Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107018136/gg3084sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107018136/gg3084Isup2.hkl |
CCDC reference: 652515
An aliquot (10 ml) of a 2.5 mM hexane solution of the blue dodecamethylcarboranyl radical [prepared by oxidation of the Cs+ salt of the dodecamethylcarba-closo-dodecaborate anion, as described earlier (King et al. 1996; Rosokha & Kochi, 2007)] was added to a 10 mM solution (5 ml) of thianthrene in CH2Cl2. The mixture immediately turned bright violet (the colour characteristic of the thianthrene cation radical) and subsequent cooling to 208 K resulted in the precipitation of a violet powder. The latter was removed by filtration, dried and dissolved in CH2Cl2 (5 ml) in a Schlenk tube under an argon atmosphere. The violet solution was layered carefully with a 1:1 mixture of CH2Cl2–hexane, and then overlaid with pure hexane. The tube was sealed, cooled slowly to 243 K and left undisturbed for 7 d at 243 K, and this led to the formation of dark-violet [Black given in CIF tables] crystals of (I) suitable for X-ray measurements.
The molecular-orbital shape of the cation radical SOMO was evaluated using the Cube = (55, orbital) option in single point HF/6–311G* computations using the cation-radical geometry optimized via B3LYP/6–311G* computations with GAUSSIAN98 (Frisch et al., 1998).
The disordered CH2Cl2 solvent has two crystallographically independent C atoms (C20 and C21) and two Cl atoms (Cl2, Cl3). They were located in a difference Fourier map with site-occupancy factors of 0.680 (14) and 0.320 (14), respectively, using SHELXTL (Bruker, 2003). The H atoms in the solvent molecules were placed in calculated positions and treated as riding atoms, with C—H = 0.95–0.99 Å and Uiso(H) = 1.2Ueq(C) [Please check added text]. All other H atoms were treated as riding atoms, with C—H = 0.95–0.99 Å [Please check added text] and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).
Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT and SADABS (Bruker, 2003); program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL; molecular graphics: XP (Bruker, 1999); software used to prepare material for publication: SHELXTL and XCIF (Bruker, 1999).
3C12H8S20.67+·2C13H36B11−·4CH2Cl2 | F(000) = 1684 |
Mr = 1611.27 | Dx = 1.273 Mg m−3 |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2y | Cell parameters from 578 reflections |
a = 21.585 (8) Å | θ = 1.5–25.0° |
b = 14.573 (4) Å | µ = 0.46 mm−1 |
c = 16.523 (5) Å | T = 173 K |
β = 126.013 (10)° | Plate, black |
V = 4204 (2) Å3 | 0.5 × 0.4 × 0.1 mm |
Z = 2 |
Bruker SMART APEX diffractometer | 6546 independent reflections |
Radiation source: fine-focus sealed tube | 5156 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
full–sphere ω scans | θmax = 30.5°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −30→30 |
Tmin = 0.793, Tmax = 0.955 | k = −20→20 |
29585 measured reflections | l = −23→22 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0937P)2] where P = (Fo2 + 2Fc2)/3 |
6546 reflections | (Δ/σ)max = 0.001 |
272 parameters | Δρmax = 0.54 e Å−3 |
0 restraints | Δρmin = −0.45 e Å−3 |
3C12H8S20.67+·2C13H36B11−·4CH2Cl2 | V = 4204 (2) Å3 |
Mr = 1611.27 | Z = 2 |
Monoclinic, C2/m | Mo Kα radiation |
a = 21.585 (8) Å | µ = 0.46 mm−1 |
b = 14.573 (4) Å | T = 173 K |
c = 16.523 (5) Å | 0.5 × 0.4 × 0.1 mm |
β = 126.013 (10)° |
Bruker SMART APEX diffractometer | 6546 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 5156 reflections with I > 2σ(I) |
Tmin = 0.793, Tmax = 0.955 | Rint = 0.038 |
29585 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.54 e Å−3 |
6546 reflections | Δρmin = −0.45 e Å−3 |
272 parameters |
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 | Occ. (<1) | |
S1 | 0.5000 | 0.11918 (3) | 0.5000 | 0.02686 (12) | |
C1 | 0.42869 (7) | 0.04848 (9) | 0.40801 (9) | 0.0248 (3) | |
C2 | 0.36514 (8) | 0.09552 (10) | 0.32706 (10) | 0.0311 (3) | |
H2 | 0.3647 | 0.1607 | 0.3266 | 0.037* | |
C3 | 0.30380 (8) | 0.04839 (12) | 0.24882 (10) | 0.0348 (3) | |
H3 | 0.2613 | 0.0810 | 0.1946 | 0.042* | |
S2 | 0.33401 (3) | 0.0000 | 0.49350 (3) | 0.02760 (12) | |
S3 | 0.50988 (3) | 0.0000 | 0.72375 (3) | 0.02882 (12) | |
C4 | 0.38157 (7) | 0.09592 (9) | 0.56706 (10) | 0.0261 (3) | |
C5 | 0.34424 (9) | 0.17947 (11) | 0.52464 (12) | 0.0353 (3) | |
H5 | 0.2956 | 0.1800 | 0.4615 | 0.042* | |
C6 | 0.37753 (10) | 0.26104 (11) | 0.57388 (13) | 0.0426 (4) | |
H6 | 0.3519 | 0.3174 | 0.5443 | 0.051* | |
C7 | 0.44853 (10) | 0.26100 (12) | 0.66670 (13) | 0.0439 (4) | |
H7 | 0.4711 | 0.3174 | 0.7001 | 0.053* | |
C8 | 0.48621 (9) | 0.17982 (11) | 0.71044 (12) | 0.0363 (3) | |
H8 | 0.5344 | 0.1805 | 0.7741 | 0.044* | |
C9 | 0.45366 (8) | 0.09565 (10) | 0.66126 (10) | 0.0271 (3) | |
B1 | 0.17823 (12) | 0.5000 | 0.17538 (17) | 0.0306 (5) | |
B2 | 0.34920 (11) | 0.5000 | 0.21207 (15) | 0.0257 (4) | |
B3 | 0.33440 (8) | 0.43867 (11) | 0.29184 (11) | 0.0264 (3) | |
B4 | 0.26621 (12) | 0.5000 | 0.29759 (16) | 0.0292 (4) | |
B5 | 0.19390 (8) | 0.43958 (11) | 0.09610 (11) | 0.0275 (3) | |
B6 | 0.23762 (9) | 0.40125 (11) | 0.21984 (12) | 0.0281 (3) | |
B7 | 0.28985 (8) | 0.40099 (10) | 0.16743 (11) | 0.0261 (3) | |
C10 | 0.40153 (9) | 0.38014 (13) | 0.38451 (12) | 0.0455 (4) | |
H10A | 0.4257 | 0.4165 | 0.4459 | 0.068* | |
H10B | 0.4399 | 0.3642 | 0.3730 | 0.068* | |
H10C | 0.3801 | 0.3239 | 0.3914 | 0.068* | |
C11 | 0.31270 (10) | 0.30793 (11) | 0.13957 (13) | 0.0449 (4) | |
H11A | 0.2678 | 0.2678 | 0.1017 | 0.067* | |
H11B | 0.3534 | 0.2768 | 0.2011 | 0.067* | |
H11C | 0.3309 | 0.3222 | 0.0989 | 0.067* | |
C12 | 0.12762 (10) | 0.38485 (13) | 0.00087 (13) | 0.0517 (5) | |
H12A | 0.0778 | 0.4094 | −0.0206 | 0.077* | |
H12B | 0.1308 | 0.3198 | 0.0178 | 0.077* | |
H12C | 0.1333 | 0.3916 | −0.0535 | 0.077* | |
C13 | 0.21246 (10) | 0.30751 (12) | 0.24350 (14) | 0.0461 (4) | |
H13A | 0.1984 | 0.2623 | 0.1914 | 0.069* | |
H13B | 0.1684 | 0.3190 | 0.2450 | 0.069* | |
H13C | 0.2552 | 0.2838 | 0.3086 | 0.069* | |
C14 | 0.26926 (17) | 0.5000 | 0.3973 (2) | 0.0526 (6) | |
H14A | 0.3200 | 0.5201 | 0.4543 | 0.079* | 0.50 |
H14B | 0.2593 | 0.4379 | 0.4098 | 0.079* | 0.50 |
H14C | 0.2303 | 0.5420 | 0.3885 | 0.079* | 0.50 |
C15 | 0.42958 (12) | 0.5000 | 0.2265 (2) | 0.0443 (6) | |
H15A | 0.4397 | 0.5615 | 0.2130 | 0.066* | 0.50 |
H15B | 0.4274 | 0.4560 | 0.1800 | 0.066* | 0.50 |
H15C | 0.4707 | 0.4824 | 0.2954 | 0.066* | 0.50 |
C16 | 0.25907 (18) | 0.5000 | −0.00515 (19) | 0.0525 (7) | |
H16A | 0.2556 | 0.5633 | −0.0275 | 0.079* | 0.50 |
H16B | 0.2141 | 0.4654 | −0.0579 | 0.079* | 0.50 |
H16C | 0.3056 | 0.4713 | 0.0092 | 0.079* | 0.50 |
C17 | 0.09697 (13) | 0.5000 | 0.1572 (2) | 0.0544 (7) | |
H17A | 0.0823 | 0.5632 | 0.1589 | 0.082* | 0.50 |
H17B | 0.1003 | 0.4640 | 0.2097 | 0.082* | 0.50 |
H17C | 0.0585 | 0.4728 | 0.0918 | 0.082* | 0.50 |
C18 | 0.26208 (12) | 0.5000 | 0.09287 (15) | 0.0344 (4) | |
C19 | 0.5000 | 0.2994 (2) | 0.0000 | 0.0652 (8) | |
H19A | 0.4664 | 0.2594 | −0.0587 | 0.078* | 0.50 |
H19B | 0.5337 | 0.2594 | 0.0587 | 0.078* | 0.50 |
Cl1 | 0.44324 (4) | 0.36597 (5) | 0.02132 (6) | 0.0781 (2) | |
C20 | 0.1068 (5) | 0.0000 | 0.2627 (12) | 0.101 (4) | 0.680 (14) |
H20A | 0.1036 | 0.0000 | 0.3201 | 0.122* | 0.680 (14) |
H20B | 0.0538 | 0.0000 | 0.2008 | 0.122* | 0.680 (14) |
Cl2 | 0.15195 (13) | 0.10120 (11) | 0.26642 (13) | 0.0429 (5) | 0.680 (14) |
C21 | 0.0954 (5) | 0.0000 | 0.2008 (6) | 0.033 (2) | 0.320 (14) |
H21A | 0.0876 | 0.0000 | 0.1355 | 0.040* | 0.320 (14) |
H21B | 0.0441 | 0.0000 | 0.1870 | 0.040* | 0.320 (14) |
Cl3 | 0.1400 (5) | 0.0973 (4) | 0.2605 (5) | 0.098 (2) | 0.320 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0324 (2) | 0.0224 (2) | 0.0293 (2) | 0.000 | 0.0201 (2) | 0.000 |
C1 | 0.0297 (6) | 0.0268 (7) | 0.0250 (6) | −0.0011 (5) | 0.0200 (5) | −0.0014 (5) |
C2 | 0.0362 (7) | 0.0331 (8) | 0.0306 (7) | 0.0059 (6) | 0.0234 (6) | 0.0046 (5) |
C3 | 0.0320 (6) | 0.0474 (9) | 0.0271 (6) | 0.0042 (6) | 0.0186 (6) | 0.0028 (6) |
S2 | 0.0282 (2) | 0.0312 (3) | 0.0255 (2) | 0.000 | 0.01693 (19) | 0.000 |
S3 | 0.0296 (2) | 0.0315 (3) | 0.0249 (2) | 0.000 | 0.01574 (19) | 0.000 |
C4 | 0.0306 (6) | 0.0283 (7) | 0.0282 (6) | 0.0007 (5) | 0.0222 (5) | −0.0003 (5) |
C5 | 0.0391 (7) | 0.0353 (8) | 0.0367 (7) | 0.0059 (6) | 0.0251 (6) | 0.0046 (6) |
C6 | 0.0548 (9) | 0.0281 (8) | 0.0537 (9) | 0.0081 (7) | 0.0369 (8) | 0.0045 (7) |
C7 | 0.0558 (9) | 0.0268 (8) | 0.0571 (10) | −0.0046 (7) | 0.0376 (9) | −0.0084 (7) |
C8 | 0.0402 (7) | 0.0356 (8) | 0.0371 (7) | −0.0044 (6) | 0.0249 (6) | −0.0060 (6) |
C9 | 0.0315 (6) | 0.0286 (7) | 0.0277 (6) | −0.0004 (5) | 0.0211 (5) | −0.0007 (5) |
B1 | 0.0241 (9) | 0.0320 (12) | 0.0360 (11) | 0.000 | 0.0179 (9) | 0.000 |
B2 | 0.0242 (9) | 0.0292 (11) | 0.0266 (9) | 0.000 | 0.0164 (8) | 0.000 |
B3 | 0.0244 (6) | 0.0296 (8) | 0.0223 (6) | 0.0005 (5) | 0.0122 (5) | 0.0022 (6) |
B4 | 0.0329 (10) | 0.0333 (12) | 0.0295 (10) | 0.000 | 0.0230 (9) | 0.000 |
B5 | 0.0257 (7) | 0.0238 (7) | 0.0266 (7) | −0.0006 (5) | 0.0119 (6) | 0.0006 (5) |
B6 | 0.0284 (7) | 0.0263 (8) | 0.0306 (7) | −0.0009 (6) | 0.0178 (6) | 0.0027 (6) |
B7 | 0.0284 (7) | 0.0239 (7) | 0.0258 (6) | 0.0022 (5) | 0.0159 (6) | −0.0002 (5) |
C10 | 0.0417 (9) | 0.0466 (10) | 0.0328 (8) | 0.0083 (7) | 0.0134 (7) | 0.0095 (7) |
C11 | 0.0527 (9) | 0.0327 (8) | 0.0508 (9) | 0.0057 (7) | 0.0313 (8) | −0.0056 (7) |
C12 | 0.0447 (9) | 0.0385 (9) | 0.0444 (9) | −0.0079 (7) | 0.0109 (8) | −0.0041 (7) |
C13 | 0.0492 (9) | 0.0358 (9) | 0.0561 (10) | −0.0050 (7) | 0.0326 (8) | 0.0087 (7) |
C14 | 0.0732 (17) | 0.0562 (16) | 0.0500 (14) | 0.000 | 0.0483 (14) | 0.000 |
C15 | 0.0329 (10) | 0.0507 (15) | 0.0600 (14) | 0.000 | 0.0333 (11) | 0.000 |
C16 | 0.0758 (18) | 0.0542 (16) | 0.0382 (12) | 0.000 | 0.0394 (13) | 0.000 |
C17 | 0.0328 (11) | 0.0607 (17) | 0.0753 (18) | 0.000 | 0.0350 (13) | 0.000 |
C18 | 0.0416 (11) | 0.0331 (11) | 0.0283 (9) | 0.000 | 0.0205 (9) | 0.000 |
C19 | 0.0754 (19) | 0.0426 (15) | 0.100 (2) | 0.000 | 0.064 (2) | 0.000 |
Cl1 | 0.0783 (4) | 0.0663 (4) | 0.1133 (5) | −0.0106 (3) | 0.0694 (4) | −0.0252 (4) |
C20 | 0.091 (5) | 0.040 (3) | 0.228 (13) | 0.000 | 0.125 (7) | 0.000 |
Cl2 | 0.0428 (6) | 0.0285 (6) | 0.0607 (7) | −0.0019 (4) | 0.0323 (5) | −0.0017 (5) |
C21 | 0.037 (4) | 0.023 (3) | 0.039 (4) | 0.000 | 0.022 (3) | 0.000 |
Cl3 | 0.062 (2) | 0.068 (2) | 0.139 (4) | −0.0195 (16) | 0.0440 (19) | −0.044 (3) |
S1—C1i | 1.7290 (14) | B5—B6 | 1.765 (2) |
S1—C1 | 1.7291 (14) | B5—B7 | 1.768 (2) |
C1—C2 | 1.4082 (19) | B6—C13 | 1.601 (2) |
C1—C1ii | 1.413 (3) | B6—B7 | 1.780 (2) |
C2—C3 | 1.372 (2) | B7—C11 | 1.600 (2) |
C2—H2 | 0.9500 | B7—C18 | 1.7580 (19) |
C3—C3ii | 1.410 (3) | C10—H10A | 0.9800 |
C3—H3 | 0.9500 | C10—H10B | 0.9800 |
S2—C4 | 1.7371 (14) | C10—H10C | 0.9800 |
S2—C4ii | 1.7371 (14) | C11—H11A | 0.9800 |
S3—C9ii | 1.7344 (15) | C11—H11B | 0.9800 |
S3—C9 | 1.7344 (15) | C11—H11C | 0.9800 |
C4—C5 | 1.400 (2) | C12—H12A | 0.9800 |
C4—C9 | 1.4128 (19) | C12—H12B | 0.9800 |
C5—C6 | 1.380 (2) | C12—H12C | 0.9800 |
C5—H5 | 0.9500 | C13—H13A | 0.9800 |
C6—C7 | 1.392 (2) | C13—H13B | 0.9800 |
C6—H6 | 0.9500 | C13—H13C | 0.9800 |
C7—C8 | 1.376 (2) | C14—H14A | 0.9800 |
C7—H7 | 0.9500 | C14—H14B | 0.9800 |
C8—C9 | 1.410 (2) | C14—H14C | 0.9800 |
C8—H8 | 0.9500 | C15—H15A | 0.9800 |
B1—C17 | 1.596 (3) | C15—H15B | 0.9800 |
B1—B5 | 1.768 (3) | C15—H15C | 0.9800 |
B1—B5iii | 1.768 (3) | C16—C18 | 1.582 (3) |
B1—B6 | 1.774 (2) | C16—H16A | 0.9800 |
B1—B6iii | 1.774 (2) | C16—H16B | 0.9800 |
B1—B4 | 1.782 (3) | C16—H16C | 0.9800 |
B2—C15 | 1.606 (3) | C17—H17A | 0.9800 |
B2—C18 | 1.749 (3) | C17—H17B | 0.9800 |
B2—B3 | 1.770 (2) | C17—H17C | 0.9800 |
B2—B3iii | 1.770 (2) | C18—B5iii | 1.743 (2) |
B2—B7iii | 1.776 (2) | C18—B7iii | 1.7579 (19) |
B2—B7 | 1.777 (2) | C19—Cl1 | 1.7532 (18) |
B3—C10 | 1.601 (2) | C19—Cl1iv | 1.7533 (18) |
B3—B7 | 1.768 (2) | C19—H19A | 0.9900 |
B3—B4 | 1.772 (2) | C19—H19B | 0.9900 |
B3—B6 | 1.776 (2) | C20—Cl2ii | 1.748 (4) |
B3—B3iii | 1.788 (3) | C20—Cl2 | 1.748 (4) |
B4—C14 | 1.609 (3) | C20—H20A | 0.9900 |
B4—B3iii | 1.772 (2) | C20—H20B | 0.9900 |
B4—B6iii | 1.780 (2) | C21—Cl3 | 1.671 (8) |
B4—B6 | 1.780 (2) | C21—Cl3ii | 1.671 (8) |
B5—C12 | 1.585 (2) | C21—H21A | 0.9900 |
B5—C18 | 1.743 (2) | C21—H21B | 0.9900 |
B5—B5iii | 1.761 (3) | ||
C1i—S1—C1 | 106.86 (10) | C13—B6—B3 | 122.18 (12) |
C2—C1—C1ii | 119.13 (8) | B5—B6—B3 | 107.22 (10) |
C2—C1—S1 | 114.30 (11) | B1—B6—B3 | 107.90 (11) |
C1ii—C1—S1 | 126.57 (5) | C13—B6—B7 | 121.31 (13) |
C3—C2—C1 | 120.83 (14) | B5—B6—B7 | 59.82 (9) |
C3—C2—H2 | 119.6 | B1—B6—B7 | 108.08 (12) |
C1—C2—H2 | 119.6 | B3—B6—B7 | 59.64 (9) |
C2—C3—C3ii | 120.04 (9) | C13—B6—B4 | 122.47 (13) |
C2—C3—H3 | 120.0 | B5—B6—B4 | 107.61 (11) |
C3ii—C3—H3 | 120.0 | B1—B6—B4 | 60.17 (11) |
C4—S2—C4ii | 107.15 (9) | B3—B6—B4 | 59.76 (10) |
C9ii—S3—C9 | 106.96 (10) | B7—B6—B4 | 107.62 (11) |
C5—C4—C9 | 119.41 (13) | C11—B7—C18 | 121.98 (13) |
C5—C4—S2 | 114.85 (11) | C11—B7—B5 | 121.08 (12) |
C9—C4—S2 | 125.71 (11) | C18—B7—B5 | 59.25 (10) |
C6—C5—C4 | 120.48 (14) | C11—B7—B3 | 123.26 (12) |
C6—C5—H5 | 119.8 | C18—B7—B3 | 106.74 (11) |
C4—C5—H5 | 119.8 | B5—B7—B3 | 107.43 (10) |
C5—C6—C7 | 120.25 (15) | C11—B7—B2 | 122.59 (13) |
C5—C6—H6 | 119.9 | C18—B7—B2 | 59.33 (10) |
C7—C6—H6 | 119.9 | B5—B7—B2 | 107.14 (11) |
C8—C7—C6 | 120.47 (15) | B3—B7—B2 | 59.91 (10) |
C8—C7—H7 | 119.8 | C11—B7—B6 | 122.15 (13) |
C6—C7—H7 | 119.8 | C18—B7—B6 | 106.66 (11) |
C7—C8—C9 | 120.35 (15) | B5—B7—B6 | 59.65 (9) |
C7—C8—H8 | 119.8 | B3—B7—B6 | 60.07 (9) |
C9—C8—H8 | 119.8 | B2—B7—B6 | 107.74 (11) |
C8—C9—C4 | 119.04 (13) | B3—C10—H10A | 109.5 |
C8—C9—S3 | 114.77 (11) | B3—C10—H10B | 109.5 |
C4—C9—S3 | 126.15 (11) | H10A—C10—H10B | 109.5 |
C17—B1—B5 | 121.89 (15) | B3—C10—H10C | 109.5 |
C17—B1—B5iii | 121.89 (15) | H10A—C10—H10C | 109.5 |
B5—B1—B5iii | 59.73 (13) | H10B—C10—H10C | 109.5 |
C17—B1—B6 | 121.64 (9) | B7—C11—H11A | 109.5 |
B5—B1—B6 | 59.76 (9) | B7—C11—H11B | 109.5 |
B5iii—B1—B6 | 107.72 (13) | H11A—C11—H11B | 109.5 |
C17—B1—B6iii | 121.64 (10) | B7—C11—H11C | 109.5 |
B5—B1—B6iii | 107.72 (13) | H11A—C11—H11C | 109.5 |
B5iii—B1—B6iii | 59.76 (9) | H11B—C11—H11C | 109.5 |
B6—B1—B6iii | 108.44 (15) | B5—C12—H12A | 109.5 |
C17—B1—B4 | 122.30 (19) | B5—C12—H12B | 109.5 |
B5—B1—B4 | 107.40 (13) | H12A—C12—H12B | 109.5 |
B5iii—B1—B4 | 107.39 (13) | B5—C12—H12C | 109.5 |
B6—B1—B4 | 60.10 (8) | H12A—C12—H12C | 109.5 |
B6iii—B1—B4 | 60.10 (8) | H12B—C12—H12C | 109.5 |
C15—B2—C18 | 121.30 (17) | B6—C13—H13A | 109.5 |
C15—B2—B3 | 122.77 (14) | B6—C13—H13B | 109.5 |
C18—B2—B3 | 107.05 (12) | H13A—C13—H13B | 109.5 |
C15—B2—B3iii | 122.77 (14) | B6—C13—H13C | 109.5 |
C18—B2—B3iii | 107.05 (12) | H13A—C13—H13C | 109.5 |
B3—B2—B3iii | 60.66 (12) | H13B—C13—H13C | 109.5 |
C15—B2—B7iii | 120.93 (9) | B4—C14—H14A | 109.5 |
C18—B2—B7iii | 59.81 (8) | B4—C14—H14B | 109.5 |
B3—B2—B7iii | 108.51 (12) | H14A—C14—H14B | 109.5 |
B3iii—B2—B7iii | 59.82 (8) | B4—C14—H14C | 109.5 |
C15—B2—B7 | 120.93 (9) | H14A—C14—H14C | 109.5 |
C18—B2—B7 | 59.81 (8) | H14B—C14—H14C | 109.5 |
B3—B2—B7 | 59.82 (8) | B2—C15—H15A | 109.5 |
B3iii—B2—B7 | 108.51 (12) | B2—C15—H15B | 109.5 |
B7iii—B2—B7 | 108.62 (14) | H15A—C15—H15B | 109.5 |
C10—B3—B7 | 120.94 (13) | B2—C15—H15C | 109.5 |
C10—B3—B2 | 121.54 (13) | H15A—C15—H15C | 109.5 |
B7—B3—B2 | 60.28 (9) | H15B—C15—H15C | 109.5 |
C10—B3—B4 | 122.06 (13) | C18—C16—H16A | 109.5 |
B7—B3—B4 | 108.53 (11) | C18—C16—H16B | 109.5 |
B2—B3—B4 | 107.73 (11) | H16A—C16—H16B | 109.5 |
C10—B3—B6 | 121.59 (13) | C18—C16—H16C | 109.5 |
B7—B3—B6 | 60.30 (9) | H16A—C16—H16C | 109.5 |
B2—B3—B6 | 108.21 (11) | H16B—C16—H16C | 109.5 |
B4—B3—B6 | 60.24 (9) | B1—C17—H17A | 109.5 |
C10—B3—B3iii | 122.19 (9) | B1—C17—H17B | 109.5 |
B7—B3—B3iii | 108.09 (7) | H17A—C17—H17B | 109.5 |
B2—B3—B3iii | 59.67 (6) | B1—C17—H17C | 109.5 |
B4—B3—B3iii | 59.70 (6) | H17A—C17—H17C | 109.5 |
B6—B3—B3iii | 107.88 (7) | H17B—C17—H17C | 109.5 |
C14—B4—B3iii | 121.31 (15) | C16—C18—B5iii | 120.28 (15) |
C14—B4—B3 | 121.31 (15) | C16—C18—B5 | 120.28 (15) |
B3iii—B4—B3 | 60.59 (13) | B5iii—C18—B5 | 60.70 (13) |
C14—B4—B6iii | 121.79 (9) | C16—C18—B2 | 121.50 (19) |
B3iii—B4—B6iii | 60.00 (8) | B5iii—C18—B2 | 109.49 (12) |
B3—B4—B6iii | 108.39 (13) | B5—C18—B2 | 109.49 (12) |
C14—B4—B6 | 121.79 (9) | C16—C18—B7iii | 120.61 (9) |
B3iii—B4—B6 | 108.39 (13) | B5iii—C18—B7iii | 60.65 (8) |
B3—B4—B6 | 60.00 (8) | B5—C18—B7iii | 109.83 (13) |
B6iii—B4—B6 | 107.85 (15) | B2—C18—B7iii | 60.86 (8) |
C14—B4—B1 | 122.34 (18) | C16—C18—B7 | 120.61 (9) |
B3iii—B4—B1 | 107.74 (13) | B5iii—C18—B7 | 109.84 (13) |
B3—B4—B1 | 107.74 (13) | B5—C18—B7 | 60.65 (8) |
B6iii—B4—B1 | 59.73 (8) | B2—C18—B7 | 60.86 (8) |
B6—B4—B1 | 59.73 (8) | B7iii—C18—B7 | 110.32 (14) |
C12—B5—C18 | 120.64 (14) | Cl1—C19—Cl1iv | 112.81 (17) |
C12—B5—B5iii | 120.22 (9) | Cl1—C19—H19A | 109.0 |
C18—B5—B5iii | 59.65 (6) | Cl1iv—C19—H19A | 109.0 |
C12—B5—B6 | 123.14 (13) | Cl1—C19—H19B | 109.0 |
C18—B5—B6 | 108.03 (11) | Cl1iv—C19—H19B | 109.0 |
B5iii—B5—B6 | 108.45 (7) | H19A—C19—H19B | 107.8 |
C12—B5—B7 | 121.45 (13) | Cl2ii—C20—Cl2 | 115.0 (3) |
C18—B5—B7 | 60.10 (9) | Cl2ii—C20—H20A | 108.5 |
B5iii—B5—B7 | 108.55 (7) | Cl2—C20—H20A | 108.5 |
B6—B5—B7 | 60.53 (9) | Cl2ii—C20—H20B | 108.5 |
C12—B5—B1 | 122.13 (14) | Cl2—C20—H20B | 108.5 |
C18—B5—B1 | 107.69 (11) | H20A—C20—H20B | 107.5 |
B5iii—B5—B1 | 60.14 (6) | Cl3—C21—Cl3ii | 116.1 (6) |
B6—B5—B1 | 60.28 (9) | Cl3—C21—H21A | 108.3 |
B7—B5—B1 | 108.90 (12) | Cl3ii—C21—H21A | 108.3 |
C13—B6—B5 | 121.72 (13) | Cl3—C21—H21B | 108.3 |
C13—B6—B1 | 121.81 (13) | Cl3ii—C21—H21B | 108.3 |
B5—B6—B1 | 59.96 (10) | H21A—C21—H21B | 107.4 |
Symmetry codes: (i) −x+1, y, −z+1; (ii) x, −y, z; (iii) x, −y+1, z; (iv) −x+1, y, −z. |
Experimental details
Crystal data | |
Chemical formula | 3C12H8S20.67+·2C13H36B11−·4CH2Cl2 |
Mr | 1611.27 |
Crystal system, space group | Monoclinic, C2/m |
Temperature (K) | 173 |
a, b, c (Å) | 21.585 (8), 14.573 (4), 16.523 (5) |
β (°) | 126.013 (10) |
V (Å3) | 4204 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.46 |
Crystal size (mm) | 0.5 × 0.4 × 0.1 |
Data collection | |
Diffractometer | Bruker SMART APEX diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.793, 0.955 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29585, 6546, 5156 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.715 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.139, 1.04 |
No. of reflections | 6546 |
No. of parameters | 272 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.54, −0.45 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAINT and SADABS (Bruker, 2003), SHELXTL (Bruker, 2003), XP (Bruker, 1999), SHELXTL and XCIF (Bruker, 1999).
S1—C1 | 1.7291 (14) | C4—C5 | 1.400 (2) |
C1—C2 | 1.4082 (19) | C4—C9 | 1.4128 (19) |
C1—C1i | 1.413 (3) | C5—C6 | 1.380 (2) |
C2—C3 | 1.372 (2) | C6—C7 | 1.392 (2) |
C3—C3i | 1.410 (3) | C7—C8 | 1.376 (2) |
S2—C4 | 1.7371 (14) | C8—C9 | 1.410 (2) |
S3—C9 | 1.7344 (15) |
Symmetry code: (i) x, −y, z. |
The elucidation of the structural features involved in the intermolecular association of planar organic ion radicals is vital to resolving the nature of the long-distance π–π intermolecular interactions (Novoa et al., 2001; Lü et al., 2003) and in the development of organic conducting and magnetic materials (Miller, 1983). Thus, according to the maximin principle (Devic et al., 2005), the ion-radical association occurs in a way that simultaneously maximizes the frontier-orbital overlap yet minimizes the interatomic contacts. On the other hand, the packing of some organic ion radicals is found to diverge noticeably in different salts, and such a variability is especially characteristic of the tetrathiafulvalene (TTF) cation radical (Miller, 1983; Rosokha & Kochi, 2007). Thus, in order to explore the intermolecular association of other S-containing analogues, we examined one of the oldest known cation radicals, thianthrene, in which single-crystal analysis shows the presence of dimeric units with the parallel thianthrenes bent towards each other at a close separation of ~3.1 Å between overlapping S atoms (Bock et al., 1994; Nishinaga & Komatsu, 2005). Here, we present the novel structure of the trimeric thianthrene dication (C12H8S2)32+, displaying a contrasting geometry with an unusual perpendicular arrangement of monomeric units. The latter thus supports the generality of the multivariant orientations observed in TTF and other long-bonded (ion radical) associates.
A dark-violet single-crystal of the title CH2Cl2 solvate of the thianthrene dication and the dodecamethylcarba-closo-dodecaborate anion, (C12H8S2)32+[CB11(CH3)12-]2·4CH2Cl2, (I), was prepared by slow diffusion of hexane into a CH2Cl2 solution containing the cation radical and the neutral thianthrene (see Experimental section).
The asymmetric unit of (I) (Fig. 1) contains two crystallographically independent thianthrenes, one carbaborate anion and two CH2Cl2 solvent molecules. One of the thianthrenes (located on a 2/m symmetry element) is planar, while the molecular plane of the second thianthrene (located on a mirror symmetry element) is essentially parallel to the first, but their S···S axes are orthogonal to one another. One of the solvent molecules is ordered and resides on a twofold rotation axis, while the other (on a mirror plane) is disordered over two orientations.
The thianthrene moieties form distinct trimeric units (Fig. 2) which are cleanly separated by carbaborate anions and CH2Cl2 solvent molecules. In these π-stacked dications, the outer C12H8S2 moieties are bent towards the central unit, and the distances between the S atoms and the central plane (3.07 and 3.12 Å for atoms S2 and S3, respectively), as well as the C···S distance of 3.224 (2) Å, are notably contracted compared with the van der Waals contacts of ~3.5 Å (Reference?). Such intermolecular separations are comparable with that observed in the π-dimer formed by the thianthrene cation radical as its AlCl4- salt (Value?; Bock et al., 1994), and this indicates the presence of considerable (long-distance) bonding among thianthrene moieties resulting from the multicentre interaction of the pair of semi-occupied orbitals of the cation radicals with the highest occupied molecular orbital (HOMO) of the neutral C12H8S2. The bonding interaction is further revealed by the bending of the outer thianthrenes towards the central thianthrene, with dihedral angles between the aromatic planes of ~170° (similar to that observed in the dimer). Indeed, since ab initio B3LYP/6–311G* computations predict a planar structure for the isolated thianthrene cation radical, such bending (in both the dimeric cations and the outer thianthrenes of the trimer dication) is related to the strong attraction extant between thianthrene moieties, with the charge concentrated primarily on the S-atom centres.
To estimate the overall +2 charge distribution within the trimer, the bond lengths of the thianthrenes are compared with those in the neutral parent and its cation radical. Indeed, one-electron oxidation of thianthrene to its cation radical is accompanied both by the shortening of the S—C bonds from ~1.771 Å (on average) to ~1.732 Å and of the outer (ab) C—C bonds from ~1.395 Å to ~1.375 Å, and also by the slight lengthening of the inner and adjacent C—C bonds from ~1.395 to \sim 1.41 Å (Larson et al., 1984; Bock et al., 1994). Thus, the geometric characteristics in Table 1 indicate that the bond lengths of the central planar thianthrene moiety [e.g. C—S bonds of 1.7290 (14) Å and (ab) C2—C3 bonds of 1.372 (2) Å] coincide with those of the thianthrene cation radical, indicating the presence of unit charge on this central planar moiety. By comparison, the average bond lengths of the two outer thianthrenes in Table 1 (with C—S bonds of 1.736 Å) lie intermediate between the corresponding values in the neutral C12H8S2 and its cation radical, but much closer to the latter. We thus conclude that the +2 charge is delocalized over the entire thianthrene trimer assembly, with the maximum found on the central C12H8S2. This is similar to the TTF trimer reported previously (Triki et al., 1989). Notably, such a charge distribution agrees qualitatively with the +1/2/+1/+1/2 estimate resulting from simple Huckel molecular-orbital computations of electron population in the trimeric system in which four electrons reside on three molecular orbitals resulting from the interaction of the frontier orbitals (two SOMO [Please define] and one HOMO) of two cation radicals and one donor molecule.
The most remarkable feature of the thianthrene trimer, however, is that the S···S axes of neighbouring thianthrenes lie orthogonal, in contrast with their parallel arrangement with overlapping S atoms in the dimeric species, as compared pictorially in Fig. 3. Indeed, both intermolecular associates result from the interaction of the (partially occupied) thianthrene HOMO. However, as illustrated in Fig. 4, the symmetry of this orbital allows the bonding combination to occur with both parallel and perpendicular approaches of the monomers, and these alternatives are observed in both the dimer and the trimer.
The symmetry of the HOMOs predicts the bonding combination in both the crossed or parallel (overlapped and shifted) TTF cation-radical dimers, as well as in the parallel or perpendicular (to main axis) shifts within tetracyanoquinodimethane (TCNQ) anion-radical dyads etc. (Miller, 1983; Rosokha & Kochi, 2007). We thus conclude that the multivariance of the ion-radical association, which results in the different bonding combinations of their frontier orbitals, is quite common. Therefore, we believe that the delicate balance between the attractive interactions of partially occupied frontier orbitals vis á vis the repulsion of filled atomic orbitals is fragile, and it must be explicitly taken into account whenever the maximin principle is invoked. The latter re-emphasizes the possibility that several close potential-energy minima can exist between the various mutual monomer arrangements. Therefore, we postulate that within a narrow range of interplanar separations, the intermolecular interactions can be easily modulated by electrostatics, crystal packing, solvation etc. to produce a variety of polymolecular associates of the same ion radical with parallel or perpendicular, overlapped or laterally shifted, monomer orientations.