Diaqua­(isonicotinamide-κN 1)(4-meth­oxy­benzoato-κ2 O,O′)(4-meth­oxy­benzoato-κO)cobalt(II)

Tuncer Hökelek; Yasemin Süzen; Barış Tercan; Erdinç Tenlik; Hacali Necefoğlu

doi:10.1107/S160053681002194X

. 2010 Jun 16;66(Pt 7):m784–m785. doi: 10.1107/S160053681002194X

Diaqua(isonicotinamide-κN ¹)(4-methoxybenzoato-κ² O,O′)(4-methoxybenzoato-κO)cobalt(II)

Tuncer Hökelek ^a,^*, Yasemin Süzen ^b, Barış Tercan ^c, Erdinç Tenlik ^d, Hacali Necefoğlu ^d

PMCID: PMC3006852 PMID: 21587710

Abstract

In the title complex, [Co(C₈H₇O₃)₂(C₆H₆N₂O)(H₂O)₂], the Co^II atom is coordinated by three O atoms from two 4-methoxybenzoate ligands, which act in different modes, viz. monodentate and bidentate, two water molecules and one N atom of the isonicotinamide ligand in a distorted octahedral geometry. The monodentate-coordinated carboxylate group is involved in an intramolecular O—H⋯O hydrogen bond with the coordinated water molecule. In the crystal structure, intermolecular O—H⋯O and N—H⋯O hydrogen bonds link the molecules into layers parallel to the ab plane. The crystal packing is further stabilized by weak C—H⋯O hydrogen bonds and π–π interactions indicated by the short distance of 3.6181 (8) Å between the centroids of the benzene and pyridine rings of neighbouring molecules.

Related literature

For general background to niacin and the nicotinic acid derivative N,N-diethylnicotinamide, see: Krishnamachari (1974 ▶) and Bigoli et al. (1972 ▶), respectively. For related structures, see: Greenaway et al. (1984 ▶); Hökelek et al. (2009a ▶,b ▶,c ▶,d ▶); Necefoğlu et al. (2010 ▶).

Experimental

Crystal data

[Co(C₈H₇O₃)₂(C₆H₆N₂O)(H₂O)₂]
M _r = 519.36
Monoclinic,
a = 8.2666 (2) Å
b = 6.8055 (2) Å
c = 20.5415 (4) Å
β = 99.808 (2)°
V = 1138.74 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.81 mm⁻¹
T = 100 K
0.39 × 0.32 × 0.28 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.739, T _max = 0.791
11263 measured reflections
4838 independent reflections
4597 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.022
wR(F ²) = 0.050
S = 1.01
4838 reflections
333 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ▶), 1761 Friedel pairs
Flack parameter: 0.015 (7)

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/S160053681002194X/cv2727sup1.cif

e-66-0m784-sup1.cif^{(24.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681002194X/cv2727Isup2.hkl

e-66-0m784-Isup2.hkl^{(232.1KB, 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—H2A⋯O2ⁱ	0.79 (3)	2.11 (3)	2.877 (2)	164.0 (17)
N2—H2B⋯O1ⁱⁱ	0.91 (3)	2.16 (3)	3.050 (2)	167 (2)
O8—H81⋯O4	0.83 (3)	1.84 (3)	2.6577 (17)	167 (3)
O8—H82⋯O7ⁱⁱⁱ	0.89 (2)	1.86 (3)	2.7427 (16)	172 (2)
O9—H91⋯O6^iv	0.786 (19)	2.078 (19)	2.8384 (16)	163 (2)
O9—H92⋯O4^v	0.91 (3)	1.72 (3)	2.6307 (18)	174.1 (15)
C8—H8A⋯O7^vi	0.96	2.53	3.466 (2)	166
C16—H16B⋯O4^vii	0.96	2.52	3.4752 (18)	171

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

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 the diffractometer. This work was supported financially by Kafkas University Research Fund (grant No. 2009-FEF-03).

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 has been synthesized. Herein we report its crystal structure.

The title compound, (I), is a monomeric complex, where the Co^II ion is surrounded by two methoxybenzoate (MB) anions, one isonicotinamide (INA) ligand and two coordinated water molecules. One of the MB anions acts as a bidentate ligand, while the other is monodentate. The structures of similar complexes , [Mn(C₉H₁₀NO₂)₂(C₆H₆N₂O)(H₂O)₂] (II) (Hökelek et al., 2009a), [Co(C₉H₁₀NO₂)₂(C₆H₆N₂O)(H₂O)₂] (III) (Hökelek et al., 2009b), [Cd(C₈H₇O₂)₂(C₆H₆N₂O)₂(H₂O)].H₂O (IV) (Necefoğlu et al., 2010), [Zn(C₉H₁₀NO₂)₂(C₆H₆N₂O)(H₂O)₂] (V) (Hökelek et al., 2009c) and [Zn(C₈H₈NO₂)₂(C₆H₆N₂O)₂].H₂O (VI) (Hökelek et al., 2009d) have also been determined.

In (I) (Fig. 1), the four O atoms (O1, O2, O5 and O9) in the equatorial plane around the Co1 form a highly distorted square-planar arrangement, while the distorted octahedral coordination geometry is completed by the N atom (N1) of INA ligand and the O atom (O8) of the second water molecule in the axial positions. The average Co—O bond length is 2.1171 (12) Å and the Co atom is displaced out of the least-squares planes of the carboxylate groups (O1/C1/O2) and (O4/C9/O5) by -0.0061 (2) Å and -0.5367 (2) Å, respectively. The dihedral angle between the planar carboxylate groups and the adjacent benzene rings A (C2—C7) and B (C9—C14) are 12.12 (12)° and 9.26 (13)°, respectively, while those between rings A, B and C (N1/C17—C21) are A/B = 78.18 (4), A/C = 74.20 (5) and B/C = 6.23 (5) °. The intramolecular O—H···O hydrogen bond (Table 1) between the monodentate-coordinated carboxyl group and a coordinated water molecule results in a six-membered ring D (Co1/O4/O5/O8/C9/H81) adopting envelope conformation, with atom Co1 displaced by -0.5481 (2) Å from the plane of the other ring atoms. In (I), the O1—Co1—O2 angle is 60.32 (4)°. The corresponding O—M—O (where M is a metal) angles are 54.71 (4)° in (IV), 60.03 (6)° in (V), 59.02 (8)° in (VI) and 55.2 (1)° in [Cu(Asp)₂(py)₂] (where Asp is acetylsalicylate and py is pyridine) [(VII); Greenaway et al., 1984].

In the crystal structure, intermolecular O—H···O and N—H···O hydrogen bonds (Table 1) link the molecules into layers parallel to ab plane. The crystal packing is further stabilized by the weak C—H···O hydrogen bonds (Table 1). The π–π contact between the benzene and pyridine rings, Cg2—Cg3ⁱ [symmetry code: (i) x, y + 1, z, where Cg2 and Cg3 are the centroids of the rings B (C9—C14) and C (N1/C17—C21), respectively] may also stabilize the structure, with centroid-centroid distance of 3.6181 (8) Å.

Experimental

The title compound was prepared by the reaction of CoSO₄.7H₂O (2.81 g, 10 mmol) in H₂O (50 ml) and INA (2.44 g, 20 mmol) in H₂O (50 ml) with sodium 4-methoxybenzoate (3.48 g, 20 mmol) in H₂O (100 ml). The mixture was filtered and set aside to crystallize at ambient temperature for one week, giving brown single crystals.