cis-Dichlorido(3-chloro-2-methyl­imino­phenyl-κ2C1,N)-trans-bis­(trimethyl­phosphine-κP)cobalt(III)

Chen, Y.; Zhou, J.; Li, X.

doi:10.1107/S1600536807062654

metal-organic compounds

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Volume 64| Part 1| January 2008| Page m210

https://doi.org/10.1107/S1600536807062654

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cis-Dichlorido(3-chloro-2-methyliminophenyl-κ²C¹,N)-trans-bis(trimethylphosphine-κP)cobalt(III)

Yue Chen,^a Jin Zhou ^a and Xiaoyan Li ^a ^*

^aDepartment of Chemistry, Shandong University, Shanda Nanlu 27, Jinan 250100, People's Republic of China
^*Correspondence e-mail: xli63@sdu.edu.cn

(Received 22 November 2007; accepted 23 November 2007; online 18 December 2007)

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.

Related literature

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

Experimental

Crystal data

[CoCl₂(C₈H₇ClN)(C₃H₉P)₂]
M_r = 434.57
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.5530 (17) Å
b = 10.543 (2) Å
c = 21.769 (4) Å
V = 1963.0 (7) Å³
Z = 4
Mo Kα radiation
μ = 1.44 mm⁻¹
T = 298 (2) K
0.30 × 0.30 × 0.28 mm

Data collection

Bruker SMART diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.672, T_max = 0.689
16045 measured reflections
4910 independent reflections
4868 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.066
S = 1.07
4910 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.43 e Å⁻³
Absolute structure: Flack (1983 ), with 2082 Friedel pairs
Flack parameter: −0.001 (9)

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807062654/ln2014sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807062654/ln2014Isup2.hkl

checkCIF report

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.

Structure description top

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

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

	Fig. 1. The molecular structure of the title complex, shown with 30% probability displacement ellipsoids.
	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]	D_x = 1.470 Mg m⁻³
M_r = 434.57	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 3063 reflections
a = 8.5530 (17) Å	θ = 3.1–20.4°
b = 10.543 (2) Å	µ = 1.44 mm⁻¹
c = 21.769 (4) Å	T = 298 K
V = 1963.0 (7) Å³	Block, red
Z = 4	0.30 × 0.30 × 0.28 mm
F(000) = 896

Data collection top

Bruker P4 diffractometer	4868 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.038
Graphite monochromator	θ_max = 28.5°, θ_min = 1.9°
ω scans	h = −11→9
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −14→14
T_min = 0.672, T_max = 0.689	l = −29→26
16045 measured reflections	2699 standard reflections every 5 reflections
4910 independent reflections	intensity decay: 0.02%

Refinement top

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)] = 0.025	H-atom parameters constrained
wR(F²) = 0.066	w = 1/[σ²(F_o²) + (0.0416P)² + 0.7929P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
4910 reflections	Δρ_max = 0.47 e Å⁻³
190 parameters	Δρ_min = −0.43 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 2082 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.001 (9)

Crystal data top

[CoCl₂(C₈H₇ClN)(C₃H₉P)₂]	V = 1963.0 (7) Å³
M_r = 434.57	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.5530 (17) Å	µ = 1.44 mm⁻¹
b = 10.543 (2) Å	T = 298 K
c = 21.769 (4) Å	0.30 × 0.30 × 0.28 mm

Data collection top

Bruker P4 diffractometer	4868 reflections with I > 2σ(I)
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	R_int = 0.038
T_min = 0.672, T_max = 0.689	2699 standard reflections every 5 reflections
16045 measured reflections	intensity decay: 0.02%
4910 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	H-atom parameters constrained
wR(F²) = 0.066	Δρ_max = 0.47 e Å⁻³
S = 1.07	Δρ_min = −0.43 e Å⁻³
4910 reflections	Absolute structure: Flack (1983), 2082 Friedel pairs
190 parameters	Absolute structure parameter: −0.001 (9)
0 restraints

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
N1	0.03793 (18)	0.45205 (14)	0.18750 (6)	0.0120 (3)
Co1	0.21282 (3)	0.51827 (2)	0.141359 (10)	0.00967 (6)
Cl1	0.41880 (5)	0.58705 (4)	0.08431 (2)	0.01627 (9)
Cl2	0.23616 (5)	0.69589 (4)	0.205711 (19)	0.01659 (9)
Cl3	−0.14169 (5)	0.09058 (4)	0.112040 (19)	0.01852 (9)
P1	0.06006 (6)	0.62472 (4)	0.07525 (2)	0.01346 (9)
P2	0.38816 (5)	0.41085 (4)	0.19781 (2)	0.01276 (9)
C1	0.1815 (2)	0.36764 (16)	0.09372 (8)	0.0121 (3)
C2	0.2656 (2)	0.32345 (17)	0.04297 (8)	0.0159 (3)
H2A	0.3464	0.3721	0.0268	0.019*
C3	0.2291 (2)	0.20742 (17)	0.01664 (8)	0.0170 (3)
H3A	0.2881	0.1787	−0.0164	0.020*
C4	0.1063 (2)	0.13253 (16)	0.03839 (8)	0.0161 (3)
H4A	0.0832	0.0549	0.0202	0.019*
C5	0.0203 (2)	0.17679 (16)	0.08749 (8)	0.0136 (3)
C6	0.0574 (2)	0.29240 (15)	0.11584 (8)	0.0122 (3)
C7	−0.0181 (2)	0.34538 (16)	0.16892 (8)	0.0129 (3)
H7A	−0.1015	0.3055	0.1884	0.015*
C8	−0.0316 (2)	0.50993 (18)	0.24222 (8)	0.0174 (3)
H8A	−0.1168	0.4584	0.2564	0.026*
H8B	−0.0696	0.5931	0.2322	0.026*
H8C	0.0460	0.5163	0.2739	0.026*
C9	0.0955 (3)	0.79342 (18)	0.07302 (10)	0.0258 (4)
H9A	0.0261	0.8322	0.0439	0.039*
H9B	0.2018	0.8089	0.0610	0.039*
H9C	0.0774	0.8290	0.1130	0.039*
C10	0.0760 (3)	0.5799 (2)	−0.00478 (8)	0.0227 (4)
H10A	0.0061	0.6308	−0.0289	0.034*
H10B	0.0489	0.4920	−0.0093	0.034*
H10C	0.1814	0.5930	−0.0185	0.034*
C11	−0.1493 (2)	0.6155 (2)	0.08898 (10)	0.0258 (4)
H11A	−0.2035	0.6640	0.0583	0.039*
H11B	−0.1726	0.6492	0.1289	0.039*
H11C	−0.1824	0.5286	0.0869	0.039*
C12	0.3113 (3)	0.3308 (2)	0.26513 (9)	0.0243 (4)
H12A	0.3947	0.2879	0.2861	0.036*
H12B	0.2337	0.2702	0.2528	0.036*
H12C	0.2648	0.3920	0.2922	0.036*
C13	0.5434 (3)	0.5051 (2)	0.23006 (12)	0.0293 (5)
H13A	0.6122	0.4516	0.2533	0.044*
H13B	0.4998	0.5688	0.2565	0.044*
H13C	0.6009	0.5452	0.1976	0.044*
C14	0.4966 (3)	0.2879 (2)	0.15854 (10)	0.0260 (4)
H14A	0.5677	0.2484	0.1868	0.039*
H14B	0.5543	0.3246	0.1252	0.039*
H14C	0.4252	0.2256	0.1428	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0100 (6)	0.0149 (6)	0.0111 (6)	0.0009 (5)	0.0003 (5)	0.0007 (5)
Co1	0.00910 (11)	0.00863 (10)	0.01127 (10)	−0.00028 (8)	0.00087 (8)	−0.00067 (7)
Cl1	0.01429 (18)	0.01469 (17)	0.01983 (19)	−0.00287 (15)	0.00548 (15)	0.00055 (15)
Cl2	0.0190 (2)	0.01338 (18)	0.01734 (19)	−0.00129 (15)	−0.00002 (15)	−0.00514 (14)
Cl3	0.0213 (2)	0.01699 (19)	0.01728 (18)	−0.00885 (16)	−0.00267 (16)	0.00191 (15)
P1	0.0146 (2)	0.01225 (19)	0.0135 (2)	0.00196 (15)	−0.00023 (16)	0.00098 (14)
P2	0.0109 (2)	0.01100 (18)	0.0164 (2)	−0.00005 (15)	−0.00138 (15)	0.00015 (16)
C1	0.0133 (8)	0.0113 (7)	0.0116 (7)	0.0004 (6)	−0.0009 (6)	0.0013 (5)
C2	0.0153 (8)	0.0150 (7)	0.0173 (8)	−0.0011 (6)	0.0024 (6)	−0.0009 (6)
C3	0.0200 (9)	0.0144 (7)	0.0166 (8)	0.0021 (7)	0.0016 (7)	−0.0038 (6)
C4	0.0204 (9)	0.0113 (7)	0.0166 (8)	0.0007 (6)	−0.0037 (7)	−0.0025 (6)
C5	0.0144 (8)	0.0116 (7)	0.0147 (7)	−0.0035 (6)	−0.0026 (6)	0.0020 (6)
C6	0.0129 (8)	0.0123 (7)	0.0113 (7)	0.0006 (6)	−0.0019 (6)	0.0015 (6)
C7	0.0115 (7)	0.0157 (7)	0.0116 (7)	−0.0008 (6)	−0.0010 (6)	0.0013 (6)
C8	0.0164 (8)	0.0204 (8)	0.0153 (8)	−0.0002 (7)	0.0047 (6)	−0.0039 (6)
C9	0.0352 (12)	0.0126 (8)	0.0296 (10)	0.0023 (8)	−0.0070 (9)	0.0045 (7)
C10	0.0277 (10)	0.0263 (9)	0.0141 (8)	0.0070 (8)	−0.0023 (7)	−0.0008 (7)
C11	0.0154 (9)	0.0350 (11)	0.0271 (10)	0.0054 (8)	−0.0009 (8)	0.0060 (8)
C12	0.0231 (10)	0.0274 (9)	0.0224 (9)	0.0053 (8)	0.0013 (7)	0.0113 (7)
C13	0.0226 (10)	0.0209 (9)	0.0444 (12)	−0.0048 (8)	−0.0165 (9)	0.0012 (8)
C14	0.0260 (10)	0.0282 (10)	0.0239 (9)	0.0162 (8)	−0.0008 (8)	−0.0016 (7)

Geometric parameters (Å, º) top

N1—C7	1.288 (2)	C6—C7	1.437 (2)
N1—C8	1.465 (2)	C7—H7A	0.9300
N1—Co1	1.9323 (15)	C8—H8A	0.9600
Co1—C1	1.9155 (17)	C8—H8B	0.9600
Co1—P1	2.2444 (6)	C8—H8C	0.9600
Co1—P2	2.2455 (5)	C9—H9A	0.9600
Co1—Cl1	2.2742 (5)	C9—H9B	0.9600
Co1—Cl2	2.3471 (6)	C9—H9C	0.9600
Cl3—C5	1.7411 (18)	C10—H10A	0.9600
P1—C9	1.805 (2)	C10—H10B	0.9600
P1—C10	1.8105 (19)	C10—H10C	0.9600
P1—C11	1.818 (2)	C11—H11A	0.9600
P2—C13	1.801 (2)	C11—H11B	0.9600
P2—C14	1.808 (2)	C11—H11C	0.9600
P2—C12	1.814 (2)	C12—H12A	0.9600
C1—C2	1.398 (2)	C12—H12B	0.9600
C1—C6	1.410 (2)	C12—H12C	0.9600
C2—C3	1.386 (2)	C13—H13A	0.9600
C2—H2A	0.9300	C13—H13B	0.9600
C3—C4	1.397 (3)	C13—H13C	0.9600
C3—H3A	0.9300	C14—H14A	0.9600
C4—C5	1.379 (3)	C14—H14B	0.9600
C4—H4A	0.9300	C14—H14C	0.9600
C5—C6	1.403 (2)

C7—N1—C8	117.90 (15)	C1—C6—C7	113.23 (15)
C7—N1—Co1	116.15 (12)	N1—C7—C6	115.12 (16)
C8—N1—Co1	125.91 (12)	N1—C7—H7A	122.4
C1—Co1—N1	82.74 (7)	C6—C7—H7A	122.4
C1—Co1—P1	89.20 (5)	N1—C8—H8A	109.5
N1—Co1—P1	93.63 (5)	N1—C8—H8B	109.5
C1—Co1—P2	88.36 (5)	H8A—C8—H8B	109.5
N1—Co1—P2	92.88 (5)	N1—C8—H8C	109.5
P1—Co1—P2	172.71 (2)	H8A—C8—H8C	109.5
C1—Co1—Cl1	94.41 (5)	H8B—C8—H8C	109.5
N1—Co1—Cl1	177.13 (5)	P1—C9—H9A	109.5
P1—Co1—Cl1	86.64 (2)	P1—C9—H9B	109.5
P2—Co1—Cl1	86.69 (2)	H9A—C9—H9B	109.5
C1—Co1—Cl2	175.19 (5)	P1—C9—H9C	109.5
N1—Co1—Cl2	92.52 (5)	H9A—C9—H9C	109.5
P1—Co1—Cl2	91.91 (2)	H9B—C9—H9C	109.5
P2—Co1—Cl2	91.09 (2)	P1—C10—H10A	109.5
Cl1—Co1—Cl2	90.33 (2)	P1—C10—H10B	109.5
C9—P1—C10	102.64 (10)	H10A—C10—H10B	109.5
C9—P1—C11	102.83 (11)	P1—C10—H10C	109.5
C10—P1—C11	102.61 (10)	H10A—C10—H10C	109.5
C9—P1—Co1	114.36 (7)	H10B—C10—H10C	109.5
C10—P1—Co1	116.27 (7)	P1—C11—H11A	109.5
C11—P1—Co1	116.19 (7)	P1—C11—H11B	109.5
C13—P2—C14	101.64 (11)	H11A—C11—H11B	109.5
C13—P2—C12	102.05 (11)	P1—C11—H11C	109.5
C14—P2—C12	103.56 (11)	H11A—C11—H11C	109.5
C13—P2—Co1	115.30 (7)	H11B—C11—H11C	109.5
C14—P2—Co1	116.43 (7)	P2—C12—H12A	109.5
C12—P2—Co1	115.76 (7)	P2—C12—H12B	109.5
C2—C1—C6	118.00 (15)	H12A—C12—H12B	109.5
C2—C1—Co1	129.22 (13)	P2—C12—H12C	109.5
C6—C1—Co1	112.76 (12)	H12A—C12—H12C	109.5
C3—C2—C1	120.33 (17)	H12B—C12—H12C	109.5
C3—C2—H2A	119.8	P2—C13—H13A	109.5
C1—C2—H2A	119.8	P2—C13—H13B	109.5
C2—C3—C4	121.86 (17)	H13A—C13—H13B	109.5
C2—C3—H3A	119.1	P2—C13—H13C	109.5
C4—C3—H3A	119.1	H13A—C13—H13C	109.5
C5—C4—C3	118.20 (16)	H13B—C13—H13C	109.5
C5—C4—H4A	120.9	P2—C14—H14A	109.5
C3—C4—H4A	120.9	P2—C14—H14B	109.5
C4—C5—C6	120.97 (16)	H14A—C14—H14B	109.5
C4—C5—Cl3	119.07 (13)	P2—C14—H14C	109.5
C6—C5—Cl3	119.90 (14)	H14A—C14—H14C	109.5
C5—C6—C1	120.59 (16)	H14B—C14—H14C	109.5
C5—C6—C7	126.16 (16)

Experimental details

Crystal data
Chemical formula	[CoCl₂(C₈H₇ClN)(C₃H₉P)₂]
M_r	434.57
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	8.5530 (17), 10.543 (2), 21.769 (4)
V (Å³)	1963.0 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.44
Crystal size (mm)	0.30 × 0.30 × 0.28

Data collection
Diffractometer	Bruker P4
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.672, 0.689
No. of measured, independent and observed [I > 2σ(I)] reflections	16045, 4910, 4868
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.066, 1.07
No. of reflections	4910
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.43
Absolute structure	Flack (1983), 2082 Friedel pairs
Absolute structure parameter	−0.001 (9)

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2001).

Acknowledgements

We gratefully acknowledge support by the NSF China (No. 20572062) and the Doctoral Program of the Ministry of Education of China (MOE) (Nos. 20050422010 and 20050422011).

References

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