Diaqua­bis­(4-formyl­benzoato-κO 1)bis­(nicotinamide-κN 1)copper(II)

Mustafa Sertçelik; Nagihan Çaylak Delibaş; Hacali Necefoğlu; Tuncer Hökelek

doi:10.1107/S1600536812028814

. 2012 Jun 30;68(Pt 7):m1010–m1011. doi: 10.1107/S1600536812028814

Diaquabis(4-formylbenzoato-κO ¹)bis(nicotinamide-κN ¹)copper(II)

Mustafa Sertçelik ^a, Nagihan Çaylak Delibaş ^b, Hacali Necefoğlu ^a, Tuncer Hökelek ^c,^*

PMCID: PMC3393247 PMID: 22807707

Abstract

In the title complex, [Cu(C₈H₅O₃)₂(C₆H₆N₂O)₂(H₂O)₂], the Cu^II cation is located on an inversion center and is coordinated by two 4-formylbenzoate (FB) anions, two nicotinamide (NA) ligands and two water molecules in an elongated distorted octahedral geometry. The dihedral angle between the carboxylate group and the adjacent benzene ring is 23.00 (10)°, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 85.34 (4)°. An intramolecular O—H⋯O hydrogen bond occurs between coordinating water molecule and the carboxylate group. 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. A weak C—H⋯π interaction also occurs in the crystal.

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. (1996 ▶, 2009a ▶,b ▶); Hökelek & Necefoğlu (1998 ▶, 2007 ▶); Necefoğlu et al. (2011a ▶,b ▶); Sertçelik et al. (2012 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[Cu(C₈H₅O₃)₂(C₆H₆N₂O)₂(H₂O)₂]
M _r = 642.08
Triclinic,
a = 7.8175 (2) Å
b = 9.6539 (3) Å
c = 9.8361 (3) Å
α = 77.053 (3)°
β = 74.041 (2)°
γ = 87.295 (3)°
V = 695.49 (4) Å³
Z = 1
Mo Kα radiation
μ = 0.85 mm⁻¹
T = 100 K
0.32 × 0.28 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.762, T _max = 0.888
12850 measured reflections
3482 independent reflections
3325 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.066
S = 1.09
3482 reflections
216 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.39 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/S1600536812028814/xu5579sup1.cif

e-68-m1010-sup1.cif^{(18.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812028814/xu5579Isup2.hkl

e-68-m1010-Isup2.hkl^{(167.3KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cu1—O1	1.9960 (9)
Cu1—O5	2.3951 (10)
Cu1—N1	2.0025 (11)

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

Cg is the centroid of the pyridine ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O2ⁱ	0.85 (2)	2.100 (19)	2.8675 (16)	150 (2)
N2—H22⋯O4ⁱⁱ	0.88 (2)	2.00 (2)	2.8685 (17)	169 (2)
O5—H51⋯O4ⁱⁱⁱ	0.81 (2)	2.11 (2)	2.8930 (15)	162 (2)
O5—H52⋯O2^iv	0.87 (3)	1.91 (3)	2.7542 (15)	163 (2)
C4—H4⋯O2ⁱⁱⁱ	0.93	2.46	3.3824 (18)	175
C13—H13⋯O3^v	0.93	2.49	3.290 (2)	144
C6—H6⋯Cg ^vi	0.93	2.75	3.656 (2)	166

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

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. This work was supported financially by Kafkas University Research Fund (grant No. 2012-FEF-12).

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 4-formylbenzoate (FB) 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(C₇H₅O₂)₂(C₁₀H₁₄N₂O)₂] (Hökelek et al., 1996), [Cu(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Necefoğlu et al., 2011a), [Co(C₆H₆N₂O)₂(C₇H₄NO₄)₂(H₂O)₂] (Hökelek & Necefoğlu, 1998), [Co(C₉H₉O₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂] (Necefoğlu et al., 2011b), [Co(C₇H₄IO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Aydın et al., 2012), [Ni(C₇H₄ClO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Hökelek et al., 2009a), [Ni(C₅H₅O₃)₂(C₆H₆N₂O)₂(H₂O)₂] (Sertçelik et al., 2012), [Mn(C₉H₁₀NO₂)₂(H₂O)₄].2H₂O (Hökelek & Necefoğlu, 2007) and [Zn(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Hökelek et al., 2009b) have also been reported. In the copper(II) complex mentioned above the two benzoate ions coordinate to the Cu^II atom as bidentate ligands, while in the other structures all the ligands coordinate in a monodentate manner.

In the title complex, the four symmetry related O atoms (O1, O1', O5 and O5') 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 [1.2689 (16) Å] and C1—O2 [1.2512 (16) Å] bonds in the carboxylate group indicate delocalized bonding arrangement, rather than localized single and double bonds. The Cu—O bond lengths are 1.9960 (9) Å (for benzoate oxygens) and 2.3951 (10) Å (for water oxygens), and the Cu—N bond length is 2.0025 (11) 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 -0.5747 (1) Å. The dihedral angle between the planar carboxylate group and the adjacent benzene ring A (C2—C7) is 23.00 (10)°. The benzene A (C2—C7) and the pyridine B (N1/C9—C13) rings are oriented at a dihedral angle of A/B = 85.34 (4)°. 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. A weak C-H···π interaction also occurs.

Experimental

The title compound was prepared by the reaction of CuSO₄.5H₂O (1.25 g, 5 mmol) in H₂O (200 ml) and NA (1.22 g, 10 mmol) in H₂O (100 ml) with sodium 4-formylbenzoate (1.72 g, 10 mmol) in H₂O (100 ml) at room temperature. The mixture was filtered and set aside to crystallize at ambient temperature for several days, giving blue single crystals.