Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109042280/sk3350sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109042280/sk3350Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109042280/sk3350IIasup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109042280/sk3350IIbsup4.hkl |
CCDC references: 760069; 760070; 760071
For related literature, see: Beckerle et al. (2007); Capacchione et al. (2004, 2005); Cohen et al. (2007); Froese et al. (1999); Meppelder et al. (2008); Snell et al. (2003).
Compound (I) was prepared as described previously (Meppelder et al., 2008). High-quality crystals were obtained by reactive crystallization: A Schlenk tube containing TiCl4 (0.2 mmol) in toluene (2 ml) was covered with a layer of pure solvent (3 ml). A solution of bis(phenol) (0.2 mmol) in the same solvent (2 ml) was carefully added on top. Crystals formed within 3 d. The proligand 2,2'-[cyclohexane-1,2-diylbis(sulfanediyl)]diphenol was synthesized according to a literature procedure (Meppelder et al., 2008) starting from o-mercaptophenol. Cyclohexene oxide (4.49 ml, 55 mmol) was added to sodium 2-mercaptophenolate (50 mmol) in ethanol (50 ml) and heated under reflux for 5 h. After removing the solvent under reduced pressure, the residue was dissolved in diethyl ether, washed with a saturated NH4Cl solution and dried over MgSO4. Evaporation of the solvent gave 10.704 g (47.7 mmol) of 2-(2-hydroxycyclohexylthio)phenol. This was dissolved in CH2Cl2 (100 ml) and thionyl chloride (3.47 ml, 47.7 mmol) was added at 243 K. Removing the volatiles under reduced pressure left a residue that was treated with CH2Cl2, washed with a solution of NaHCO3 and dried over MgSO4. Evaporation of the solvent gave 10.143 g (41.8 mmol) of 2-(2-chlorocyclohexylthio)phenol as a brown oil. It was dissolved in MeOH and CH2Cl2 and added to o-mercaptophenolate (41.8 mmol). After refluxing for 3 h and removing the solvent in vacuo a residue was obtained that was treated with CH2Cl2 and filtered. Crystallization from ethanol and pentane (3:1) at 243 K gave 2,2'-[cyclohexane-1,2-diylbis(sulfanediyl)]diphenol as colorless needles in a yield of 69% (9.53 g, 28.7 mmol). 1H NMR (400 MHz, CDCl3): δ 1.00–1.15 (m, 2H, CH of C6H10), 1.23–1.41 (CH2 of C6H10), 2.67 (qd, 2H, J = 9.7 amd 3.3 Hz, CH—S), 6.80 (dt, 2H, J = 7.6 and 1.3 Hz, arom. CH), 6.96 (dd, 2H, J = 8.2 and 1.1 Hz, arom. CH), 7.18 (s, 2H, OH), 7.24 (ddd, 2H, J = 8.1, 7.4 and 1.6 Hz, arom. CH), 7.39 (dd, 2H, J = 7.7 and 1.5 Hz, arom. CH); 13C NMR (100 MHz, CDCl3): δ 25.5 (s, CH of C6H10), 33.8 (s, CH of C6H10), 52.3 (s, CH—S), 115.3 (s, arom. C), 115.8 (s, arom. C), 120.6 (s, arom. C), 131.8 (s, arom. C), 137.6 (s, arom. C), 158.1 (s, arom. C).
Compound (II) was obtained by reactive crystallization from TiCl4 and bis(phenol) using the solvent benzene (IIa) or toluene (IIb) [quantities of reageants?]. 1H NMR (400 MHz, tetrahydrofuran-d8): δ 1.08–1.27 (m, 2H, CH of C6H10), 1.29–1.43 (m, 2H, CH of C6H10), 1.46–1.59 (m, 2H, CH2 of C6H10), 1.95–2.07 (m, 2H, CH2 of C6H10), 2.90–3.02 (m, 2H, S—CH), 6.59–6.68 (m, 2H, arom. CH), 6.73 (dd, 2H, J = 8.1 and 1.2 Hz, arom. CH), 7.05 (ddd, 2H, J = 8.1, 7.3 and 1.7 Hz, arom. CH), 7.22 (dd, 2H, J = 7.7 and 1.6 Hz, arom. CH); 13C NMR (100 MHz, tetrahydrofuran-d8): δ 23.8 (s, CH of C6H10), 30.9 (s, CH of C6H10), 50.4 (s, CH—S), 114.8 (s, arom. C), 115.1 (s, arom. C), 119.3 (s, arom. C), 129.6 (s, arom. C), 135.5 (s, arom. C), 157.9 (s, arom. C).
All H atoms were placed in idealized positions and allowed to ride on their parent atoms, with C—H distances of 0.95 (aromatic), 0.98 (methyl), 0.99 (cyclohexyl CH2) or 1.00 Å (cyclohexyl CH), and with Uiso(H) set at 1.2Ueq(C) or 1.5Ueq(methyl C) [this is not the case for Uiso(H) values for (I); were these refined freely?].
For all compounds, data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Ti(C20H22O2S2)Cl2] | F(000) = 984 |
Mr = 477.30 | Dx = 1.468 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.7948 (2) Å | Cell parameters from 6964 reflections |
b = 10.9672 (2) Å | θ = 2.7–42.9° |
c = 18.5874 (3) Å | µ = 0.85 mm−1 |
β = 101.105 (1)° | T = 100 K |
V = 2159.34 (7) Å3 | Prism, red |
Z = 4 | 0.29 × 0.24 × 0.15 mm |
Bruker SMART CCD area-detector diffractometer | 10145 independent reflections |
Radiation source: fine-focus sealed tube | 7452 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.060 |
ω scans | θmax = 47.8°, θmin = 2.2° |
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2009) | h = −22→22 |
Tmin = 0.791, Tmax = 0.883 | k = −22→21 |
52551 measured reflections | l = −32→38 |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0479P)2 + 0.2037P] where P = (Fo2 + 2Fc2)/3 |
10145 reflections | (Δ/σ)max = 0.001 |
134 parameters | Δρmax = 1.07 e Å−3 |
0 restraints | Δρmin = −0.75 e Å−3 |
[Ti(C20H22O2S2)Cl2] | V = 2159.34 (7) Å3 |
Mr = 477.30 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 10.7948 (2) Å | µ = 0.85 mm−1 |
b = 10.9672 (2) Å | T = 100 K |
c = 18.5874 (3) Å | 0.29 × 0.24 × 0.15 mm |
β = 101.105 (1)° |
Bruker SMART CCD area-detector diffractometer | 10145 independent reflections |
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2009) | 7452 reflections with I > 2σ(I) |
Tmin = 0.791, Tmax = 0.883 | Rint = 0.060 |
52551 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.07 | Δρmax = 1.07 e Å−3 |
10145 reflections | Δρmin = −0.75 e Å−3 |
134 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 F\^2\^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F\^2\^, conventional R-factors R are based on F, with F set to zero for negative F\^2\^. The threshold expression of F\^2\^ > σ(F\^2\^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F\^2\^ 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 | ||
Ti1 | 0.5000 | 0.468358 (18) | 0.2500 | 0.01403 (4) | |
Cl1 | 0.65277 (2) | 0.34440 (2) | 0.310568 (12) | 0.02210 (5) | |
S1 | 0.629178 (16) | 0.651102 (19) | 0.317412 (11) | 0.01551 (4) | |
O1 | 0.41634 (6) | 0.50037 (5) | 0.32706 (3) | 0.01667 (10) | |
C1 | 0.44142 (7) | 0.57781 (7) | 0.38397 (4) | 0.01485 (11) | |
C2 | 0.54474 (7) | 0.65682 (7) | 0.39009 (4) | 0.01555 (12) | |
C3 | 0.57655 (8) | 0.73407 (9) | 0.45066 (4) | 0.01971 (14) | |
H3 | 0.6491 | 0.7846 | 0.4552 | 0.025 (3)* | |
C4 | 0.50272 (8) | 0.73765 (9) | 0.50438 (4) | 0.02122 (15) | |
C5 | 0.39833 (8) | 0.65958 (9) | 0.49692 (4) | 0.02047 (14) | |
H5 | 0.3470 | 0.6612 | 0.5331 | 0.030 (4)* | |
C6 | 0.36794 (7) | 0.57997 (8) | 0.43824 (4) | 0.01809 (13) | |
H6 | 0.2974 | 0.5270 | 0.4349 | 0.030 (4)* | |
C7 | 0.53420 (12) | 0.82285 (12) | 0.56888 (6) | 0.0332 (2) | |
H7A | 0.5990 | 0.8808 | 0.5604 | 0.056 (5)* | |
H7B | 0.5659 | 0.7757 | 0.6134 | 0.064 (6)* | |
H7C | 0.4581 | 0.8675 | 0.5748 | 0.050 (5)* | |
C8 | 0.57147 (7) | 0.78640 (7) | 0.26277 (4) | 0.01534 (12) | |
H8 | 0.6098 | 0.7849 | 0.2179 | 0.022 (3)* | |
C9 | 0.61727 (10) | 0.90263 (9) | 0.30505 (5) | 0.02400 (17) | |
H9A | 0.5856 | 0.9041 | 0.3516 | 0.019 (3)* | |
H9B | 0.7107 | 0.9027 | 0.3172 | 0.035 (4)* | |
C10 | 0.57160 (13) | 1.01629 (9) | 0.26044 (7) | 0.0330 (2) | |
H10A | 0.6003 | 1.0901 | 0.2896 | 0.044 (4)* | |
H10B | 0.6082 | 1.0182 | 0.2155 | 0.037 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ti1 | 0.01743 (7) | 0.01138 (7) | 0.01543 (8) | 0.000 | 0.00853 (6) | 0.000 |
Cl1 | 0.02806 (9) | 0.01894 (9) | 0.02266 (9) | 0.00812 (7) | 0.01326 (7) | 0.00696 (7) |
S1 | 0.01036 (6) | 0.01779 (9) | 0.01892 (8) | 0.00076 (5) | 0.00421 (5) | −0.00193 (6) |
O1 | 0.0187 (2) | 0.0162 (2) | 0.0173 (2) | −0.00272 (18) | 0.00900 (19) | −0.00378 (18) |
C1 | 0.0152 (2) | 0.0164 (3) | 0.0136 (3) | 0.0014 (2) | 0.0044 (2) | −0.0004 (2) |
C2 | 0.0132 (2) | 0.0189 (3) | 0.0143 (3) | 0.0010 (2) | 0.0020 (2) | −0.0003 (2) |
C3 | 0.0182 (3) | 0.0243 (4) | 0.0153 (3) | −0.0017 (3) | −0.0003 (2) | −0.0024 (3) |
C4 | 0.0238 (3) | 0.0257 (4) | 0.0132 (3) | 0.0003 (3) | 0.0011 (2) | −0.0032 (3) |
C5 | 0.0237 (3) | 0.0254 (4) | 0.0132 (3) | 0.0010 (3) | 0.0057 (2) | −0.0019 (3) |
C6 | 0.0191 (3) | 0.0208 (4) | 0.0159 (3) | −0.0007 (3) | 0.0073 (2) | −0.0015 (2) |
C7 | 0.0384 (5) | 0.0423 (6) | 0.0186 (4) | −0.0100 (5) | 0.0049 (4) | −0.0130 (4) |
C8 | 0.0165 (3) | 0.0128 (3) | 0.0189 (3) | −0.0031 (2) | 0.0089 (2) | −0.0021 (2) |
C9 | 0.0320 (4) | 0.0180 (4) | 0.0258 (4) | −0.0109 (3) | 0.0152 (3) | −0.0077 (3) |
C10 | 0.0572 (7) | 0.0132 (3) | 0.0360 (5) | −0.0096 (4) | 0.0276 (5) | −0.0042 (3) |
Ti1—O1 | 1.8678 (6) | C5—C6 | 1.3863 (12) |
Ti1—O1i | 1.8678 (6) | C5—H5 | 0.9500 |
Ti1—Cl1i | 2.2628 (2) | C6—H6 | 0.9500 |
Ti1—Cl1 | 2.2628 (2) | C7—H7A | 0.9800 |
Ti1—S1 | 2.6188 (2) | C7—H7B | 0.9800 |
Ti1—S1i | 2.6188 (2) | C7—H7C | 0.9800 |
S1—C2 | 1.7703 (8) | C8—C8i | 1.5246 (15) |
S1—C8 | 1.8378 (8) | C8—C9 | 1.5288 (11) |
O1—C1 | 1.3428 (9) | C8—H8 | 1.0000 |
C1—C6 | 1.3984 (10) | C9—C10 | 1.5255 (15) |
C1—C2 | 1.3996 (11) | C9—H9A | 0.9900 |
C2—C3 | 1.3979 (11) | C9—H9B | 0.9900 |
C3—C4 | 1.3930 (12) | C10—C10i | 1.520 (3) |
C3—H3 | 0.9500 | C10—H10A | 0.9900 |
C4—C5 | 1.4007 (13) | C10—H10B | 0.9900 |
C4—C7 | 1.5062 (13) | ||
O1—Ti1—O1i | 158.33 (4) | C6—C5—C4 | 121.79 (8) |
O1—Ti1—Cl1i | 94.633 (19) | C6—C5—H5 | 119.1 |
O1i—Ti1—Cl1i | 98.34 (2) | C4—C5—H5 | 119.1 |
O1—Ti1—Cl1 | 98.34 (2) | C5—C6—C1 | 119.81 (8) |
O1i—Ti1—Cl1 | 94.633 (19) | C5—C6—H6 | 120.1 |
Cl1i—Ti1—Cl1 | 106.142 (15) | C1—C6—H6 | 120.1 |
O1—Ti1—S1 | 77.337 (19) | C4—C7—H7A | 109.5 |
O1i—Ti1—S1 | 86.07 (2) | C4—C7—H7B | 109.5 |
Cl1i—Ti1—S1 | 165.407 (9) | H7A—C7—H7B | 109.5 |
Cl1—Ti1—S1 | 87.242 (8) | C4—C7—H7C | 109.5 |
O1—Ti1—S1i | 86.07 (2) | H7A—C7—H7C | 109.5 |
O1i—Ti1—S1i | 77.337 (19) | H7B—C7—H7C | 109.5 |
Cl1i—Ti1—S1i | 87.242 (8) | C8i—C8—C9 | 111.58 (5) |
Cl1—Ti1—S1i | 165.407 (9) | C8i—C8—S1 | 112.77 (4) |
S1—Ti1—S1i | 80.132 (10) | C9—C8—S1 | 110.33 (6) |
C2—S1—C8 | 102.92 (3) | C8i—C8—H8 | 107.3 |
C2—S1—Ti1 | 95.00 (3) | C9—C8—H8 | 107.3 |
C8—S1—Ti1 | 105.12 (3) | S1—C8—H8 | 107.3 |
C1—O1—Ti1 | 131.99 (5) | C10—C9—C8 | 111.30 (8) |
O1—C1—C6 | 121.51 (7) | C10—C9—H9A | 109.4 |
O1—C1—C2 | 119.49 (6) | C8—C9—H9A | 109.4 |
C6—C1—C2 | 118.99 (7) | C10—C9—H9B | 109.4 |
C3—C2—C1 | 120.60 (7) | C8—C9—H9B | 109.4 |
C3—C2—S1 | 123.59 (6) | H9A—C9—H9B | 108.0 |
C1—C2—S1 | 115.81 (6) | C10i—C10—C9 | 110.19 (7) |
C4—C3—C2 | 120.57 (8) | C10i—C10—H10A | 109.6 |
C4—C3—H3 | 119.7 | C9—C10—H10A | 109.6 |
C2—C3—H3 | 119.7 | C10i—C10—H10B | 109.6 |
C3—C4—C5 | 118.18 (8) | C9—C10—H10B | 109.6 |
C3—C4—C7 | 121.03 (9) | H10A—C10—H10B | 108.1 |
C5—C4—C7 | 120.79 (8) |
Symmetry code: (i) −x+1, y, −z+1/2. |
[Ti(C18H18O2S2)Cl2] | F(000) = 920 |
Mr = 449.24 | Dx = 1.593 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4627 (7) Å | Cell parameters from 82760 reflections |
b = 16.8985 (4) Å | θ = 2.9–36.3° |
c = 12.0810 (11) Å | µ = 0.98 mm−1 |
β = 104.195 (6)° | T = 100 K |
V = 1872.8 (2) Å3 | Fragment, red |
Z = 4 | 0.30 × 0.22 × 0.18 mm |
Bruker SMART CCD area-detector diffractometer | 28176 independent reflections |
Radiation source: fine-focus sealed tube | 22536 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
ω scans | θmax = 60.0°, θmin = 2.7° |
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2009) | h = −22→22 |
Tmin = 0.759, Tmax = 0.844 | k = 0→41 |
257682 measured reflections | l = 0→29 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.24 | w = 1/[σ^2^(Fo^2^) + (0.0269P)^2^ + 0.5527P] where P = (Fo^2^ + 2Fc^2^)/3 |
28176 reflections | (Δ/σ)max = 0.002 |
226 parameters | Δρmax = 0.84 e Å−3 |
0 restraints | Δρmin = −0.73 e Å−3 |
[Ti(C18H18O2S2)Cl2] | V = 1872.8 (2) Å3 |
Mr = 449.24 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.4627 (7) Å | µ = 0.98 mm−1 |
b = 16.8985 (4) Å | T = 100 K |
c = 12.0810 (11) Å | 0.30 × 0.22 × 0.18 mm |
β = 104.195 (6)° |
Bruker SMART CCD area-detector diffractometer | 28176 independent reflections |
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2009) | 22536 reflections with I > 2σ(I) |
Tmin = 0.759, Tmax = 0.844 | Rint = 0.053 |
257682 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.24 | Δρmax = 0.84 e Å−3 |
28176 reflections | Δρmin = −0.73 e Å−3 |
226 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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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 | ||
Ti1 | 0.391941 (11) | 0.404359 (6) | 0.177709 (8) | 0.01005 (1) | |
Cl1 | 0.45087 (2) | 0.337295 (10) | 0.033394 (14) | 0.01702 (3) | |
Cl2 | 0.216452 (18) | 0.330863 (10) | 0.224790 (16) | 0.01741 (3) | |
S1 | 0.362857 (16) | 0.507412 (9) | 0.333419 (12) | 0.01013 (2) | |
S2 | 0.603073 (17) | 0.501657 (8) | 0.167314 (12) | 0.01033 (2) | |
O1 | 0.26987 (5) | 0.48047 (3) | 0.09177 (4) | 0.01341 (6) | |
O2 | 0.54628 (5) | 0.36568 (3) | 0.29468 (4) | 0.01151 (6) | |
C1 | 0.19830 (6) | 0.54178 (3) | 0.12310 (5) | 0.01175 (7) | |
C2 | 0.22848 (6) | 0.56395 (3) | 0.23886 (5) | 0.01125 (7) | |
C3 | 0.15042 (7) | 0.62488 (4) | 0.27487 (6) | 0.01427 (8) | |
H3 | 0.1707 | 0.6390 | 0.3533 | 0.017* | |
C4 | 0.04283 (7) | 0.66467 (4) | 0.19517 (7) | 0.01665 (10) | |
H4 | −0.0100 | 0.7066 | 0.2188 | 0.020* | |
C5 | 0.01283 (7) | 0.64277 (4) | 0.08041 (7) | 0.01740 (10) | |
H5 | −0.0619 | 0.6695 | 0.0265 | 0.021* | |
C6 | 0.09026 (7) | 0.58249 (4) | 0.04333 (6) | 0.01548 (9) | |
H6 | 0.0701 | 0.5691 | −0.0353 | 0.019* | |
C7 | 0.52787 (6) | 0.56925 (3) | 0.35809 (4) | 0.00966 (6) | |
H7 | 0.6094 | 0.5376 | 0.4063 | 0.012* | |
C8 | 0.57159 (6) | 0.58972 (3) | 0.24800 (4) | 0.00953 (6) | |
H8 | 0.4889 | 0.6198 | 0.1984 | 0.011* | |
C9 | 0.70609 (6) | 0.64374 (4) | 0.27085 (5) | 0.01288 (7) | |
H9A | 0.7921 | 0.6139 | 0.3141 | 0.015* | |
H9B | 0.7253 | 0.6600 | 0.1972 | 0.015* | |
C10 | 0.68506 (7) | 0.71749 (4) | 0.33840 (6) | 0.01612 (9) | |
H10A | 0.7750 | 0.7498 | 0.3545 | 0.019* | |
H10B | 0.6045 | 0.7499 | 0.2927 | 0.019* | |
C11 | 0.64989 (7) | 0.69342 (4) | 0.45034 (6) | 0.01599 (9) | |
H11A | 0.6368 | 0.7414 | 0.4939 | 0.019* | |
H11B | 0.7320 | 0.6625 | 0.4971 | 0.019* | |
C12 | 0.51054 (7) | 0.64357 (4) | 0.42650 (5) | 0.01285 (7) | |
H12A | 0.4276 | 0.6754 | 0.3829 | 0.015* | |
H12B | 0.4891 | 0.6279 | 0.4997 | 0.015* | |
C13 | 0.73737 (6) | 0.44920 (3) | 0.26808 (5) | 0.01115 (7) | |
C14 | 0.68789 (6) | 0.38515 (3) | 0.32288 (5) | 0.01003 (6) | |
C15 | 0.78821 (6) | 0.34152 (4) | 0.40452 (5) | 0.01281 (7) | |
H15 | 0.7562 | 0.2983 | 0.4423 | 0.015* | |
C16 | 0.93511 (7) | 0.36186 (4) | 0.43007 (7) | 0.01683 (10) | |
H16 | 1.0029 | 0.3326 | 0.4863 | 0.020* | |
C17 | 0.98442 (7) | 0.42461 (5) | 0.37431 (8) | 0.01889 (11) | |
H17 | 1.0851 | 0.4379 | 0.3926 | 0.023* | |
C18 | 0.88586 (7) | 0.46771 (4) | 0.29187 (7) | 0.01576 (9) | |
H18 | 0.9192 | 0.5094 | 0.2520 | 0.019* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ti1 | 0.01124 (3) | 0.00770 (3) | 0.00980 (3) | −0.00018 (2) | −0.00011 (2) | −0.00017 (2) |
Cl2 | 0.01375 (5) | 0.01515 (6) | 0.02212 (7) | −0.00376 (4) | 0.00206 (5) | 0.00236 (5) |
Cl1 | 0.02394 (7) | 0.01283 (5) | 0.01256 (5) | 0.00360 (5) | 0.00112 (5) | −0.00339 (4) |
S2 | 0.01379 (5) | 0.00906 (4) | 0.00876 (4) | 0.00020 (3) | 0.00399 (4) | 0.00046 (3) |
S1 | 0.01093 (4) | 0.00999 (4) | 0.00968 (4) | −0.00039 (3) | 0.00293 (3) | 0.00146 (3) |
O2 | 0.01050 (13) | 0.01058 (13) | 0.01218 (13) | −0.00130 (10) | 0.00037 (10) | 0.00228 (10) |
O1 | 0.01617 (16) | 0.01114 (14) | 0.01108 (14) | 0.00266 (12) | −0.00020 (12) | 0.00011 (11) |
C14 | 0.01012 (15) | 0.00943 (15) | 0.01054 (15) | 0.00046 (12) | 0.00250 (12) | 0.00056 (12) |
C13 | 0.01105 (16) | 0.01013 (16) | 0.01311 (17) | 0.00084 (12) | 0.00457 (13) | 0.00111 (13) |
C18 | 0.01141 (18) | 0.0139 (2) | 0.0237 (3) | 0.00090 (15) | 0.00764 (18) | 0.00303 (18) |
C17 | 0.00997 (18) | 0.0174 (2) | 0.0294 (3) | 0.00157 (17) | 0.00508 (19) | 0.0042 (2) |
C16 | 0.01062 (18) | 0.0164 (2) | 0.0223 (3) | 0.00236 (16) | 0.00176 (17) | 0.00342 (19) |
C15 | 0.01141 (17) | 0.01236 (18) | 0.01418 (19) | 0.00127 (14) | 0.00220 (14) | 0.00264 (14) |
C8 | 0.01051 (15) | 0.00856 (14) | 0.00939 (14) | −0.00047 (11) | 0.00218 (12) | 0.00030 (11) |
C7 | 0.00998 (15) | 0.01011 (15) | 0.00861 (14) | 0.00046 (12) | 0.00174 (12) | 0.00001 (11) |
C12 | 0.01235 (17) | 0.01337 (18) | 0.01265 (18) | 0.00124 (14) | 0.00272 (14) | −0.00327 (14) |
C11 | 0.0142 (2) | 0.0158 (2) | 0.0167 (2) | −0.00076 (16) | 0.00135 (16) | −0.00694 (17) |
C10 | 0.0152 (2) | 0.01112 (18) | 0.0211 (2) | −0.00255 (15) | 0.00275 (18) | −0.00228 (17) |
C9 | 0.01178 (17) | 0.01226 (18) | 0.01469 (19) | −0.00265 (14) | 0.00346 (14) | −0.00054 (14) |
C2 | 0.00961 (15) | 0.01063 (16) | 0.01315 (17) | −0.00005 (12) | 0.00212 (13) | 0.00064 (13) |
C1 | 0.01165 (16) | 0.00952 (15) | 0.01267 (17) | −0.00008 (13) | 0.00026 (13) | 0.00139 (13) |
C6 | 0.0151 (2) | 0.01141 (18) | 0.0168 (2) | 0.00019 (15) | −0.00211 (17) | 0.00264 (15) |
C5 | 0.01241 (19) | 0.01174 (19) | 0.0249 (3) | 0.00063 (15) | −0.00144 (18) | 0.00335 (18) |
C4 | 0.01074 (18) | 0.01207 (19) | 0.0264 (3) | 0.00072 (15) | 0.00315 (18) | 0.00037 (18) |
C3 | 0.01046 (17) | 0.01338 (19) | 0.0194 (2) | 0.00020 (14) | 0.00444 (16) | −0.00133 (16) |
Ti1—O1 | 1.8649 (5) | C8—H8 | 1.0000 |
Ti1—O2 | 1.8828 (5) | C7—C12 | 1.5341 (8) |
Ti1—Cl2 | 2.2554 (2) | C7—H7 | 1.0000 |
Ti1—Cl1 | 2.2609 (2) | C12—C11 | 1.5314 (9) |
Ti1—S2 | 2.6141 (2) | C12—H12A | 0.9900 |
Ti1—S1 | 2.6270 (2) | C12—H12B | 0.9900 |
S2—C13 | 1.7675 (6) | C11—C10 | 1.5249 (11) |
S2—C8 | 1.8428 (5) | C11—H11A | 0.9900 |
S1—C2 | 1.7670 (6) | C11—H11B | 0.9900 |
S1—C7 | 1.8413 (6) | C10—C9 | 1.5293 (9) |
O2—C14 | 1.3401 (7) | C10—H10A | 0.9900 |
O1—C1 | 1.3421 (8) | C10—H10B | 0.9900 |
C14—C15 | 1.3993 (8) | C9—H9A | 0.9900 |
C14—C13 | 1.4076 (8) | C9—H9B | 0.9900 |
C13—C18 | 1.3988 (8) | C2—C3 | 1.3973 (8) |
C18—C17 | 1.3916 (10) | C2—C1 | 1.4078 (8) |
C18—H18 | 0.9500 | C1—C6 | 1.4014 (8) |
C17—C16 | 1.3965 (10) | C6—C5 | 1.3914 (10) |
C17—H17 | 0.9500 | C6—H6 | 0.9500 |
C16—C15 | 1.3912 (9) | C5—C4 | 1.3952 (12) |
C16—H16 | 0.9500 | C5—H5 | 0.9500 |
C15—H15 | 0.9500 | C4—C3 | 1.3911 (10) |
C8—C7 | 1.5264 (7) | C4—H4 | 0.9500 |
C8—C9 | 1.5352 (8) | C3—H3 | 0.9500 |
O1—Ti1—O2 | 156.60 (2) | C8—C7—S1 | 112.82 (4) |
O1—Ti1—Cl2 | 97.257 (18) | C12—C7—S1 | 110.70 (4) |
O2—Ti1—Cl2 | 95.919 (16) | C8—C7—H7 | 107.1 |
O1—Ti1—Cl1 | 98.778 (17) | C12—C7—H7 | 107.1 |
O2—Ti1—Cl1 | 96.440 (17) | S1—C7—H7 | 107.1 |
Cl2—Ti1—Cl1 | 104.745 (9) | C11—C12—C7 | 110.54 (5) |
O1—Ti1—S2 | 85.172 (18) | C11—C12—H12A | 109.5 |
O2—Ti1—S2 | 78.060 (15) | C7—C12—H12A | 109.5 |
Cl2—Ti1—S2 | 167.716 (8) | C11—C12—H12B | 109.5 |
Cl1—Ti1—S2 | 86.693 (8) | C7—C12—H12B | 109.5 |
O1—Ti1—S1 | 77.416 (16) | H12A—C12—H12B | 108.1 |
O2—Ti1—S1 | 83.735 (16) | C10—C11—C12 | 110.18 (5) |
Cl2—Ti1—S1 | 88.369 (8) | C10—C11—H11A | 109.6 |
Cl1—Ti1—S1 | 166.765 (8) | C12—C11—H11A | 109.6 |
S2—Ti1—S1 | 80.384 (7) | C10—C11—H11B | 109.6 |
C13—S2—C8 | 102.88 (3) | C12—C11—H11B | 109.6 |
C13—S2—Ti1 | 94.61 (2) | H11A—C11—H11B | 108.1 |
C8—S2—Ti1 | 104.946 (18) | C11—C10—C9 | 109.95 (5) |
C2—S1—C7 | 104.18 (3) | C11—C10—H10A | 109.7 |
C2—S1—Ti1 | 94.63 (2) | C9—C10—H10A | 109.7 |
C7—S1—Ti1 | 104.983 (18) | C11—C10—H10B | 109.7 |
C14—O2—Ti1 | 130.45 (4) | C9—C10—H10B | 109.7 |
C1—O1—Ti1 | 131.45 (4) | H10A—C10—H10B | 108.2 |
O2—C14—C15 | 120.87 (5) | C10—C9—C8 | 111.71 (5) |
O2—C14—C13 | 119.76 (5) | C10—C9—H9A | 109.3 |
C15—C14—C13 | 119.36 (5) | C8—C9—H9A | 109.3 |
C18—C13—C14 | 120.57 (5) | C10—C9—H9B | 109.3 |
C18—C13—S2 | 123.07 (5) | C8—C9—H9B | 109.3 |
C14—C13—S2 | 116.34 (4) | H9A—C9—H9B | 107.9 |
C17—C18—C13 | 119.55 (6) | C3—C2—C1 | 120.76 (5) |
C17—C18—H18 | 120.2 | C3—C2—S1 | 123.28 (5) |
C13—C18—H18 | 120.2 | C1—C2—S1 | 115.90 (4) |
C18—C17—C16 | 119.87 (6) | O1—C1—C6 | 121.24 (6) |
C18—C17—H17 | 120.1 | O1—C1—C2 | 119.48 (5) |
C16—C17—H17 | 120.1 | C6—C1—C2 | 119.24 (6) |
C15—C16—C17 | 120.96 (6) | C5—C6—C1 | 119.40 (6) |
C15—C16—H16 | 119.5 | C5—C6—H6 | 120.3 |
C17—C16—H16 | 119.5 | C1—C6—H6 | 120.3 |
C16—C15—C14 | 119.63 (6) | C6—C5—C4 | 121.28 (6) |
C16—C15—H15 | 120.2 | C6—C5—H5 | 119.4 |
C14—C15—H15 | 120.2 | C4—C5—H5 | 119.4 |
C7—C8—C9 | 111.59 (4) | C3—C4—C5 | 119.71 (6) |
C7—C8—S2 | 113.04 (4) | C3—C4—H4 | 120.1 |
C9—C8—S2 | 109.93 (4) | C5—C4—H4 | 120.1 |
C7—C8—H8 | 107.3 | C4—C3—C2 | 119.58 (6) |
C9—C8—H8 | 107.3 | C4—C3—H3 | 120.2 |
S2—C8—H8 | 107.3 | C2—C3—H3 | 120.2 |
C8—C7—C12 | 111.80 (5) | ||
O1—Ti1—S2—C13 | 170.16 (2) | C13—C18—C17—C16 | 1.93 (12) |
O2—Ti1—S2—C13 | 6.57 (2) | C18—C17—C16—C15 | −0.02 (12) |
Cl2—Ti1—S2—C13 | 68.16 (4) | C17—C16—C15—C14 | −0.85 (11) |
Cl1—Ti1—S2—C13 | −90.73 (2) | O2—C14—C15—C16 | 178.40 (6) |
S1—Ti1—S2—C13 | 92.13 (2) | C13—C14—C15—C16 | −0.19 (9) |
O1—Ti1—S2—C8 | 65.51 (2) | C13—S2—C8—C7 | −56.25 (4) |
O2—Ti1—S2—C8 | −98.09 (2) | Ti1—S2—C8—C7 | 42.16 (4) |
Cl2—Ti1—S2—C8 | −36.49 (4) | C13—S2—C8—C9 | 69.17 (4) |
Cl1—Ti1—S2—C8 | 164.615 (18) | Ti1—S2—C8—C9 | 167.58 (3) |
S1—Ti1—S2—C8 | −12.519 (18) | C9—C8—C7—C12 | 52.39 (6) |
O1—Ti1—S1—C2 | 7.49 (3) | S2—C8—C7—C12 | 176.90 (4) |
O2—Ti1—S1—C2 | 173.55 (2) | C9—C8—C7—S1 | 177.93 (4) |
Cl2—Ti1—S1—C2 | −90.32 (2) | S2—C8—C7—S1 | −57.55 (4) |
Cl1—Ti1—S1—C2 | 82.05 (4) | C2—S1—C7—C8 | −57.88 (4) |
S2—Ti1—S1—C2 | 94.65 (2) | Ti1—S1—C7—C8 | 40.96 (4) |
O1—Ti1—S1—C7 | −98.54 (2) | C2—S1—C7—C12 | 68.26 (4) |
O2—Ti1—S1—C7 | 67.52 (2) | Ti1—S1—C7—C12 | 167.10 (3) |
Cl2—Ti1—S1—C7 | 163.655 (18) | C8—C7—C12—C11 | −55.21 (6) |
Cl1—Ti1—S1—C7 | −23.98 (4) | S1—C7—C12—C11 | 178.08 (4) |
S2—Ti1—S1—C7 | −11.383 (18) | C7—C12—C11—C10 | 58.77 (7) |
O1—Ti1—O2—C14 | −53.67 (9) | C12—C11—C10—C9 | −59.51 (7) |
Cl2—Ti1—O2—C14 | −177.69 (5) | C11—C10—C9—C8 | 56.91 (7) |
Cl1—Ti1—O2—C14 | 76.70 (5) | C7—C8—C9—C10 | −53.41 (7) |
S2—Ti1—O2—C14 | −8.53 (5) | S2—C8—C9—C10 | −179.65 (4) |
S1—Ti1—O2—C14 | −89.99 (5) | C7—S1—C2—C3 | −82.14 (5) |
O2—Ti1—O1—C1 | −48.06 (9) | Ti1—S1—C2—C3 | 171.13 (5) |
Cl2—Ti1—O1—C1 | 75.73 (6) | C7—S1—C2—C1 | 100.72 (5) |
Cl1—Ti1—O1—C1 | −178.05 (5) | Ti1—S1—C2—C1 | −6.02 (4) |
S2—Ti1—O1—C1 | −92.16 (6) | Ti1—O1—C1—C6 | −167.58 (5) |
S1—Ti1—O1—C1 | −10.95 (5) | Ti1—O1—C1—C2 | 10.15 (9) |
Ti1—O2—C14—C15 | −171.68 (4) | C3—C2—C1—O1 | −176.67 (6) |
Ti1—O2—C14—C13 | 6.91 (8) | S1—C2—C1—O1 | 0.55 (7) |
O2—C14—C13—C18 | −176.49 (6) | C3—C2—C1—C6 | 1.10 (9) |
C15—C14—C13—C18 | 2.12 (9) | S1—C2—C1—C6 | 178.32 (5) |
O2—C14—C13—S2 | 2.04 (7) | O1—C1—C6—C5 | 176.31 (6) |
C15—C14—C13—S2 | −179.35 (5) | C2—C1—C6—C5 | −1.42 (9) |
C8—S2—C13—C18 | −81.11 (6) | C1—C6—C5—C4 | 1.43 (10) |
Ti1—S2—C13—C18 | 172.40 (5) | C6—C5—C4—C3 | −1.08 (10) |
C8—S2—C13—C14 | 100.40 (5) | C5—C4—C3—C2 | 0.73 (10) |
Ti1—S2—C13—C14 | −6.09 (4) | C1—C2—C3—C4 | −0.76 (9) |
C14—C13—C18—C17 | −2.99 (10) | S1—C2—C3—C4 | −177.77 (5) |
S2—C13—C18—C17 | 178.58 (6) |
[Ti(C18H18O2S2)Cl2]·0.5C7H8 | F(000) = 1020 |
Mr = 445.31 | Dx = 1.477 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.7622 (3) Å | Cell parameters from 8975 reflections |
b = 16.3667 (4) Å | θ = 2.5–38.8° |
c = 14.5713 (4) Å | µ = 0.83 mm−1 |
β = 106.899 (1)° | T = 100 K |
V = 2227.60 (11) Å3 | Fragment, red |
Z = 4 | 0.36 × 0.22 × 0.10 mm |
Bruker SMART CCD area-detector diffractometer | 20925 independent reflections |
Radiation source: fine-focus sealed tube | 13853 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.067 |
ω scans | θmax = 47.8°, θmin = 2.2° |
Absorption correction: multi-scan (PLATON in MULABS; Spek, 2009) | h = −20→18 |
Tmin = 0.755, Tmax = 0.922 | k = −33→33 |
179195 measured reflections | l = −30→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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0356P)2] where P = (Fo2 + 2Fc2)/3 |
20925 reflections | (Δ/σ)max = 0.001 |
290 parameters | Δρmax = 0.73 e Å−3 |
0 restraints | Δρmin = −0.47 e Å−3 |
[Ti(C18H18O2S2)Cl2]·0.5C7H8 | V = 2227.60 (11) Å3 |
Mr = 445.31 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.7622 (3) Å | µ = 0.83 mm−1 |
b = 16.3667 (4) Å | T = 100 K |
c = 14.5713 (4) Å | 0.36 × 0.22 × 0.10 mm |
β = 106.899 (1)° |
Bruker SMART CCD area-detector diffractometer | 20925 independent reflections |
Absorption correction: multi-scan (PLATON in MULABS; Spek, 2009) | 13853 reflections with I > 2σ(I) |
Tmin = 0.755, Tmax = 0.922 | Rint = 0.067 |
179195 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.73 e Å−3 |
20925 reflections | Δρmin = −0.47 e Å−3 |
290 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | 0.041197 (12) | 0.286190 (7) | 0.156257 (8) | 0.01464 (2) | |
S1 | −0.118760 (18) | 0.378771 (11) | 0.230720 (11) | 0.01575 (3) | |
S2 | 0.138962 (17) | 0.429596 (10) | 0.130125 (11) | 0.01455 (3) | |
Cl1 | 0.18707 (2) | 0.233422 (13) | 0.076972 (14) | 0.02423 (4) | |
Cl2 | −0.06435 (2) | 0.179752 (11) | 0.206305 (14) | 0.02203 (4) | |
O1 | −0.11228 (5) | 0.31199 (3) | 0.04852 (3) | 0.01663 (8) | |
O2 | 0.18164 (5) | 0.30299 (3) | 0.27280 (4) | 0.01707 (9) | |
C1 | −0.24227 (7) | 0.34235 (5) | 0.04379 (5) | 0.01745 (11) | |
C2 | −0.26617 (7) | 0.37672 (5) | 0.12607 (5) | 0.01907 (12) | |
C3 | −0.40278 (9) | 0.40227 (6) | 0.12514 (6) | 0.02968 (18) | |
H3 | −0.4192 | 0.4235 | 0.1817 | 0.036* | |
C4 | −0.51458 (9) | 0.39651 (8) | 0.04111 (7) | 0.0389 (2) | |
H4 | −0.6077 | 0.4145 | 0.0397 | 0.047* | |
C5 | −0.49008 (9) | 0.36432 (7) | −0.04116 (7) | 0.0361 (2) | |
H5 | −0.5671 | 0.3608 | −0.0985 | 0.043* | |
C6 | −0.35504 (8) | 0.33733 (6) | −0.04088 (5) | 0.02439 (15) | |
H6 | −0.3396 | 0.3157 | −0.0976 | 0.029* | |
C7 | −0.04673 (7) | 0.48290 (4) | 0.23326 (5) | 0.01496 (10) | |
H7 | 0.0386 | 0.4865 | 0.2911 | 0.018* | |
C8 | 0.00470 (7) | 0.50249 (4) | 0.14639 (5) | 0.01525 (10) | |
H8 | −0.0803 | 0.4985 | 0.0883 | 0.018* | |
C9 | 0.06174 (8) | 0.59004 (5) | 0.15029 (6) | 0.02065 (12) | |
H9A | 0.1493 | 0.5954 | 0.2051 | 0.025* | |
H9B | 0.0875 | 0.6019 | 0.0908 | 0.025* | |
C10 | −0.04993 (10) | 0.65164 (5) | 0.16116 (7) | 0.02612 (15) | |
H10A | −0.0098 | 0.7075 | 0.1655 | 0.031* | |
H10B | −0.1350 | 0.6492 | 0.1042 | 0.031* | |
C11 | −0.09385 (10) | 0.63286 (5) | 0.25107 (7) | 0.02543 (15) | |
H11B | −0.1667 | 0.6729 | 0.2573 | 0.031* | |
H11A | −0.0096 | 0.6379 | 0.3083 | 0.031* | |
C12 | −0.15506 (8) | 0.54645 (5) | 0.24612 (6) | 0.02106 (13) | |
H12B | −0.2435 | 0.5427 | 0.1917 | 0.025* | |
H12A | −0.1804 | 0.5347 | 0.3058 | 0.025* | |
C13 | 0.27574 (7) | 0.43012 (4) | 0.24071 (5) | 0.01487 (10) | |
C14 | 0.27983 (7) | 0.36233 (4) | 0.30054 (5) | 0.01440 (10) | |
C15 | 0.38773 (7) | 0.35644 (4) | 0.38758 (5) | 0.01746 (11) | |
H15 | 0.3911 | 0.3110 | 0.4288 | 0.021* | |
C16 | 0.48990 (8) | 0.41767 (5) | 0.41316 (6) | 0.02184 (13) | |
H16 | 0.5634 | 0.4139 | 0.4723 | 0.026* | |
C17 | 0.48676 (8) | 0.48460 (5) | 0.35371 (6) | 0.02361 (14) | |
H17 | 0.5574 | 0.5261 | 0.3726 | 0.028* | |
C18 | 0.38027 (7) | 0.49079 (4) | 0.26669 (5) | 0.01908 (12) | |
H18 | 0.3787 | 0.5359 | 0.2253 | 0.023* | |
C19 | 0.0738 (2) | 0.35039 (13) | 0.48981 (13) | 0.0330 (4) | 0.50 |
H19A | 0.0945 | 0.3427 | 0.4285 | 0.050* | 0.50 |
H19B | −0.0017 | 0.3124 | 0.4940 | 0.050* | 0.50 |
H19C | 0.1606 | 0.3398 | 0.5426 | 0.050* | 0.50 |
C20 | 0.02500 (17) | 0.43645 (11) | 0.49653 (11) | 0.0205 (3) | 0.50 |
C21 | 0.1140 (2) | 0.50270 (16) | 0.49496 (13) | 0.0279 (3) | 0.50 |
H21 | 0.2060 | 0.4935 | 0.4869 | 0.033* | 0.50 |
C22 | 0.0700 (3) | 0.58138 (15) | 0.50497 (14) | 0.0376 (5) | 0.50 |
H22 | 0.1330 | 0.6257 | 0.5054 | 0.045* | 0.50 |
C23 | −0.0653 (3) | 0.59670 (12) | 0.51447 (13) | 0.0350 (4) | 0.50 |
H23 | −0.0956 | 0.6511 | 0.5203 | 0.042* | 0.50 |
C24 | −0.1555 (2) | 0.53149 (12) | 0.51528 (12) | 0.0269 (3) | 0.50 |
H24 | −0.2483 | 0.5409 | 0.5218 | 0.032* | 0.50 |
C25 | −0.10965 (17) | 0.45266 (13) | 0.50657 (12) | 0.0197 (3) | 0.50 |
H25 | −0.1720 | 0.4083 | 0.5075 | 0.024* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ti1 | 0.01347 (4) | 0.01610 (5) | 0.01207 (4) | 0.00095 (3) | 0.00013 (3) | −0.00192 (3) |
S1 | 0.01704 (7) | 0.01911 (7) | 0.01160 (6) | −0.00099 (5) | 0.00495 (5) | −0.00059 (5) |
S2 | 0.01368 (6) | 0.01941 (7) | 0.01053 (6) | 0.00182 (5) | 0.00347 (5) | 0.00036 (5) |
Cl1 | 0.01813 (7) | 0.02942 (9) | 0.02360 (8) | 0.00511 (6) | 0.00363 (6) | −0.00880 (7) |
Cl2 | 0.02056 (7) | 0.01707 (7) | 0.02458 (8) | −0.00248 (5) | 0.00047 (6) | 0.00089 (6) |
O1 | 0.01322 (19) | 0.0229 (2) | 0.01230 (18) | 0.00279 (16) | 0.00146 (14) | −0.00201 (16) |
O2 | 0.0171 (2) | 0.0169 (2) | 0.01371 (18) | −0.00198 (16) | −0.00096 (15) | 0.00005 (15) |
C1 | 0.0131 (2) | 0.0243 (3) | 0.0142 (2) | 0.0009 (2) | 0.00275 (19) | −0.0011 (2) |
C2 | 0.0140 (3) | 0.0277 (3) | 0.0157 (3) | −0.0005 (2) | 0.0047 (2) | −0.0029 (2) |
C3 | 0.0159 (3) | 0.0482 (5) | 0.0265 (4) | 0.0001 (3) | 0.0086 (3) | −0.0111 (4) |
C4 | 0.0143 (3) | 0.0665 (7) | 0.0341 (5) | 0.0066 (4) | 0.0042 (3) | −0.0156 (5) |
C5 | 0.0145 (3) | 0.0621 (7) | 0.0266 (4) | 0.0068 (4) | −0.0021 (3) | −0.0120 (4) |
C6 | 0.0148 (3) | 0.0390 (4) | 0.0169 (3) | 0.0035 (3) | 0.0007 (2) | −0.0045 (3) |
C7 | 0.0160 (2) | 0.0169 (2) | 0.0123 (2) | 0.00183 (19) | 0.00474 (19) | 0.00093 (19) |
C8 | 0.0146 (2) | 0.0190 (3) | 0.0124 (2) | 0.0037 (2) | 0.00429 (18) | 0.00319 (19) |
C9 | 0.0222 (3) | 0.0190 (3) | 0.0228 (3) | 0.0027 (2) | 0.0098 (2) | 0.0052 (2) |
C10 | 0.0298 (4) | 0.0199 (3) | 0.0315 (4) | 0.0077 (3) | 0.0135 (3) | 0.0085 (3) |
C11 | 0.0303 (4) | 0.0195 (3) | 0.0305 (4) | 0.0064 (3) | 0.0150 (3) | 0.0015 (3) |
C12 | 0.0218 (3) | 0.0212 (3) | 0.0235 (3) | 0.0052 (2) | 0.0118 (3) | 0.0021 (2) |
C13 | 0.0128 (2) | 0.0175 (3) | 0.0135 (2) | 0.00176 (19) | 0.00254 (18) | 0.00017 (19) |
C14 | 0.0130 (2) | 0.0159 (2) | 0.0130 (2) | 0.00058 (18) | 0.00161 (18) | −0.00121 (19) |
C15 | 0.0163 (3) | 0.0176 (3) | 0.0152 (2) | 0.0007 (2) | −0.0006 (2) | 0.0006 (2) |
C16 | 0.0175 (3) | 0.0213 (3) | 0.0206 (3) | −0.0011 (2) | −0.0041 (2) | 0.0008 (2) |
C17 | 0.0179 (3) | 0.0209 (3) | 0.0264 (3) | −0.0038 (2) | −0.0023 (2) | 0.0018 (3) |
C18 | 0.0153 (3) | 0.0191 (3) | 0.0210 (3) | −0.0007 (2) | 0.0023 (2) | 0.0026 (2) |
C19 | 0.0393 (10) | 0.0374 (10) | 0.0218 (7) | 0.0170 (8) | 0.0081 (7) | 0.0007 (7) |
C20 | 0.0190 (6) | 0.0279 (7) | 0.0141 (5) | 0.0032 (5) | 0.0039 (4) | 0.0002 (5) |
C21 | 0.0197 (7) | 0.0429 (12) | 0.0190 (7) | −0.0066 (8) | 0.0022 (5) | 0.0020 (7) |
C22 | 0.0491 (13) | 0.0374 (11) | 0.0211 (8) | −0.0235 (10) | 0.0021 (8) | 0.0017 (7) |
C23 | 0.0562 (13) | 0.0223 (8) | 0.0190 (7) | 0.0007 (8) | −0.0006 (8) | −0.0032 (6) |
C24 | 0.0255 (8) | 0.0331 (9) | 0.0181 (6) | 0.0073 (7) | 0.0001 (5) | −0.0054 (6) |
C25 | 0.0174 (6) | 0.0234 (8) | 0.0175 (6) | −0.0005 (6) | 0.0037 (5) | −0.0035 (6) |
Ti1—O2 | 1.8670 (5) | C10—H10B | 0.9900 |
Ti1—O1 | 1.8763 (5) | C11—C12 | 1.5288 (12) |
Ti1—Cl1 | 2.2506 (2) | C11—H11B | 0.9900 |
Ti1—Cl2 | 2.2506 (2) | C11—H11A | 0.9900 |
Ti1—S2 | 2.6031 (2) | C12—H12B | 0.9900 |
Ti1—S1 | 2.6261 (2) | C12—H12A | 0.9900 |
S1—C2 | 1.7668 (7) | C13—C18 | 1.3951 (10) |
S1—C7 | 1.8400 (7) | C13—C14 | 1.4045 (9) |
S2—C13 | 1.7688 (6) | C14—C15 | 1.3967 (9) |
S2—C8 | 1.8379 (7) | C15—C16 | 1.3864 (10) |
O1—C1 | 1.3457 (8) | C15—H15 | 0.9500 |
O2—C14 | 1.3416 (8) | C16—C17 | 1.3912 (11) |
C1—C6 | 1.3969 (10) | C16—H16 | 0.9500 |
C1—C2 | 1.4040 (10) | C17—C18 | 1.3902 (10) |
C2—C3 | 1.3939 (11) | C17—H17 | 0.9500 |
C3—C4 | 1.3865 (13) | C18—H18 | 0.9500 |
C3—H3 | 0.9500 | C19—C20 | 1.499 (3) |
C4—C5 | 1.3924 (14) | C19—H19A | 0.9800 |
C4—H4 | 0.9500 | C19—H19B | 0.9800 |
C5—C6 | 1.3892 (11) | C19—H19C | 0.9800 |
C5—H5 | 0.9500 | C20—C25 | 1.390 (2) |
C6—H6 | 0.9500 | C20—C21 | 1.394 (3) |
C7—C8 | 1.5253 (9) | C21—C22 | 1.379 (4) |
C7—C12 | 1.5331 (10) | C21—H21 | 0.9500 |
C7—H7 | 1.0000 | C22—C23 | 1.391 (4) |
C8—C9 | 1.5324 (10) | C22—H22 | 0.9500 |
C8—H8 | 1.0000 | C23—C24 | 1.386 (3) |
C9—C10 | 1.5265 (11) | C23—H23 | 0.9500 |
C9—H9A | 0.9900 | C24—C25 | 1.383 (3) |
C9—H9B | 0.9900 | C24—H24 | 0.9500 |
C10—C11 | 1.5235 (12) | C25—H25 | 0.9500 |
C10—H10A | 0.9900 | ||
O2—Ti1—O1 | 157.61 (2) | C8—C9—H9B | 109.4 |
O2—Ti1—Cl1 | 96.689 (18) | H9A—C9—H9B | 108.0 |
O1—Ti1—Cl1 | 97.320 (17) | C11—C10—C9 | 110.12 (6) |
O2—Ti1—Cl2 | 95.948 (17) | C11—C10—H10A | 109.6 |
O1—Ti1—Cl2 | 96.654 (18) | C9—C10—H10A | 109.6 |
Cl1—Ti1—Cl2 | 106.674 (9) | C11—C10—H10B | 109.6 |
O2—Ti1—S2 | 78.271 (17) | C9—C10—H10B | 109.6 |
O1—Ti1—S2 | 84.964 (18) | H10A—C10—H10B | 108.2 |
Cl1—Ti1—S2 | 87.553 (8) | C10—C11—C12 | 110.48 (7) |
Cl2—Ti1—S2 | 165.282 (8) | C10—C11—H11B | 109.6 |
O2—Ti1—S1 | 84.656 (18) | C12—C11—H11B | 109.6 |
O1—Ti1—S1 | 77.861 (16) | C10—C11—H11A | 109.6 |
Cl1—Ti1—S1 | 167.027 (9) | C12—C11—H11A | 109.6 |
Cl2—Ti1—S1 | 85.957 (8) | H11B—C11—H11A | 108.1 |
S2—Ti1—S1 | 80.068 (6) | C11—C12—C7 | 111.05 (6) |
C2—S1—C7 | 104.22 (3) | C11—C12—H12B | 109.4 |
C2—S1—Ti1 | 93.75 (2) | C7—C12—H12B | 109.4 |
C7—S1—Ti1 | 105.85 (2) | C11—C12—H12A | 109.4 |
C13—S2—C8 | 104.90 (3) | C7—C12—H12A | 109.4 |
C13—S2—Ti1 | 94.75 (2) | H12B—C12—H12A | 108.0 |
C8—S2—Ti1 | 105.12 (2) | C18—C13—C14 | 120.48 (6) |
C1—O1—Ti1 | 129.62 (4) | C18—C13—S2 | 123.34 (5) |
C14—O2—Ti1 | 130.70 (4) | C14—C13—S2 | 116.07 (5) |
O1—C1—C6 | 120.85 (6) | O2—C14—C15 | 120.52 (6) |
O1—C1—C2 | 119.51 (6) | O2—C14—C13 | 119.73 (6) |
C6—C1—C2 | 119.60 (6) | C15—C14—C13 | 119.74 (6) |
C3—C2—C1 | 120.53 (7) | C16—C15—C14 | 119.21 (6) |
C3—C2—S1 | 122.66 (6) | C16—C15—H15 | 120.4 |
C1—C2—S1 | 116.66 (5) | C14—C15—H15 | 120.4 |
C4—C3—C2 | 119.57 (8) | C15—C16—C17 | 121.19 (6) |
C4—C3—H3 | 120.2 | C15—C16—H16 | 119.4 |
C2—C3—H3 | 120.2 | C17—C16—H16 | 119.4 |
C3—C4—C5 | 119.86 (8) | C18—C17—C16 | 120.04 (7) |
C3—C4—H4 | 120.1 | C18—C17—H17 | 120.0 |
C5—C4—H4 | 120.1 | C16—C17—H17 | 120.0 |
C6—C5—C4 | 121.21 (8) | C17—C18—C13 | 119.32 (7) |
C6—C5—H5 | 119.4 | C17—C18—H18 | 120.3 |
C4—C5—H5 | 119.4 | C13—C18—H18 | 120.3 |
C5—C6—C1 | 119.17 (7) | C25—C20—C21 | 117.82 (17) |
C5—C6—H6 | 120.4 | C25—C20—C19 | 120.97 (18) |
C1—C6—H6 | 120.4 | C21—C20—C19 | 121.20 (18) |
C8—C7—C12 | 111.35 (5) | C22—C21—C20 | 120.65 (19) |
C8—C7—S1 | 113.20 (5) | C22—C21—H21 | 119.7 |
C12—C7—S1 | 110.96 (5) | C20—C21—H21 | 119.7 |
C8—C7—H7 | 107.0 | C21—C22—C23 | 120.88 (18) |
C12—C7—H7 | 107.0 | C21—C22—H22 | 119.6 |
S1—C7—H7 | 107.0 | C23—C22—H22 | 119.6 |
C7—C8—C9 | 111.68 (6) | C24—C23—C22 | 119.1 (2) |
C7—C8—S2 | 112.94 (4) | C24—C23—H23 | 120.5 |
C9—C8—S2 | 110.29 (5) | C22—C23—H23 | 120.5 |
C7—C8—H8 | 107.2 | C25—C24—C23 | 119.62 (19) |
C9—C8—H8 | 107.2 | C25—C24—H24 | 120.2 |
S2—C8—H8 | 107.2 | C23—C24—H24 | 120.2 |
C10—C9—C8 | 111.02 (6) | C24—C25—C20 | 121.93 (18) |
C10—C9—H9A | 109.4 | C24—C25—H25 | 119.0 |
C8—C9—H9A | 109.4 | C20—C25—H25 | 119.0 |
C10—C9—H9B | 109.4 | ||
O2—Ti1—S1—C2 | 177.38 (3) | C2—C1—C6—C5 | −1.92 (13) |
O1—Ti1—S1—C2 | 11.46 (3) | C2—S1—C7—C8 | −61.36 (5) |
Cl1—Ti1—S1—C2 | 80.78 (4) | Ti1—S1—C7—C8 | 36.81 (5) |
Cl2—Ti1—S1—C2 | −86.25 (3) | C2—S1—C7—C12 | 64.67 (5) |
S2—Ti1—S1—C2 | 98.39 (3) | Ti1—S1—C7—C12 | 162.84 (4) |
O2—Ti1—S1—C7 | 71.46 (3) | C12—C7—C8—C9 | 53.30 (7) |
O1—Ti1—S1—C7 | −94.47 (3) | S1—C7—C8—C9 | 179.13 (5) |
Cl1—Ti1—S1—C7 | −25.15 (4) | C12—C7—C8—S2 | 178.29 (5) |
Cl2—Ti1—S1—C7 | 167.83 (2) | S1—C7—C8—S2 | −55.89 (6) |
S2—Ti1—S1—C7 | −7.54 (2) | C13—S2—C8—C7 | −54.89 (5) |
O2—Ti1—S2—C13 | 4.46 (3) | Ti1—S2—C8—C7 | 44.36 (5) |
O1—Ti1—S2—C13 | 169.53 (3) | C13—S2—C8—C9 | 70.85 (5) |
Cl1—Ti1—S2—C13 | −92.90 (2) | Ti1—S2—C8—C9 | 170.10 (4) |
Cl2—Ti1—S2—C13 | 72.50 (4) | C7—C8—C9—C10 | −55.03 (8) |
S1—Ti1—S2—C13 | 91.00 (2) | S2—C8—C9—C10 | 178.52 (5) |
O2—Ti1—S2—C8 | −102.39 (3) | C8—C9—C10—C11 | 57.56 (9) |
O1—Ti1—S2—C8 | 62.69 (3) | C9—C10—C11—C12 | −58.84 (9) |
Cl1—Ti1—S2—C8 | 160.26 (2) | C10—C11—C12—C7 | 57.44 (9) |
Cl2—Ti1—S2—C8 | −34.35 (4) | C8—C7—C12—C11 | −54.53 (8) |
S1—Ti1—S2—C8 | −15.84 (2) | S1—C7—C12—C11 | 178.41 (5) |
O2—Ti1—O1—C1 | −55.74 (10) | C8—S2—C13—C18 | −79.62 (7) |
Cl1—Ti1—O1—C1 | 175.94 (6) | Ti1—S2—C13—C18 | 173.35 (6) |
Cl2—Ti1—O1—C1 | 68.11 (6) | C8—S2—C13—C14 | 104.16 (5) |
S2—Ti1—O1—C1 | −97.19 (6) | Ti1—S2—C13—C14 | −2.88 (5) |
S1—Ti1—O1—C1 | −16.29 (6) | Ti1—O2—C14—C15 | −171.11 (5) |
O1—Ti1—O2—C14 | −49.66 (10) | Ti1—O2—C14—C13 | 7.63 (10) |
Cl1—Ti1—O2—C14 | 78.76 (6) | C18—C13—C14—O2 | −177.47 (6) |
Cl2—Ti1—O2—C14 | −173.62 (6) | S2—C13—C14—O2 | −1.13 (8) |
S2—Ti1—O2—C14 | −7.33 (6) | C18—C13—C14—C15 | 1.28 (10) |
S1—Ti1—O2—C14 | −88.26 (6) | S2—C13—C14—C15 | 177.61 (5) |
Ti1—O1—C1—C6 | −162.71 (6) | O2—C14—C15—C16 | 178.32 (7) |
Ti1—O1—C1—C2 | 14.88 (10) | C13—C14—C15—C16 | −0.42 (10) |
O1—C1—C2—C3 | −174.58 (8) | C14—C15—C16—C17 | −0.06 (12) |
C6—C1—C2—C3 | 3.04 (12) | C15—C16—C17—C18 | −0.30 (13) |
O1—C1—C2—S1 | 1.11 (10) | C16—C17—C18—C13 | 1.14 (12) |
C6—C1—C2—S1 | 178.73 (6) | C14—C13—C18—C17 | −1.63 (11) |
C7—S1—C2—C3 | −86.40 (8) | S2—C13—C18—C17 | −177.69 (6) |
Ti1—S1—C2—C3 | 166.20 (7) | C25—C20—C21—C22 | 1.2 (2) |
C7—S1—C2—C1 | 98.01 (6) | C19—C20—C21—C22 | −177.44 (16) |
Ti1—S1—C2—C1 | −9.38 (6) | C20—C21—C22—C23 | −1.6 (3) |
C1—C2—C3—C4 | −2.50 (14) | C21—C22—C23—C24 | 1.0 (3) |
S1—C2—C3—C4 | −177.92 (9) | C22—C23—C24—C25 | −0.1 (3) |
C2—C3—C4—C5 | 0.86 (17) | C23—C24—C25—C20 | −0.3 (3) |
C3—C4—C5—C6 | 0.24 (19) | C21—C20—C25—C24 | −0.3 (2) |
C4—C5—C6—C1 | 0.30 (17) | C19—C20—C25—C24 | 178.37 (16) |
O1—C1—C6—C5 | 175.66 (9) |
Experimental details
(I) | (IIa) | (IIb) | |
Crystal data | |||
Chemical formula | [Ti(C20H22O2S2)Cl2] | [Ti(C18H18O2S2)Cl2] | [Ti(C18H18O2S2)Cl2]·0.5C7H8 |
Mr | 477.30 | 449.24 | 445.31 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 100 | 100 | 100 |
a, b, c (Å) | 10.7948 (2), 10.9672 (2), 18.5874 (3) | 9.4627 (7), 16.8985 (4), 12.0810 (11) | 9.7622 (3), 16.3667 (4), 14.5713 (4) |
β (°) | 101.105 (1) | 104.195 (6) | 106.899 (1) |
V (Å3) | 2159.34 (7) | 1872.8 (2) | 2227.60 (11) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.85 | 0.98 | 0.83 |
Crystal size (mm) | 0.29 × 0.24 × 0.15 | 0.30 × 0.22 × 0.18 | 0.36 × 0.22 × 0.10 |
Data collection | |||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (MULABS in PLATON; Spek, 2009) | Multi-scan (MULABS in PLATON; Spek, 2009) | Multi-scan (PLATON in MULABS; Spek, 2009) |
Tmin, Tmax | 0.791, 0.883 | 0.759, 0.844 | 0.755, 0.922 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 52551, 10145, 7452 | 257682, 28176, 22536 | 179195, 20925, 13853 |
Rint | 0.060 | 0.053 | 0.067 |
(sin θ/λ)max (Å−1) | 1.043 | 1.218 | 1.042 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.112, 1.07 | 0.049, 0.098, 1.24 | 0.035, 0.087, 0.97 |
No. of reflections | 10145 | 28176 | 20925 |
No. of parameters | 134 | 226 | 290 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.07, −0.75 | 0.84, −0.73 | 0.73, −0.47 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).
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Bis(phenolate) complexes of the early transition metals such as titanium are precatalysts for olefin polymerization. The ligand structure has a strong influence on the stereochemistry of the resulting polymer (Capacchione et al., 2004; Beckerle et al., 2007; Cohen et al., 2007). For this reason the bis(phenolate) ligands have been tuned by different substituents on the aromatic rings (R1 and R2) as well as by modifying the bridging unit. S atoms as part of the bridge can improve the catalytic activity, obviously as a result of hemilabile interactions between the soft donor S atom and the hard metal center (Froese et al., 1999). In several S—C—C—S bridged bis(phenolato)titanium complexes, the M···S interactions lead to a stereorigid tetradentate (OSSO) coordination in solution (Capacchione et al., 2005). The nature of this so-called mismatched interaction is still not well understood and further details are not available from routine structure data. Ideal model compounds for structural studies should be as simple as possible, keeping the number of parameters low. Catalytically active systems usually contain bulky substituents such as t-butyl groups in ortho position of the ring systems, which are often found disordered in the solid state. According to a previous structural comparison, the ortho substituents in bis(phenolate)–metal complexes barely influence the bond parameters around the metal center (Capacchione et al., 2005).
Comparatively good results were obtained recently for a routine crystal structure determination of (I) (Meppelder et al., 2008). We have now obtained high-quality crystals of this compound by reactive crystallization. In an analogous reaction, we have obtained crystals of a compound without the 4-methyl substituents and without solvent in the crystal structure, (IIa), as well as a toluene solvate, (IIb). Excellent diffraction results gave a resolution of sinθ/λ > 1.03 for all of these examples and have led to good agreement factors in spite of the outstanding ratio of reflections to parameters. The molecular structures of the three compounds are shown in Figs. 1–3.
Although the structure model of (IIb) should be even more simple than that of (I), it only shows idealized C2 symmetry. As reported previously, (I) crystallizes on a crystallographic C2 axis. In addition in (IIb), solvent molecules are incorporated around inversion centers in the space group P21/n. The incorporated toluene solvent molecules are disordered in the crystal structure. There are no significant differences between the molecular structures. As in the parent molecule with a CH2CH2 bridge (Snell et al., 2003), the metal center adopts a distorted octahedral geometry, coordinated by the two chloro ligands, both O-atom donors of the bis(phenolate) ligands and both S atoms. The Cl ligands and the S atoms are found in one plane. Both O atoms occupy pseudoapical positions. The Ti—S distances are 2.6188 (2) Å in (I), 2.6141 (2) and 2.6270 (2) Å in (IIa), and 2.6030 (3) and 2.6261 (3) Å in (IIb), and are comparable to the Ti—S lengths in related compounds (ranging from 2.6 to 2.9 Å; Capacchione et al., 2005). The stabilization of the helical configuration of the molecules by the relatively short Ti—S bond distances was noted previously. The overall geometry is chiral with a gauche-like conformation of the S—C—C—S bridge. The centrosymmetric packing arrangement contains both enantiomers.
Packing diagrams (Figs. 4 and 5) show similarities between the arrangement of (IIa) and (IIb), which both crystallize in space group P 21/n. The projections along the crystallographic a axis show the positions of the toluene solvent molecules. All three crystal structures exhibit close interactomic interactions involving the H atoms of the cyclohexyl fragment and the O atoms of neighboring bis(phenolate) ligands.
The close similarity of the molecular structure parameters underlines that (I) and (IIa) are suitable model compounds for bis(phenolate)–metal-based precatalysts. We are currently working on the further interpretation of the diffraction data. By multipole refinement, we are now determining the electron density distribution in (I) and (IIa) to establish the nature of the interaction between the hard metal center and the soft S atom. These data will give further insight into the extent of oxygen–Ti π interaction in this class of compounds (Snell et al., 2003).