transition metal complexes to form macromolecular arrays as bidentate ligands (Blake et al., 1998; Boag et al., 1999; Carlucci et al., 1997; Du & Li, 2007; Xiong et al., 1999). Here we report the structure of the title compound, a new zinc(II) complex with phen and 4,4'-bipy ligands.

In the title complex (Fig. 1), the Zn^II atom adopts a six-coordinated distorted octahedral geometry, where the donor atoms are two N atoms from a chelating phen ligand, two N atoms from two 4,4'-bipy ligands and two O atoms from two water molecules. The 4,4'-bipy ligands bridge the Zn^II atoms into a chain structure along [100] (Fig. 2). Two nitrate anions, half of a 4,4'-bipy molecule and a water molecule in the asymmetric unit are involved in the formation of O—H···O and O—H···N hydrogen bonds (Table 1). Compared with the similar comlpexes reported in literature (Bai et al., 2009; Blake et al., 1998; Du & Li, 2007), the Zn—N distances are longer, the Zn—O distances are shorter, and the N—Zn—N bite angles are smaller. The O—Zn—O bite angle is smaller than those in the reported zinc complexes (Bai et al., 2009).

Experimental

Zn(NO₃)₂ (0.2 mmol) was dissolved in 5 ml water and a hot methanolic solution (5 ml) of 4,4'-bipyridine (0.2 mmol) was added to the solution. After the mixture was stirred for 10 min, 1,10-phenanthroline (0.4 mmol) was added. The resulting solution was refluxed for 30 min and then allowed to cool to ambient temperature. The filtrate was evaporated slowly at room temperature for several weeks to yield yellow crystalline products.