metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

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

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 CrIII 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[Chan, E. J., Cox, G., Harrowfield, M., Ogden, I., Skelton, B. W. & White, A. H. (2004). Inorg. Chim. Acta, 357, 2365-2372.]); Desiraju & Steiner (1999[Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond, pp. 40-107. Oxford University Press.]); Öhrström & Svensson (2000[Öhrström, L. & Svensson, G. (2000). Inorg. Chim. Acta, 305, 157-163.]); Persson et al. (1995[Persson, I., Sandström, M., Yokoyama, H. & Chaudhry, M. (1995). Z. Naturforsch. Teil A, 50, 21-30.], and references therein); Reynolds (1970[Reynolds, W. L. (1970). Prog. Inorg. Chem. 12, 1-29.]).

[Scheme 1]

Experimental

Crystal data
  • Cr(C2H6OS)6]Cl3

  • Mr = 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[North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351-359.]) Tmin = 0.688, Tmax = 0.795

  • 10865 measured reflections

  • 1044 independent reflections

  • 855 reflections with I > 2σ(I)

  • Rint = 0.051

Refinement
  • R[F2 > 2σ(F2)] = 0.042

  • wR(F2) = 0.135

  • S = 1.14

  • 1044 reflections

  • 46 parameters

  • H-atom parameters constrained

  • Δρmax = 0.82 e Å−3

  • Δρmin = −0.48 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2005[Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381-388.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXL97.

Supporting information


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 SO 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).

Refinement top

The H atoms were positioned geometrically (C—H 0.98 Å) and allowed to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C).

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
[Figure 1] 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.]
[Figure 2] Fig. 2. 1H-pyrazole-3,5-dicarbohydrazide
Hexakis(dimethyl sulfoxide-κO)chromium(III) trichloride top
Crystal data top
[Cr(C2H6OS)6]Cl3Dx = 1.533 Mg m3
Mr = 627.12Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3Cell parameters from 6073 reflections
Hall symbol: -R 3θ = 1.0–27.5°
a = 10.5499 (6) ŵ = 1.20 mm1
c = 21.1370 (13) ÅT = 120 K
V = 2037.4 (2) Å3Block, green
Z = 30.34 × 0.29 × 0.20 mm
F(000) = 981
Data collection top
Nonius KappaCCD
diffractometer
1044 independent reflections
Radiation source: fine-focus sealed tube855 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromatorRint = 0.051
Detector resolution: 9 pixels mm-1θmax = 27.6°, θmin = 2.4°
ϕ scans and ω scans with κ offseth = 1313
Absorption correction: multi-scan
(North et al., 1968)
k = 1313
Tmin = 0.688, Tmax = 0.795l = 2627
10865 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.135H-atom parameters constrained
S = 1.14 w = 1/[σ2(Fo2) + (0.0789P)2 + 3.3338P]
where P = (Fo2 + 2Fc2)/3
1044 reflections(Δ/σ)max < 0.001
46 parametersΔρmax = 0.82 e Å3
0 restraintsΔρmin = 0.48 e Å3
Crystal data top
[Cr(C2H6OS)6]Cl3Z = 3
Mr = 627.12Mo Kα radiation
Trigonal, R3µ = 1.20 mm1
a = 10.5499 (6) ÅT = 120 K
c = 21.1370 (13) Å0.34 × 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)
Tmin = 0.688, Tmax = 0.795Rint = 0.051
10865 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.135H-atom parameters constrained
S = 1.14Δρmax = 0.82 e Å3
1044 reflectionsΔρmin = 0.48 e Å3
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
xyzUiso*/Ueq
Cr10.33330.66670.16670.0214 (3)
Cl10.00000.00000.00000.0324 (5)
Cl20.00000.00000.25064 (7)0.0416 (4)
S10.24193 (8)0.38772 (8)0.08860 (4)0.0261 (3)
O10.3687 (2)0.5325 (2)0.11455 (10)0.0270 (5)
C10.3083 (4)0.3721 (4)0.01371 (16)0.0336 (7)
H1A0.31410.44850.01450.050*
H1B0.24160.27570.00440.050*
H1C0.40580.38340.01860.050*
C20.2577 (4)0.2497 (4)0.12936 (18)0.0384 (8)
H2A0.35760.26700.12480.058*
H2B0.18830.15380.11160.058*
H2C0.23600.25180.17430.058*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cr10.0165 (4)0.0165 (4)0.0311 (6)0.00824 (19)0.0000.000
Cl10.0245 (6)0.0245 (6)0.0480 (11)0.0123 (3)0.0000.000
Cl20.0421 (6)0.0421 (6)0.0405 (9)0.0211 (3)0.0000.000
S10.0221 (4)0.0207 (4)0.0346 (5)0.0099 (3)0.0004 (3)0.0004 (3)
O10.0202 (10)0.0222 (10)0.0374 (12)0.0096 (9)0.0015 (8)0.0045 (8)
C10.0339 (17)0.0279 (16)0.0331 (17)0.0111 (13)0.0028 (13)0.0017 (13)
C20.045 (2)0.0278 (16)0.044 (2)0.0196 (15)0.0007 (16)0.0063 (14)
Geometric parameters (Å, º) top
Cr1—O1i1.972 (2)S1—C11.772 (3)
Cr1—O1ii1.971 (2)C1—H1A0.9800
Cr1—O1iii1.971 (2)C1—H1B0.9800
Cr1—O11.970 (2)C1—H1C0.9800
Cr1—O1iv1.971 (2)C2—H2A0.9800
Cr1—O1v1.971 (2)C2—H2B0.9800
S1—O11.542 (2)C2—H2C0.9800
S1—C21.770 (3)
O1i—Cr1—O1ii180.0O1—S1—C1102.86 (14)
O1i—Cr1—O1iii91.81 (9)C2—S1—C198.87 (17)
O1ii—Cr1—O1iii88.19 (9)S1—O1—Cr1121.86 (12)
O1i—Cr1—O191.81 (9)S1—C1—H1A109.5
O1ii—Cr1—O188.19 (9)S1—C1—H1B109.5
O1iii—Cr1—O191.81 (9)H1A—C1—H1B109.5
O1i—Cr1—O1iv88.19 (9)S1—C1—H1C109.5
O1ii—Cr1—O1iv91.81 (9)H1A—C1—H1C109.5
O1iii—Cr1—O1iv180.0H1B—C1—H1C109.5
O1—Cr1—O1iv88.19 (9)S1—C2—H2A109.5
O1i—Cr1—O1v88.19 (9)S1—C2—H2B109.5
O1ii—Cr1—O1v91.81 (9)H2A—C2—H2B109.5
O1iii—Cr1—O1v88.19 (9)S1—C2—H2C109.5
O1—Cr1—O1v179.999 (1)H2A—C2—H2C109.5
O1iv—Cr1—O1v91.81 (9)H2B—C2—H2C109.5
O1—S1—C2104.46 (15)
C2—S1—O1—Cr1112.64 (17)O1ii—Cr1—O1—S1140.87 (18)
C1—S1—O1—Cr1144.52 (16)O1iii—Cr1—O1—S1131.00 (10)
O1i—Cr1—O1—S139.13 (18)O1iv—Cr1—O1—S149.00 (10)
Symmetry codes: (i) x+y, x+1, z; (ii) xy+2/3, x+1/3, z+1/3; (iii) y+1, xy+1, z; (iv) y1/3, 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···AD—HH···AD···AD—H···A
C1—H1B···Cl10.982.753.647 (3)153
C1—H1A···Cl2vi0.982.643.614 (4)176
Symmetry code: (vi) x+1/3, y+2/3, z1/3.

Experimental details

Crystal data
Chemical formula[Cr(C2H6OS)6]Cl3
Mr627.12
Crystal system, space groupTrigonal, R3
Temperature (K)120
a, c (Å)10.5499 (6), 21.1370 (13)
V3)2037.4 (2)
Z3
Radiation typeMo Kα
µ (mm1)1.20
Crystal size (mm)0.34 × 0.29 × 0.20
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(North et al., 1968)
Tmin, Tmax0.688, 0.795
No. of measured, independent and
observed [I > 2σ(I)] reflections
10865, 1044, 855
Rint0.051
(sin θ/λ)max1)0.652
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.135, 1.14
No. of reflections1044
No. of parameters46
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
C1—H1B···Cl10.982.753.647 (3)152.9
C1—H1A···Cl2i0.982.643.614 (4)175.6
Symmetry code: (i) x+1/3, y+2/3, z1/3.
 

References

First citationBruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBurla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381–388.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationChan, E. J., Cox, G., Harrowfield, M., Ogden, I., Skelton, B. W. & White, A. H. (2004). Inorg. Chim. Acta, 357, 2365–2372.  Web of Science CSD CrossRef CAS Google Scholar
First citationDesiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond, pp. 40–107. Oxford University Press.  Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationNorth, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.  CrossRef IUCr Journals Web of Science Google Scholar
First citationÖhrström, L. & Svensson, G. (2000). Inorg. Chim. Acta, 305, 157–163.  Google Scholar
First citationOtwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.  Google Scholar
First citationPersson, I., Sandström, M., Yokoyama, H. & Chaudhry, M. (1995). Z. Naturforsch. Teil A, 50, 21–30.  CAS Google Scholar
First citationReynolds, W. L. (1970). Prog. Inorg. Chem. 12, 1–29.  CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds