Bis(3-chloro­benzoato-κ2 O,O′)bis­(nicotinamide-κN)copper(II)

Nihat Bozkurt; Nefise Dilek; Nagihan Çaylak Delibaş; Hacali Necefoğlu; Tuncer Hökelek

doi:10.1107/S1600536813014694

. 2013 Jun 8;69(Pt 7):m356–m357. doi: 10.1107/S1600536813014694

Bis(3-chlorobenzoato-κ² O,O′)bis(nicotinamide-κN)copper(II)

Nihat Bozkurt ^a, Nefise Dilek ^b, Nagihan Çaylak Delibaş ^c, Hacali Necefoğlu ^a, Tuncer Hökelek ^d,^*

PMCID: PMC3772403 PMID: 24046546

Abstract

The molecule of the title Cu^II complex, [Cu(C₇H₄ClO₂)₂(C₆H₆N₂O)₂], contains two 3-chlorobenzoate (CB) and two nicotinamide (NA) ligands; the CB act as bidentate ligands, while the NA are monodentate ligands. The resulting CuN₂O₄ coordination polyhedron is a considerably distorted octahedron. The dihedral angles between the carboxylate groups and the adjacent benzene rings are 17.92 (12) and 24.69 (16)°, while the two benzene rings and the two pyridine rings are oriented at dihedral angles of 52.20 (8) and 1.56 (6)°. In the crystal, N—H⋯N and C—H⋯O hydrogen bonds link the molecules into a three–dimensional network. The π–π contact between the benzene rings [centroid–centroid distance = 3.982 (2) Å] may further stabilize the crystal structure.

Related literature

For niacin, see: Krishnamachari (1974 ▶). For the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972 ▶). For related structures, see: Greenaway et al. (1984 ▶); Hökelek & Necefoğlu (1996 ▶); Hökelek et al. (1996 ▶); Hökelek, Dal et al. (2009 ▶); Hökelek, Yılmaz et al. (2009 ▶); Necefoğlu et al. (2011 ▶); Sertçelik et al. (2013 ▶).

Experimental

Crystal data

[Cu(C₇H₄ClO₂)₂(C₆H₆N₂O)₂]
M _r = 618.91
Triclinic,
a = 9.6614 (2) Å
b = 12.5429 (3) Å
c = 12.8728 (3) Å
α = 61.598 (2)°
β = 87.386 (3)°
γ = 77.115 (3)°
V = 1334.30 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.07 mm⁻¹
T = 296 K
0.35 × 0.20 × 0.15 mm

Data collection

Bruker SMART BREEZE CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2012 ▶) T _min = 0.774, T _max = 0.852
19053 measured reflections
5434 independent reflections
4970 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.083
S = 1.06
5434 reflections
368 parameters
117 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Data collection: APEX2 (Bruker, 2012 ▶); cell refinement: SAINT (Bruker, 2012 ▶); 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, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813014694/rk2404sup1.cif

e-69-0m356-sup1.cif^{(26KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813014694/rk2404Isup2.hkl

e-69-0m356-Isup2.hkl^{(260.7KB, 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	0.80 (2)	2.12 (2)	2.896 (2)	164 (2)
N2—H2B⋯O6ⁱⁱ	0.84 (3)	2.02 (3)	2.790 (2)	153 (2)
N4—H4A⋯O5ⁱ	0.83 (3)	2.01 (3)	2.817 (2)	164 (2)
N4—H4B⋯O4ⁱⁱ	0.81 (2)	2.05 (2)	2.836 (2)	162 (3)
C19—H19⋯O1ⁱⁱⁱ	0.93	2.45	3.100 (2)	127
C21—H21⋯O5ⁱ	0.93	2.56	3.416 (2)	154
C24—H24⋯O3^iv	0.93	2.59	3.475 (3)	158

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

Acknowledgments

The authors are indebted to Aksaray University and the Science and Technology Application and Research Center of Aksaray University, Aksaray, Turkey, for the use of X–ray diffractometer.

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, an important respiratory stimulant (Bigoli et al., 1972), the title compound was synthesized and its crystal structure is reported herein.

In the monomeric title complex, I, the Cu^II ion is surrounded by two 3–chlorobenzoate (CB) and two (NA) ligands. The CB act as bidentate ligands, while the NA are monodentate ligands. The structures of similar complexes of Zn(II) and Cd(II) ions, [Zn₂(C₁₀H₁₄N₂O)₂(C₇H₅O₃)₄]^.2H₂O, II, (Hökelek & Necefoğlu, 1996), [Zn(C₉H₁₀NO₂)₂(C₆H₆N₂O)^.2H₂O], III, (Hökelek, Dal et al., 2009) and [Cd(C₈H₅O₃)₂(C₆H₆N₂O)₂]^.H₂O, IV, (Hökelek, Yılmaz et al., 2009) have also been determined.

In the title compound (Fig. 1), the Cu atom is displaced out of the least–squares planes of the carboxylate groups (O1/C1/O2) and (O3/C8/O4) by 0.1556 (2)Å and -0.0577 (2)Å, respectively. The dihedral angle between the planar carboxylate groups and the adjacent benzene rings A (C2—C7) and B (C9—C14) are 17.92 (12)° and 24.69 (16)°, respectively, while those between rings A, B, C (N1/C15—C19) and D (N3/C21—C25) are A/B = 52.20 (8)°, A/C = 85.61 (7)°, A/D = 84.86 (7)°, B/C = 71.49 (7)°, B/D = 69.95 (6)° and C/D = 1.56 (6)°. The two four–membered rings, (Cu1/O1/O2/C1) and (Cu1/O3/O4/C8), are oriented at a dihedral angle of 12.07 (7)°.

In I, the O1–Cu1–O2 and O3–Cu1–O4 angles are 59.76 (5)° and 55.08 (5)°, respectively. The corresponding O–M–O (where M is a metal) angles are 58.3 (3)° in II, 60.03 (6)° in III, 52.91 (4) and 53.96 (4)° in IV, 53.50 (14)° in [Cu₂(C₈H₅O₃)₄(C₆H₆N₂O)₄], V, (Sertçelik et al., 2013), 57.75 (2)° in [Cu(C₇H₄FO₂)₂(C₇H₅FO₂)(C₆H₆N₂O)₂], VI, (Necefoğlu et al., 2011), 58.3 (3)° in [Cu(C₇H₅O₂)₂(C₁₀H₁₄N₂O)₂], VII, (Hökelek et al., 1996) and 55.2 (1)° in [Cu(Asp)₂(Py)₂], where Asp is acetylsalicylate and Py is pyridine, VIII, (Greenaway et al., 1984).

In the crystal structure, intermolecular N—H···O and C—H···O hydrogen bonds (Table 1) link the molecules into a three–dimensional network, in which they may be effective in the stabilization of the structure. The π–π contact between the benzene rings, Cg2···Cg2ⁱ, where Cg2 is the centroid of the ring B (C9–C14) may further stabilize the structure, with Cg···Cg distance of 3.982 (2)Å. Symmetry code: (i) -x, 1-y, -z.

Experimental

The title compound was prepared by the reaction of CuSO₄^.5H₂O (1.25 g, 5 mmol) in H₂O (50 ml) and NA (1.22 g, 10 mmol) in H₂O (50 ml) with sodium 3–chlorobenzoate (1.79 g, 10 mmol) in H₂O (100 ml). The mixture was filtered and set aside to crystallize at ambient temperature for one week, giving blue single crystals.