Bis­(4-fluoro­benzoato)-κ2 O,O′;κO-(4-fluoro­benzoic acid-κO)bis­(nico­tinamide-κN 1)copper(II)

Hacali Necefoğlu; Füreya Elif Özbek; Vijdan Öztürk; Barış Tercan; Tuncer Hökelek

doi:10.1107/S1600536811020897

. 2011 Jun 11;67(Pt 7):m887–m888. doi: 10.1107/S1600536811020897

Bis(4-fluorobenzoato)-κ² O,O′;κO-(4-fluorobenzoic acid-κO)bis(nicotinamide-κN ¹)copper(II)

Hacali Necefoğlu ^a, Füreya Elif Özbek ^a, Vijdan Öztürk ^a, Barış Tercan ^b, Tuncer Hökelek ^c,^*

PMCID: PMC3151872 PMID: 21836879

Abstract

In the title Cu^II complex, [Cu(C₇H₄FO₂)₂(C₇H₅FO₂)(C₆H₆N₂O)₂], the Cu^II cation is coordinated by two N atoms of two nicotinamide (NA) ligands, and by four O atoms from two 4-fluorobenzoate (PFB) anions and one 4-fluorobenzoic acid (PFBA) molecule, in a distorted octahedral geometry. In the molecule, two Cu—O bond lengths are significantly longer than the other two. The dihedral angles between the carboxylate groups and the adjacent benzene rings are 11.08 (14), 7.62 (13) and 5.73 (11)°, while the benzene rings are oriented at dihedral angles of 15.62 (6), 33.71 (8) and 26.60 (8)°. In the crystal structure, extensive N—H⋯O, C—H⋯F and C—H⋯O hydrogen bonds link the molecules into a three-dimensional network. π–π contacts between the benzene rings [centroid-to-centroid distances = 3.5517 (15), 3.8456 (14) and 3.9265 (13) Å] further stabilize the crystal structure.

Related literature

For background 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: Greenaway et al. (1984 ▶); Hökelek et al. (2010a ▶,b ▶,c ▶,d ▶,e ▶); Hökelek et al. (2009a ▶,b ▶).

Experimental

Crystal data

[Cu(C₇H₄FO₂)₂(C₇H₅FO₂)(C₆H₆N₂O)₂]
M _r = 726.12
Triclinic,
a = 10.3370 (2) Å
b = 11.6707 (3) Å
c = 14.1121 (4) Å
α = 110.824 (4)°
β = 101.333 (3)°
γ = 95.761 (2)°
V = 1533.09 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.79 mm⁻¹
T = 100 K
0.48 × 0.32 × 0.24 mm

Data collection

Bruker APEXII Kappa CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.745, T _max = 0.827
27657 measured reflections
7686 independent reflections
6584 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.087
S = 1.08
7686 reflections
461 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.53 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 ▶) and Mercury (Macrae et al., 2008 ▶); 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/S1600536811020897/xu5224sup1.cif

e-67-0m887-sup1.cif^{(28.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811020897/xu5224Isup2.hkl

e-67-0m887-Isup2.hkl^{(368.4KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cu1—O1	2.0661 (13)
Cu1—O2	2.4581 (14)
Cu1—O3	2.2397 (14)
Cu1—O5	1.9701 (14)
Cu1—N1	2.0024 (15)
Cu1—N3	2.0084 (15)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O7ⁱ	0.83 (3)	2.17 (4)	2.990 (3)	175 (3)
N2—H2B⋯O2ⁱⁱ	0.90 (3)	2.07 (3)	2.943 (2)	163 (3)
N4—H4A⋯O1ⁱⁱⁱ	0.79 (3)	2.18 (3)	2.953 (2)	165 (3)
N4—H4B⋯O8^iv	0.80 (3)	2.08 (3)	2.880 (3)	174 (2)
O4—H41⋯O6	0.85 (3)	1.62 (3)	2.457 (2)	169 (3)
C4—H4⋯F2^v	0.93	2.50	3.248 (3)	137
C23—H23⋯O2ⁱⁱ	0.93	2.42	3.333 (2)	167
C25—H25⋯O8^vi	0.93	2.60	3.275 (2)	130
C31—H31⋯O7^vii	0.93	2.55	3.251 (3)	132

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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 X-ray diffractometer. This work was financially supported by the Scientific and Technological Research Council of Turkey (grant No. 108T657).

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^II complex, (I), (Fig. 1), consisting of two nicotinamide (NA), two 4-fluorobenzoate (PFB) and one 4-fluorobenzoic acid (PFBA) ligands. The Cu^II center is coordinated by four O atoms from two (PFB) and one (PFBA) ligands, which act in different modes - monodentate, bidentate and monodentate, respectively, and two N atoms of two nicotinamide ligands (Fig. 1). So that, the molecule is six-coordinated. The structures of similar complexes of Cu^II, Co^II, Ni^II and Zn^II ions, [Cu(C₈H₇O₂)₂(C₆H₆N₂O)₂].2(H₂O), (II) (Hökelek et al., 2010c), [Co(C₈H₇O₃)₂(C₆H₆N₂O)(H₂O)₂], (III) (Hökelek et al., 2010e), [Co(C₈H₇O₃)₂(C₆H₆N₂O)₂(H₂O)₂].2H₂O, (IV) (Hökelek et al., 2010b), [Ni(C₈H₇O₃)₂(C₆H₆N₂O)₂(H₂O)₂].2H₂O, (V) (Hökelek et al., 2010a), [Zn(C₈H₈NO₂)₂(C₆H₆N₂O)₂].H₂O, (VI) (Hökelek et al., 2009a), [Zn(C₉H₁₀NO₂)₂(C₆H₆N₂O)₂(H₂O)₂], (VII) (Hökelek et al., 2009b) and [Zn(C₈H₇O₃)₂(C₆H₆N₂O)₂], (VIII) (Hökelek et al., 2010d) have also been determined.

In the title compound (Fig. 1), two Cu—O bond distances [2.4581 (14) and 2.2397 (14) Å] are significantly longer than the other two, and the average Cu—O bond length is 2.1835 (14) Å. The Cu1 atom is displaced out of the least-squares planes of the carboxylate groups (O1/C1/O2), (O3/C8/O4) and (O5/C15/O6) by 0.0717 (3), 0.6121 (3) and 0.7391 (3) Å, respectively. The intramolecular O—H···O hydrogen bond links the monodentately coordinated (PFB) and (PFBA) ligands (Table 1). The dihedral angles between the planar carboxylate groups and the adjacent benzene rings A (C2–C7), B (C9–C14) and C (C16–C21) are 11.08 (14), 7.62 (13) and 5.73 (11)°, respectively, while those between rings A, B, C, D (N1/C22–C26), E (N3/C28–C32) and F (Cu1/O1/C1/O2) are A/B = 15.62 (6), A/C = 33.71 (8), A/D = 78.60 (6), A/E = 81.00 (6), A/F = 11.19 (6), B/C = 26.60 (8), B/D = 70.02 (6), B/E = 86.56 (6), B/F = 23.92 (6), C/D = 44.98 (6), C/E = 66.30 (6), C/F = 32.33 (6), D/E = 26.76 (6) and D/F = 75.15 (5)°.

In (I), the O1—Cu1—O2 angle is 57.75 (2)°. The corresponding O—M—O (where M is a metal) angles are 60.32 (4)° in (III), 59.02 (8)° in (VI), 60.03 (6)° in (VII), 57.53 (5)°, 56.19 (5)° and 59.04 (4)° in (VIII) and 55.2 (1)° in [Cu(Asp)₂(py)₂] (where Asp is acetylsalicylate and py is pyridine) [(IX); Greenaway et al., 1984].

In the crystal structure, intermolecular N—H···O, C—H···F and C—H···O hydrogen bonds link the molecules into a three-dimensional network (Table 1 and Fig. 2). The π–π contacts between the benzene rings, Cg1–Cg1ⁱ, Cg1–Cg2ⁱⁱ and Cg2–Cg3ⁱⁱⁱ [symmetry codes: (i) 1 - x, -y, -z, (ii) 1 + x, y, z, (iii) -x, -y, 1 - z, where Cg1, Cg2 and Cg3 are the centroids of the rings A (C2–C7), B (C9–C14) and C (C16–C21), respectively] may also stabilize the structure, with centroid–centroid distances of 3.5517 (15), 3.8456 (14) and 3.9265 (13) Å, respectively.

Experimental

The title compound was prepared by the reaction of CuSO₄.5H₂O (1.23 g, 5 mmol) in H₂O (20 ml) and NA (1.22 g, 10 mmol) in H₂O (20 ml) with sodium 4-fluorobenzoate (1.62 g, 10 mmol) in H₂O (50 ml) at room temperature. The mixture was filtered and set aside to crystallize at ambient temperature for one month, giving blue single crystals.