Diaqua­bis­(N,N′-diethyl­nicotinamide-κN 1)bis­(4-ethyl­benzoato-κO)copper(II)

Hacali Necefoğlu; Ali Maracı; Vedat Aktaş; Barış Tercan; Tuncer Hökelek

doi:10.1107/S1600536811018666

. 2011 May 20;67(Pt 6):m780–m781. doi: 10.1107/S1600536811018666

Diaquabis(N,N′-diethylnicotinamide-κN ¹)bis(4-ethylbenzoato-κO)copper(II)

Hacali Necefoğlu ^a, Ali Maracı ^a, Vedat Aktaş ^a, Barış Tercan ^b, Tuncer Hökelek ^c,^*

PMCID: PMC3120545 PMID: 21754663

Abstract

The title Cu^II complex, [Cu(C₉H₉O₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂], contains two 4-ethylbenzoate (PEB) ligands, two monodentate diethylnicotinamide (DENA) ligands and two water molecules. The four O atoms in the equatorial plane around the Cu^II ion form a slightly distorted square-planar arrangement, while the distorted octahedral coordination is completed by the two N atoms of the DENA ligands in the axial positions. Intramolecular O—H⋯O hydrogen bonds link the water molecules to the carboxylate groups. The dihedral angles between the carboxylate groups and the adjacent benzene rings are 4.6 (3) and 3.7 (2)°, while the pyridine rings and the benzene rings are oriented at dihedral angles of 6.82 (11) and 3.63 (14)°. In the crystal, intermolecular O—H⋯O hydrogen bonds link the molecules into chains propagating along [010]. C—H⋯O interactions and a π–π contact between the pyridine rings [centroid–centroid distance = 3.469 (2) Å] are also observed.

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

Experimental

Crystal data

[Cu(C₉H₉O₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]
M _r = 754.37
Monoclinic,
a = 8.3607 (2) Å
b = 12.4053 (4) Å
c = 17.8932 (6) Å
β = 98.132 (3)°
V = 1837.17 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.65 mm⁻¹
T = 100 K
0.34 × 0.32 × 0.24 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
18349 measured reflections
8952 independent reflections
6851 reflections with I > 2σ(I)
R _int = 0.068

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.130
S = 1.06
8952 reflections
479 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.88 e Å⁻³
Δρ_min = −1.09 e Å⁻³
Absolute structure: Flack (1983 ▶), 4105 Friedel pairs
Flack parameter: 0.394 (13)

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/S1600536811018666/su2274sup1.cif

e-67-0m780-sup1.cif^{(31.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811018666/su2274Isup2.hkl

e-67-0m780-Isup2.hkl^{(429KB, 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
O7—H71⋯O2	0.85 (2)	1.86 (2)	2.706 (4)	170 (5)
O7—H72⋯O6ⁱ	0.83 (4)	2.03 (4)	2.846 (4)	166 (5)
O8—H81⋯O4	0.85 (2)	1.88 (2)	2.699 (4)	161 (5)
O8—H82⋯O2ⁱⁱ	0.86 (4)	2.00 (4)	2.852 (4)	167 (5)
C6—H6⋯O5ⁱⁱⁱ	0.93	2.55	3.240 (5)	131
C20—H20⋯O2ⁱⁱⁱ	0.93	2.53	3.412 (5)	158
C30—H30⋯O6^iv	0.93	2.43	3.316 (5)	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. This work was supported financially by the Scientific and Technological Research Council of Turkey (grant No. 108 T657).

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.

The title mononuclear Cu^IIcomplex, (Fig. 1), consisting of two N,N-diethylnicotinamide (DENA), two 4-ethylbenzoate (PEB) ligands and two coordinated water molecules, all ligands coordinating in a monodentate manner. The crystal structures of similar omplexes of Cu^II, Co^II, Ni^II, Mn^II and Zn^II ions, [Cu(C₇H₅O₂)₂(C₁₀H₁₄N₂O)₂] (Hökelek et al., 1996), [Co(C₆H₆N₂O)₂(C₇H₄NO₄)₂(H₂O)₂] (Hökelek & Necefoğlu, 1998), [Co(C₉H₉O₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂] (Necefoğlu et al., 2011), [Ni(C₇H₄ClO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Hökelek et al., 2009a), [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 O atoms (O1, O3, O7 and O8) 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 N atoms of the DENA ligands (N1 and N3) in the axial positions. Intramolecular O-H···O hydrogen bonds link the water molecules to the carboxylate groups (Table 1 and Fig. 1). The near equalities of the C1—O1 [1.275 (4) Å], C1—O2 [1.253 (4) Å] and C10—O3 [1.268 (4) Å], C10—O4 [1.234 (4) Å] bonds in the carboxylate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The Cu—O bond lengths are 1.968 (2) and 1.979 (2) Å (for benzoate oxygens) and 2.486 (3) and 2.439 (3) Å (for water oxygens), and the Cu—N bond lengths are 2.004 (3) and 2.004 (3) Å, close to standard values (Allen et al., 1987). The Cu atom is displaced out of the mean-planes of the carboxylate groups (O1/C1/O2) and (O3/C10/O4) by -0.7205 (4) and 0.7343 (4) Å, respectively. The dihedral angles between the planar carboxylate groups and the adjacent benzene rings A (C2—C7) and B (C11—C16) are 4.64 (25) and 3.67 (23) °, respectively. The benzene A (C2—C7) and B (C11—C16) rings and the pyridine C (N1/C19—C23) and D (N3/C29—C33) rings are oriented at dihedral angles of A/B = 3.63 (14), A/C = 66.65 (14), A/D = 61.40 (14), B/C = 66.93 (13), B/D = 61.39 (13) and C/D = 6.82 (11) °.

In the crystal, intermolecular O—H···O hydrogen bonds link the molecules into chains propagating along [010] (Table 1 and Fig. 2). There also exist C-H···O interactions leading to the formation of two-dimensional networks lying parallel to (110). The π–π contact between the pyridine rings, Cg3—Cg4ⁱ, may further stabilize the structure [centroid-centroid distance = 3.469 (2) Å; symmetry code: (i) x - 1, y, z; Cg3 and Cg4 are the centroids of the rings C (N1/C19—C23) and D (N3/C29—C33), respectively].

Experimental

The title compound was prepared by the reaction of CuSO₄.5H₂O (1.23 g, 5 mmol) in H₂O (100 ml) and DENA (1.78 g, 10 mmol) in H₂O (50 ml) with sodium 4-ethylbenzoate (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 three days, giving blue single crystals.