Bis(chlorido)(dimethyl­sulfoxide-κO)barium(II)

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.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](S-C) = 0.006 Å
• R factor = 0.023
• wR factor = 0.057
• Data-to-parameter ratio = 32.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT201_ALERT_2_B Isotropic non-H Atoms in Main Residue(s) .......          2
PLAT774_ALERT_1_B Suspect X-Y Bond in CIF:   BA1    --  BA1     ..       4.31 Ang.
PLAT774_ALERT_1_B Suspect X-Y Bond in CIF:   BA1    --  BA1     ..       4.62 Ang.
PLAT774_ALERT_1_B Suspect X-Y Bond in CIF:   BA1    --  BA1     ..       4.62 Ang.
PLAT774_ALERT_1_B Suspect X-Y Bond in CIF:   BA1    --  BA1     ..       4.78 Ang.

Alert level C
PLAT431_ALERT_2_C Short Inter HL..A  Contact  Cl1    ..  S1      .       3.43 Ang.
PLAT431_ALERT_2_C Short Inter HL..A  Contact  Cl1    ..  S1      .       3.43 Ang.
PLAT431_ALERT_2_C Short Inter HL..A  Contact  Cl2    ..  S1      .       3.29 Ang.
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.495
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          4
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large.      30.08
PLAT152_ALERT_1_G The Supplied and Calc. Volume s.u. Differ by ...          3 Units
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       2.36 Ratio
PLAT804_ALERT_5_G ARU-Pack Problem in PLATON Analysis ............          1 Times
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          2

   0 ALERT level A = Most likely a serious problem - resolve or explain
   5 ALERT level B = A potentially serious problem, consider carefully
   7 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Comment

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 ų.

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

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).

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.5U_eq(C). Potential Solvent Area Volume = 63.2 ų. A small void of less than 1% was found in the crystal structure. It was not considered in the refinement.

Computing details

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

	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.
	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.
	Fig. 3. A view along the z-axis of the crystal packing of the title compound.

Bis(chlorido)(dimethylsulfoxide-κO)barium(II)

Crystal data

[BaCl2(C2H6OS)]	Dx = 2.375 Mg m^−3
Mr = 286.37	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3c	Cell parameters from 28704 reflections
Hall symbol: -R 3 2"c	θ = 1.5–57.3°
a = 15.680 (7) Å	µ = 5.79 mm^−1
c = 33.848 (6) Å	T = 298 K
V = 7207 (5) Å^3	Bloc, colourless
Z = 36	0.18 × 0.12 × 0.10 mm
F(000) = 4752

Data collection

Stoe IPDS 2 diffractometer	1807 independent reflections
Radiation source: fine-focus sealed tube	1783 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
Detector resolution: 6.67 pixels mm^-1	θmax = 27.3°, θmin = 2.6°
ω and ϕ scans	h = −20→19
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 2009)	k = −20→20
Tmin = 0.422, Tmax = 0.595	l = −43→43
28344 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.057	H-atom parameters constrained
S = 1.25	w = 1/[σ^2(Fo^2) + (0.0207P)^2 + 30.0844P] where P = (Fo^2 + 2Fc^2)/3
1807 reflections	(Δ/σ)max < 0.001
55 parameters	Δρmax = 0.51 e Å^−3
0 restraints	Δρmin = −0.54 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.

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.24622 (7)	0.39751 (7)	0.00510 (3)	0.0417 (2)
O1	0.1864 (2)	0.38899 (19)	0.04210 (7)	0.0463 (6)
C2	0.2400 (4)	0.4882 (3)	−0.02432 (13)	0.0576 (10)*
H2A	0.1744	0.4620	−0.0344	0.086*
H2B	0.2855	0.5063	−0.0459	0.086*
H2C	0.2567	0.5452	−0.0085	0.086*
C1	0.3718 (4)	0.4668 (4)	0.01944 (14)	0.0614 (11)*
H1A	0.3880	0.4270	0.0359	0.092*
H1B	0.3826	0.5241	0.0339	0.092*
H1C	0.4128	0.4868	−0.0037	0.092*
Cl1	−0.03305 (8)	0.3333	0.0833	0.0548 (4)
Cl2	0.23027 (6)	0.18744 (6)	0.03813 (3)	0.03946 (18)
Cl4	0.0000	0.0000	0.10413 (4)	0.0396 (3)
Ba1	0.037103 (14)	0.191429 (13)	0.054807 (5)	0.03329 (8)
Cl3	0.0000	0.0000	0.0000	0.0356 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0425 (4)	0.0386 (4)	0.0401 (4)	0.0172 (4)	0.0055 (3)	−0.0018 (3)
O1	0.0454 (14)	0.0441 (14)	0.0408 (13)	0.0160 (12)	0.0088 (11)	−0.0018 (11)
Cl1	0.0436 (4)	0.0669 (9)	0.0617 (8)	0.0334 (4)	−0.0147 (3)	−0.0295 (7)
Cl2	0.0385 (4)	0.0382 (4)	0.0424 (4)	0.0197 (3)	0.0019 (3)	−0.0004 (3)
Cl4	0.0412 (4)	0.0412 (4)	0.0363 (7)	0.0206 (2)	0.000	0.000
Ba1	0.03337 (11)	0.03172 (11)	0.03353 (12)	0.01533 (8)	0.00041 (7)	−0.00300 (7)
Cl3	0.0367 (5)	0.0367 (5)	0.0334 (9)	0.0183 (3)	0.000	0.000

Geometric parameters (Å, º)

S1—O1	1.530 (3)	Cl4—Ba1^iv	3.2232 (13)
S1—C1	1.776 (5)	Cl4—Ba1^ii	3.2232 (13)
S1—C2	1.778 (5)	Cl4—Ba1	3.2232 (13)
O1—Ba1^i	2.752 (2)	Ba1—O1^i	2.752 (2)
O1—Ba1	2.830 (3)	Ba1—Cl2^iv	3.1528 (16)
C2—H2A	0.9600	Ba1—Cl2^v	3.1968 (11)
C2—H2B	0.9600	Ba1—Cl3	3.3231 (11)
C2—H2C	0.9600	Ba1—Ba1^i	4.3106 (16)
C1—H1A	0.9600	Ba1—Ba1^v	4.6225 (10)
C1—H1B	0.9600	Ba1—Ba1^iii	4.6225 (10)
C1—H1C	0.9600	Ba1—Ba1^iv	4.776 (2)
Cl1—Ba1	3.0888 (16)	Cl3—Ba1^v	3.3231 (11)
Cl1—Ba1^i	3.0888 (16)	Cl3—Ba1^vi	3.3231 (11)
Cl2—Ba1	3.1123 (16)	Cl3—Ba1^iii	3.3231 (11)
Cl2—Ba1^ii	3.1528 (16)	Cl3—Ba1^iv	3.3231 (11)
Cl2—Ba1^iii	3.1968 (11)	Cl3—Ba1^ii	3.3231 (11)
O1—S1—C1	105.9 (2)	O1^i—Ba1—Ba1^i	40.11 (5)
O1—S1—C2	104.60 (19)	O1—Ba1—Ba1^i	38.79 (5)
C1—S1—C2	98.7 (2)	Cl1—Ba1—Ba1^i	45.751 (18)
S1—O1—Ba1^i	146.52 (15)	Cl2—Ba1—Ba1^i	95.556 (16)
S1—O1—Ba1	110.82 (13)	Cl2^iv—Ba1—Ba1^i	130.725 (16)
Ba1^i—O1—Ba1	101.09 (8)	Cl2^v—Ba1—Ba1^i	107.06 (2)
S1—C2—H2A	109.5	Cl4—Ba1—Ba1^i	119.27 (3)
S1—C2—H2B	109.5	Cl3—Ba1—Ba1^i	161.700 (5)
H2A—C2—H2B	109.5	O1^i—Ba1—Ba1^v	173.27 (6)
S1—C2—H2C	109.5	O1—Ba1—Ba1^v	114.60 (5)
H2A—C2—H2C	109.5	Cl1—Ba1—Ba1^v	104.838 (18)
H2B—C2—H2C	109.5	Cl2—Ba1—Ba1^v	103.16 (2)
S1—C1—H1A	109.5	Cl2^iv—Ba1—Ba1^v	43.656 (18)
S1—C1—H1B	109.5	Cl2^v—Ba1—Ba1^v	42.18 (2)
H1A—C1—H1B	109.5	Cl4—Ba1—Ba1^v	99.24 (3)
S1—C1—H1C	109.5	Cl3—Ba1—Ba1^v	45.933 (9)
H1A—C1—H1C	109.5	Ba1^i—Ba1—Ba1^v	139.897 (6)
H1B—C1—H1C	109.5	O1^i—Ba1—Ba1^iii	124.48 (6)
Ba1—Cl1—Ba1^i	88.50 (3)	O1—Ba1—Ba1^iii	79.47 (5)
Ba1—Cl2—Ba1^ii	99.32 (2)	Cl1—Ba1—Ba1^iii	137.642 (7)
Ba1—Cl2—Ba1^iii	94.21 (2)	Cl2—Ba1—Ba1^iii	43.606 (18)
Ba1^ii—Cl2—Ba1^iii	93.44 (2)	Cl2^iv—Ba1—Ba1^iii	102.98 (2)
Ba1^iv—Cl4—Ba1^ii	95.60 (3)	Cl2^v—Ba1—Ba1^iii	42.91 (2)
Ba1^iv—Cl4—Ba1	95.60 (3)	Cl4—Ba1—Ba1^iii	99.24 (3)
Ba1^ii—Cl4—Ba1	95.60 (3)	Cl3—Ba1—Ba1^iii	45.933 (9)
O1^i—Ba1—O1	69.29 (9)	Ba1^i—Ba1—Ba1^iii	117.194 (11)
O1^i—Ba1—Cl1	70.89 (6)	Ba1^v—Ba1—Ba1^iii	62.20 (2)
O1—Ba1—Cl1	69.92 (6)	O1^i—Ba1—Ba1^iv	118.10 (6)
O1^i—Ba1—Cl2	83.11 (6)	O1—Ba1—Ba1^iv	169.45 (5)
O1—Ba1—Cl2	73.36 (6)	Cl1—Ba1—Ba1^iv	118.845 (16)
Cl1—Ba1—Cl2	140.52 (2)	Cl2—Ba1—Ba1^iv	99.356 (16)
O1^i—Ba1—Cl2^iv	129.87 (6)	Cl2^iv—Ba1—Ba1^iv	40.024 (16)
O1—Ba1—Cl2^iv	142.06 (6)	Cl2^v—Ba1—Ba1^iv	98.624 (16)
Cl1—Ba1—Cl2^iv	85.41 (2)	Cl4—Ba1—Ba1^iv	42.200 (17)
Cl2—Ba1—Cl2^iv	133.71 (3)	Cl3—Ba1—Ba1^iv	44.067 (9)
O1^i—Ba1—Cl2^v	142.50 (6)	Ba1^i—Ba1—Ba1^iv	151.522 (11)
O1—Ba1—Cl2^v	73.31 (5)	Ba1^v—Ba1—Ba1^iv	58.899 (11)
Cl1—Ba1—Cl2^v	99.01 (2)	Ba1^iii—Ba1—Ba1^iv	90.0
Cl2—Ba1—Cl2^v	83.71 (2)	Ba1^v—Cl3—Ba1	88.135 (18)
Cl2^iv—Ba1—Cl2^v	83.06 (2)	Ba1^v—Cl3—Ba1^vi	91.865 (18)
O1^i—Ba1—Cl4	79.44 (6)	Ba1—Cl3—Ba1^vi	180.000 (5)
O1—Ba1—Cl4	139.76 (6)	Ba1^v—Cl3—Ba1^iii	91.865 (18)
Cl1—Ba1—Cl4	123.06 (3)	Ba1—Cl3—Ba1^iii	88.135 (18)
Cl2—Ba1—Cl4	78.438 (19)	Ba1^vi—Cl3—Ba1^iii	91.865 (18)
Cl2^iv—Ba1—Cl4	77.857 (19)	Ba1^v—Cl3—Ba1^iv	88.135 (18)
Cl2^v—Ba1—Cl4	131.44 (3)	Ba1—Cl3—Ba1^iv	91.865 (18)
O1^i—Ba1—Cl3	137.07 (5)	Ba1^vi—Cl3—Ba1^iv	88.135 (18)
O1—Ba1—Cl3	125.40 (5)	Ba1^iii—Cl3—Ba1^iv	180.000 (9)
Cl1—Ba1—Cl3	149.383 (17)	Ba1^v—Cl3—Ba1^ii	180.000 (8)
Cl2—Ba1—Cl3	67.244 (16)	Ba1—Cl3—Ba1^ii	91.865 (18)
Cl2^iv—Ba1—Cl3	66.799 (16)	Ba1^vi—Cl3—Ba1^ii	88.135 (18)
Cl2^v—Ba1—Cl3	66.32 (2)	Ba1^iii—Cl3—Ba1^ii	88.135 (18)
Cl4—Ba1—Cl3	65.13 (3)	Ba1^iv—Cl3—Ba1^ii	91.865 (18)

Symmetry codes: (i) x−y+1/3, −y+2/3, −z+1/6; (ii) −x+y, −x, z; (iii) y, −x+y, −z; (iv) −y, x−y, z; (v) x−y, x, −z; (vi) −x, −y, −z.