Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100014979/qa0422sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100014979/qa0422Isup2.hkl |
CCDC reference: 156188
Mixing TiCl4.2THF with LiSPh in a 1:6 stoichiometry in diethyl ether and storing the filtered solution at 263 K afforded black crystals of the title compound in low isolated yield.
Data collection: CAD-4 Operations Manual (Enraf-Nonius, 1977); cell refinement: CAD-4 Operations Manual; data reduction: PROCESS MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
[Li(C4H8O)4][Ti2(C6H5S)9] | Mo Kα radiation, λ = 0.71073 Å |
Mr = 1372.91 | Cell parameters from 25 reflections |
Cubic, P213 | θ = 7.4–8.3° |
a = 19.096 (3) Å | µ = 0.55 mm−1 |
V = 6963.9 (19) Å3 | T = 120 K |
Z = 4 | Block, black |
F(000) = 2880 | 0.30 × 0.25 × 0.20 mm |
Dx = 1.300 Mg m−3 |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.000 |
Graphite monochromator | θmax = 26.1°, θmin = 1.5° |
θ/2θ scans | h = 0→23 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→23 |
Tmin = 0.885, Tmax = 0.897 | l = 0→23 |
2511 measured reflections | 3 standard reflections every 50 min |
2511 independent reflections | intensity decay: 0.1% |
1802 reflections with I > 2σ(I) |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.127 | w = 1/[σ2(Fo2) + (0.0892P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.98 | (Δ/σ)max = 0.022 |
2511 reflections | Δρmax = 0.57 e Å−3 |
251 parameters | Δρmin = −0.27 e Å−3 |
36 restraints | Absolute structure: Flack (1983), no Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.05 (7) |
[Li(C4H8O)4][Ti2(C6H5S)9] | Z = 4 |
Mr = 1372.91 | Mo Kα radiation |
Cubic, P213 | µ = 0.55 mm−1 |
a = 19.096 (3) Å | T = 120 K |
V = 6963.9 (19) Å3 | 0.30 × 0.25 × 0.20 mm |
Enraf-Nonius CAD-4 diffractometer | 1802 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.000 |
Tmin = 0.885, Tmax = 0.897 | 3 standard reflections every 50 min |
2511 measured reflections | intensity decay: 0.1% |
2511 independent reflections |
R[F2 > 2σ(F2)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.127 | Δρmax = 0.57 e Å−3 |
S = 0.98 | Δρmin = −0.27 e Å−3 |
2511 reflections | Absolute structure: Flack (1983), no Friedel pairs |
251 parameters | Absolute structure parameter: 0.05 (7) |
36 restraints |
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) | |
Ti1 | 0.38661 (5) | 0.11339 (5) | 0.88661 (5) | 0.0477 (4) | |
Ti2 | 0.49381 (4) | 0.00619 (4) | 0.99381 (4) | 0.0413 (3) | |
S1 | 0.28124 (8) | 0.07822 (9) | 0.83549 (8) | 0.0618 (4) | |
S2 | 0.50131 (7) | 0.13194 (6) | 0.95058 (7) | 0.0461 (3) | |
S3 | 0.59641 (7) | −0.03528 (7) | 0.94316 (7) | 0.0525 (3) | |
C1 | 0.2171 (3) | 0.0403 (3) | 0.8905 (3) | 0.0574 (14) | |
C2 | 0.2016 (3) | 0.0655 (3) | 0.9556 (4) | 0.0632 (15) | |
H2A | 0.2257 | 0.1040 | 0.9730 | 0.076* | |
C3 | 0.1509 (3) | 0.0343 (4) | 0.9952 (4) | 0.0772 (19) | |
H3A | 0.1412 | 0.0516 | 1.0397 | 0.093* | |
C4 | 0.1136 (4) | −0.0229 (4) | 0.9699 (5) | 0.084 (2) | |
H4A | 0.0798 | −0.0445 | 0.9976 | 0.101* | |
C5 | 0.1275 (4) | −0.0475 (4) | 0.9026 (4) | 0.0769 (19) | |
H5A | 0.1019 | −0.0846 | 0.8841 | 0.092* | |
C6 | 0.1797 (3) | −0.0163 (3) | 0.8638 (4) | 0.0685 (16) | |
H6A | 0.1901 | −0.0332 | 0.8193 | 0.082* | |
C7 | 0.5771 (3) | 0.1514 (3) | 0.9002 (3) | 0.0493 (12) | |
C8 | 0.6192 (3) | 0.2057 (3) | 0.9230 (3) | 0.0608 (14) | |
H8A | 0.6056 | 0.2320 | 0.9617 | 0.073* | |
C9 | 0.6816 (3) | 0.2216 (3) | 0.8890 (4) | 0.0696 (17) | |
H9A | 0.7094 | 0.2583 | 0.9049 | 0.083* | |
C10 | 0.7017 (3) | 0.1834 (4) | 0.8328 (4) | 0.0700 (18) | |
H10A | 0.7440 | 0.1928 | 0.8105 | 0.084* | |
C11 | 0.6592 (3) | 0.1310 (4) | 0.8094 (3) | 0.0640 (16) | |
H11A | 0.6729 | 0.1053 | 0.7704 | 0.077* | |
C12 | 0.5967 (3) | 0.1150 (3) | 0.8414 (3) | 0.0578 (14) | |
H12A | 0.5681 | 0.0800 | 0.8234 | 0.069* | |
C13 | 0.6659 (3) | −0.0333 (3) | 1.0036 (3) | 0.0587 (14) | |
C14 | 0.6881 (4) | −0.0919 (5) | 1.0352 (4) | 0.091 (2) | |
H14A | 0.6668 | −0.1346 | 1.0257 | 0.109* | |
C15 | 0.7462 (5) | −0.0878 (6) | 1.0848 (5) | 0.110 (3) | |
H15A | 0.7610 | −0.1272 | 1.1093 | 0.132* | |
C16 | 0.7774 (4) | −0.0265 (6) | 1.0940 (5) | 0.104 (3) | |
H16A | 0.8150 | −0.0239 | 1.1248 | 0.125* | |
C17 | 0.7577 (4) | 0.0301 (5) | 1.0620 (4) | 0.086 (2) | |
H17A | 0.7813 | 0.0720 | 1.0703 | 0.104* | |
C18 | 0.7024 (3) | 0.0289 (4) | 1.0159 (4) | 0.0703 (17) | |
H18A | 0.6893 | 0.0697 | 0.9928 | 0.084* | |
Li1 | 0.8070 (7) | −0.1930 (7) | 0.8070 (7) | 0.078 (5)* | |
O1 | 0.7208 (6) | −0.1396 (6) | 0.7979 (7) | 0.082 (4)* | 0.50 |
C21 | 0.6628 (10) | −0.1808 (10) | 0.7719 (14) | 0.121 (7)* | 0.50 |
H21A | 0.6706 | −0.1921 | 0.7230 | 0.145* | 0.50 |
H21B | 0.6598 | −0.2243 | 0.7980 | 0.145* | 0.50 |
C22 | 0.6049 (9) | −0.1463 (9) | 0.7784 (9) | 0.176 (6)* | 0.50 |
H22A | 0.5908 | −0.1404 | 0.8268 | 0.211* | 0.50 |
H22B | 0.5669 | −0.1664 | 0.7513 | 0.211* | 0.50 |
C23 | 0.6347 (7) | −0.0778 (7) | 0.7453 (8) | 0.076 (4)* | 0.50 |
H23A | 0.6409 | −0.0829 | 0.6951 | 0.091* | 0.50 |
H23B | 0.6039 | −0.0384 | 0.7542 | 0.091* | 0.50 |
C24 | 0.7055 (7) | −0.0681 (7) | 0.7823 (8) | 0.079 (4)* | 0.50 |
H24A | 0.7403 | −0.0476 | 0.7516 | 0.094* | 0.50 |
H24B | 0.7011 | −0.0400 | 0.8244 | 0.094* | 0.50 |
O1A | 0.7204 (7) | −0.1589 (8) | 0.7790 (8) | 0.098 (5)* | 0.50 |
C21A | 0.6583 (7) | −0.1818 (8) | 0.8163 (9) | 0.079 (4)* | 0.50 |
H21C | 0.6526 | −0.2322 | 0.8139 | 0.095* | 0.50 |
H21D | 0.6594 | −0.1674 | 0.8650 | 0.095* | 0.50 |
C22A | 0.6049 (9) | −0.1463 (9) | 0.7784 (9) | 0.176 (6)* | 0.50 |
H22C | 0.5676 | −0.1794 | 0.7688 | 0.211* | 0.50 |
H22D | 0.5857 | −0.1100 | 0.8082 | 0.211* | 0.50 |
C23A | 0.6235 (9) | −0.1180 (10) | 0.7198 (9) | 0.095 (5)* | 0.50 |
H23C | 0.6115 | −0.0686 | 0.7194 | 0.114* | 0.50 |
H23D | 0.6003 | −0.1408 | 0.6808 | 0.114* | 0.50 |
C24A | 0.6963 (12) | −0.1267 (16) | 0.7151 (14) | 0.160 (10)* | 0.50 |
H24C | 0.7189 | −0.0816 | 0.7088 | 0.192* | 0.50 |
H24D | 0.7078 | −0.1561 | 0.6754 | 0.192* | 0.50 |
O2A | 0.8842 (7) | −0.1439 (10) | 0.8539 (10) | 0.082 (5)* | 0.33 |
C31 | 0.9383 (19) | −0.118 (3) | 0.901 (2) | 0.265 (18)* | 0.33 |
H31A | 0.9194 | −0.0909 | 0.9391 | 0.318* | 0.33 |
H31B | 0.9676 | −0.1556 | 0.9187 | 0.318* | 0.33 |
C32 | 0.972 (3) | −0.078 (3) | 0.853 (3) | 0.265 (18)* | 0.33 |
H32A | 1.0143 | −0.0572 | 0.8721 | 0.318* | 0.33 |
H32B | 0.9422 | −0.0414 | 0.8344 | 0.318* | 0.33 |
C33 | 0.989 (2) | −0.134 (4) | 0.797 (3) | 0.265 (18)* | 0.33 |
H33A | 0.9994 | −0.1126 | 0.7518 | 0.318* | 0.33 |
H33B | 1.0277 | −0.1634 | 0.8110 | 0.318* | 0.33 |
C34 | 0.930 (2) | −0.167 (3) | 0.796 (2) | 0.265 (18)* | 0.33 |
H34A | 0.9384 | −0.2172 | 0.8009 | 0.318* | 0.33 |
H34B | 0.9062 | −0.1596 | 0.7519 | 0.318* | 0.33 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ti1 | 0.0477 (4) | 0.0477 (4) | 0.0477 (4) | 0.0015 (4) | −0.0015 (4) | 0.0015 (4) |
Ti2 | 0.0413 (3) | 0.0413 (3) | 0.0413 (3) | −0.0006 (4) | 0.0006 (4) | −0.0006 (4) |
S1 | 0.0502 (8) | 0.0751 (10) | 0.0602 (9) | 0.0004 (7) | −0.0082 (7) | 0.0007 (7) |
S2 | 0.0480 (7) | 0.0435 (6) | 0.0469 (6) | −0.0024 (6) | 0.0007 (6) | 0.0013 (5) |
S3 | 0.0489 (7) | 0.0551 (8) | 0.0536 (8) | 0.0033 (6) | 0.0045 (6) | −0.0030 (6) |
C1 | 0.042 (3) | 0.064 (3) | 0.066 (3) | 0.005 (3) | −0.006 (3) | −0.001 (3) |
C2 | 0.043 (3) | 0.071 (4) | 0.076 (4) | 0.011 (3) | −0.004 (3) | −0.001 (3) |
C3 | 0.053 (3) | 0.092 (5) | 0.086 (5) | 0.017 (3) | 0.014 (4) | −0.002 (4) |
C4 | 0.053 (4) | 0.086 (5) | 0.114 (6) | 0.002 (3) | 0.012 (4) | 0.018 (4) |
C5 | 0.068 (4) | 0.059 (4) | 0.104 (5) | −0.007 (3) | −0.007 (4) | 0.003 (4) |
C6 | 0.058 (3) | 0.067 (4) | 0.081 (4) | 0.008 (3) | −0.007 (3) | −0.013 (3) |
C7 | 0.050 (3) | 0.050 (3) | 0.049 (3) | −0.004 (2) | −0.003 (2) | 0.011 (2) |
C8 | 0.057 (3) | 0.056 (3) | 0.070 (4) | −0.006 (3) | −0.002 (3) | −0.002 (3) |
C9 | 0.061 (4) | 0.064 (4) | 0.084 (4) | −0.017 (3) | −0.010 (3) | 0.013 (4) |
C10 | 0.053 (3) | 0.082 (4) | 0.075 (4) | −0.004 (3) | 0.010 (3) | 0.028 (4) |
C11 | 0.064 (4) | 0.073 (4) | 0.056 (3) | −0.005 (3) | 0.003 (3) | 0.013 (3) |
C12 | 0.059 (3) | 0.065 (3) | 0.050 (3) | −0.003 (3) | 0.000 (3) | 0.012 (3) |
C13 | 0.044 (3) | 0.070 (4) | 0.062 (3) | 0.011 (3) | 0.004 (3) | 0.000 (3) |
C14 | 0.074 (4) | 0.105 (6) | 0.093 (6) | 0.012 (4) | −0.001 (4) | 0.021 (5) |
C15 | 0.079 (5) | 0.135 (8) | 0.117 (7) | 0.042 (6) | −0.004 (5) | 0.045 (6) |
C16 | 0.061 (5) | 0.130 (8) | 0.120 (7) | 0.008 (5) | −0.018 (5) | −0.012 (6) |
C17 | 0.058 (4) | 0.110 (6) | 0.090 (5) | −0.003 (4) | −0.014 (4) | −0.002 (5) |
C18 | 0.053 (3) | 0.085 (4) | 0.074 (4) | −0.009 (3) | −0.003 (3) | −0.008 (3) |
Ti1—S1i | 2.3351 (17) | C14—C15 | 1.462 (13) |
Ti1—S1ii | 2.3351 (17) | C15—C16 | 1.325 (14) |
Ti1—S1 | 2.3351 (17) | C16—C17 | 1.298 (13) |
Ti1—S2 | 2.5329 (17) | C17—C18 | 1.374 (10) |
Ti1—S2ii | 2.5330 (17) | Li1—O1A | 1.856 (17) |
Ti1—S2i | 2.5330 (17) | Li1—O1Aiii | 1.856 (17) |
Ti2—S3i | 2.3240 (15) | Li1—O1Aiv | 1.856 (17) |
Ti2—S3 | 2.3240 (15) | Li1—O1iii | 1.944 (13) |
Ti2—S3ii | 2.3241 (15) | Li1—O1 | 1.944 (13) |
Ti2—S2ii | 2.5434 (16) | Li1—O1iv | 1.944 (13) |
Ti2—S2 | 2.5435 (16) | Li1—O2Aiv | 1.96 (3) |
Ti2—S2i | 2.5435 (16) | Li1—O2A | 1.96 (3) |
S1—C1 | 1.770 (6) | Li1—O2Aiii | 1.96 (3) |
S2—C7 | 1.778 (5) | Li1—C34iv | 2.40 (4) |
S3—C13 | 1.759 (6) | Li1—C34 | 2.40 (4) |
C1—C2 | 1.365 (9) | Li1—C34iii | 2.40 (4) |
C1—C6 | 1.392 (9) | O1—C24 | 1.428 (14) |
C2—C3 | 1.365 (9) | O1—C21 | 1.446 (16) |
C3—C4 | 1.392 (11) | C21—C22 | 1.29 (2) |
C4—C5 | 1.394 (11) | C22—C23 | 1.56 (2) |
C5—C6 | 1.378 (10) | C23—C24 | 1.536 (19) |
C7—C12 | 1.373 (8) | O1A—C24A | 1.44 (2) |
C7—C8 | 1.382 (8) | O1A—C21A | 1.452 (18) |
C8—C9 | 1.391 (9) | C23A—C24A | 1.40 (2) |
C9—C10 | 1.353 (10) | O2A—C31 | 1.452 (19) |
C10—C11 | 1.365 (10) | O2A—C34 | 1.471 (19) |
C11—C12 | 1.375 (8) | C31—C32 | 1.36 (4) |
C13—C14 | 1.341 (10) | C32—C33 | 1.54 (4) |
C13—C18 | 1.397 (9) | C33—C34 | 1.31 (4) |
S1i—Ti1—S1ii | 90.46 (7) | O1—Li1—O1iv | 114.5 (6) |
S1i—Ti1—S1 | 90.45 (7) | O1A—Li1—O2Aiv | 106.3 (9) |
S1ii—Ti1—S1 | 90.45 (7) | O1Aiii—Li1—O2Aiv | 118.8 (11) |
S1i—Ti1—S2 | 96.22 (5) | O1Aiv—Li1—O2Aiv | 129.3 (10) |
S1ii—Ti1—S2 | 95.87 (5) | O1iii—Li1—O2Aiv | 103.4 (10) |
S1—Ti1—S2 | 170.75 (7) | O1—Li1—O2Aiv | 92.0 (8) |
S1i—Ti1—S2ii | 95.87 (5) | O1iv—Li1—O2Aiv | 115.2 (10) |
S1ii—Ti1—S2ii | 170.75 (7) | O1A—Li1—O2A | 129.3 (11) |
S1—Ti1—S2ii | 96.22 (5) | O1Aiii—Li1—O2A | 106.3 (9) |
S2—Ti1—S2ii | 76.78 (6) | O1Aiv—Li1—O2A | 118.8 (11) |
S1i—Ti1—S2i | 170.75 (7) | O1iii—Li1—O2A | 92.0 (8) |
S1ii—Ti1—S2i | 96.22 (5) | O1—Li1—O2A | 115.2 (10) |
S1—Ti1—S2i | 95.87 (5) | O1iv—Li1—O2A | 103.4 (10) |
S2—Ti1—S2i | 76.78 (6) | O2Aiv—Li1—O2A | 23.2 (7) |
S2ii—Ti1—S2i | 76.78 (6) | O1A—Li1—O2Aiii | 118.8 (11) |
S3i—Ti2—S3 | 101.86 (6) | O1Aiii—Li1—O2Aiii | 129.3 (11) |
S3i—Ti2—S3ii | 101.85 (6) | O1Aiv—Li1—O2Aiii | 106.3 (9) |
S3—Ti2—S3ii | 101.86 (6) | O1iii—Li1—O2Aiii | 115.2 (10) |
S3i—Ti2—S2ii | 158.44 (7) | O1—Li1—O2Aiii | 103.4 (10) |
S3—Ti2—S2ii | 82.04 (5) | O1iv—Li1—O2Aiii | 92.0 (8) |
S3ii—Ti2—S2ii | 97.99 (5) | O2Aiv—Li1—O2Aiii | 23.2 (7) |
S3i—Ti2—S2 | 82.04 (5) | O2A—Li1—O2Aiii | 23.2 (7) |
S3—Ti2—S2 | 98.00 (5) | O1A—Li1—C34iv | 68.9 (9) |
S3ii—Ti2—S2 | 158.43 (7) | O1Aiii—Li1—C34iv | 119.5 (19) |
S2ii—Ti2—S2 | 76.41 (6) | O1Aiv—Li1—C34iv | 140.6 (19) |
S3i—Ti2—S2i | 98.00 (5) | O1iii—Li1—C34iv | 107.7 (19) |
S3—Ti2—S2i | 158.43 (7) | O1—Li1—C34iv | 55.6 (10) |
S3ii—Ti2—S2i | 82.04 (5) | O1iv—Li1—C34iv | 135.4 (18) |
S2ii—Ti2—S2i | 76.41 (6) | O2Aiv—Li1—C34iv | 37.7 (8) |
S2—Ti2—S2i | 76.41 (6) | O2A—Li1—C34iv | 60.4 (11) |
C1—S1—Ti1 | 117.8 (2) | O2Aiii—Li1—C34iv | 56.2 (12) |
C7—S2—Ti1 | 118.21 (18) | O1A—Li1—C34 | 140.6 (19) |
C7—S2—Ti2 | 114.77 (18) | O1Aiii—Li1—C34 | 68.9 (9) |
Ti1—S2—Ti2 | 88.61 (5) | O1Aiv—Li1—C34 | 119.5 (19) |
C13—S3—Ti2 | 110.84 (19) | O1iii—Li1—C34 | 55.6 (10) |
C2—C1—C6 | 119.8 (6) | O1—Li1—C34 | 135.4 (18) |
C2—C1—S1 | 123.1 (5) | O1iv—Li1—C34 | 107.7 (19) |
C6—C1—S1 | 117.0 (5) | O2Aiv—Li1—C34 | 56.2 (12) |
C1—C2—C3 | 120.2 (6) | O2A—Li1—C34 | 37.7 (8) |
C2—C3—C4 | 120.9 (7) | O2Aiii—Li1—C34 | 60.4 (11) |
C3—C4—C5 | 119.1 (7) | C34iv—Li1—C34 | 84.4 (12) |
C6—C5—C4 | 119.3 (7) | O1A—Li1—C34iii | 119.5 (19) |
C5—C6—C1 | 120.6 (6) | O1Aiii—Li1—C34iii | 140.6 (19) |
C12—C7—C8 | 118.7 (5) | O1Aiv—Li1—C34iii | 68.9 (9) |
C12—C7—S2 | 124.0 (4) | O1iii—Li1—C34iii | 135.4 (18) |
C8—C7—S2 | 117.4 (4) | O1—Li1—C34iii | 107.7 (19) |
C7—C8—C9 | 121.0 (6) | O1iv—Li1—C34iii | 55.6 (10) |
C10—C9—C8 | 119.8 (6) | O2Aiv—Li1—C34iii | 60.4 (11) |
C9—C10—C11 | 119.1 (6) | O2A—Li1—C34iii | 56.2 (12) |
C10—C11—C12 | 122.2 (6) | O2Aiii—Li1—C34iii | 37.7 (8) |
C7—C12—C11 | 119.2 (6) | C34iv—Li1—C34iii | 84.4 (12) |
C14—C13—C18 | 118.4 (6) | C34—Li1—C34iii | 84.4 (12) |
C14—C13—S3 | 121.0 (6) | C24—O1—C21 | 106.9 (12) |
C18—C13—S3 | 120.4 (5) | C24—O1—Li1 | 133.9 (10) |
C13—C14—C15 | 119.1 (9) | C21—O1—Li1 | 113.2 (13) |
C16—C15—C14 | 118.3 (8) | C22—C21—O1 | 110.3 (16) |
C17—C16—C15 | 122.9 (8) | C21—C22—C23 | 94.4 (15) |
C16—C17—C18 | 120.6 (8) | C24—C23—C22 | 103.6 (12) |
C17—C18—C13 | 120.4 (7) | O1—C24—C23 | 99.3 (10) |
O1A—Li1—O1Aiii | 99.0 (11) | C24A—O1A—C21A | 106.5 (13) |
O1A—Li1—O1Aiv | 99.0 (11) | C24A—O1A—Li1 | 132.7 (13) |
O1Aiii—Li1—O1Aiv | 99.0 (11) | C21A—O1A—Li1 | 118.7 (10) |
O1A—Li1—O1iii | 104.7 (9) | C23A—C24A—O1A | 108.3 (18) |
O1Aiii—Li1—O1iii | 15.4 (6) | C31—O2A—C34 | 98 (2) |
O1Aiv—Li1—O1iii | 111.7 (10) | C31—O2A—Li1 | 168 (3) |
O1A—Li1—O1 | 15.4 (6) | C34—O2A—Li1 | 87.5 (19) |
O1Aiii—Li1—O1 | 111.7 (10) | C32—C31—O2A | 97 (3) |
O1Aiv—Li1—O1 | 104.7 (9) | C31—C32—C33 | 100 (3) |
O1iii—Li1—O1 | 114.6 (6) | C34—C33—C32 | 99 (3) |
O1A—Li1—O1iv | 111.7 (10) | C33—C34—O2A | 111 (3) |
O1Aiii—Li1—O1iv | 104.7 (9) | C33—C34—Li1 | 161 (4) |
O1Aiv—Li1—O1iv | 15.4 (6) | O2A—C34—Li1 | 54.8 (14) |
O1iii—Li1—O1iv | 114.5 (6) | ||
S1i—Ti1—S1—C1 | −173.2 (2) | C34iii—Li1—O1—C21 | −111.8 (18) |
S1ii—Ti1—S1—C1 | −82.8 (2) | C24—O1—C21—C22 | −34 (3) |
S2—Ti1—S1—C1 | 50.4 (4) | Li1—O1—C21—C22 | 169.0 (16) |
S2ii—Ti1—S1—C1 | 90.8 (2) | O1—C21—C22—C23 | 48 (2) |
S2i—Ti1—S1—C1 | 13.5 (2) | C21—C22—C23—C24 | −46.6 (17) |
S1i—Ti1—S2—C7 | −16.7 (2) | C21—O1—C24—C23 | −0.6 (18) |
S1ii—Ti1—S2—C7 | −107.8 (2) | Li1—O1—C24—C23 | 149.2 (14) |
S1—Ti1—S2—C7 | 119.3 (4) | C22—C23—C24—O1 | 27.6 (14) |
S2ii—Ti1—S2—C7 | 77.9 (2) | O1Aiii—Li1—O1A—C24A | −30 (3) |
S2i—Ti1—S2—C7 | 157.2 (2) | O1Aiv—Li1—O1A—C24A | −131 (2) |
S1i—Ti1—S2—Ti2 | −134.22 (5) | O1iii—Li1—O1A—C24A | −16 (3) |
S1ii—Ti1—S2—Ti2 | 134.67 (5) | O1—Li1—O1A—C24A | 116 (4) |
S1—Ti1—S2—Ti2 | 1.8 (3) | O1iv—Li1—O1A—C24A | −140 (2) |
S2ii—Ti1—S2—Ti2 | −39.633 (19) | O2Aiv—Li1—O1A—C24A | 93 (2) |
S2i—Ti1—S2—Ti2 | 39.638 (19) | O2A—Li1—O1A—C24A | 89 (3) |
S3i—Ti2—S2—C7 | 99.6 (2) | O2Aiii—Li1—O1A—C24A | 114 (2) |
S3—Ti2—S2—C7 | −1.4 (2) | C34iv—Li1—O1A—C24A | 88 (3) |
S3ii—Ti2—S2—C7 | −158.3 (2) | C34—Li1—O1A—C24A | 37 (4) |
S2ii—Ti2—S2—C7 | −81.1 (2) | C34iii—Li1—O1A—C24A | 158 (2) |
S2i—Ti2—S2—C7 | −160.15 (19) | O1Aiii—Li1—O1A—C21A | 130.4 (11) |
S3i—Ti2—S2—Ti1 | −139.79 (5) | O1Aiv—Li1—O1A—C21A | 30 (2) |
S3—Ti2—S2—Ti1 | 119.27 (5) | O1iii—Li1—O1A—C21A | 145.1 (13) |
S3ii—Ti2—S2—Ti1 | −37.64 (15) | O1—Li1—O1A—C21A | −83 (3) |
S2ii—Ti2—S2—Ti1 | 39.511 (19) | O1iv—Li1—O1A—C21A | 21 (2) |
S2i—Ti2—S2—Ti1 | −39.516 (19) | O2Aiv—Li1—O1A—C21A | −105.9 (16) |
S3i—Ti2—S3—C13 | 12.7 (2) | O2A—Li1—O1A—C21A | −109.8 (15) |
S3ii—Ti2—S3—C13 | −92.2 (2) | O2Aiii—Li1—O1A—C21A | −84.6 (16) |
S2ii—Ti2—S3—C13 | 171.2 (2) | C34iv—Li1—O1A—C21A | −111 (2) |
S2—Ti2—S3—C13 | 96.2 (2) | C34—Li1—O1A—C21A | −161.9 (18) |
S2i—Ti2—S3—C13 | 169.4 (2) | C34iii—Li1—O1A—C21A | −41 (2) |
Ti1—S1—C1—C2 | 42.1 (5) | C21A—O1A—C24A—C23A | 11 (3) |
Ti1—S1—C1—C6 | −140.3 (4) | Li1—O1A—C24A—C23A | 173.7 (18) |
C6—C1—C2—C3 | 1.7 (9) | O1A—Li1—O2A—C31 | 117 (10) |
S1—C1—C2—C3 | 179.2 (5) | O1Aiii—Li1—O2A—C31 | −126 (10) |
C1—C2—C3—C4 | −0.7 (10) | O1Aiv—Li1—O2A—C31 | −16 (10) |
C2—C3—C4—C5 | −1.4 (10) | O1iii—Li1—O2A—C31 | −132 (10) |
C3—C4—C5—C6 | 2.5 (10) | O1—Li1—O2A—C31 | 109 (10) |
C4—C5—C6—C1 | −1.6 (10) | O1iv—Li1—O2A—C31 | −16 (10) |
C2—C1—C6—C5 | −0.5 (9) | O2Aiv—Li1—O2A—C31 | 107 (10) |
S1—C1—C6—C5 | −178.2 (5) | O2Aiii—Li1—O2A—C31 | 46 (10) |
Ti1—S2—C7—C12 | −47.5 (5) | C34iv—Li1—O2A—C31 | 119 (10) |
Ti2—S2—C7—C12 | 55.1 (5) | C34—Li1—O2A—C31 | −118 (11) |
Ti1—S2—C7—C8 | 133.9 (4) | C34iii—Li1—O2A—C31 | 14 (10) |
Ti2—S2—C7—C8 | −123.6 (4) | O1A—Li1—O2A—C34 | −125 (3) |
C12—C7—C8—C9 | −2.6 (9) | O1Aiii—Li1—O2A—C34 | −8 (3) |
S2—C7—C8—C9 | 176.1 (5) | O1Aiv—Li1—O2A—C34 | 102 (3) |
C7—C8—C9—C10 | −0.1 (9) | O1iii—Li1—O2A—C34 | −14 (3) |
C8—C9—C10—C11 | 1.8 (10) | O1—Li1—O2A—C34 | −133 (3) |
C9—C10—C11—C12 | −0.7 (9) | O1iv—Li1—O2A—C34 | 102 (3) |
C8—C7—C12—C11 | 3.6 (8) | O2Aiv—Li1—O2A—C34 | −135 (5) |
S2—C7—C12—C11 | −175.1 (4) | O2Aiii—Li1—O2A—C34 | 164 (5) |
C10—C11—C12—C7 | −2.0 (9) | C34iv—Li1—O2A—C34 | −123.4 (15) |
Ti2—S3—C13—C14 | 103.0 (6) | C34iii—Li1—O2A—C34 | 132.3 (15) |
Ti2—S3—C13—C18 | −81.5 (5) | C34—O2A—C31—C32 | 50 (4) |
C18—C13—C14—C15 | 4.2 (10) | Li1—O2A—C31—C32 | 167 (8) |
S3—C13—C14—C15 | 179.8 (6) | O2A—C31—C32—C33 | −57 (4) |
C13—C14—C15—C16 | −3.5 (13) | C31—C32—C33—C34 | 42 (7) |
C14—C15—C16—C17 | 1.3 (15) | C32—C33—C34—O2A | −9 (8) |
C15—C16—C17—C18 | −0.1 (15) | C32—C33—C34—Li1 | 27 (19) |
C16—C17—C18—C13 | 0.9 (12) | C31—O2A—C34—C33 | −24 (7) |
C14—C13—C18—C17 | −3.0 (10) | Li1—O2A—C34—C33 | 167 (6) |
S3—C13—C18—C17 | −178.6 (5) | C31—O2A—C34—Li1 | 169 (3) |
O1A—Li1—O1—C24 | −118 (3) | O1A—Li1—C34—C33 | 50 (17) |
O1Aiii—Li1—O1—C24 | −82 (2) | O1Aiii—Li1—C34—C33 | 129 (17) |
O1Aiv—Li1—O1—C24 | 171.9 (14) | O1Aiv—Li1—C34—C33 | −143 (16) |
O1iii—Li1—O1—C24 | −65 (2) | O1iii—Li1—C34—C33 | 120 (17) |
O1iv—Li1—O1—C24 | 159.3 (13) | O1—Li1—C34—C33 | 29 (17) |
O2Aiv—Li1—O1—C24 | 40.3 (17) | O1iv—Li1—C34—C33 | −132 (16) |
O2A—Li1—O1—C24 | 39.5 (19) | O2Aiv—Li1—C34—C33 | −23 (15) |
O2Aiii—Li1—O1—C24 | 60.8 (16) | O2A—Li1—C34—C33 | −43 (14) |
C34iv—Li1—O1—C24 | 30 (2) | O2Aiii—Li1—C34—C33 | −50 (15) |
C34—Li1—O1—C24 | 0 (3) | C34iv—Li1—C34—C33 | 4 (15) |
C34iii—Li1—O1—C24 | 99.8 (16) | C34iii—Li1—C34—C33 | −81 (15) |
O1A—Li1—O1—C21 | 30 (2) | O1A—Li1—C34—O2A | 93 (3) |
O1Aiii—Li1—O1—C21 | 66.6 (16) | O1Aiii—Li1—C34—O2A | 171 (3) |
O1Aiv—Li1—O1—C21 | −39.6 (19) | O1Aiv—Li1—C34—O2A | −100 (3) |
O1iii—Li1—O1—C21 | 83.0 (16) | O1iii—Li1—C34—O2A | 163 (4) |
O1iv—Li1—O1—C21 | −52.3 (19) | O1—Li1—C34—O2A | 71 (4) |
O2Aiv—Li1—O1—C21 | −171.2 (15) | O1iv—Li1—C34—O2A | −89 (3) |
O2A—Li1—O1—C21 | −172.1 (15) | O2Aiv—Li1—C34—O2A | 20 (2) |
O2Aiii—Li1—O1—C21 | −150.8 (14) | O2Aiii—Li1—C34—O2A | −7 (2) |
C34iv—Li1—O1—C21 | 178 (3) | C34iv—Li1—C34—O2A | 46.8 (15) |
C34—Li1—O1—C21 | 148 (2) | C34iii—Li1—C34—O2A | −38.1 (15) |
Symmetry codes: (i) −y+1/2, −z+1, x+1/2; (ii) z−1/2, −x+1/2, −y+1; (iii) y+1, z−1, x; (iv) z, x−1, y+1. |
Experimental details
Crystal data | |
Chemical formula | [Li(C4H8O)4][Ti2(C6H5S)9] |
Mr | 1372.91 |
Crystal system, space group | Cubic, P213 |
Temperature (K) | 120 |
a (Å) | 19.096 (3) |
V (Å3) | 6963.9 (19) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.55 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.885, 0.897 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2511, 2511, 1802 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.618 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.127, 0.98 |
No. of reflections | 2511 |
No. of parameters | 251 |
No. of restraints | 36 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.57, −0.27 |
Absolute structure | Flack (1983), no Friedel pairs |
Absolute structure parameter | 0.05 (7) |
Computer programs: CAD-4 Operations Manual (Enraf-Nonius, 1977), CAD-4 Operations Manual, PROCESS MolEN (Fair, 1990), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).
Ti1—S1i | 2.3351 (17) | Ti2—S3i | 2.3240 (15) |
Ti1—S2 | 2.5329 (17) | Ti2—S2ii | 2.5434 (16) |
S1i—Ti1—S1ii | 90.46 (7) | S3i—Ti2—S3 | 101.86 (6) |
S1i—Ti1—S2 | 96.22 (5) | S3i—Ti2—S2ii | 158.44 (7) |
S1ii—Ti1—S2 | 95.87 (5) | S3—Ti2—S2ii | 82.04 (5) |
S1—Ti1—S2 | 170.75 (7) | S3ii—Ti2—S2ii | 97.99 (5) |
S2—Ti1—S2ii | 76.78 (6) | S2ii—Ti2—S2 | 76.41 (6) |
S1i—Ti1—S2i | 170.75 (7) | S3i—Ti2—S2i | 98.00 (5) |
S1ii—Ti1—S2i | 96.22 (5) | S3—Ti2—S2i | 158.43 (7) |
S1—Ti1—S2i | 95.87 (5) | S3ii—Ti2—S2i | 82.04 (5) |
S2—Ti1—S2i | 76.78 (6) |
Symmetry codes: (i) −y+1/2, −z+1, x+1/2; (ii) z−1/2, −x+1/2, −y+1. |
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