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The title compound, meso-C13H12O2S2, is in an anti conformation, with R and S configurations around the S atoms. The two O atoms are trans to each other, and the same applies for the two benzene rings. The phenyl­sulfinyl groups are nearly orthogonal to the central di­thio­methane group, and the orientation of the two phenyl rings are determined by the interactions in which they are involved. The packing is built from molecular columns stabilized by weak C—H...O interactions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103006991/na1603sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103006991/na1603Isup2.hkl
Contains datablock I

CCDC reference: 214179

Comment top

Bifunctional chelating ligands, such as carbonyl methyl phosphonates (CMP), carbonyl methyl phophine oxides (CMPO), malonamides (MA) and β-diphosphine oxides, are known to be effective liquid–liquid extractants for lanthanide and actinide ions from the acid media (Horwitz, Kalina & Muscatello, 1981; Horwitz, Muscatello et al., 1981; Kalina et al., 1981; Horwitz & Kalina, 1984; Musikas, 1987; Mathur et al., 1991). The fundamental coordination chemistry of these ligands with lanthanide and actinide ions has been well established (Bowen et al., 1982; Karthikeyan et al., 1988; Kannan & Ferguson, 1997). This prompted us to synthesize the β-disulfoxide ligand bis(phenylsulfinyl)methane, and to study its coordination behaviours with the actinide ions (Rajalakshmi et al., 2003). Two isomeric forms of this ligand, viz. meso and dl, have been separated by fractional crystallization and shown from the 1H NMR spectroscopy that the isomer having lower melting point (391–393 K) is meso and higher melting point (455–458 K) is dl (Geen Jun & Shevlin, 1971). Other data supporting this observation of both isomers have not yet been reported. We report here the crystal structure analysis of the meso isomer, (I).

The structure of (I) shows that the molecule is in an anti conformation. The two O atoms are trans to one another, and the same applies for the two benzene rings. These were shown by the O1—S1···S2—O2 and Ph—S1···S2—Ph torsion angles of −178.0 (1) and 158.8 (1)°, respectively. The streochemistry around the S atoms are R and S, respectively, which is expected for the meso-isomer. The bond lengths and angles of (I) (Table 1) show normal values (Allen et al., 1987). The SO, Csp2—S, and Csp3—S bond lengths agree well with the corresponding values in previously reported β-disulfoxide compounds (Beckhaus et al., 1979; Pelizzi, Coghi et al., 1976; Pelizzi, Michelon & Bonivento, 1976). The bond angles at both the S atoms are in the range of 98.0 (1)–107.3 (1)° corresponding to tetrahedral geometry. The dihedral angle between the two phenyl rings is 61.3 (1)°, and the torsion angles describing the conformation of the central chain joining the two benzene rings are listed in Table 1. The phenylsulfinyl group are nearly orthogonal to the central dithiomethane S1—C7—S2 group, with dihedral angles of 88.4 (1) and 84.7 (1)° formed with that group by the weighted least-squares planes through C1–C6/S1/O1 and C8–C13/S2/O2, respectively. The two SO groups are coplanar with the phenyl to which they are attached, as shown by the the C5—C6—S1—O1 and C13—C8—S2—O2 torsion angles of 0.1 (2) and −6.4 (2)°, respectively. The difference is due to the C—H···O interactions in which these benzene rings are involved. This quasi-coplanar nature of the SO groups with their phenyl rings is due to the conjugation between the sulfur lone pair and the π-system of the phenyl ring. This was also observed in the phenylsulfinyl derivative previously reported with the corresponding angle of −2° (Olivato et al., 2000). The C—S (average 1.796 Å) and SO (average 1493 Å) bond distances are also indicative of π-conjugation along the phenylsulfinyl group.

The molecules facilitate seven C—H···O interactions (Table 2). Considering the intramolecular interactions, C5—H5···O1 and C13—H13···O2 appear to form similar approximately planar S(5) graph rings (Etter et el., 1990), viz. O1—S1—C6—C5—H5 and O2—S2—C8—C13—H13, in the two chemically equivalent parts of the molecule. This is not observed for the S(7) graph-ring, O2—S2—C7—S1—C6—C1—H1, generated by the C1—H1···O2 interaction, since the H9···O1 distance (4.11 Å) is too long to be an interaction. In the packing, the molecules are interconnected by three weak C—H···O interactions (Table 2). C10—H10···O2iii interactions link the molecules into chains parallel to the a direction and two adjacent chains are interconnected by C7—H7B···O1ii and C9—H9···O1ii interactions into columns (Fig. 2; symmetry codes as in Table 2). It is noteworthy that the orientation of the C1–C6 benzene ring is determined by the C1—H1···O2 and C5—H5···O1 intramolecular interactions, together with the C4—H4···O2i intermolecular interaction, while the orientation of the C8–C13 benzene ring is determined by the C13—H13···O2 intramolecular interaction, together with the C9—H9···O1ii and C10—H10···O2iii intermolecular interactions (symmetry codes as in Table 2). This different structural situation is reflected in the conformation about the two S1—C7 and S2—C7 bonds, as shown by the emarkably different C6—S1—C7—S2 and C8—S2—C7—S1 torsion angles of 112.3 (1) and 53.4 (1)°, respectively.

Experimental top

The title compound was prepared according to a reported method using SeO2/H2O2 (Drabowicz & Mikolajczyk, 1978). To a suspension of bis(phenylthio)methane (10 g, 0.043 mol) in methanol (100 ml) was added a solution of selenium dioxide (9.56 g, 0.086 mol) and H2O2 (9.8 ml of 30% H2O, 2.94 g, 0.086 mol) in methanol dropwise with stirring. The resulting solution was stirred for a further 2 h, and was the left to evaporate in a fume hood overnight. The residue obtained after drying was extracted with chloroform (100 ml) and dried over anhydrous sodium sulfate and filtered. The volume of the solution was reduced to 40 ml on a hotplate and left to evaporate overnight. The paste-like solid obtained was suspended in ethanol (100 ml) and heated on a hotplate. The clear solution was filtered, the volume reduced to 50 ml and the resulting solution allowed to cool in a fume hood for 3 h, whereupon a white crystalline solid was deposited. This solid was filtered off, washed with cold ethanol (5 ml) and dried (yield: 3.5 mg, 39.5%). The resulting solid was recrystallized from chloroform/ethanol as the pure dl form. The ethanol-soluble part, on evaporation, yielded a white powder which was recrystallized from chloroform/dodecane as a white crystalline solid (yield: 6.5 mg, 57.2%)·The 1H NMR spectrum showed this solid to be a mixture of the meso and dl isomers. Repeating the crystallization three times yielded 98% pure meso form. The crystal used for X-ray analysis was obtained from a chloroform/dodecane mixture.

Refinement top

All H atoms were located in difference Fourier maps and were refined isotropically [C—H = 0.85 (3)–0.98 (2) Å]. The highest peak and deepest hole are located at 0.93 Å from S2 and 1.15 Å from C4, respectively.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Figures top
[Figure 1] Fig. 1. The structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. Packing diagram of the title compound, showing the molecular columns parallel to the a direction.
meso-Bis(phenylsulfinyl)methane top
Crystal data top
C13H12O2S2Z = 2
Mr = 264.35F(000) = 276
Triclinic, P1Dx = 1.396 Mg m3
a = 8.2540 (9) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.9037 (10) ÅCell parameters from 2403 reflections
c = 9.069 (1) Åθ = 2.8–28.3°
α = 106.875 (2)°µ = 0.41 mm1
β = 98.782 (2)°T = 293 K
γ = 90.897 (2)°Needle, yellow
V = 629.05 (12) Å30.60 × 0.20 × 0.14 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer
2936 independent reflections
Radiation source: fine-focus sealed tube2466 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.014
Detector resolution: 8.33 pixels mm-1θmax = 28.3°, θmin = 2.8°
ω scansh = 1010
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
k = 911
Tmin = 0.792, Tmax = 0.945l = 129
3960 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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094All H-atom parameters refined
S = 1.09 w = 1/[σ2(Fo2) + (0.0386P)2 + 0.1734P]
where P = (Fo2 + 2Fc2)/3
2936 reflections(Δ/σ)max < 0.001
202 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.22 e Å3
Crystal data top
C13H12O2S2γ = 90.897 (2)°
Mr = 264.35V = 629.05 (12) Å3
Triclinic, P1Z = 2
a = 8.2540 (9) ÅMo Kα radiation
b = 8.9037 (10) ŵ = 0.41 mm1
c = 9.069 (1) ÅT = 293 K
α = 106.875 (2)°0.60 × 0.20 × 0.14 mm
β = 98.782 (2)°
Data collection top
Siemens SMART CCD area-detector
diffractometer
2936 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
2466 reflections with I > 2σ(I)
Tmin = 0.792, Tmax = 0.945Rint = 0.014
3960 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.094All H-atom parameters refined
S = 1.09Δρmax = 0.26 e Å3
2936 reflectionsΔρmin = 0.22 e Å3
202 parameters
Special details top

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 5 cm and the detector swing angle was −35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

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
S10.32060 (5)0.25191 (5)0.53573 (5)0.03953 (13)
S20.21846 (6)0.06588 (6)0.19403 (5)0.04685 (15)
O10.45788 (16)0.22187 (18)0.64959 (16)0.0542 (4)
O20.09191 (17)0.1827 (2)0.18870 (18)0.0674 (5)
C10.0022 (2)0.3166 (2)0.5502 (2)0.0463 (4)
C20.1382 (3)0.3440 (3)0.6242 (3)0.0532 (5)
C30.1301 (3)0.3338 (2)0.7744 (3)0.0513 (5)
C40.0134 (3)0.2966 (2)0.8517 (2)0.0490 (5)
C50.1508 (2)0.2686 (2)0.7791 (2)0.0426 (4)
C60.1411 (2)0.27821 (19)0.62845 (19)0.0366 (4)
C70.2568 (3)0.0588 (2)0.3935 (2)0.0425 (4)
C80.4110 (2)0.1612 (2)0.19247 (19)0.0377 (4)
C90.5529 (2)0.0802 (2)0.1993 (2)0.0465 (4)
C100.6983 (3)0.1509 (3)0.1879 (2)0.0553 (5)
C110.7021 (3)0.2980 (3)0.1678 (3)0.0584 (6)
C120.5603 (3)0.3767 (3)0.1595 (3)0.0590 (6)
C130.4129 (3)0.3084 (2)0.1715 (2)0.0474 (4)
H50.248 (3)0.246 (2)0.831 (2)0.048 (5)*
H7B0.343 (3)0.003 (3)0.406 (3)0.061 (7)*
H20.235 (3)0.367 (3)0.570 (3)0.071 (7)*
H100.797 (3)0.098 (3)0.190 (3)0.068 (7)*
H130.316 (3)0.355 (3)0.170 (3)0.060 (6)*
H90.547 (3)0.022 (3)0.213 (3)0.058 (6)*
H110.793 (3)0.341 (3)0.161 (3)0.071 (7)*
H10.006 (3)0.325 (3)0.448 (3)0.058 (6)*
H30.225 (3)0.352 (3)0.829 (3)0.067 (7)*
H7A0.161 (3)0.013 (2)0.413 (2)0.051 (6)*
H40.020 (3)0.290 (3)0.952 (3)0.057 (6)*
H120.560 (3)0.473 (3)0.139 (3)0.068 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0367 (2)0.0426 (2)0.0412 (2)0.00252 (17)0.01047 (18)0.01328 (18)
S20.0339 (2)0.0648 (3)0.0394 (2)0.0039 (2)0.00764 (18)0.0112 (2)
O10.0354 (7)0.0688 (9)0.0548 (8)0.0069 (6)0.0015 (6)0.0154 (7)
O20.0326 (7)0.1150 (14)0.0685 (10)0.0178 (8)0.0108 (7)0.0468 (10)
C10.0454 (10)0.0532 (11)0.0438 (10)0.0115 (8)0.0086 (8)0.0186 (9)
C20.0421 (11)0.0571 (12)0.0625 (13)0.0143 (9)0.0103 (9)0.0194 (10)
C30.0484 (12)0.0485 (11)0.0586 (12)0.0074 (9)0.0227 (10)0.0111 (9)
C40.0574 (12)0.0512 (11)0.0411 (10)0.0050 (9)0.0176 (9)0.0127 (9)
C50.0431 (10)0.0469 (10)0.0398 (9)0.0063 (8)0.0070 (8)0.0158 (8)
C60.0375 (9)0.0358 (8)0.0370 (9)0.0034 (7)0.0088 (7)0.0103 (7)
C70.0449 (11)0.0419 (9)0.0427 (10)0.0030 (8)0.0142 (8)0.0118 (8)
C80.0314 (8)0.0487 (10)0.0317 (8)0.0024 (7)0.0077 (6)0.0086 (7)
C90.0394 (10)0.0524 (11)0.0489 (11)0.0090 (8)0.0120 (8)0.0141 (9)
C100.0353 (10)0.0758 (15)0.0519 (12)0.0069 (10)0.0126 (8)0.0116 (10)
C110.0439 (12)0.0788 (16)0.0496 (12)0.0139 (11)0.0131 (9)0.0124 (11)
C120.0686 (15)0.0549 (13)0.0537 (12)0.0101 (11)0.0091 (10)0.0177 (10)
C130.0447 (11)0.0516 (11)0.0457 (10)0.0079 (9)0.0078 (8)0.0137 (9)
Geometric parameters (Å, º) top
S1—O11.495 (2)C5—C61.384 (2)
S1—C61.798 (2)C5—H50.92 (2)
S1—C71.837 (2)C7—H7B0.92 (2)
S2—O21.491 (2)C7—H7A0.95 (2)
S2—C81.794 (2)C8—C131.378 (3)
S2—C71.808 (2)C8—C91.388 (2)
C1—C21.383 (3)C9—C101.378 (3)
C1—C61.385 (3)C9—H90.95 (2)
C1—H10.94 (2)C10—C111.375 (3)
C2—C31.383 (3)C10—H100.95 (2)
C2—H20.93 (2)C11—C121.377 (3)
C3—C41.378 (3)C11—H110.85 (3)
C3—H30.98 (2)C12—C131.385 (3)
C4—C51.386 (3)C12—H120.93 (2)
C4—H40.92 (2)C13—H130.91 (2)
O1—S1—C6107.3 (1)S2—C7—S1112.99 (10)
O1—S1—C7105.2 (1)S2—C7—H7B109.8 (14)
C6—S1—C798.0 (1)S1—C7—H7B104.9 (15)
O2—S2—C8106.6 (1)S2—C7—H7A107.9 (13)
O2—S2—C7106.1 (1)S1—C7—H7A112.0 (12)
C8—S2—C798.2 (1)H7B—C7—H7A109.1 (19)
C2—C1—C6119.05 (18)C13—C8—C9121.26 (18)
C2—C1—H1120.9 (14)C13—C8—S2119.17 (14)
C6—C1—H1120.0 (14)C9—C8—S2119.35 (15)
C1—C2—C3120.2 (2)C10—C9—C8118.8 (2)
C1—C2—H2118.6 (16)C10—C9—H9121.9 (14)
C3—C2—H2121.1 (16)C8—C9—H9119.2 (14)
C4—C3—C2120.33 (19)C11—C10—C9120.5 (2)
C4—C3—H3117.8 (14)C11—C10—H10118.1 (15)
C2—C3—H3121.9 (14)C9—C10—H10121.4 (15)
C3—C4—C5120.17 (19)C10—C11—C12120.2 (2)
C3—C4—H4120.8 (14)C10—C11—H11120.1 (17)
C5—C4—H4119.1 (14)C12—C11—H11119.7 (17)
C6—C5—C4119.04 (18)C11—C12—C13120.3 (2)
C6—C5—H5120.1 (13)C11—C12—H12121.0 (15)
C4—C5—H5120.8 (13)C13—C12—H12118.6 (15)
C5—C6—C1121.20 (17)C8—C13—C12118.9 (2)
C5—C6—S1119.76 (14)C8—C13—H13116.3 (15)
C1—C6—S1118.94 (13)C12—C13—H13124.8 (15)
C6—C1—C2—C30.3 (3)O1—S1—C7—S2137.3 (1)
C1—C2—C3—C40.1 (3)C6—S1—C7—S2112.18 (11)
C2—C3—C4—C50.2 (3)O2—S2—C8—C136.38 (17)
C3—C4—C5—C60.2 (3)C7—S2—C8—C13115.92 (15)
C4—C5—C6—C10.6 (3)O2—S2—C8—C9178.95 (14)
C4—C5—C6—S1176.94 (15)C7—S2—C8—C969.4 (2)
C2—C1—C6—C50.7 (3)C13—C8—C9—C101.3 (3)
C2—C1—C6—S1177.06 (16)S2—C8—C9—C10175.88 (15)
O1—S1—C6—C50.05 (17)C8—C9—C10—C111.0 (3)
C7—S1—C6—C5108.79 (15)C9—C10—C11—C120.3 (3)
O1—S1—C6—C1176.45 (15)C10—C11—C12—C130.1 (3)
C7—S1—C6—C174.8 (2)C9—C8—C13—C120.9 (3)
O2—S2—C7—S156.6 (1)S2—C8—C13—C12175.52 (15)
C8—S2—C7—S153.41 (12)C11—C12—C13—C80.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···O20.95 (3)2.58 (3)3.363 (2)140 (2)
C5—H5···O10.92 (2)2.54 (2)2.939 (2)107 (2)
C13—H13···O20.91 (2)2.44 (3)2.904 (3)112 (2)
C4—H4···O2i0.92 (3)2.59 (3)3.465 (2)159 (2)
C7—H7B···O1ii0.92 (3)2.56 (3)3.441 (3)162 (2)
C9—H9···O1ii0.95 (3)2.45 (3)3.360 (2)158 (2)
C10—H10···O2iii0.95 (3)2.54 (3)3.255 (3)132 (2)
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z+1; (iii) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC13H12O2S2
Mr264.35
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)8.2540 (9), 8.9037 (10), 9.069 (1)
α, β, γ (°)106.875 (2), 98.782 (2), 90.897 (2)
V3)629.05 (12)
Z2
Radiation typeMo Kα
µ (mm1)0.41
Crystal size (mm)0.60 × 0.20 × 0.14
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.792, 0.945
No. of measured, independent and
observed [I > 2σ(I)] reflections
3960, 2936, 2466
Rint0.014
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.094, 1.09
No. of reflections2936
No. of parameters202
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.26, 0.22

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Selected geometric parameters (Å, º) top
S1—O11.495 (2)S2—O21.491 (2)
S1—C61.798 (2)S2—C81.794 (2)
S1—C71.837 (2)S2—C71.808 (2)
O1—S1—C6107.3 (1)O2—S2—C8106.6 (1)
O1—S1—C7105.2 (1)O2—S2—C7106.1 (1)
C6—S1—C798.0 (1)C8—S2—C798.2 (1)
C7—S1—C6—C174.8 (2)O1—S1—C7—S2137.3 (1)
O2—S2—C7—S156.6 (1)C7—S2—C8—C969.4 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···O20.95 (3)2.58 (3)3.363 (2)140 (2)
C5—H5···O10.92 (2)2.54 (2)2.939 (2)107 (2)
C13—H13···O20.91 (2)2.44 (3)2.904 (3)112 (2)
C4—H4···O2i0.92 (3)2.59 (3)3.465 (2)159 (2)
C7—H7B···O1ii0.92 (3)2.56 (3)3.441 (3)162 (2)
C9—H9···O1ii0.95 (3)2.45 (3)3.360 (2)158 (2)
C10—H10···O2iii0.95 (3)2.54 (3)3.255 (3)132 (2)
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z+1; (iii) x+1, y, z.
 

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