Tris(2,2′-bi-1H-imidazole-κ2 N 3,N 3′)cobalt(II) hydrogen phosphate

Zhiqiang Liang; Fuxiang Wang; Qihui Wu; Xia Zhi; Qinhe Pan

doi:10.1107/S1600536811037299

. 2011 Sep 17;67(Pt 10):m1399. doi: 10.1107/S1600536811037299

Tris(2,2′-bi-1H-imidazole-κ² N ³,N ^3′)cobalt(II) hydrogen phosphate

Zhiqiang Liang ^a, Fuxiang Wang ^b, Qihui Wu ^b, Xia Zhi ^b, Qinhe Pan ^b,^*

PMCID: PMC3201263 PMID: 22058703

Abstract

The title compound, [Co(C₆H₆N₄)₃]HPO₄, was synthesized under hydrothermal conditions. In the cation, the Co^II atom is octahedrally coordinated by six N atoms from three 2,2′-bi-1H-imidazole ligands [Co—N bond lengths are in the range 2.084 (5)–2.133 (6) Å]. Intermolecular N—H⋯O hydrogen bonds form an extensive hydrogen-bonding network, which links cations and anions into a three-dimensional crystal structure.

Related literature

For related compounds, see Pan et al. (2005 ▶, 2008 ▶, 2010a ▶,b ▶, 2011 ▶); Rothammel et al. (1998 ▶); Stalder & Wilkinson (1997 ▶); Tong & Pan (2011 ▶); Wang et al. (2003a ▶,b ▶).

Experimental

Crystal data

[Co(C₆H₆N₄)₃]HPO₄
M _r = 557.35
Monoclinic,
a = 12.700 (3) Å
b = 21.447 (4) Å
c = 9.1140 (18) Å
β = 95.84 (3)°
V = 2469.6 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.81 mm⁻¹
T = 293 K
0.20 × 0.17 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID-S diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002 ▶) T _min = 0.850, T _max = 0.886
12597 measured reflections
5593 independent reflections
3373 reflections with I > 2σ(I)
R _int = 0.098

Refinement

R[F ² > 2σ(F ²)] = 0.077
wR(F ²) = 0.152
S = 1.06
5593 reflections
325 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.32 e Å⁻³
Absolute structure: Flack (1983 ▶), 2755 Friedel pairs
Flack parameter: −0.02 (2)

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); 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 datablock(s) I, global. DOI: 10.1107/S1600536811037299/aa2021sup1.cif

e-67-m1399-sup1.cif^{(21.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037299/aa2021Isup2.hkl

e-67-m1399-Isup2.hkl^{(273.8KB, 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
N2—H2⋯O4	0.86	1.82	2.678 (7)	172.1
N4—H4⋯O2	0.86	1.87	2.717 (7)	168.3
N6—H6A⋯O3ⁱ	0.86	1.96	2.725 (8)	148.3
N8—H8⋯O3ⁱ	0.86	1.89	2.669 (8)	149.3
N10—H10⋯O2ⁱⁱ	0.86	2.23	2.887 (7)	133.7
N10—H10⋯O4ⁱⁱⁱ	0.86	2.39	3.034 (9)	132.5
N12—H12A⋯O4ⁱⁱⁱ	0.86	1.93	2.685 (8)	146.0

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

Acknowledgments

This work was supported by the National Natural Science Foundation of China (Nos. 21001052 and 21101047), the Natural Science Foundation of Hainan Province (No. 211010) and the Priming Scientific Research Foundation of Hainan University (No. kyqd1051).

supplementary crystallographic information

Comment

Recently, more attention has been paid to chiral metal complexes, which could be employed as an interesting template for the synthesis of novel materials, because they are versatile and can be made with a wide of shapes, charges and particularly chirality. Up to now, series of open-frameworks, such as metal phosphates (for example: Stalder & Wilkinson (1997); Wang et al. (2003a,b)) and germanates (for example: Pan et al. (2005, 2008)), have been synthesized with [M(dien)₂]ⁿ⁺ or [M(en)₃]ⁿ⁺ (M = Co, Ni; n = 2, 3; dien = diethylenediamine, en = ethylenediamine) cations. Recently the chiral metal complexes have been introduced into coordination polymers, see Pan et al. (2010a, 2010b, 2011), Tong et al. (2011). In this paper, we present an other metal complex [Co(biim)₃]HPO₄ (biim is 2,2'-biimidazole).

As shown in Fig. 1, the crystal structure of title compound consists of a discrete [Co(biim)₃]²⁺ cations and HPO₄^2- anions. In [Co(biim)₃]²⁺, the Co^II center is six coorinated and linked by six N atoms from three different biim ligands, resulting in a slightly distorted octahedral geometry. The Co^II—N bond distances are in the range of 2.084 (5)–2.133 (6) Å. The P atom displays a slightly distorted tetrahedal geometry and is bonded to three O atoms and one OH group with the P—O distances of 1.484 (6)–1.564 (5) Å. N—H···O hydrogen bonds connect cations and anions into a three-dimensional network (see Table 1).

Experimental

In a typical synthesis, a mixture of Co(OAc)₂.2H₂O (0.25 g), biimidazole (0.067 g), H₃PO₄ (0.12 ml) and H₂O (10 ml) were added to a 25 ml Teflon-lined reactor and kept under autogenous pressure at 120 °C for 3 days.