[μ-Butane-1,4-diylbis(di­phenyl­phos­phane)-κ2 P:P′]bis­{[butane-1,4-diylbis(di­phenyl­phosphane)-κ2 P,P′]copper(I)} bis­(hexa­fluorido­phosphate) diethyl ether disolvate

Michihiro Nishikawa; Asumi Akiyama; Taro Tsubomura

doi:10.1107/S1600536814009763

. 2014 May 10;70(Pt 6):m204–m205. doi: 10.1107/S1600536814009763

[μ-Butane-1,4-diylbis(diphenylphosphane)-κ² P:P′]bis{[butane-1,4-diylbis(diphenylphosphane)-κ² P,P′]copper(I)} bis(hexafluoridophosphate) diethyl ether disolvate

Michihiro Nishikawa ^a, Asumi Akiyama ^a, Taro Tsubomura ^a,^*

PMCID: PMC4051095 PMID: 24940196

Abstract

In the centrosymmetric dinuclear copper(I) complex cation of the title compound, [Cu₂(C₂₈H₂₈P₂)₃](PF₆)₂·2C₄H₁₀O, the Cu^I atom is bonded to three P atoms of two butane-1,4-diylbis(diphenylphosphane) (dppb) ligands with a triangular coordination geometry. One of these P atoms belongs to a bridging dppb ligand [Cu—P = 2.2381 (5) Å] and two belong to a chelating dppb ligand [Cu—P = 2.2450 (6) and 2.2628 (5) Å]. The bridging dppb ligand lies on an inversion centre. In the crystal, the cation and the PF₆ ⁻ anion are linked by C—H⋯F interactions, forming a tape along [110]. The cation and the diethyl ether solvent molecule are also linked by a C—H⋯O interaction.

Related literature

For general background to emissive copper(I) complexes, see: McMillin & McNett (1998 ▶). For copper(I) complexes bearing dppb ligands, see: Comba et al. (1999 ▶); Kitagawa et al. (1995 ▶). For our previous work related to the photophysical properties of copper(I) complexes bearing dppb and diimine ligands, see: Saito et al. (2006 ▶).

Experimental

Crystal data

[Cu₂(C₂₈H₂₈P₂)₃](PF₆)₂·2C₄H₁₀O
M _r = 1844.61
Triclinic,
a = 12.7912 (13) Å
b = 13.7023 (16) Å
c = 14.3811 (13) Å
α = 105.595 (3)°
β = 90.858 (2)°
γ = 111.932 (3)°
V = 2233.2 (4) Å³
Z = 1
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 123 K
0.5 × 0.5 × 0.4 mm

Data collection

Rigaku Saturn70 CCD diffractometer
Absorption correction: multi-scan (REQAB; Rigaku, 1998 ▶) T _min = 0.687, T _max = 0.758
20774 measured reflections
9436 independent reflections
8266 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.090
S = 1.06
9436 reflections
523 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: CrystalClear (Rigaku, 2000 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814009763/is5355sup1.cif

e-70-0m204-sup1.cif^{(49.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814009763/is5355Isup2.hkl

e-70-0m204-Isup2.hkl^{(452.2KB, hkl)}

CCDC reference: 1000315

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C016—H016⋯F006	0.95	2.47	3.318 (3)	149
C018—H018⋯F008ⁱ	0.95	2.53	3.286 (3)	137
C043—H04C⋯F006	0.99	2.45	3.345 (3)	150
C043—H04C⋯F009	0.99	2.53	3.458 (3)	156
C049—H049⋯O012ⁱⁱ	0.95	2.46	3.393 (3)	169

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

Acknowledgments

This work was partially supported by a grant from Seikei University.

supplementary crystallographic information

1. Comment

Copper(I) complexes bearing diphosphane ligands are of much interest for luminescence devices (McMillin & McNett, 1998) and catalysts. The spectroscopic study for the coordination compounds of copper(I) ion and 1,4-bis(diphenylphosphino)butane(dppb) ligand has been reported (Comba et al., 1999). The crystal structure of a copper(I) complex bearing dppb, such as [Cu₂(dppb)₂(ClO₄)₂] where two copper atoms are bridged by two dppb unit, has been reported (Kitagawa et al., 1995). We have reported the crystal structure of an emissive dinuclear copper(I) complex bearing dppb and diimine ligands (Saito et al., 2006), in which the copper atoms are also bridged by two dppb ligands.

We describe herein the structure of a dinuclear copper(I) complex cation bearing two types of dppb ligands; one is a bridging ligand which connects two copper atoms using two phosphorus atoms, and the other is the chelating ligand which binds one copper atom using two phosphorus atoms. In other words, two copper atoms in the complex are bridged by one dppb ligand. The centre of inversion lies on the bridging dppb ligand. The asymmetric unit consists of a half of the complex cation, a PF₆ anion and a diethylether solvent molecule (Fig. 1). Each copper atom is connected by three phosphorus atoms with a triangle coordination geometry. The bond length between copper and phosphorus atom of the bridging dppb ligand is Cu—P = 2.2381 (5) Å, and those between copper and phosphorus atoms of the chelating ligands are Cu—P = 2.2450 (6) and 2.2628 (5) Å. This finding is useful for strategy for creation of characteristic dinuclear copper(I) complexes which exhibit unique properties.

2. Experimental

Under an argon atmosphere, [Cu(MeCN)₄]PF₆ (75 mg, 0.20 mmol) was added to dppb (82 mg, 0.30 mmol) in a 5 mL dichloromethane. The reaction mixture was stirred for 30 min at room temperature. Diethyl ether was added to the solution to precipitate the product as a white solid, which was filtered and washed with diethyl ether: yield, 126 mg (0.162 mmol, 81%). Elemental Analysis Calcd. for C₈₄H₈₄F₁₂P₈Cu₂: C 59.47, H 4.99, found C 58.58, H 4.92. Single crystals suitable for X-ray diffraction were obtained by slow diffusion of diethylether in a dichloromethane solution of the complex.