[μ-1,2-Bis(diphenyl­phosphino)ethane-κ2 P:P′]bis­{[1,2-bis­(diphenyl­phosphino)ethane-κ2 P,P′]cyanidocopper(I)} methanol disolvate

Rong Wang; Ye-Lan Xiao; Qiong-Hua Jin; Cun-Lin Zhang

doi:10.1107/S1600536810029545

. 2010 Jul 31;66(Pt 8):m1032. doi: 10.1107/S1600536810029545

[μ-1,2-Bis(diphenylphosphino)ethane-κ² P:P′]bis{[1,2-bis(diphenylphosphino)ethane-κ² P,P′]cyanidocopper(I)} methanol disolvate

Rong Wang ^a, Ye-Lan Xiao ^a, Qiong-Hua Jin ^a,^*, Cun-Lin Zhang ^b

PMCID: PMC3007356 PMID: 21588106

Abstract

The title centrosymmetric complex, [Cu₂(CN)₂(C₂₆H₂₄P₂)₃]·2CH₃OH, consists of two five-membered [Cu(dppe)CN] rings [dppe is 1,2-bis(diphenylphosphino)ethane] bridged by one μ₂-dppe ligand, and two methanol solvent molecules. The angles around the central metal atom indicate that each Cu^I atom is located in the center of a distorted tetrahedron. The coordination sphere of each Cu^I atom is formed by three P atoms from two dppe ligands, and one C atom from the cyanide ligand. The crystal structure is stabilized by O—H⋯N hydrogen bonds, which are formed by the O—H donor group from methanol and the N-atom acceptor from a cyanide ligand.

Related literature

For related structures, see: Jin et al. (2009 ▶); Effendy et al. (2006 ▶); Sivasankar et al. (2004 ▶); Di Nicola et al. (2006 ▶); Saravanabharathi et al. (2002 ▶). For general background to the photophysical properties of similar compounds, see: Cingolani et al. (2005 ▶); Song et al. (2007 ▶).

Experimental

Crystal data

[Cu₂(CN)₂(C₂₆H₂₄P₂)₃]·2CH₄O
M _r = 1438.38
Monoclinic,
a = 23.423 (2) Å
b = 17.7912 (16) Å
c = 17.6614 (18) Å
β = 92.194 (1)°
V = 7354.6 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.76 mm⁻¹
T = 298 K
0.44 × 0.40 × 0.25 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.732, T _max = 0.833
18242 measured reflections
6494 independent reflections
4140 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.149
S = 1.06
6494 reflections
425 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT-Plus (Bruker, 2007 ▶); data reduction: SAINT-Plus; 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 global, I. DOI: 10.1107/S1600536810029545/su2196sup1.cif

e-66-m1032-sup1.cif^{(30.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810029545/su2196Isup2.hkl

e-66-m1032-Isup2.hkl^{(317.9KB, 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
O1—H1⋯N1ⁱ	0.82	2.02	2.829 (11)	171

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the National Keystone Basic Research Program (973 Program – grant Nos. 2007CB310408 and 2006CB302901), the Funding Project for Academic Human Resources Development in Institutions of Higher Learning Under the Jurisdiction of the Beijing Municipality and the State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences.

supplementary crystallographic information

Comment

Copper(I) complexes containing the diphosphine ligands bis(diphenylphosphinoethane)(Dppe) are extensively studied because of their interesting structures and photophysical properties (Cingolani et al., 2005; Song et al., 2007). dppe is a very efficient bridging bidentate ligand and its chelating tendency is very suitable to lock the metal atom. As a part of the extension of our study on the systematic structural chemistry of copper(I) complexes with ligands containing phosphine and nitrogen atoms (Jin et al., 2009), we synthesized the new title complex, (1), in the presence of (NH₄)₂WS₄ and 1,10-phenanthroline.

The molecular structure of complex (1) is depicted in Fig. 1. It consists of two five-membered [Cu(dppe)CN] rings that are bridged by one µ₂-dppe ligand, and two methanol solvent molecules. The copper atom is four-coordinated by three P-atoms from two dppe ligands, and one C-atom from the cyanide ion. The Cu—P distances of 2.2832 (12) Å, 2.3041 (13) Å and 2.3291 (12) Å are longer than those in complex [Cu₂(dppe)₃(CN)₂].2(CH₃CN) (2), which vary from 2.2784 (4) to 2.3158 (4) Å (Effendy et al., 2006), but are almost equal to those in complex [Cu₂(dppe)₃(CN)₂] (3), which vary from 2.2808 (8) to 2.3276 (8) Å (Saravanabharathi et al., 2002). The Cu—C distance of 1.952 (6)Å in complex (1) is shorter than the same distance observed in complexes (2) and (3); 1.975 (2) Å and 1.964 (4) Å, respectively.

In (1) the P—Cu—C angles are in the range 107.59 (14) - 119.11 (14)°, and the P—Cu—P angles are in the range 89.03 (4) - 115.07 (5)°. This confirms the distored tetrahedral environment around the copper(I) atom. These values are very close to those observed for complex (3), where the P—Cu—C angles range from 107.05 (9) to 120.73 (9)°, and the P—Cu—P angles are in the range 89.22 (3) - 115.16 (3) °.

Though both (NH₄)₂WS₄ and 1,10-phenanthroline were starting materials in the prepartion of (1), they do not appear in the final product. This may be related to the solvent methanol because the O—H donor from methanol can form an O—H···N hydrogen bond with the N atom from the cyanide anion (Table 1), and this can stablize the molecular structure of the complex.

The crystal structure of complex (1) is similar with that of complex (2). Other similar complexes are adducts CuX:dppe:X, where X is a simple inorganic anion, for example, a halide (Effendy et al., 2006; Di Nicola et al., 2006), thiocyanate (Saravanabharathi et al., 2002), nitrate (Saravanabharathi et al., 2002), perchlorate (Sivasankar et al., 2004; Jin et al., 2009) and tetrafluoroborate (Jin et al., 2009).

Experimental

A mixture of CuCN, bis(diphenylphosphinoethane), (NH₄)₂WS₄ and 1,10-Phenanthroline, in the molar ratio of 3:3:1:1 in CH₂Cl₂ and MeOH (10 ml,V/V=1/1), was stirred for 4 h at RT, then filtered. Subsequent slow evaporation of the filtrate resulted in the formation of yellow crystals of complex (1). Crystals suitable for single-crystal X-ray diffraction were selected directly from the sample as prepared.