Chlorido[1H-1,2,4-triazole-5(4H)-thione-κS]bis­(triphenyl­phosphane-κP)copper(I) acetronitrile monosolvate

Kofsoh Wani; Chaveng Pakawatchai; Saowanit Saithong

doi:10.1107/S1600536812049537

. 2012 Dec 8;69(Pt 1):m34–m35. doi: 10.1107/S1600536812049537

Chlorido[1H-1,2,4-triazole-5(4H)-thione-κS]bis(triphenylphosphane-κP)copper(I) acetronitrile monosolvate

Kofsoh Wani ^a, Chaveng Pakawatchai ^a, Saowanit Saithong ^a,^*

PMCID: PMC3588355 PMID: 23476332

Abstract

In the title solvate, [CuCl(C₂H₃N₃S)(C₁₈H₁₅P)₂]·CH₃CN, the Cu^I ion is bonded to two triphenylphosphane ligands, one 1H-1,2,4-triazole-5(4H)-thione ligand via its S atom and one chloride ion in a distorted CuP₂SCl tetrahedron. An intramolecular N—H⋯Cl hydrogen bond, which closes an S(6) ring, helps to establish the conformation of the complex. In the crystal, N—H⋯Cl hydrogen bonds and C—H⋯π interactions link the components, generating (110) layers.

Related literature

For the properties of mixed-ligand copper(I) complexes, see: Oshio et al. (1996 ▶); Henary et al. (1997 ▶); Vitale & Ford (2001 ▶); Zhang & Chen (2003 ▶). For structurally related mixed-ligand complexes of triphenylphosphane and thione ligands, see: Skoulika et al. (1991 ▶); Aslanidis et al. (1998 ▶); Chen et al. (2001 ▶); Li et al. (2004 ▶); Lobana et al. (2008 ▶); La-o et al. (2009 ▶). For complexes of 1,2,4-triazole-2-thione and its derivatives, see: Sen et al. (1996 ▶); Zhang et al. (2008 ▶). graphic file with name e-69-00m34-scheme1.jpg

Experimental

Crystal data

[CuCl(C₂H₃N₃S)(C₁₈H₁₅P)₂]·C₂H₃N
M _r = 765.72
Orthorhombic,
a = 10.2348 (4) Å
b = 16.4046 (7) Å
c = 22.3632 (9) Å
V = 3754.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.83 mm⁻¹
T = 293 K
0.27 × 0.18 × 0.09 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.840, T _max = 0.928
30968 measured reflections
6602 independent reflections
6040 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.086
S = 1.11
6602 reflections
449 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ▶), 2890 Friedel pairs
Flack parameter: −0.001 (11)

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT (Bruker, 2003 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶), PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(40.1KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812049537/hb7008sup1.cif

e-69-00m34-sup1.cif^{(40.1KB, cif)}

Click here for additional data file.^{(323.1KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812049537/hb7008Isup2.hkl

e-69-00m34-Isup2.hkl^{(323.1KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cu1—P1	2.2802 (9)
Cu1—P2	2.2824 (9)
Cu1—S1	2.3582 (9)
Cu1—Cl1	2.4035 (9)

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

Cg7 is the centroid of the C31–C36 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯Cl1	0.84 (2)	2.41 (3)	3.183 (3)	155 (5)
N1—H1A⋯Cl1ⁱ	0.84 (2)	2.34 (2)	3.154 (3)	163 (5)
C15—H15⋯Cg7ⁱⁱ	0.93	2.88	3.749 (4)	155

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

Acknowledgments

Financial support from the Center of Excellence for Innovation in Chemistry (PERCH-CIC), the Office of the Higher Education Commission, the Ministry of Education and the Graduate School, Prince of Songkla University, are gratefully acknowledged.

supplementary crystallographic information

Comment

The mixed ligand metal(I) complexes of IB group have been studied and characterized due to various properties such as magnetism (Oshio et al., 1996), mocroporus (Zhang & Chen, 2003) and luminescent properties (Vitale & Ford, 2001). Besides, some mixed ligand of copper(I) with drug has been studied (Chen et al., 2001).

For the 1,2,4-triazole-2-thione and its derivatives group have been used as an active ligand to coordinate metals with interesting intrinsic properties (Sen et al., 1996; Zhang et al., 2008). This study reports the crystal structure analysis and self-assembly of the tiltle complex base on mixed ligand copper(I) complex containing triphenylphosphosphane (PPh₃) and 1H-1,2,4-triazole-2-thione (C₂H₃N₃S).

The title compound, [Cu(C₂H₃N₃S)(PPh₃)₂Cl].CH₃CN, is a mononuclear complex. The asymetric unit of the complex contains one formula unit with no crystallographically imposed symmetry and a non-coordinating acetonitrile solvent molecule (Fig.1), in which Cu center is in distorted tetrahedral geometry coordinated by two P atoms of two PPh₃ molecules, one S atom from C₂H₃N₃S molecule and one Cl atom. Similar to those copper(I) complexes coordinating with mixed PPh₃/ heterocyclic thione and Cl ligands, the geometry around copper center and the coordination modes are in agreement with the previous reports (Aslanidis et al., 1998; Li et al., 2004; Lobana et al.,2008).

The short non-bonding distance between N at 3-positon of triazole ring and Cl atom (N3–H3A···Cl1) in the molecule can be accepted as an intra-molecular hydrogen bond with the N3···Cl1 distance = 3.183 (3) Å and the N3–H3A···Cl1 bond angle = 155 (5)°. In crystal packing, the one-dimensional interaction chain along [100] is connected by inter- hydrogen bonding interactions, N–H···Cl, between N at 1-position of triazole ring and the Cl atom of neighbouring molecule (N1···Cl1ⁱ = 3.154 (3) Å; i: x + 1/2, -y + 3/2, -z + 2). In addition, each chain is further linked to each other to form two-dimensional network parallel to (001) due to C—H···π interactions between C15 of phenyl ring and the Cg7 centroid (Cg7: C31–C32–C33–C34–C35–C36) of the nearby phenyl ring of adjacent molecule with the C···Cg7ⁱⁱ distance of 3.749 (4) Å (ii: -x - 1, y + 5/2, -z + 5/2). Two perspective views of intra- and inter-interactions are depicted in Fig. 2 and 3.

Experimental

A mixture of CuCl (0.15 g: 1.50 mmol), C₂H₃N₃S (0.15 g: 1.48 mmol) and PPh₃ (0.80: 3.05 mmol) in acetronitrile 30 ml was refluxed for 4 h. Then, the fitrate was kept to evaporate at room temperature over night. The polygon colorless crystals were obtained. The complex melts at 140–142°C.