[4,6-Dimethyl­pyrimidine-2(1H)-thione-κS]iodidobis(triphenyl­phosphane-κP)copper(I)

Chaveng Pakawatchai; Yupa Wattanakanjana; Patcharanan Choto; Ruthairat Nimthong

doi:10.1107/S1600536812021010

. 2012 May 16;68(Pt 6):m773–m774. doi: 10.1107/S1600536812021010

[4,6-Dimethylpyrimidine-2(1H)-thione-κS]iodidobis(triphenylphosphane-κP)copper(I)

Chaveng Pakawatchai ^a,^*, Yupa Wattanakanjana ^b, Patcharanan Choto ^a, Ruthairat Nimthong ^a

PMCID: PMC3379106 PMID: 22719327

Abstract

In the mononuclear title complex, [CuI(C₆H₈N₂S)(C₁₈H₁₅P)₂], the Cu^I ion is in a slightly distorted tetrahedral coordination geometry formed by two P atoms from two triphenylphosphane ligands, one S atom from a 4,6-dimethylpyrimidine-2(1H)-thione ligand and one iodide ion. There is an intramolecular N—H⋯I hydrogen bond. In the crystal, π–π stacking interactions [centroid–centroid distance = 3.594 (1) Å] are observed.

Related literature

For the coordination and potential applications of Cu^I complexes, see: Santra et al. (1999 ▶); Fujisawa et al. (2004 ▶); Tian et al. (2004 ▶); Kang (2006 ▶); Reymond & Cossy (2008 ▶); Gong et al. (2010 ▶). For relevant examples of discrete complexes, see: Voutsas et al. (1995 ▶); Lemos et al. (2001 ▶); Lobana et al. (2008 ▶); Nimthong et al. (2008 ▶). graphic file with name e-68-0m773-scheme1.jpg

Experimental

Crystal data

[CuI(C₆H₈N₂S)(C₁₈H₁₅P)₂]
M _r = 855.18
Triclinic,
a = 11.5605 (7) Å
b = 13.0076 (8) Å
c = 13.6456 (8) Å
α = 92.243 (1)°
β = 99.247 (1)°
γ = 106.092 (1)°
V = 1938.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.53 mm⁻¹
T = 293 K
0.32 × 0.16 × 0.08 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.744, T _max = 0.882
26730 measured reflections
9368 independent reflections
8066 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.075
S = 1.03
9368 reflections
448 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.90 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; 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: SHELXL97 and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812021010/lh5472sup1.cif

e-68-0m773-sup1.cif^{(26.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812021010/lh5472Isup2.hkl

e-68-0m773-Isup2.hkl^{(448.9KB, 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—H1N⋯I1	0.87 (3)	2.62 (3)	3.4858 (18)	176 (3)

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Acknowledgments

We gratefully acknowledge financial support from the Center for Innovation in Chemistry (PERCH–CIC), the Commission on Higher Education, Ministry of Education, the Department of Chemistry and the Graduate School, Prince of Songkla University.

supplementary crystallographic information

Comment

The synthesis and coordination chemistry of copper(I) complexes have been widely studied. Some of these complexes have been found to have unusual structural features, exhibit corrosion-inhibiting properties (Tian et al., 2004), catalytic activity in photo-redox reactions (Santra et al., 1999), phosphorescence due to close Cu···Cu interactions (Gong, et al., 2010), precursors to blue copper–protein model (Fujisawa et al., 2004) and catalysts in enantiomer selective Diels–Alder reactions (Reymond & Cossy, 2008). Moreover, the role of copper(I) is evident in several biologically important reactions, such as a dioxygen carrier and models for several enzymes (Kang, 2006).

The molecular structure of the title compound is shown in Fig. 1. The complex is monomeric with a slightly distorted tetrahedral coordination enviroment around Cu1. The Cu1—S bond length of 2.3404 (6) Å, is in good agreement with values reported for other copper(I) complexes with heterocyclic thione ligands, such as 2.3723 (12) Å for [Cu(N₃)(dmpymtH)(PPh₃)₂] (Lemos et al., 2001) and 2.344 (3) Å for [CuI(1κs-imzsH)(PPh₃)₂] (Lobana et al., 2008). The Cu1—P1 and Cu1—P2 bond distances, 2.2897 (5) and 2.3047 (5) Å, are as expected. The bond distance of Cu1—I1, 2.6801 (3), is comparable to those found [2.6658 (8) Å] for [Cu₂(C₇H₈N₂S)(C₁₈ H₁₃P)₂I] (Nimthong et al., 2008) and 2.674 (2) Å for [Cu(PPh₃)₂(pymtH)I] (Voutsas et al., 1995). In the crystal, π(pyrimidine)···π(pyrimidine) (centroid-centroid distances = 3.594 Å) interactions are observed. In addition, an intramolecular hydrogen bond is also observed (see Table 1 and Fig. 2).

Experimental

A solution of 4,6-dimethylpyrimidine-2(1H)-thione, (0.08 g, 0.52 mmol) in 30 cm³ of methanol was stirred at 333 K then CuI (0.10 g, 0.52 mmol) solid was added and stirred for 3 h. Solid of triphenylphosphane (0.27 g, 1.04 mmol) was added and heated with continuous stirring for a period of 2 h. The clear yellow solution was formed then filtered off and kept at room temperature. Slow evaporation of the solvent gave the yellow colored crystalline solids, which were filtered off and dried in vacuo. Analysis found: C 60.11, H 4.46, N 2.88, S 3.22%; calculated for C₄₂H₃₇CuIN₂P₂S: C 59.03, H 4.37, N 3.28, S 3.76%.