Tetra­kis(triphenyl­arsine)copper(I) hexa­fluoridophosphate

Kern, T.; Knör, G.; Zabel, M.; Monkowius, U.

doi:10.1107/S1600536807064458

metal-organic compounds

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Volume 64| Part 1| January 2008| Page m99

https://doi.org/10.1107/S1600536807064458

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Tetrakis(triphenylarsine)copper(I) hexafluoridophosphate

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

^aJohannes Kepler Universität Linz, Institut für Anorganische Chemie, Altenbergerstr. 69, 4040 Linz, Austria, and ^bUniversität Regensburg, Zentrale Analytik, Röntgenstrukturanalyse, Universitätsstr. 31, 93053 Regensburg, Germany
^*Correspondence e-mail: uwe.monkowius@jku.at

(Received 22 November 2007; accepted 29 November 2007; online 6 December 2007)

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 $[\overline{3}]$ . 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, $[R \overline 3]$
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[F² > 2σ(F²)] = 0.037
wR(F²) = 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

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)

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)
Symmetry codes: (i) -y+1, x-y, z; (ii) -y, x-y, z; (iii) -x, -y, -z; (iv) -x+y+2, -x+2, z; (v) $[x-y+{\script{2\over 3}}, x-{\script{2\over 3}}, -z+{\script{1\over 3}}]$ .

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.

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807064458/bt2651Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Structure description top

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

Computing details top

Data collection: IPDS Software (Stoe, 1998); cell refinement: IPDS Software (Stoe, 1998); data reduction: IPDS Software (Stoe, 1998); 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 (Spek, 2003).

Figures top

Fig. 1. : View of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.

Tetrakis(triphenylarsine)copper(I) hexafluoridophosphate top

Crystal data top

[Cu(C₁₈H₁₅As)₄]PF₆	Cell parameters were determined by indexing 8000 reflections with I/sigma limit 6.0.
M_r = 1433.40	D_x = 1.528 Mg m⁻³
Trigonal, R3	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -R 3	Cell parameters from 8000 reflections
a = 14.4025 (10) Å	θ = 2.4–25.9°
c = 52.015 (4) Å	µ = 2.55 mm⁻¹
V = 9344.1 (12) Å³	T = 296 K
Z = 6	Prism, light yellow, translucent
F(000) = 4332	0.14 × 0.12 × 0.10 mm

Data collection top

Stoe IPDS diffractometer	4049 independent reflections
Radiation source: fine-focus sealed tube	3118 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
rotation scans	θ_max = 25.9°, θ_min = 2.4°
Absorption correction: part of the refinement model (ΔF) refined from delta-F (Walker & Stuart, 1983)	h = −17→17
T_min = 0.349, T_max = 0.769	k = −17→17
23664 measured reflections	l = −63→61

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.P)²] where P = (F_o² + 2F_c²)/3
4049 reflections	(Δ/σ)_max = 0.001
254 parameters	Δρ_max = 1.77 e Å⁻³
0 restraints	Δρ_min = −0.62 e Å⁻³

Crystal data top

[Cu(C₁₈H₁₅As)₄]PF₆	Z = 6
M_r = 1433.40	Mo Kα radiation
Trigonal, R3	µ = 2.55 mm⁻¹
a = 14.4025 (10) Å	T = 296 K
c = 52.015 (4) Å	0.14 × 0.12 × 0.10 mm
V = 9344.1 (12) Å³

Data collection top

Stoe IPDS diffractometer	4049 independent reflections
Absorption correction: part of the refinement model (ΔF) refined from delta-F (Walker & Stuart, 1983)	3118 reflections with I > 2σ(I)
T_min = 0.349, T_max = 0.769	R_int = 0.032
23664 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.04	Δρ_max = 1.77 e Å⁻³
4049 reflections	Δρ_min = −0.62 e Å⁻³
254 parameters

Special details top

Experimental. Data were collected applying an imaging plate system (Stoe) with the following measurement parameters:

Detector distance [mm] 70 Phi movement mode Oscillation Phi incr. [degrees] 1.0 Number of exposures 192 Irradiation / exposure [min] 2.50

For a detailed description of the method see: Sheldrick, G.M., Paulus, E. Vertesy, L. & Hahn, F. (1995) Acta Cryst. B51, 89–98.

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
As1	0.47917 (3)	0.20088 (3)	0.06525 (1)	0.0440 (1)
As2	0.66667	0.33333	0.12958 (1)	0.0398 (1)
Cu1	0.66667	0.33333	0.08144 (1)	0.0466 (2)
C1	0.4361 (3)	0.0520 (3)	0.07350 (6)	0.0448 (10)
C2	0.5099 (3)	0.0188 (3)	0.06918 (8)	0.0610 (14)
C3	0.4877 (4)	−0.0818 (4)	0.07706 (10)	0.0771 (19)
C4	0.3929 (4)	−0.1499 (3)	0.08911 (9)	0.0730 (16)
C5	0.3189 (4)	−0.1186 (3)	0.09291 (9)	0.0699 (16)
C6	0.3402 (3)	−0.0175 (3)	0.08519 (7)	0.0564 (12)
C7	0.4540 (3)	0.1926 (3)	0.02816 (6)	0.0491 (11)
C8	0.3857 (4)	0.0974 (4)	0.01602 (8)	0.0779 (18)
C9	0.3650 (6)	0.0970 (5)	−0.00996 (10)	0.106 (3)
C10	0.4128 (6)	0.1912 (5)	−0.02384 (9)	0.096 (2)
C11	0.4819 (5)	0.2846 (5)	−0.01205 (9)	0.082 (2)
C12	0.5020 (3)	0.2858 (3)	0.01399 (7)	0.0604 (12)
C13	0.3514 (3)	0.2028 (3)	0.07735 (6)	0.0457 (10)
C14	0.2602 (3)	0.1674 (4)	0.06245 (8)	0.0648 (14)
C15	0.1694 (4)	0.1644 (4)	0.07263 (9)	0.0786 (19)
C16	0.1697 (4)	0.1970 (4)	0.09752 (9)	0.0730 (17)
C17	0.2590 (4)	0.2334 (4)	0.11206 (8)	0.0699 (16)
C18	0.3503 (3)	0.2367 (3)	0.10222 (7)	0.0584 (12)
C19	0.7988 (3)	0.4342 (3)	0.14716 (6)	0.0420 (10)
C20	0.8947 (3)	0.4451 (3)	0.13850 (7)	0.0541 (11)
C21	0.9898 (3)	0.5153 (3)	0.15034 (9)	0.0653 (16)
C22	0.9904 (4)	0.5749 (4)	0.17108 (9)	0.0732 (17)
C23	0.8955 (4)	0.5649 (4)	0.17971 (9)	0.0786 (17)
C24	0.7999 (3)	0.4955 (3)	0.16784 (7)	0.0620 (14)
P1	0.00000	0.00000	0.00000	0.0713 (7)
F1	0.0013 (5)	0.0885 (4)	0.01719 (9)	0.185 (3)
P2	1.33333	0.66667	0.16667	0.0504 (6)
F2	1.2304 (2)	0.6030 (3)	0.18418 (6)	0.0990 (11)
H2	0.57430	0.06430	0.06100	0.0730*
H3	0.53770	−0.10360	0.07420	0.0930*
H4	0.37920	−0.21700	0.09470	0.0880*
H5	0.25380	−0.16520	0.10070	0.0830*
H6	0.28950	0.00340	0.08790	0.0680*
H8	0.35360	0.03350	0.02530	0.0940*
H9	0.31860	0.03270	−0.01810	0.1270*
H10	0.39760	0.19070	−0.04120	0.1160*
H11	0.51590	0.34790	−0.02150	0.0990*
H12	0.54850	0.35030	0.02200	0.0730*
H14	0.25960	0.14560	0.04560	0.0780*
H15	0.10820	0.14010	0.06260	0.0940*
H16	0.10850	0.19410	0.10430	0.0870*
H17	0.25940	0.25630	0.12880	0.0840*
H18	0.41120	0.26190	0.11240	0.0700*
H20	0.89480	0.40460	0.12460	0.0650*
H21	1.05390	0.52250	0.14430	0.0780*
H22	1.05460	0.62170	0.17920	0.0880*
H23	0.89590	0.60540	0.19370	0.0950*
H24	0.73620	0.48980	0.17370	0.0740*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
As1	0.0427 (2)	0.0399 (2)	0.0462 (2)	0.0183 (2)	−0.0025 (1)	−0.0001 (1)
As2	0.0426 (2)	0.0426 (2)	0.0341 (3)	0.0213 (1)	0.0000	0.0000
Cu1	0.0483 (3)	0.0483 (3)	0.0431 (4)	0.0241 (1)	0.0000	0.0000
C1	0.0454 (19)	0.0368 (17)	0.0476 (17)	0.0171 (15)	−0.0056 (14)	−0.0021 (13)
C2	0.051 (2)	0.050 (2)	0.081 (3)	0.0245 (19)	0.0029 (19)	0.0043 (19)
C3	0.079 (3)	0.063 (3)	0.106 (4)	0.048 (3)	0.000 (3)	0.002 (2)
C4	0.087 (3)	0.043 (2)	0.087 (3)	0.031 (2)	−0.010 (2)	0.003 (2)
C5	0.064 (3)	0.047 (2)	0.083 (3)	0.016 (2)	0.012 (2)	0.012 (2)
C6	0.050 (2)	0.045 (2)	0.070 (2)	0.0205 (18)	0.0069 (17)	0.0076 (17)
C7	0.049 (2)	0.053 (2)	0.0471 (17)	0.0269 (17)	−0.0011 (14)	−0.0021 (15)
C8	0.102 (4)	0.061 (3)	0.055 (2)	0.029 (3)	−0.014 (2)	−0.0080 (19)
C9	0.148 (6)	0.099 (4)	0.065 (3)	0.058 (4)	−0.034 (3)	−0.032 (3)
C10	0.145 (5)	0.129 (5)	0.047 (2)	0.093 (5)	−0.008 (3)	−0.002 (3)
C11	0.110 (4)	0.099 (4)	0.061 (3)	0.070 (4)	0.017 (3)	0.024 (3)
C12	0.061 (2)	0.060 (2)	0.060 (2)	0.030 (2)	0.0038 (18)	0.0097 (18)
C13	0.0430 (18)	0.0395 (18)	0.0536 (18)	0.0199 (15)	−0.0032 (14)	0.0017 (14)
C14	0.059 (2)	0.080 (3)	0.061 (2)	0.039 (2)	−0.0094 (19)	−0.009 (2)
C15	0.056 (3)	0.105 (4)	0.085 (3)	0.048 (3)	−0.013 (2)	−0.004 (3)
C16	0.067 (3)	0.076 (3)	0.087 (3)	0.044 (3)	0.015 (2)	0.010 (2)
C17	0.079 (3)	0.071 (3)	0.063 (2)	0.040 (3)	0.011 (2)	−0.002 (2)
C18	0.055 (2)	0.058 (2)	0.058 (2)	0.025 (2)	−0.0021 (17)	−0.0078 (17)
C19	0.0421 (18)	0.0405 (17)	0.0400 (15)	0.0181 (15)	0.0002 (13)	0.0029 (13)
C20	0.054 (2)	0.058 (2)	0.0539 (19)	0.0306 (19)	−0.0005 (16)	−0.0032 (16)
C21	0.041 (2)	0.067 (3)	0.088 (3)	0.027 (2)	0.0015 (19)	0.005 (2)
C22	0.054 (3)	0.065 (3)	0.093 (3)	0.024 (2)	−0.020 (2)	−0.014 (2)
C23	0.067 (3)	0.080 (3)	0.081 (3)	0.031 (3)	−0.020 (2)	−0.039 (2)
C24	0.051 (2)	0.069 (3)	0.062 (2)	0.027 (2)	−0.0027 (17)	−0.0179 (19)
P1	0.0817 (12)	0.0817 (12)	0.0507 (13)	0.0409 (6)	0.0000	0.0000
F1	0.229 (6)	0.182 (5)	0.173 (4)	0.124 (5)	−0.008 (4)	−0.076 (4)
P2	0.0409 (7)	0.0409 (7)	0.0694 (14)	0.0205 (4)	0.0000	0.0000
F2	0.0655 (17)	0.101 (2)	0.117 (2)	0.0315 (17)	0.0315 (16)	0.0196 (18)

Geometric parameters (Å, º) top

As1—Cu1	2.5472 (5)	C13—C14	1.384 (6)
As1—C1	1.959 (4)	C13—C18	1.386 (5)
As1—C7	1.956 (3)	C14—C15	1.391 (8)
As1—C13	1.958 (5)	C15—C16	1.376 (7)
As2—Cu1	2.5044 (9)	C16—C17	1.352 (8)
As2—C19	1.950 (4)	C17—C18	1.390 (8)
As2—C19ⁱ	1.950 (5)	C19—C20	1.385 (7)
As2—C19ⁱⁱ	1.950 (4)	C19—C24	1.387 (5)
P1—F1ⁱⁱⁱ	1.549 (8)	C20—C21	1.376 (6)
P1—F1^iv	1.549 (5)	C21—C22	1.376 (7)
P1—F1^v	1.549 (7)	C22—C23	1.376 (9)
P1—F1^vi	1.549 (8)	C23—C24	1.378 (7)
P1—F1^vii	1.549 (7)	C2—H2	0.9300
P1—F1	1.549 (5)	C3—H3	0.9300
P2—F2^viii	1.584 (5)	C4—H4	0.9300
P2—F2	1.584 (3)	C5—H5	0.9300
P2—F2^ix	1.583 (5)	C6—H6	0.9300
P2—F2^x	1.585 (3)	C8—H8	0.9300
P2—F2^xi	1.584 (3)	C9—H9	0.9300
P2—F2^xii	1.584 (3)	C10—H10	0.9300
C1—C2	1.385 (7)	C11—H11	0.9300
C1—C6	1.377 (6)	C12—H12	0.9300
C2—C3	1.381 (6)	C14—H14	0.9300
C3—C4	1.371 (8)	C15—H15	0.9300
C4—C5	1.363 (8)	C16—H16	0.9300
C5—C6	1.389 (6)	C17—H17	0.9300
C7—C8	1.378 (6)	C18—H18	0.9300
C7—C12	1.377 (5)	C20—H20	0.9300
C8—C9	1.383 (7)	C21—H21	0.9300
C9—C10	1.379 (8)	C22—H22	0.9300
C10—C11	1.356 (9)	C23—H23	0.9300
C11—C12	1.383 (6)	C24—H24	0.9300

As1···H2ⁱⁱ	3.1700	C14···H9^vi	3.0700
Cu1···H2	3.5700	C19···H24ⁱⁱ	2.6000
Cu1···H12	3.6000	C19···H18ⁱⁱ	2.6700
Cu1···H18	3.6600	C20···H24ⁱⁱ	3.0000
Cu1···H20	3.6800	C20···H18ⁱⁱ	2.8000
Cu1···H2ⁱ	3.5700	C21···H22^x	2.9700
Cu1···H12ⁱ	3.6000	C24···H24ⁱⁱ	3.0700
Cu1···H18ⁱ	3.6600	H2···Cu1	3.5700
Cu1···H20ⁱ	3.6800	H2···C13ⁱ	2.9300
Cu1···H2ⁱⁱ	3.5700	H2···As1ⁱ	3.1700
Cu1···H12ⁱⁱ	3.6000	H3···H10^xiii	2.5600
Cu1···H18ⁱⁱ	3.6600	H4···H4^xiv	2.5300
Cu1···H20ⁱⁱ	3.6800	H4···H4^xv	2.5300
F2···C22	3.343 (7)	H6···C14	2.9200
F1···H14^vii	2.7500	H6···C13	2.6000
F1···H15	2.7100	H8···C1	2.7300
F2···H22	2.6900	H8···C11^v	3.0300
C6···C14	3.590 (7)	H9···C14^v	3.0700
C8···C14	3.455 (7)	H10···H3^xiii	2.5600
C14···C8	3.455 (7)	H12···Cu1	3.6000
C14···C6	3.590 (7)	H12···C12ⁱⁱ	3.0000
C18···C19ⁱ	3.574 (6)	H12···C7ⁱⁱ	2.8000
C18···C20ⁱ	3.551 (6)	H14···C7	2.6900
C19···C18ⁱⁱ	3.574 (5)	H14···C8	2.7200
C20···C24ⁱⁱ	3.590 (6)	H14···F1ⁱⁱⁱ	2.7500
C20···C18ⁱⁱ	3.551 (6)	H15···F1	2.7100
C22···F2	3.343 (7)	H18···C20ⁱ	2.8000
C24···C20ⁱ	3.590 (7)	H18···Cu1	3.6600
C1···H8	2.7300	H18···C19ⁱ	2.6700
C1···H20ⁱⁱ	2.8200	H20···C1ⁱ	2.8200
C6···H20ⁱⁱ	3.0000	H20···C6ⁱ	3.0000
C7···H12ⁱ	2.8000	H20···Cu1	3.6800
C7···H14	2.6900	H21···H22^x	2.3900
C8···H14	2.7200	H22···F2	2.6900
C11···H8^vi	3.0300	H22···C21^ix	2.9700
C12···H12ⁱ	3.0000	H22···H21^ix	2.3900
C13···H6	2.6000	H24···C20ⁱ	3.0000
C13···H2ⁱⁱ	2.9300	H24···C24ⁱ	3.0700
C14···H6	2.9200	H24···C19ⁱ	2.6000

Cu1—As1—C1	112.61 (13)	C8—C9—C10	120.5 (5)
Cu1—As1—C7	117.80 (13)	C9—C10—C11	119.8 (5)
Cu1—As1—C13	122.35 (11)	C10—C11—C12	120.0 (5)
C1—As1—C7	101.64 (15)	C7—C12—C11	120.8 (4)
C1—As1—C13	99.19 (17)	As1—C13—C18	118.8 (3)
C7—As1—C13	99.85 (17)	C14—C13—C18	118.5 (4)
Cu1—As2—C19	117.96 (10)	As1—C13—C14	122.7 (3)
Cu1—As2—C19ⁱ	117.96 (11)	C13—C14—C15	120.2 (4)
Cu1—As2—C19ⁱⁱ	117.96 (10)	C14—C15—C16	120.3 (5)
C19—As2—C19ⁱ	99.81 (18)	C15—C16—C17	119.9 (6)
C19—As2—C19ⁱⁱ	99.81 (18)	C16—C17—C18	120.5 (4)
C19ⁱ—As2—C19ⁱⁱ	99.8 (2)	C13—C18—C17	120.6 (4)
As1—Cu1—As2	109.30 (2)	As2—C19—C24	122.3 (4)
As1—Cu1—As1ⁱ	109.65 (2)	C20—C19—C24	119.1 (4)
As1—Cu1—As1ⁱⁱ	109.65 (2)	As2—C19—C20	118.6 (3)
As1ⁱ—Cu1—As2	109.30 (2)	C19—C20—C21	120.5 (4)
As1ⁱⁱ—Cu1—As2	109.30 (2)	C20—C21—C22	120.2 (5)
As1ⁱ—Cu1—As1ⁱⁱ	109.65 (2)	C21—C22—C23	119.6 (5)
F1^vii—P1—F1^iv	90.0 (3)	C22—C23—C24	120.6 (4)
F1^vii—P1—F1^v	180.00	C19—C24—C23	119.9 (5)
F1^vii—P1—F1^vi	90.0 (3)	C1—C2—H2	120.00
F1ⁱⁱⁱ—P1—F1^iv	90.0 (3)	C3—C2—H2	120.00
F1ⁱⁱⁱ—P1—F1^v	90.0 (3)	C4—C3—H3	120.00
F1ⁱⁱⁱ—P1—F1^vi	180.00	C2—C3—H3	120.00
F1^iv—P1—F1^v	90.0 (3)	C3—C4—H4	120.00
F1^iv—P1—F1^vi	90.0 (3)	C5—C4—H4	120.00
F1^v—P1—F1^vi	90.0 (3)	C4—C5—H5	120.00
F1—P1—F1^vii	90.0 (3)	C6—C5—H5	120.00
F1—P1—F1ⁱⁱⁱ	90.0 (3)	C1—C6—H6	120.00
F1—P1—F1^iv	180.00	C5—C6—H6	120.00
F1—P1—F1^v	90.0 (3)	C9—C8—H8	120.00
F1—P1—F1^vi	90.0 (3)	C7—C8—H8	120.00
F1^vii—P1—F1ⁱⁱⁱ	90.0 (3)	C8—C9—H9	120.00
F2^viii—P2—F2^ix	180.00	C10—C9—H9	120.00
F2^viii—P2—F2^x	89.8 (2)	C11—C10—H10	120.00
F2^xi—P2—F2^xii	89.8 (2)	C9—C10—H10	120.00
F2^xi—P2—F2^ix	89.8 (2)	C10—C11—H11	120.00
F2^xi—P2—F2^x	180.00	C12—C11—H11	120.00
F2^xii—P2—F2^ix	90.2 (2)	C7—C12—H12	120.00
F2^xii—P2—F2^x	90.2 (2)	C11—C12—H12	120.00
F2^ix—P2—F2^x	90.2 (2)	C15—C14—H14	120.00
F2^viii—P2—F2^xii	89.8 (2)	C13—C14—H14	120.00
F2—P2—F2^viii	90.2 (2)	C16—C15—H15	120.00
F2—P2—F2^xi	90.2 (2)	C14—C15—H15	120.00
F2—P2—F2^xii	180.00	C15—C16—H16	120.00
F2—P2—F2^ix	89.8 (2)	C17—C16—H16	120.00
F2—P2—F2^x	89.8 (2)	C16—C17—H17	120.00
F2^viii—P2—F2^xi	90.2 (2)	C18—C17—H17	120.00
C2—C1—C6	119.0 (4)	C17—C18—H18	120.00
As1—C1—C2	117.7 (3)	C13—C18—H18	120.00
As1—C1—C6	123.1 (3)	C19—C20—H20	120.00
C1—C2—C3	120.0 (4)	C21—C20—H20	120.00
C2—C3—C4	120.8 (5)	C22—C21—H21	120.00
C3—C4—C5	119.6 (4)	C20—C21—H21	120.00
C4—C5—C6	120.4 (4)	C21—C22—H22	120.00
C1—C6—C5	120.3 (5)	C23—C22—H22	120.00
As1—C7—C8	122.1 (3)	C24—C23—H23	120.00
C8—C7—C12	119.1 (3)	C22—C23—H23	120.00
As1—C7—C12	118.8 (3)	C23—C24—H24	120.00
C7—C8—C9	119.8 (5)	C19—C24—H24	120.00

C1—As1—Cu1—As2	−66.60 (12)	Cu1—As2—C19—C24	134.7 (3)
C7—As1—Cu1—As2	175.59 (14)	C19ⁱ—As2—C19—C24	5.6 (3)
C13—As1—Cu1—As2	51.33 (12)	C19ⁱⁱ—As2—C19—C24	−96.2 (3)
C1—As1—Cu1—As1ⁱ	53.18 (12)	As1—C1—C2—C3	173.5 (3)
C7—As1—Cu1—As1ⁱ	−64.63 (15)	As1—C1—C6—C5	−173.4 (3)
C13—As1—Cu1—As1ⁱ	171.12 (12)	C2—C1—C6—C5	1.1 (6)
C1—As1—Cu1—As1ⁱⁱ	173.61 (12)	C6—C1—C2—C3	−1.4 (6)
C7—As1—Cu1—As1ⁱⁱ	55.80 (15)	C1—C2—C3—C4	0.2 (7)
C13—As1—Cu1—As1ⁱⁱ	−68.45 (13)	C2—C3—C4—C5	1.3 (7)
C13—As1—C1—C2	−176.1 (3)	C3—C4—C5—C6	−1.5 (7)
Cu1—As1—C1—C6	129.4 (3)	C4—C5—C6—C1	0.3 (6)
Cu1—As1—C13—C14	151.9 (3)	C12—C7—C8—C9	−1.1 (9)
C1—As1—C13—C14	−83.8 (4)	As1—C7—C8—C9	175.6 (6)
C7—As1—C13—C14	19.8 (4)	C8—C7—C12—C11	0.3 (8)
Cu1—As1—C1—C2	−45.2 (3)	As1—C7—C12—C11	−176.5 (5)
C7—As1—C1—C2	81.8 (3)	C7—C8—C9—C10	0.4 (12)
C13—As1—C7—C8	−80.5 (5)	C8—C9—C10—C11	1.1 (13)
Cu1—As1—C7—C12	−38.7 (4)	C9—C10—C11—C12	−1.8 (13)
C7—As1—C1—C6	−103.6 (3)	C10—C11—C12—C7	1.2 (10)
C13—As1—C1—C6	−1.5 (3)	As1—C13—C14—C15	176.0 (4)
C13—As1—C7—C12	96.2 (4)	C14—C13—C18—C17	1.1 (6)
Cu1—As1—C7—C8	144.6 (4)	C18—C13—C14—C15	−1.2 (7)
C1—As1—C7—C8	21.1 (5)	As1—C13—C18—C17	−176.2 (3)
C1—As1—C13—C18	93.4 (3)	C13—C14—C15—C16	0.3 (7)
Cu1—As1—C13—C18	−30.9 (3)	C14—C15—C16—C17	0.8 (8)
C1—As1—C7—C12	−162.2 (4)	C15—C16—C17—C18	−1.0 (7)
C7—As1—C13—C18	−163.0 (3)	C16—C17—C18—C13	0.0 (7)
C19ⁱⁱ—As2—C19—C20	84.2 (3)	As2—C19—C20—C21	−180.0 (3)
C19ⁱⁱ—As2—Cu1—As1	63.5 (2)	C24—C19—C20—C21	0.4 (6)
C19—As2—Cu1—As1	−176.49 (15)	As2—C19—C24—C23	179.4 (3)
C19—As2—Cu1—As1ⁱⁱ	−56.49 (15)	C20—C19—C24—C23	−1.0 (6)
C19ⁱ—As2—Cu1—As1	−56.49 (17)	C19—C20—C21—C22	0.5 (6)
C19—As2—Cu1—As1ⁱ	63.51 (15)	C20—C21—C22—C23	−0.8 (7)
Cu1—As2—C19—C20	−44.9 (3)	C21—C22—C23—C24	0.2 (7)
C19ⁱ—As2—C19—C20	−174.0 (3)	C22—C23—C24—C19	0.7 (7)

Symmetry codes: (i) −y+1, x−y, z; (ii) −x+y+1, −x+1, z; (iii) −x+y, −x, z; (iv) −x, −y, −z; (v) y, −x+y, −z; (vi) x−y, x, −z; (vii) −y, x−y, z; (viii) −y+2, x−y, z; (ix) y+2/3, −x+y+4/3, −z+1/3; (x) x−y+2/3, x−2/3, −z+1/3; (xi) −x+y+2, −x+2, z; (xii) −x+8/3, −y+4/3, −z+1/3; (xiii) −x+1, −y, −z; (xiv) −y, x−y−1, z; (xv) −x+y+1, −x, z.

Experimental details

Crystal data
Chemical formula	[Cu(C₁₈H₁₅As)₄]PF₆
M_r	1433.40
Crystal system, space group	Trigonal, R3
Temperature (K)	296
a, c (Å)	14.4025 (10), 52.015 (4)
V (Å³)	9344.1 (12)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	2.55
Crystal size (mm)	0.14 × 0.12 × 0.10

Data collection
Diffractometer	Stoe IPDS diffractometer
Absorption correction	Part of the refinement model (ΔF) refined from delta-F (Walker & Stuart, 1983)
T_min, T_max	0.349, 0.769
No. of measured, independent and observed [I > 2σ(I)] reflections	23664, 4049, 3118
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.614

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.097, 1.04
No. of reflections	4049
No. of parameters	254
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.77, −0.62

Computer programs: IPDS Software (Stoe, 1998), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003).

Selected geometric parameters (Å, º) top

As1—Cu1	2.5472 (5)	As2—Cu1	2.5044 (9)
As1—C1	1.959 (4)	As2—C19	1.950 (4)
As1—C7	1.956 (3)	P1—F1	1.549 (5)
As1—C13	1.958 (5)	P2—F2	1.584 (3)

Cu1—As1—C1	112.61 (13)	As1—Cu1—As1ⁱ	109.65 (2)
Cu1—As1—C7	117.80 (13)	F1ⁱⁱ—P1—F1ⁱⁱⁱ	90.0 (3)
Cu1—As1—C13	122.35 (11)	F2^iv—P2—F2^v	180.00
C1—As1—C7	101.64 (15)	As1—C1—C2	117.7 (3)
C1—As1—C13	99.19 (17)	As1—C7—C8	122.1 (3)
C7—As1—C13	99.85 (17)	As1—C13—C18	118.8 (3)
Cu1—As2—C19	117.96 (10)	As2—C19—C24	122.3 (4)
C19—As2—C19ⁱ	99.81 (18)	As2—C19—C20	118.6 (3)
As1—Cu1—As2	109.30 (2)

Symmetry codes: (i) −y+1, x−y, z; (ii) −y, x−y, z; (iii) −x, −y, −z; (iv) −x+y+2, −x+2, z; (v) x−y+2/3, x−2/3, −z+1/3.

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bowmaker, G. A., Healy, P. C., Engelhardt, L. M., Kildea, J. D., Skelton, B. W. & White, A. H. (1990). Aust. J. Chem. 43, 1697–1705. CSD CrossRef CAS Web of Science Google Scholar
Engelhardt, L. M., Pakawatchai, C., White, A. H. & Healy, P. C. (1985). J. Chem. Soc. Dalton Trans. pp. 125–133. CSD CrossRef Web of Science Google Scholar
Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe (1998). IPDS Software. Version 2.89. Stoe & Cie GmbH, Darmstadt, Germany. Google Scholar
Walker, N. & Stuart, D. (1983). Acta Cryst. A39, 158–166. CrossRef CAS Web of Science IUCr Journals Google Scholar