Bis(2-amino­pyridine-κN 1)bis­(benzoato-κO)cobalt(II)

Di-Chang Zhong; Gui-Quan Guo; Xiao-Hua Zuo; Ji-Hua Deng; Lin Yuan; Rong-Hua Zhu

doi:10.1107/S1600536807063933

. 2007 Dec 6;64(Pt 1):m88–m89. doi: 10.1107/S1600536807063933

Bis(2-aminopyridine-κN ¹)bis(benzoato-κO)cobalt(II)

Di-Chang Zhong ^a, Gui-Quan Guo ^b, Xiao-Hua Zuo ^c, Ji-Hua Deng ^a,^*, Lin Yuan ^a, Rong-Hua Zhu ^a

PMCID: PMC2947776 PMID: 21200656

Abstract

In the title compound, [Co(C₇H₅O₂)₂(C₅H₆N₂)₂], the Co^II atom is hexacoordinated by four O atoms from two benzoate anions, and two N atoms from two 2-aminopyridine molecules, resulting in a distorted octahedral geometry. Both benzoate anions act as bidentate ligands and both 2-aminopyridine molecules are coordinated to the metal through their pyridyl N atoms. The crystal packing is stabilized by intermolecular N—H⋯O hydrogen bonds, C—H⋯π, and π–π stacking interactions involving benzoate anions and 2-aminopyridine molecules.

Related literature

For related literature, see: Benbellat et al. (2006 ▶); Brechin et al. (2000 ▶); Dirnitrou et al. (1995 ▶); Kozlevčar et al. (2001 ▶); Zhu, Shao et al. (2003 ▶); Zhu, Usman et al. (2003 ▶).

Experimental

Crystal data

[Co(C₇H₅O₂)₂(C₅H₆N₂)₂]
M _r = 489.39
Monoclinic,
a = 9.0230 (9) Å
b = 11.3787 (12) Å
c = 22.451 (2) Å
β = 96.7650 (10)°
V = 2288.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.79 mm⁻¹
T = 296 (2) K
0.36 × 0.28 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.770, T _max = 0.835
19674 measured reflections
5288 independent reflections
4198 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.092
S = 1.05
5288 reflections
298 parameters
357 restraints
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a ▶); molecular graphics: SHELXTL (Sheldrick, 1997b ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807063933/kp2149sup1.cif

e-64-00m88-sup1.cif^{(20.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063933/kp2149Isup2.hkl

e-64-00m88-Isup2.hkl^{(259KB, hkl)}

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

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

Co1—O4	2.0364 (15)
Co1—N3	2.1033 (16)
Co1—N1	2.1050 (16)
Co1—O1	2.1426 (18)
Co1—O2	2.2340 (17)
Co1—O3	2.4016 (17)

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O4—Co1—N3	102.55 (6)
O4—Co1—N1	100.77 (7)
N3—Co1—N1	99.40 (6)
N3—Co1—O1	95.25 (7)
N1—Co1—O1	100.34 (6)
O4—Co1—O2	93.20 (7)
N3—Co1—O2	99.72 (7)
N1—Co1—O2	153.21 (7)
O1—Co1—O2	59.31 (6)
O4—Co1—O3	57.88 (5)
N3—Co1—O3	160.43 (6)
N1—Co1—O3	85.79 (6)
O1—Co1—O3	102.40 (6)
O2—Co1—O3	82.44 (6)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1	0.86	2.03	2.866 (2)	163
N2—H2B⋯O3ⁱ	0.86	2.07	2.891 (2)	158
N4—H4A⋯O4	0.86	1.99	2.810 (2)	160
N4—H4B⋯O2ⁱⁱ	0.86	2.14	2.980 (2)	167
C13—H13⋯Cg1ⁱⁱⁱ	0.93	2.95	3.719 (3)	141

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) −x, 1 − y, −z. Cg1 is the centroid of the N1/C20–C24 ring.

Table 3. π–π Interactions (Å, °).

π–π Contacts	Cg⋯Cg	α^a	β^b	Cg⋯Plane
Cg(N3→C19)⋯Cg(C2→C7)^iv	3.7145 (16)	6.3	16.0	3.535
Cg(C2→C7)⋯Cg(N3→C19)^v	3.7145 (16)	6.3	17.9	3.570

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Notes: α^a = angle between planes of two aromatic rings. β^b = angle between Cg⋯Cg line and normal to the plane of the first aromatic ring. Symmetry codes: (iv) −1 + x, y, z; (v) 1 + x, y, z.

Acknowledgments

The authors thank the National Natural Science Foundation of China (Nos. 20361002 and 30460153), 973 Plan of China (2007CB516805).

supplementary crystallographic information

Comment

In recent years the study of crystal structures and properties of cobalt complexes based on carboxyl ligand, owing to their novel geometries and magnetic behaviours, have attracted chemists (Tan et al., 2003; Zheng et al., 2004; Wang et al., 2004; Shi et al., 2004) to explore their use. The structures of the mixed ligand complexes containing benzoate as the most simple aromatic carboxyl compoud with well antibacterial activity and 2-aminopyridine reported by (Kozlevčar et al., 2001; Zhu, Usman et al., 2003; Zhu, Shao et al., 2004). Herein, we report the synthesis and crystal structure of mixed ligands cobalt(II) complex.

The stucture of the title compound (I) is isostructural with the nickel (I) complex (Zhu, Shao et al., 2003) with the Co^II atom hexa-coordinated by four O atoms of two benzoato anions, and two independent pyridine N atoms from two 2-aminopyridine molecules in distorted octahedral geometry (Fig. 1). The Co—N bond lengths of 2.1030 (14) Å and 2.1054 (14) Å, the Co—O distances ranging from 2.0363 (13) to 2.4016 (15) Å, are in the normal range. The close carboxylato distances O1—C8 and O2—C8, 1.260 (2) Å and 1.250 (2) Å, O3—C1 and O4—C1, 1.241 (2) Å and 1.274 (2) Å reveal the bidentate benzoato function. The molecules are held together by intramolecular and intermolecular hydrogen bonds, C—H···π and π–π stacking interactions generating three-dimensional supramolecular network.The amide N2 and N4 donate H atoms to the carboxyl O atoms O1and O4 in intramolecular N2—H2A···O1 and N4—H4A···O4 hydrogen bonds. The N2 and N4 also donate H atoms to O2 and O3 to form intermolecular N2—H2B···O2 and N4—H4B···O3 hydrogen bonds. Intermolecular C—H···π interation is pronounced in this crystal structure involving methyl group C13 of the benzoato and the pyridyl rings N1→C24, with the distance 2.95 Å between the methyl hydrogen and the centroid of the nearest aromatic ring. In addition, π–π stacking interactions are also observed; the distance between centroids of the pyridyl ring N3→C19 and the aromatic ring C2→C7 is 3.7145 (16) Å (Table 1, Fig. 2).

Experimental

The reagents available commercially were used without further purification. Co(NO₃)₂.6H₂O (0.5 mmol), benzoate sodium (1 mmol) and 2-aminopyridine (1 mmol) were mixed in solution containing 8 ml of ethanol and 8 ml of water. After stirring 1.5 h, the mixture was placed in 25 ml Teflon-lined reactor and heated at 383 K in an oven for 7 days. The resulting solution was filtered and the filtrate was allowed to stay at ambience temperature. Well shaped purple crystals suitable for X-rays diffraction were obtained after two weeks. Yield: 78%.