Tetra­kis(triphenyl­arsine)copper(I) hexa­fluoridophosphate

Thomas Kern; Günther Knör; Manfred Zabel; Uwe Monkowius

doi:10.1107/S1600536807064458

. 2007 Dec 6;64(Pt 1):m99. doi: 10.1107/S1600536807064458

Tetrakis(triphenylarsine)copper(I) hexafluoridophosphate

Thomas Kern ^a, Günther Knör ^a, Manfred Zabel ^b, Uwe Monkowius ^a,^*

PMCID: PMC2914971 PMID: 21200664

Abstract

In the crystal structure of the title compound, [Cu(C₁₈H₁₅As)₄]PF₆, the Cu atom is coordinated by four As atoms of triphenylarsine ligands in a tetrahedral geometry. The complex cation is located on a crystallographic threefold axis. Both PF₆ ⁻ anions are located on special positions of site symmetry Inline graphic . The Cu—As bond of the independent arsine ligand is shorter than the Cu—As bonds of the three symmetry-related arsine ligands.

Related literature

For related literature, see: Bowmaker et al. (1990 ▶); Engelhardt et al. (1985 ▶).

Experimental

Crystal data

[Cu(C₁₈H₁₅As)₄]PF₆
M _r = 1433.40
Trigonal,
a = 14.4025 (10) Å
c = 52.015 (4) Å
V = 9344.1 (12) Å³
Z = 6
Mo Kα radiation
μ = 2.55 mm⁻¹
T = 296 K
0.14 × 0.12 × 0.10 mm

Data collection

Stoe IPDS diffractometer
Absorption correction: refined from ΔF (Walker & Stuart, 1983 ▶) T _min = 0.349, T _max = 0.769
23664 measured reflections
4049 independent reflections
3118 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.097
S = 1.04
4049 reflections
254 parameters
H-atom parameters constrained
Δρ_max = 1.77 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Data collection: IPDS Software (Stoe, 1998 ▶); cell refinement: IPDS Software; data reduction: IPDS Software; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807064458/bt2651sup1.cif

e-64-00m99-sup1.cif^{(27.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807064458/bt2651Isup2.hkl

e-64-00m99-Isup2.hkl^{(198.8KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

As1—Cu1	2.5472 (5)
As1—C1	1.959 (4)
As1—C7	1.956 (3)
As1—C13	1.958 (5)
As2—Cu1	2.5044 (9)
As2—C19	1.950 (4)

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Cu1—As1—C1	112.61 (13)
Cu1—As1—C7	117.80 (13)
Cu1—As1—C13	122.35 (11)
C1—As1—C7	101.64 (15)
C1—As1—C13	99.19 (17)
C7—As1—C13	99.85 (17)
Cu1—As2—C19	117.96 (10)
C19—As2—C19ⁱ	99.81 (18)
As1—Cu1—As2	109.30 (2)
As1—Cu1—As1ⁱ	109.65 (2)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

supplementary crystallographic information

Comment

Crystals of the title compound were obtained as a side-product in the preparation of [(Ph-BIAN)Cu(I)(Ph₃As)₂][PF₆] (Ph-BIAN = Bis(phenyl-imino)acenaphthene) in methylene chloride solution. To identify this compound a single-crystal structure analysis was performed.

The title compound contains [(Ph₃As)₄Cu]⁺ ions which are disposed about crystallographic threefold axes, the metal atom lying on a special position of symmetry 3 is coordinated by two independent ligands. One of it is totally independent, whereas the other three are symmetry-related completing the nearly regular tetrahedral environment of the copper atom. The bond angles are 109.30 (2) and 109.65 (2) ° for As1—Cu1—As2 and As1—Cu1—As1', respectively. Two independent phosphorus and fluorine atoms are found. The Cu—As2 bond of the independent (axial) arsine ligand is significantly shorter than the value for the off-axis Cu—As1 bonds (2.5044 (9) versus 2.5472 (5) Å). A similar distortion was previously found for the analogous salts [(Ph₃P)₄Cu]⁺ (with ClO₄^- or PF₆^- as anions), which also crystallize in the same space group (Bowmaker et al., 1990, Engelhardt et al., 1985).

Experimental

The title compound was isolated as a side-product in the preparation of [(Ph-BIAN)Cu(I)(Ph₃As)₂][PF₆] (Ph-BIAN = Bis(phenyl-imino)acenaphthene). [Cu(NCMe)₄]PF₆ (50 mg, 0.13 mmol) and Ph₃As (93 mg, 0.30 mmol) was stirred in methylene chloride (10 ml) for 2 h. Ph-BIAN (51 mg, 0.15 mmol) was added and stirring was continued for another 2 h. The product was precipitated with pentane. Slow diffusion of diethyl ether into a methylene chloride solution of the product mixture yielded a dark powder and the title compound as colourless crystals. To identify the colourless crystals a single-crystal analysis was performed.