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Acta Cryst. (2007). E63, m2590    [ doi:10.1107/S1600536807045163 ]

(2-Formyl-4-phenylcyclohexen-1-olato)-cis-dimethyl-trans-bis(trimethylphosphine)cobalt(III)

J. Zhou, S. Fang, H. Sun and X. Li

Abstract top

In the title compound, [Co(CH3)2(C13H13O2)(C3H9P)2], the Co is at the centre of a distorted octahedron, with two methyl groups trans to the chelating 2-formyl-4-phenylcyclohexen-1-olato ligand forming the equatorial plane and two trimethylphosphine groups in the axial positions. The cyclohexene is partially disordered equally over two positions.

Comment top

Reaction of substituted enolated malonic dialdehydes (enol-form: b-keton-aldehyde) with [CoMe3(PMe3)3] was recently reported (Li et al., 2005). 2-Hydroxy-5-phenyl-cyclohex-1-enecarbaldehyde reacts with [CoMe3(PMe3)3] (Scheme) by elimination of methane and trimethylphosphine utilizing both the phenolato and the keto-oxygen functions to afford the hexacoordinate title cobalt(III) complex as red solids that are soluble in pentane or diethyl ether. Single crystals suitable for X-ray diffraction analysis of title compound were obtained.

A view of the molecular structure is given in Figure 1. Cobalt atom displays an octahedral coordination with two equatorial cis-methyl groups (C20 and C21) and two axial trimethylphosphines as well as a bidentate ligand. The angle P1–Co–P2 of 174.59 (5) implies a slight distortion from an ideal octahedron. The substituted salicylaldehyde ligands have Co—O bond lengths of Co1—O1 1.987 (2), Co1—O2 1.980 (3). The chelate ring is planar with the largest deviation from the plane being 0.030 (3)Å at O2.

Related literature top

For related literature, see: Li et al. (2005).

Experimental top

Standard vacuum techniques were used in manipulations of volatile and air-sensitive material. 2-Hydroxy-5-phenyl-cyclohex-1-enecarbaldehyde (958 mg, 4.74 mmol) in diethyl ether (20 mL) was combined with [CoMe3(PMe3)3] (1,810 mg, 5.45 mmol) in diethyl ether(40 ml) at room temperature. The mixture was stirred for 20 h. During this period the solution turned red. The volatiles were removed in vacuo and the residue was extracted with pentane. Crystallization at −20 °C afforded red microcrystals.

Refinement top

All H atoms were fixed geometrically and treated as riding on their parent atoms with C—H = 0.93Å (aromatic), 0.96Å (methyl), 0.97Å (methylene) and 0.98Å (methine) with Uiso(H) = xUeq(C), x having the value 1.2 or 1.5(methylene).

The cyclohexene is partially stastically distributed over two positions. This disordered moiety was treated using the restraints available in SHELXL97 (SAME and PART instructions). The value of the occupancy factor, 1/2, was determined in the first stages of the refinement. The thermal displacement parameters for the disordered atoms were restrained using equal Uij constraint.

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: ORTEPIII (Burnett & Johnson, 1996); ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title complex. Ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. Only one component of the disordered moiety is represented.
[Figure 2] Fig. 2. Preparation of the title compound.
(2-Formyl-4-phenylcyclohexen-1-olato- cis-dimethyl-trans-bis(trimethylphosphine)cobalt(III) top
Crystal data top
[Co(CH3)2(C13H13O2)(C3H9P)2]F(000) = 944
Mr = 442.38Dx = 1.199 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4681 reflections
a = 14.109 (3) Åθ = 2.3–24.3°
b = 9.2740 (19) ŵ = 0.84 mm−1
c = 19.577 (4) ÅT = 423 K
β = 106.94 (3)°Block, red
V = 2450.4 (10) Å30.32 × 0.20 × 0.12 mm
Z = 4
Data collection top
CCD area-detector
diffractometer		4287 independent reflections
Radiation source: fine-focus sealed tube3853 reflections with I > 2σ(I)
graphiteRint = 0.056
φ and ω scansθmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −16→16
Tmin = 0.774, Tmax = 0.906k = −10→11
15313 measured reflectionsl = −23→23
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.061Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.171H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0921P)2 + 3.5216P]
where P = (Fo2 + 2Fc2)/3
4287 reflections(Δ/σ)max = 0.008
249 parametersΔρmax = 1.68 e Å−3
11 restraintsΔρmin = −0.85 e Å−3
Crystal data top
[Co(CH3)2(C13H13O2)(C3H9P)2]V = 2450.4 (10) Å3
Mr = 442.38Z = 4
Monoclinic, P21/cMo Kα radiation
a = 14.109 (3) ŵ = 0.84 mm−1
b = 9.2740 (19) ÅT = 423 K
c = 19.577 (4) Å0.32 × 0.20 × 0.12 mm
β = 106.94 (3)°
Data collection top
CCD area-detector
diffractometer		4287 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3853 reflections with I > 2σ(I)
Tmin = 0.774, Tmax = 0.906Rint = 0.056
15313 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.061H-atom parameters constrained
wR(F2) = 0.171Δρmax = 1.68 e Å−3
S = 1.05Δρmin = −0.85 e Å−3
4287 reflectionsAbsolute structure: ?
249 parametersFlack parameter: ?
11 restraintsRogers parameter: ?
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*/UeqOcc. (<1)
C10.3655 (3)0.6037 (5)0.2286 (2)0.0656 (13)
H10.41820.54040.23330.079*
C20.3761 (3)0.7006 (4)0.2847 (2)0.0507 (9)
C30.3028 (3)0.8021 (4)0.28556 (19)0.0443 (8)
C4A0.3159 (10)0.8974 (17)0.3510 (6)0.0588 (14)0.50
H4A10.27800.85650.38050.071*0.50
H4A20.28840.99180.33540.071*0.50
C5A0.4261 (6)0.9165 (10)0.3979 (5)0.0588 (14)0.50
H5A10.46360.97090.37230.071*0.50
H5A20.42910.96670.44190.071*0.50
C6A0.4676 (7)0.7631 (11)0.4136 (5)0.050 (2)0.50
H6A0.42490.70520.43440.059*0.50
C7A0.4736 (15)0.696 (3)0.3447 (11)0.0588 (14)0.50
H7A10.49410.59620.35370.071*0.50
H7A20.52400.74580.32900.071*0.50
C4B0.3213 (10)0.9155 (16)0.3432 (6)0.0588 (14)0.50
H4B10.25930.93880.35270.071*0.50
H4B20.34571.00250.32650.071*0.50
C5B0.3982 (6)0.8638 (11)0.4139 (4)0.0588 (14)0.50
H5B10.41350.94140.44860.071*0.50
H5B20.37180.78320.43420.071*0.50
C6B0.4903 (6)0.8187 (12)0.3946 (5)0.051 (2)0.50
H6B0.51440.89870.37150.061*0.50
C7B0.4707 (15)0.688 (3)0.3465 (12)0.0588 (14)0.50
H7B10.46620.60380.37450.071*0.50
H7B20.52630.67460.32740.071*0.50
C80.5720 (3)0.7739 (6)0.4658 (3)0.0711 (14)
C90.6592 (3)0.8420 (5)0.4667 (2)0.0612 (11)
H90.66110.90200.42910.073*
C100.7440 (3)0.8217 (4)0.5234 (2)0.0528 (9)
H100.80230.86850.52340.063*
C110.7430 (3)0.7336 (5)0.5794 (2)0.0538 (9)
H110.80020.72050.61710.065*
C120.6567 (3)0.6648 (6)0.5793 (3)0.0705 (12)
H120.65510.60430.61680.085*
C130.5718 (3)0.6866 (6)0.5224 (3)0.0806 (16)
H130.51330.64080.52270.097*
C140.1131 (4)0.5802 (6)0.2979 (2)0.0703 (12)
H14A0.08430.67310.30060.106*
H14B0.18190.58170.32500.106*
H14C0.07910.50850.31720.106*
C150.1576 (5)0.3580 (6)0.2137 (3)0.0924 (18)
H15A0.22820.36590.23310.139*
H15B0.14190.31440.16730.139*
H15C0.13180.29950.24460.139*
C16−0.0301 (4)0.4970 (8)0.1689 (4)0.108 (2)
H16A−0.05030.43180.20000.162*
H16B−0.04140.45330.12270.162*
H16C−0.06770.58450.16430.162*
C170.2460 (7)1.0381 (7)0.1306 (4)0.130 (3)
H17A0.28471.02600.17950.194*
H17B0.18481.08530.12890.194*
H17C0.28221.09570.10600.194*
C180.1411 (6)0.9086 (10)−0.0004 (3)0.131 (3)
H18A0.16550.9942−0.01710.197*
H18B0.07470.92500.00160.197*
H18C0.14120.8303−0.03240.197*
C190.3384 (6)0.8276 (11)0.0729 (5)0.145 (3)
H19A0.33280.74390.04320.218*
H19B0.38750.81070.11780.218*
H19C0.35760.90910.04980.218*
C200.0439 (3)0.8123 (5)0.1320 (2)0.0554 (10)
H20A0.01730.80090.17160.083*
H20B−0.00340.77800.08920.083*
H20C0.05740.91240.12650.083*
C210.1195 (4)0.5831 (5)0.0613 (2)0.0681 (12)
H21A0.16370.59410.03250.102*
H21B0.05460.61560.03500.102*
H21C0.11660.48330.07370.102*
Co10.16868 (3)0.69957 (5)0.14988 (2)0.0409 (2)
O10.22006 (17)0.8152 (3)0.23848 (13)0.0436 (6)
O20.2941 (2)0.5894 (4)0.17176 (15)0.0665 (9)
P20.10199 (9)0.53792 (12)0.20619 (6)0.0583 (3)
P30.22019 (9)0.86373 (15)0.08824 (6)0.0626 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.047 (2)0.077 (3)0.059 (2)0.026 (2)−0.0057 (18)−0.028 (2)
C20.0403 (19)0.056 (2)0.046 (2)0.0117 (16)−0.0029 (16)−0.0164 (17)
C30.0372 (18)0.047 (2)0.0448 (19)0.0013 (14)0.0054 (15)−0.0117 (15)
C4A0.0450 (16)0.066 (3)0.0544 (18)0.0138 (15)−0.0031 (14)−0.0238 (17)
C5A0.0450 (16)0.066 (3)0.0544 (18)0.0138 (15)−0.0031 (14)−0.0238 (17)
C6A0.032 (4)0.068 (6)0.045 (5)−0.001 (4)0.004 (3)−0.015 (4)
C7A0.0450 (16)0.066 (3)0.0544 (18)0.0138 (15)−0.0031 (14)−0.0238 (17)
C4B0.0450 (16)0.066 (3)0.0544 (18)0.0138 (15)−0.0031 (14)−0.0238 (17)
C5B0.0450 (16)0.066 (3)0.0544 (18)0.0138 (15)−0.0031 (14)−0.0238 (17)
C6B0.032 (4)0.070 (7)0.045 (5)−0.003 (4)0.002 (4)−0.008 (4)
C7B0.0450 (16)0.066 (3)0.0544 (18)0.0138 (15)−0.0031 (14)−0.0238 (17)
C80.045 (2)0.091 (4)0.059 (3)0.018 (2)−0.013 (2)−0.037 (3)
C90.068 (3)0.060 (2)0.044 (2)0.017 (2)−0.0030 (19)−0.0113 (18)
C100.048 (2)0.054 (2)0.049 (2)−0.0056 (17)0.0014 (17)−0.0088 (17)
C110.041 (2)0.060 (2)0.051 (2)−0.0029 (17)−0.0020 (16)−0.0057 (18)
C120.056 (3)0.083 (3)0.068 (3)−0.013 (2)0.011 (2)−0.005 (2)
C130.041 (2)0.100 (4)0.095 (4)−0.016 (2)0.011 (2)−0.041 (3)
C140.081 (3)0.071 (3)0.060 (3)−0.002 (2)0.023 (2)0.014 (2)
C150.137 (5)0.049 (3)0.082 (4)0.013 (3)0.018 (3)0.006 (2)
C160.073 (3)0.111 (5)0.112 (5)−0.039 (3)−0.015 (3)0.039 (4)
C170.200 (9)0.068 (4)0.147 (7)−0.038 (5)0.094 (7)0.002 (4)
C180.131 (6)0.165 (7)0.083 (4)−0.028 (5)0.007 (4)0.065 (5)
C190.104 (5)0.196 (9)0.174 (8)−0.001 (6)0.102 (6)0.018 (7)
C200.039 (2)0.071 (3)0.051 (2)0.0045 (18)0.0064 (17)0.0070 (19)
C210.074 (3)0.072 (3)0.042 (2)0.006 (2)−0.0099 (19)−0.017 (2)
Co10.0373 (3)0.0430 (3)0.0352 (3)0.00283 (18)−0.0010 (2)−0.00375 (18)
O10.0340 (12)0.0474 (14)0.0433 (13)0.0069 (10)0.0016 (10)−0.0100 (10)
O20.0526 (16)0.077 (2)0.0533 (16)0.0230 (14)−0.0101 (13)−0.0320 (15)
P20.0603 (6)0.0510 (6)0.0514 (6)−0.0060 (5)−0.0028 (5)0.0062 (4)
P30.0606 (7)0.0753 (8)0.0574 (6)−0.0078 (6)0.0259 (5)0.0036 (5)
Geometric parameters (Å, °) top
C1—O21.271 (5)C12—C131.393 (7)
C1—C21.394 (5)C12—H120.9300
C1—H10.9300C13—H130.9300
C2—C31.403 (5)C14—P21.800 (5)
C2—C7B1.521 (10)C14—H14A0.9600
C2—C7A1.526 (10)C14—H14B0.9600
C3—O11.265 (4)C14—H14C0.9600
C3—C4A1.523 (10)C15—P21.831 (5)
C3—C4B1.509 (10)C15—H15A0.9600
C4A—C5A1.569 (12)C15—H15B0.9600
C4A—H4A10.9700C15—H15C0.9600
C4A—H4A20.9700C16—P21.832 (5)
C5A—C6A1.534 (11)C16—H16A0.9600
C5A—H5A10.9700C16—H16B0.9600
C5A—H5A20.9700C16—H16C0.9600
C6A—C7A1.510 (16)C17—P31.806 (7)
C6A—C81.533 (9)C17—H17A0.9600
C6A—H6A0.9800C17—H17B0.9600
C7A—H7A10.9700C17—H17C0.9600
C7A—H7A20.9700C18—P31.817 (6)
C4B—C5B1.565 (12)C18—H18A0.9600
C4B—H4B10.9700C18—H18B0.9600
C4B—H4B20.9700C18—H18C0.9600
C5B—C6B1.514 (10)C19—P31.810 (6)
C5B—H5B10.9700C19—H19A0.9600
C5B—H5B20.9700C19—H19B0.9600
C6B—C7B1.508 (16)C19—H19C0.9600
C6B—C81.584 (10)C20—Co11.990 (4)
C6B—H6B0.9800C20—H20A0.9600
C7B—H7B10.9700C20—H20B0.9600
C7B—H7B20.9700C20—H20C0.9600
C8—C131.372 (8)C21—Co11.989 (4)
C8—C91.377 (7)C21—H21A0.9600
C9—C101.388 (6)C21—H21B0.9600
C9—H90.9300C21—H21C0.9600
C10—C111.370 (6)Co1—O21.980 (3)
C10—H100.9300Co1—O11.987 (2)
C11—C121.374 (6)Co1—P32.1938 (13)
C11—H110.9300Co1—P22.2254 (13)
O2—C1—C2129.3 (4)C8—C13—C12121.8 (5)
O2—C1—H1115.4C8—C13—H13119.1
C2—C1—H1115.4C12—C13—H13119.1
C1—C2—C3122.2 (3)P2—C14—H14A109.5
C1—C2—C7B116.5 (5)P2—C14—H14B109.5
C3—C2—C7B121.3 (5)H14A—C14—H14B109.5
C1—C2—C7A117.0 (5)P2—C14—H14C109.5
C3—C2—C7A120.8 (5)H14A—C14—H14C109.5
C7B—C2—C7A3(3)H14B—C14—H14C109.5
O1—C3—C2125.7 (3)P2—C15—H15A109.5
O1—C3—C4A114.7 (5)P2—C15—H15B109.5
C2—C3—C4A119.4 (5)H15A—C15—H15B109.5
O1—C3—C4B113.6 (5)P2—C15—H15C109.5
C2—C3—C4B120.6 (5)H15A—C15—H15C109.5
C4A—C3—C4B9.6 (15)H15B—C15—H15C109.5
C3—C4A—C5A114.4 (8)P2—C16—H16A109.5
C3—C4A—H4A1108.6P2—C16—H16B109.5
C5A—C4A—H4A1108.6H16A—C16—H16B109.5
C3—C4A—H4A2108.7P2—C16—H16C109.5
C5A—C4A—H4A2108.7H16A—C16—H16C109.5
H4A1—C4A—H4A2107.6H16B—C16—H16C109.5
C6A—C5A—C4A105.6 (8)P3—C17—H17A109.5
C6A—C5A—H5A1110.6P3—C17—H17B109.5
C4A—C5A—H5A1110.6H17A—C17—H17B109.5
C6A—C5A—H5A2110.6P3—C17—H17C109.5
C4A—C5A—H5A2110.6H17A—C17—H17C109.5
H5A1—C5A—H5A2108.8H17B—C17—H17C109.5
C5A—C6A—C7A108.7 (13)P3—C18—H18A109.5
C5A—C6A—C8108.0 (7)P3—C18—H18B109.5
C7A—C6A—C8109.3 (8)H18A—C18—H18B109.5
C5A—C6A—H6A110.2P3—C18—H18C109.5
C7A—C6A—H6A110.2H18A—C18—H18C109.5
C8—C6A—H6A110.2H18B—C18—H18C109.5
C6A—C7A—C2113.8 (11)P3—C19—H19A109.5
C6A—C7A—H7A1108.8P3—C19—H19B109.5
C2—C7A—H7A1108.8H19A—C19—H19B109.5
C6A—C7A—H7A2108.8P3—C19—H19C109.5
C2—C7A—H7A2108.8H19A—C19—H19C109.5
H7A1—C7A—H7A2107.7H19B—C19—H19C109.5
C3—C4B—C5B111.9 (8)Co1—C20—H20A109.5
C3—C4B—H4B1109.2Co1—C20—H20B109.5
C5B—C4B—H4B1109.2H20A—C20—H20B109.5
C3—C4B—H4B2109.2Co1—C20—H20C109.5
C5B—C4B—H4B2109.2H20A—C20—H20C109.5
H4B1—C4B—H4B2107.9H20B—C20—H20C109.5
C6B—C5B—C4B106.8 (9)Co1—C21—H21A109.5
C6B—C5B—H5B1110.4Co1—C21—H21B109.5
C4B—C5B—H5B1110.4H21A—C21—H21B109.5
C6B—C5B—H5B2110.4Co1—C21—H21C109.5
C4B—C5B—H5B2110.4H21A—C21—H21C109.5
H5B1—C5B—H5B2108.6H21B—C21—H21C109.5
C5B—C6B—C7B111.3 (13)O2—Co1—O190.80 (10)
C5B—C6B—C8108.1 (7)O2—Co1—C2188.33 (16)
C7B—C6B—C8107.1 (10)O1—Co1—C21179.06 (16)
C5B—C6B—H6B110.1O2—Co1—C20177.72 (14)
C7B—C6B—H6B110.1O1—Co1—C2087.09 (15)
C8—C6B—H6B110.1C21—Co1—C2093.79 (19)
C6B—C7B—C2113.3 (11)O2—Co1—P393.37 (12)
C6B—C7B—H7B1108.9O1—Co1—P390.61 (9)
C2—C7B—H7B1108.9C21—Co1—P389.12 (16)
C6B—C7B—H7B2108.9C20—Co1—P387.51 (13)
C2—C7B—H7B2108.9O2—Co1—P291.46 (12)
H7B1—C7B—H7B2107.7O1—Co1—P291.75 (9)
C13—C8—C9118.2 (4)C21—Co1—P288.60 (16)
C13—C8—C6A105.8 (6)C20—Co1—P287.76 (13)
C9—C8—C6A136.0 (6)P3—Co1—P2174.60 (5)
C13—C8—C6B133.8 (6)C3—O1—Co1127.5 (2)
C9—C8—C6B108.0 (6)C1—O2—Co1124.5 (2)
C6A—C8—C6B28.1 (4)C14—P2—C15102.0 (3)
C8—C9—C10120.4 (5)C14—P2—C16103.1 (3)
C8—C9—H9119.8C15—P2—C16101.9 (3)
C10—C9—H9119.8C14—P2—Co1114.89 (17)
C11—C10—C9120.8 (4)C15—P2—Co1114.9 (2)
C11—C10—H10119.6C16—P2—Co1118.0 (2)
C9—C10—H10119.6C17—P3—C1999.8 (5)
C10—C11—C12119.5 (4)C17—P3—C18102.7 (4)
C10—C11—H11120.3C19—P3—C18102.9 (4)
C12—C11—H11120.3C17—P3—Co1115.1 (2)
C11—C12—C13119.3 (5)C19—P3—Co1115.6 (3)
C11—C12—H12120.4C18—P3—Co1118.3 (2)
C13—C12—H12120.4
Acknowledgements top

Financial support of this work by the Excellent Young Teachers Program of MOE, People's Republic of China, and by the Scientific Research Foundation for the Returned Overseas Chinese Scholars/State Education Ministry, Natural Science Foundation of Shandong University for Young Scientists, is gratefully acknowledged.

references
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