Hexakis(dimethyl sulfoxide-κO)cobalt(III) trinitrate

Li, Q.; Ng, S.W.

doi:10.1107/S1600536809051423

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page m21

doi:10.1107/S1600536809051423

Open

access

Hexakis(dimethyl sulfoxide-κO)cobalt(III) trinitrate

Qiuhong Li ^a ^* and Seik Weng Ng ^b

^aCollege of Materials Science and Engineering, Shandong University of Technology, Zibo 255049, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: bingxueer79@163.com

(Received 20 October 2009; accepted 29 November 2009; online 9 December 2009)

The metal atom of the title salt, [Co(C₂H₆OS)₆](NO₃)₃, is coordinated by six dimethyl sulfoxide molecules in an octahedral geometry. The metal atom lies on a special position of $[\overline{3}]$ site symmetry. One of the nitrate ions lies on a special position of 3 site symmetry and the other independent ion is disordered about a special position of $[\overline{3}]$ site symmetry.

Related literature

For the isostructural chromium(III) and iron(III) analogs, see: Öhrström & Svensson (2000 ); Tzou et al. (1995 ).

Experimental

Crystal data

[Co(C₂H₆OS)₆](NO₃)₃
M_r = 713.73
Trigonal, $[R \overline 3]$
a = 11.526 (3) Å
c = 19.998 (5) Å
V = 2300.8 (10) Å³
Z = 3
Mo Kα radiation
μ = 1.03 mm⁻¹
T = 298 K
0.49 × 0.41 × 0.38 mm

Data collection

Bruker SMART 1000 area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.632, T_max = 0.695
3840 measured reflections
1158 independent reflections
879 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.136
S = 1.07
1158 reflections
67 parameters
7 restraints
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Data collection: SMART (Bruker, 1996 ); cell refinement: SAINT (Bruker, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809051423/ci2949sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809051423/ci2949Isup2.hkl

checkCIF report

Related literature top

For the isostructural chromium(III) and iron(III) analogs, see: Öhrström & Svensson (2000); Tzou et al. (1995).

Experimental top

To a solution of cobalt(II) nitrate hexahydrate (0.10 g, 0.4 mmol) in methanol (10 ml) was added a solution of 1,2-disalicyloylhydrazine (0.05 g, 0.2 mmol) in DMSO (10 ml). The red solution was allowed to stand for one week, whereupon red block-shaped crystals were obtained in 60% yield (m.p. > 573 K). CH&N elemental analysis for C₁₂H₃₆CoN₃O₁₅S₆: Calculated: C 20.19, H 5.08, N 5.89%; found: C 20.10, H 5.17, N 5.81%.

Computing details top

Data collection: SMART (Bruker, 1996); cell refinement: SAINT (Bruker, 1996); data reduction: SAINT (Bruker, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

Fig. 1. Displacement ellispoid plot (Barbour, 2001) of hexakis(dimethylsulfoxide)cobalt(III) trinitrate at the 50% probability level.

Hexakis(dimethyl sulfoxide-κO)cobalt(III) trinitrate top

Crystal data top

[Co(C₂H₆OS)₆](NO₃)₃	D_x = 1.545 Mg m⁻³
M_r = 713.73	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 1446 reflections
Hall symbol: -R 3	θ = 2.3–27.2°
a = 11.526 (3) Å	µ = 1.03 mm⁻¹
c = 19.998 (5) Å	T = 298 K
V = 2300.8 (10) Å³	Block, red
Z = 3	0.49 × 0.41 × 0.38 mm
F(000) = 1116

Data collection top

Bruker SMART 1000 area-detector diffractometer	1158 independent reflections
Radiation source: fine-focus sealed tube	879 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
ϕ and ω scans	θ_max = 27.4°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→5
T_min = 0.632, T_max = 0.695	k = −11→14
3840 measured reflections	l = −25→25

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.136	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0617P)² + 5.5038P] where P = (F_o² + 2F_c²)/3
1158 reflections	(Δ/σ)_max = 0.001
67 parameters	Δρ_max = 0.59 e Å⁻³
7 restraints	Δρ_min = −0.62 e Å⁻³

Crystal data top

[Co(C₂H₆OS)₆](NO₃)₃	Z = 3
M_r = 713.73	Mo Kα radiation
Trigonal, R3	µ = 1.03 mm⁻¹
a = 11.526 (3) Å	T = 298 K
c = 19.998 (5) Å	0.49 × 0.41 × 0.38 mm
V = 2300.8 (10) Å³

Data collection top

Bruker SMART 1000 area-detector diffractometer	1158 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	879 reflections with I > 2σ(I)
T_min = 0.632, T_max = 0.695	R_int = 0.062
3840 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	7 restraints
wR(F²) = 0.136	H-atom parameters constrained
S = 1.07	Δρ_max = 0.59 e Å⁻³
1158 reflections	Δρ_min = −0.62 e Å⁻³
67 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.6667	0.3333	0.3333	0.0336 (3)
S1	0.48481 (8)	0.41879 (8)	0.25413 (4)	0.0388 (3)
C1	0.3940 (4)	0.3538 (5)	0.17922 (18)	0.0567 (10)
H1A	0.4494	0.3427	0.1470	0.085*
H1B	0.3673	0.4147	0.1620	0.085*
H1C	0.3158	0.2686	0.1880	0.085*
C2	0.3544 (4)	0.4062 (5)	0.3061 (2)	0.0591 (10)
H2A	0.2805	0.3160	0.3051	0.089*
H2B	0.3254	0.4662	0.2903	0.089*
H2C	0.3867	0.4296	0.3511	0.089*
O1	0.5100 (2)	0.3062 (2)	0.27796 (11)	0.0379 (5)
O2	0.6649 (4)	0.4393 (3)	0.0814 (2)	0.0838 (11)
N1	0.6667	0.3333	0.0819 (3)	0.0516 (13)
N2	0.331 (2)	0.657 (2)	0.1524 (6)	0.060 (4)*	0.1667
O3	0.246 (2)	0.612 (3)	0.1984 (10)	0.104 (5)*	0.1667
O4	0.407 (3)	0.7797 (19)	0.1464 (11)	0.104 (5)*	0.1667
O5	0.338 (2)	0.578 (2)	0.1132 (11)	0.104 (5)*	0.1667

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0312 (4)	0.0312 (4)	0.0385 (5)	0.01558 (19)	0.000	0.000
S1	0.0334 (5)	0.0343 (5)	0.0474 (5)	0.0159 (4)	−0.0051 (3)	0.0031 (3)
C1	0.057 (2)	0.077 (3)	0.0426 (19)	0.038 (2)	−0.0106 (17)	0.0001 (18)
C2	0.063 (3)	0.069 (3)	0.062 (2)	0.046 (2)	0.000 (2)	−0.009 (2)
O1	0.0327 (12)	0.0352 (12)	0.0462 (12)	0.0173 (10)	−0.0078 (9)	−0.0010 (10)
O2	0.078 (2)	0.0523 (19)	0.130 (3)	0.0389 (18)	0.007 (2)	0.0059 (19)
N1	0.047 (2)	0.047 (2)	0.061 (3)	0.0234 (10)	0.000	0.000

Geometric parameters (Å, º) top

Co1—O1ⁱ	2.005 (2)	C1—H1C	0.96
Co1—O1ⁱⁱ	2.005 (2)	C2—H2A	0.96
Co1—O1ⁱⁱⁱ	2.005 (2)	C2—H2B	0.96
Co1—O1^iv	2.005 (2)	C2—H2C	0.96
Co1—O1	2.005 (2)	O2—N1	1.232 (3)
Co1—O1^v	2.005 (2)	N1—O2^iv	1.232 (3)
S1—O1	1.540 (2)	N1—O2ⁱⁱⁱ	1.232 (3)
S1—C1	1.765 (4)	N2—O4	1.238 (9)
S1—C2	1.773 (4)	N2—O5	1.238 (9)
C1—H1A	0.96	N2—O3	1.253 (9)
C1—H1B	0.96

O1ⁱ—Co1—O1ⁱⁱ	92.45 (9)	S1—C1—H1B	109.5
O1ⁱ—Co1—O1ⁱⁱⁱ	180.0	H1A—C1—H1B	109.5
O1ⁱⁱ—Co1—O1ⁱⁱⁱ	87.55 (9)	S1—C1—H1C	109.5
O1ⁱ—Co1—O1^iv	87.56 (9)	H1A—C1—H1C	109.5
O1ⁱⁱ—Co1—O1^iv	180.0	H1B—C1—H1C	109.5
O1ⁱⁱⁱ—Co1—O1^iv	92.44 (9)	S1—C2—H2A	109.5
O1ⁱ—Co1—O1	87.56 (9)	S1—C2—H2B	109.5
O1ⁱⁱ—Co1—O1	87.56 (9)	H2A—C2—H2B	109.5
O1ⁱⁱⁱ—Co1—O1	92.44 (9)	S1—C2—H2C	109.5
O1^iv—Co1—O1	92.44 (9)	H2A—C2—H2C	109.5
O1ⁱ—Co1—O1^v	92.45 (9)	H2B—C2—H2C	109.5
O1ⁱⁱ—Co1—O1^v	92.44 (9)	S1—O1—Co1	125.03 (13)
O1ⁱⁱⁱ—Co1—O1^v	87.55 (9)	O2^iv—N1—O2ⁱⁱⁱ	119.996 (15)
O1^iv—Co1—O1^v	87.56 (9)	O2^iv—N1—O2	119.995 (10)
O1—Co1—O1^v	179.998 (1)	O2ⁱⁱⁱ—N1—O2	119.996 (15)
O1—S1—C1	103.10 (17)	O4—N2—O5	120.6 (10)
O1—S1—C2	104.99 (17)	O4—N2—O3	120.3 (10)
C1—S1—C2	99.5 (2)	O5—N2—O3	119.0 (10)
S1—C1—H1A	109.5

C1—S1—O1—Co1	151.6 (2)	O1ⁱⁱ—Co1—O1—S1	135.7 (2)
C2—S1—O1—Co1	−104.7 (2)	O1ⁱⁱⁱ—Co1—O1—S1	−136.90 (12)
O1ⁱ—Co1—O1—S1	43.10 (12)	O1^iv—Co1—O1—S1	−44.3 (2)

Symmetry codes: (i) y+1/3, −x+y+2/3, −z+2/3; (ii) x−y+1/3, x−1/3, −z+2/3; (iii) −y+1, x−y, z; (iv) −x+y+1, −x+1, z; (v) −x+4/3, −y+2/3, −z+2/3.

Experimental details

Crystal data
Chemical formula	[Co(C₂H₆OS)₆](NO₃)₃
M_r	713.73
Crystal system, space group	Trigonal, R3
Temperature (K)	298
a, c (Å)	11.526 (3), 19.998 (5)
V (Å³)	2300.8 (10)
Z	3
Radiation type	Mo Kα
µ (mm⁻¹)	1.03
Crystal size (mm)	0.49 × 0.41 × 0.38

Data collection
Diffractometer	Bruker SMART 1000 area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.632, 0.695
No. of measured, independent and observed [I > 2σ(I)] reflections	3840, 1158, 879
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.136, 1.07
No. of reflections	1158
No. of parameters	67
No. of restraints	7
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.62

Computer programs: SMART (Bruker, 1996), SAINT (Bruker, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Acknowledgements

We thank Shandong University of Technology and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (1996). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Öhrström, L. & Svensson, G. (2000). Inorg. Chim. Acta, 305, 157–162. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tzou, J.-R., Mullaney, M., Norman, R. E. & Chang, S.-C. (1995). Acta Cryst. C51, 2249–2252. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar