Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111003064/sf3147sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111003064/sf3147IIsup2.hkl |
CCDC reference: 819295
For related literature, see: Birdsall et al. (2000); Bjørnevåg et al. (1982); Cea-Olivares, Canseco-Melchor, Garcia-Montalvo, Hernández-Ortego & Novosad (1998); Cea-Olivares, Moya-Cabrera, Garcia-Montalvo, Castro-Blanco, Toscano & Hernández-Ortego (2005); Chivers et al. (1998); Husebye & Maartmann-Moe (1983); Novosad et al. (1998); Ritch et al. (2007); Sekar & Ibers (2003); Steudel et al. (2005).
The oxidation of (TMEDA)Na[(SPtBu2)2N] with one half-equivalent of I2 in tetrahydrofuran (THF) was carried out according to the literature (Ritch et al., 2007). Recrystallization of the crude yellow product from toluene (268 K, several days) gave a small crop of colourless crystals of the title complex, (SPtBu2NPtBu2PS)2S, (II). Spectroscopic analysis: 31P NMR (D8-THF, 233 K, δ, p.p.m.): 79.2 (d, 2JP,P = 50 Hz), 59.5 (d, 2JP,P = 50 Hz). The THF solvent was dried with Na/benzophenone and distilled onto 4 Å molecular sieves before use. The reaction and the manipulation of the air- and moisture-sensitive reagent (TMEDA)Na[(SPtBu2)2N] were carried out under an atmosphere of argon or under vacuum. All glassware was carefully dried prior to use. Complex (II) can be handled in air for short periods of time without significant decomposition.
The structure was solved by direct methods. Subsequent difference Fourier syntheses allowed the remaining atoms to be located. Only one half of the molecule was present in the asymmetric unit, as the central S atom lies on a crystallographic twofold axis. The molecule was well ordered and no special considerations were necessary for the refinement. A solvent toluene molecule was also present in the asymmetric unit and was disordered over a crystallographic twofold axis, hence it was modelled at 50% occupancy. Several restraints were applied to obtain a well behaved toluene molecule: all seven atoms were fitted to coplanarity within 0.005 Å, the aromatic C—C bond lengths were set to be 1.390 (5) Å and the methyl group was fixed to be equidistant from the ortho-C atoms within the aromatic ring (±0.005 Å). H atoms were calculated geometrically, with C—H = 0.95–0.98 Å, and treated as riding on their respective C atoms, with Uiso(H) = 1.2Ueq(C), or 1.5Ueq(C) for methyl H. [Please check added text]
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).
C32H72N2P4S5·C7H8 | F(000) = 1872 |
Mr = 861.23 | Dx = 1.182 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 19034 reflections |
a = 22.271 (5) Å | θ = 3.4–25.0° |
b = 18.970 (4) Å | µ = 0.40 mm−1 |
c = 15.610 (3) Å | T = 173 K |
β = 132.79 (3)° | Rod, colourless |
V = 4840 (3) Å3 | 0.10 × 0.03 × 0.03 mm |
Z = 4 |
Nonius Kappa CCD area-detector diffractometer | 4274 independent reflections |
Radiation source: fine-focus sealed tube | 2612 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.070 |
ϕ scans | θmax = 25.0°, θmin = 3.4° |
Absorption correction: integration (SCALEPACK; Otwinowski & Minor, 1997) | h = −26→26 |
Tmin = 0.961, Tmax = 0.988 | k = −22→22 |
19034 measured reflections | l = −18→18 |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0446P)2 + 1.989P] where P = (Fo2 + 2Fc2)/3 |
4274 reflections | (Δ/σ)max < 0.001 |
271 parameters | Δρmax = 0.29 e Å−3 |
11 restraints | Δρmin = −0.35 e Å−3 |
C32H72N2P4S5·C7H8 | V = 4840 (3) Å3 |
Mr = 861.23 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 22.271 (5) Å | µ = 0.40 mm−1 |
b = 18.970 (4) Å | T = 173 K |
c = 15.610 (3) Å | 0.10 × 0.03 × 0.03 mm |
β = 132.79 (3)° |
Nonius Kappa CCD area-detector diffractometer | 4274 independent reflections |
Absorption correction: integration (SCALEPACK; Otwinowski & Minor, 1997) | 2612 reflections with I > 2σ(I) |
Tmin = 0.961, Tmax = 0.988 | Rint = 0.070 |
19034 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 11 restraints |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.29 e Å−3 |
4274 reflections | Δρmin = −0.35 e Å−3 |
271 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 | 0.19425 (6) | 1.04079 (6) | 0.73454 (9) | 0.0393 (3) | |
P1 | 0.23930 (5) | 0.96662 (5) | 0.85338 (8) | 0.0260 (3) | |
C1 | 0.2245 (2) | 0.9949 (2) | 0.9529 (3) | 0.0322 (9) | |
C2 | 0.2695 (3) | 1.0646 (2) | 1.0155 (4) | 0.0520 (13) | |
H2A | 0.2505 | 1.0836 | 1.0520 | 0.078* | |
H2B | 0.2581 | 1.0986 | 0.9587 | 0.078* | |
H2C | 0.3285 | 1.0558 | 1.0757 | 0.078* | |
C3 | 0.1322 (2) | 1.0071 (2) | 0.8758 (4) | 0.0424 (11) | |
H3A | 0.1218 | 1.0227 | 0.9246 | 0.064* | |
H3B | 0.1026 | 0.9630 | 0.8364 | 0.064* | |
H3C | 0.1133 | 1.0433 | 0.8173 | 0.064* | |
C4 | 0.2536 (2) | 0.9388 (2) | 1.0462 (3) | 0.0481 (12) | |
H4A | 0.2294 | 0.9485 | 1.0789 | 0.072* | |
H4B | 0.3134 | 0.9403 | 1.1086 | 0.072* | |
H4C | 0.2365 | 0.8919 | 1.0102 | 0.072* | |
C5 | 0.3498 (2) | 0.9543 (2) | 0.9337 (3) | 0.0359 (10) | |
C6 | 0.3511 (2) | 0.9230 (3) | 0.8439 (4) | 0.0554 (14) | |
H6A | 0.4078 | 0.9165 | 0.8804 | 0.083* | |
H6B | 0.3232 | 0.9552 | 0.7774 | 0.083* | |
H6C | 0.3229 | 0.8774 | 0.8166 | 0.083* | |
C7 | 0.3933 (2) | 0.9033 (2) | 1.0368 (4) | 0.0521 (13) | |
H7A | 0.4459 | 0.8892 | 1.0631 | 0.078* | |
H7B | 0.3591 | 0.8614 | 1.0122 | 0.078* | |
H7C | 0.4025 | 0.9265 | 1.1010 | 0.078* | |
C8 | 0.3958 (2) | 1.0247 (2) | 0.9769 (4) | 0.0564 (14) | |
H8A | 0.4513 | 1.0173 | 1.0086 | 0.085* | |
H8B | 0.3988 | 1.0438 | 1.0381 | 0.085* | |
H8C | 0.3668 | 1.0581 | 0.9117 | 0.085* | |
N1 | 0.20202 (15) | 0.88758 (15) | 0.8071 (2) | 0.0241 (7) | |
P2 | 0.13316 (5) | 0.83193 (5) | 0.72915 (8) | 0.0237 (2) | |
C9 | 0.04269 (19) | 0.86144 (19) | 0.5795 (3) | 0.0275 (9) | |
C10 | −0.0195 (2) | 0.8024 (2) | 0.5019 (3) | 0.0369 (10) | |
H10A | −0.0677 | 0.8222 | 0.4266 | 0.055* | |
H10B | −0.0360 | 0.7808 | 0.5403 | 0.055* | |
H10C | 0.0055 | 0.7666 | 0.4893 | 0.055* | |
C11 | 0.0722 (2) | 0.8925 (2) | 0.5223 (3) | 0.0348 (10) | |
H11A | 0.0258 | 0.9137 | 0.4471 | 0.052* | |
H11B | 0.0958 | 0.8549 | 0.5099 | 0.052* | |
H11C | 0.1138 | 0.9286 | 0.5735 | 0.052* | |
C12 | 0.0013 (2) | 0.9204 (2) | 0.5904 (3) | 0.0342 (10) | |
H12A | −0.0456 | 0.9385 | 0.5126 | 0.051* | |
H12B | 0.0405 | 0.9587 | 0.6382 | 0.051* | |
H12C | −0.0175 | 0.9019 | 0.6275 | 0.051* | |
C13 | 0.1768 (2) | 0.74676 (19) | 0.7332 (3) | 0.0295 (9) | |
C14 | 0.2594 (2) | 0.7380 (2) | 0.8587 (3) | 0.0390 (11) | |
H14A | 0.2826 | 0.6918 | 0.8670 | 0.059* | |
H14B | 0.2514 | 0.7413 | 0.9130 | 0.059* | |
H14C | 0.2969 | 0.7752 | 0.8762 | 0.059* | |
C15 | 0.1917 (2) | 0.7478 (2) | 0.6506 (4) | 0.0429 (11) | |
H15A | 0.2232 | 0.7060 | 0.6646 | 0.064* | |
H15B | 0.2223 | 0.7904 | 0.6649 | 0.064* | |
H15C | 0.1390 | 0.7477 | 0.5696 | 0.064* | |
C16 | 0.1236 (2) | 0.6828 (2) | 0.7054 (3) | 0.0378 (10) | |
H16A | 0.1504 | 0.6395 | 0.7118 | 0.057* | |
H16B | 0.0700 | 0.6872 | 0.6259 | 0.057* | |
H16C | 0.1166 | 0.6811 | 0.7609 | 0.057* | |
S2 | 0.09992 (5) | 0.81247 (5) | 0.82883 (8) | 0.0269 (2) | |
S3 | 0.0000 | 0.74758 (7) | 0.7500 | 0.0297 (3) | |
C17 | 0.1317 (6) | 0.7722 (6) | 0.3311 (9) | 0.093 (5) | 0.50 |
H17A | 0.1264 | 0.8135 | 0.2886 | 0.139* | 0.50 |
H17B | 0.1531 | 0.7324 | 0.3185 | 0.139* | 0.50 |
H17C | 0.1695 | 0.7831 | 0.4146 | 0.139* | 0.50 |
C18 | 0.0498 (5) | 0.7534 (4) | 0.2876 (7) | 0.055 (3) | 0.50 |
C19 | 0.0323 (5) | 0.6839 (5) | 0.2918 (8) | 0.067 (4) | 0.50 |
H19A | 0.0730 | 0.6489 | 0.3226 | 0.081* | 0.50 |
C20 | −0.0429 (5) | 0.6641 (5) | 0.2525 (8) | 0.072 (4) | 0.50 |
H20A | −0.0539 | 0.6163 | 0.2560 | 0.087* | 0.50 |
C21 | −0.1016 (6) | 0.7159 (5) | 0.2079 (7) | 0.073 (3) | 0.50 |
H21A | −0.1537 | 0.7039 | 0.1803 | 0.087* | 0.50 |
C22 | −0.0839 (6) | 0.7852 (5) | 0.2039 (11) | 0.063 (4) | 0.50 |
H22A | −0.1246 | 0.8202 | 0.1732 | 0.075* | 0.50 |
C23 | −0.0089 (5) | 0.8052 (5) | 0.2431 (11) | 0.053 (2) | 0.50 |
H23A | 0.0020 | 0.8530 | 0.2395 | 0.063* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0432 (6) | 0.0353 (6) | 0.0335 (6) | −0.0011 (5) | 0.0237 (5) | 0.0088 (5) |
P1 | 0.0254 (5) | 0.0275 (6) | 0.0267 (5) | −0.0005 (4) | 0.0184 (4) | 0.0022 (4) |
C1 | 0.043 (2) | 0.026 (2) | 0.035 (2) | −0.0058 (18) | 0.0298 (19) | −0.0052 (18) |
C2 | 0.064 (3) | 0.044 (3) | 0.058 (3) | −0.017 (2) | 0.045 (3) | −0.017 (2) |
C3 | 0.049 (2) | 0.037 (3) | 0.062 (3) | −0.002 (2) | 0.046 (2) | −0.009 (2) |
C4 | 0.063 (3) | 0.051 (3) | 0.039 (3) | −0.013 (2) | 0.038 (2) | −0.004 (2) |
C5 | 0.0260 (19) | 0.040 (3) | 0.037 (2) | −0.0035 (18) | 0.0195 (18) | −0.001 (2) |
C6 | 0.033 (2) | 0.079 (4) | 0.063 (3) | −0.002 (2) | 0.036 (2) | −0.006 (3) |
C7 | 0.027 (2) | 0.052 (3) | 0.046 (3) | 0.012 (2) | 0.012 (2) | 0.012 (2) |
C8 | 0.040 (2) | 0.051 (3) | 0.076 (3) | −0.017 (2) | 0.039 (3) | −0.009 (3) |
N1 | 0.0247 (15) | 0.0245 (17) | 0.0235 (16) | 0.0015 (13) | 0.0165 (14) | 0.0000 (14) |
P2 | 0.0224 (5) | 0.0264 (6) | 0.0246 (5) | 0.0022 (4) | 0.0169 (4) | 0.0024 (4) |
C9 | 0.0216 (18) | 0.033 (2) | 0.0239 (19) | −0.0015 (16) | 0.0137 (17) | 0.0027 (18) |
C10 | 0.032 (2) | 0.039 (3) | 0.028 (2) | −0.0026 (19) | 0.0159 (18) | 0.002 (2) |
C11 | 0.034 (2) | 0.040 (3) | 0.030 (2) | −0.0006 (18) | 0.0219 (19) | 0.0044 (19) |
C12 | 0.030 (2) | 0.037 (3) | 0.035 (2) | 0.0093 (18) | 0.0221 (19) | 0.0105 (19) |
C13 | 0.0298 (19) | 0.029 (2) | 0.035 (2) | 0.0031 (17) | 0.0239 (18) | −0.0015 (18) |
C14 | 0.033 (2) | 0.030 (2) | 0.048 (3) | 0.0108 (18) | 0.025 (2) | 0.007 (2) |
C15 | 0.050 (2) | 0.044 (3) | 0.055 (3) | 0.009 (2) | 0.044 (2) | −0.001 (2) |
C16 | 0.040 (2) | 0.027 (2) | 0.048 (3) | −0.0022 (18) | 0.031 (2) | −0.007 (2) |
S2 | 0.0253 (5) | 0.0324 (6) | 0.0265 (5) | −0.0007 (4) | 0.0190 (4) | 0.0016 (4) |
S3 | 0.0317 (7) | 0.0255 (8) | 0.0392 (8) | 0.000 | 0.0269 (7) | 0.000 |
C17 | 0.070 (9) | 0.126 (14) | 0.092 (11) | −0.007 (9) | 0.059 (9) | 0.015 (10) |
C18 | 0.041 (6) | 0.062 (8) | 0.053 (6) | −0.012 (6) | 0.028 (6) | −0.003 (6) |
C19 | 0.054 (6) | 0.042 (7) | 0.098 (11) | 0.013 (5) | 0.048 (7) | 0.020 (6) |
C20 | 0.070 (8) | 0.056 (8) | 0.092 (10) | 0.005 (6) | 0.055 (7) | 0.015 (7) |
C21 | 0.045 (6) | 0.084 (9) | 0.074 (8) | −0.014 (6) | 0.034 (6) | −0.013 (7) |
C22 | 0.070 (9) | 0.051 (8) | 0.083 (9) | 0.004 (8) | 0.059 (8) | 0.009 (7) |
C23 | 0.068 (6) | 0.042 (5) | 0.045 (5) | −0.020 (10) | 0.037 (5) | −0.006 (11) |
S1—P1 | 1.9745 (15) | C10—H10C | 0.9800 |
P1—N1 | 1.626 (3) | C11—H11A | 0.9800 |
P1—C5 | 1.869 (4) | C11—H11B | 0.9800 |
P1—C1 | 1.872 (4) | C11—H11C | 0.9800 |
C1—C3 | 1.539 (5) | C12—H12A | 0.9800 |
C1—C2 | 1.542 (5) | C12—H12B | 0.9800 |
C1—C4 | 1.546 (5) | C12—H12C | 0.9800 |
C2—H2A | 0.9800 | C13—C15 | 1.533 (5) |
C2—H2B | 0.9800 | C13—C14 | 1.534 (5) |
C2—H2C | 0.9800 | C13—C16 | 1.537 (5) |
C3—H3A | 0.9800 | C14—H14A | 0.9800 |
C3—H3B | 0.9800 | C14—H14B | 0.9800 |
C3—H3C | 0.9800 | C14—H14C | 0.9800 |
C4—H4A | 0.9800 | C15—H15A | 0.9800 |
C4—H4B | 0.9800 | C15—H15B | 0.9800 |
C4—H4C | 0.9800 | C15—H15C | 0.9800 |
C5—C8 | 1.532 (5) | C16—H16A | 0.9800 |
C5—C7 | 1.533 (5) | C16—H16B | 0.9800 |
C5—C6 | 1.540 (6) | C16—H16C | 0.9800 |
C6—H6A | 0.9800 | S2—S3 | 2.0642 (13) |
C6—H6B | 0.9800 | S3—S2i | 2.0642 (13) |
C6—H6C | 0.9800 | C17—C18 | 1.495 (13) |
C7—H7A | 0.9800 | C17—H17A | 0.9800 |
C7—H7B | 0.9800 | C17—H17B | 0.9800 |
C7—H7C | 0.9800 | C17—H17C | 0.9800 |
C8—H8A | 0.9800 | C18—C23 | 1.386 (5) |
C8—H8B | 0.9800 | C18—C19 | 1.389 (5) |
C8—H8C | 0.9800 | C19—C20 | 1.388 (5) |
N1—P2 | 1.553 (3) | C19—H19A | 0.9500 |
P2—C9 | 1.853 (3) | C20—C21 | 1.386 (5) |
P2—C13 | 1.864 (4) | C20—H20A | 0.9500 |
P2—S2 | 2.1612 (14) | C21—C22 | 1.386 (5) |
C9—C12 | 1.531 (5) | C21—H21A | 0.9500 |
C9—C10 | 1.536 (5) | C22—C23 | 1.387 (5) |
C9—C11 | 1.542 (5) | C22—H22A | 0.9500 |
C10—H10A | 0.9800 | C23—H23A | 0.9500 |
C10—H10B | 0.9800 | ||
N1—P1—C5 | 103.02 (17) | C10—C9—P2 | 113.6 (3) |
N1—P1—C1 | 107.95 (16) | C11—C9—P2 | 108.6 (2) |
C5—P1—C1 | 111.93 (18) | C9—C10—H10A | 109.5 |
N1—P1—S1 | 117.34 (11) | C9—C10—H10B | 109.5 |
C5—P1—S1 | 108.42 (14) | H10A—C10—H10B | 109.5 |
C1—P1—S1 | 108.19 (13) | C9—C10—H10C | 109.5 |
C3—C1—C2 | 108.4 (3) | H10A—C10—H10C | 109.5 |
C3—C1—C4 | 108.8 (3) | H10B—C10—H10C | 109.5 |
C2—C1—C4 | 108.5 (3) | C9—C11—H11A | 109.5 |
C3—C1—P1 | 106.8 (3) | C9—C11—H11B | 109.5 |
C2—C1—P1 | 111.5 (3) | H11A—C11—H11B | 109.5 |
C4—C1—P1 | 112.8 (3) | C9—C11—H11C | 109.5 |
C1—C2—H2A | 109.5 | H11A—C11—H11C | 109.5 |
C1—C2—H2B | 109.5 | H11B—C11—H11C | 109.5 |
H2A—C2—H2B | 109.5 | C9—C12—H12A | 109.5 |
C1—C2—H2C | 109.5 | C9—C12—H12B | 109.5 |
H2A—C2—H2C | 109.5 | H12A—C12—H12B | 109.5 |
H2B—C2—H2C | 109.5 | C9—C12—H12C | 109.5 |
C1—C3—H3A | 109.5 | H12A—C12—H12C | 109.5 |
C1—C3—H3B | 109.5 | H12B—C12—H12C | 109.5 |
H3A—C3—H3B | 109.5 | C15—C13—C14 | 108.6 (3) |
C1—C3—H3C | 109.5 | C15—C13—C16 | 109.8 (3) |
H3A—C3—H3C | 109.5 | C14—C13—C16 | 107.4 (3) |
H3B—C3—H3C | 109.5 | C15—C13—P2 | 111.5 (3) |
C1—C4—H4A | 109.5 | C14—C13—P2 | 106.4 (2) |
C1—C4—H4B | 109.5 | C16—C13—P2 | 113.0 (2) |
H4A—C4—H4B | 109.5 | C13—C14—H14A | 109.5 |
C1—C4—H4C | 109.5 | C13—C14—H14B | 109.5 |
H4A—C4—H4C | 109.5 | H14A—C14—H14B | 109.5 |
H4B—C4—H4C | 109.5 | C13—C14—H14C | 109.5 |
C8—C5—C7 | 109.4 (3) | H14A—C14—H14C | 109.5 |
C8—C5—C6 | 108.5 (4) | H14B—C14—H14C | 109.5 |
C7—C5—C6 | 108.9 (4) | C13—C15—H15A | 109.5 |
C8—C5—P1 | 111.6 (3) | C13—C15—H15B | 109.5 |
C7—C5—P1 | 112.8 (3) | H15A—C15—H15B | 109.5 |
C6—C5—P1 | 105.5 (2) | C13—C15—H15C | 109.5 |
C5—C6—H6A | 109.5 | H15A—C15—H15C | 109.5 |
C5—C6—H6B | 109.5 | H15B—C15—H15C | 109.5 |
H6A—C6—H6B | 109.5 | C13—C16—H16A | 109.5 |
C5—C6—H6C | 109.5 | C13—C16—H16B | 109.5 |
H6A—C6—H6C | 109.5 | H16A—C16—H16B | 109.5 |
H6B—C6—H6C | 109.5 | C13—C16—H16C | 109.5 |
C5—C7—H7A | 109.5 | H16A—C16—H16C | 109.5 |
C5—C7—H7B | 109.5 | H16B—C16—H16C | 109.5 |
H7A—C7—H7B | 109.5 | S3—S2—P2 | 115.50 (5) |
C5—C7—H7C | 109.5 | S2—S3—S2i | 106.79 (8) |
H7A—C7—H7C | 109.5 | C23—C18—C19 | 119.8 (10) |
H7B—C7—H7C | 109.5 | C23—C18—C17 | 120.2 (6) |
C5—C8—H8A | 109.5 | C19—C18—C17 | 120.0 (6) |
C5—C8—H8B | 109.5 | C20—C19—C18 | 122.0 (9) |
H8A—C8—H8B | 109.5 | C20—C19—H19A | 119.0 |
C5—C8—H8C | 109.5 | C18—C19—H19A | 119.0 |
H8A—C8—H8C | 109.5 | C21—C20—C19 | 118.2 (10) |
H8B—C8—H8C | 109.5 | C21—C20—H20A | 120.9 |
P2—N1—P1 | 155.41 (19) | C19—C20—H20A | 120.9 |
N1—P2—C9 | 115.57 (16) | C20—C21—C22 | 119.7 (10) |
N1—P2—C13 | 110.37 (15) | C20—C21—H21A | 120.1 |
C9—P2—C13 | 113.57 (17) | C22—C21—H21A | 120.1 |
N1—P2—S2 | 101.01 (12) | C21—C22—C23 | 122.3 (11) |
C9—P2—S2 | 110.37 (12) | C21—C22—H22A | 118.9 |
C13—P2—S2 | 104.67 (13) | C23—C22—H22A | 118.9 |
C12—C9—C10 | 109.4 (3) | C18—C23—C22 | 118.0 (11) |
C12—C9—C11 | 108.1 (3) | C18—C23—H23A | 121.0 |
C10—C9—C11 | 109.4 (3) | C22—C23—H23A | 121.0 |
C12—C9—P2 | 107.6 (2) | ||
P2—S2—S3—S2i | −96.81 (6) | S2—P2—N1—P1 | −87.9 (5) |
S1—P1—N1—P2 | −43.0 (5) | N1—P2—S2—S3 | 174.00 (12) |
Symmetry code: (i) −x, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C32H72N2P4S5·C7H8 |
Mr | 861.23 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 173 |
a, b, c (Å) | 22.271 (5), 18.970 (4), 15.610 (3) |
β (°) | 132.79 (3) |
V (Å3) | 4840 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.40 |
Crystal size (mm) | 0.10 × 0.03 × 0.03 |
Data collection | |
Diffractometer | Nonius Kappa CCD area-detector diffractometer |
Absorption correction | Integration (SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.961, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19034, 4274, 2612 |
Rint | 0.070 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.122, 1.01 |
No. of reflections | 4274 |
No. of parameters | 271 |
No. of restraints | 11 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.35 |
Computer programs: COLLECT (Nonius, 1998), DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).
S1—P1 | 1.9745 (15) | P2—S2 | 2.1612 (14) |
P1—N1 | 1.626 (3) | S2—S3 | 2.0642 (13) |
N1—P2 | 1.553 (3) | ||
N1—P1—S1 | 117.34 (11) | S3—S2—P2 | 115.50 (5) |
P2—N1—P1 | 155.41 (19) | S2—S3—S2i | 106.79 (8) |
N1—P2—S2 | 101.01 (12) | ||
P2—S2—S3—S2i | −96.81 (6) | S2—P2—N1—P1 | −87.9 (5) |
S1—P1—N1—P2 | −43.0 (5) | N1—P2—S2—S3 | 174.00 (12) |
Symmetry code: (i) −x, y, −z+3/2. |
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Recently, we described the synthesis and structure of the dimer (SPtBu2NPtBu2PS–)2, (I), which is formed by one-electron oxidation of the corresponding monoanion, [(SPtBu2)2N]-, with iodine (Fig. 1; Ritch et al., 2007). Compound (I) was obtained upon recrystallization of a concentrated solution of the crude product from tetrahydrofuran (THF). We now report the isolation of the minor product of that oxidation, (SPtBu2NPtBu2PS–)2S, (II), as colourless block-like crystals when toluene is used as the recrystallization solvent. The identity of complex (II) as the toluene solvate was established by a single-crystal X-ray diffraction study.
Complexes (III) (Fig. 1), in which a central divalent chalcogen EII (E = Se or Te) is coordinated to two dichalcogenoimidodiphosphinate ligands, [(E'PR2)2N]- (E' = S or Se), have been prepared and structurally characterized for the following combinations of chalcogens: Se(S4) (Husebye & Maartmann-Moe, 1983), Te(S4) (Bjørnevåg et al., 1982, Birdsall et al., 2000), Se(Se4) (Cea-Olivares et al., 1998, 2005), Te(Se4) (Novosad et al., 1998, Birdsall et al., 2000) and Te(S2Se2) (Sekar & Ibers, 2003). All these examples exhibit a central four-coordinate chalcogen(II) atom which is chelated by two bidentate dichalcogenoimidodiphosphinate ligands. The geometry of the complexes is regular square-planar in the cases of Se(Se4) and Te(Se4), but distortions arising from the different sizes of chalcogen donors are observed for Te(S2Se2). The majority of the Te(S4) complexes are also square-planar, even for unsymmetrical dichalcogenoimidodiphosphinate ligands, [(E'PR2)(E'PR'2)N]- (R ≠ R'). However, in one example the different electronic effects of the substituents in Te[(SP(OPh)2)(SPEt2)N]2 result in Te—S bond lengths that differ by ca 0.4 Å (Birdsall et al., 2000). In contrast with the Te(S4) complexes, the only known Se(S4) complex adopts an approximately trapezoidal planar arrangement, with a disparity of 0.7–0.8 Å in the Se—S distances (Husebye & Maartmann-Moe, 1983).
The title complex, (II), is the first example of a bis(dichalcogenoimidodiphosphinate) in which the central chalcogen is sulfur(II). In contrast with the congeneric Se(S4) and Te(S4) complexes (see above), (II) adopts an acyclic rather than a spirocyclic (or pseudo-spirocyclic) structure; a two-coordinate SII atom is bonded in an S-monodentate fashion to two [(SPtBu2)2N]- monoanions, each of which carries a non-bonding (terminal) P═S functionality. The molecules of (II) reside on a twofold axis that bisects the S—S—S angle of 106.79 (8)°, which is consistent with two stereochemically active lone pairs on S. A view of the structure of (II) is shown in Fig. 2, with selected bond distances and angles listed in Table 1. As expected, the terminal P═S distance [1.9745 (15) Å] reflects a typical double-bond value [cf. 1.974 (1) Å for the related disulfide, (I)], while the internal P—S distance is significantly longer [Shorter in Abstract - please clarify] (by ca 0.19 Å) and close to the distance of 2.135 (1) Å reported for (I) (Ritch et al., 2007). Bond-order alternation in the P—N linkages is indicated by a difference of ca 0.07 Å in the bond lengths. The S—S distances are close to the single-bond value of 2.05 Å (Steudel et al., 2005) and the S—S—S bond angle is similar to reported values for trisulfides (Chivers et al., 1998). The S—P—N—P torsion angles within each [(SPtBu2)2N]- ligand indicate the non-planarity of this framework, and the virtual torsion angle S1—P1—P2—S2 of ca 125° demonstrates the anti configuration of the two S atoms. The two ligands also coordinate to the central S atom in an anti fashion.
Consistent with the solid-state structure, the solution 31P NMR spectrum of (II) in D8-THF at 233 K consists of two mutually coupled doublets. However, upon warming the solution to room temperature a (reversible) collapse of these signals to give one broad resonance is observed, suggesting the occurrence of a dynamic exchange process that renders the two P environments equivalent at higher temperatures. A four-coordinate complex of the type (III) is a possible intermediate in this interchange. In a related observation, two broad resonances were reported for the distorted square-planar complex Te[(SP(OPh)2)(SPEt2)N]2 (see above) at room temperature, indicative of fluxional behaviour, but decomposition occurred at higher temperatures (Birdsall et al., 2000).
The structural characterization of (II) reveals an interesting trend in the bonding arrangements for bis(imidodithiodiphosphinates) with a central E(S4) core. As the size of the central chalcogen decreases from Te to S, the structure changes from square-planar (E = Te) to trapezoidal planar (E = Se) and, finally, to an acyclic two-coordinate complex (E = S), despite the large bite of the ligand. This sequence manifests the decreasing ability of the central chalcogen(II) along the series Te > Se > S to accept ligand electron density from imidodithiodiphosphinates, which are relatively weak ligands (Husebye & Maartmann-Moe, 1983).