Tetraphenyl-arsonium cis-bis-[1,2-bis-(tri-fluoro-meth-yl)ethene-1,2-dithiol-ato]platinate(II).

In the title compound, (C(24)H(20)As)[Pt(C(4)F(6)S(2))(2)], the cation lies on a twofold rotation axis while the anion has crystallographic inversion symmetry. The Pt(II) ion is in a slightly distorted square-planar coordination environment. The F atoms of both unique -CF(3) groups are disordered over two sets of sites, the ratios of refined occupancies being 0.677 (15):0.323 (15) and 0.640 (16):0.360 (16). The crystal structure is the first to date of a monoanionic [Pt(tfd)(2)](-) species [tfd is 1,2-bis-(trifluoro-meth-yl)ethene-1,2-dithiol-ate] with a non-redox-active cation.

Related literature

For background information, see: Ray et al. (2005 ▶); Wang & Stiefel (2001 ▶); Harrison et al. (2006 ▶). For related crystal structures, see: Kogut et al. (2006 ▶); Tang et al. (2009 ▶); Kasper & Inter­rante (1976 ▶); Lim et al. (2001 ▶). For synthetic details, see: Davison et al. (1964 ▶). For the treatment of disordered solvent of crystallization, see: Spek (2009 ▶); Stähler et al. (2001 ▶); Cox et al. (2003 ▶); Mohamed et al. (2003 ▶); Athimoolam et al. (2005 ▶). For a detailed description of the electronic structure of metal–dithiol­ene complexes, see: Kirk et al. (2004 ▶).

Experimental

Crystal data

(C24H20As)[Pt(C4F6S2)2]

M = 1030.76

Monoclinic,

a = 24.9649 (10) Å

b = 7.3189 (3) Å

c = 23.6773 (6) Å

β = 117.779 (2)°

V = 3827.6 (2) Å3

Z = 4

Mo Kα radiation

μ = 4.82 mm−1

T = 150 K

0.24 × 0.21 × 0.16 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T min = 0.341, T max = 0.471

13097 measured reflections

4282 independent reflections

3269 reflections with I > 2σ(I)

R int = 0.051

Refinement

R[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.156

S = 1.09

4282 reflections

230 parameters

60 restraints

H-atom parameters constrained

Δρmax = 4.18 e Å−3

Δρmin = −2.83 e Å−3

Data collection: COLLECT (Nonius, 2002 ▶); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997 ▶); data reduction: DENZO–SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809021527/su2119sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809021527/su2119Isup2.hkl

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

(C24H20As)[Pt(C4F6S2)2]	F(000) = 1980
Mr = 1030.76	Dx = 1.789 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 13097 reflections
a = 24.9649 (10) Å	θ = 2.9–27.5°
b = 7.3189 (3) Å	µ = 4.82 mm−1
c = 23.6773 (6) Å	T = 150 K
β = 117.779 (2)°	Block, orange
V = 3827.6 (2) Å3	0.24 × 0.21 × 0.16 mm
Z = 4

Nonius KappaCCD diffractometer	4282 independent reflections
Radiation source: fine-focus sealed tube	3269 reflections with I > 2σ(I)
graphite	Rint = 0.051
Detector resolution: 9 pixels mm-1	θmax = 27.5°, θmin = 2.9°
φ scans and ω scans with κ offsets	h = −32→25
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −8→9
Tmin = 0.341, Tmax = 0.471	l = −25→30
13097 measured reflections

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.156	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0976P)2 + 3.8529P] where P = (Fo2 + 2Fc2)/3
4282 reflections	(Δ/σ)max < 0.001
230 parameters	Δρmax = 4.18 e Å−3
60 restraints	Δρmin = −2.83 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pt1	0.2500	0.2500	0.5000	0.02912 (17)
S1	0.22659 (8)	0.5216 (3)	0.44973 (9)	0.0371 (4)
S2	0.30913 (9)	0.1915 (3)	0.45362 (10)	0.0408 (5)
F1	0.2074 (3)	0.7827 (10)	0.3529 (5)	0.061 (2)	0.676 (15)
F2	0.3033 (3)	0.8005 (11)	0.3897 (5)	0.061 (2)	0.676 (15)
F3	0.2523 (3)	0.6463 (10)	0.3070 (3)	0.061 (2)	0.676 (15)
F1A	0.2129 (6)	0.680 (3)	0.3037 (4)	0.078 (7)*	0.324 (15)
F2A	0.2298 (8)	0.795 (2)	0.3910 (9)	0.071 (6)*	0.324 (15)
F3A	0.2988 (6)	0.796 (2)	0.3648 (8)	0.061 (6)*	0.324 (15)
F4	0.3847 (4)	0.2453 (10)	0.3995 (4)	0.062 (2)	0.638 (16)
F5	0.3645 (4)	0.5234 (10)	0.3690 (4)	0.062 (2)	0.638 (16)
F6	0.3084 (3)	0.3029 (13)	0.3109 (3)	0.062 (2)	0.638 (16)
F6A	0.2985 (6)	0.440 (3)	0.3141 (6)	0.092 (7)*	0.362 (16)
F4A	0.3588 (9)	0.212 (2)	0.3578 (12)	0.137 (12)*	0.362 (16)
F5A	0.3837 (5)	0.4871 (18)	0.3956 (7)	0.068 (6)*	0.362 (16)
C1	0.2649 (3)	0.5226 (11)	0.4045 (3)	0.0394 (17)
C2	0.3007 (4)	0.3803 (12)	0.4073 (4)	0.0438 (19)
C3	0.2566 (3)	0.6806 (13)	0.3656 (3)	0.059 (2)
C4	0.3370 (3)	0.3656 (8)	0.3723 (3)	0.059 (2)
As1	0.0000	0.61646 (13)	0.2500	0.0248 (2)
C11	0.0654 (3)	0.4612 (9)	0.2596 (3)	0.0261 (13)
C12	0.0908 (3)	0.4759 (10)	0.2191 (3)	0.0367 (16)
H12A	0.0767	0.5658	0.1864	0.044*
C13	0.1372 (3)	0.3578 (12)	0.2266 (4)	0.0415 (19)
H13A	0.1550	0.3674	0.1989	0.050*
C14	0.1573 (4)	0.2281 (10)	0.2733 (5)	0.041 (2)
H14A	0.1892	0.1483	0.2781	0.049*
C15	0.1313 (4)	0.2115 (11)	0.3144 (4)	0.0393 (19)
H15A	0.1455	0.1211	0.3469	0.047*
C16	0.0849 (3)	0.3278 (11)	0.3071 (3)	0.0348 (16)
H16A	0.0665	0.3170	0.3341	0.042*
C21	−0.0245 (3)	0.7717 (8)	0.1779 (3)	0.0254 (14)
C22	0.0166 (3)	0.9043 (10)	0.1792 (3)	0.0302 (15)
H22A	0.0563	0.9104	0.2141	0.036*
C23	−0.0014 (3)	1.0262 (10)	0.1288 (3)	0.0354 (16)
H23A	0.0260	1.1159	0.1286	0.042*
C24	−0.0600 (4)	1.0162 (11)	0.0784 (4)	0.0425 (18)
H24A	−0.0722	1.0999	0.0439	0.051*
C25	−0.1002 (3)	0.8881 (12)	0.0776 (3)	0.0426 (19)
H25A	−0.1401	0.8838	0.0430	0.051*
C26	−0.0826 (3)	0.7638 (9)	0.1277 (4)	0.0333 (17)
H26A	−0.1103	0.6744	0.1274	0.040*

	U11	U22	U33	U12	U13	U23
Pt1	0.0227 (2)	0.0289 (2)	0.0304 (2)	0.00284 (14)	0.00796 (18)	−0.00095 (14)
S1	0.0276 (9)	0.0297 (10)	0.0446 (10)	0.0037 (7)	0.0090 (8)	0.0038 (8)
S2	0.0384 (11)	0.0366 (10)	0.0520 (12)	0.0004 (9)	0.0248 (9)	−0.0049 (9)
F1	0.053 (3)	0.061 (3)	0.075 (4)	0.007 (2)	0.035 (3)	0.029 (3)
F2	0.053 (3)	0.061 (3)	0.075 (4)	0.007 (2)	0.035 (3)	0.029 (3)
F3	0.053 (3)	0.061 (3)	0.075 (4)	0.007 (2)	0.035 (3)	0.029 (3)
F4	0.056 (4)	0.080 (5)	0.066 (4)	0.015 (3)	0.042 (3)	0.001 (3)
F5	0.056 (4)	0.080 (5)	0.066 (4)	0.015 (3)	0.042 (3)	0.001 (3)
F6	0.056 (4)	0.080 (5)	0.066 (4)	0.015 (3)	0.042 (3)	0.001 (3)
C1	0.034 (4)	0.036 (4)	0.037 (4)	−0.014 (3)	0.007 (3)	−0.001 (3)
C2	0.047 (4)	0.040 (5)	0.045 (4)	−0.019 (4)	0.021 (4)	−0.014 (4)
C3	0.056 (6)	0.062 (6)	0.056 (6)	−0.021 (5)	0.023 (5)	0.001 (5)
C4	0.073 (7)	0.055 (6)	0.056 (5)	−0.009 (5)	0.036 (5)	−0.009 (4)
As1	0.0215 (5)	0.0261 (5)	0.0256 (5)	0.000	0.0099 (4)	0.000
C11	0.020 (3)	0.026 (3)	0.031 (3)	−0.001 (3)	0.010 (3)	−0.010 (3)
C12	0.042 (4)	0.036 (4)	0.036 (4)	0.009 (3)	0.021 (3)	0.003 (3)
C13	0.035 (4)	0.055 (6)	0.042 (4)	0.008 (4)	0.025 (3)	0.002 (4)
C14	0.028 (4)	0.032 (5)	0.061 (6)	0.006 (3)	0.018 (4)	−0.010 (3)
C15	0.028 (4)	0.038 (4)	0.037 (4)	0.002 (3)	0.002 (3)	0.002 (3)
C16	0.031 (4)	0.034 (4)	0.041 (4)	0.004 (3)	0.018 (3)	0.005 (3)
C21	0.020 (3)	0.028 (4)	0.027 (3)	0.000 (2)	0.010 (3)	−0.002 (2)
C22	0.026 (3)	0.033 (4)	0.027 (3)	−0.004 (3)	0.009 (3)	0.002 (3)
C23	0.035 (4)	0.030 (4)	0.040 (4)	−0.001 (3)	0.016 (3)	0.011 (3)
C24	0.054 (5)	0.039 (5)	0.037 (4)	0.007 (4)	0.023 (4)	0.009 (3)
C25	0.031 (4)	0.054 (5)	0.031 (4)	0.008 (4)	0.004 (3)	0.009 (4)
C26	0.019 (3)	0.043 (5)	0.034 (4)	0.003 (3)	0.009 (3)	0.005 (3)

Pt1—S1i	2.2496 (18)	As1—C11	1.913 (6)
Pt1—S1	2.2496 (19)	C11—C12	1.378 (9)
Pt1—S2i	2.254 (2)	C11—C16	1.394 (10)
Pt1—S2	2.254 (2)	C12—C13	1.390 (10)
S1—C1	1.737 (8)	C12—H12A	0.9500
S2—C2	1.715 (9)	C13—C14	1.364 (12)
F1—C3	1.346 (7)	C13—H13A	0.9500
F2—C3	1.355 (6)	C14—C15	1.402 (13)
F3—C3	1.365 (6)	C14—H14A	0.9500
F1A—C3	1.360 (7)	C15—C16	1.382 (11)
F2A—C3	1.372 (7)	C15—H15A	0.9500
F3A—C3	1.359 (7)	C16—H16A	0.9500
F4—C4	1.376 (6)	C21—C26	1.382 (10)
F5—C4	1.365 (6)	C21—C22	1.403 (9)
F6—C4	1.366 (6)	C22—C23	1.386 (10)
F6A—C4	1.371 (6)	C22—H22A	0.9500
F4A—C4	1.360 (6)	C23—C24	1.394 (11)
F5A—C4	1.362 (6)	C23—H23A	0.9500
C1—C2	1.353 (12)	C24—C25	1.368 (11)
C1—C3	1.432 (13)	C24—H24A	0.9500
C2—C4	1.489 (12)	C25—C26	1.394 (11)
As1—C21ii	1.899 (7)	C25—H25A	0.9500
As1—C21	1.899 (7)	C26—H26A	0.9500
As1—C11ii	1.913 (6)
S1i—Pt1—S1	180.00 (10)	C21ii—As1—C11	110.4 (3)
S1i—Pt1—S2i	88.73 (8)	C21—As1—C11	111.2 (3)
S1—Pt1—S2i	91.27 (8)	C11ii—As1—C11	107.1 (4)
S1i—Pt1—S2	91.27 (8)	C12—C11—C16	120.9 (6)
S1—Pt1—S2	88.73 (8)	C12—C11—As1	121.0 (5)
S2i—Pt1—S2	180.000 (1)	C16—C11—As1	118.0 (5)
C1—S1—Pt1	104.3 (3)	C11—C12—C13	119.4 (7)
C2—S2—Pt1	104.2 (3)	C11—C12—H12A	120.3
C2—C1—C3	123.2 (7)	C13—C12—H12A	120.3
C2—C1—S1	120.5 (6)	C14—C13—C12	120.3 (7)
C3—C1—S1	116.3 (6)	C14—C13—H13A	119.8
C1—C2—C4	126.0 (7)	C12—C13—H13A	119.8
C1—C2—S2	122.1 (6)	C13—C14—C15	120.6 (7)
C4—C2—S2	111.9 (6)	C13—C14—H14A	119.7
F1—C3—F2	104.5 (7)	C15—C14—H14A	119.7
F3A—C3—F1A	102.9 (8)	C16—C15—C14	119.4 (8)
F1—C3—F3	104.1 (7)	C16—C15—H15A	120.3
F2—C3—F3	101.0 (6)	C14—C15—H15A	120.3
F3A—C3—F2A	99.4 (7)	C15—C16—C11	119.3 (7)
F1A—C3—F2A	99.5 (7)	C15—C16—H16A	120.3
F1—C3—C1	115.9 (7)	C11—C16—H16A	120.3
F2—C3—C1	114.5 (7)	C26—C21—C22	120.8 (6)
F1A—C3—C1	119.6 (10)	C26—C21—As1	121.1 (5)
F3—C3—C1	115.2 (7)	C22—C21—As1	117.9 (5)
F2A—C3—C1	99.6 (11)	C23—C22—C21	119.1 (6)
F4A—C4—F5A	105.9 (8)	C23—C22—H22A	120.5
F5—C4—F6	104.5 (6)	C21—C22—H22A	120.5
F4A—C4—F6A	104.3 (8)	C22—C23—C24	119.5 (7)
F5A—C4—F6A	102.4 (7)	C22—C23—H23A	120.2
F5—C4—F4	102.7 (6)	C24—C23—H23A	120.2
F6—C4—F4	101.1 (6)	C25—C24—C23	121.3 (7)
F4A—C4—C2	128.2 (13)	C25—C24—H24A	119.4
F5A—C4—C2	110.8 (9)	C23—C24—H24A	119.4
F5—C4—C2	115.0 (6)	C24—C25—C26	119.8 (7)
F6—C4—C2	117.8 (7)	C24—C25—H25A	120.1
F6A—C4—C2	102.1 (10)	C26—C25—H25A	120.1
F4—C4—C2	113.8 (7)	C21—C26—C25	119.5 (7)
C21ii—As1—C21	106.5 (4)	C21—C26—H26A	120.2
C21ii—As1—C11ii	111.2 (3)	C25—C26—H26A	120.2
C21—As1—C11ii	110.4 (3)