Tetra­kis[μ-4-(diethyl­amino)­benzoato-κ2 O:O′]bis­[(N,N-diethyl­nicotinamide-κN 1)cobalt(II)]

Tuncer Hökelek; Ertuğrul Gazi Sağlam; Barış Tercan; Özgür Aybirdi; Hacali Necefoğlu

doi:10.1107/S160053681005004X

. 2010 Dec 4;67(Pt 1):m28–m29. doi: 10.1107/S160053681005004X

Tetrakis[μ-4-(diethylamino)benzoato-κ² O:O′]bis[(N,N-diethylnicotinamide-κN ¹)cobalt(II)]

Tuncer Hökelek ^a,^*, Ertuğrul Gazi Sağlam ^b, Barış Tercan ^c, Özgür Aybirdi ^d, Hacali Necefoğlu ^d

PMCID: PMC3050165 PMID: 21522552

Abstract

In the centrosymmetric binuclear title complex, [Co₂(C₁₁H₁₄NO₂)₄(C₁₀H₁₄N₂O)₂], the two Co^II cations [Co⋯Co = 2.6199 (5) Å] are bridged by four 4-(diethylamino)benzoate (DEAB) anions. The four nearest O atoms around each Co^II ion form a distorted square-planar arrangement, the distorted square-pyramidal coordination geometry being completed by the pyridine N atom of an N,N-diethylnicotinamide (DENA) ligand. The dihedral angle between the benzene ring and the carboxylate group is 7.06 (11)° in one of the independent DEAB ligands and 4.42 (9)° in the other. The benzene rings of the two independent DEAB ligands are oriented at a dihedral angle of 86.35 (8)°. The pyridine ring is oriented at dihedral angles of 31.43 (6) and 57.92 (7)° with respect to the two benzene rings. In the crystal, weak intermolecular C—H⋯O interactions link the molecules into a three-dimensional network. Weak C—H⋯π interactions are also present in the crystal structure.

Related literature

For niacin, see: Krishnamachari (1974 ▶). For N,N-diethylnicotinamide, see: Bigoli et al. (1972 ▶). For related structures, see: Speier & Fulop (1989 ▶); Usubaliev et al. (1980 ▶); Hökelek et al. (1995 ▶, 2009a ▶,b ▶,c ▶); Necefoğlu et al. (2010a ▶,b ▶).

Experimental

Crystal data

[Co₂(C₁₁H₁₄NO₂)₄(C₁₀H₁₄N₂O)₂]
M _r = 1243.25
Monoclinic,
a = 10.3518 (2) Å
b = 13.4393 (2) Å
c = 22.5105 (3) Å
β = 94.189 (2)°
V = 3123.32 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.60 mm⁻¹
T = 100 K
0.44 × 0.36 × 0.21 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.771, T _max = 0.881
29642 measured reflections
7775 independent reflections
6209 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.119
S = 1.04
7775 reflections
385 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.86 e Å⁻³
Δρ_min = −0.63 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: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681005004X/xu5109sup1.cif

e-67-00m28-sup1.cif^{(29.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681005004X/xu5109Isup2.hkl

e-67-00m28-Isup2.hkl^{(372.7KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Co1—O1	2.0287 (15)
Co1—O2	2.0262 (16)
Co1—O3	2.0347 (15)
Co1—O4	2.0223 (15)
Co1—N1	2.0702 (18)

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

Cg1 is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10B⋯O5ⁱ	0.97	2.49	3.380 (3)	153
C24—H24⋯O5ⁱⁱ	0.93	2.57	3.307 (3)	136
C19—H19A⋯Cg1ⁱⁱⁱ	0.97	2.94	3.872 (3)	162
C31—H31B⋯Cg1^iv	0.97	2.88	3.637 (2)	136

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

Acknowledgments

The authors are indebted to Anadolu University and the Medicinal Plants and Medicine Research Centre of Anadolu University, Eskişehir, Turkey, for the use of X-ray diffractometer.

supplementary crystallographic information

Comment

As a part of our ongoing investigation on transition metal complexes of nicotinamide (NA), one form of niacin (Krishnamachari, 1974), and/or the nicotinic acid derivative N,N-diethylnicotinamide (DENA), an important respiratory stimulant (Bigoli et al., 1972), the title compound was synthesized and its crystal structure is reported herein.

The title compound is a binuclear compound, consisting of two DENA and four diethylaminobenzoate (DEAB) ligands. The structures of similar complexes of the Cu²⁺ and Zn²⁺ ions, [Cu(C₆H₅COO)₂(C₅H₅N)]₂ (Usubaliev et al., 1980); [Cu(C₆H₅CO₂)₂(Py)]₂ (Speier & Fulop, 1989); [Cu₂(C₆H₅COO)₄(C₁₀H₁₄N₂O)₂] (Hökelek et al., 1995) [Cu₂(C₈H₇O₂)₄(C₆H₆N₂O)₂] (Necefoğlu et al., 2010a) [Zn₂(C₁₁H₁₄NO₂)₄(C₁₀H₁₄N₂O)₂] (Hökelek et al., 2009a); [Zn₂(C₈H₈NO₂)₄(C₁₀H₁₄N₂O)₂].2H₂O (Hökelek et al., 2009b); [Zn₂(C₉H₁₀NO₂)₄(C₁₀H₁₄N₂O)₂] (Hökelek et al., 2009c); [Zn₂(C₈H₇O₂)₄(C₁₀H₁₄N₂O)₂] (Necefoğlu et al., 2010b) have also been determined. In these structures, the benzoate ion acts as a bidentate ligand.

The title dimeric complex, [Co₂(DEAB)₄(DENA)₂], has a centre of symmetry and two Co^II atoms are surrounded by four DEAB groups and two DENA ligands. The DENA ligands are coordinated to Co atoms through pyridine N atoms only. The DEAB groups act as bridging ligands. The Co···Co' distance is 2.6199 (5) Å. The average Co-O distance is 2.0280 (15) Å (Table 1), and four O atoms of the bridging DEAB ligands around each Co atom form a distorted square plane. The Co atom lies 0.1857 (3) Å below the least-squares plane. The average O-Co-O bond angle is 89.36 (7)°. A distorted square-pyramidal arrangement around each Co atom is completed by the pyridine N atom of DENA ligand at 2.0702 (18) Å from the Co atom (Table 1). The N1-Co1···Co1' angle is 171.59 (5)° and the dihedral angle between plane through Co1, O1, O2, C1, Co1', O1', O2', C1' and the plane through Co1, O3, O4, C12, Co1', O3', O4', C12' is 89.51 (6)°. The dihedral angles between the planar carboxylate groups and the adjacent benzene rings A (C2-C7) and B (C13-C18) are 7.06 (11) and 4.42 (9) °, respectively, while that between rings A and B is A/B = 86.35 (8)°. Ring C (N1/C23-C27) is oriented with respect to rings A and B at dihedral angles A/C = 31.43 (6) and B/C = 57.92 (7) °.

In the crystal structure, weak intermolecular C-H···O interactions (Table 2) link the molecules into a two-dimensional network, in which they may be effective in the stabilization of the structure. Two weak C-H···π interactions (Table 2) are also found.

Experimental

The title compound was prepared by the reaction of CoSO₄.7H₂O (1.41 g, 5 mmol) in H₂O (50 ml) and DENA (1.78 g, 10 mmol) in H₂O (50 ml) with sodium p-diethylaminobenzoate (2.16 g, 10 mmol) in H₂O (100 ml). The mixture was filtered and set aside to crystallize at ambient temperature for one week, giving blue single crystals.