Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010901066X/eg3006sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010901066X/eg3006Isup2.hkl |
CCDC reference: 735123
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.]
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].
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).
C18H26N2S22+·2I−·2C3H6O | F(000) = 1400 |
Mr = 704.48 | Dx = 1.558 Mg m−3 |
Orthorhombic, Pnna | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: -P 2a 2bc | Cell parameters from 4567 reflections |
a = 12.398 (2) Å | θ = 3.0–25° |
b = 10.1902 (19) Å | µ = 2.26 mm−1 |
c = 23.773 (5) Å | T = 193 K |
V = 3003.4 (10) Å3 | Block, yellow |
Z = 4 | 0.13 × 0.12 × 0.10 mm |
Rigaku Mercury diffractometer | 3437 independent reflections |
Radiation source: fine-focus sealed tube | 3348 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
ω scans | θmax = 27.5°, θmin = 3.1° |
Absorption correction: multi-scan (Jacobson, 1998) | h = −16→16 |
Tmin = 0.758, Tmax = 0.806 | k = −12→13 |
31366 measured reflections | l = −29→30 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H 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 parameters | Δρmax = 0.63 e Å−3 |
0 restraints | Δρmin = −0.80 e Å−3 |
C18H26N2S22+·2I−·2C3H6O | V = 3003.4 (10) Å3 |
Mr = 704.48 | Z = 4 |
Orthorhombic, Pnna | Mo Kα radiation |
a = 12.398 (2) Å | µ = 2.26 mm−1 |
b = 10.1902 (19) Å | T = 193 K |
c = 23.773 (5) Å | 0.13 × 0.12 × 0.10 mm |
Rigaku Mercury diffractometer | 3437 independent reflections |
Absorption correction: multi-scan (Jacobson, 1998) | 3348 reflections with I > 2σ(I) |
Tmin = 0.758, Tmax = 0.806 | Rint = 0.039 |
31366 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.099 | H 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 | Δρmax = 0.63 e Å−3 |
201 parameters | Δρmin = −0.80 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
I1 | 0.7500 | 0.0000 | 0.03612 (2) | 0.04179 (14) | |
I2 | 0.19261 (4) | 0.7500 | 0.2500 | 0.05564 (18) | |
S1 | −0.17267 (11) | 0.53097 (12) | 0.27874 (5) | 0.0393 (3) | |
O1 | 0.4334 (4) | 0.4128 (5) | 0.06145 (18) | 0.0603 (11) | |
N1 | 0.0786 (3) | 0.2279 (4) | 0.10427 (17) | 0.0359 (9) | |
C1 | −0.1070 (4) | 0.4385 (4) | 0.22510 (18) | 0.0295 (9) | |
C2 | 0.0013 (4) | 0.4655 (5) | 0.2189 (2) | 0.0379 (11) | |
H2 | 0.036 (4) | 0.535 (5) | 0.240 (2) | 0.043 (15)* | |
C3 | 0.0625 (4) | 0.3988 (5) | 0.1797 (2) | 0.0383 (11) | |
H3 | 0.138 (6) | 0.418 (7) | 0.177 (3) | 0.08 (2)* | |
C4 | 0.0139 (4) | 0.3045 (4) | 0.14630 (18) | 0.0285 (9) | |
C5 | −0.0949 (4) | 0.2770 (4) | 0.15229 (19) | 0.0292 (10) | |
H5 | −0.125 (4) | 0.220 (5) | 0.131 (2) | 0.035 (14)* | |
C6 | −0.1555 (4) | 0.3440 (5) | 0.19190 (19) | 0.0306 (10) | |
H6 | −0.231 (4) | 0.322 (5) | 0.1942 (19) | 0.032 (13)* | |
C7 | 0.1875 (5) | 0.2898 (7) | 0.0930 (3) | 0.0486 (14) | |
H7B | 0.173 (5) | 0.378 (7) | 0.080 (3) | 0.057 (19)* | |
H7C | 0.235 (6) | 0.290 (7) | 0.129 (3) | 0.07 (2)* | |
H7A | 0.220 (4) | 0.235 (6) | 0.064 (2) | 0.045 (15)* | |
C8 | 0.0198 (5) | 0.2237 (9) | 0.0486 (3) | 0.0548 (17) | |
H8A | −0.041 (6) | 0.171 (7) | 0.052 (3) | 0.07 (2)* | |
H8B | 0.068 (6) | 0.180 (7) | 0.024 (3) | 0.08 (2)* | |
H8C | 0.008 (7) | 0.319 (9) | 0.037 (3) | 0.10 (3)* | |
C9 | 0.0980 (7) | 0.0936 (7) | 0.1272 (4) | 0.064 (2) | |
H9A | 0.139 (6) | 0.044 (7) | 0.102 (3) | 0.07 (2)* | |
H9B | 0.032 (5) | 0.060 (6) | 0.133 (3) | 0.06 (2)* | |
H9C | 0.147 (7) | 0.095 (8) | 0.162 (4) | 0.10 (3)* | |
C10 | 0.5056 (8) | 0.2388 (9) | 0.1139 (5) | 0.123 (4) | |
H10B | 0.5610 | 0.1766 | 0.1016 | 0.185* | |
H10C | 0.4341 | 0.1995 | 0.1089 | 0.185* | |
H10A | 0.5166 | 0.2600 | 0.1537 | 0.185* | |
C11 | 0.5131 (5) | 0.3593 (6) | 0.0802 (2) | 0.0484 (14) | |
C12 | 0.6237 (6) | 0.4117 (7) | 0.0705 (3) | 0.0624 (18) | |
H12B | 0.6708 | 0.3408 | 0.0574 | 0.094* | |
H12C | 0.6521 | 0.4478 | 0.1057 | 0.094* | |
H12A | 0.6209 | 0.4810 | 0.0420 | 0.094* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.0330 (2) | 0.0430 (3) | 0.0494 (3) | 0.0029 (2) | 0.000 | 0.000 |
I2 | 0.0347 (3) | 0.0631 (4) | 0.0691 (4) | 0.000 | 0.000 | −0.0279 (3) |
S1 | 0.0489 (7) | 0.0371 (7) | 0.0319 (6) | 0.0120 (6) | −0.0088 (5) | −0.0070 (5) |
O1 | 0.063 (3) | 0.064 (3) | 0.054 (3) | 0.011 (2) | −0.002 (2) | −0.005 (2) |
N1 | 0.034 (2) | 0.037 (2) | 0.038 (2) | 0.0006 (18) | 0.0075 (17) | 0.0016 (18) |
C1 | 0.036 (2) | 0.028 (2) | 0.024 (2) | 0.0049 (19) | −0.0039 (18) | 0.0034 (18) |
C2 | 0.041 (3) | 0.035 (3) | 0.037 (3) | −0.005 (2) | −0.010 (2) | −0.004 (2) |
C3 | 0.030 (2) | 0.046 (3) | 0.039 (3) | −0.005 (2) | −0.007 (2) | 0.000 (2) |
C4 | 0.028 (2) | 0.032 (2) | 0.026 (2) | 0.0018 (19) | 0.0005 (17) | 0.0029 (18) |
C5 | 0.031 (2) | 0.027 (2) | 0.030 (2) | −0.0061 (19) | 0.0030 (18) | −0.0026 (19) |
C6 | 0.027 (2) | 0.035 (2) | 0.030 (2) | −0.005 (2) | 0.0018 (18) | 0.0005 (19) |
C7 | 0.031 (3) | 0.060 (4) | 0.055 (4) | −0.003 (3) | 0.012 (3) | 0.002 (3) |
C8 | 0.041 (3) | 0.088 (5) | 0.036 (3) | −0.003 (3) | 0.005 (2) | −0.016 (3) |
C9 | 0.071 (5) | 0.037 (3) | 0.086 (6) | 0.016 (3) | 0.037 (5) | 0.010 (3) |
C10 | 0.136 (8) | 0.075 (6) | 0.158 (9) | 0.053 (6) | 0.092 (7) | 0.062 (6) |
C11 | 0.063 (4) | 0.043 (3) | 0.040 (3) | 0.009 (3) | 0.009 (3) | −0.008 (2) |
C12 | 0.066 (4) | 0.054 (4) | 0.067 (4) | 0.000 (3) | −0.015 (3) | −0.012 (3) |
S1—C1 | 1.782 (5) | C7—H7B | 0.97 (7) |
S1—S1i | 2.019 (3) | C7—H7C | 1.05 (7) |
O1—C11 | 1.214 (7) | C7—H7A | 0.98 (6) |
N1—C9 | 1.493 (8) | C8—H8A | 0.93 (7) |
N1—C4 | 1.500 (6) | C8—H8B | 0.94 (7) |
N1—C8 | 1.510 (7) | C8—H8C | 1.02 (9) |
N1—C7 | 1.514 (7) | C9—H9A | 0.94 (7) |
C1—C2 | 1.378 (7) | C9—H9B | 0.89 (6) |
C1—C6 | 1.384 (6) | C9—H9C | 1.03 (9) |
C2—C3 | 1.381 (7) | C10—C11 | 1.468 (9) |
C2—H2 | 0.98 (5) | C10—H10B | 0.9800 |
C3—C4 | 1.385 (7) | C10—H10C | 0.9800 |
C3—H3 | 0.95 (7) | C10—H10A | 0.9800 |
C4—C5 | 1.385 (6) | C11—C12 | 1.490 (9) |
C5—C6 | 1.385 (6) | C12—H12B | 0.9800 |
C5—H5 | 0.86 (5) | C12—H12C | 0.9800 |
C6—H6 | 0.96 (5) | C12—H12A | 0.9800 |
C1—S1—S1i | 105.60 (17) | H7B—C7—H7A | 112 (5) |
C9—N1—C4 | 108.6 (4) | H7C—C7—H7A | 111 (5) |
C9—N1—C8 | 111.8 (6) | N1—C8—H8A | 109 (4) |
C4—N1—C8 | 109.9 (4) | N1—C8—H8B | 104 (4) |
C9—N1—C7 | 107.7 (5) | H8A—C8—H8B | 107 (6) |
C4—N1—C7 | 112.2 (4) | N1—C8—H8C | 106 (5) |
C8—N1—C7 | 106.7 (5) | H8A—C8—H8C | 117 (6) |
C2—C1—C6 | 120.2 (4) | H8B—C8—H8C | 112 (6) |
C2—C1—S1 | 114.6 (4) | N1—C9—H9A | 111 (4) |
C6—C1—S1 | 125.3 (4) | N1—C9—H9B | 105 (4) |
C1—C2—C3 | 120.6 (5) | H9A—C9—H9B | 113 (6) |
C1—C2—H2 | 121 (3) | N1—C9—H9C | 112 (5) |
C3—C2—H2 | 118 (3) | H9A—C9—H9C | 101 (6) |
C2—C3—C4 | 119.3 (5) | H9B—C9—H9C | 115 (6) |
C2—C3—H3 | 119 (4) | C11—C10—H10B | 109.5 |
C4—C3—H3 | 121 (4) | C11—C10—H10C | 109.5 |
C5—C4—C3 | 120.3 (4) | H10B—C10—H10C | 109.5 |
C5—C4—N1 | 118.9 (4) | C11—C10—H10A | 109.5 |
C3—C4—N1 | 120.7 (4) | H10B—C10—H10A | 109.5 |
C6—C5—C4 | 120.0 (4) | H10C—C10—H10A | 109.5 |
C6—C5—H5 | 119 (4) | O1—C11—C10 | 121.6 (7) |
C4—C5—H5 | 121 (4) | O1—C11—C12 | 122.1 (6) |
C1—C6—C5 | 119.6 (4) | C10—C11—C12 | 116.3 (7) |
C1—C6—H6 | 123 (3) | C11—C12—H12B | 109.5 |
C5—C6—H6 | 117 (3) | C11—C12—H12C | 109.5 |
N1—C7—H7B | 106 (4) | H12B—C12—H12C | 109.5 |
N1—C7—H7C | 111 (4) | C11—C12—H12A | 109.5 |
H7B—C7—H7C | 111 (5) | H12B—C12—H12A | 109.5 |
N1—C7—H7A | 105 (3) | H12C—C12—H12A | 109.5 |
C1—S1—S1i—C1i | −84.1 (2) | C7—N1—C4—C5 | 166.6 (5) |
S1i—S1—C1—C2 | −179.1 (3) | C9—N1—C4—C3 | 103.7 (6) |
S1i—S1—C1—C6 | −0.6 (4) | C8—N1—C4—C3 | −133.7 (5) |
C6—C1—C2—C3 | 0.0 (7) | C7—N1—C4—C3 | −15.2 (6) |
S1—C1—C2—C3 | 178.6 (4) | C3—C4—C5—C6 | 0.0 (7) |
C1—C2—C3—C4 | 0.3 (8) | N1—C4—C5—C6 | 178.2 (4) |
C2—C3—C4—C5 | −0.3 (7) | C2—C1—C6—C5 | −0.3 (7) |
C2—C3—C4—N1 | −178.5 (4) | S1—C1—C6—C5 | −178.7 (4) |
C9—N1—C4—C5 | −74.6 (6) | C4—C5—C6—C1 | 0.3 (7) |
C8—N1—C4—C5 | 48.0 (6) |
Symmetry code: (i) −x−1/2, −y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7C···I2ii | 1.05 (7) | 3.03 (7) | 4.038 (7) | 162 (5) |
C7—H7B···O1ii | 0.97 (7) | 2.54 (7) | 3.463 (8) | 158 (5) |
C2—H2···I2 | 0.98 (5) | 2.93 (5) | 3.818 (5) | 151 (4) |
Symmetry code: (ii) −x+1/2, −y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C18H26N2S22+·2I−·2C3H6O |
Mr | 704.48 |
Crystal system, space group | Orthorhombic, Pnna |
Temperature (K) | 193 |
a, b, c (Å) | 12.398 (2), 10.1902 (19), 23.773 (5) |
V (Å3) | 3003.4 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.26 |
Crystal size (mm) | 0.13 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Rigaku Mercury diffractometer |
Absorption correction | Multi-scan (Jacobson, 1998) |
Tmin, Tmax | 0.758, 0.806 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 31366, 3437, 3348 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.099, 1.15 |
No. of reflections | 3437 |
No. of parameters | 201 |
H-atom treatment | H 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 Å−3) | 0.63, −0.80 |
Computer programs: CrystalClear (Rigaku, 2000), CrystalStructure (Rigaku, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7C···I2i | 1.05 (7) | 3.03 (7) | 4.038 (7) | 162 (5) |
C7—H7B···O1i | 0.97 (7) | 2.54 (7) | 3.463 (8) | 158 (5) |
C2—H2···I2 | 0.98 (5) | 2.93 (5) | 3.818 (5) | 151 (4) |
Symmetry code: (i) −x+1/2, −y+1, z. |
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.