Diaqua­bis­(2-iodo­benzoato-κO)bis­(nicotinamide-κN 1)copper(II)

Ömür Aydın; Nagihan Çaylak Delibaş; Hacali Necefoğlu; Tuncer Hökelek

doi:10.1107/S1600536812034587

. 2012 Aug 8;68(Pt 9):m1162–m1163. doi: 10.1107/S1600536812034587

Diaquabis(2-iodobenzoato-κO)bis(nicotinamide-κN ¹)copper(II)

Ömür Aydın ^a, Nagihan Çaylak Delibaş ^b, Hacali Necefoğlu ^a, Tuncer Hökelek ^c,^*

PMCID: PMC3435587 PMID: 22969460

Abstract

In the title complex, [Cu(C₇H₄IO₂)₂(C₆H₆N₂O)₂(H₂O)₂], the Cu^II cation is located on an inversion center and is coordinated by two monodentate 2-iodobenzoate (IB) anions, two nicotinamide (NA) ligands and two water molecules in a distorted octahedral coordination geometry. The dihedral angle between the carboxylate group and the adjacent benzene ring is 32.12 (14)°, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 82.02 (5)°. The coordinating water molecule links with the carboxylate group via an intramolecular O—H⋯O hydrogen bond. In the crystal, N—H⋯O, O—H⋯O and weak C—H⋯O hydrogen bonds link the molecules into a three-dimensional supramolecular network.

Related literature

For literature on niacin, see: Krishnamachari (1974 ▶). For information on the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972 ▶). For related structures, see: Aydın et al. (2012 ▶); Hökelek et al. (2009 ▶); Necefoğlu et al. (2011 ▶); Sertçelik et al. (2012a ▶,b ▶); Sertçelik et al. (2009 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[Cu(C₇H₄IO₂)₂(C₆H₆N₂O)₂(H₂O)₂]
M _r = 837.85
Monoclinic,
a = 8.1617 (2) Å
b = 18.3365 (4) Å
c = 9.7047 (3) Å
β = 103.573 (3)°
V = 1411.81 (7) Å³
Z = 2
Mo Kα radiation
μ = 3.02 mm⁻¹
T = 100 K
0.39 × 0.36 × 0.24 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.528, T _max = 0.661
13216 measured reflections
3531 independent reflections
3337 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.021
wR(F ²) = 0.058
S = 1.13
3531 reflections
203 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.97 e Å⁻³
Δρ_min = −0.50 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 datablock(s) I, global. DOI: 10.1107/S1600536812034587/xu5599sup1.cif

e-68-m1162-sup1.cif^{(18KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812034587/xu5599Isup2.hkl

e-68-m1162-Isup2.hkl^{(169.7KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cu1—O1	1.9937 (14)
Cu1—O4	2.5078 (16)
Cu1—N1	1.9984 (16)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O3ⁱ	0.84 (3)	2.17 (3)	2.942 (3)	154 (3)
N2—H22⋯O2ⁱⁱ	0.83 (3)	2.11 (3)	2.881 (2)	154 (3)
O4—H41⋯O2ⁱⁱⁱ	0.87 (4)	1.87 (4)	2.720 (2)	165 (4)
O4—H42⋯O3^iv	0.80 (4)	2.16 (4)	2.923 (2)	160 (4)
C10—H10⋯O2ⁱⁱ	0.93	2.49	3.368 (2)	158

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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 investigations of 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.

In the title mononuclear complex, Cu^II cation is located on an inversion center and is coordinated by two 2-iodobenzoate (IB) anions, two nicotinamide (NA) ligands and two water molecules, all ligands coordinating in a monodentate manner (Fig. 1). The crystal structures of similar complexes of Cu^II, Co^II, Ni^II, Mn^II and Zn^II ions, [Cu(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Necefoğlu et al., 2011), [Co(C₇H₄IO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Aydın et al., 2012), [Ni(C₈H₅O₃)₂(C₆H₆N₂O)₂(H₂O)₂] (Sertçelik et al., 2012a), [Mn(C₈H₅O₃)₂(C₁₀H₁₄N₂O)₂(H₂O)₂] (Sertçelik et al., 2009), [Zn(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Hökelek et al., 2009) and [Zn(C₈H₅O₃)₂(C₆H₆N₂O)₂(H₂O)₂] (Sertçelik et al., 2012b) have also been reported, where all the ligands coordinate to the metal atoms in a monodentate manner.

In the title complex, the four symmetry related O atoms (O1, O1', O4 and O4') in the equatorial plane around the Cu^II ion form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination is completed by the two symmetry related N atoms of the NA ligands (N1 and N1') in the axial positions. The near equalities of the C1—O1 [1.275 (2) Å] and C1—O2 [1.245 (2) Å] bonds in the carboxylate group indicate delocalized bonding arrangement, rather than localized single and double bonds. The Cu—O bond lengths are 1.9937 (14) Å (for benzoate oxygens) and 2.5078 (16) Å (for water oxygens), and the Cu—N bond length is 1.9984 (16) Å, close to standard values (Allen et al., 1987). The Cu atom is displaced out of the mean-plane of the carboxylate group (O1/C1/O2) by -0.5995 (1) Å. The dihedral angle between the planar carboxylate group and the adjacent benzene ring A (C2—C7) is 32.12 (14)°. The benzene A (C2—C7) and the pyridine B (N1/C8—C12) rings are oriented at a dihedral angle of A/B = 82.02 (5)°. The coordinating water molecule links with the carboxylate group via an O—H···O hydrogen bond (Table 1).

In the crystal, intermolecular N—H···O, O—H···O and weak C—H···O hydrogen bonds (Table 1) link the molecules into a three-dimensional supramolecular network, in which they may be effective in the stabilization of the structure.

Experimental

The title compound was prepared by the reaction of CuSO₄.5H₂O (1.248 g, 5 mmol) in H₂O (200 ml) and NA (1.220 g, 200 mmol) in H₂O (20 ml) with 2-iodobenzoic acid (2.700 g, 10 mmol) in H₂O (20 ml) at room temperature. The mixture was filtered and set aside to crystallize at ambient temperature for one week, giving blue single crystals.