Acta Cryst. (2008). E64, m112 [ doi:10.1107/S1600536807064781 ]
The title molecule, [Co(C6H5)(CN)(C3H9P)3], lies on a crystallographic mirror plane with the CoII 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.
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.
H atoms were included in calculated positions and refined as riding atoms with C—H = 0.93–0.96 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C).
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).
![[Figure 1]](./lh2572fig1thm.gif)
| 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]. |
| [Co(C6H5)(CN)(C3H9P)3] | F000 = 828 |
| Mr = 390.27 | Dx = 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 = 2.1–22.5º |
| b = 11.420 (2) Å | µ = 1.06 mm−1 |
| c = 14.495 (3) Å | T = 373 (2) K |
| V = 2061.9 (7) Å3 | Block, dark red |
| Z = 4 | 0.30 × 0.25 × 0.20 mm |
| Bruker SMART CCD diffractometer | 2373 independent reflections |
| Radiation source: fine-focus sealed tube | 2185 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.057 |
| T = 193(2) K | θmax = 27.1º |
| ω scans | θmin = 2.2º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −15→15 |
| Tmin = 0.742, Tmax = 0.816 | k = −14→14 |
| 12996 measured reflections | l = −18→16 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
| wR(F2) = 0.077 | w = 1/[σ2(Fo2) + (0.042P)2 + 0.7567P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.04 | (Δ/σ)max = 0.019 |
| 2373 reflections | Δρmax = 0.39 e Å−3 |
| 117 parameters | Δρmin = −0.59 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| [Co(C6H5)(CN)(C3H9P)3] | V = 2061.9 (7) Å3 |
| Mr = 390.27 | Z = 4 |
| Orthorhombic, Pnma | Mo Kα |
| a = 12.456 (3) Å | µ = 1.06 mm−1 |
| b = 11.420 (2) Å | T = 373 (2) K |
| c = 14.495 (3) Å | 0.30 × 0.25 × 0.20 mm |
| Bruker SMART CCD diffractometer | 2373 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2185 reflections with I > 2σ(I) |
| Tmin = 0.742, Tmax = 0.816 | Rint = 0.057 |
| 12996 measured reflections |
| R[F2 > 2σ(F2)] = 0.029 | 117 parameters |
| wR(F2) = 0.077 | H-atom parameters constrained |
| S = 1.04 | Δρmax = 0.39 e Å−3 |
| 2373 reflections | Δρmin = −0.59 e Å−3 |
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. |
| x | y | z | Uiso*/Ueq | 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) |
| 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 |
| 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 codes: (i) x, −y+1/2, z. |
| 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 codes: (i) x, −y+1/2, z. |
Bruker (2001). SMART, SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.
Li, X. Y., Sun, H. J., Yu, F. L., Florke, U. & Klein, H.-F. (2006). Organometallics, 25, 4695–4697.
Sheldrick, G. M. (1990). Acta Cryst. A46, 467–473.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany.
In the molecular structure of the title compound the CoII 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).