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Acta Cryst. (2008). E64, m210    [ doi:10.1107/S1600536807062654 ]

cis-Dichlorido(3-chloro-2-methyliminophenyl-[kappa]2C1,N)-trans-bis(trimethylphosphine-[kappa]P)cobalt(III)

Y. Chen, J. Zhou and X. Li

Abstract top

In the title compound, [CoCl2(C8H7ClN)(C3H9P)2], the Co atom displays an octahedral coordination, with two cis Cl atoms perpendicular to two trans trimethylphosphine ligands as well as trans to the bidentate 3-chloro-2-methyliminophenyl ligand.

Comment top

Reaction of chlorinated phenyl Schiff bases with [CoCl(PMe3)3] has been reported recently (Chen et al., 2007). N-(2,6-Dichlorobenzylidene)methanamine reacts with [CoCl(PMe3)3] by a cyclometallation reaction involving C—Cl bond activation at cobalt(I) centers and with imine as pre-chelate ligands to afford the hexacoordinate title cobalt(III) complex as a red solid that is soluble in pentane or diethyl ether.

A view of the molecular structure is given in Fig. 1. The cobalt atom displays an octahedral coordination with two cis-chlorine atoms (Cl1 and Cl2) perpendicular to two trans trimethylphosphine ligands as well as trans to the bidentate 3-chloro-2-methyliminophenyl ligand. The P1—Co—P2 angle of 172.71 (2)° implies a slight distortion from an ideal octahedron. The sum of the internal angles (540°) indicates planarity of the chelate ring. The C?N bond length C7—N1 [1.288 (2) Å] is relatively long, indicating significant bond weakening upon coordination of the nitrogen donor atom. The longer Co1—Cl5 bond [2.3471 (6) Å], when compared with Co1—Cl1 [2.2742 (5) Å], reflects the stronger trans-influence of the carbon atom (C1) than that of the nitrogen atom (N1).

Related literature top

For reactions of chlorinated phenyl Schiff bases with [CoCl(PMe3)3], see: Chen et al. (2007).

Experimental top

Standard vacuum techniques were used in the manipulations of volatile and air-sensitive materials. Chlorotris(trimethylphosphane)cobalt(I) (1.11 g, 3.44 mmol) was dissolved in 40 ml of tetrahydrofuran (THF). To this solution was added N-(2,6-dichlorobenzylidene)methanamine (0.63 g, 3.43 mmol) in 20 ml of THF at 193 K. The mixture was allowed to warm to 293 K and stirred for 18 h to form a red-brown turbid mixture. The filtrate was evaporated in vacuo, and the residue was extracted with pentane (60 ml)and diethyl ether (60 ml), respectively. Crystallization in diethyl ether at 246 K afforded the title complex as red crystals in 57% yield.

Refinement top

The H atoms were introduced at calculated positions as riding atoms, with C—H bond lengths of 0.93 (CH) or 0.96 Å (CH3) and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C), respectively.

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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title complex, shown with 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. The formation of the title compound.
cis-Dichlorido(3-chloro-2-methyliminophenyl-κ2C1,N)-trans- bis(trimethylphosphine-κP)cobalt(III) top
Crystal data top
[CoCl2(C8H7ClN)(C3H9P)2]Dx = 1.470 Mg m−3
Mr = 434.57Mo Kα radiation
λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 3063 reflections
a = 8.5530 (17) Åθ = 3.1–20.4º
b = 10.543 (2) ŵ = 1.44 mm−1
c = 21.769 (4) ÅT = 298 (2) K
V = 1963.0 (7) Å3Block, red
Z = 40.30 × 0.30 × 0.28 mm
F000 = 896
Data collection top
Bruker P4
diffractometer		Rint = 0.038
Radiation source: fine-focus sealed tubeθmax = 28.5º
Monochromator: graphiteθmin = 1.9º
T = 298(2) Kh = −11→9
ω scansk = −14→14
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		l = −29→26
Tmin = 0.672, Tmax = 0.6892699 standard reflections
16045 measured reflections every 5 reflections
4910 independent reflections intensity decay: 0.02%
4868 reflections with I > 2σ(I)
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.025  w = 1/[σ2(Fo2) + (0.0416P)2 + 0.7929P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.066(Δ/σ)max = 0.001
S = 1.07Δρmax = 0.47 e Å−3
4910 reflectionsΔρmin = −0.43 e Å−3
190 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 2082 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: −0.001 (9)
Crystal data top
[CoCl2(C8H7ClN)(C3H9P)2]V = 1963.0 (7) Å3
Mr = 434.57Z = 4
Orthorhombic, P212121Mo Kα
a = 8.5530 (17) ŵ = 1.44 mm−1
b = 10.543 (2) ÅT = 298 (2) K
c = 21.769 (4) Å0.30 × 0.30 × 0.28 mm
Data collection top
Bruker P4
diffractometer		4868 reflections with I > 2σ(I)
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		Rint = 0.038
Tmin = 0.672, Tmax = 0.6892699 standard reflections
16045 measured reflections every 5 reflections
4910 independent reflections intensity decay: 0.02%
Refinement top
R[F2 > 2σ(F2)] = 0.025H-atom parameters constrained
wR(F2) = 0.066Δρmax = 0.47 e Å−3
S = 1.07Δρmin = −0.43 e Å−3
4910 reflectionsAbsolute structure: Flack (1983), 2082 Friedel pairs
190 parametersFlack parameter: −0.001 (9)
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
xyzUiso*/Ueq
N10.03793 (18)0.45205 (14)0.18750 (6)0.0120 (3)
Co10.21282 (3)0.51827 (2)0.141359 (10)0.00967 (6)
Cl10.41880 (5)0.58705 (4)0.08431 (2)0.01627 (9)
Cl20.23616 (5)0.69589 (4)0.205711 (19)0.01659 (9)
Cl3−0.14169 (5)0.09058 (4)0.112040 (19)0.01852 (9)
P10.06006 (6)0.62472 (4)0.07525 (2)0.01346 (9)
P20.38816 (5)0.41085 (4)0.19781 (2)0.01276 (9)
C10.1815 (2)0.36764 (16)0.09372 (8)0.0121 (3)
C20.2656 (2)0.32345 (17)0.04297 (8)0.0159 (3)
H2A0.34640.37210.02680.019*
C30.2291 (2)0.20742 (17)0.01664 (8)0.0170 (3)
H3A0.28810.1787−0.01640.020*
C40.1063 (2)0.13253 (16)0.03839 (8)0.0161 (3)
H4A0.08320.05490.02020.019*
C50.0203 (2)0.17679 (16)0.08749 (8)0.0136 (3)
C60.0574 (2)0.29240 (15)0.11584 (8)0.0122 (3)
C7−0.0181 (2)0.34538 (16)0.16892 (8)0.0129 (3)
H7A−0.10150.30550.18840.015*
C8−0.0316 (2)0.50993 (18)0.24222 (8)0.0174 (3)
H8A−0.11680.45840.25640.026*
H8B−0.06960.59310.23220.026*
H8C0.04600.51630.27390.026*
C90.0955 (3)0.79342 (18)0.07302 (10)0.0258 (4)
H9A0.02610.83220.04390.039*
H9B0.20180.80890.06100.039*
H9C0.07740.82900.11300.039*
C100.0760 (3)0.5799 (2)−0.00478 (8)0.0227 (4)
H10A0.00610.6308−0.02890.034*
H10B0.04890.4920−0.00930.034*
H10C0.18140.5930−0.01850.034*
C11−0.1493 (2)0.6155 (2)0.08898 (10)0.0258 (4)
H11A−0.20350.66400.05830.039*
H11B−0.17260.64920.12890.039*
H11C−0.18240.52860.08690.039*
C120.3113 (3)0.3308 (2)0.26513 (9)0.0243 (4)
H12A0.39470.28790.28610.036*
H12B0.23370.27020.25280.036*
H12C0.26480.39200.29220.036*
C130.5434 (3)0.5051 (2)0.23006 (12)0.0293 (5)
H13A0.61220.45160.25330.044*
H13B0.49980.56880.25650.044*
H13C0.60090.54520.19760.044*
C140.4966 (3)0.2879 (2)0.15854 (10)0.0260 (4)
H14A0.56770.24840.18680.039*
H14B0.55430.32460.12520.039*
H14C0.42520.22560.14280.039*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0100 (6)0.0149 (6)0.0111 (6)0.0009 (5)0.0003 (5)0.0007 (5)
Co10.00910 (11)0.00863 (10)0.01127 (10)−0.00028 (8)0.00087 (8)−0.00067 (7)
Cl10.01429 (18)0.01469 (17)0.01983 (19)−0.00287 (15)0.00548 (15)0.00055 (15)
Cl20.0190 (2)0.01338 (18)0.01734 (19)−0.00129 (15)−0.00002 (15)−0.00514 (14)
Cl30.0213 (2)0.01699 (19)0.01728 (18)−0.00885 (16)−0.00267 (16)0.00191 (15)
P10.0146 (2)0.01225 (19)0.0135 (2)0.00196 (15)−0.00023 (16)0.00098 (14)
P20.0109 (2)0.01100 (18)0.0164 (2)−0.00005 (15)−0.00138 (15)0.00015 (16)
C10.0133 (8)0.0113 (7)0.0116 (7)0.0004 (6)−0.0009 (6)0.0013 (5)
C20.0153 (8)0.0150 (7)0.0173 (8)−0.0011 (6)0.0024 (6)−0.0009 (6)
C30.0200 (9)0.0144 (7)0.0166 (8)0.0021 (7)0.0016 (7)−0.0038 (6)
C40.0204 (9)0.0113 (7)0.0166 (8)0.0007 (6)−0.0037 (7)−0.0025 (6)
C50.0144 (8)0.0116 (7)0.0147 (7)−0.0035 (6)−0.0026 (6)0.0020 (6)
C60.0129 (8)0.0123 (7)0.0113 (7)0.0006 (6)−0.0019 (6)0.0015 (6)
C70.0115 (7)0.0157 (7)0.0116 (7)−0.0008 (6)−0.0010 (6)0.0013 (6)
C80.0164 (8)0.0204 (8)0.0153 (8)−0.0002 (7)0.0047 (6)−0.0039 (6)
C90.0352 (12)0.0126 (8)0.0296 (10)0.0023 (8)−0.0070 (9)0.0045 (7)
C100.0277 (10)0.0263 (9)0.0141 (8)0.0070 (8)−0.0023 (7)−0.0008 (7)
C110.0154 (9)0.0350 (11)0.0271 (10)0.0054 (8)−0.0009 (8)0.0060 (8)
C120.0231 (10)0.0274 (9)0.0224 (9)0.0053 (8)0.0013 (7)0.0113 (7)
C130.0226 (10)0.0209 (9)0.0444 (12)−0.0048 (8)−0.0165 (9)0.0012 (8)
C140.0260 (10)0.0282 (10)0.0239 (9)0.0162 (8)−0.0008 (8)−0.0016 (7)
Geometric parameters (Å, °) top
N1—C71.288 (2)C6—C71.437 (2)
N1—C81.465 (2)C7—H7A0.9300
N1—Co11.9323 (15)C8—H8A0.9600
Co1—C11.9155 (17)C8—H8B0.9600
Co1—P12.2444 (6)C8—H8C0.9600
Co1—P22.2455 (5)C9—H9A0.9600
Co1—Cl12.2742 (5)C9—H9B0.9600
Co1—Cl22.3471 (6)C9—H9C0.9600
Cl3—C51.7411 (18)C10—H10A0.9600
P1—C91.805 (2)C10—H10B0.9600
P1—C101.8105 (19)C10—H10C0.9600
P1—C111.818 (2)C11—H11A0.9600
P2—C131.801 (2)C11—H11B0.9600
P2—C141.808 (2)C11—H11C0.9600
P2—C121.814 (2)C12—H12A0.9600
C1—C21.398 (2)C12—H12B0.9600
C1—C61.410 (2)C12—H12C0.9600
C2—C31.386 (2)C13—H13A0.9600
C2—H2A0.9300C13—H13B0.9600
C3—C41.397 (3)C13—H13C0.9600
C3—H3A0.9300C14—H14A0.9600
C4—C51.379 (3)C14—H14B0.9600
C4—H4A0.9300C14—H14C0.9600
C5—C61.403 (2)
C7—N1—C8117.90 (15)C1—C6—C7113.23 (15)
C7—N1—Co1116.15 (12)N1—C7—C6115.12 (16)
C8—N1—Co1125.91 (12)N1—C7—H7A122.4
C1—Co1—N182.74 (7)C6—C7—H7A122.4
C1—Co1—P189.20 (5)N1—C8—H8A109.5
N1—Co1—P193.63 (5)N1—C8—H8B109.5
C1—Co1—P288.36 (5)H8A—C8—H8B109.5
N1—Co1—P292.88 (5)N1—C8—H8C109.5
P1—Co1—P2172.71 (2)H8A—C8—H8C109.5
C1—Co1—Cl194.41 (5)H8B—C8—H8C109.5
N1—Co1—Cl1177.13 (5)P1—C9—H9A109.5
P1—Co1—Cl186.64 (2)P1—C9—H9B109.5
P2—Co1—Cl186.69 (2)H9A—C9—H9B109.5
C1—Co1—Cl2175.19 (5)P1—C9—H9C109.5
N1—Co1—Cl292.52 (5)H9A—C9—H9C109.5
P1—Co1—Cl291.91 (2)H9B—C9—H9C109.5
P2—Co1—Cl291.09 (2)P1—C10—H10A109.5
Cl1—Co1—Cl290.33 (2)P1—C10—H10B109.5
C9—P1—C10102.64 (10)H10A—C10—H10B109.5
C9—P1—C11102.83 (11)P1—C10—H10C109.5
C10—P1—C11102.61 (10)H10A—C10—H10C109.5
C9—P1—Co1114.36 (7)H10B—C10—H10C109.5
C10—P1—Co1116.27 (7)P1—C11—H11A109.5
C11—P1—Co1116.19 (7)P1—C11—H11B109.5
C13—P2—C14101.64 (11)H11A—C11—H11B109.5
C13—P2—C12102.05 (11)P1—C11—H11C109.5
C14—P2—C12103.56 (11)H11A—C11—H11C109.5
C13—P2—Co1115.30 (7)H11B—C11—H11C109.5
C14—P2—Co1116.43 (7)P2—C12—H12A109.5
C12—P2—Co1115.76 (7)P2—C12—H12B109.5
C2—C1—C6118.00 (15)H12A—C12—H12B109.5
C2—C1—Co1129.22 (13)P2—C12—H12C109.5
C6—C1—Co1112.76 (12)H12A—C12—H12C109.5
C3—C2—C1120.33 (17)H12B—C12—H12C109.5
C3—C2—H2A119.8P2—C13—H13A109.5
C1—C2—H2A119.8P2—C13—H13B109.5
C2—C3—C4121.86 (17)H13A—C13—H13B109.5
C2—C3—H3A119.1P2—C13—H13C109.5
C4—C3—H3A119.1H13A—C13—H13C109.5
C5—C4—C3118.20 (16)H13B—C13—H13C109.5
C5—C4—H4A120.9P2—C14—H14A109.5
C3—C4—H4A120.9P2—C14—H14B109.5
C4—C5—C6120.97 (16)H14A—C14—H14B109.5
C4—C5—Cl3119.07 (13)P2—C14—H14C109.5
C6—C5—Cl3119.90 (14)H14A—C14—H14C109.5
C5—C6—C1120.59 (16)H14B—C14—H14C109.5
C5—C6—C7126.16 (16)
Acknowledgements top

We gratefully acknowledge support by the NSF China (No. 20772072) and the Doctoral Program of the Ministry of Education of China (MOE) (Nos. 20050422010 and 20050422011).

references
References top

Bruker (1997). SMART (Version 5.6) and SAINT (Version 5.06A). Bruker AXS Inc., Madison, Wisconsin, USA.

Chen, Y., Sun, H. & Li, X. (2007). Organometallics In the press..Any update?

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Sheldrick, G. M. (2001). SHELXTL. Version 6.12. Bruker AXS Inc., Madison, Wisconsin, USA.