Aqua­bis­(4-chloro­benzoato)-κ2 O,O′;κO-bis­(pyridine-κN)cobalt(II)

Ya-Li Chen; Chun-E Zhang; Peng Fei; Chao Deng; Bi-Tao Su

doi:10.1107/S1600536813006752

. 2013 Mar 16;69(Pt 4):m210. doi: 10.1107/S1600536813006752

Aquabis(4-chlorobenzoato)-κ² O,O′;κO-bis(pyridine-κN)cobalt(II)

Ya-Li Chen ^a, Chun-E Zhang ^a, Peng Fei ^a, Chao Deng ^a, Bi-Tao Su ^a,^*

PMCID: PMC3629487 PMID: 23634005

Abstract

In the title compound, [Co(C₇H₄ClO₂)₂(C₅H₅N)₂(H₂O)], the Co^II atom is six-coordinated by three O atoms from a bidentate and a monodentate 4-chlorobenzoate ligand, two N atoms from two pyridine ligands and a water O atom, giving a distorted octahedral geometry. In the crystal, the complex molecules are connected by O—H⋯O hydrogen bonds and π–π interactions between the benzene rings [centroid–centroid distance = 3.8924 (17) Å] into a chain along [010]. Between adjacent chains, π–π interactions occur between the pyridine rings [centroid–centroid distance = 3.898 (2) Å], giving an overall two-dimensional architecture.

Related literature

For structures and applications of related compounds, see: Macgillivray et al. (1998 ▶); Masaoka et al. (2001 ▶); Qiu et al. (2008 ▶); Wang & Sun (2012 ▶).

Experimental

Crystal data

[Co(C₇H₄ClO₂)₂(C₅H₅N)₂(H₂O)]
M _r = 546.25
Monoclinic,
a = 15.1157 (8) Å
b = 5.8696 (3) Å
c = 28.5419 (9) Å
β = 109.682 (3)°
V = 2384.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.98 mm⁻¹
T = 298 K
0.40 × 0.30 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.695, T _max = 0.828
15626 measured reflections
4175 independent reflections
3590 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.082
S = 1.10
4175 reflections
307 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.43 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

Click here for additional data file.^{(29.2KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813006752/hy2620sup1.cif

e-69-0m210-sup1.cif^{(29.2KB, cif)}

Click here for additional data file.^{(200.5KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813006752/hy2620Isup2.hkl

e-69-0m210-Isup2.hkl^{(200.5KB, 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
O5—H1W⋯O4ⁱ	0.84	1.81	2.648 (3)	178
O5—H2W⋯O2ⁱ	0.81	1.99	2.737 (3)	154

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the Natural Science Foundation of China (No. 21174114), the Plan for the Yangtze River Scholar and Innovation Team Development of the Ministry of Education (No. IRT1177), the Scientific and Technical Plan Project of Gansu Province (No. 1204 GKCA006), the Natural Science Foundation of Gansu Province (No. 1010RJZA024) and the Scientific and Technical Innovation Project of Northwest Normal University (nwnu-kjcxgc-03–63).

supplementary crystallographic information

Comment

Metal-organic frameworks (MOFs) of aromatic acid are of great interest not only owing to their various structural motifs, but also due to their potential applications in the areas of material chemistry, medical chemistry, biological chemistry, molecular recognition and molecular device (Macgillivray et al., 1998; Masaoka et al., 2001). Sometimes hydrogen bonds play important roles in MOFs (Qiu et al., 2008; Wang & Sun, 2012). In order to achieve MOFs by self-assembly and to explore their hydrogen bonds, herein we report the synthesis and crystal structure of a cobalt complex with 4-chlorobenzoic acid.

As shown in Fig. 1, the Co^II atom is six-coordinated by three O atoms from two 4-chlorobenzoate ligands, two N atoms from two pyridine molecules and a water molecule. The Co^II atom adopts a distorted octahedral geometry, in which two N atoms occupy the axial sites. The axial Co—N bond distances are 2.158 (2) and 2.168 (2) Å. The Co1—O3 bond distance [1.9931 (19) Å] for the monodentate 4-chlorobenzoate ligand is slightly shorter than Co1—O1 and Co1—O2 [2.1674 (18) and 2.2196 (18) Å] for the bidentate ligand. The crystal packing shows that the molecules are linked by O—H···O hydrogen bonds and π–π interactions between the benzene rings [centroid–centroid distances = 3.8924 (17) Å] into a polymeric chain along [010], as shown in Fig. 2. Between the adjacent chains, π–π interactions exist between the pyridine rings [centroid–centroid distance is 3.898 (2) Å] to give an overall 2D architecture.

Experimental

A pyridine solution (5 ml) of Co(NO₃)₂.4H₂O (0.1 mmol) was added dropwise to an ethyl acetate solution (15 ml) of 4-chlorobenzoic acid (0.2 mmol). The mixture was sealed in a Teflon-lined autoclave and heated under autogenous pressure to 120°C for 3 days and then allowed to cool to room temperature at a rate of 1°C per minute. Block-shaped purple crystals of the title complex were collected in 43% yield.