Dichlorido[2,3,5,6-tetra-fluoro-4-(tri-fluoro-meth-yl)phenyl-κC]bis-(tri-methyl-phosphine-κP)cobalt(III).

In the title compound, [Co(C(7)F(7))Cl(2)(C(3)H(9)P)(2)], the Co(III) atom displays a trigonal-bipyramidal coordination geometry, with the two Cl ligands and the C atom of the perfluoro-tolyl ligand in the equatorial plane and the two phosphine ligands occupying axial positions. The mol-ecule has an approximate C(2v) symmetry. The trifluoro-methyl group is disordered over two positions, with nearly equal occupancies.

Related literature

For general background on the activation of C—F bonds and the formation of C—C bonds, see: Schaub et al. (2006 ▶); Böhm et al. (2001 ▶); Zheng et al. (2009 ▶).

Experimental

Crystal data

[Co(C7F7)Cl2(C3H9P)2]

M = 499.04

Orthorhombic,

a = 12.3321 (19) Å

b = 13.3657 (19) Å

c = 25.426 (4) Å

V = 4190.8 (11) Å3

Z = 8

Mo Kα radiation

μ = 1.28 mm−1

T = 293 K

0.25 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.740, T max = 0.802

18353 measured reflections

3373 independent reflections

2345 reflections with I > 2σ(I)

R int = 0.052

Refinement

R[F 2 > 2σ(F 2)] = 0.061

wR(F 2) = 0.186

S = 1.07

3373 reflections

223 parameters

8 restraints

H-atom parameters constrained

Δρmax = 0.78 e Å−3

Δρmin = −0.69 e Å−3

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810014066/gk2264sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810014066/gk2264Isup2.hkl

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

[Co(C7F7)Cl2(C3H9P)2]	Dx = 1.582 Mg m−3
Mr = 499.04	Melting point: 380 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2967 reflections
a = 12.3321 (19) Å	θ = 2.3–21.0°
b = 13.3657 (19) Å	µ = 1.28 mm−1
c = 25.426 (4) Å	T = 293 K
V = 4190.8 (11) Å3	Block, red
Z = 8	0.25 × 0.20 × 0.18 mm
F(000) = 2000

Bruker SMART CCD area-detector diffractometer	3373 independent reflections
Radiation source: fine-focus sealed tube	2345 reflections with I > 2σ(I)
graphite	Rint = 0.052
φ and ω scans	θmax = 24.2°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→10
Tmin = 0.740, Tmax = 0.802	k = −15→12
18353 measured reflections	l = −27→29

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.186	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0935P)2 + 7.5678P] where P = (Fo2 + 2Fc2)/3
3373 reflections	(Δ/σ)max = 0.013
223 parameters	Δρmax = 0.78 e Å−3
8 restraints	Δρmin = −0.69 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)
C1	0.9572 (5)	0.1013 (5)	0.1322 (3)	0.0593 (16)
C2	0.9141 (7)	0.1728 (6)	0.0990 (3)	0.080 (2)
C3	0.8099 (8)	0.1731 (9)	0.0813 (3)	0.102 (3)
C4	0.7378 (6)	0.0992 (11)	0.0944 (4)	0.109 (4)
C5	0.7789 (7)	0.0239 (8)	0.1266 (3)	0.094 (3)
C6	0.8834 (6)	0.0266 (6)	0.1449 (3)	0.073 (2)
C8	1.3056 (6)	−0.0189 (6)	0.0919 (3)	0.087 (2)
H8A	1.3203	−0.0538	0.1241	0.130*
H8B	1.3477	0.0414	0.0907	0.130*
H8C	1.3244	−0.0607	0.0626	0.130*
C9	1.1447 (8)	0.0770 (7)	0.0268 (3)	0.101 (3)
H9A	1.1794	0.1413	0.0286	0.151*
H9B	1.0687	0.0858	0.0201	0.151*
H9C	1.1766	0.0384	−0.0010	0.151*
C10	1.0943 (7)	−0.1069 (5)	0.0800 (3)	0.087 (2)
H10A	1.1015	−0.1461	0.1115	0.130*
H10B	1.1264	−0.1422	0.0510	0.130*
H10C	1.0189	−0.0954	0.0729	0.130*
C11	1.1647 (6)	0.2311 (6)	0.2713 (3)	0.092 (3)
H11A	1.2031	0.1723	0.2824	0.137*
H11B	1.1369	0.2656	0.3016	0.137*
H11C	1.2131	0.2744	0.2524	0.137*
C12	0.9874 (8)	0.3117 (6)	0.2110 (4)	0.105 (3)
H12A	1.0344	0.3495	0.1884	0.157*
H12B	0.9727	0.3495	0.2423	0.157*
H12C	0.9206	0.2979	0.1931	0.157*
C13	0.9579 (7)	0.1302 (8)	0.2711 (3)	0.101 (3)
H13A	0.9885	0.0672	0.2816	0.151*
H13B	0.8913	0.1187	0.2525	0.151*
H13C	0.9438	0.1701	0.3017	0.151*
Cl1	1.22875 (15)	0.22034 (13)	0.13739 (8)	0.0772 (6)
Cl2	1.18147 (13)	−0.01081 (11)	0.21464 (6)	0.0566 (4)
Co1	1.10845 (6)	0.10295 (6)	0.15914 (3)	0.0498 (3)
F1	0.9169 (4)	−0.0490 (4)	0.17618 (19)	0.0965 (15)
F2	0.7167 (4)	−0.0546 (6)	0.1418 (2)	0.146 (3)
F3	0.7792 (5)	0.2497 (5)	0.0496 (2)	0.156 (3)
F4	0.9791 (5)	0.2502 (4)	0.0832 (2)	0.1083 (16)
P1	1.05246 (15)	0.19513 (14)	0.22862 (7)	0.0664 (5)
P2	1.16269 (14)	0.01209 (14)	0.08875 (7)	0.0622 (5)
C7	0.6149 (13)	0.0863 (14)	0.0797 (8)	0.106 (9)*	0.487 (13)
F6	0.5612 (14)	0.0191 (12)	0.1062 (6)	0.154 (7)*	0.487 (13)
F5	0.5737 (12)	0.1839 (12)	0.0899 (6)	0.138 (6)*	0.487 (13)
F7	0.6077 (13)	0.0920 (13)	0.0284 (6)	0.150 (6)*	0.487 (13)
C7'	0.6232 (14)	0.1080 (15)	0.0695 (8)	0.141 (12)*	0.513 (13)
F6'	0.6148 (12)	0.1727 (13)	0.0306 (6)	0.158 (6)*	0.513 (13)
F7'	0.6005 (11)	0.0140 (10)	0.0511 (5)	0.133 (5)*	0.513 (13)
F5'	0.5527 (11)	0.1180 (11)	0.1069 (5)	0.131 (5)*	0.513 (13)

	U11	U22	U33	U12	U13	U23
C1	0.046 (4)	0.069 (4)	0.062 (4)	0.006 (3)	−0.001 (3)	−0.001 (3)
C2	0.072 (5)	0.092 (6)	0.077 (5)	0.023 (5)	−0.004 (4)	0.012 (4)
C3	0.078 (6)	0.152 (9)	0.074 (5)	0.056 (7)	−0.024 (5)	−0.011 (6)
C4	0.042 (4)	0.209 (12)	0.076 (6)	0.027 (6)	−0.010 (4)	−0.035 (7)
C5	0.052 (5)	0.157 (9)	0.072 (5)	−0.024 (6)	0.013 (4)	−0.030 (6)
C6	0.053 (4)	0.095 (6)	0.072 (5)	−0.008 (4)	0.003 (4)	0.004 (4)
C8	0.055 (4)	0.104 (6)	0.101 (6)	0.014 (4)	0.009 (4)	−0.010 (5)
C9	0.121 (7)	0.113 (7)	0.068 (5)	0.018 (6)	0.002 (5)	0.006 (5)
C10	0.083 (6)	0.072 (5)	0.105 (6)	0.012 (4)	−0.018 (5)	−0.019 (4)
C11	0.075 (5)	0.096 (6)	0.103 (6)	0.012 (5)	−0.017 (5)	−0.031 (5)
C12	0.111 (7)	0.081 (6)	0.122 (7)	0.042 (5)	−0.003 (6)	−0.018 (5)
C13	0.078 (6)	0.148 (8)	0.078 (5)	−0.005 (6)	0.021 (4)	−0.005 (5)
Cl1	0.0681 (11)	0.0602 (10)	0.1034 (14)	−0.0203 (9)	0.0083 (10)	0.0143 (9)
Cl2	0.0546 (9)	0.0522 (9)	0.0629 (9)	0.0059 (7)	−0.0052 (7)	0.0159 (7)
Co1	0.0414 (5)	0.0477 (5)	0.0603 (5)	0.0008 (3)	0.0002 (4)	0.0075 (4)
F1	0.088 (3)	0.098 (3)	0.103 (3)	−0.031 (3)	−0.006 (3)	0.027 (3)
F2	0.076 (3)	0.227 (7)	0.136 (5)	−0.073 (5)	0.010 (3)	−0.025 (5)
F3	0.138 (5)	0.199 (6)	0.130 (5)	0.083 (5)	−0.048 (4)	0.023 (4)
F4	0.112 (4)	0.089 (3)	0.124 (4)	0.017 (3)	−0.012 (3)	0.042 (3)
P1	0.0549 (11)	0.0721 (12)	0.0723 (11)	0.0116 (9)	0.0003 (9)	−0.0081 (9)
P2	0.0544 (10)	0.0683 (11)	0.0638 (11)	0.0091 (9)	−0.0010 (8)	0.0011 (8)

C1—C2	1.382 (10)	C10—H10C	0.9600
C1—C6	1.389 (10)	C11—P1	1.823 (8)
C1—Co1	1.987 (6)	C11—H11A	0.9600
C2—C3	1.362 (12)	C11—H11B	0.9600
C2—F4	1.369 (9)	C11—H11C	0.9600
C3—F3	1.358 (11)	C12—P1	1.808 (8)
C3—C4	1.370 (15)	C12—H12A	0.9600
C4—C5	1.393 (14)	C12—H12B	0.9600
C4—C7'	1.554 (17)	C12—H12C	0.9600
C4—C7	1.570 (16)	C13—P1	1.811 (8)
C5—F2	1.357 (11)	C13—H13A	0.9600
C5—C6	1.370 (11)	C13—H13B	0.9600
C6—F1	1.350 (9)	C13—H13C	0.9600
C8—P2	1.812 (7)	Cl1—Co1	2.2290 (18)
C8—H8A	0.9600	Cl2—Co1	2.2613 (16)
C8—H8B	0.9600	Co1—P1	2.262 (2)
C8—H8C	0.9600	Co1—P2	2.264 (2)
C9—P2	1.812 (8)	C7—F6	1.302 (16)
C9—H9A	0.9600	C7—F7	1.311 (17)
C9—H9B	0.9600	C7—F5	1.424 (17)
C9—H9C	0.9600	C7'—F5'	1.296 (17)
C10—P2	1.814 (8)	C7'—F6'	1.317 (17)
C10—H10A	0.9600	C7'—F7'	1.368 (17)
C10—H10B	0.9600
C2—C1—C6	112.8 (7)	P1—C12—H12B	109.5
C2—C1—Co1	124.3 (6)	H12A—C12—H12B	109.5
C6—C1—Co1	122.9 (5)	P1—C12—H12C	109.5
C3—C2—F4	117.0 (8)	H12A—C12—H12C	109.5
C3—C2—C1	124.5 (9)	H12B—C12—H12C	109.5
F4—C2—C1	118.5 (7)	P1—C13—H13A	109.5
F3—C3—C2	117.5 (11)	P1—C13—H13B	109.5
F3—C3—C4	120.4 (9)	H13A—C13—H13B	109.5
C2—C3—C4	122.1 (9)	P1—C13—H13C	109.5
C3—C4—C5	115.3 (7)	H13A—C13—H13C	109.5
C3—C4—C7'	115.9 (12)	H13B—C13—H13C	109.5
C5—C4—C7'	128.7 (13)	C1—Co1—Cl1	123.2 (2)
C3—C4—C7	130.4 (12)	C1—Co1—Cl2	125.5 (2)
C5—C4—C7	114.3 (12)	Cl1—Co1—Cl2	111.29 (7)
C7'—C4—C7	14.8 (11)	C1—Co1—P1	89.36 (19)
F2—C5—C6	117.1 (9)	Cl1—Co1—P1	90.78 (8)
F2—C5—C4	121.3 (8)	Cl2—Co1—P1	90.03 (7)
C6—C5—C4	121.6 (9)	C1—Co1—P2	89.93 (19)
F1—C6—C5	118.0 (8)	Cl1—Co1—P2	89.13 (8)
F1—C6—C1	118.3 (6)	Cl2—Co1—P2	90.86 (7)
C5—C6—C1	123.8 (8)	P1—Co1—P2	179.08 (8)
P2—C8—H8A	109.5	C12—P1—C13	105.9 (5)
P2—C8—H8B	109.5	C12—P1—C11	104.9 (4)
H8A—C8—H8B	109.5	C13—P1—C11	105.1 (4)
P2—C8—H8C	109.5	C12—P1—Co1	114.3 (3)
H8A—C8—H8C	109.5	C13—P1—Co1	113.6 (3)
H8B—C8—H8C	109.5	C11—P1—Co1	112.1 (3)
P2—C9—H9A	109.5	C9—P2—C8	105.5 (4)
P2—C9—H9B	109.5	C9—P2—C10	104.9 (4)
H9A—C9—H9B	109.5	C8—P2—C10	104.9 (4)
P2—C9—H9C	109.5	C9—P2—Co1	113.2 (3)
H9A—C9—H9C	109.5	C8—P2—Co1	112.0 (3)
H9B—C9—H9C	109.5	C10—P2—Co1	115.5 (3)
P2—C10—H10A	109.5	F6—C7—F7	121.3 (17)
P2—C10—H10B	109.5	F6—C7—F5	110.9 (16)
H10A—C10—H10B	109.5	F7—C7—F5	96.0 (15)
P2—C10—H10C	109.5	F6—C7—C4	116.3 (16)
H10A—C10—H10C	109.5	F7—C7—C4	107.2 (14)
H10B—C10—H10C	109.5	F5—C7—C4	101.6 (13)
P1—C11—H11A	109.5	F5'—C7'—F6'	115.5 (17)
P1—C11—H11B	109.5	F5'—C7'—F7'	102.1 (16)
H11A—C11—H11B	109.5	F6'—C7'—F7'	109.3 (16)
P1—C11—H11C	109.5	F5'—C7'—C4	108.5 (15)
H11A—C11—H11C	109.5	F6'—C7'—C4	115.3 (16)
H11B—C11—H11C	109.5	F7'—C7'—C4	104.8 (14)
P1—C12—H12A	109.5
C6—C1—C2—C3	1.7 (11)	C1—Co1—P1—C12	−57.7 (4)
Co1—C1—C2—C3	−178.6 (6)	Cl1—Co1—P1—C12	65.5 (4)
C6—C1—C2—F4	−179.5 (7)	Cl2—Co1—P1—C12	176.8 (4)
Co1—C1—C2—F4	0.2 (10)	C1—Co1—P1—C13	64.1 (4)
F4—C2—C3—F3	0.1 (12)	Cl1—Co1—P1—C13	−172.7 (3)
C1—C2—C3—F3	178.9 (7)	Cl2—Co1—P1—C13	−61.4 (3)
F4—C2—C3—C4	179.7 (8)	C1—Co1—P1—C11	−176.9 (4)
C1—C2—C3—C4	−1.5 (14)	Cl1—Co1—P1—C11	−53.7 (3)
F3—C3—C4—C5	179.1 (7)	Cl2—Co1—P1—C11	57.6 (3)
C2—C3—C4—C5	−0.4 (13)	C1—Co1—P2—C9	63.6 (4)
F3—C3—C4—C7'	1.8 (15)	Cl1—Co1—P2—C9	−59.6 (4)
C2—C3—C4—C7'	−177.8 (11)	Cl2—Co1—P2—C9	−170.8 (4)
F3—C3—C4—C7	−2.0 (17)	C1—Co1—P2—C8	−177.3 (4)
C2—C3—C4—C7	178.5 (12)	Cl1—Co1—P2—C8	59.6 (3)
C3—C4—C5—F2	−178.9 (8)	Cl2—Co1—P2—C8	−51.7 (3)
C7'—C4—C5—F2	−1.9 (16)	C1—Co1—P2—C10	−57.3 (3)
C7—C4—C5—F2	2.0 (14)	Cl1—Co1—P2—C10	179.5 (3)
C3—C4—C5—C6	2.0 (13)	Cl2—Co1—P2—C10	68.2 (3)
C7'—C4—C5—C6	179.0 (12)	C3—C4—C7—F6	−166.9 (13)
C7—C4—C5—C6	−177.1 (10)	C5—C4—C7—F6	12.0 (19)
F2—C5—C6—F1	0.5 (11)	C7'—C4—C7—F6	180 (5)
C4—C5—C6—F1	179.6 (7)	C3—C4—C7—F7	54 (2)
F2—C5—C6—C1	179.0 (7)	C5—C4—C7—F7	−127.5 (14)
C4—C5—C6—C1	−1.8 (13)	C7'—C4—C7—F7	40 (4)
C2—C1—C6—F1	178.4 (7)	C3—C4—C7—F5	−46.5 (19)
Co1—C1—C6—F1	−1.3 (10)	C5—C4—C7—F5	132.4 (12)
C2—C1—C6—C5	−0.1 (11)	C7'—C4—C7—F5	−60 (4)
Co1—C1—C6—C5	−179.8 (6)	C3—C4—C7'—F5'	−118.0 (15)
C2—C1—Co1—Cl1	−1.3 (7)	C5—C4—C7'—F5'	65 (2)
C6—C1—Co1—Cl1	178.4 (5)	C7—C4—C7'—F5'	51 (4)
C2—C1—Co1—Cl2	178.8 (5)	C3—C4—C7'—F6'	13 (2)
C6—C1—Co1—Cl2	−1.5 (7)	C5—C4—C7'—F6'	−163.6 (13)
C2—C1—Co1—P1	89.2 (6)	C7—C4—C7'—F6'	−178 (5)
C6—C1—Co1—P1	−91.1 (6)	C3—C4—C7'—F7'	133.6 (13)
C2—C1—Co1—P2	−90.2 (6)	C5—C4—C7'—F7'	−43.3 (19)
C6—C1—Co1—P2	89.5 (6)	C7—C4—C7'—F7'	−58 (4)

C1—Co1	1.987 (6)
Cl1—Co1	2.2290 (18)
Cl2—Co1	2.2613 (16)
Co1—P1	2.262 (2)
Co1—P2	2.264 (2)

C1—Co1—Cl1	123.2 (2)
C1—Co1—Cl2	125.5 (2)
Cl1—Co1—Cl2	111.29 (7)
C1—Co1—P1	89.36 (19)
Cl1—Co1—P1	90.78 (8)
Cl2—Co1—P1	90.03 (7)
C1—Co1—P2	89.93 (19)
Cl1—Co1—P2	89.13 (8)
Cl2—Co1—P2	90.86 (7)
P1—Co1—P2	179.08 (8)