Cyanidotetra­kis­(trimethyl­phosphine)cobalt(I)

Xu, X.; Feng, L.; Li, X.

doi:10.1107/S160053681101083X

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page m503

doi:10.1107/S160053681101083X

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Cyanidotetrakis(trimethylphosphine)cobalt(I)

Xiaofeng Xu,^a Lei Feng ^a ^* and Xiaoyan Li ^a

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

(Received 15 January 2011; accepted 23 March 2011; online 26 March 2011)

The title compound, [Co(CN)(C₃H₉P)₄], was obtained as a product of the reaction of [Co(PMe₃)₄] with a molar equivalent of 2,6-difluorobenzonitrile in diethyl ether. This compound is stable in the air for several hours, but rapidly decomposes at room temperature in solution. The cobalt(I) atom has s trigonal–bipyramidal coordination enviroment in which the cyano group and one of the PMe₃ groups are in the axial positions.

Related literature

For related cobalt(II) compounds, see: Yu et al. (2008 ); Li et al. (2006 ).

Experimental

Crystal data

[Co(CN)(C₃H₉P)₄]
M_r = 389.24
Monoclinic, P 2₁ /c
a = 13.160 (3) Å
b = 9.6136 (19) Å
c = 17.971 (4) Å
β = 93.09 (3)°
V = 2270.3 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.03 mm⁻¹
T = 293 K
0.25 × 0.23 × 0.22 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.395, T_max = 0.434
11732 measured reflections
4438 independent reflections
3663 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.216
S = 1.06
4438 reflections
185 parameters
150 restraints
H-atom parameters constrained
Δρ_max = 1.06 e Å⁻³
Δρ_min = −2.00 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

C13—N1	1.166 (7)
Co1—C13	1.896 (5)
Co1—P2	2.2018 (15)
Co1—P1	2.2082 (17)
Co1—P4	2.2115 (17)
Co1—P3	2.2272 (17)

N1—C13—Co1	178.8 (6)
C13—Co1—P2	179.02 (19)
C13—Co1—P1	83.92 (19)
P2—Co1—P1	97.05 (7)
C13—Co1—P4	83.39 (18)
P2—Co1—P4	96.24 (6)
P1—Co1—P4	119.14 (8)
C13—Co1—P3	84.66 (19)
P2—Co1—P3	94.75 (7)
P1—Co1—P3	118.05 (8)
P4—Co1—P3	119.55 (8)

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; 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 global, I. DOI: 10.1107/S160053681101083X/om2401sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681101083X/om2401Isup2.hkl

checkCIF report

Comment top

In the title molecule (Fig. 1, Table 1) the cobalt(I) atom has trigonal planar coordination geometry. Three PMe₃ groups using P1, P3 and P4 form the trigonal plane and the fourth PMe₃ group, using P2, and the cyano group are in the axial position. The axial groups are linear with P2-Co1-C13 of 179.02 (1)°. The sum of the bond angles in the trigonal plane (356.75 (8)°) indicates only slightly distorted planarity. We have previously reported two related cobalt(II) structures. In one, (Yu et al., 2008), the axial PMe₃ group is replaced by a phenyl and in the other, it is replaced by a 2,6-difluorophenyl group (Li et al., 2006). These structures show a distorted square pyramidal coordination, which is different from the title compound.

Related literature top

For related cobalt(II) compounds see: Yu et al. (2008); Li et al. (2006).

Experimental top

A sample of Co(PMe₃)₄ (1.0 g, 2.75 mmol) in 30 ml of diethyl ether was combined with a solution of 2,6-difluorobenzonitrile (0.19 g, 1.36 mmol) in diethyl ether (20 ml) at -80%A. The reaction mixture was warmed to ambient temperature and stirred for 24 h to form a red solution. The volatiles were removed in vacuo, and the resulting solid was extracted with pentane (50 ml). Crystallization from its pentane solution at -15 °C afforded red crystals suitable for X-ray diffraction analysis (yield 0.22 g, 42%), dec > 120 °C. The datum crystal was coated with perfluoropolyether to retard decomposition due to air sensitivity during data collection.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); 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. A view of the structure of the title compound showing 30% probability displacement ellipsoids.

Cyanidotetrakis(trimethylphosphine)cobalt(I) top

Crystal data top

[Co(CN)(C₃H₉P)₄]	F(000) = 832.0
M_r = 389.24	D_x = 1.139 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4976 reflections
a = 13.160 (3) Å	θ = 2.3–26.0°
b = 9.6136 (19) Å	µ = 1.03 mm⁻¹
c = 17.971 (4) Å	T = 293 K
β = 93.09 (3)°	Block, red
V = 2270.3 (8) Å³	0.25 × 0.23 × 0.22 mm
Z = 4

Data collection top

Bruker APEXII diffractometer	4438 independent reflections
Radiation source: fine-focus sealed tube	3663 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −15→16
T_min = 0.395, T_max = 0.434	k = −11→11
11732 measured reflections	l = −15→22

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.216	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.1278P)² + 4.380P] where P = (F_o² + 2F_c²)/3
4438 reflections	(Δ/σ)_max < 0.001
185 parameters	Δρ_max = 1.06 e Å⁻³
150 restraints	Δρ_min = −2.00 e Å⁻³

Crystal data top

[Co(CN)(C₃H₉P)₄]	V = 2270.3 (8) Å³
M_r = 389.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.160 (3) Å	µ = 1.03 mm⁻¹
b = 9.6136 (19) Å	T = 293 K
c = 17.971 (4) Å	0.25 × 0.23 × 0.22 mm
β = 93.09 (3)°

Data collection top

Bruker APEXII diffractometer	4438 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3663 reflections with I > 2σ(I)
T_min = 0.395, T_max = 0.434	R_int = 0.020
11732 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	150 restraints
wR(F²) = 0.216	H-atom parameters constrained
S = 1.06	Δρ_max = 1.06 e Å⁻³
4438 reflections	Δρ_min = −2.00 e Å⁻³
185 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
C1	0.0427 (7)	0.5719 (11)	0.6108 (6)	0.112 (3)
H1A	−0.0142	0.5545	0.6407	0.167*
H1B	0.0756	0.4855	0.6002	0.167*
H1C	0.0194	0.6154	0.5649	0.167*
C2	0.1727 (9)	0.5681 (11)	0.7382 (6)	0.125 (4)
H2A	0.2114	0.6174	0.7766	0.187*
H2B	0.2134	0.4948	0.7192	0.187*
H2C	0.1130	0.5292	0.7585	0.187*
C3	0.0419 (8)	0.7949 (12)	0.7113 (7)	0.123 (4)
H3A	−0.0118	0.7361	0.7271	0.184*
H3B	0.0140	0.8651	0.6782	0.184*
H3C	0.0754	0.8383	0.7540	0.184*
C4	0.3468 (6)	0.7624 (9)	0.4375 (4)	0.080 (2)
H4A	0.4136	0.7418	0.4588	0.120*
H4B	0.3416	0.8603	0.4273	0.120*
H4C	0.3353	0.7112	0.3920	0.120*
C5	0.1325 (6)	0.7398 (9)	0.4449 (4)	0.0768 (19)
H5A	0.1354	0.6858	0.4002	0.115*
H5B	0.1263	0.8366	0.4323	0.115*
H5C	0.0748	0.7115	0.4716	0.115*
C6	0.2570 (7)	0.5211 (8)	0.4942 (4)	0.080 (2)
H6A	0.1998	0.4794	0.5167	0.120*
H6B	0.3189	0.4877	0.5186	0.120*
H6C	0.2557	0.4971	0.4424	0.120*
C7	0.5231 (5)	0.8559 (9)	0.6188 (4)	0.0783 (9)
H7A	0.5086	0.8925	0.5697	0.117*
H7B	0.5871	0.8078	0.6203	0.117*
H7C	0.5264	0.9309	0.6541	0.117*
C8	0.4623 (6)	0.7086 (8)	0.7401 (4)	0.0771 (9)
H8A	0.4308	0.6273	0.7597	0.116*
H8B	0.4438	0.7887	0.7682	0.116*
H8C	0.5349	0.6975	0.7436	0.116*
C9	0.4766 (5)	0.5759 (8)	0.6060 (4)	0.0770 (9)
H9A	0.5466	0.5704	0.6237	0.115*
H9B	0.4727	0.5797	0.5525	0.115*
H9C	0.4407	0.4954	0.6222	0.115*
C10	0.1996 (9)	1.0851 (10)	0.4832 (5)	0.114 (3)
H10A	0.1993	1.1849	0.4826	0.172*
H10B	0.1330	1.0512	0.4683	0.172*
H10C	0.2479	1.0513	0.4493	0.172*
C11	0.1338 (10)	1.1173 (12)	0.6267 (7)	0.134 (3)
H11A	0.1330	1.0866	0.6775	0.201*
H11B	0.0691	1.0984	0.6016	0.201*
H11C	0.1470	1.2154	0.6255	0.201*
C12	0.3430 (9)	1.1417 (11)	0.5971 (7)	0.123 (3)
H12A	0.4025	1.1046	0.5757	0.185*
H12B	0.3557	1.1521	0.6499	0.185*
H12C	0.3270	1.2308	0.5754	0.185*
C13	0.2731 (5)	0.8878 (6)	0.7120 (3)	0.0545 (13)
Co1	0.26139 (5)	0.80567 (6)	0.61596 (3)	0.0371 (3)
N1	0.2797 (6)	0.9405 (7)	0.7705 (3)	0.0869 (19)
P1	0.13485 (13)	0.68895 (18)	0.66233 (9)	0.0621 (5)
P2	0.25026 (12)	0.71209 (15)	0.50400 (7)	0.0479 (4)
P3	0.41947 (12)	0.7316 (2)	0.64284 (9)	0.0605 (4)
P4	0.23568 (14)	1.02279 (15)	0.57888 (9)	0.0598 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.099 (5)	0.129 (7)	0.109 (6)	−0.062 (5)	0.023 (5)	−0.026 (5)
C2	0.133 (7)	0.130 (7)	0.111 (6)	−0.039 (6)	0.015 (5)	0.045 (6)
C3	0.097 (6)	0.142 (8)	0.136 (7)	−0.010 (5)	0.061 (6)	−0.021 (6)
C4	0.091 (5)	0.105 (5)	0.046 (3)	−0.014 (4)	0.021 (3)	−0.007 (3)
C5	0.079 (4)	0.086 (4)	0.063 (4)	−0.010 (4)	−0.019 (3)	−0.003 (3)
C6	0.104 (5)	0.061 (4)	0.076 (4)	0.000 (4)	0.002 (4)	−0.019 (3)
C7	0.0674 (16)	0.0953 (17)	0.0713 (16)	0.0130 (15)	−0.0047 (14)	−0.0044 (15)
C8	0.0674 (15)	0.0951 (17)	0.0678 (16)	0.0156 (15)	−0.0053 (14)	−0.0044 (15)
C9	0.0670 (15)	0.0934 (17)	0.0696 (16)	0.0167 (15)	−0.0053 (14)	−0.0069 (15)
C10	0.149 (6)	0.085 (5)	0.106 (5)	0.007 (5)	−0.026 (5)	0.023 (4)
C11	0.153 (7)	0.102 (6)	0.147 (7)	0.044 (5)	0.013 (6)	0.008 (5)
C12	0.141 (6)	0.082 (5)	0.142 (6)	−0.031 (5)	−0.036 (5)	0.022 (5)
C13	0.063 (3)	0.056 (3)	0.044 (3)	0.002 (3)	0.003 (2)	−0.005 (2)
Co1	0.0414 (4)	0.0375 (4)	0.0323 (4)	0.0004 (2)	0.0023 (3)	−0.0018 (2)
N1	0.117 (5)	0.090 (4)	0.053 (3)	0.013 (4)	0.001 (3)	−0.026 (3)
P1	0.0630 (10)	0.0687 (10)	0.0564 (9)	−0.0182 (7)	0.0193 (7)	−0.0050 (7)
P2	0.0575 (8)	0.0509 (8)	0.0353 (7)	−0.0059 (6)	0.0012 (6)	−0.0048 (5)
P3	0.0509 (8)	0.0800 (10)	0.0498 (8)	0.0160 (7)	−0.0038 (6)	−0.0075 (7)
P4	0.0747 (10)	0.0405 (8)	0.0628 (9)	0.0027 (7)	−0.0097 (8)	0.0039 (6)

Geometric parameters (Å, º) top

C1—P1	1.863 (8)	C7—H7C	0.9600
C1—H1A	0.9600	C8—P3	1.820 (7)
C1—H1B	0.9600	C8—H8A	0.9600
C1—H1C	0.9600	C8—H8B	0.9600
C2—P1	1.840 (10)	C8—H8C	0.9600
C2—H2A	0.9600	C9—P3	1.816 (7)
C2—H2B	0.9600	C9—H9A	0.9600
C2—H2C	0.9600	C9—H9B	0.9600
C3—P1	1.850 (9)	C9—H9C	0.9600
C3—H3A	0.9600	C10—P4	1.858 (9)
C3—H3B	0.9600	C10—H10A	0.9600
C3—H3C	0.9600	C10—H10B	0.9600
C4—P2	1.855 (7)	C10—H10C	0.9600
C4—H4A	0.9600	C11—P4	1.866 (11)
C4—H4B	0.9600	C11—H11A	0.9600
C4—H4C	0.9600	C11—H11B	0.9600
C5—P2	1.850 (7)	C11—H11C	0.9600
C5—H5A	0.9600	C12—P4	1.833 (10)
C5—H5B	0.9600	C12—H12A	0.9600
C5—H5C	0.9600	C12—H12B	0.9600
C6—P2	1.847 (7)	C12—H12C	0.9600
C6—H6A	0.9600	C13—N1	1.166 (7)
C6—H6B	0.9600	Co1—C13	1.896 (5)
C6—H6C	0.9600	Co1—P2	2.2018 (15)
C7—P3	1.881 (8)	Co1—P1	2.2082 (17)
C7—H7A	0.9600	Co1—P4	2.2115 (17)
C7—H7B	0.9600	Co1—P3	2.2272 (17)

P1—C1—H1A	109.5	P4—C10—H10B	109.5
P1—C1—H1B	109.5	P4—C10—H10C	109.5
H1A—C1—H1B	109.5	P4—C11—H11A	109.5
P1—C1—H1C	109.5	P4—C11—H11B	109.5
H1A—C1—H1C	109.5	P4—C11—H11C	109.5
H1B—C1—H1C	109.5	P4—C12—H12A	109.5
P1—C2—H2A	109.5	P4—C12—H12B	109.5
P1—C2—H2B	109.5	P4—C12—H12C	109.5
H2A—C2—H2B	109.5	N1—C13—Co1	178.8 (6)
P1—C2—H2C	109.5	C13—Co1—P2	179.02 (19)
H2A—C2—H2C	109.5	C13—Co1—P1	83.92 (19)
H2B—C2—H2C	109.5	P2—Co1—P1	97.05 (7)
P1—C3—H3A	109.5	C13—Co1—P4	83.39 (18)
P1—C3—H3B	109.5	P2—Co1—P4	96.24 (6)
P1—C3—H3C	109.5	P1—Co1—P4	119.14 (8)
P2—C4—H4A	109.5	C13—Co1—P3	84.66 (19)
P2—C4—H4B	109.5	P2—Co1—P3	94.75 (7)
H4A—C4—H4B	109.5	P1—Co1—P3	118.05 (8)
P2—C4—H4C	109.5	P4—Co1—P3	119.55 (8)
H4A—C4—H4C	109.5	C2—P1—C3	98.9 (6)
H4B—C4—H4C	109.5	C2—P1—C1	97.5 (5)
P2—C5—H5A	109.5	C3—P1—C1	98.0 (5)
P2—C5—H5B	109.5	C2—P1—Co1	114.9 (3)
H5A—C5—H5B	109.5	C3—P1—Co1	115.5 (4)
P2—C5—H5C	109.5	C1—P1—Co1	127.1 (3)
H5A—C5—H5C	109.5	C6—P2—C5	97.6 (4)
H5B—C5—H5C	109.5	C6—P2—C4	99.2 (4)
P2—C6—H6A	109.5	C5—P2—C4	100.1 (4)
P2—C6—H6B	109.5	C6—P2—Co1	119.5 (3)
H6A—C6—H6B	109.5	C5—P2—Co1	118.6 (3)
P2—C6—H6C	109.5	C4—P2—Co1	117.9 (3)
H6A—C6—H6C	109.5	C9—P3—C8	97.9 (3)
H6B—C6—H6C	109.5	C9—P3—C7	96.9 (4)
P3—C7—H7A	109.5	C8—P3—C7	96.1 (4)
P3—C7—H7B	109.5	C9—P3—Co1	125.8 (2)
P3—C7—H7C	109.5	C8—P3—Co1	119.0 (2)
P3—C8—H8A	109.5	C7—P3—Co1	115.3 (2)
P3—C8—H8B	109.5	C12—P4—C10	96.9 (5)
P3—C8—H8C	109.5	C12—P4—C11	100.4 (6)
P3—C9—H9A	109.5	C10—P4—C11	96.6 (5)
P3—C9—H9B	109.5	C12—P4—Co1	115.5 (4)
P3—C9—H9C	109.5	C10—P4—Co1	127.6 (3)
P4—C10—H10A	109.5	C11—P4—Co1	115.0 (4)

Experimental details

Crystal data
Chemical formula	[Co(CN)(C₃H₉P)₄]
M_r	389.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	13.160 (3), 9.6136 (19), 17.971 (4)
β (°)	93.09 (3)
V (Å³)	2270.3 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.03
Crystal size (mm)	0.25 × 0.23 × 0.22

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.395, 0.434
No. of measured, independent and observed [I > 2σ(I)] reflections	11732, 4438, 3663
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.216, 1.06
No. of reflections	4438
No. of parameters	185
No. of restraints	150
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.06, −2.00

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

C13—N1	1.166 (7)	Co1—P1	2.2082 (17)
Co1—C13	1.896 (5)	Co1—P4	2.2115 (17)
Co1—P2	2.2018 (15)	Co1—P3	2.2272 (17)

N1—C13—Co1	178.8 (6)	P1—Co1—P4	119.14 (8)
C13—Co1—P2	179.02 (19)	C13—Co1—P3	84.66 (19)
C13—Co1—P1	83.92 (19)	P2—Co1—P3	94.75 (7)
P2—Co1—P1	97.05 (7)	P1—Co1—P3	118.05 (8)
C13—Co1—P4	83.39 (18)	P4—Co1—P3	119.55 (8)
P2—Co1—P4	96.24 (6)

Acknowledgements

We gratefully acknowledge support by the NSF China (No. 20872080/20772072) and the Science Foundation of Shandong Province (Nos. Y2007B06/Y2006B18).

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