Dichlorido[2,3,5,6-tetra­fluoro-4-(tri­fluoro­meth­yl)phenyl-κC1]bis­(tri­methyl­phosphine-κP)cobalt(III)

Zheng, T.; Sun, H.

doi:10.1107/S1600536810014066

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page m574

https://doi.org/10.1107/S1600536810014066

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Dichlorido[2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl-κC¹]bis(trimethylphosphine-κP)cobalt(III)

Tingting Zheng ^a and Hongjian Sun ^a ^*

^aSchool of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, People's Republic of China
^*Correspondence e-mail: hjsun@sdu.edu.cn

(Received 22 March 2010; accepted 16 April 2010; online 24 April 2010)

In the title compound, [Co(C₇F₇)Cl₂(C₃H₉P)₂], the Co^III atom displays a trigonal–bipyramidal coordination geometry, with the two Cl ligands and the C atom of the perfluorotolyl ligand in the equatorial plane and the two phosphine ligands occupying axial positions. The molecule has an approximate C_2v symmetry. The trifluoromethyl 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_r = 499.04
Orthorhombic, P b c a
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[F² > 2σ(F²)] = 0.061
wR(F²) = 0.186
S = 1.07
3373 reflections
223 parameters
8 restraints
H-atom parameters constrained
Δρ_max = 0.78 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

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)

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.

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810014066/gk2264Isup2.hkl

checkCIF report

Comment top

The activation of C—F bonds by transition metal compounds has blossomed in the past few years. There has also been considerable interest in the chemistry of carbon-fluorine bond cleavage followed by carbon-carbon bond formation because they play a key role in the organic synthesis (Schaub et al., 2006; Böhm et al., 2001). Recently we have reported the stoichiometric reaction involving one-electron oxidative addition of bromobenzene and (1-perflurotoluene-κC)tris(trimethylphosphine-κP)cobalt gaining bromo(1-perflurotoluene-κC)tris(trimethylphosphine-κP)cobalt and C—C coupling product (Zheng et al., 2009). We tried to synthesise the compound 1, through the reaction of bromopentafluorobenzene with the(1-perflurotoluene-κC)tris(trimethylphosphine-κP)cobalt. We added the solution of hydrochloric acid in order to abolish the organometallic compounds and gain the organic compound 1. Surprisingly we isolated complex 2 ( Scheme 2) as red crystals and its molecular structure is shown in Fig.1. The cobalt atom displays a trigonal bipyramidal coordination, with two Cl atoms and C atom in the equatorial plane and two P atoms occupying axial positions. The Cl1—Co1 and Cl2—Co1) distances are 2.2290 (18) Å and 2.2613 (16) Å, respectively. The angle between the phosphine ligands and the Co atom, P1–Co1–P2 is 179.08 (8)°.

Related literature top

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 top

The reaction leading to the title compound is shown in Scheme 2. To a solution of 1 (0.50 g,1.00 mmol) in 30 mL of pentane was added bromopentafluorobenzene (0.74 g, 3.00 mmol) with stirring at 213 K. The mixture was allowed to warm-up to 293 K and was stirred for 18 h. The color changed from green to yellow-brown. The reaction mixture was added to a solution of hydrochloric acid with a color change to red-brown. Pentane was used to estract the organic product. Crystallization from pentane at 273 K afforded the title compound as red crystals in 37% yield.

Structure description top

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).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure and aAtom numbering scheme for the title compound with the displacement ellipsoids shown at the 30% probability level.
	Fig. 2. Preparation of the title compound.

Dichlorido[2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl- κC¹]bis(trimethylphosphine-κP)cobalt(III) top

Crystal data top

[Co(C₇F₇)Cl₂(C₃H₉P)₂]	D_x = 1.582 Mg m⁻³
M_r = 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

Data collection top

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

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.186	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0935P)² + 7.5678P] where P = (F_o² + 2F_c²)/3
3373 reflections	(Δ/σ)_max = 0.013
223 parameters	Δρ_max = 0.78 e Å⁻³
8 restraints	Δρ_min = −0.69 e Å⁻³

Crystal data top

[Co(C₇F₇)Cl₂(C₃H₉P)₂]	V = 4190.8 (11) Å³
M_r = 499.04	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 12.3321 (19) Å	µ = 1.28 mm⁻¹
b = 13.3657 (19) Å	T = 293 K
c = 25.426 (4) Å	0.25 × 0.20 × 0.18 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3373 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2345 reflections with I > 2σ(I)
T_min = 0.740, T_max = 0.802	R_int = 0.052
18353 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	8 restraints
wR(F²) = 0.186	H-atom parameters constrained
S = 1.07	Δρ_max = 0.78 e Å⁻³
3373 reflections	Δρ_min = −0.69 e Å⁻³
223 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq	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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Experimental details

Crystal data
Chemical formula	[Co(C₇F₇)Cl₂(C₃H₉P)₂]
M_r	499.04
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	12.3321 (19), 13.3657 (19), 25.426 (4)
V (Å³)	4190.8 (11)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.28
Crystal size (mm)	0.25 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.740, 0.802
No. of measured, independent and observed [I > 2σ(I)] reflections	18353, 3373, 2345
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.577

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.186, 1.07
No. of reflections	3373
No. of parameters	223
No. of restraints	8
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.78, −0.69

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

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

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

Acknowledgements

The authors gratefully acknowledge support by the NSF of China within the project No. 20872080/20772072.

References

Böhm, V., Gstöttmayr, C., Weskamp, T. & Herrmann, W. (2001). Angew. Chem. Int. Ed. 40, 3387–3389. Google Scholar
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Zheng, T., Sun, H., Chen, Y., Li, X., Dürr, S., Radius, U. & Harms, K. (2009). Organometallics, 28, 5771–5776. Web of Science CrossRef CAS Google Scholar

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