Crystal structure of di­chlorido­[2-(di­phenyl­phosphan­yl)-3,4,5,6-tetra­fluoro­benzene-1-thiol­ato-κ² P,S]gold(III)

Abstract

The title compound, [Au(C₁₈H₁₀F₄PS)Cl₂], crystallizes as neutral mol­ecules, with the Au^III atom coordinated by two Cl atoms and by the P and S atoms of the bidentate phosphanyl thiol­ate ligand, in a slightly distorted square-planar environment. The mol­ecules are linked into centrosymmetric dimers via long axial Au—Cl bonds of 3.393 (4) Å. This axial Au—Cl distance is longer than is usually seen, although one other example has been given. Dimer formation may explain the unexpectedly low solubility of the compound in common polar solvents. There is also a separate inter­molecular Au—F contact of 3.561 (6) Å, but this distance seems too long to be regarded as a bond. Two putative C—H⋯F hydrogen bonds appear to link the dimers into sheets parallel to (110). There is a short inter­molecular F⋯F contact of 2.695 (10) Å between two dimers related by the twofold axis.

Related literature  

For synthetic details, see: Eller (1971 ▸); Eller & Meek (1970 ▸). Hollis & Lippard (1983 ▸) describe a similarly long axial Au—Cl bond in a mixed-valence gold compound, although other axial Au—Cl bonds in the literature are in the 3.0–3.1 Å range, as in Elder & Watkins (1986 ▸).

Experimental  

Crystal data  

• [Au(C₁₈H₁₀F₄PS)Cl₂]

• M _r = 633.16

• Monoclinic,

• a = 18.90 (2) Å

• b = 8.388 (12) Å

• c = 24.15 (3) Å

• β = 100.75 (3)°

• V = 3761 (8) ų

• Z = 8

• Mo Kα radiation

• μ = 8.15 mm⁻¹

• T = 298 K

• 0.22 × 0.16 × 0.13 mm

Data collection  

• Picker 4-circle diffractometer

• Absorption correction: gaussian (Busing & Levy, 1957 ▸) T _min = 0.384, T _max = 0.442

• 4262 measured reflections

• 4142 independent reflections

• 3209 reflections with I > 2σ(I)

• R _int = 0.025

• 18 standard reflections every 500 reflections intensity decay: −1.0(3)

Refinement  

• R[F ² > 2σ(F ²)] = 0.032

• wR(F ²) = 0.086

• S = 1.03

• 4142 reflections

• 220 parameters

• H-atom parameters constrained

• Δρ_max = 1.00 e Å⁻³

• Δρ_min = −0.87 e Å⁻³

Data collection: Corfield (1972 ▸); cell refinement: Corfield (1972 ▸); data reduction: Corfield et al. (1973 ▸); program(s) used to solve structure: Corfield (1972 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▸); software used to prepare material for publication: SHELXL2014.

Supplementary Material

CCDC reference: 1422931

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

Table 1. Selected geometric parameters (, ).

AuS	2.273(3)
AuP	2.258(3)
AuCl2	2.337(3)
AuCl1	2.305(3)

SAuP	90.22(10)
SAuCl2	87.51(10)
PAuCl2	177.69(6)
SAuCl1	176.59(7)
PAuCl1	88.36(10)
Cl2AuCl1	93.88(11)
SAuCl2i	88.12(7)
PAuCl2i	90.45(9)
Cl2AuCl2i	89.91(9)
Cl1AuCl2i	94.99(7)

Symmetry code: (i) .

Table 2. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C12H12F3ii	0.93	2.60	3.444(7)	151
C18H18F4iii	0.93	2.50	3.082(7)	121

Symmetry codes: (ii) ; (iii) .

supplementary crystallographic information

S1. Synthesis and crystallization

The preparation of the compound is described by Eller (1971), and synthesis of the then novel ligand is given in Eller & Meek (1970).

S2. Refinement

To reduce the number of parameters varied, the phenyl groups C16—C21 and C22—C27 were constrained as rigid hexagons, with C—C distances of 1.385 Å. Aromatic H atoms were placed geometrically, with their U_eq values set 1.2 times the U_iso of their bonded C atoms.

Figures

Fig. 1.

The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

Fig. 2.

Packing of the title complex, viewed along a direction near to the a axis. The centrosymmetric dimers are shown, as well as the proximity of F3(1,y - 1,z) to a sixth coordination site for the gold atom. Long Au—Cl bonds are gived as dashed lines.

Crystal data

[Au(C18H10F4PS)Cl2]	F(000) = 2384
Mr = 633.16	Dx = 2.236 Mg m−3Dm = 2.181 (3) Mg m−3Dm measured by flotation in carbon tetrachloride/bromoforom mixture. Discrepancy may be due to an uncalibrated pycnometer.
Monoclinic, C2/c	Mo Kα radiation, λ = 0.7107 Å
a = 18.90 (2) Å	Cell parameters from 24 reflections
b = 8.388 (12) Å	θ = 4.2–25.1°
c = 24.15 (3) Å	µ = 8.15 mm−1
β = 100.75 (3)°	T = 298 K
V = 3761 (8) Å3	Irregular, red
Z = 8	0.22 × 0.16 × 0.13 mm

Data collection

Picker 4-circle diffractometer	3209 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube	Rint = 0.025
Oriented graphite 200 reflection monochromator	θmax = 27.5°, θmin = 2.5°
θ/2θ scans	h = 0→24
Absorption correction: gaussian (Busing & Levy, 1957)	k = 0→9
Tmin = 0.384, Tmax = 0.442	l = −31→30
4262 measured reflections	18 standard reflections every 500 reflections
4142 independent reflections	intensity decay: −1.0 (3)

Refinement

Refinement on F2	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2)] where P = (Fo2 + 2Fc2)/3
4142 reflections	(Δ/σ)max < 0.001
220 parameters	Δρmax = 1.00 e Å−3
0 restraints	Δρmin = −0.87 e Å−3

Special details

Experimental. Data reduction followed procedures in Corfield et al. (1973), with programs written by Corfield and by Graeme Gainsford.

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. To reduce the number of parameters varied, the phenyl groups C16—C21 and C22—C27 were constrained as rigid hexagons, with C—C distances of 1.385 Å. Ueq values for the aromatic H atoms were set 1.2 times the Uiso of their bonded C atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Au	0.03240 (2)	0.02779 (3)	0.08580 (2)	0.03238 (9)
Cl1	0.14260 (10)	−0.0955 (2)	0.09200 (9)	0.0544 (5)
Cl2	−0.03221 (10)	−0.1909 (2)	0.04280 (8)	0.0503 (4)
S	−0.07524 (9)	0.1492 (2)	0.08537 (8)	0.0438 (4)
P	0.09063 (8)	0.2433 (2)	0.12802 (7)	0.0309 (3)
F2	0.1031 (2)	0.5694 (5)	0.1812 (2)	0.0572 (12)
F3	−0.0040 (3)	0.7682 (6)	0.1937 (2)	0.0681 (13)
F4	−0.1413 (3)	0.6750 (6)	0.1616 (2)	0.0757 (15)
F5	−0.1734 (2)	0.3959 (6)	0.1090 (2)	0.0622 (12)
C1	0.0205 (3)	0.3780 (8)	0.1371 (3)	0.0343 (14)
C2	0.0351 (4)	0.5243 (9)	0.1633 (3)	0.0431 (16)
C3	−0.0190 (4)	0.6241 (9)	0.1708 (3)	0.0479 (18)
C4	−0.0886 (4)	0.5795 (9)	0.1527 (3)	0.0488 (18)
C5	−0.1042 (3)	0.4341 (10)	0.1269 (3)	0.0461 (18)
C6	−0.0507 (3)	0.3312 (8)	0.1186 (3)	0.0363 (14)
C7	0.1393 (2)	0.1964 (5)	0.19702 (13)	0.0336 (14)
C8	0.2018 (2)	0.2774 (5)	0.21989 (18)	0.0490 (18)
H8	0.2215	0.3507	0.1981	0.059*
C9	0.2350 (2)	0.2494 (6)	0.27517 (19)	0.058 (2)
H9	0.2769	0.3038	0.2905	0.070*
C10	0.2057 (3)	0.1403 (6)	0.30757 (14)	0.055 (2)
H10	0.2279	0.1215	0.3447	0.066*
C11	0.1432 (3)	0.0592 (6)	0.28470 (17)	0.060 (2)
H11	0.1235	−0.0140	0.3065	0.072*
C12	0.1100 (2)	0.0873 (5)	0.22942 (18)	0.0462 (17)
H12	0.0681	0.0329	0.2141	0.055*
C13	0.1473 (2)	0.3410 (5)	0.08744 (17)	0.0352 (14)
C14	0.12320 (19)	0.4760 (5)	0.05659 (18)	0.0400 (15)
H14	0.0771	0.5146	0.0566	0.048*
C15	0.1678 (3)	0.5534 (4)	0.02581 (18)	0.0487 (18)
H15	0.1516	0.6441	0.0051	0.058*
C16	0.2365 (2)	0.4959 (6)	0.0259 (2)	0.051 (2)
H16	0.2664	0.5480	0.0052	0.062*
C17	0.26061 (18)	0.3610 (6)	0.0567 (2)	0.0527 (19)
H17	0.3068	0.3224	0.0568	0.063*
C18	0.2160 (2)	0.2835 (5)	0.08750 (19)	0.0433 (16)
H18	0.2323	0.1929	0.1082	0.052*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Au	0.03286 (13)	0.03025 (15)	0.03249 (12)	−0.00327 (11)	0.00210 (8)	−0.00023 (11)
Cl1	0.0446 (10)	0.0441 (11)	0.0717 (13)	0.0115 (8)	0.0038 (9)	−0.0094 (9)
Cl2	0.0572 (11)	0.0408 (10)	0.0499 (10)	−0.0166 (8)	0.0022 (8)	−0.0058 (8)
S	0.0279 (8)	0.0472 (11)	0.0541 (10)	−0.0065 (7)	0.0017 (7)	−0.0028 (8)
P	0.0258 (7)	0.0295 (9)	0.0361 (8)	−0.0005 (6)	0.0022 (6)	0.0001 (6)
F2	0.048 (2)	0.046 (3)	0.074 (3)	−0.006 (2)	0.000 (2)	−0.019 (2)
F3	0.082 (3)	0.051 (3)	0.071 (3)	0.010 (3)	0.012 (3)	−0.023 (2)
F4	0.066 (3)	0.073 (4)	0.088 (4)	0.037 (3)	0.015 (3)	−0.013 (3)
F5	0.034 (2)	0.072 (3)	0.080 (3)	0.009 (2)	0.008 (2)	0.005 (3)
C1	0.030 (3)	0.031 (4)	0.041 (3)	0.004 (3)	0.005 (3)	0.001 (3)
C2	0.047 (4)	0.038 (4)	0.043 (4)	0.005 (3)	0.004 (3)	−0.008 (3)
C3	0.060 (5)	0.034 (4)	0.049 (4)	0.013 (3)	0.007 (4)	−0.003 (3)
C4	0.051 (4)	0.045 (5)	0.052 (4)	0.021 (4)	0.015 (3)	0.002 (3)
C5	0.025 (3)	0.065 (5)	0.048 (4)	0.010 (3)	0.005 (3)	0.013 (4)
C6	0.036 (3)	0.041 (4)	0.032 (3)	0.003 (3)	0.005 (3)	0.007 (3)
C7	0.037 (3)	0.031 (4)	0.031 (3)	0.004 (3)	0.001 (3)	0.001 (3)
C8	0.047 (4)	0.048 (5)	0.046 (4)	−0.011 (3)	−0.006 (3)	0.006 (3)
C9	0.050 (4)	0.065 (6)	0.051 (4)	−0.001 (4)	−0.012 (4)	−0.011 (4)
C10	0.068 (5)	0.054 (5)	0.040 (4)	0.016 (4)	0.001 (4)	−0.002 (4)
C11	0.089 (6)	0.053 (5)	0.039 (4)	−0.003 (5)	0.014 (4)	0.012 (3)
C12	0.054 (4)	0.040 (4)	0.044 (4)	−0.008 (3)	0.008 (3)	0.000 (3)
C13	0.031 (3)	0.036 (4)	0.038 (3)	0.000 (3)	0.003 (3)	0.000 (3)
C14	0.042 (4)	0.039 (4)	0.040 (3)	−0.001 (3)	0.009 (3)	0.002 (3)
C15	0.070 (5)	0.031 (4)	0.047 (4)	−0.007 (4)	0.017 (4)	0.004 (3)
C16	0.059 (5)	0.051 (5)	0.047 (4)	−0.017 (4)	0.017 (4)	−0.003 (3)
C17	0.041 (4)	0.062 (5)	0.057 (5)	−0.006 (4)	0.016 (3)	−0.002 (4)
C18	0.034 (3)	0.045 (4)	0.051 (4)	0.001 (3)	0.006 (3)	−0.001 (3)

Geometric parameters (Å, º)

Au—S	2.273 (3)	C7—C12	1.3850
Au—P	2.258 (3)	C8—C9	1.3850
Au—Cl2	2.337 (3)	C8—H8	0.9300
Au—Cl1	2.305 (3)	C9—C10	1.3850
Au—Cl2i	3.393 (4)	C9—H9	0.9300
Au—F3ii	3.560 (6)	C10—C11	1.3850
S—C6	1.747 (7)	C10—H10	0.9300
P—C1	1.787 (6)	C11—C12	1.3850
P—C7	1.791 (4)	C11—H11	0.9300
P—C13	1.781 (4)	C12—H12	0.9300
F2—C2	1.331 (8)	C13—C14	1.3850
F3—C3	1.337 (9)	C13—C18	1.3850
F4—C4	1.328 (8)	C14—C15	1.3850
F5—C5	1.338 (8)	C14—H14	0.9300
C1—C6	1.393 (8)	C15—C16	1.3850
C1—C2	1.385 (10)	C15—H15	0.9300
C2—C3	1.360 (10)	C16—C17	1.3850
C3—C4	1.358 (10)	C16—H16	0.9300
C4—C5	1.375 (11)	C17—C18	1.3850
C5—C6	1.372 (9)	C17—H17	0.9300
C7—C8	1.3850	C18—H18	0.9300
S—Au—P	90.22 (10)	C5—C6—S	118.5 (5)
S—Au—Cl2	87.51 (10)	C1—C6—S	123.4 (5)
P—Au—Cl2	177.69 (6)	C8—C7—C12	120.0
S—Au—Cl1	176.59 (7)	C8—C7—P	121.0 (3)
P—Au—Cl1	88.36 (10)	C12—C7—P	118.7 (3)
Cl2—Au—Cl1	93.88 (11)	C7—C8—C9	120.0
S—Au—Cl2i	88.12 (7)	C7—C8—H8	120.0
P—Au—Cl2i	90.45 (9)	C9—C8—H8	120.0
Cl2—Au—Cl2i	89.91 (9)	C10—C9—C8	120.0
Cl1—Au—Cl2i	94.99 (7)	C10—C9—H9	120.0
S—Au—F3ii	88.98 (11)	C8—C9—H9	120.0
P—Au—F3ii	107.67 (12)	C11—C10—C9	120.0
Cl2—Au—F3ii	71.87 (12)	C11—C10—H10	120.0
Cl1—Au—F3ii	88.50 (11)	C9—C10—H10	120.0
Cl2i—Au—F3ii	161.66 (8)	C10—C11—C12	120.0
C6—S—Au	103.2 (2)	C10—C11—H11	120.0
C1—P—C7	106.8 (3)	C12—C11—H11	120.0
C1—P—C13	108.2 (3)	C11—C12—C7	120.0
C7—P—C13	110.8 (2)	C11—C12—H12	120.0
C1—P—Au	104.6 (2)	C7—C12—H12	120.0
C7—P—Au	111.53 (17)	C14—C13—C18	120.0
C13—P—Au	114.36 (18)	C14—C13—P	120.0 (2)
C6—C1—C2	119.7 (6)	C18—C13—P	120.0 (2)
C6—C1—P	118.5 (5)	C15—C14—C13	120.0
C2—C1—P	121.8 (5)	C15—C14—H14	120.0
F2—C2—C3	119.1 (6)	C13—C14—H14	120.0
F2—C2—C1	119.9 (6)	C16—C15—C14	120.0
C3—C2—C1	121.0 (7)	C16—C15—H15	120.0
C4—C3—C2	119.7 (7)	C14—C15—H15	120.0
C4—C3—F3	120.0 (7)	C17—C16—C15	120.0
C2—C3—F3	120.3 (7)	C17—C16—H16	120.0
F4—C4—C3	119.5 (7)	C15—C16—H16	120.0
F4—C4—C5	120.2 (7)	C16—C17—C18	120.0
C3—C4—C5	120.2 (6)	C16—C17—H17	120.0
C6—C5—F5	120.3 (7)	C18—C17—H17	120.0
C6—C5—C4	121.4 (6)	C17—C18—C13	120.0
F5—C5—C4	118.3 (6)	C17—C18—H18	120.0
C5—C6—C1	118.0 (6)	C13—C18—H18	120.0

Symmetry codes: (i) −x, −y, −z; (ii) x, y−1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···F3ii	0.93	2.60	3.444 (7)	151
C18—H18···F4iii	0.93	2.50	3.082 (7)	121

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