Iodido(N-phenyl­thio­urea)bis­(triphenyl­phosphine)copper(I)

Ruthairat Nimthong; Chaveng Pakawatchai; Saowanit Saithong; Jonathan P H Charmant

doi:10.1107/S1600536808019119

. 2008 Jun 28;64(Pt 7):m977. doi: 10.1107/S1600536808019119

Iodido(N-phenylthiourea)bis(triphenylphosphine)copper(I)

Ruthairat Nimthong ^a, Chaveng Pakawatchai ^a,^*, Saowanit Saithong ^a, Jonathan P H Charmant ^b

PMCID: PMC2961665 PMID: 21202821

Abstract

The coordination geometry of the Cu atom in the title compound, [CuI(C₇H₈N₂S)(C₁₈H₁₅P)₂], is distorted tetrahedral; it is coordinated by two triphenylphosphine P atoms, one S atom from N-phenylthiourea (ptu) and one I atom. The crystal structure is stabilized by intra- and intermolecular N—H⋯I and N—H⋯S interactions.

Related literature

For related literature, see: Aslanidis et al. (1993 ▶, 1998 ▶); Bowmaker et al. (1987 ▶); Cox et al. (1999 ▶); Jianping & Kazuyuki (1996 ▶); Karagiannidis et al. (1990 ▶); Lecomte et al. (1989 ▶); Skoulika et al. (1991 ▶).

Experimental

Crystal data

[CuI(C₇H₈N₂S)(C₁₈H₁₅P)₂]
M _r = 867.19
Triclinic,
a = 10.9505 (9) Å
b = 18.7294 (15) Å
c = 21.3731 (18) Å
α = 67.422 (1)°
β = 77.215 (1)°
γ = 73.224 (1)°
V = 3844.9 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.54 mm⁻¹
T = 173 (2) K
0.50 × 0.30 × 0.07 mm

Data collection

Bruker SMART Platform diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.582, T _max = 0.898
42789 measured reflections
15698 independent reflections
8887 reflections with I > 2σ(I)
R _int = 0.088

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.108
S = 0.98
15698 reflections
901 parameters
H-atom parameters constrained
Δρ_max = 0.82 e Å⁻³
Δρ_min = −0.74 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT and SHELXTL (Sheldrick, 2008 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808019119/hg2408sup1.cif

e-64-0m977-sup1.cif^{(49.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808019119/hg2408Isup2.hkl

e-64-0m977-Isup2.hkl^{(767.2KB, 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
N1—H1B⋯S2ⁱ	0.88	2.58	3.455 (5)	173
N3—H3B⋯S1ⁱⁱ	0.88	2.63	3.396 (5)	146
N2—H2A⋯I1	0.88	2.65	3.511 (5)	166
N4—H4A⋯I2	0.88	2.71	3.567 (4)	165

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

Acknowledgments

We gratefully acknowledge financial assistance from the Center for Innovation in Chemistry: Postgraduate Education and Research Program in Chemistry (PERCH-CIC), Department of Chemistry and Graduate School, Prince of Songkla University.

supplementary crystallographic information

Comment

Studies of copper(I) complexes with mixed ligand systems containing triphenylphosphine and ligands containing S and N donors, have been increasing because of the versatility of these ligands as well as the different steric characteristics of the phosphine ligands, which can modify the compound geometry (Cox et al., 1999). The title complex, (I), is a monomeric complex which crystallizes in the triclinic system space group P1. The structure consists of two independent [CuI(PPh₃)₂(ptu)] molecules in the asymmetric unit. The molecules feature a distorted tetrahedral copper(I) center with two triphenylphosphine P atoms, one S atom from ptu ligand and one iodide atom (Figures 1, 2). A distorted tetrahedral geometry is also found in the copper(I) halide complexes with mixed PPh₃/sulfur base ligands (Lecomte et al., 1989; Karagiannidis et al., 1990; Skoulika et al., 1991; Jianping & Kazuyuki., 1996; Aslanidis et al., 1998; Cox et al., 1999). The P—Cu—P angle deviates considerably from tetrahedral value at 118.63 (5)° and 122.18 (5)° in molecule A and B, respectively. The Cu—P distances of the molecule A [Cu(1)—P(1), 2.2908 (15)Å and Cu(1)—P(2), 2.3024 (16) Å] and of the molecule B [Cu(2)—P(3), 2.2876 (15)Å and Cu(2)—P(4), 2.2974 (16) Å] are slightly shorter as compared to the observed value for [Cu(PPh₃)₃I] (Bowmaker et al., 1987). The observed Cu—S distances of 2.4148 (16) and 2.3942 (15) Å in molecule A and B are consistent with the distances usually found for tetrahedrally coordinated copper(I) with thioamide-sulfur donors (Aslanidis et al., 1993). The mean plane of the phenyl ring (C45—C50) of ptu ligand in the molecule B forms a dihedral angle of 83.9 (2)° with one of phenyl ring (C81—C86) of PPh₃ molecules. Weak intra-molecular hydrogen bonding between the amide group and iodide atom is observed [N2···I1= 3.511 (5) Å, H2A···I1 = 2.65 Å, N2—H2A···I1 = 166 ° for molecule A and N4···I2 = 3.567 (4) Å, H4A···I2 = 2.71 Å, N4—H4A···I2 = 165 ° for molecule B]. However, only one C—H···π interaction between C-sp² (C46—H46···π) of the phenyl ring from ptu ligand and the centroid of one phenyl ring (Cg14, C81—C86) of the PPh₃ molecules is observed in molecule B. In addition, the weak inter-molecular interactions between the one H atom of NH₂ group of ptu ligand of molecule A and the thione-S atom of ptu of molecule B [N1···S2 = 3.455 (5) Å, H1B···S2 = 2.58 Å, N1—H1B···S2 = 173 °] are found and vice versa [N3···S1 = 3.396 (5) Å, H3B···S1 = 2.63 Å, N3—H3B···S1 = 146 °]. The intra- and inter-molecular interactions of this complex are shown in Figure 3.

Experimental

Triphenylphosphine (0.27 g, 1.05 mmol) was dissolved in 30 cm³of acetonitrile at 70–75°C. CuI (0.1 g, 0.52 mmol) was added and the mixture was stirred for 2 h. After the formation of a complete clear solution, N-phenylthiourea (0.24 g, 1.57 mmol) was added slowly and the reaction mixture was stirring for 3 h. The resulting clear solution was filtered off and left to evaporate at room temperature. The microcrystalline solid, which deposited upon standing for several days, was filtered off and dried in vacuo. Single crystals suitable for X-ray diffraction studies were obtained by slow evaporation in acetonitrile. The melting point of the complex is 456-457 K. Elemental analysis, calculated for [CuI(PPh₃)₂(ptu)]: C, 59.55; H, 4.43; N, 3.23; S, 3.70%, found: C, 60.28; H, 4.46; N, 3.56; S, 3.93%.