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Acta Cryst. (2012). E68, m1319    [ doi:10.1107/S160053681204069X ]

Bis(chlorido)(dimethylsulfoxide-[kappa]O)barium(II)

F. Gschwind and M. Jansen

Abstract top

The title compound, [BaCl2(C2H6SO)], forms a Ba6Cl9 cluster in which the BaCl2 units are connected via dimethylsulfoxide (DMSO) and chloride bridges. The central Cl atom of the Ba6Cl9 cluster is located on a threefold inversion axis and is coordinated octahedrally to six barium cations. In the crystal, the clusters are arranged in rows, which are interconnected by the DMSO molecules, forming a three-dimensional network.

Comment top

The title compound crystallizes in the trigonal space group R3c and its asymmetric unit consists of one barium ion and four chloride ions (three of which are located on special positions and have partial occupancies: Cl1 1/2; Cl3 1/6; Cl4 1/3) and one DMSO solvent molecule (Fig. 1). The complete structure forms a Ba6Cl9 cluster (Fig. 2). Atom Cl3 occupies the center of the polyhedron located at position (0,0,0: 3); it is coordinated to six barium ions and has an octahedral configuration. Each barium ion sits on a corner of the cluster and coordinates via two O atoms of the DMSO molecule (O1 and its symmetry equivalent O1i; Ba1—O1 2.752 (3) Å, Ba1—O1i 2.830 (1) Å; symmetry code: (i) x - y + 1/3, -y + 2/3, -z + 1/6) and one chloride (Ba1—Cl1 = Cl1—Ba1i = 3.088 (1) Å) to the next BaCl cluster. The average Ba—O bond distance lies in the typical range for a Ba—O(DMSO) bond length (2.637–2.875 Å). The Ba—Cl bond distances in the title compound vary between 3.0888 (16)–3.3231 (11) Å, while a similar bridging Ba—Cl—Ba structure shows bond lengths between (3.114–3.253 Å).

The average Ba···Ba distance in the cluster is about 4.69 Å, while the distance between the two bridged barium ions is shorter at 4.3106 (19) Å.

Due to the high symmetry the Ba–DMSO bridge spreads out in all three dimensions (Fig. 3). In the z-dimension wheel-shaped structures of the rows of BaCl clusters are visible. The `DMSO-chloride' bridges are arranged around the wheels. The closest distance from the BaCl clusters is about 10.6 Å (measured between Cl3 and Cl3ii; symmetry code: (ii) 1/3 + y, 2/3 + x, 1/6 - z). There are no classical hydrogen bonds present but there is a small solvent accessible void of ca 63 Å3.

A literature search (Allen, 2002) revealed no similar barium-chloride clusters, but there are several examples of barium chloride bridged structures. For instance barium sulfonate complexes with layered structures (Yang et al., 2006) or chloride bridged macrocyclic barium complexes (Arion et al., 2001; Fenske et al. 1993). There exist also clusters of barium and O atoms with a bridging central chloride ion (Drozdov et al., 1994). Furthermore, there exist different examples of barium DMSO complexes (Harrowfield et al., 2004; Pi et al. 2009).

Related literature top

For general background to barium complexes with chloride bridges, see: Yang et al. (2006); Arion et al. (2001); Fenske et al. (1993). For further information on chelated barium clusters with a central chloride atom, see: Drozdov et al. (1994). For examples of barium–DMSO complexes, see: Harrowfield et al. (2004); Pi et al. (2009). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

The title compound was obtained incidentally as a side-product in the following reaction:

Solution A: To a solution of BaCl2 (1 g) dissolved in methanol (10 ml) was added 1,5 g of tetraethylene glycol. Product B: Phosphomolybdic acid hydrate (0.25 g, 0.54 mmol) was dissolved in acetone (5 ml) and precipitated with an excess of cobaltocenium hexafluorophosphate (0.2 g) in acetonitrile (5 ml).

Product B was then dissolved in acetonitrile (10 ml) and precipitated with solution A. The precipitate was dissolved in hot DMSO (15 ml). After cooling the solution was layered with diethylether. A few colorless crystals the title compound appeared as a side-product after a few weeks.

Refinement top

Atoms C1 and C2 were treated isotropically due to thermal disorder. The H atoms were included in calculated positions and treated as rding atoms: C—H = 0.96 Å with Uiso(H) = 1.5Ueq(C). Potential Solvent Area Volume = 63.2 Å3. A small void of less than 1% was found in the crystal structure. It was not considered in the refinement.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2009); cell refinement: X-AREA (Stoe & Cie, 2009); data reduction: X-RED32 (Stoe & Cie, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. A view of the asymmetric unit of the title compound. Three of the four Cl atoms are located on special positions and have partial occupancies of Cl1 1/2, Cl3 1/6 and Cl4 1/3.
[Figure 2] Fig. 2. A view of the molecular structure of the title compound, with the atom numbering. The displacement ellipsoids are drawn at the 50% probability level. Symmetry codes: (1) -y, x - y, z (2) -x + y, -y, z (3) -x, -y, -z (4) x - y, x, -z (5) y, x + y, -z.
[Figure 3] Fig. 3. A view along the z-axis of the crystal packing of the title compound.
Bis(chlorido)(dimethylsulfoxide-κO)barium(II) top
Crystal data top
[BaCl2(C2H6OS)]Dx = 2.375 Mg m3
Mr = 286.37Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3cCell parameters from 28704 reflections
Hall symbol: -R 3 2"cθ = 1.5–57.3°
a = 15.680 (7) ŵ = 5.79 mm1
c = 33.848 (6) ÅT = 298 K
V = 7207 (5) Å3Bloc, colourless
Z = 360.18 × 0.12 × 0.10 mm
F(000) = 4752
Data collection top
Stoe IPDS 2
diffractometer
1807 independent reflections
Radiation source: fine-focus sealed tube1783 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.059
Detector resolution: 6.67 pixels mm-1θmax = 27.3°, θmin = 2.6°
ω and φ scansh = 2019
Absorption correction: numerical
(X-SHAPE; Stoe & Cie, 2009)
k = 2020
Tmin = 0.422, Tmax = 0.595l = 4343
28344 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)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.057H-atom parameters constrained
S = 1.25 w = 1/[σ2(Fo2) + (0.0207P)2 + 30.0844P]
where P = (Fo2 + 2Fc2)/3
1807 reflections(Δ/σ)max < 0.001
55 parametersΔρmax = 0.51 e Å3
0 restraintsΔρmin = 0.54 e Å3
Crystal data top
[BaCl2(C2H6OS)]Z = 36
Mr = 286.37Mo Kα radiation
Trigonal, R3cµ = 5.79 mm1
a = 15.680 (7) ÅT = 298 K
c = 33.848 (6) Å0.18 × 0.12 × 0.10 mm
V = 7207 (5) Å3
Data collection top
Stoe IPDS 2
diffractometer
1807 independent reflections
Absorption correction: numerical
(X-SHAPE; Stoe & Cie, 2009)
1783 reflections with I > 2σ(I)
Tmin = 0.422, Tmax = 0.595Rint = 0.059
28344 measured reflectionsθmax = 27.3°
Refinement top
R[F2 > 2σ(F2)] = 0.023 w = 1/[σ2(Fo2) + (0.0207P)2 + 30.0844P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.057Δρmax = 0.51 e Å3
S = 1.25Δρmin = 0.54 e Å3
1807 reflectionsAbsolute structure: ?
55 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
H-atom parameters constrained
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
S10.24622 (7)0.39751 (7)0.00510 (3)0.0417 (2)
O10.1864 (2)0.38899 (19)0.04210 (7)0.0463 (6)
C20.2400 (4)0.4882 (3)0.02432 (13)0.0576 (10)*
H2A0.17440.46200.03440.086*
H2B0.28550.50630.04590.086*
H2C0.25670.54520.00850.086*
C10.3718 (4)0.4668 (4)0.01944 (14)0.0614 (11)*
H1A0.38800.42700.03590.092*
H1B0.38260.52410.03390.092*
H1C0.41280.48680.00370.092*
Cl10.03305 (8)0.33330.08330.0548 (4)
Cl20.23027 (6)0.18744 (6)0.03813 (3)0.03946 (18)
Cl40.00000.00000.10413 (4)0.0396 (3)
Ba10.037103 (14)0.191429 (13)0.054807 (5)0.03329 (8)
Cl30.00000.00000.00000.0356 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0425 (4)0.0386 (4)0.0401 (4)0.0172 (4)0.0055 (3)0.0018 (3)
O10.0454 (14)0.0441 (14)0.0408 (13)0.0160 (12)0.0088 (11)0.0018 (11)
Cl10.0436 (4)0.0669 (9)0.0617 (8)0.0334 (4)0.0147 (3)0.0295 (7)
Cl20.0385 (4)0.0382 (4)0.0424 (4)0.0197 (3)0.0019 (3)0.0004 (3)
Cl40.0412 (4)0.0412 (4)0.0363 (7)0.0206 (2)0.0000.000
Ba10.03337 (11)0.03172 (11)0.03353 (12)0.01533 (8)0.00041 (7)0.00300 (7)
Cl30.0367 (5)0.0367 (5)0.0334 (9)0.0183 (3)0.0000.000
Geometric parameters (Å, º) top
S1—O11.530 (3)Cl4—Ba1iv3.2232 (13)
S1—C11.776 (5)Cl4—Ba1ii3.2232 (13)
S1—C21.778 (5)Cl4—Ba13.2232 (13)
O1—Ba1i2.752 (2)Ba1—O1i2.752 (2)
O1—Ba12.830 (3)Ba1—Cl2iv3.1528 (16)
C2—H2A0.9600Ba1—Cl2v3.1968 (11)
C2—H2B0.9600Ba1—Cl33.3231 (11)
C2—H2C0.9600Ba1—Ba1i4.3106 (16)
C1—H1A0.9600Ba1—Ba1v4.6225 (10)
C1—H1B0.9600Ba1—Ba1iii4.6225 (10)
C1—H1C0.9600Ba1—Ba1iv4.776 (2)
Cl1—Ba13.0888 (16)Cl3—Ba1v3.3231 (11)
Cl1—Ba1i3.0888 (16)Cl3—Ba1vi3.3231 (11)
Cl2—Ba13.1123 (16)Cl3—Ba1iii3.3231 (11)
Cl2—Ba1ii3.1528 (16)Cl3—Ba1iv3.3231 (11)
Cl2—Ba1iii3.1968 (11)Cl3—Ba1ii3.3231 (11)
O1—S1—C1105.9 (2)O1i—Ba1—Ba1i40.11 (5)
O1—S1—C2104.60 (19)O1—Ba1—Ba1i38.79 (5)
C1—S1—C298.7 (2)Cl1—Ba1—Ba1i45.751 (18)
S1—O1—Ba1i146.52 (15)Cl2—Ba1—Ba1i95.556 (16)
S1—O1—Ba1110.82 (13)Cl2iv—Ba1—Ba1i130.725 (16)
Ba1i—O1—Ba1101.09 (8)Cl2v—Ba1—Ba1i107.06 (2)
S1—C2—H2A109.5Cl4—Ba1—Ba1i119.27 (3)
S1—C2—H2B109.5Cl3—Ba1—Ba1i161.700 (5)
H2A—C2—H2B109.5O1i—Ba1—Ba1v173.27 (6)
S1—C2—H2C109.5O1—Ba1—Ba1v114.60 (5)
H2A—C2—H2C109.5Cl1—Ba1—Ba1v104.838 (18)
H2B—C2—H2C109.5Cl2—Ba1—Ba1v103.16 (2)
S1—C1—H1A109.5Cl2iv—Ba1—Ba1v43.656 (18)
S1—C1—H1B109.5Cl2v—Ba1—Ba1v42.18 (2)
H1A—C1—H1B109.5Cl4—Ba1—Ba1v99.24 (3)
S1—C1—H1C109.5Cl3—Ba1—Ba1v45.933 (9)
H1A—C1—H1C109.5Ba1i—Ba1—Ba1v139.897 (6)
H1B—C1—H1C109.5O1i—Ba1—Ba1iii124.48 (6)
Ba1—Cl1—Ba1i88.50 (3)O1—Ba1—Ba1iii79.47 (5)
Ba1—Cl2—Ba1ii99.32 (2)Cl1—Ba1—Ba1iii137.642 (7)
Ba1—Cl2—Ba1iii94.21 (2)Cl2—Ba1—Ba1iii43.606 (18)
Ba1ii—Cl2—Ba1iii93.44 (2)Cl2iv—Ba1—Ba1iii102.98 (2)
Ba1iv—Cl4—Ba1ii95.60 (3)Cl2v—Ba1—Ba1iii42.91 (2)
Ba1iv—Cl4—Ba195.60 (3)Cl4—Ba1—Ba1iii99.24 (3)
Ba1ii—Cl4—Ba195.60 (3)Cl3—Ba1—Ba1iii45.933 (9)
O1i—Ba1—O169.29 (9)Ba1i—Ba1—Ba1iii117.194 (11)
O1i—Ba1—Cl170.89 (6)Ba1v—Ba1—Ba1iii62.20 (2)
O1—Ba1—Cl169.92 (6)O1i—Ba1—Ba1iv118.10 (6)
O1i—Ba1—Cl283.11 (6)O1—Ba1—Ba1iv169.45 (5)
O1—Ba1—Cl273.36 (6)Cl1—Ba1—Ba1iv118.845 (16)
Cl1—Ba1—Cl2140.52 (2)Cl2—Ba1—Ba1iv99.356 (16)
O1i—Ba1—Cl2iv129.87 (6)Cl2iv—Ba1—Ba1iv40.024 (16)
O1—Ba1—Cl2iv142.06 (6)Cl2v—Ba1—Ba1iv98.624 (16)
Cl1—Ba1—Cl2iv85.41 (2)Cl4—Ba1—Ba1iv42.200 (17)
Cl2—Ba1—Cl2iv133.71 (3)Cl3—Ba1—Ba1iv44.067 (9)
O1i—Ba1—Cl2v142.50 (6)Ba1i—Ba1—Ba1iv151.522 (11)
O1—Ba1—Cl2v73.31 (5)Ba1v—Ba1—Ba1iv58.899 (11)
Cl1—Ba1—Cl2v99.01 (2)Ba1iii—Ba1—Ba1iv90.0
Cl2—Ba1—Cl2v83.71 (2)Ba1v—Cl3—Ba188.135 (18)
Cl2iv—Ba1—Cl2v83.06 (2)Ba1v—Cl3—Ba1vi91.865 (18)
O1i—Ba1—Cl479.44 (6)Ba1—Cl3—Ba1vi180.000 (5)
O1—Ba1—Cl4139.76 (6)Ba1v—Cl3—Ba1iii91.865 (18)
Cl1—Ba1—Cl4123.06 (3)Ba1—Cl3—Ba1iii88.135 (18)
Cl2—Ba1—Cl478.438 (19)Ba1vi—Cl3—Ba1iii91.865 (18)
Cl2iv—Ba1—Cl477.857 (19)Ba1v—Cl3—Ba1iv88.135 (18)
Cl2v—Ba1—Cl4131.44 (3)Ba1—Cl3—Ba1iv91.865 (18)
O1i—Ba1—Cl3137.07 (5)Ba1vi—Cl3—Ba1iv88.135 (18)
O1—Ba1—Cl3125.40 (5)Ba1iii—Cl3—Ba1iv180.000 (9)
Cl1—Ba1—Cl3149.383 (17)Ba1v—Cl3—Ba1ii180.000 (8)
Cl2—Ba1—Cl367.244 (16)Ba1—Cl3—Ba1ii91.865 (18)
Cl2iv—Ba1—Cl366.799 (16)Ba1vi—Cl3—Ba1ii88.135 (18)
Cl2v—Ba1—Cl366.32 (2)Ba1iii—Cl3—Ba1ii88.135 (18)
Cl4—Ba1—Cl365.13 (3)Ba1iv—Cl3—Ba1ii91.865 (18)
Symmetry codes: (i) xy+1/3, y+2/3, z+1/6; (ii) x+y, x, z; (iii) y, x+y, z; (iv) y, xy, z; (v) xy, x, z; (vi) x, y, z.
Acknowledgements top

The authors thank Helen Stöckli-Evans for valuable help.

references
References top

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