Hexakis(dimethyl sulfoxide-κO)chromium(III) trichloride

Mikhaylichenko, Y.M.; Haukka, M.; Pavlenko, V.O.; Fritsky, I.O.; Iskenderov, T.S.

doi:10.1107/S1600536808016784

metal-organic compounds

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Hexakis(dimethyl sulfoxide-κO)chromium(III) trichloride

Yuliya M. Mikhaylichenko,^a Matti Haukka,^b Vadim O. Pavlenko,^a Igor O. Fritsky ^a and Turganbay S. Iskenderov ^c ^*

^aNational Taras Shevchenko University, Department of Chemistry, Volodymyrska Street 64, 01601 Kiev, Ukraine, ^bDepartment of Chemistry, University of Joensuu, PO Box 111, 80101 Joensuu, Finland, and ^cDepartment of Chemistry, Karakalpakian University, Universitet Keshesi 1, 742012 Nukus, Uzbekistan
^*Correspondence e-mail: turgiskend@freemail.ru

(Received 30 April 2008; accepted 2 June 2008; online 13 June 2008)

In the title compound, [Cr(C₂H₆OS)₆]Cl₃, each Cr^III ion is located on a three-fold inversion axis and is coordinated by six dimethylsulfoxide ligands [Cr—O = 1.970 (2)–1.972 (2) Å; O—Cr—O = 88.19 (9) and 91.81 (9)°] in a slightly distorted octahedral geometry. The Cl⁻ anions take part in the formation of weak C—H⋯Cl hydrogen bonds, which contribute to the crystal packing stabilization.

Related literature

For related literature, see: Chan et al. (2004 ); Desiraju & Steiner (1999 ); Öhrström & Svensson (2000 ); Persson et al. (1995 , and references therein); Reynolds (1970 ).

Experimental

Crystal data

Cr(C₂H₆OS)₆]Cl₃
M_r = 627.12
Trigonal, $[R \overline 3]$
a = 10.5499 (6) Å
c = 21.1370 (13) Å
V = 2037.4 (2) Å³
Z = 3
Mo Kα radiation
μ = 1.20 mm⁻¹
T = 120 (2) K
0.34 × 0.29 × 0.20 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (North et al., 1968 ) T_min = 0.688, T_max = 0.795
10865 measured reflections
1044 independent reflections
855 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.135
S = 1.14
1044 reflections
46 parameters
H-atom parameters constrained
Δρ_max = 0.82 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1B⋯Cl1	0.98	2.75	3.647 (3)	153
C1—H1A⋯Cl2ⁱ	0.98	2.64	3.614 (4)	176
Symmetry code: (i) $[x+{\script{1\over 3}}, y+{\script{2\over 3}}, z-{\script{1\over 3}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808016784/cv2410sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808016784/cv2410Isup2.hkl

checkCIF report

Comment top

Dimethylsulfoxide (dmso) has often been used as solvent and a ligand in inorganic chemistry since the beginning of the 1960th. Dimethylsulfoxide is a monodentate O–,S-donor ligand (Reynolds, 1970). Solvates of some transition metal ions have been prepared and structurally charaterized (Persson et al., 1995 and references therein).

The title compound, (I), is composed of [Cr(C₂H₆OS)₆]³⁺ cations and chloride anions. The Cr(III) ion is located on a 3-fold inversion axis being coordinated by the six dimethylsulfoxide ligands in a slightly distorted octahedral geometry (Fig. 1), with Cr—O 1.970 (2)–1.972 (2) Å interatomic distances and O—Cr—O 88.19 (9), 91.81 (9)° bond angles. A search in the Cambridge Structural Database revealed 14 reports of compounds containing transition metal hexakis(dimethylsulfoxide) cations, of which two described the structure of the [Cr(C₂H₆OS)₆]³⁺ cation in [Cr(C₂H₆OS)₆](ClO₄)₃ (Chan et al., 2004) and [Cr(C₂H₆OS)₆](NO₃)₃ (Ohrstrom & Svensson, 2000). The S═O bond lengths in the aforementioned compounds are almost identical, 1.542 (3) Å versus 1.543 (2) Å for the title compound, as well as the O—Cr—O angles, 87.9/92.2° versus 88.19–91.81°. In the present structure the average value of Cr—O—S angles (121.9°) is somewhat smaller than that in [Cr(C₂H₆OS)₆](NO₃)₃ (123.6°). All other angles and bonds of the title compound are very similar to the above mentioned structures.

In (I), the Cl anions take part in formation of weak C—H···Cl hydrogen bonds (Table 1), which contribute to the crystal packing stabilization.

Related literature top

For related literature, see: Chan et al. (2004); Desiraju & Steiner (1999); Ohrstrom & Svensson (2000); Persson et al. (1995, and references therein); Reynolds (1970).

Experimental top

Complex (I) was synthesized during the attempt to prepare chromium (III) complex with 1H-pyrazole-3,5-dicarbohydrazide (Fig. 2) by adding CrCl₃.6H₂O (0.3 mmol, 3 ml of 0.1M aqueous solution) to the 1H-pyrazole-3,5-dicarbohydrazide (0.0552 g, 0.3 mmol) in dimethylsulfoxide solution (6 ml). The mixture was stirred for 30 min at ambient temperature. The resulting green solution was filtered and the filtrate was left to stand at room temperature. Slow evaporation of the solvent during 2 weeks yielded green crystals of (I).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids at the 60% probability level [symmetry codes: (i) -x + y, 1 - x, z; (ii) 2/3 + x-y, 1/3 + x, 1/3 - z; (iii) 1 - y, 1 + x-y, z; (iv) -1/3 + y, 1/3 - x + y, 1/3 - z; (v) 2/3 - x, 4/3 - y, 1/3 - z.]
	Fig. 2. 1H-pyrazole-3,5-dicarbohydrazide

Hexakis(dimethyl sulfoxide-κO)chromium(III) trichloride top

Crystal data top

[Cr(C₂H₆OS)₆]Cl₃	D_x = 1.533 Mg m⁻³
M_r = 627.12	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 6073 reflections
Hall symbol: -R 3	θ = 1.0–27.5°
a = 10.5499 (6) Å	µ = 1.20 mm⁻¹
c = 21.1370 (13) Å	T = 120 K
V = 2037.4 (2) Å³	Block, green
Z = 3	0.34 × 0.29 × 0.20 mm
F(000) = 981

Data collection top

Nonius KappaCCD diffractometer	1044 independent reflections
Radiation source: fine-focus sealed tube	855 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	R_int = 0.051
Detector resolution: 9 pixels mm^-1	θ_max = 27.6°, θ_min = 2.4°
ϕ scans and ω scans with κ offset	h = −13→13
Absorption correction: multi-scan (North et al., 1968)	k = −13→13
T_min = 0.688, T_max = 0.795	l = −26→27
10865 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.135	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0789P)² + 3.3338P] where P = (F_o² + 2F_c²)/3
1044 reflections	(Δ/σ)_max < 0.001
46 parameters	Δρ_max = 0.82 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

[Cr(C₂H₆OS)₆]Cl₃	Z = 3
M_r = 627.12	Mo Kα radiation
Trigonal, R3	µ = 1.20 mm⁻¹
a = 10.5499 (6) Å	T = 120 K
c = 21.1370 (13) Å	0.34 × 0.29 × 0.20 mm
V = 2037.4 (2) Å³

Data collection top

Nonius KappaCCD diffractometer	1044 independent reflections
Absorption correction: multi-scan (North et al., 1968)	855 reflections with I > 2σ(I)
T_min = 0.688, T_max = 0.795	R_int = 0.051
10865 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.135	H-atom parameters constrained
S = 1.14	Δρ_max = 0.82 e Å⁻³
1044 reflections	Δρ_min = −0.48 e Å⁻³
46 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
Cr1	0.3333	0.6667	0.1667	0.0214 (3)
Cl1	0.0000	0.0000	0.0000	0.0324 (5)
Cl2	0.0000	0.0000	0.25064 (7)	0.0416 (4)
S1	0.24193 (8)	0.38772 (8)	0.08860 (4)	0.0261 (3)
O1	0.3687 (2)	0.5325 (2)	0.11455 (10)	0.0270 (5)
C1	0.3083 (4)	0.3721 (4)	0.01371 (16)	0.0336 (7)
H1A	0.3141	0.4485	−0.0145	0.050*
H1B	0.2416	0.2757	−0.0044	0.050*
H1C	0.4058	0.3834	0.0186	0.050*
C2	0.2577 (4)	0.2497 (4)	0.12936 (18)	0.0384 (8)
H2A	0.3576	0.2670	0.1248	0.058*
H2B	0.1883	0.1538	0.1116	0.058*
H2C	0.2360	0.2518	0.1743	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cr1	0.0165 (4)	0.0165 (4)	0.0311 (6)	0.00824 (19)	0.000	0.000
Cl1	0.0245 (6)	0.0245 (6)	0.0480 (11)	0.0123 (3)	0.000	0.000
Cl2	0.0421 (6)	0.0421 (6)	0.0405 (9)	0.0211 (3)	0.000	0.000
S1	0.0221 (4)	0.0207 (4)	0.0346 (5)	0.0099 (3)	−0.0004 (3)	−0.0004 (3)
O1	0.0202 (10)	0.0222 (10)	0.0374 (12)	0.0096 (9)	−0.0015 (8)	−0.0045 (8)
C1	0.0339 (17)	0.0279 (16)	0.0331 (17)	0.0111 (13)	0.0028 (13)	−0.0017 (13)
C2	0.045 (2)	0.0278 (16)	0.044 (2)	0.0196 (15)	−0.0007 (16)	0.0063 (14)

Geometric parameters (Å, º) top

Cr1—O1ⁱ	1.972 (2)	S1—C1	1.772 (3)
Cr1—O1ⁱⁱ	1.971 (2)	C1—H1A	0.9800
Cr1—O1ⁱⁱⁱ	1.971 (2)	C1—H1B	0.9800
Cr1—O1	1.970 (2)	C1—H1C	0.9800
Cr1—O1^iv	1.971 (2)	C2—H2A	0.9800
Cr1—O1^v	1.971 (2)	C2—H2B	0.9800
S1—O1	1.542 (2)	C2—H2C	0.9800
S1—C2	1.770 (3)

O1ⁱ—Cr1—O1ⁱⁱ	180.0	O1—S1—C1	102.86 (14)
O1ⁱ—Cr1—O1ⁱⁱⁱ	91.81 (9)	C2—S1—C1	98.87 (17)
O1ⁱⁱ—Cr1—O1ⁱⁱⁱ	88.19 (9)	S1—O1—Cr1	121.86 (12)
O1ⁱ—Cr1—O1	91.81 (9)	S1—C1—H1A	109.5
O1ⁱⁱ—Cr1—O1	88.19 (9)	S1—C1—H1B	109.5
O1ⁱⁱⁱ—Cr1—O1	91.81 (9)	H1A—C1—H1B	109.5
O1ⁱ—Cr1—O1^iv	88.19 (9)	S1—C1—H1C	109.5
O1ⁱⁱ—Cr1—O1^iv	91.81 (9)	H1A—C1—H1C	109.5
O1ⁱⁱⁱ—Cr1—O1^iv	180.0	H1B—C1—H1C	109.5
O1—Cr1—O1^iv	88.19 (9)	S1—C2—H2A	109.5
O1ⁱ—Cr1—O1^v	88.19 (9)	S1—C2—H2B	109.5
O1ⁱⁱ—Cr1—O1^v	91.81 (9)	H2A—C2—H2B	109.5
O1ⁱⁱⁱ—Cr1—O1^v	88.19 (9)	S1—C2—H2C	109.5
O1—Cr1—O1^v	179.999 (1)	H2A—C2—H2C	109.5
O1^iv—Cr1—O1^v	91.81 (9)	H2B—C2—H2C	109.5
O1—S1—C2	104.46 (15)

C2—S1—O1—Cr1	−112.64 (17)	O1ⁱⁱ—Cr1—O1—S1	140.87 (18)
C1—S1—O1—Cr1	144.52 (16)	O1ⁱⁱⁱ—Cr1—O1—S1	−131.00 (10)
O1ⁱ—Cr1—O1—S1	−39.13 (18)	O1^iv—Cr1—O1—S1	49.00 (10)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···Cl1	0.98	2.75	3.647 (3)	153
C1—H1A···Cl2^vi	0.98	2.64	3.614 (4)	176

Symmetry code: (vi) x+1/3, y+2/3, z−1/3.

Experimental details

Crystal data
Chemical formula	[Cr(C₂H₆OS)₆]Cl₃
M_r	627.12
Crystal system, space group	Trigonal, R3
Temperature (K)	120
a, c (Å)	10.5499 (6), 21.1370 (13)
V (Å³)	2037.4 (2)
Z	3
Radiation type	Mo Kα
µ (mm⁻¹)	1.20
Crystal size (mm)	0.34 × 0.29 × 0.20

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (North et al., 1968)
T_min, T_max	0.688, 0.795
No. of measured, independent and observed [I > 2σ(I)] reflections	10865, 1044, 855
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.652

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.135, 1.14
No. of reflections	1044
No. of parameters	46
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.82, −0.48

Computer programs: APEX2 (Bruker, 2004), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···Cl1	0.98	2.75	3.647 (3)	152.9
C1—H1A···Cl2ⁱ	0.98	2.64	3.614 (4)	175.6

Symmetry code: (i) x+1/3, y+2/3, z−1/3.

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page m904

doi:10.1107/S1600536808016784

Open

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