Bis[bis-(penta-methyl-cyclo-penta-dien-yl)cobalt(III)] tetra-chlorido-cobaltate(II) di-chloro-methane disolvate.

The title compound, [Co(C10H15)2]2[CoCl4]·2CH2Cl2, was isolated as a dichloromethane solvate and was formed in the reaction between lithium penta-methyl-cyclo-penta-dienide and anyhydrous cobalt(II) chloride in tetra-hydro-furan. There are two deca-methyl-cobaltocenium cations, one tetrachloridocobaltate(II) anion and two di-chloro-methane solvent mol-ecules in the formula unit. There is a slight disorder of the di-chloro-methane solvent which was treated with a two-site model [occupancy rates = 0.765 (4) and 0.235 (4)]. The di-chloro-methane mol-ecules display significant C-H⋯Cl inter-actions with the tetrachloridocobaltate(II) dianion. The cobalt atom of the deca-methyl-cobaltocenium cation sits on a twofold rotation axis, with only one penta-methyl-cyclo-penta-diene ligand being unique and the second generated by symmetry. The cobalt atom of the [CoCl4](-2) ion sits on a special site with -4 symmetry, with one unique chloride ligand and the others generated by the fourfold inversion axis.

Related literature

For a related structure with a (THF)2LiCl2CoCl2 monoanion and the deca­methyl­cobaltocenium cation, see: Dehnen & Zimmermann (2000 ▶) (CCDC 135478). The structure of a related dimer synthesized by Koelle et al. (1986 ▶) was determined by Olson & Dahl (1986 ▶) (CCDC 566220). For a discussion of the role of chloro­form and di­chloro­methane solvent mol­ecules in crystal packing, see: Allen et al. (2013 ▶).

Experimental

Crystal data

[Co(C10H15)2]2[CoCl4]·2CH2Cl2

M = 1033.35

Tetragonal,

a = 12.20980 (12) Å

c = 16.2811 (3) Å

V = 2427.17 (7) Å3

Z = 2

Mo Kα radiation

μ = 1.48 mm−1

T = 101 K

0.27 × 0.24 × 0.18 mm

Data collection

Agilent Xcalibur Gemini Ultra diffractometer with Eos detector

Absorption correction: gaussian (CrysAlis PRO; Agilent, 2013 ▶) T min = 0.755, T max = 0.821

26858 measured reflections

4161 independent reflections

3394 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.091

S = 1.04

4161 reflections

130 parameters

H-atom parameters constrained

Δρmax = 1.21 e Å−3

Δρmin = −1.07 e Å−3

Data collection: CrysAlis PRO (Agilent, 2013 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S160053681302254X/zl2564sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681302254X/zl2564Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Co(C10H15)2]2[CoCl4]·2CH2Cl2	Dx = 1.408 Mg m−3
Mr = 1029.32	Mo Kα radiation, λ = 0.7107 Å
Tetragonal, P42/n	Cell parameters from 8251 reflections
a = 12.20980 (12) Å	θ = 4.2–32.2°
c = 16.2811 (3) Å	µ = 1.48 mm−1
V = 2427.17 (7) Å3	T = 101 K
Z = 2	Prism, clear green
F(000) = 1066	0.27 × 0.24 × 0.18 mm

Agilent Xcalibur (Eos, Gemini ultra) diffractometer	4161 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3394 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
Detector resolution: 16.0122 pixels mm-1	θmax = 32.5°, θmin = 3.4°
ω scans	h = −18→17
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2013)	k = −18→12
Tmin = 0.755, Tmax = 0.821	l = −24→21
26858 measured reflections

Refinement on F2	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037	Hydrogen site location: constr
wR(F2) = 0.091	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0319P)2 + 2.9104P] where P = (Fo2 + 2Fc2)/3
4161 reflections	(Δ/σ)max = 0.001
130 parameters	Δρmax = 1.21 e Å−3
0 restraints	Δρmin = −1.07 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	0.7500	0.2500	0.361342 (19)	0.01381 (8)
C1	0.86792 (13)	0.37038 (14)	0.36190 (10)	0.0171 (3)
C2	0.79973 (13)	0.38033 (14)	0.29066 (10)	0.0169 (3)
C3	0.68885 (14)	0.39523 (14)	0.31700 (11)	0.0193 (3)
C4	0.68838 (14)	0.39480 (15)	0.40471 (11)	0.0206 (3)
C5	0.79870 (14)	0.37984 (14)	0.43257 (10)	0.0188 (3)
C6	0.98932 (14)	0.35672 (16)	0.36341 (11)	0.0221 (3)
H6A	1.0095	0.3102	0.4085	0.033*
H6B	1.0235	0.4270	0.3699	0.033*
H6C	1.0131	0.3242	0.3128	0.033*
C7	0.83672 (15)	0.38171 (16)	0.20305 (11)	0.0231 (4)
H7A	0.9052	0.3436	0.1984	0.035*
H7B	0.8459	0.4561	0.1853	0.035*
H7C	0.7828	0.3464	0.1693	0.035*
C8	0.59249 (15)	0.41374 (17)	0.26198 (13)	0.0268 (4)
H8A	0.5987	0.3678	0.2144	0.040*
H8B	0.5906	0.4891	0.2452	0.040*
H8C	0.5263	0.3962	0.2910	0.040*
C9	0.59133 (16)	0.41372 (19)	0.45881 (14)	0.0318 (4)
H9A	0.5256	0.3966	0.4292	0.048*
H9B	0.5896	0.4891	0.4756	0.048*
H9C	0.5965	0.3676	0.5064	0.048*
C10	0.83534 (17)	0.38163 (18)	0.52022 (12)	0.0281 (4)
H10A	0.7814	0.3462	0.5539	0.042*
H10B	0.8443	0.4561	0.5379	0.042*
H10C	0.9039	0.3437	0.5251	0.042*
Co2	1.2500	0.2500	0.2500	0.01550 (10)
Cl1	1.11315 (3)	0.29420 (4)	0.15956 (3)	0.02050 (9)
C11	1.2500	0.2500	0.5298 (2)	0.0505 (9)
H	1.2150	0.1964	0.4946	0.061*	0.3825 (19)
HA	1.2850	0.3036	0.4946	0.061*	0.3825 (19)
HB	1.2469	0.1859	0.4946	0.061*	0.1175 (19)
HC	1.2531	0.3141	0.4946	0.061*	0.1175 (19)
Cl2	1.35262 (12)	0.1830 (2)	0.58797 (8)	0.0726 (5)	0.765 (4)
Cl2A	1.3635 (4)	0.2446 (6)	0.5851 (3)	0.0726 (5)	0.235 (4)

	U11	U22	U33	U12	U13	U23
Co1	0.01106 (14)	0.01787 (15)	0.01251 (14)	0.00152 (11)	0.000	0.000
C1	0.0155 (7)	0.0193 (7)	0.0167 (7)	−0.0010 (6)	−0.0006 (6)	−0.0008 (6)
C2	0.0162 (7)	0.0183 (7)	0.0163 (7)	0.0004 (6)	−0.0001 (6)	0.0012 (6)
C3	0.0172 (7)	0.0186 (7)	0.0221 (8)	0.0032 (6)	−0.0017 (6)	−0.0003 (6)
C4	0.0186 (8)	0.0208 (8)	0.0224 (8)	0.0032 (6)	0.0015 (6)	−0.0042 (6)
C5	0.0177 (7)	0.0217 (8)	0.0171 (7)	−0.0002 (6)	0.0007 (6)	−0.0042 (6)
C6	0.0151 (7)	0.0317 (9)	0.0195 (8)	−0.0029 (7)	−0.0005 (6)	0.0007 (7)
C7	0.0219 (8)	0.0304 (9)	0.0169 (8)	−0.0021 (7)	0.0005 (6)	0.0031 (7)
C8	0.0191 (8)	0.0298 (9)	0.0316 (10)	0.0068 (7)	−0.0050 (7)	0.0037 (8)
C9	0.0223 (9)	0.0390 (11)	0.0342 (11)	0.0054 (8)	0.0083 (8)	−0.0124 (9)
C10	0.0272 (9)	0.0399 (11)	0.0171 (8)	−0.0027 (8)	−0.0007 (7)	−0.0060 (8)
Co2	0.01459 (13)	0.01459 (13)	0.0173 (2)	0.000	0.000	0.000
Cl1	0.01695 (18)	0.0238 (2)	0.02071 (18)	0.00320 (14)	−0.00162 (14)	−0.00033 (15)
C11	0.056 (2)	0.069 (3)	0.0266 (16)	0.000 (2)	0.000	0.000
Cl2	0.0681 (7)	0.0970 (14)	0.0527 (5)	0.0388 (9)	−0.0021 (5)	0.0055 (8)
Cl2A	0.0681 (7)	0.0970 (14)	0.0527 (5)	0.0388 (9)	−0.0021 (5)	0.0055 (8)

Co1—C1i	2.0576 (17)	C7—H7B	0.9600
Co1—C1	2.0576 (17)	C7—H7C	0.9600
Co1—C2i	2.0556 (17)	C8—H8A	0.9600
Co1—C2	2.0556 (17)	C8—H8B	0.9600
Co1—C3	2.0550 (17)	C8—H8C	0.9600
Co1—C3i	2.0550 (17)	C9—H9A	0.9600
Co1—C4i	2.0470 (17)	C9—H9B	0.9600
Co1—C4	2.0470 (17)	C9—H9C	0.9600
Co1—C5i	2.0521 (17)	C10—H10A	0.9600
Co1—C5	2.0522 (17)	C10—H10B	0.9600
C1—C2	1.433 (2)	C10—H10C	0.9600
C1—C5	1.432 (2)	Co2—Cl1ii	2.2915 (4)
C1—C6	1.492 (2)	Co2—Cl1iii	2.2915 (4)
C2—C3	1.432 (2)	Co2—Cl1	2.2915 (4)
C2—C7	1.496 (2)	Co2—Cl1iv	2.2915 (4)
C3—C4	1.428 (3)	C11—H	0.9700
C3—C8	1.496 (2)	C11—HA	0.9700
C4—C5	1.433 (2)	C11—HB	0.9700
C4—C9	1.494 (3)	C11—HC	0.9700
C5—C10	1.496 (3)	C11—Cl2iii	1.771 (2)
C6—H6A	0.9600	C11—Cl2	1.771 (2)
C6—H6B	0.9600	C11—Cl2Aiii	1.654 (5)
C6—H6C	0.9600	C11—Cl2A	1.654 (5)
C7—H7A	0.9600
C1—Co1—C1i	179.49 (9)	C9—C4—Co1	128.93 (14)
C2—Co1—C1i	139.66 (7)	C1—C5—Co1	69.81 (9)
C2i—Co1—C1i	40.78 (6)	C1—C5—C4	108.10 (15)
C2—Co1—C1	40.78 (6)	C1—C5—C10	126.23 (16)
C2i—Co1—C1	139.66 (7)	C4—C5—Co1	69.34 (10)
C2—Co1—C2i	111.91 (9)	C4—C5—C10	125.54 (16)
C3—Co1—C1i	111.33 (7)	C10—C5—Co1	129.57 (14)
C3i—Co1—C1i	68.86 (7)	C1—C6—H6A	109.5
C3i—Co1—C1	111.33 (7)	C1—C6—H6B	109.5
C3—Co1—C1	68.86 (7)	C1—C6—H6C	109.5
C3i—Co1—C2	111.35 (7)	H6A—C6—H6B	109.5
C3—Co1—C2	40.77 (7)	H6A—C6—H6C	109.5
C3—Co1—C2i	111.35 (7)	H6B—C6—H6C	109.5
C3i—Co1—C2i	40.77 (7)	C2—C7—H7A	109.5
C3—Co1—C3i	138.87 (10)	C2—C7—H7B	109.5
C4i—Co1—C1	110.99 (7)	C2—C7—H7C	109.5
C4—Co1—C1	68.82 (7)	H7A—C7—H7B	109.5
C4—Co1—C1i	110.99 (7)	H7A—C7—H7C	109.5
C4i—Co1—C1i	68.82 (7)	H7B—C7—H7C	109.5
C4i—Co1—C2i	68.47 (7)	C3—C8—H8A	109.5
C4i—Co1—C2	138.86 (7)	C3—C8—H8B	109.5
C4—Co1—C2	68.47 (7)	C3—C8—H8C	109.5
C4—Co1—C2i	138.86 (7)	H8A—C8—H8B	109.5
C4i—Co1—C3	179.56 (8)	H8A—C8—H8C	109.5
C4—Co1—C3	40.75 (7)	H8B—C8—H8C	109.5
C4i—Co1—C3i	40.74 (7)	C4—C9—H9A	109.5
C4—Co1—C3i	179.56 (8)	C4—C9—H9B	109.5
C4i—Co1—C4	139.65 (11)	C4—C9—H9C	109.5
C4i—Co1—C5i	40.92 (7)	H9A—C9—H9B	109.5
C4i—Co1—C5	111.46 (7)	H9A—C9—H9C	109.5
C4—Co1—C5i	111.46 (7)	H9B—C9—H9C	109.5
C4—Co1—C5	40.92 (7)	C5—C10—H10A	109.5
C5—Co1—C1	40.79 (7)	C5—C10—H10B	109.5
C5i—Co1—C1	138.77 (7)	C5—C10—H10C	109.5
C5i—Co1—C1i	40.79 (7)	H10A—C10—H10B	109.5
C5—Co1—C1i	138.77 (7)	H10A—C10—H10C	109.5
C5—Co1—C2i	179.55 (7)	H10B—C10—H10C	109.5
C5i—Co1—C2i	68.45 (7)	Cl1iii—Co2—Cl1ii	114.385 (12)
C5i—Co1—C2	179.55 (7)	Cl1iii—Co2—Cl1	100.04 (2)
C5—Co1—C2	68.45 (7)	Cl1ii—Co2—Cl1	114.385 (11)
C5i—Co1—C3	139.45 (7)	Cl1iii—Co2—Cl1iv	114.386 (11)
C5—Co1—C3	68.73 (7)	Cl1ii—Co2—Cl1iv	100.04 (2)
C5—Co1—C3i	139.45 (7)	Cl1—Co2—Cl1iv	114.385 (11)
C5i—Co1—C3i	68.72 (7)	H—C11—HA	107.5
C5i—Co1—C5	111.19 (10)	H—C11—HC	102.2
C2—C1—Co1	69.54 (9)	HA—C11—HB	102.2
C2—C1—C6	126.87 (15)	HB—C11—HC	107.6
C5—C1—Co1	69.40 (10)	Cl2iii—C11—H	108.4
C5—C1—C2	107.49 (14)	Cl2—C11—H	108.4
C5—C1—C6	125.60 (15)	Cl2iii—C11—HA	108.4
C6—C1—Co1	127.98 (13)	Cl2—C11—HA	108.4
C1—C2—Co1	69.69 (9)	Cl2iii—C11—HB	131.4
C1—C2—C7	126.67 (15)	Cl2—C11—HB	88.3
C3—C2—Co1	69.59 (10)	Cl2iii—C11—HC	88.3
C3—C2—C1	108.52 (14)	Cl2—C11—HC	131.4
C3—C2—C7	124.72 (15)	Cl2—C11—Cl2iii	115.3 (2)
C7—C2—Co1	129.17 (13)	Cl2Aiii—C11—H	88.8
C2—C3—Co1	69.64 (9)	Cl2A—C11—H	131.6
C2—C3—C8	125.70 (16)	Cl2Aiii—C11—HA	131.6
C4—C3—Co1	69.33 (10)	Cl2A—C11—HA	88.8
C4—C3—C2	107.63 (15)	Cl2A—C11—HB	108.7
C4—C3—C8	126.60 (16)	Cl2Aiii—C11—HB	108.7
C8—C3—Co1	128.79 (13)	Cl2A—C11—HC	108.7
C3—C4—Co1	69.93 (10)	Cl2Aiii—C11—HC	108.7
C3—C4—C5	108.25 (15)	Cl2A—C11—Cl2iii	108.7 (2)
C3—C4—C9	126.30 (17)	Cl2Aiii—C11—Cl2	108.7 (2)
C5—C4—Co1	69.73 (10)	Cl2A—C11—Cl2Aiii	114.1 (4)
C5—C4—C9	125.35 (17)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H···Cl1iv	0.97	2.71	3.548 (3)	145
C11—HA···Cl1ii	0.97	2.71	3.548 (3)	145

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H⋯Cl1i	0.97	2.71	3.548 (3)	145
C11—HA⋯Cl1ii	0.97	2.71	3.548 (3)	145

Symmetry codes: (i) ; (ii) .