Iodidotris(triphenyl­phosphine)copper(I) acetonitrile solvate

Ramaiyer Venkatraman; Frank R Fronczek

doi:10.1107/S1600536808007174

. 2008 Mar 29;64(Pt 4):m577. doi: 10.1107/S1600536808007174

Iodidotris(triphenylphosphine)copper(I) acetonitrile solvate

Ramaiyer Venkatraman ^a, Frank R Fronczek ^b,^*

PMCID: PMC2960968 PMID: 21202027

Abstract

The title compound, [CuI(C₁₈H₁₅P)₃]·C₂H₃N, was obtained from the reaction of triphenylphosphine and copper(I) iodide in acetonitrile. The monomeric form of the complex has slightly distorted coordination of Cu by the I atom and three P atoms. The crystal structure is stabilized by C—H⋯π interactions between phenyl H atoms and phenyl rings. In addition, the complex molecules exhibit C—H⋯N hydrogen bonds between phenyl H atoms and acetonitrile N atoms. The crystal used was an inversion twin, with nearly equal component populations of 0.522 (8) and 0.478 (8).

Related literature

For details of the crystal structures of organophosphinecopper(I) halide derivatives, see: Caulton et al. (1990 ▶); Bowmaker et al. (2000 ▶); Eller et al. (1977 ▶); Hamel et al. (2002 ▶); Hanna et al. (2005 ▶); Venkatraman et al. (2006 ▶); Barron et al. (1987 ▶); Kräuter & Newmüller (1996 ▶).

Experimental

Crystal data

[CuI(C₁₈H₁₅P)₃]·C₂H₃N
M _r = 1018.30
Orthorhombic,
a = 18.5726 (10) Å
b = 20.2631 (12) Å
c = 12.7839 (5) Å
V = 4811.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 1.23 mm⁻¹
T = 115 (2) K
0.30 × 0.25 × 0.17 mm

Data collection

Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.709, T _max = 0.818
156685 measured reflections
15969 independent reflections
13488 reflections with I > 2σ(I)

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.068
S = 1.03
15969 reflections
561 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.66 e Å⁻³
Absolute structure: Flack (1983 ▶), 7443 Friedel pairs
Flack parameter: 0.478 (8)

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808007174/lx2043sup1.cif

e-64-0m577-sup1.cif^{(36.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808007174/lx2043Isup2.hkl

e-64-0m577-Isup2.hkl^{(780.5KB, 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
C9—H9⋯Cg1ⁱ	0.95	2.94	3.732	141
C40—H40⋯Cg2ⁱ	0.95	2.94	3.696	137
C39—H39⋯N1Sⁱⁱ	0.95	2.58	3.468 (4)	157

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Symmetry codes: (i) Inline graphic ; (ii) . Cg1 and Cg2 are the centroids of the C1–C6 and C7–C12 phenyl rings, respectively.

Acknowledgments

The purchase of the diffractometer was made possible by grant No. LEQSF(1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents.

supplementary crystallographic information

Comment

Organophosphinecopper (I) halides have widely investigated system due to the formation of varying types of crystal structures (Caulton et al., 1990). Eller et al. (1977) used the organophosphinecopper (I) systems for the direct Cu–SO₂ adduct formation. Recently Hanna et al. (2005) reported the structural and solid state NMR studies of the four coordinate copper (I) complexes with different cations except iodide. During our study on the interaction of heterocyclic thiosemicarbazones with copper (I) halides, we were able to isolate the title compound (1), Venkatraman et al., (2006).

The structure consists of CuI(PPh₃)₃ unit similar to the structure described by Eller et al. (1977) for CuI(PPh₂Me)₃. The asymmetric unit of (1) contains one formula unit of the complex with no crystallographically imposed symmetry (Fig.1), and one acetonitrile solvent molecule. The Cu atom is surrounded by three phosphorus atoms and the iodide atom in a distorted tetrahedral geometry. The three independent Cu—P distances are not grossly different (2.3421 (6), 2.3463 (6), and 2.3295 (7) Å) for P1, P2, and P3, respectively, and the Cu—I distance is 2.6843 (3) Å. The Cu—P bond lengths in compound (1) are similar to values recorded for a range of other [Cu-(PPh3)₃X] complexes [Bowmaker et al., (2000)]. The three P—Cu—I angles are 104.75 (2), 113.66 (2), and 97.69 (2)°, for P1, P2, and P3, respectively, [average 105.2°], and sums to 316.0°. The wide range of P—Cu—P/I angles indicate an irregular tetrahedral structure.

The molecular packing (Fig. 2) is stabilized by CH₂—H···π interactions between the hydrogen of phenyl group and the phenyl ring, with C9—H9···Cg1ⁱ and C40—H40···Cg2ⁱ separations of 2.94 Å (Fig. 2 & Table 1) (Cg1 and Cg2 are the centroids of C1—C6 and C7—C12 phenyl rings, respectively). Further stability comes from weak C—H···N1Sⁱⁱ hydrogen bond in Fig. 2 and Table 1. A l l symmetry codes as in Table 1.

Experimental

To a solution of copper (I) iodide (Aldrich; 0.190 g, 1 mmol) in acetonitrile (Aldrich; 50 ml) was added solid triphenylphosphine (Aldrich; 0.262 g, 2 mmol) in presence 0.5 ml HCl. The resulting mixture was stirred overnight. The clear solution was filtered and allowed to evaporate at room temperature in the presence of air. A colorless crystalline product suitable for X-ray diffraction was formed (yield ca 70%).