Cyanidophenyl­tris(trimethyl­phosphine)cobalt(II)

Yu, F.; Wang, Q.; Li, X.

doi:10.1107/S1600536807064781

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page m112

https://doi.org/10.1107/S1600536807064781

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Cyanidophenyltris(trimethylphosphine)cobalt(II)

Fengli Yu,^a,^b Qibao Wang ^a and Xiaoyan Li ^a ^*

^aSchool of Chemistry and Chemical Engineering, Shandong University, Shanda Nanlu 27, Jinan 250100, People's Republic of China, and ^bCollege of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Zhengzhou Road 58, Qingdao 266042, People's Republic of China
^*Correspondence e-mail: xli63@sdu.edu.cn

(Received 12 November 2007; accepted 30 November 2007; online 6 December 2007)

The title molecule, [Co(C₆H₅)(CN)(C₃H₉P)₃], lies on a crystallographic mirror plane with the Co^II ion coordinated in a distorted square-pyramidal environment with one of the P atoms in the apical position. In the basal plane, the phenyl substituent is trans to the cyanide group with a C—Co—C angle which is significantly distorted from linearity.

Related literature

For related structures, see: Li et al. (2006 ).

Experimental

Crystal data

[Co(C₆H₅)(CN)(C₃H₉P)₃]
M_r = 390.27
Orthorhombic, P n m a
a = 12.456 (3) Å
b = 11.420 (2) Å
c = 14.495 (3) Å
V = 2061.9 (7) Å³
Z = 4
Mo Kα radiation
μ = 1.06 mm⁻¹
T = 373 (2) K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.742, T_max = 0.816
12996 measured reflections
2373 independent reflections
2185 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.077
S = 1.04
2373 reflections
117 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Co1—C2	1.970 (2)
Co1—C1	2.011 (3)
Co1—P2	2.2034 (6)
Co1—P1	2.2745 (7)

C2—Co1—C1	157.00 (9)
C2—Co1—P2	88.168 (17)
C1—Co1—P2	87.783 (16)
P2—Co1—P2ⁱ	159.58 (3)
C2—Co1—P1	104.05 (6)
C1—Co1—P1	98.96 (6)
P2—Co1—P1	100.188 (13)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807064781/lh2572sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807064781/lh2572Isup2.hkl

checkCIF report

Comment top

In the molecular structure of the title compound the Co^II ion is in a distorted square-pyramidal coordination environment with atom P1 in the apical position. In the equatorial plane, the phenyl ring substituent and cyano group are trans to each other. The distortion from ideal geometry of the angles around Co1 is most likely due to the steric effects of the bulky P(Me)₃ groups. The Co1—C2 bond is relatively short, while the Co—C1 bond is relatively long compared to related distances in a complex reported by Li et al. (2006).

Related literature top

For related structures, see: Li et al. (2006).

Experimental top

All air-sensitive and volatile materials were handled in vacuo or under argon atmosphere using standard Schlenk techniques. A solution of benzonitrile (0.63 g, 1.74 mmol) in 10 ml of pentane was combined with a solution of tetra(trimethylphosphine)cobalt(0) (0.18 g, 1.75 mmol) in 50 ml of pentane at 193 K. The reaction mixture was allowed to warm to ambient temperature and stirred for 16 h to form a red-brown, turbid solution, which was filtered. Red-brown crystals of the title compound were obtained from the filtrate at 251 K.

Structure description top

For related structures, see: Li et al. (2006).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top

Fig. 1. The molecular structure with atom labels and 30% probability displacement ellipsoids for non-H atoms [symmetry code: (A) x - y + 1/2, z].

Cyanidophenyltris(trimethylphosphine)cobalt(II) top

Crystal data top

[Co(C₆H₅)(CN)(C₃H₉P)₃]	F(000) = 828
M_r = 390.27	D_x = 1.257 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 11258 reflections
a = 12.456 (3) Å	θ = 2.1–22.5°
b = 11.420 (2) Å	µ = 1.06 mm⁻¹
c = 14.495 (3) Å	T = 373 K
V = 2061.9 (7) Å³	Block, dark red
Z = 4	0.30 × 0.25 × 0.20 mm

Data collection top

Bruker SMART CCD diffractometer	2373 independent reflections
Radiation source: fine-focus sealed tube	2185 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
ω scans	θ_max = 27.1°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
T_min = 0.742, T_max = 0.816	k = −14→14
12996 measured reflections	l = −18→16

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.042P)² + 0.7567P] where P = (F_o² + 2F_c²)/3
2373 reflections	(Δ/σ)_max = 0.019
117 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

[Co(C₆H₅)(CN)(C₃H₉P)₃]	V = 2061.9 (7) Å³
M_r = 390.27	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 12.456 (3) Å	µ = 1.06 mm⁻¹
b = 11.420 (2) Å	T = 373 K
c = 14.495 (3) Å	0.30 × 0.25 × 0.20 mm

Data collection top

Bruker SMART CCD diffractometer	2373 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2185 reflections with I > 2σ(I)
T_min = 0.742, T_max = 0.816	R_int = 0.057
12996 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.077	H-atom parameters constrained
S = 1.04	Δρ_max = 0.39 e Å⁻³
2373 reflections	Δρ_min = −0.59 e Å⁻³
117 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.75567 (2)	0.2500	0.524811 (19)	0.02152 (10)
P1	0.66451 (4)	0.2500	0.66077 (4)	0.02425 (13)
P2	0.77302 (3)	0.06011 (3)	0.50237 (3)	0.02474 (11)
C1	0.9064 (2)	0.2500	0.57450 (15)	0.0281 (4)
C2	0.64192 (16)	0.2500	0.43042 (14)	0.0243 (4)
C3	0.53100 (17)	0.2500	0.44650 (15)	0.0272 (4)
H3	0.5067	0.2500	0.5072	0.033*
C4	0.45567 (18)	0.2500	0.37551 (17)	0.0328 (5)
H4	0.3828	0.2500	0.3895	0.039*
C5	0.4886 (2)	0.2500	0.28431 (17)	0.0358 (5)
H5	0.4384	0.2500	0.2368	0.043*
C6	0.5977 (2)	0.2500	0.26512 (16)	0.0341 (5)
H6	0.6213	0.2500	0.2043	0.041*
C7	0.67166 (18)	0.2500	0.33676 (15)	0.0290 (4)
H7	0.7444	0.2500	0.3222	0.035*
C8	0.87110 (13)	0.03228 (14)	0.41206 (12)	0.0352 (4)
H8A	0.8863	−0.0500	0.4094	0.053*
H8B	0.9359	0.0745	0.4253	0.053*
H8C	0.8428	0.0577	0.3538	0.053*
C9	0.65951 (13)	−0.02741 (14)	0.46370 (12)	0.0324 (3)
H9A	0.6314	0.0049	0.4076	0.049*
H9B	0.6047	−0.0269	0.5102	0.049*
H9C	0.6826	−0.1064	0.4529	0.049*
C10	0.82540 (13)	−0.02849 (15)	0.59702 (12)	0.0347 (4)
H10A	0.8433	−0.1051	0.5745	0.052*
H10B	0.7719	−0.0350	0.6444	0.052*
H10C	0.8885	0.0081	0.6218	0.052*
C11	0.57347 (13)	0.12794 (15)	0.68682 (11)	0.0323 (3)
H11A	0.6130	0.0558	0.6862	0.048*
H11B	0.5177	0.1248	0.6412	0.048*
H11C	0.5421	0.1394	0.7467	0.048*
C12	0.74842 (18)	0.2500	0.76408 (16)	0.0333 (5)
H12A	0.7893	0.3212	0.7665	0.050*	0.50
H12B	0.7964	0.1842	0.7622	0.050*	0.50
H12C	0.7037	0.2446	0.8178	0.050*	0.50
N1	0.9851 (2)	0.2500	0.59240 (15)	0.0423 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.01951 (15)	0.02179 (16)	0.02326 (17)	0.000	−0.00048 (10)	0.000
P1	0.0231 (3)	0.0276 (3)	0.0220 (2)	0.000	−0.00096 (19)	0.000
P2	0.0226 (2)	0.0224 (2)	0.0292 (2)	0.00031 (14)	0.00004 (14)	−0.00009 (14)
C1	0.0460 (14)	0.0156 (9)	0.0227 (9)	0.000	0.0052 (9)	0.000
C2	0.0265 (9)	0.0215 (9)	0.0247 (9)	0.000	−0.0022 (8)	0.000
C3	0.0265 (10)	0.0286 (10)	0.0266 (10)	0.000	−0.0016 (8)	0.000
C4	0.0275 (10)	0.0345 (11)	0.0364 (11)	0.000	−0.0065 (9)	0.000
C5	0.0409 (12)	0.0341 (11)	0.0325 (11)	0.000	−0.0139 (10)	0.000
C6	0.0470 (13)	0.0310 (11)	0.0244 (10)	0.000	−0.0019 (9)	0.000
C7	0.0306 (11)	0.0290 (10)	0.0275 (10)	0.000	0.0013 (8)	0.000
C8	0.0325 (8)	0.0308 (8)	0.0421 (9)	0.0023 (7)	0.0067 (7)	−0.0037 (7)
C9	0.0302 (8)	0.0272 (7)	0.0398 (8)	−0.0031 (6)	−0.0006 (6)	−0.0024 (7)
C10	0.0327 (8)	0.0307 (8)	0.0407 (9)	0.0046 (6)	−0.0022 (7)	0.0065 (7)
C11	0.0321 (7)	0.0359 (8)	0.0289 (7)	−0.0044 (7)	0.0023 (6)	0.0010 (6)
C12	0.0315 (11)	0.0434 (13)	0.0251 (11)	0.000	−0.0037 (8)	0.000
N1	0.0585 (15)	0.0298 (10)	0.0386 (11)	0.000	0.0021 (11)	0.000

Geometric parameters (Å, º) top

Co1—C2	1.970 (2)	C5—H5	0.9300
Co1—C1	2.011 (3)	C6—C7	1.388 (3)
Co1—P2	2.2034 (6)	C6—H6	0.9300
Co1—P2ⁱ	2.2034 (6)	C7—H7	0.9300
Co1—P1	2.2745 (7)	C8—H8A	0.9600
P1—C12	1.826 (2)	C8—H8B	0.9600
P1—C11	1.8362 (16)	C8—H8C	0.9600
P1—C11ⁱ	1.8362 (16)	C9—H9A	0.9600
P2—C9	1.8200 (16)	C9—H9B	0.9600
P2—C8	1.8186 (16)	C9—H9C	0.9600
P2—C10	1.8252 (16)	C10—H10A	0.9600
C1—N1	1.014 (3)	C10—H10B	0.9600
C2—C3	1.401 (3)	C10—H10C	0.9600
C2—C7	1.407 (3)	C11—H11A	0.9600
C3—C4	1.393 (3)	C11—H11B	0.9600
C3—H3	0.9300	C11—H11C	0.9600
C4—C5	1.384 (4)	C12—H12A	0.9602
C4—H4	0.9300	C12—H12B	0.9602
C5—C6	1.388 (4)	C12—H12C	0.9602

C2—Co1—C1	157.00 (9)	C5—C6—H6	120.0
C2—Co1—P2	88.168 (17)	C7—C6—H6	120.0
C1—Co1—P2	87.783 (16)	C6—C7—C2	123.2 (2)
C2—Co1—P2ⁱ	88.168 (17)	C6—C7—H7	118.4
C1—Co1—P2ⁱ	87.783 (16)	C2—C7—H7	118.4
P2—Co1—P2ⁱ	159.58 (3)	P2—C8—H8A	109.5
C2—Co1—P1	104.05 (6)	P2—C8—H8B	109.5
C1—Co1—P1	98.96 (6)	H8A—C8—H8B	109.5
P2—Co1—P1	100.188 (13)	P2—C8—H8C	109.5
P2ⁱ—Co1—P1	100.188 (13)	H8A—C8—H8C	109.5
C12—P1—C11	100.65 (7)	H8B—C8—H8C	109.5
C12—P1—C11ⁱ	100.65 (7)	P2—C9—H9A	109.5
C11—P1—C11ⁱ	98.78 (11)	P2—C9—H9B	109.5
C12—P1—Co1	115.14 (8)	H9A—C9—H9B	109.5
C11—P1—Co1	119.11 (5)	P2—C9—H9C	109.5
C11ⁱ—P1—Co1	119.11 (5)	H9A—C9—H9C	109.5
C9—P2—C8	101.78 (8)	H9B—C9—H9C	109.5
C9—P2—C10	101.81 (8)	P2—C10—H10A	109.5
C8—P2—C10	101.78 (8)	P2—C10—H10B	109.5
C9—P2—Co1	120.65 (6)	H10A—C10—H10B	109.5
C8—P2—Co1	110.13 (6)	P2—C10—H10C	109.5
C10—P2—Co1	118.01 (6)	H10A—C10—H10C	109.5
N1—C1—Co1	173.8 (2)	H10B—C10—H10C	109.5
C3—C2—C7	114.84 (19)	P1—C11—H11A	109.5
C3—C2—Co1	126.43 (16)	P1—C11—H11B	109.5
C7—C2—Co1	118.73 (16)	H11A—C11—H11B	109.5
C4—C3—C2	122.8 (2)	P1—C11—H11C	109.5
C4—C3—H3	118.6	H11A—C11—H11C	109.5
C2—C3—H3	118.6	H11B—C11—H11C	109.5
C5—C4—C3	120.4 (2)	P1—C12—H12A	109.5
C5—C4—H4	119.8	P1—C12—H12B	109.5
C3—C4—H4	119.8	H12A—C12—H12B	109.5
C4—C5—C6	118.8 (2)	P1—C12—H12C	109.5
C4—C5—H5	120.6	H12A—C12—H12C	109.5
C6—C5—H5	120.6	H12B—C12—H12C	109.5
C5—C6—C7	120.0 (2)

Symmetry code: (i) x, −y+1/2, z.

Experimental details

Crystal data
Chemical formula	[Co(C₆H₅)(CN)(C₃H₉P)₃]
M_r	390.27
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	373
a, b, c (Å)	12.456 (3), 11.420 (2), 14.495 (3)
V (Å³)	2061.9 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.06
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.742, 0.816
No. of measured, independent and observed [I > 2σ(I)] reflections	12996, 2373, 2185
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.640

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.077, 1.04
No. of reflections	2373
No. of parameters	117
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.59

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).

Selected geometric parameters (Å, º) top

Co1—C2	1.970 (2)	Co1—P2	2.2034 (6)
Co1—C1	2.011 (3)	Co1—P1	2.2745 (7)

C2—Co1—C1	157.00 (9)	C2—Co1—P1	104.05 (6)
C2—Co1—P2	88.168 (17)	C1—Co1—P1	98.96 (6)
C1—Co1—P2	87.783 (16)	P2—Co1—P1	100.188 (13)
P2—Co1—P2ⁱ	159.58 (3)

Symmetry code: (i) x, −y+1/2, z.

Acknowledgements

This work was supported by the NSFC (grant Nos. 20572062 and 20372042).

References

Bruker (2001). SMART, SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Li, X. Y., Sun, H. J., Yu, F. L., Florke, U. & Klein, H.-F. (2006). Organometallics, 25, 4695–4697. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1990). Acta Cryst. A46, 467–473. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany. Google Scholar