μ3-Oxido-hexa-μ2-pivalato-tris[(methanol-κO)cobalt(III)] chloride

Sun, Y.; Zhu, L.-L.; Zhang, H.-H.

doi:10.1107/S1600536809041907

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Pages m1402-m1403

https://doi.org/10.1107/S1600536809041907

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μ₃-Oxido-hexa-μ₂-pivalato-tris[(methanol-κO)cobalt(III)] chloride

Yu Sun,^a,^b ^* Li-Li Zhu ^c and Huai-Hong Zhang ^a

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China, ^bCollege of Pharmacy, Jiangsu University, Zhenjiang 212013, People's Republic of China, and ^cDepartment of Chemistry, Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, Yunnan University, Kunming 650091, People's Republic of China
^*Correspondence e-mail: whsunyu@163.com

(Received 22 September 2009; accepted 13 October 2009; online 23 October 2009)

The crystal structure of the title compound, [Co₃(C₅H₉O₂)₆O(CH₄O)₃]Cl, consists of trinuclear Co^III complex cations and chloride anions. The Co^III cation has site symmetry m, and is coordinated by four oxygen atoms from four bridging pivalate groups, one central O anion and a methanol oxygen atom, forming a distorted octahedral geometry. The coordinated methanol molecule is located on a crystallographic special position, the C and O atoms being located on the mirror plane. The central O anion lies in the crystallographic $[\overline6]$ position, and acts as a μ₃-O bridge, linking three equivalent Co^III cations and generating the oxo-centered trinuclear Co^III complex. The chloride anion, which acts as the counter-ion, is located on crystallographic $[\overline6]$ position. O—H⋯Cl hydrogen bonding between the Cl anion and hydroxyl group of the coordinated methanol molecule links the molecules into a supramolecular network.

Related literature

For oxido-centered triangular Co complexes, see: Aromì et al. (2003 ); Fursova et al. (2007 ). For related structures, see: Beattie et al. (1996 ).

Experimental

Crystal data

[Co₃(C₅H₉O₂)₆O(CH₄O)₃]Cl
M_r = 931.10
Hexagonal, P 6₃ /m
a = 10.4868 (15) Å
c = 22.794 (5) Å
V = 2170.9 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.26 mm⁻¹
T = 293 K
0.16 × 0.14 × 0.11 mm

Data collection

Rigaku SCXmini 1K CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.818, T_max = 0.871
9038 measured reflections
1317 independent reflections
1133 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.102
S = 1.11
1317 reflections
89 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3D⋯Cl1	0.90 (2)	2.17 (2)	3.070 (3)	175 (6)

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809041907/xu2614sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809041907/xu2614Isup2.hkl

checkCIF report

Comment top

Oxo-centered triangular Co complexes, Co₃(µ₃-O), have been considered as effective models for studying M—M interactions in metal clusters (Aromì et al., 2003; Fursova et al.,2007). We report here the synthesis and crystal structure of the title complex, (I). The complex is a typical oxo-centered carboxylate triangle, featuring exclusively, Co^III sites around a central µ₃-oxide. Each edge of the triangle is further bridged by two pivalates with a terminal methanol ligand completing the coordination environment around each octahedral cobalt site (Fig. 1). The Co^III cation has site symmetry m. The central µ₃-O lies in the -6 rotainversion axis. The coordinated methanol molecule is located on a crystallographic special position, the C and O atoms have site symmetry m. A similar oxo-centered cobalt(III) triangle has been reported for acetate (Beattie et al., 1996). The O—H···Cl hydrogen bond between the Cl ion serving as a trifurcated acceptor and hydroxyl of the coordinated methanol molecule as donor link molecules into two-dimensional hydrogen-bonded networks (Fig. 2).

Related literature top

For oxo-centered triangular Co complexes, see: Aromì et al. (2003); Fursova et al. (2007). For related structures, see: Beattie et al. (1996).

Experimental top

Hydrochloric acid (0.01 mmol) was added with constant stirring to a methanol solution (15 ml) containing Co(OOCC(CH₃)₃)₂.4H₂O (0.5 mmol), then filtered off. After a few days, red well shaped single crystals in the form of rectangular blocks deposited in the mother liquid. They were separated off, washed with cold methanol and dried in air at room temperature.

Structure description top

For oxo-centered triangular Co complexes, see: Aromì et al. (2003); Fursova et al. (2007). For related structures, see: Beattie et al. (1996).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 20% probability level. H atoms have been omitted for clarity [symmetry codes: (A) x, y, -z + 1/2; (B) -y + 1, x-y + 1, z; (C) -x + y, -x + 1, z].
	Fig. 2. Crystal packing of the compound (I). The tertbutyl methyl groups and H atoms, except for those of the methanol ligands, have been omitted for clarity. Hydrogen bonds are shown as dashed lines.

µ₃-Oxido-hexa-µ₂-pivalato-tri(methanol-κO) tricobalt(III) chloride top

Crystal data top

[Co₃(C₅H₉O₂)₆O(CH₄O)₃]Cl	D_x = 1.424 Mg m⁻³
M_r = 931.10	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6₃/m	Cell parameters from 1832 reflections
Hall symbol: -P 6c	θ = 2.8–25.3°
a = 10.4868 (15) Å	µ = 1.26 mm⁻¹
c = 22.794 (5) Å	T = 293 K
V = 2170.9 (6) Å³	Block, red
Z = 2	0.16 × 0.14 × 0.11 mm
F(000) = 980

Data collection top

Rigaku SCXmini 1K CCD area-detector diffractometer	1317 independent reflections
Radiation source: fine-focus sealed tube	1133 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
Detector resolution: 8.192 pixels mm^-1	θ_max = 25.0°, θ_min = 1.8°
thin–slice ω scans	h = −12→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −12→12
T_min = 0.818, T_max = 0.871	l = −23→26
9038 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.0515P)² + 1.7379P] where P = (F_o² + 2F_c²)/3
1317 reflections	(Δ/σ)_max < 0.001
89 parameters	Δρ_max = 0.40 e Å⁻³
1 restraint	Δρ_min = −0.33 e Å⁻³

Crystal data top

[Co₃(C₅H₉O₂)₆O(CH₄O)₃]Cl	Z = 2
M_r = 931.10	Mo Kα radiation
Hexagonal, P6₃/m	µ = 1.26 mm⁻¹
a = 10.4868 (15) Å	T = 293 K
c = 22.794 (5) Å	0.16 × 0.14 × 0.11 mm
V = 2170.9 (6) Å³

Data collection top

Rigaku SCXmini 1K CCD area-detector diffractometer	1317 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1133 reflections with I > 2σ(I)
T_min = 0.818, T_max = 0.871	R_int = 0.046
9038 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	1 restraint
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.40 e Å⁻³
1317 reflections	Δρ_min = −0.33 e Å⁻³
89 parameters

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	Occ. (<1)
Co1	0.51834 (5)	0.84488 (5)	0.2500	0.0226 (2)
Cl1	1.0000	1.0000	0.2500	0.0400 (5)
O4	0.3333	0.6667	0.2500	0.0196 (9)
O3	0.7249 (3)	1.0326 (3)	0.2500	0.0325 (7)
O2	0.6044 (2)	0.7791 (2)	0.18650 (10)	0.0401 (6)
O1	0.4642 (2)	0.9451 (2)	0.18684 (9)	0.0343 (5)
C1	0.3430 (3)	0.9136 (3)	0.16434 (12)	0.0249 (6)
C2	0.3400 (3)	0.9828 (3)	0.10576 (13)	0.0303 (7)
C3	0.2450 (4)	1.0559 (4)	0.11139 (17)	0.0530 (10)
H3A	0.1473	0.9838	0.1234	0.079*
H3B	0.2408	1.0966	0.0742	0.079*
H3C	0.2876	1.1331	0.1401	0.079*
C4	0.4953 (4)	1.0946 (4)	0.08584 (16)	0.0508 (9)
H4B	0.5528	1.0470	0.0821	0.076*
H4C	0.5402	1.1723	0.1143	0.076*
H4D	0.4908	1.1351	0.0486	0.076*
C6	0.7597 (6)	1.1820 (5)	0.2500	0.0530 (14)
H6A	0.8647	1.2450	0.2500	0.080*
H6B	0.7190	1.2010	0.2844	0.080*	0.50
H6C	0.7190	1.2010	0.2156	0.080*	0.50
C5	0.2695 (5)	0.8587 (5)	0.06128 (16)	0.0605 (11)
H5A	0.3284	0.8126	0.0574	0.091*
H5B	0.2630	0.8977	0.0240	0.091*
H5C	0.1726	0.7873	0.0743	0.091*
H3D	0.801 (5)	1.016 (7)	0.2500	0.08 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0220 (3)	0.0214 (3)	0.0235 (3)	0.0101 (2)	0.000	0.000
Cl1	0.0312 (6)	0.0312 (6)	0.0575 (13)	0.0156 (3)	0.000	0.000
O4	0.0184 (13)	0.0184 (13)	0.022 (2)	0.0092 (7)	0.000	0.000
O3	0.0204 (14)	0.0222 (14)	0.0514 (19)	0.0081 (12)	0.000	0.000
O2	0.0346 (12)	0.0285 (11)	0.0463 (14)	0.0076 (9)	0.0183 (10)	−0.0086 (10)
O1	0.0280 (11)	0.0297 (11)	0.0382 (13)	0.0091 (9)	−0.0056 (9)	0.0128 (9)
C1	0.0303 (15)	0.0219 (13)	0.0251 (15)	0.0150 (11)	−0.0001 (12)	0.0010 (11)
C2	0.0311 (16)	0.0334 (15)	0.0274 (16)	0.0170 (13)	0.0008 (12)	0.0073 (12)
C3	0.061 (2)	0.068 (2)	0.049 (2)	0.047 (2)	0.0104 (18)	0.0244 (19)
C4	0.045 (2)	0.057 (2)	0.046 (2)	0.0223 (17)	0.0121 (17)	0.0272 (18)
C6	0.052 (3)	0.028 (2)	0.067 (4)	0.011 (2)	0.000	0.000
C5	0.081 (3)	0.064 (2)	0.032 (2)	0.032 (2)	−0.0127 (19)	−0.0090 (18)

Geometric parameters (Å, º) top

Co1—O4	1.9055 (5)	C2—C5	1.519 (5)
Co1—O2ⁱ	2.002 (2)	C2—C4	1.524 (4)
Co1—O2	2.002 (2)	C2—C3	1.537 (4)
Co1—O1ⁱ	2.0244 (19)	C3—H3A	0.9600
Co1—O1	2.0244 (19)	C3—H3B	0.9600
Co1—O3	2.074 (3)	C3—H3C	0.9600
Cl1—Cl1	0.0000	C4—H4B	0.9600
O4—Co1ⁱⁱ	1.9055 (6)	C4—H4C	0.9600
O4—Co1ⁱⁱⁱ	1.9055 (6)	C4—H4D	0.9600
O3—C6	1.420 (5)	C6—H6A	0.9600
O3—H3D	0.90 (2)	C6—H6B	0.9600
O2—C1ⁱⁱⁱ	1.252 (3)	C6—H6C	0.9600
O1—C1	1.251 (3)	C5—H5A	0.9600
C1—O2ⁱⁱ	1.252 (3)	C5—H5B	0.9600
C1—C2	1.528 (4)	C5—H5C	0.9600

O4—Co1—O2ⁱ	94.33 (6)	C4—C2—C1	111.0 (2)
O4—Co1—O2	94.33 (6)	C5—C2—C3	108.9 (3)
O2ⁱ—Co1—O2	92.60 (15)	C4—C2—C3	110.5 (3)
O4—Co1—O1ⁱ	95.56 (6)	C1—C2—C3	109.7 (3)
O2ⁱ—Co1—O1ⁱ	87.52 (10)	C2—C3—H3A	109.5
O2—Co1—O1ⁱ	170.07 (9)	C2—C3—H3B	109.5
O4—Co1—O1	95.56 (6)	H3A—C3—H3B	109.5
O2ⁱ—Co1—O1	170.07 (9)	C2—C3—H3C	109.5
O2—Co1—O1	87.52 (10)	H3A—C3—H3C	109.5
O1ⁱ—Co1—O1	90.66 (13)	H3B—C3—H3C	109.5
O4—Co1—O3	177.12 (8)	C2—C4—H4B	109.5
O2ⁱ—Co1—O3	83.69 (8)	C2—C4—H4C	109.5
O2—Co1—O3	83.69 (8)	H4B—C4—H4C	109.5
O1ⁱ—Co1—O3	86.46 (8)	C2—C4—H4D	109.5
O1—Co1—O3	86.46 (8)	H4B—C4—H4D	109.5
Co1ⁱⁱ—O4—Co1	120.0	H4C—C4—H4D	109.5
Co1ⁱⁱ—O4—Co1ⁱⁱⁱ	120.0	O3—C6—H6A	109.5
Co1—O4—Co1ⁱⁱⁱ	120.0	O3—C6—H6B	109.5
C6—O3—Co1	128.1 (3)	H6A—C6—H6B	109.5
C6—O3—H3D	117 (4)	O3—C6—H6C	109.5
Co1—O3—H3D	115 (4)	H6A—C6—H6C	109.5
C1ⁱⁱⁱ—O2—Co1	134.27 (18)	H6B—C6—H6C	109.5
C1—O1—Co1	131.72 (18)	C2—C5—H5A	109.5
O1—C1—O2ⁱⁱ	123.9 (3)	C2—C5—H5B	109.5
O1—C1—C2	119.5 (2)	H5A—C5—H5B	109.5
O2ⁱⁱ—C1—C2	116.6 (2)	C2—C5—H5C	109.5
C5—C2—C4	109.6 (3)	H5A—C5—H5C	109.5
C5—C2—C1	107.0 (3)	H5B—C5—H5C	109.5

O2ⁱ—Co1—O4—Co1ⁱⁱ	133.53 (7)	O1—Co1—O2—C1ⁱⁱⁱ	−111.7 (3)
O2—Co1—O4—Co1ⁱⁱ	−133.53 (7)	O3—Co1—O2—C1ⁱⁱⁱ	161.6 (3)
O1ⁱ—Co1—O4—Co1ⁱⁱ	45.60 (6)	O4—Co1—O1—C1	12.6 (3)
O1—Co1—O4—Co1ⁱⁱ	−45.60 (6)	O2—Co1—O1—C1	106.7 (3)
O2ⁱ—Co1—O4—Co1ⁱⁱⁱ	−46.47 (7)	O1ⁱ—Co1—O1—C1	−83.1 (3)
O2—Co1—O4—Co1ⁱⁱⁱ	46.47 (7)	O3—Co1—O1—C1	−169.5 (3)
O1ⁱ—Co1—O4—Co1ⁱⁱⁱ	−134.40 (6)	Co1—O1—C1—O2ⁱⁱ	16.6 (4)
O1—Co1—O4—Co1ⁱⁱⁱ	134.40 (6)	Co1—O1—C1—C2	−162.2 (2)
O2ⁱ—Co1—O3—C6	−133.34 (7)	O1—C1—C2—C5	114.9 (3)
O2—Co1—O3—C6	133.34 (7)	O2ⁱⁱ—C1—C2—C5	−64.0 (3)
O1ⁱ—Co1—O3—C6	−45.44 (6)	O1—C1—C2—C4	−4.6 (4)
O1—Co1—O3—C6	45.44 (6)	O2ⁱⁱ—C1—C2—C4	176.5 (3)
O4—Co1—O2—C1ⁱⁱⁱ	−16.3 (3)	O1—C1—C2—C3	−127.0 (3)
O2ⁱ—Co1—O2—C1ⁱⁱⁱ	78.2 (3)	O2ⁱⁱ—C1—C2—C3	54.0 (4)

Symmetry codes: (i) x, y, −z+1/2; (ii) −y+1, x−y+1, z; (iii) −x+y, −x+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3D···Cl1	0.90 (2)	2.17 (2)	3.070 (3)	175 (6)

Experimental details

Crystal data
Chemical formula	[Co₃(C₅H₉O₂)₆O(CH₄O)₃]Cl
M_r	931.10
Crystal system, space group	Hexagonal, P6₃/m
Temperature (K)	293
a, c (Å)	10.4868 (15), 22.794 (5)
V (Å³)	2170.9 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.26
Crystal size (mm)	0.16 × 0.14 × 0.11

Data collection
Diffractometer	Rigaku SCXmini 1K CCD area-detector
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.818, 0.871
No. of measured, independent and observed [I > 2σ(I)] reflections	9038, 1317, 1133
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.102, 1.11
No. of reflections	1317
No. of parameters	89
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.33

Computer programs: CrystalClear (Rigaku, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3D···Cl1	0.90 (2)	2.17 (2)	3.070 (3)	175 (6)

References

Aromì, G., Batsanov, A. S., Christian, P., Helliwell, M., Parkin, A., Parsons, S., Smith, A. A., Timco, G. A. & Winpenny, R. E. P. (2003). Chem. Eur. J. 9, 5142–5161. PubMed Google Scholar
Beattie, J. K., Hambley, T. W., Kleptko, J. A., Masters, A. F. & Turner, P. (1996). Polyhedron 15, 2141–2150. CSD CrossRef CAS Web of Science Google Scholar
Fursova, E., Kuznetsova, O., Ovcharenko, V., Romanenko, G., Ikorskii, V., Eremenko, I. & Sidorov, A. (2007). Polyhedron, 26, 2079–2088. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 65| Part 11| November 2009| Pages m1402-m1403

https://doi.org/10.1107/S1600536809041907

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