Bis[(dimethyl-λ4-sulfanyl­idene)oxonium] hexa­bromidotellurate(IV) dimethyl sulfoxide disolvate

Rudd, M.D.; Kokke, G.; Lindeman, S.V.

doi:10.1107/S1600536808015468

organic compounds

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Volume 64| Part 6| June 2008| Page o1161

doi:10.1107/S1600536808015468

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Bis[(dimethyl-λ⁴-sulfanylidene)oxonium] hexabromidotellurate(IV) dimethyl sulfoxide disolvate

Martin D. Rudd,^a ^* Gregory Kokke ^a and Sergey V. Lindeman ^b

^aUniversity of Wisconsin–Fox Valley, Menasha, Wisconsin 54952, USA, and ^bMarquette University, Milwaukee, Wisconsin 53201, USA
^*Correspondence e-mail: martin.rudd@uwc.edu

(Received 3 April 2008; accepted 22 May 2008; online 30 May 2008)

The structure of the title salt, 2C₂H₇OS⁺·Br₆Te²⁻·2C₂H₆OS, displays O—H⋯O hydrogen bonding between one protonated dimethyl sulfoxide molecule and a neighboring dimethyl sulfoxide molecule, and an octahedral geometry for the Te atom; the latter is situated on a center of inversion.

Related literature

For the structure of the related compound [(dmso-H)₂][TeCl₆], see: Laitinen et al. (2002 ); Viossat et al. (1981 ). For related literature, see Abriel (1987 ); Abriel & du Bois (1989 ); Borgias et al. (1985 ); Jaswal et al. (1990 ); Keefer et al. (1988 ).

Experimental

Crystal data

2C₂H₇OS⁺·Br₆Te²⁻·2C₂H₆OS
M_r = 921.59
Triclinic, $[P \overline 1]$
a = 8.0087 (2) Å
b = 9.2428 (2) Å
c = 10.5249 (3) Å
α = 66.280 (1)°
β = 70.732 (1)°
γ = 66.340 (1)°
V = 639.98 (3) Å³
Z = 1
Cu Kα radiation
μ = 23.30 mm⁻¹
T = 100 (2) K
0.23 × 0.20 × 0.16 mm

Data collection

Bruker APEX2 CCD detector diffractometer
Absorption correction: numerical [based on real shape of the crystal; absorption correction followed by the application of SADABS (Bruker, 2005 )] T_min = 0.075, T_max = 0.118
5232 measured reflections
2112 independent reflections
2112 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.056
S = 1.15
2112 reflections
159 parameters
All H-atom parameters refined
Δρ_max = 1.02 e Å⁻³
Δρ_min = −0.68 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯O1	0.83 (7)	1.62 (8)	2.448 (4)	175 (7)

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: XS in SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Bruker, 1998 ); software used to prepare material for publication: XCIF in SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808015468/tk2262sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808015468/tk2262Isup2.hkl

checkCIF report

Comment top

The structure of (I) consists of two units of two H⁺ hydrogen bonded dimethylsulfoxide molecules, Fig. 1, and a centrosymmetric hexabromotellurate(IV) anion, Fig. 2. At 2.448 (4) Å, the O1···O2 distance is relatively short, and is consistent with the presence of a moderately strong hydrogen bond (Keefer et al., 1988). The IR spectrum reveals peaks typical for the [(dmso)₂H]⁺ cation with a strong band at 731 cm^-1. This is in line with similar samples in which the same cation has been analyzed (Jaswal et al., 1990). A closely related tellurium complex, [(dmso)₂H]₂[TeCl₆] has been structurally reported at room temperature (Viossat et al., 1981) and at low temperature (Laitinen et al., 2002). The cation in the latter experiment shows a O1···O2 distance of 2.435 (3) Å and the authors describe this as a "relatively strong hydrogen bond".

The hexabromotellurate(IV) anion in (I) shows an approximately octahedral geometry as expected. A review of some related structures shows that there are packing factors that slightly distort the geometry. One example where [TeBr₆]^2- shows deviations away from the regular octahedral geometry indicates that there is a 0.024Å difference between the longest and shortest bond Te—Br bond lengths (Borgias et al., 1985). In that report, the Te atom is located in a general position. In other literature, the Te is located at a center of inversion and displays a larger angular deviation from 90° [87.56 (3) - 92.44 (3)°] (Abriel & du Bois, 1989) which is greater than those reported here [less than 0.9° away from 90°]. A review of structural data for MX₆E^2- compounds (M = Se, Te and X = Cl, Br, I) was published to provide an explanation of the stereochemistry of the lone pair electrons (Abriel, 1987).

The unit cell shows, Fig. 3, the pairs of hydrogen bonded dmso molecule and dmso-H ions and anions, Table 1.

Related literature top

For the structure of thw related compound [(dmso-H)₂][TeCl₆], see: Laitinen et al. (2002); Viossat et al. (1981). For related literature, see Abriel (1987); Abriel & du Bois (1989); Borgias et al. (1985); Jaswal et al. (1990); Keefer et al. (1988).

Experimental top

Compound (I) was prepared by the slow cooling to room temperature of a hot solution (333 K) of tellurium dioxide (0.30 g, 0.19 mmol) dissolved in hydrobromic acid (1 mL) to which dimethylsulfoxide (5 mL) had been added. After 2 weeks, a crop of orange crystals formed although they are prone to solvent loss and decomposition. Analysis found: C 10.57; H 2.91; C₈H₂₆Br₆O₄S₄Te requires: C 10.42, H 2.84. The IR spectrum showed strong bands at 3392, 1056, 731 cm^-1.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SADABS (Bruker, 2005); program(s) used to solve structure: XS in SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Bruker, 1998); software used to prepare material for publication: XCIF in SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Numbering Scheme for [(DMSO)₂H]⁺ (the hydrogen bond is shown as a dashed line). Displacement ellipsoids are shown at the 50% level.
	Fig. 2. Numbering Scheme for [TeBr₆]^2-. Displacement ellipsoids are shown at the 50% level.
	Fig. 3. Hydrogen-bond formation and projection of the unit cell content of [(DMSO)₂H]₂[TeBr₆]. Symmetry operators: Te1A [x, y+1, z]; O1A and O2A [1-x, 1-y, -z]; O1B and O2B [x, y, z+1]

Bis[(dimethyl-λ⁴-sulfanylidene)oxonium] hexabromidotellurate(IV) dimethyl sulfoxide disolvate top

Crystal data top

2C₂H₇OS⁺·Br₆Te²⁻·2C₂H₆OS	Z = 1
M_r = 921.59	F(000) = 432
Triclinic, P1	D_x = 2.391 Mg m⁻³
Hall symbol: -P 1	Melting point: 343 K
a = 8.0087 (2) Å	Cu Kα radiation, λ = 1.54178 Å
b = 9.2428 (2) Å	Cell parameters from 4736 reflections
c = 10.5249 (3) Å	θ = 5–66°
α = 66.280 (1)°	µ = 23.30 mm⁻¹
β = 70.732 (1)°	T = 100 K
γ = 66.340 (1)°	Block, orange
V = 639.98 (3) Å³	0.23 × 0.20 × 0.16 mm

Data collection top

Bruker APEX2 CCD detector diffractometer	2112 independent reflections
Radiation source: fine-focus sealed tube	2112 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scans	θ_max = 66.8°, θ_min = 4.7°
Absorption correction: numerical [based on real shape of the crystal; absorption correction followed by the application of SADABS (Bruker, 2005)]	h = −8→9
T_min = 0.075, T_max = 0.118	k = −9→10
5232 measured reflections	l = 0→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.021	All H-atom parameters refined
wR(F²) = 0.056	w = 1/[σ²(F_o²) + (0.0268P)² + 1.1408P] where P = (F_o² + 2F_c²)/3
S = 1.15	(Δ/σ)_max = 0.004
2112 reflections	Δρ_max = 1.02 e Å⁻³
159 parameters	Δρ_min = −0.68 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00507 (17)

Crystal data top

2C₂H₇OS⁺·Br₆Te²⁻·2C₂H₆OS	γ = 66.340 (1)°
M_r = 921.59	V = 639.98 (3) Å³
Triclinic, P1	Z = 1
a = 8.0087 (2) Å	Cu Kα radiation
b = 9.2428 (2) Å	µ = 23.30 mm⁻¹
c = 10.5249 (3) Å	T = 100 K
α = 66.280 (1)°	0.23 × 0.20 × 0.16 mm
β = 70.732 (1)°

Data collection top

Bruker APEX2 CCD detector diffractometer	2112 independent reflections
Absorption correction: numerical [based on real shape of the crystal; absorption correction followed by the application of SADABS (Bruker, 2005)]	2112 reflections with I > 2σ(I)
T_min = 0.075, T_max = 0.118	R_int = 0.023
5232 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	0 restraints
wR(F²) = 0.056	All H-atom parameters refined
S = 1.15	Δρ_max = 1.02 e Å⁻³
2112 reflections	Δρ_min = −0.68 e Å⁻³
159 parameters

Special details top

Experimental. Analysis found: C 10.57; H 2.91; C~8~H~26~Br~6Õ~4~S~4~Te requires: C 10.42, H 2.84

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
Te1	0.5000	0.0000	0.5000	0.01240 (12)
Br1	0.47203 (5)	0.30103 (4)	0.30479 (4)	0.01875 (12)
Br2	0.13998 (5)	0.11843 (5)	0.62389 (4)	0.01970 (12)
Br3	0.39388 (5)	−0.09389 (5)	0.33507 (4)	0.02004 (12)
S1	0.72250 (12)	0.24280 (11)	−0.11647 (9)	0.0176 (2)
O1	0.8060 (4)	0.2997 (3)	−0.0395 (3)	0.0229 (6)
C1	0.4776 (5)	0.3040 (5)	−0.0455 (4)	0.0213 (8)
H1A	0.459 (7)	0.246 (6)	0.054 (5)	0.030 (12)*
H1B	0.440 (7)	0.421 (7)	−0.066 (5)	0.032 (13)*
H1C	0.424 (6)	0.263 (6)	−0.088 (5)	0.026 (12)*
C2	0.7743 (6)	0.0237 (5)	−0.0301 (4)	0.0215 (8)
H2A	0.700 (7)	−0.016 (6)	−0.060 (5)	0.027 (11)*
H2B	0.741 (6)	0.002 (6)	0.070 (5)	0.027 (12)*
H2C	0.907 (7)	−0.020 (6)	−0.066 (5)	0.025 (11)*
S2	1.03170 (12)	0.54942 (12)	−0.30476 (10)	0.0219 (2)
O2	1.0726 (4)	0.4039 (4)	−0.1636 (3)	0.0256 (6)
H2O	0.985 (10)	0.364 (9)	−0.123 (8)	0.07 (2)*
C3	1.2525 (6)	0.5183 (6)	−0.4190 (5)	0.0266 (9)
H3A	1.340 (7)	0.519 (6)	−0.369 (5)	0.029 (12)*
H3B	1.245 (7)	0.614 (7)	−0.496 (6)	0.040 (14)*
H3C	1.284 (8)	0.410 (7)	−0.440 (6)	0.049 (15)*
C4	1.0161 (7)	0.7251 (6)	−0.2660 (6)	0.0321 (10)
H4A	1.015 (7)	0.822 (7)	−0.346 (6)	0.040 (14)*
H4B	0.913 (8)	0.747 (7)	−0.207 (6)	0.043 (15)*
H4C	1.125 (7)	0.695 (6)	−0.222 (5)	0.035 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Te1	0.01221 (17)	0.01490 (18)	0.01250 (17)	−0.00478 (12)	−0.00205 (12)	−0.00641 (12)
Br1	0.0217 (2)	0.0180 (2)	0.0169 (2)	−0.00800 (15)	−0.00436 (15)	−0.00352 (15)
Br2	0.0143 (2)	0.0229 (2)	0.0215 (2)	−0.00556 (15)	0.00073 (15)	−0.01025 (16)
Br3	0.0237 (2)	0.0221 (2)	0.0211 (2)	−0.00733 (16)	−0.00826 (16)	−0.01003 (16)
S1	0.0187 (4)	0.0208 (4)	0.0158 (4)	−0.0096 (4)	−0.0020 (3)	−0.0059 (3)
O1	0.0228 (14)	0.0314 (15)	0.0234 (13)	−0.0161 (12)	−0.0018 (11)	−0.0118 (11)
C1	0.0215 (19)	0.026 (2)	0.022 (2)	−0.0115 (17)	−0.0024 (16)	−0.0095 (17)
C2	0.025 (2)	0.0208 (19)	0.021 (2)	−0.0087 (17)	−0.0077 (17)	−0.0047 (16)
S2	0.0167 (4)	0.0226 (5)	0.0279 (5)	−0.0070 (4)	−0.0058 (4)	−0.0075 (4)
O2	0.0243 (15)	0.0295 (15)	0.0261 (14)	−0.0158 (13)	−0.0052 (12)	−0.0042 (12)
C3	0.026 (2)	0.028 (2)	0.028 (2)	−0.0117 (18)	0.0002 (18)	−0.0107 (18)
C4	0.024 (2)	0.025 (2)	0.049 (3)	−0.0039 (18)	−0.002 (2)	−0.021 (2)

Geometric parameters (Å, º) top

Te1—Br1ⁱ	2.6865 (4)	C2—H2B	0.95 (5)
Te1—Br1	2.6865 (4)	C2—H2C	0.97 (5)
Te1—Br3	2.6956 (4)	S2—O2	1.576 (3)
Te1—Br3ⁱ	2.6956 (4)	S2—C3	1.767 (4)
Te1—Br2ⁱ	2.7103 (4)	S2—C4	1.776 (4)
Te1—Br2	2.7103 (4)	O2—H2O	0.83 (7)
S1—O1	1.537 (3)	C3—H3A	1.00 (5)
S1—C2	1.787 (4)	C3—H3B	0.92 (6)
S1—C1	1.791 (4)	C3—H3C	1.03 (6)
C1—H1A	0.96 (5)	C4—H4A	0.95 (6)
C1—H1B	0.95 (5)	C4—H4B	0.86 (6)
C1—H1C	0.97 (5)	C4—H4C	1.01 (5)
C2—H2A	0.98 (5)

Br1ⁱ—Te1—Br1	180.0	H1B—C1—H1C	117 (4)
Br1ⁱ—Te1—Br3	89.604 (11)	S1—C2—H2A	107 (3)
Br1—Te1—Br3	90.395 (11)	S1—C2—H2B	110 (3)
Br1ⁱ—Te1—Br3ⁱ	90.397 (11)	H2A—C2—H2B	110 (4)
Br1—Te1—Br3ⁱ	89.604 (11)	S1—C2—H2C	103 (3)
Br3—Te1—Br3ⁱ	179.999 (1)	H2A—C2—H2C	112 (4)
Br1ⁱ—Te1—Br2ⁱ	89.151 (11)	H2B—C2—H2C	114 (4)
Br1—Te1—Br2ⁱ	90.849 (11)	O2—S2—C3	102.38 (19)
Br3—Te1—Br2ⁱ	89.485 (12)	O2—S2—C4	102.5 (2)
Br3ⁱ—Te1—Br2ⁱ	90.515 (11)	C3—S2—C4	100.2 (2)
Br1ⁱ—Te1—Br2	90.848 (11)	S2—O2—H2O	112 (5)
Br1—Te1—Br2	89.151 (11)	S2—C3—H3A	106 (3)
Br3—Te1—Br2	90.515 (11)	S2—C3—H3B	107 (3)
Br3ⁱ—Te1—Br2	89.485 (12)	H3A—C3—H3B	104 (4)
Br2ⁱ—Te1—Br2	180.0	S2—C3—H3C	107 (3)
O1—S1—C2	103.95 (17)	H3A—C3—H3C	115 (4)
O1—S1—C1	104.47 (17)	H3B—C3—H3C	116 (5)
C2—S1—C1	98.62 (19)	S2—C4—H4A	114 (3)
S1—C1—H1A	108 (3)	S2—C4—H4B	107 (4)
S1—C1—H1B	106 (3)	H4A—C4—H4B	108 (5)
H1A—C1—H1B	113 (4)	S2—C4—H4C	108 (3)
S1—C1—H1C	106 (3)	H4A—C4—H4C	110 (4)
H1A—C1—H1C	108 (4)	H4B—C4—H4C	111 (5)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O1	0.83 (7)	1.62 (8)	2.448 (4)	175 (7)

Experimental details

Crystal data
Chemical formula	2C₂H₇OS⁺·Br₆Te²⁻·2C₂H₆OS
M_r	921.59
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	8.0087 (2), 9.2428 (2), 10.5249 (3)
α, β, γ (°)	66.280 (1), 70.732 (1), 66.340 (1)
V (Å³)	639.98 (3)
Z	1
Radiation type	Cu Kα
µ (mm⁻¹)	23.30
Crystal size (mm)	0.23 × 0.20 × 0.16

Data collection
Diffractometer	Bruker APEX2 CCD detector diffractometer
Absorption correction	Numerical [based on real shape of the crystal; absorption correction followed by the application of SADABS (Bruker, 2005)]
T_min, T_max	0.075, 0.118
No. of measured, independent and observed [I > 2σ(I)] reflections	5232, 2112, 2112
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.056, 1.15
No. of reflections	2112
No. of parameters	159
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	1.02, −0.68

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SADABS (Bruker, 2005), XS in SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Bruker, 1998), XCIF in SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O1	0.83 (7)	1.62 (8)	2.448 (4)	175 (7)

Acknowledgements

This work was supported in part by a University of Wisconsin Colleges Summer Faculty Research Grant. MDR acknowledges Marquette University for the use of X-ray diffraction facilities and the University of Wisconsin - Fox Valley's Professional Development Committee for travel funding.

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