Chlorido(1,3-dimethyl­thio­urea-κS)bis­(triphenyl­phosphine-κP)copper(I) acetonitrile hemisolvate

Latipah La-o; Chaveng Pakawatchai; Saowanit Saithong; Brian W Skelton

doi:10.1107/S1600536809026798

. 2009 Jul 15;65(Pt 8):m926. doi: 10.1107/S1600536809026798

Chlorido(1,3-dimethylthiourea-κS)bis(triphenylphosphine-κP)copper(I) acetonitrile hemisolvate

Latipah La-o ^a, Chaveng Pakawatchai ^a,^*, Saowanit Saithong ^a, Brian W Skelton ^b

PMCID: PMC2977114 PMID: 21583381

Abstract

The title compound, [CuCl(C₃H₈N₂S)(C₁₈H₁₅P)₂]·0.5CH₃CN, was prepared by the reaction of copper(I) chloride with 1,3-dimethylthiourea (dmtu) and triphenylphosphine (PPh₃) in acetonitrile. The Cu^I atom has a distorted tetrahedral environment formed by two P atoms from triphenylphosphine, one S atom from the dmtu ligand and one Cl atom. In addition, the molecules exhibit intra- and intermolecular N—H⋯Cl interactions.

Related literature

For related structures, see: Aslanidis et al. (1993 ▶, 1998 ▶); Cox et al. (1999 ▶); Karagiannidis et al. (1990 ▶); Lecomte et al. (1989 ▶); Singh & Dikshit (1995 ▶); Skoulika et al. (1991 ▶).

Experimental

Crystal data

[CuCl(C₃H₈N₂S)(C₁₈H₁₅P)₂]·0.5C₂H₃N
M _r = 748.23
Monoclinic,
a = 13.7503 (4) Å
b = 30.0495 (9) Å
c = 18.4227 (5) Å
β = 90.874 (1)°
V = 7611.2 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.81 mm⁻¹
T = 293 K
0.36 × 0.12 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.777, T _max = 0.940
70507 measured reflections
13413 independent reflections
10371 reflections with I > 2s(I)
R _int = 0.059

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.111
S = 1.10
13413 reflections
873 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.25 e Å⁻³

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

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809026798/pk2174sup1.cif

e-65-0m926-sup1.cif^{(51.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809026798/pk2174Isup2.hkl

e-65-0m926-Isup2.hkl^{(655.7KB, 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
N1A—H1AA⋯Cl1Bⁱ	0.875 (18)	2.43 (2)	3.234 (3)	153 (3)
N2A—H2AA⋯Cl1A	0.875 (18)	2.326 (19)	3.197 (3)	173 (3)
N1B—H1BB⋯Cl1A	0.869 (18)	2.47 (2)	3.262 (3)	152 (3)
N2B—H2BB⋯Cl1B	0.879 (18)	2.36 (2)	3.230 (3)	169 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

We gratefully acknowledge support of this work by a grant from the Research Assistantship (RA), the Department of Chemistry and Graduate School, Prince of Songkla University.

supplementary crystallographic information

Comment

Treatment of [Cu(PPh₃)₃Cl] (PPh₃= triphenylphosphine) in acetonitrile with N,N'-dimethylthiourea(dmtu) in a 1:2 metal-thione ratio yielded a product of formula [Cu(PPh₃)₂(dmtu)Cl], 0.5 CH₃CN. Its crystal structure consists of two independent [CuCl(PPh₃)₂(dmtu)] molecules (A and B) plus a CH₃CN solvent molecule in the asymmetric unit. The Cu^I atoms display a distorted tetrahedral environment (Fig. 1). Distorted tetrahedral geometries are also found in similar phosphine adducts of Cu^I halides (Aslanidis et al., 1993, 1998; Cox et al., 1999; Karagiannidis et al., 1990; Lecomte et al., 1989; Singh & Dikshit, 1995; Skoulika et al., 1991). In both A and B molecules the distorted tetrahedral coordination consists of the S donor of the N,N'-dimethylthiourea ligand, two P atoms of two phosphine ligands, as well as the Cl atom. The Cu—P(1) and Cu—P(2) distances of 2.2847 (9), 2.2850 (9) Å and 2.2831 (9), 2.2989 (9) Å in molecule A and B, are slightly shorter than the corresponding lengths observed in [Cu(PPh₃)₂(tzdtH)Cl](Aslanidis et al., 1998). The P(1)—Cu—P(2) angle deviates considerably from the ideal tetrahedral value of 109.4° [124.71 (4)° (A) and 120.07 (3)° (B)]. These values are more similar to those found in trigonally coordinated Cu^I, a mode which is essentially determined by steric bulky ligands and by constraints related to intra-molecular hydrogen bridging bonds. Other significant features of the present structure are the Cu—S and Cu—Cl bond lengths which lie in the range normally observed for tetrahedrally coordinated Cu^I complexes with terminal chloride and thione-sulfur donors. The Cu—S bond lengths [2.3715 (10) (A) 2.3857 (9) Å (B)] are longer than in [Cu(PPh₃)₂(pymtH)I][2.338 (4) Å] (Aslanidis et al., 1993) but shorter than in [Cu(PPh₃)₂ (tzdtH)Cl] [2.418 (5) Å] (Aslanidis et al., 1998). The observed Cu—Cl distances of 2.4014 (9), 2.3956 (9) Å in molecule A and B, respectively, are very close to those observed in [Cu(PPh₃)₂(bztzdtH)Cl] [2.40 (2) Å] (Cox et al., 1999). In both molecules, the Cl atom is hydrogen bonded to the N,N'-dimethylthiourea NH atoms as shown in Table 1. These hydrogen bonds may be the main reason for the conformational changes, i.e. the increase of the P—Cu—P angle and distortion from the tetrahedral configuration. This hydrogen bonding may also influence the orientation of the complexed ligands (Skoulika et al., 1991).

Experimental

Triphenylphosphine was added to an acetonitrile suspension of Cu^I chloride. After stirring for 2 h, N,N'-dimethylthiourea was added. The mixture was refluxed for 5 h to afford a colorless solution. Single crystals were obtained after cooling followed by slow evaporation overnight at room temperature. The melting point of the complex is 469–470 K. Elemental analysis, calculated for [CuCl(dmtu)(PPh₃)₂], 0.5 CH₃CN: C, 64.37; H, 5.26; N, 3.85; S,4.40%, found: C, 64.54; H, 5.58; N, 3.70; S, 4.52%.