cis-Bis[N′-(4-bromo­benzo­yl)-N,N-dimethyl­thio­ureato-κ2 O,S]copper(II)

Gün Binzet; Ulrich Flörke; Nevzat Külcü; Hakan Arslan

doi:10.1107/S1600536811015789

. 2011 Apr 29;67(Pt 5):m648–m649. doi: 10.1107/S1600536811015789

cis-Bis[N′-(4-bromobenzoyl)-N,N-dimethylthioureato-κ² O,S]copper(II)

Gün Binzet ^a, Ulrich Flörke ^b, Nevzat Külcü ^c, Hakan Arslan ^c,^d,^*

PMCID: PMC3089271 PMID: 21754354

Abstract

The asymmetric unit of the title compound, [Cu(C₁₀H₁₀BrN₂OS)₂], contains two independent complex molecules with almost identical conformations. Two S and two O atoms form the coordination environment of the Cu atom, resulting in a slightly distorted square-planar coordination. The S atoms are in a cis configuration. The crystal structure is stabilized by weak intermolecular C—H⋯Br hydrogen-bonding interactions.

Related literature

For the synthesis of the title compound, see: Binzet et al. (2009 ▶); Emen et al. (2005 ▶). For complexes with thiourea derivatives, see: Sacht et al. (2000 ▶); Arslan et al. (2009 ▶); Avşar et al. (2002 ▶, 2003 ▶); Mansuroğlu et al. (2008 ▶); Henderson et al. (2002 ▶). For related compounds, see: Arslan et al. (2003 ▶, 2006 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

[Cu(C₁₀H₁₀BrN₂OS)₂]
M _r = 635.88
Triclinic,
a = 9.1780 (11) Å
b = 11.0028 (13) Å
c = 23.241 (3) Å
α = 94.857 (2)°
β = 96.144 (3)°
γ = 95.095 (2)°
V = 2313.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 4.60 mm⁻¹
T = 120 K
0.28 × 0.21 × 0.12 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.359, T _max = 0.608
20433 measured reflections
10926 independent reflections
8446 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.117
S = 1.00
10926 reflections
567 parameters
H-atom parameters constrained
Δρ_max = 0.98 e Å⁻³
Δρ_min = −0.84 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶), OLEX2, publCIF (Westrip, 2010 ▶) and Mercury (Macrae et al., 2006 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811015789/bt5534sup1.cif

e-67-0m648-sup1.cif^{(33.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015789/bt5534Isup2.hkl

e-67-0m648-Isup2.hkl^{(534.2KB, 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
C13—H13C⋯Br2ⁱ	0.98	2.92	3.809 (4)	150
C19—H19A⋯Br4ⁱⁱ	0.95	2.91	3.858 (4)	174
C27—H27A⋯Br1ⁱⁱⁱ	0.95	2.90	3.849 (4)	176
C37—H37A⋯Br3^iv	0.95	2.93	3.845 (4)	163

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

Acknowledgments

This work was supported by Mersin University Research Fund [project Nos. BAP-ECZ-F-TBB-(HA) 2004–3 and BAP-FEF-KB-(NK) 2006–3].

supplementary crystallographic information

Comment

The ability of thiourea derivatives to complex with transition metal cations is well known (Arslan et al., 2009; Avşar et al., 2002, Arslan et al., 2006). Thioureas are able to coordinate a range of metal centers as neutral ligands, monoanions or dianions (Sacht et al., 2000; Henderson et al., 2002). The oxygen, nitrogen and sulfur donors of thioureas provide a multitude of bonding possibilities.

In view of this information and in continuation of our research into the thiourea derivatives, we synthesized and characterized a series of substituted thiourea derivatives (Binzet et al., 2009; Arslan et al., 2003; Avşar et al., 2003; Emen et al., 2005; Mansuroğlu et al., 2008). The title compound, cis-bis(N,N-dimethyl-N'-4-bromobenzoylthioureato)copper(II), (I), is another example of our synthesized thiourea derivatives that contains both aryl and alkyl groups.

There are two similar molecules in the asymmetric unit, so discussion will primarily focus on one of these independent molecules; see Fig. 1 and 2 for a view of one of the two independent molecules. There is very little difference between the bond lengths and angles of these molecules. The crystal structure of the title compound confirms N,N-dimethyl-N'-4-bromobenzoylthiourea ligand is a bidentate chelating ligand, coordinating to the copper atom through the thiocarbonyl and carbonyl groups. The central copper atom shows slightly distorted square-planar coordination and the sulfur atoms are in a cis configuration. The maximum deviations from the S₂O₂ mean plane are 0.065 (3) Å for oxygen, 0.054 (1) Å for sulfur and 0.000 (1) Å for copper. The Cu1/S2/C11/N3/C14/O2 ring adopts an envelope conformation with puckering parameter Q = 0.2593 (19) Å, θ = 121.0 (7)°, φ = 181.3 (8) ° (Cremer & Pople, 1975). Cu—O [average 1.857 (3) Å] and Cu—S [average 2.1442 (10) Å] bond lengths are in the expected ranges. The dihedral angle between these chelate planes of 6.23 (10)° indicates slight distortion from square planar towards tetrahedral geometry. C–O, C–S and C–N bond lengths of the complex suggest considerable electronic delocalization in the chelate rings. The bond lengths of the carbonyl O1–C4 1.265 (4) Å; O2–C14 1.270 (4) Å and thiocarbonyl S1–C1 1.738 (4) Å; S2–C11 1.734 (4) Å groups lie between those for double and single bonds, similar to related structures (Arslan et al. 2003, 2006; Avşar et al., 2003; Binzet et al., 2009), while both C–O and C–S bond lengths are typical of double bonds in the free ligand. The other bond lengths in title compound show normal values.

Experimental

A solution of 4-bromobenzoyl chloride (0.005 M) in acetone (50 cm³) was added dropwise to a suspension of potassium thiocyanate (0.005 M) in anhydrous acetone (50 cm³). The reaction mixture was heated under reflux for 30 min and then cooled to room temperature. A solution of dimethylamine (0.005 M) in acetone (30 cm³) was added and the resulting mixture was stirred for 2 h. Hydrochloric acid (0.1 N, 300 cm³) was added and the solution filtered. The solid product was washed with water and purified by recrystallization from ethanol: dichloromethane (1: 2). M.p.: 222–224 °C. C₂₀H₂₀Br₂CuN₄O₂S₂: C, 37.78; H, 3.17; N, 8.81. Found: C, 37.97; H, 3.20; N, 8.79%.