Tetra­aqua­diazido­cobalt(II) 3,3′-dicarb­oxy­l­ato-1,1′-ethyl­enedipyridinium

Yan-Qing Wen; Chun-Yan Tian; En-Qing Gao

doi:10.1107/S1600536810046143

. 2010 Nov 13;66(Pt 12):m1566–m1567. doi: 10.1107/S1600536810046143

Tetraaquadiazidocobalt(II) 3,3′-dicarboxylato-1,1′-ethylenedipyridinium

Yan-Qing Wen ^a, Chun-Yan Tian ^a, En-Qing Gao ^a,^*

PMCID: PMC3011402 PMID: 21589255

Abstract

The asymmetric unit of the title compound, [Co(N₃)₂(H₂O)₄]·C₁₄H₁₂N₂O₄, comprises half of the cobalt(II) complex molecule and a half of the 3,3′-dicarboxylato-1,1′-ethylenedipyridinium molecule. The Co^II atom is located on an inversion centre and hence the complex molecule adopts a centrosymmetric trans-octahedral geometry. The zwitterionic organic molecule is also centrosymmetric with the centre of the C—C bond of the ethylene moiety coinciding with an inversion centre. The adduct of metal complex and organic molecule is associated into a three-dimenional network through O—H⋯O hydrogen bonds.

Related literature

For background to hydrogen bonds, see: Braga & Grepioni (2000 ▶); Fabbiani et al. (2010 ▶); Salitros et al. (2010 ▶); Schultheis et al. (2010 ▶). For the synthesis of the ligand, see: Loeb et al. (2006 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶); Etter (1990 ▶).

Experimental

Crystal data

[Co(N₃)₂(H₂O)₄]·C₁₄H₁₂N₂O₄
M _r = 487.31
Triclinic,
a = 7.4309 (6) Å
b = 7.7507 (7) Å
c = 8.5582 (7) Å
α = 95.463 (2)°
β = 90.586 (2)°
γ = 95.011 (2)°
V = 488.71 (7) Å³
Z = 1
Mo Kα radiation
μ = 0.94 mm⁻¹
T = 296 K
0.25 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.799, T _max = 0.872
6091 measured reflections
1907 independent reflections
1889 reflections with I > 2σ(I)
R _int = 0.015

Refinement

R[F ² > 2σ(F ²)] = 0.024
wR(F ²) = 0.074
S = 1.12
1907 reflections
154 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810046143/kp2284sup1.cif

e-66-m1566-sup1.cif^{(16.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810046143/kp2284Isup2.hkl

e-66-m1566-Isup2.hkl^{(93.9KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Co1—O4	2.0780 (12)
Co1—N2	2.0958 (15)
Co1—O3	2.1431 (12)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3B⋯O1ⁱ	0.84 (2)	2.01 (2)	2.8180 (18)	163 (2)
O3—H3C⋯O1ⁱⁱ	0.84 (2)	1.91 (2)	2.7395 (17)	172 (2)
O4—H4C⋯O2ⁱⁱⁱ	0.86 (2)	1.84 (2)	2.6901 (18)	173 (3)
O4—H4B⋯O2	0.81 (2)	2.03 (2)	2.8028 (18)	159 (2)

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

Acknowledgments

We are thankful for financial support from the Shanghai Leading Academic Discipline Project (B409).

supplementary crystallographic information

Comment

Hydrogen bonds play a key role in biological systems and materials, and they have been widely used as a putative supramolecular tool for engineering organic and metal-organic solids (Fabbiani et al., 2010; Salitros et al., 2010; Schultheis et al., 2010; Braga & Grepioni, 2000). In this paper, we report the structure of the title compound, (I), which contains a neutral metal complex molecule, [Co(N₃)₂(H₂O)₄], and a zwitterionic dicarboxylate, 1,2-bis(3-carboxylatopyridinium)ethane (Fig. 1). The metal complex molecule is centrosymmetric, with the octahedral-coordinated Co^II by two azide anions and four water molecules in a trans arrangement (Fig. 1, Table 1). Two opposite Co—O distances are longer than the Co—N and other Co—O ones, defining an axially elongated geometry. The zwitterionic molecule is also centrosymmetric (Fig.1 ). The inorganic complex molecules and the carboxylate groups are associated into a sheet through O—H···O hydrogen bonds involving the coordinated aqua ligands (O3 and O4) and the carboxylate oxygen atoms (O1 and O2) (Fig. 2, Table 2). The two O4 aqua ligands from symmetry related complex molecules and two O2 atoms from symmetry related organic molecules form a hydrogen-bonded ring which can be denoted by the graph set R₄²(8) (Bernstein et al., 1995; Etter, 1990). Similar hydrogen-bonded rings are formed by O1 and O3. The carboxylate group forms a R₂²(8) hydrogen-bonded ring with two aqua ligands from the same complex molecule. Besides, a large hydrogen-bonded ring [R₄⁴(16)] is formed by two carboxylate groups and four aqua ligands from two complex molecules. The organic ligands interlink the hydrogen-bonded sheets of the metal complexes into the three-dimensional structure (Fig. 3).

Experimental

The zwitterionic ligand ([H₂L¹]Br₂) was synthesised from 1,2-dibromoethane and ethyl nicotinate according to the published procedure (Loeb et al., 2006). An aqueous solution (4 mL) of [H₂L¹]Br₂ (0.1 mmol) and NaN₃ (1 mmol) was added to a DMF solution (1.5 mL) of Co(ClO₄)₂.6H₂O (0.2 mmol) with stirring. The resulting solution was allowed to evaporate slowly at room temperature, yielding light-red block crystals of (I) in three days. Yield: 75%. Anal. calcd (found) (%) for CoC₁₄H₂₀N₈O₈: C, 34.79 (34.51); H, 4.39 (4.14); N, 22.87 (23.00). Main IR bands (KBr, ν/cm^-1): 3427m, 3097w, 2042 s, 1637 s, 1606 s, 1392m, 765m, 688m.