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The title compound, C18H26N2S22+·2I·2C3H6O, is an inter­mediate in the design of the zwitterionic thiol­ate 4-(trimethyl­ammonio)benzene­thiol­ate (Tab), in which a pair of aryl-substituted S atoms are linked by a covalent bond. The central S—S bond length is 2.020 (3) Å and the Car—S—S—Car torsion angle is −84.1 (2)°. The crystal structure is stabilized by nonclassical hydrogen bonds which occur as intra­molecular C—H...I inter­actions and inter­molecular C—H...S and C—H...O contacts. In the crystal structure, both the dication and the two symmetrically independent iodide counter-anions are located on twofold crystallographic axes, whereas the acetone solvent mol­ecule occupies a general position.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010901066X/eg3006sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010901066X/eg3006Isup2.hkl
Contains datablock I

CCDC reference: 735123

Comment top

Over the last few decades, disulfides have stimulated intense interest owing to their donor capabilities towards metal ions (Bernal et al., 1976; Haller & Treichel, 1983; Roesky et al., 1984; Kitaura et al., 2002) and their potential application in biological systems (Hald et al., 1948; Ricci & Bernal, 1969). However, structural information for aromatic disulfides is limited (Woodard et al., 1976; Cannon et al., 2000; Anacona et al., 2003; Nicholson et al., 2006; Clegg & Coxall, 2005), especially as far as aromatic disulfides containing an ammonium (—NR3) group (Chen, Xu, Zhang, Zain et al., 2004) are concerned.

Recently, we have engaged in the synthesis of metal complexes of the zwitterionic ammonium thiolate Tab [4-(trimethylammonio)benzenethiolate] with different transition metals such as HgII, AuI and AgI (Chen, Xu, Xu et al., 2004; Chen, Xu, Zhang, Chen & Lang, 2004; Chen, Zhang, Tang, Ren, Li et al., 2006; Chen, Zhang, Tang, Ren, Zhang & Lang, 2006). The title compound, (I), represents an intermediate in the design of Tab (DePamphilis et al., 1974) and can be used as a large cation to form metal disulfides (Chen, Zhang, Ren & Lang, 2006; Chen et al., 2005). In order to investigate its properties further, the title compound was synthesized and characterized.

The unit cell of compound (I) contains one dication and two symmetrically independent iodide anions on twofold crystallographic axes, and a solvent molecule of acetone in a general position. A perspective view of (I) is shown in Fig. 1. The disulfide dication has positive charges formally located on the NMe3 groups. The torsion angle about the S—S bond [C1i—S1i—C1—S1; symmetry code: (i) Please complete] is -84.1 (2)° and hence smaller than those reported for two other compounds containing the [(Tab–Tab)]2+ dication, [(Tab–Tab)][HgI4] (92.1°; Chen et al., 2005) and [Tab–Tab][CuBr4] (93.05 (5)°; Tang et al., 2006). Comparable values have also been observed in [Tab–Tab][CuBr3] [82.1 (4)°], [Tab–Tab][CuI3] [81.9 (5)°] and {[Tab–Tab][Cu2I4]}n [80.34 (4)°] (Chen, Zhang, Ren & Lang 2006), and in [Tab–Tab]2[Hg3Cl10] [81.47 (4)°; Chen, Zhang, Tang, Ren, Zhang & Lang, 2006]. The different torsion angles about the S—S bonds in these compounds may be due to the steric requirements of the anions or solvents. The S—S bond is 2.030 (3) Å, which is similar to the values observed in [(Tab–Tab)][HgI4] [2.030 (3) Å], [Tab–Tab][CuBr3] [2.0538 (17) Å], [Tab–Tab][CuI3] [2.049 (3) Å], {[Tab–Tab][Cu2I4]}n [2.026 (2) Å], [Tab–Tab][CuBr4] [2.020 (3) Å] and [Tab–Tab]2[Hg3Cl10] [2.034 (2) Å].

The dications in (I) are parallel, with interionic distances of ca 4.669 Å (along the a axis) and ca 10.190 Å (along the b axis). I- anions and acetone solvent molecules are located between the dications. Looking down the a axis, it appears that each pair of I1 anions acts as an anionic template, with four symmetry-related quaternary ammonium ions arranged around them as shown in Fig. 2. With the non-classical hydrogen-bonding interactions between atom I2 and the phenyl group containing atom C2 or the methyl group containing atom C7, the I2 anions are positioned near the phenyl groups. The I2 anions are arranged in strands along b axis with a distance between neighbouring strands of ca 13.786 Å. The solvent molecules are situated between the dications near the NMe3 groups, with non-classical intermolecular hydrogen-bonding interactions between the acetone atom O1 and atom C7 of the methyl group.

Experimental top

Bis-(4-dimethylaminophenyl)disulfide (dads) was prepared according to the literature procedure of Clegg & Coxall (2005). [How was the title compound prepared from dads? Please give quantities and reaction conditions, and crystallisation details.]

Refinement top

The H atoms of the Tab–Tab group were determined by Fourier synthesis [Please give range of refined C—H distances], while the H atoms of the methyl group of the acetone solvent molecule were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C). [Please check added text].

Computing details top

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalStructure (Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A plot of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry code: (i) -x - 1/2, -y + 1, z.]
[Figure 2] Fig. 2. A packing diagram for (I), viewed approximately down the a axis. Hydrogen-bonding interactions are shown as dashed lines. [Symmetry codes: (i) ?; (ii) ?; (iii) ?. Please complete.]
Bis[4-(trimethylammonio)phenyl] disulfide diiodide acetone solvate top
Crystal data top
C18H26N2S22+·2I·2C3H6OF(000) = 1400
Mr = 704.48Dx = 1.558 Mg m3
Orthorhombic, PnnaMo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2a 2bcCell parameters from 4567 reflections
a = 12.398 (2) Åθ = 3.0–25°
b = 10.1902 (19) ŵ = 2.26 mm1
c = 23.773 (5) ÅT = 193 K
V = 3003.4 (10) Å3Block, yellow
Z = 40.13 × 0.12 × 0.10 mm
Data collection top
Rigaku Mercury
diffractometer
3437 independent reflections
Radiation source: fine-focus sealed tube3348 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.039
ω scansθmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan
(Jacobson, 1998)
h = 1616
Tmin = 0.758, Tmax = 0.806k = 1213
31366 measured reflectionsl = 2930
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)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H atoms treated by a mixture of independent and constrained refinement
S = 1.15 w = 1/[σ2(Fo2) + (0.0042P)2 + 18.2139P]
where P = (Fo2 + 2Fc2)/3
3437 reflections(Δ/σ)max < 0.001
201 parametersΔρmax = 0.63 e Å3
0 restraintsΔρmin = 0.80 e Å3
Crystal data top
C18H26N2S22+·2I·2C3H6OV = 3003.4 (10) Å3
Mr = 704.48Z = 4
Orthorhombic, PnnaMo Kα radiation
a = 12.398 (2) ŵ = 2.26 mm1
b = 10.1902 (19) ÅT = 193 K
c = 23.773 (5) Å0.13 × 0.12 × 0.10 mm
Data collection top
Rigaku Mercury
diffractometer
3437 independent reflections
Absorption correction: multi-scan
(Jacobson, 1998)
3348 reflections with I > 2σ(I)
Tmin = 0.758, Tmax = 0.806Rint = 0.039
31366 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0560 restraints
wR(F2) = 0.099H atoms treated by a mixture of independent and constrained refinement
S = 1.15 w = 1/[σ2(Fo2) + (0.0042P)2 + 18.2139P]
where P = (Fo2 + 2Fc2)/3
3437 reflectionsΔρmax = 0.63 e Å3
201 parametersΔρmin = 0.80 e Å3
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
I10.75000.00000.03612 (2)0.04179 (14)
I20.19261 (4)0.75000.25000.05564 (18)
S10.17267 (11)0.53097 (12)0.27874 (5)0.0393 (3)
O10.4334 (4)0.4128 (5)0.06145 (18)0.0603 (11)
N10.0786 (3)0.2279 (4)0.10427 (17)0.0359 (9)
C10.1070 (4)0.4385 (4)0.22510 (18)0.0295 (9)
C20.0013 (4)0.4655 (5)0.2189 (2)0.0379 (11)
H20.036 (4)0.535 (5)0.240 (2)0.043 (15)*
C30.0625 (4)0.3988 (5)0.1797 (2)0.0383 (11)
H30.138 (6)0.418 (7)0.177 (3)0.08 (2)*
C40.0139 (4)0.3045 (4)0.14630 (18)0.0285 (9)
C50.0949 (4)0.2770 (4)0.15229 (19)0.0292 (10)
H50.125 (4)0.220 (5)0.131 (2)0.035 (14)*
C60.1555 (4)0.3440 (5)0.19190 (19)0.0306 (10)
H60.231 (4)0.322 (5)0.1942 (19)0.032 (13)*
C70.1875 (5)0.2898 (7)0.0930 (3)0.0486 (14)
H7B0.173 (5)0.378 (7)0.080 (3)0.057 (19)*
H7C0.235 (6)0.290 (7)0.129 (3)0.07 (2)*
H7A0.220 (4)0.235 (6)0.064 (2)0.045 (15)*
C80.0198 (5)0.2237 (9)0.0486 (3)0.0548 (17)
H8A0.041 (6)0.171 (7)0.052 (3)0.07 (2)*
H8B0.068 (6)0.180 (7)0.024 (3)0.08 (2)*
H8C0.008 (7)0.319 (9)0.037 (3)0.10 (3)*
C90.0980 (7)0.0936 (7)0.1272 (4)0.064 (2)
H9A0.139 (6)0.044 (7)0.102 (3)0.07 (2)*
H9B0.032 (5)0.060 (6)0.133 (3)0.06 (2)*
H9C0.147 (7)0.095 (8)0.162 (4)0.10 (3)*
C100.5056 (8)0.2388 (9)0.1139 (5)0.123 (4)
H10B0.56100.17660.10160.185*
H10C0.43410.19950.10890.185*
H10A0.51660.26000.15370.185*
C110.5131 (5)0.3593 (6)0.0802 (2)0.0484 (14)
C120.6237 (6)0.4117 (7)0.0705 (3)0.0624 (18)
H12B0.67080.34080.05740.094*
H12C0.65210.44780.10570.094*
H12A0.62090.48100.04200.094*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.0330 (2)0.0430 (3)0.0494 (3)0.0029 (2)0.0000.000
I20.0347 (3)0.0631 (4)0.0691 (4)0.0000.0000.0279 (3)
S10.0489 (7)0.0371 (7)0.0319 (6)0.0120 (6)0.0088 (5)0.0070 (5)
O10.063 (3)0.064 (3)0.054 (3)0.011 (2)0.002 (2)0.005 (2)
N10.034 (2)0.037 (2)0.038 (2)0.0006 (18)0.0075 (17)0.0016 (18)
C10.036 (2)0.028 (2)0.024 (2)0.0049 (19)0.0039 (18)0.0034 (18)
C20.041 (3)0.035 (3)0.037 (3)0.005 (2)0.010 (2)0.004 (2)
C30.030 (2)0.046 (3)0.039 (3)0.005 (2)0.007 (2)0.000 (2)
C40.028 (2)0.032 (2)0.026 (2)0.0018 (19)0.0005 (17)0.0029 (18)
C50.031 (2)0.027 (2)0.030 (2)0.0061 (19)0.0030 (18)0.0026 (19)
C60.027 (2)0.035 (2)0.030 (2)0.005 (2)0.0018 (18)0.0005 (19)
C70.031 (3)0.060 (4)0.055 (4)0.003 (3)0.012 (3)0.002 (3)
C80.041 (3)0.088 (5)0.036 (3)0.003 (3)0.005 (2)0.016 (3)
C90.071 (5)0.037 (3)0.086 (6)0.016 (3)0.037 (5)0.010 (3)
C100.136 (8)0.075 (6)0.158 (9)0.053 (6)0.092 (7)0.062 (6)
C110.063 (4)0.043 (3)0.040 (3)0.009 (3)0.009 (3)0.008 (2)
C120.066 (4)0.054 (4)0.067 (4)0.000 (3)0.015 (3)0.012 (3)
Geometric parameters (Å, º) top
S1—C11.782 (5)C7—H7B0.97 (7)
S1—S1i2.019 (3)C7—H7C1.05 (7)
O1—C111.214 (7)C7—H7A0.98 (6)
N1—C91.493 (8)C8—H8A0.93 (7)
N1—C41.500 (6)C8—H8B0.94 (7)
N1—C81.510 (7)C8—H8C1.02 (9)
N1—C71.514 (7)C9—H9A0.94 (7)
C1—C21.378 (7)C9—H9B0.89 (6)
C1—C61.384 (6)C9—H9C1.03 (9)
C2—C31.381 (7)C10—C111.468 (9)
C2—H20.98 (5)C10—H10B0.9800
C3—C41.385 (7)C10—H10C0.9800
C3—H30.95 (7)C10—H10A0.9800
C4—C51.385 (6)C11—C121.490 (9)
C5—C61.385 (6)C12—H12B0.9800
C5—H50.86 (5)C12—H12C0.9800
C6—H60.96 (5)C12—H12A0.9800
C1—S1—S1i105.60 (17)H7B—C7—H7A112 (5)
C9—N1—C4108.6 (4)H7C—C7—H7A111 (5)
C9—N1—C8111.8 (6)N1—C8—H8A109 (4)
C4—N1—C8109.9 (4)N1—C8—H8B104 (4)
C9—N1—C7107.7 (5)H8A—C8—H8B107 (6)
C4—N1—C7112.2 (4)N1—C8—H8C106 (5)
C8—N1—C7106.7 (5)H8A—C8—H8C117 (6)
C2—C1—C6120.2 (4)H8B—C8—H8C112 (6)
C2—C1—S1114.6 (4)N1—C9—H9A111 (4)
C6—C1—S1125.3 (4)N1—C9—H9B105 (4)
C1—C2—C3120.6 (5)H9A—C9—H9B113 (6)
C1—C2—H2121 (3)N1—C9—H9C112 (5)
C3—C2—H2118 (3)H9A—C9—H9C101 (6)
C2—C3—C4119.3 (5)H9B—C9—H9C115 (6)
C2—C3—H3119 (4)C11—C10—H10B109.5
C4—C3—H3121 (4)C11—C10—H10C109.5
C5—C4—C3120.3 (4)H10B—C10—H10C109.5
C5—C4—N1118.9 (4)C11—C10—H10A109.5
C3—C4—N1120.7 (4)H10B—C10—H10A109.5
C6—C5—C4120.0 (4)H10C—C10—H10A109.5
C6—C5—H5119 (4)O1—C11—C10121.6 (7)
C4—C5—H5121 (4)O1—C11—C12122.1 (6)
C1—C6—C5119.6 (4)C10—C11—C12116.3 (7)
C1—C6—H6123 (3)C11—C12—H12B109.5
C5—C6—H6117 (3)C11—C12—H12C109.5
N1—C7—H7B106 (4)H12B—C12—H12C109.5
N1—C7—H7C111 (4)C11—C12—H12A109.5
H7B—C7—H7C111 (5)H12B—C12—H12A109.5
N1—C7—H7A105 (3)H12C—C12—H12A109.5
C1—S1—S1i—C1i84.1 (2)C7—N1—C4—C5166.6 (5)
S1i—S1—C1—C2179.1 (3)C9—N1—C4—C3103.7 (6)
S1i—S1—C1—C60.6 (4)C8—N1—C4—C3133.7 (5)
C6—C1—C2—C30.0 (7)C7—N1—C4—C315.2 (6)
S1—C1—C2—C3178.6 (4)C3—C4—C5—C60.0 (7)
C1—C2—C3—C40.3 (8)N1—C4—C5—C6178.2 (4)
C2—C3—C4—C50.3 (7)C2—C1—C6—C50.3 (7)
C2—C3—C4—N1178.5 (4)S1—C1—C6—C5178.7 (4)
C9—N1—C4—C574.6 (6)C4—C5—C6—C10.3 (7)
C8—N1—C4—C548.0 (6)
Symmetry code: (i) x1/2, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H7C···I2ii1.05 (7)3.03 (7)4.038 (7)162 (5)
C7—H7B···O1ii0.97 (7)2.54 (7)3.463 (8)158 (5)
C2—H2···I20.98 (5)2.93 (5)3.818 (5)151 (4)
Symmetry code: (ii) x+1/2, y+1, z.

Experimental details

Crystal data
Chemical formulaC18H26N2S22+·2I·2C3H6O
Mr704.48
Crystal system, space groupOrthorhombic, Pnna
Temperature (K)193
a, b, c (Å)12.398 (2), 10.1902 (19), 23.773 (5)
V3)3003.4 (10)
Z4
Radiation typeMo Kα
µ (mm1)2.26
Crystal size (mm)0.13 × 0.12 × 0.10
Data collection
DiffractometerRigaku Mercury
diffractometer
Absorption correctionMulti-scan
(Jacobson, 1998)
Tmin, Tmax0.758, 0.806
No. of measured, independent and
observed [I > 2σ(I)] reflections
31366, 3437, 3348
Rint0.039
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.056, 0.099, 1.15
No. of reflections3437
No. of parameters201
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(Fo2) + (0.0042P)2 + 18.2139P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.63, 0.80

Computer programs: CrystalClear (Rigaku, 2000), CrystalStructure (Rigaku, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H7C···I2i1.05 (7)3.03 (7)4.038 (7)162 (5)
C7—H7B···O1i0.97 (7)2.54 (7)3.463 (8)158 (5)
C2—H2···I20.98 (5)2.93 (5)3.818 (5)151 (4)
Symmetry code: (i) x+1/2, y+1, z.
 

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