Bis(2-hydroxy­benzonitrile-κN)dimethyl­bis(trimethyl­phosphine-κP)cobalt(III) iodide

In the title compound, [Co(CH₃)₂(C₇H₅NO)₂(C₃H₉P)₂]I, the Co^III atom lies in the centre of a distorted octa­hedron. The central Co^III atom is coordinated by the N atoms of two 2-hydroxy­benzonitrile ligands, which are positioned in the equatorial plane. The cation lies on a mirror plane (passing through Co and the phosphine ligands) and has approximate C2v symmetry except for the OH groups. The anion also lies on a mirror plane.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.039
• wR factor = 0.101
• Data-to-parameter ratio = 20.0

checkCIF/PLATON results

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Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         P1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         P2
PLAT245_ALERT_2_C U(iso) H1      Smaller than U(eq) O       by ...       0.01 AngSq
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C1     -   C2     ...       1.45 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Many organometallic nitrile complexes were synthesized. Pozdeeva and co-workers prepared the palladium(II) complexes with benzonitrile ligands in an aprotic medium and studied electrochemical reduction of these compounds (Pozdeeva et al., 1983). Wang and co-workers reported the synthesis and the crystal structure of nickel(II) complex with 2-hydroxybenzonitrile. (Wang et al., 2006).

The title compound, [Co(CH₃)₂(C₃H₉P)₂(C₇H₅NO)₂]I, was synthesized by the reaction of (dimethyl)tris(trimethylphosphine)cobalt(III) iodide with 2-hydroxybenzonitrile. The Co^III atom is hexa-coordinated by two N atoms of cis-(2-hydroxybenzonitrile) ligands and two cis-methyl groups and two axial trans-trimethylphosphine ligands, and is in the center of distorted octahedral configuration (Fig.1). The title compound has C2v (mm2) symmetry. The angular deviation of P1—Co—P2 = 170.53 (8)° from 180° may result from the steric hindrance of equatorial 2-hydroxybenzonitrile ligands. The C—N distance of 1.135 (5) Å is relatively long due to the coordination of the N atom to the Co atom. The Co—N distance of 1.956 (4) Å is longer than the Ni—N distance of 1.858 (5) Å in nickel(II) complex with 2-hydroxybenzonitrile. (Wang et al., 2006).

Related literature

For related literature, see: Daran et al. (1984); Duff et al. (1990); Pozdeeva et al. (1983); Wang et al. (2006).

S2. Experimental

All air-sensitive and volatile materials were handled in vacuo or under argon atmosphere using standard Schlenk techniques. The title compound was synthesized through the reaction of (dimethyl)tris(trimethylphosphine)cobalt(III) iodide (0.53 g, 1.17 mmol) with 2-hydroxybenzonitrile (0.28 g, 2.36 mmol) in diethyl ether (80 ml) for 18 h at room temperature. Yellow crystals suitable for X-ray diffraction analysis were obtained from the solution of the title compound in diethyl ether at 253 K.

S3. Refinement

The O bond H atom is positioned in the different Fourier maps and freely refined. Other all H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å for aromatic H atoms and 0.96 Å for methyl H atoms, respectively, and with U_iso(H) = 1.2Ueq(C) for aromatic H atoms and 1.5Ueq(C) for methyl H atoms. The highest peak in the difference map is 0.85 Å from Co and the largest hole is 1.70 Å from H8C.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2001).

Figures

Fig. 1. The molecular structure of the title complex, shown with 50% probability displacement ellipsoids. [Symmetry code: (i) x, 3/2 - y, z.]

Bis(2-hydroxybenzonitrile-κN)dimethylbis(trimethylphosphine-κP)cobalt(III) iodide

Crystal data

[Co(CH3)2(C7H5NO)2(C3H9P)2]I	F(000) = 1224
Mr = 606.28	Dx = 1.435 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ac 2n	Cell parameters from 2687 reflections
a = 13.749 (6) Å	θ = 2.5–22.1°
b = 13.817 (6) Å	µ = 1.84 mm^−1
c = 14.771 (7) Å	T = 294 K
V = 2806 (2) Å^3	Block, yellow
Z = 4	0.22 × 0.18 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2980 independent reflections
Radiation source: fine-focus sealed tube	1677 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.067
Detector resolution: 10 pixels mm^-1	θmax = 26.4°, θmin = 2.0°
φ and ω scans	h = −17→14
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −16→17
Tmin = 0.687, Tmax = 0.757	l = −15→18
15120 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0371P)^2 + 2.8161P] where P = (Fo^2 + 2Fc^2)/3
2980 reflections	(Δ/σ)max < 0.001
149 parameters	Δρmax = 0.73 e Å^−3
0 restraints	Δρmin = −0.46 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co	0.51637 (6)	0.7500	0.12124 (5)	0.0395 (2)
I	0.35233 (4)	0.2500	0.38891 (3)	0.0675 (2)
P1	0.52454 (12)	0.7500	−0.02964 (11)	0.0497 (4)
P2	0.53498 (15)	0.7500	0.27142 (12)	0.0614 (5)
N	0.4156 (3)	0.6501 (3)	0.1238 (2)	0.0441 (9)
O	0.3357 (3)	0.4629 (3)	0.2627 (3)	0.0831 (13)
H1	0.338 (3)	0.412 (4)	0.298 (3)	0.071 (17)*
C1	0.3565 (3)	0.5930 (3)	0.1243 (3)	0.0451 (10)
C2	0.2783 (3)	0.5229 (3)	0.1237 (3)	0.0484 (11)
C3	0.2679 (4)	0.4589 (3)	0.1967 (4)	0.0570 (13)
C4	0.1891 (4)	0.3960 (4)	0.1970 (4)	0.0737 (16)
H4	0.1798	0.3543	0.2456	0.088*
C5	0.1248 (4)	0.3953 (4)	0.1259 (5)	0.087 (2)
H5	0.0723	0.3528	0.1269	0.104*
C6	0.1366 (4)	0.4564 (4)	0.0530 (5)	0.0834 (18)
H6	0.0932	0.4541	0.0049	0.100*
C7	0.2130 (4)	0.5209 (4)	0.0517 (4)	0.0692 (15)
H7	0.2210	0.5628	0.0030	0.083*
C8	0.6466 (5)	0.7500	−0.0769 (5)	0.076 (2)
H8A	0.6775	0.8109	−0.0643	0.115*	0.50
H8B	0.6431	0.7405	−0.1412	0.115*	0.50
H8C	0.6838	0.6986	−0.0501	0.115*	0.50
C9	0.4688 (4)	0.8524 (4)	−0.0866 (3)	0.0831 (18)
H9A	0.4841	0.8501	−0.1500	0.125*
H9B	0.4933	0.9115	−0.0611	0.125*
H9C	0.3995	0.8497	−0.0788	0.125*
C10	0.6603 (6)	0.7500	0.3117 (5)	0.093 (3)
H10A	0.6612	0.7633	0.3754	0.139*	0.50
H10B	0.6966	0.7989	0.2802	0.139*	0.50
H10C	0.6890	0.6878	0.3006	0.139*	0.50
C11	0.4839 (5)	0.8528 (5)	0.3307 (4)	0.111 (2)
H11A	0.4142	0.8492	0.3289	0.166*
H11B	0.5049	0.9115	0.3021	0.166*
H11C	0.5054	0.8522	0.3925	0.166*
C12	0.6168 (3)	0.8572 (3)	0.1187 (3)	0.0610 (13)
H12A	0.6079	0.8957	0.0652	0.091*
H12B	0.6808	0.8295	0.1184	0.091*
H12C	0.6092	0.8974	0.1713	0.091*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.0443 (5)	0.0331 (4)	0.0411 (5)	0.000	−0.0009 (4)	0.000
I	0.0849 (4)	0.0531 (3)	0.0645 (3)	0.000	−0.0021 (3)	0.000
P1	0.0541 (11)	0.0531 (11)	0.0420 (10)	0.000	0.0048 (8)	0.000
P2	0.0831 (15)	0.0558 (12)	0.0452 (11)	0.000	−0.0119 (10)	0.000
N	0.054 (2)	0.0358 (19)	0.043 (2)	−0.0006 (18)	−0.0003 (18)	0.0010 (16)
O	0.102 (3)	0.073 (3)	0.075 (3)	−0.031 (2)	−0.010 (2)	0.025 (2)
C1	0.053 (3)	0.034 (2)	0.048 (3)	0.002 (2)	0.001 (2)	0.003 (2)
C2	0.045 (3)	0.036 (2)	0.065 (3)	−0.003 (2)	0.004 (2)	−0.005 (2)
C3	0.056 (3)	0.042 (3)	0.073 (4)	−0.005 (3)	0.015 (3)	−0.001 (2)
C4	0.066 (4)	0.050 (3)	0.105 (5)	−0.015 (3)	0.028 (4)	0.002 (3)
C5	0.048 (3)	0.051 (3)	0.162 (7)	−0.013 (3)	0.007 (4)	−0.010 (4)
C6	0.064 (4)	0.059 (4)	0.127 (5)	−0.005 (3)	−0.026 (4)	−0.014 (4)
C7	0.070 (4)	0.055 (3)	0.082 (4)	−0.001 (3)	−0.020 (3)	0.002 (3)
C8	0.070 (5)	0.086 (6)	0.074 (5)	0.000	0.025 (4)	0.000
C9	0.102 (4)	0.095 (4)	0.052 (3)	0.030 (4)	0.006 (3)	0.017 (3)
C10	0.113 (7)	0.081 (6)	0.084 (6)	0.000	−0.048 (5)	0.000
C11	0.160 (6)	0.118 (6)	0.054 (4)	0.040 (5)	−0.006 (4)	−0.030 (4)
C12	0.059 (3)	0.051 (3)	0.073 (3)	−0.016 (2)	−0.004 (3)	−0.007 (3)

Geometric parameters (Å, º)

Co—N	1.956 (4)	C4—H4	0.9300
Co—N^i	1.956 (4)	C5—C6	1.378 (8)
Co—C12	2.026 (4)	C5—H5	0.9300
Co—C12^i	2.026 (4)	C6—C7	1.377 (7)
Co—P1	2.232 (2)	C6—H6	0.9300
Co—P2	2.233 (2)	C7—H7	0.9300
Co—C1	3.089 (5)	C8—H8A	0.9600
P1—C9^i	1.816 (5)	C8—H8B	0.9600
P1—C9	1.816 (5)	C8—H8C	0.9600
P1—C8	1.818 (7)	C9—H9A	0.9600
P2—C11^i	1.810 (6)	C9—H9B	0.9600
P2—C11	1.810 (6)	C9—H9C	0.9600
P2—C10	1.822 (7)	C10—H10A	0.9600
N—C1	1.133 (5)	C10—H10B	0.9600
O—C3	1.350 (6)	C10—H10C	0.9600
O—H1	0.88 (5)	C11—H11A	0.9600
C1—C2	1.447 (6)	C11—H11B	0.9600
C2—C7	1.391 (6)	C11—H11C	0.9600
C2—C3	1.402 (6)	C12—H12A	0.9600
C3—C4	1.389 (6)	C12—H12B	0.9600
C4—C5	1.372 (7)	C12—H12C	0.9600
N—Co—N^i	89.8 (2)	C6—C5—H5	119.4
N—Co—C12	177.90 (17)	C7—C6—C5	119.9 (6)
N^i—Co—C12	88.08 (18)	C7—C6—H6	120.1
N^i—Co—C12^i	177.90 (17)	C5—C6—H6	120.1
C12—Co—C12^i	94.0 (3)	C6—C7—C2	119.6 (5)
N—Co—P1	93.14 (10)	C6—C7—H7	120.2
C12—Co—P1	86.96 (14)	C2—C7—H7	120.2
N—Co—P2	93.57 (10)	P1—C8—H8A	109.5
C12—Co—P2	86.59 (14)	P1—C8—H8B	109.5
P1—Co—P2	170.53 (8)	H8A—C8—H8B	109.5
N^i—Co—C1	89.53 (13)	P1—C8—H8C	109.5
C12—Co—C1	177.60 (16)	H8A—C8—H8C	109.5
C12^i—Co—C1	88.36 (16)	H8B—C8—H8C	109.5
P1—Co—C1	92.88 (8)	P1—C9—H9A	109.5
P2—Co—C1	93.85 (9)	P1—C9—H9B	109.5
C9^i—P1—C9	102.4 (4)	H9A—C9—H9B	109.5
C9—P1—C8	102.2 (2)	P1—C9—H9C	109.5
C9—P1—Co	116.20 (17)	H9A—C9—H9C	109.5
C8—P1—Co	115.5 (3)	H9B—C9—H9C	109.5
C11^i—P2—C11	103.3 (5)	P2—C10—H10A	109.5
C11—P2—C10	102.1 (3)	P2—C10—H10B	109.5
C11—P2—Co	115.8 (2)	H10A—C10—H10B	109.5
C10—P2—Co	115.6 (3)	P2—C10—H10C	109.5
C1—N—Co	179.0 (4)	H10A—C10—H10C	109.5
C3—O—H1	114 (3)	H10B—C10—H10C	109.5
N—C1—C2	177.7 (5)	P2—C11—H11A	109.5
C2—C1—Co	177.1 (3)	P2—C11—H11B	109.5
C7—C2—C3	120.6 (4)	H11A—C11—H11B	109.5
C7—C2—C1	119.8 (4)	P2—C11—H11C	109.5
C3—C2—C1	119.5 (4)	H11A—C11—H11C	109.5
O—C3—C4	124.2 (5)	H11B—C11—H11C	109.5
O—C3—C2	117.3 (4)	Co—C12—H12A	109.5
C4—C3—C2	118.4 (5)	Co—C12—H12B	109.5
C5—C4—C3	120.3 (5)	H12A—C12—H12B	109.5
C5—C4—H4	119.8	Co—C12—H12C	109.5
C3—C4—H4	119.8	H12A—C12—H12C	109.5
C4—C5—C6	121.1 (5)	H12B—C12—H12C	109.5
C4—C5—H5	119.4
N—Co—P1—C9^i	−15.3 (2)	N^i—Co—P2—C11	−15.6 (3)
N^i—Co—P1—C9^i	−105.3 (3)	C12—Co—P2—C11	72.2 (3)
C12—Co—P1—C9^i	166.8 (3)	C12^i—Co—P2—C11	166.5 (3)
C12^i—Co—P1—C9^i	72.6 (3)	C1—Co—P2—C11	−105.4 (3)
C1—Co—P1—C9^i	−15.6 (2)	N—Co—P2—C10	134.98 (10)
N—Co—P1—C9	105.3 (3)	N^i—Co—P2—C10	−134.98 (10)
N^i—Co—P1—C9	15.3 (2)	C12—Co—P2—C10	−47.12 (14)
C12—Co—P1—C9	−72.6 (3)	C12^i—Co—P2—C10	47.12 (14)
C12^i—Co—P1—C9	−166.8 (3)	C1—Co—P2—C10	135.24 (8)
C1—Co—P1—C9	105.0 (2)	C7—C2—C3—O	177.9 (4)
N—Co—P1—C8	−135.01 (10)	C1—C2—C3—O	−3.4 (6)
N^i—Co—P1—C8	135.01 (10)	C7—C2—C3—C4	−2.3 (7)
C12—Co—P1—C8	47.10 (14)	C1—C2—C3—C4	176.4 (4)
C12^i—Co—P1—C8	−47.10 (14)	O—C3—C4—C5	−178.4 (5)
C1—Co—P1—C8	−135.30 (8)	C2—C3—C4—C5	1.8 (7)
N—Co—P2—C11^i	15.6 (3)	C3—C4—C5—C6	−0.1 (9)
N^i—Co—P2—C11^i	105.7 (3)	C4—C5—C6—C7	−1.2 (9)
C12—Co—P2—C11^i	−166.5 (3)	C5—C6—C7—C2	0.7 (8)
C12^i—Co—P2—C11^i	−72.2 (3)	C3—C2—C7—C6	1.1 (7)
C1—Co—P2—C11^i	15.9 (3)	C1—C2—C7—C6	−177.6 (5)
N—Co—P2—C11	−105.7 (3)

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O—H1···I	0.88 (5)	2.62 (5)	3.490 (4)	175 (4)