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

Abstract

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 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 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,

• a = 11.526 (3) Å

• c = 19.998 (5) Å

• V = 2300.8 (10) ų

• 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[F ² > 2σ(F ²)] = 0.046

• wR(F ²) = 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 ▶).

Supplementary Material

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

supplementary crystallographic information

Experimental

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%.

Refinement

The nitrate anion lying on the Wyckoff 3b position is disordered. This was refined off the special position as a planar four-atom species, with N–O distances restrained to 1.24 (1) Å and O···O distances restrained to 2.15 (1) Å. The isotropic displacement parameters of the three O atoms were restrained to be identical; the O and N atoms were refined isotropically. The methyl H-atoms were placed in idealized positions and treated as riding on their parent atoms with a C–H distance of 0.96 Å [U_iso(H) = 1.5U_eq(C)].

Figures

Fig. 1.

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

Crystal data

[Co(C2H6OS)6](NO3)3	Dx = 1.545 Mg m−3
Mr = 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

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

Refinement

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(Fo2) + (0.0617P)2 + 5.5038P] where P = (Fo2 + 2Fc2)/3
1158 reflections	(Δ/σ)max = 0.001
67 parameters	Δρmax = 0.59 e Å−3
7 restraints	Δρmin = −0.62 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	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 (Ų)

	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, °)

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—O1iv	2.005 (2)	C2—H2C	0.96
Co1—O1	2.005 (2)	O2—N1	1.232 (3)
Co1—O1v	2.005 (2)	N1—O2iv	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—O1iv	87.56 (9)	H1A—C1—H1C	109.5
O1ii—Co1—O1iv	180.0	H1B—C1—H1C	109.5
O1iii—Co1—O1iv	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
O1iv—Co1—O1	92.44 (9)	H2A—C2—H2C	109.5
O1i—Co1—O1v	92.45 (9)	H2B—C2—H2C	109.5
O1ii—Co1—O1v	92.44 (9)	S1—O1—Co1	125.03 (13)
O1iii—Co1—O1v	87.55 (9)	O2iv—N1—O2iii	119.996 (15)
O1iv—Co1—O1v	87.56 (9)	O2iv—N1—O2	119.995 (10)
O1—Co1—O1v	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)	O1iv—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.