Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801008856/tk6025sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801008856/tk6025Isup2.hkl |
CCDC reference: 170739
The title compound was prepared from the stoichiometric reaction of Ti(NMe2)4 with N-(2-p-tolylsulfonamido-propyl)-cyclopentadiene followed by treatment with excess Me3SiCl. Crystals were obtained from dichloromethane/pentane. Details and spectroscopic data will be reported in a future publication.
Atom C15 was disordered into two sites (A and B) with final occupancies 0.589:411 (17). All H atoms except those on methyl carbons and C8 were constrained to an isotropic displacement parameter 1.2 times that of the equivalent U of their parent atom. This factor was 1.5 times for the other H atoms.
Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996) and SADABS (Sheldrick, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) based on ORTEPIIa (Johnson, 1976); software used to prepare material for publication: CIFTAB (Sheldrick, 1997).
[TiCl2(C15H17NO2S)] | F(000) = 808 |
Mr = 394.16 | Dx = 1.509 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1024 reflections |
a = 10.874 (4) Å | θ = 3.1–25.9° |
b = 13.517 (5) Å | µ = 0.93 mm−1 |
c = 12.057 (4) Å | T = 168 K |
β = 101.717 (5)° | Block, yellow |
V = 1735.4 (10) Å3 | 0.50 × 0.44 × 0.12 mm |
Z = 4 |
CCD area-detector diffractometer | 3504 independent reflections |
Radiation source: fine-focus sealed tube | 2182 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.078 |
Detector resolution: 8.192 pixels mm-1 | θmax = 26.3°, θmin = 2.3° |
ϕ and ω scans | h = −13→13 |
Absorption correction: multi-scan (Blessing, 1995) | k = −16→16 |
Tmin = 0.710, Tmax = 0.895 | l = −14→15 |
21781 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0443P)2 + 3.0084P] where P = (Fo2 + 2Fc2)/3 |
3504 reflections | (Δ/σ)max = 0.009 |
201 parameters | Δρmax = 0.52 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
[TiCl2(C15H17NO2S)] | V = 1735.4 (10) Å3 |
Mr = 394.16 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.874 (4) Å | µ = 0.93 mm−1 |
b = 13.517 (5) Å | T = 168 K |
c = 12.057 (4) Å | 0.50 × 0.44 × 0.12 mm |
β = 101.717 (5)° |
CCD area-detector diffractometer | 3504 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 2182 reflections with I > 2σ(I) |
Tmin = 0.710, Tmax = 0.895 | Rint = 0.078 |
21781 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.52 e Å−3 |
3504 reflections | Δρmin = −0.41 e Å−3 |
201 parameters |
Experimental. Crystal decay was monitored by repeating the initial 10 frames at the end of the data collection and analyzing duplicate reflections. The standard 0.8 mm diameter collimator was used. |
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 | 0.76496 (7) | 0.26292 (6) | 0.79217 (6) | 0.0381 (2) | |
S1 | 0.84144 (11) | 0.23930 (8) | 0.58208 (9) | 0.0427 (3) | |
Cl1 | 0.55497 (11) | 0.28838 (13) | 0.72130 (10) | 0.0712 (5) | |
Cl2 | 0.79521 (17) | 0.10179 (9) | 0.85442 (12) | 0.0768 (5) | |
O1 | 0.9433 (3) | 0.1856 (3) | 0.5505 (3) | 0.0670 (11) | |
O2 | 0.7421 (3) | 0.1814 (2) | 0.6185 (3) | 0.0549 (9) | |
N1 | 0.8785 (3) | 0.3088 (3) | 0.6919 (3) | 0.0395 (8) | |
C1 | 0.7750 (4) | 0.3142 (3) | 0.4660 (3) | 0.0360 (9) | |
C2 | 0.8168 (5) | 0.3037 (4) | 0.3651 (4) | 0.0604 (15) | |
H2 | 0.8795 | 0.2563 | 0.3588 | 0.072* | |
C3 | 0.7657 (6) | 0.3637 (4) | 0.2736 (4) | 0.0707 (17) | |
H3 | 0.7945 | 0.3567 | 0.2047 | 0.085* | |
C4 | 0.6740 (5) | 0.4331 (3) | 0.2801 (4) | 0.0488 (12) | |
C5 | 0.6334 (4) | 0.4419 (3) | 0.3815 (4) | 0.0496 (12) | |
H5 | 0.5696 | 0.4885 | 0.3875 | 0.060* | |
C6 | 0.6844 (4) | 0.3837 (3) | 0.4747 (4) | 0.0454 (11) | |
H6 | 0.6571 | 0.3919 | 0.5442 | 0.054* | |
C7 | 0.6197 (6) | 0.4986 (4) | 0.1800 (4) | 0.0737 (17) | |
H7A | 0.6294 | 0.5681 | 0.2030 | 0.111* | |
H7B | 0.5304 | 0.4834 | 0.1540 | 0.111* | |
H7C | 0.6644 | 0.4865 | 0.1184 | 0.111* | |
C8 | 0.9750 (6) | 0.3863 (5) | 0.7047 (5) | 0.087 (2) | |
H8 | 0.9224 | 0.4388 | 0.6597 | 0.130* | |
C9 | 0.9881 (6) | 0.4325 (5) | 0.8156 (5) | 0.0799 (19) | |
H9A | 0.9743 | 0.5046 | 0.8057 | 0.096* | |
H9B | 1.0749 | 0.4223 | 0.8587 | 0.096* | |
C10 | 0.8976 (4) | 0.3917 (3) | 0.8823 (4) | 0.0469 (11) | |
C11 | 0.7707 (5) | 0.4213 (3) | 0.8755 (4) | 0.0521 (12) | |
H11 | 0.7303 | 0.4754 | 0.8325 | 0.063* | |
C12 | 0.7154 (5) | 0.3577 (4) | 0.9423 (4) | 0.0550 (13) | |
H12 | 0.6314 | 0.3617 | 0.9532 | 0.066* | |
C13 | 0.8037 (5) | 0.2874 (4) | 0.9905 (4) | 0.0576 (14) | |
H13 | 0.7912 | 0.2354 | 1.0401 | 0.069* | |
C14 | 0.9149 (5) | 0.3074 (4) | 0.9523 (4) | 0.0526 (12) | |
H14 | 0.9901 | 0.2698 | 0.9709 | 0.063* | |
C15A | 1.0712 (12) | 0.3790 (12) | 0.6351 (10) | 0.081 (3)* | 0.589 (17) |
H151 | 1.1233 | 0.3204 | 0.6577 | 0.121* | 0.589 (17) |
H152 | 1.1241 | 0.4383 | 0.6461 | 0.121* | 0.589 (17) |
H153 | 1.0302 | 0.3734 | 0.5550 | 0.121* | 0.589 (17) |
C15B | 1.0306 (18) | 0.4286 (16) | 0.6171 (14) | 0.081 (3)* | 0.411 (17) |
H154 | 1.0503 | 0.3758 | 0.5677 | 0.121* | 0.411 (17) |
H155 | 1.1079 | 0.4636 | 0.6514 | 0.121* | 0.411 (17) |
H156 | 0.9714 | 0.4752 | 0.5723 | 0.121* | 0.411 (17) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ti1 | 0.0434 (5) | 0.0437 (5) | 0.0277 (4) | −0.0051 (4) | 0.0081 (3) | −0.0022 (3) |
S1 | 0.0514 (7) | 0.0435 (6) | 0.0352 (6) | 0.0126 (5) | 0.0137 (5) | −0.0021 (5) |
Cl1 | 0.0378 (7) | 0.1377 (14) | 0.0384 (7) | −0.0109 (8) | 0.0085 (5) | −0.0158 (7) |
Cl2 | 0.1282 (14) | 0.0449 (7) | 0.0548 (8) | −0.0139 (8) | 0.0128 (8) | 0.0079 (6) |
O1 | 0.081 (3) | 0.075 (2) | 0.049 (2) | 0.047 (2) | 0.0232 (18) | 0.0031 (18) |
O2 | 0.077 (2) | 0.0465 (18) | 0.0444 (18) | −0.0137 (17) | 0.0195 (17) | −0.0065 (15) |
N1 | 0.038 (2) | 0.046 (2) | 0.0343 (19) | 0.0025 (17) | 0.0082 (16) | −0.0039 (16) |
C1 | 0.040 (2) | 0.034 (2) | 0.033 (2) | 0.0019 (19) | 0.0064 (18) | −0.0062 (18) |
C2 | 0.097 (4) | 0.053 (3) | 0.035 (3) | 0.030 (3) | 0.021 (3) | −0.005 (2) |
C3 | 0.125 (5) | 0.060 (3) | 0.029 (3) | 0.027 (3) | 0.019 (3) | −0.005 (2) |
C4 | 0.061 (3) | 0.035 (2) | 0.042 (3) | −0.004 (2) | −0.009 (2) | −0.007 (2) |
C5 | 0.035 (3) | 0.044 (3) | 0.070 (3) | 0.007 (2) | 0.010 (2) | 0.008 (2) |
C6 | 0.042 (3) | 0.048 (3) | 0.051 (3) | 0.005 (2) | 0.022 (2) | 0.000 (2) |
C7 | 0.105 (5) | 0.044 (3) | 0.055 (3) | 0.005 (3) | −0.022 (3) | −0.001 (3) |
C8 | 0.085 (4) | 0.120 (5) | 0.068 (4) | −0.056 (4) | 0.046 (3) | −0.037 (4) |
C9 | 0.073 (4) | 0.107 (5) | 0.061 (4) | −0.045 (4) | 0.018 (3) | −0.012 (3) |
C10 | 0.047 (3) | 0.059 (3) | 0.033 (2) | −0.011 (2) | 0.002 (2) | −0.011 (2) |
C11 | 0.068 (4) | 0.047 (3) | 0.036 (3) | 0.007 (3) | −0.002 (2) | −0.011 (2) |
C12 | 0.047 (3) | 0.082 (4) | 0.037 (3) | −0.002 (3) | 0.010 (2) | −0.021 (3) |
C13 | 0.079 (4) | 0.068 (3) | 0.026 (2) | −0.010 (3) | 0.011 (2) | −0.003 (2) |
C14 | 0.050 (3) | 0.065 (3) | 0.036 (3) | 0.009 (3) | −0.007 (2) | −0.003 (2) |
Ti1—N1 | 1.994 (3) | C7—H7A | 0.9800 |
Ti1—Cl1 | 2.2958 (16) | C7—H7B | 0.9800 |
Ti1—Cl2 | 2.3055 (17) | C7—H7C | 0.9800 |
Ti1—O2 | 2.334 (3) | C8—C15B | 1.439 (16) |
Ti1—C14 | 2.339 (5) | C8—C9 | 1.456 (7) |
Ti1—C11 | 2.361 (5) | C8—C15A | 1.472 (12) |
Ti1—C13 | 2.366 (4) | C8—H8 | 1.0000 |
Ti1—C12 | 2.368 (4) | C9—C10 | 1.497 (7) |
Ti1—C10 | 2.378 (4) | C9—H9A | 0.9900 |
S1—O1 | 1.439 (3) | C9—H9B | 0.9900 |
S1—O2 | 1.471 (3) | C10—C14 | 1.408 (6) |
S1—N1 | 1.608 (3) | C10—C11 | 1.424 (7) |
S1—C1 | 1.759 (4) | C11—C12 | 1.396 (7) |
N1—C8 | 1.468 (6) | C11—H11 | 0.9500 |
C1—C6 | 1.381 (6) | C12—C13 | 1.392 (7) |
C1—C2 | 1.390 (6) | C12—H12 | 0.9500 |
C2—C3 | 1.391 (7) | C13—C14 | 1.404 (7) |
C2—H2 | 0.9500 | C13—H13 | 0.9500 |
C3—C4 | 1.383 (7) | C14—H14 | 0.9500 |
C3—H3 | 0.9500 | C15A—H151 | 0.9800 |
C4—C5 | 1.387 (6) | C15A—H152 | 0.9800 |
C4—C7 | 1.516 (6) | C15A—H153 | 0.9800 |
C5—C6 | 1.391 (6) | C15B—H154 | 0.9800 |
C5—H5 | 0.9500 | C15B—H155 | 0.9800 |
C6—H6 | 0.9500 | C15B—H156 | 0.9800 |
N1—Ti1—Cl1 | 114.78 (11) | C5—C6—H6 | 120.1 |
N1—Ti1—Cl2 | 115.24 (11) | C4—C7—H7A | 109.5 |
Cl1—Ti1—Cl2 | 109.16 (7) | C4—C7—H7B | 109.5 |
N1—Ti1—O2 | 64.50 (13) | H7A—C7—H7B | 109.5 |
Cl1—Ti1—O2 | 79.65 (10) | C4—C7—H7C | 109.5 |
Cl2—Ti1—O2 | 80.10 (9) | H7A—C7—H7C | 109.5 |
N1—Ti1—C14 | 90.40 (17) | H7B—C7—H7C | 109.5 |
Cl1—Ti1—C14 | 137.96 (13) | C15B—C8—C9 | 121.8 (8) |
Cl2—Ti1—C14 | 86.82 (13) | C15B—C8—N1 | 127.2 (8) |
O2—Ti1—C14 | 142.31 (16) | C9—C8—N1 | 109.7 (4) |
N1—Ti1—C11 | 90.53 (16) | C15B—C8—C15A | 32.2 (7) |
Cl1—Ti1—C11 | 87.75 (13) | C9—C8—C15A | 127.1 (6) |
Cl2—Ti1—C11 | 136.79 (13) | N1—C8—C15A | 117.9 (7) |
O2—Ti1—C11 | 143.00 (14) | C15B—C8—H8 | 66.3 |
C14—Ti1—C11 | 57.45 (17) | C9—C8—H8 | 97.6 |
N1—Ti1—C13 | 124.33 (17) | N1—C8—H8 | 97.6 |
Cl1—Ti1—C13 | 108.36 (14) | C15A—C8—H8 | 97.6 |
Cl2—Ti1—C13 | 79.55 (14) | C8—C9—C10 | 112.4 (4) |
O2—Ti1—C13 | 159.62 (16) | C8—C9—H9A | 109.1 |
C14—Ti1—C13 | 34.73 (17) | C10—C9—H9A | 109.1 |
C11—Ti1—C13 | 57.26 (17) | C8—C9—H9B | 109.1 |
N1—Ti1—C12 | 124.08 (17) | C10—C9—H9B | 109.1 |
Cl1—Ti1—C12 | 80.78 (13) | H9A—C9—H9B | 107.8 |
Cl2—Ti1—C12 | 107.56 (15) | C14—C10—C11 | 105.8 (4) |
O2—Ti1—C12 | 160.39 (16) | C14—C10—C9 | 126.8 (5) |
C14—Ti1—C12 | 57.21 (17) | C11—C10—C9 | 126.9 (5) |
C11—Ti1—C12 | 34.35 (16) | C14—C10—Ti1 | 71.1 (3) |
C13—Ti1—C12 | 34.20 (17) | C11—C10—Ti1 | 71.9 (3) |
N1—Ti1—C10 | 69.90 (15) | C9—C10—Ti1 | 115.4 (3) |
Cl1—Ti1—C10 | 121.71 (13) | C12—C11—C10 | 108.6 (4) |
Cl2—Ti1—C10 | 120.63 (13) | C12—C11—Ti1 | 73.1 (3) |
O2—Ti1—C10 | 134.40 (14) | C10—C11—Ti1 | 73.2 (3) |
C14—Ti1—C10 | 34.72 (16) | C12—C11—H11 | 125.7 |
C11—Ti1—C10 | 34.97 (16) | C10—C11—H11 | 125.7 |
C13—Ti1—C10 | 57.90 (17) | Ti1—C11—H11 | 119.8 |
C12—Ti1—C10 | 57.72 (17) | C13—C12—C11 | 108.6 (4) |
O1—S1—O2 | 117.5 (2) | C13—C12—Ti1 | 72.8 (3) |
O1—S1—N1 | 115.8 (2) | C11—C12—Ti1 | 72.5 (3) |
O2—S1—N1 | 98.12 (18) | C13—C12—H12 | 125.7 |
O1—S1—C1 | 107.10 (19) | C11—C12—H12 | 125.7 |
O2—S1—C1 | 109.6 (2) | Ti1—C12—H12 | 120.7 |
N1—S1—C1 | 108.23 (19) | C12—C13—C14 | 107.4 (5) |
S1—O2—Ti1 | 93.78 (15) | C12—C13—Ti1 | 73.0 (3) |
C8—N1—S1 | 123.9 (3) | C14—C13—Ti1 | 71.6 (3) |
C8—N1—Ti1 | 132.5 (3) | C12—C13—H13 | 126.3 |
S1—N1—Ti1 | 103.60 (18) | C14—C13—H13 | 126.3 |
C6—C1—C2 | 120.1 (4) | Ti1—C13—H13 | 120.9 |
C6—C1—S1 | 121.0 (3) | C13—C14—C10 | 109.5 (4) |
C2—C1—S1 | 118.9 (3) | C13—C14—Ti1 | 73.7 (3) |
C1—C2—C3 | 119.1 (4) | C10—C14—Ti1 | 74.2 (3) |
C1—C2—H2 | 120.5 | C13—C14—H14 | 125.3 |
C3—C2—H2 | 120.5 | C10—C14—H14 | 125.3 |
C4—C3—C2 | 121.8 (4) | Ti1—C14—H14 | 118.7 |
C4—C3—H3 | 119.1 | C8—C15A—H151 | 109.5 |
C2—C3—H3 | 119.1 | C8—C15A—H152 | 109.5 |
C3—C4—C5 | 118.1 (4) | C8—C15A—H153 | 109.5 |
C3—C4—C7 | 121.3 (5) | C8—C15B—H154 | 109.5 |
C5—C4—C7 | 120.6 (5) | C8—C15B—H155 | 109.5 |
C4—C5—C6 | 121.2 (4) | H154—C15B—H155 | 109.5 |
C4—C5—H5 | 119.4 | C8—C15B—H156 | 109.5 |
C6—C5—H5 | 119.4 | H154—C15B—H156 | 109.5 |
C1—C6—C5 | 119.8 (4) | H155—C15B—H156 | 109.5 |
C1—C6—H6 | 120.1 | ||
O1—S1—O2—Ti1 | 124.22 (19) | C14—Ti1—C10—C9 | 122.5 (5) |
N1—S1—O2—Ti1 | −0.56 (17) | C11—Ti1—C10—C9 | −123.0 (5) |
C1—S1—O2—Ti1 | −113.28 (17) | C13—Ti1—C10—C9 | 159.6 (5) |
N1—Ti1—O2—S1 | 0.49 (15) | C12—Ti1—C10—C9 | −159.8 (5) |
Cl1—Ti1—O2—S1 | 124.49 (16) | C14—C10—C11—C12 | 1.6 (5) |
Cl2—Ti1—O2—S1 | −123.76 (16) | C9—C10—C11—C12 | 173.6 (4) |
C14—Ti1—O2—S1 | −52.3 (3) | Ti1—C10—C11—C12 | 65.0 (3) |
C11—Ti1—O2—S1 | 52.5 (3) | C14—C10—C11—Ti1 | −63.5 (3) |
C13—Ti1—O2—S1 | −120.2 (4) | C9—C10—C11—Ti1 | 108.5 (5) |
C12—Ti1—O2—S1 | 121.2 (5) | N1—Ti1—C11—C12 | −168.3 (3) |
C10—Ti1—O2—S1 | −0.2 (3) | Cl1—Ti1—C11—C12 | 76.9 (3) |
O1—S1—N1—C8 | 55.1 (5) | Cl2—Ti1—C11—C12 | −39.1 (4) |
O2—S1—N1—C8 | −179.0 (5) | O2—Ti1—C11—C12 | 146.3 (3) |
C1—S1—N1—C8 | −65.1 (5) | C14—Ti1—C11—C12 | −78.2 (3) |
O1—S1—N1—Ti1 | −125.3 (2) | C13—Ti1—C11—C12 | −36.7 (3) |
O2—S1—N1—Ti1 | 0.7 (2) | C10—Ti1—C11—C12 | −116.1 (4) |
C1—S1—N1—Ti1 | 114.5 (2) | N1—Ti1—C11—C10 | −52.2 (3) |
Cl1—Ti1—N1—C8 | 115.2 (5) | Cl1—Ti1—C11—C10 | −167.0 (3) |
Cl2—Ti1—N1—C8 | −116.7 (5) | Cl2—Ti1—C11—C10 | 77.1 (3) |
O2—Ti1—N1—C8 | 179.1 (5) | O2—Ti1—C11—C10 | −97.5 (3) |
C14—Ti1—N1—C8 | −30.0 (5) | C14—Ti1—C11—C10 | 37.9 (3) |
C11—Ti1—N1—C8 | 27.4 (5) | C13—Ti1—C11—C10 | 79.5 (3) |
C13—Ti1—N1—C8 | −22.1 (6) | C12—Ti1—C11—C10 | 116.1 (4) |
C12—Ti1—N1—C8 | 19.5 (6) | C10—C11—C12—C13 | −0.7 (5) |
C10—Ti1—N1—C8 | −1.4 (5) | Ti1—C11—C12—C13 | 64.3 (3) |
Cl1—Ti1—N1—S1 | −64.40 (19) | C10—C11—C12—Ti1 | −65.1 (3) |
Cl2—Ti1—N1—S1 | 63.72 (19) | N1—Ti1—C12—C13 | −102.5 (3) |
O2—Ti1—N1—S1 | −0.47 (14) | Cl1—Ti1—C12—C13 | 143.8 (3) |
C14—Ti1—N1—S1 | 150.4 (2) | Cl2—Ti1—C12—C13 | 36.5 (3) |
C11—Ti1—N1—S1 | −152.2 (2) | O2—Ti1—C12—C13 | 147.0 (4) |
C13—Ti1—N1—S1 | 158.27 (19) | C14—Ti1—C12—C13 | −37.7 (3) |
C12—Ti1—N1—S1 | −160.09 (19) | C11—Ti1—C12—C13 | −116.6 (4) |
C10—Ti1—N1—S1 | 179.0 (2) | C10—Ti1—C12—C13 | −79.1 (3) |
O1—S1—C1—C6 | −172.2 (4) | N1—Ti1—C12—C11 | 14.1 (4) |
O2—S1—C1—C6 | 59.4 (4) | Cl1—Ti1—C12—C11 | −99.6 (3) |
N1—S1—C1—C6 | −46.6 (4) | Cl2—Ti1—C12—C11 | 153.1 (3) |
O1—S1—C1—C2 | 6.6 (5) | O2—Ti1—C12—C11 | −96.4 (5) |
O2—S1—C1—C2 | −121.9 (4) | C14—Ti1—C12—C11 | 78.9 (3) |
N1—S1—C1—C2 | 132.1 (4) | C13—Ti1—C12—C11 | 116.6 (4) |
C6—C1—C2—C3 | −0.4 (8) | C10—Ti1—C12—C11 | 37.5 (3) |
S1—C1—C2—C3 | −179.2 (4) | C11—C12—C13—C14 | −0.4 (5) |
C1—C2—C3—C4 | −0.2 (9) | Ti1—C12—C13—C14 | 63.8 (3) |
C2—C3—C4—C5 | 0.0 (8) | C11—C12—C13—Ti1 | −64.2 (3) |
C2—C3—C4—C7 | 179.5 (5) | N1—Ti1—C13—C12 | 101.7 (3) |
C3—C4—C5—C6 | 0.9 (7) | Cl1—Ti1—C13—C12 | −37.9 (3) |
C7—C4—C5—C6 | −178.6 (4) | Cl2—Ti1—C13—C12 | −144.8 (3) |
C2—C1—C6—C5 | 1.3 (7) | O2—Ti1—C13—C12 | −148.4 (4) |
S1—C1—C6—C5 | −180.0 (3) | C14—Ti1—C13—C12 | 115.6 (5) |
C4—C5—C6—C1 | −1.6 (7) | C11—Ti1—C13—C12 | 36.9 (3) |
S1—N1—C8—C15B | 15.3 (16) | C10—Ti1—C13—C12 | 78.5 (3) |
Ti1—N1—C8—C15B | −164.2 (13) | N1—Ti1—C13—C14 | −13.9 (4) |
S1—N1—C8—C9 | −177.8 (4) | Cl1—Ti1—C13—C14 | −153.5 (3) |
Ti1—N1—C8—C9 | 2.7 (9) | Cl2—Ti1—C13—C14 | 99.6 (3) |
S1—N1—C8—C15A | −21.5 (11) | O2—Ti1—C13—C14 | 96.0 (5) |
Ti1—N1—C8—C15A | 159.0 (8) | C11—Ti1—C13—C14 | −78.7 (3) |
C15B—C8—C9—C10 | 165.4 (12) | C12—Ti1—C13—C14 | −115.6 (5) |
N1—C8—C9—C10 | −2.3 (8) | C10—Ti1—C13—C14 | −37.0 (3) |
C15A—C8—C9—C10 | −155.8 (10) | C12—C13—C14—C10 | 1.4 (5) |
C8—C9—C10—C14 | 86.2 (7) | Ti1—C13—C14—C10 | 66.1 (3) |
C8—C9—C10—C11 | −84.2 (7) | C12—C13—C14—Ti1 | −64.7 (3) |
C8—C9—C10—Ti1 | 1.5 (7) | C11—C10—C14—C13 | −1.8 (5) |
N1—Ti1—C10—C14 | −122.8 (3) | C9—C10—C14—C13 | −173.8 (4) |
Cl1—Ti1—C10—C14 | 129.9 (3) | Ti1—C10—C14—C13 | −65.8 (3) |
Cl2—Ti1—C10—C14 | −14.6 (3) | C11—C10—C14—Ti1 | 64.0 (3) |
O2—Ti1—C10—C14 | −122.1 (3) | C9—C10—C14—Ti1 | −108.1 (5) |
C11—Ti1—C10—C14 | 114.5 (4) | N1—Ti1—C14—C13 | 168.5 (3) |
C13—Ti1—C10—C14 | 37.0 (3) | Cl1—Ti1—C14—C13 | 39.2 (4) |
C12—Ti1—C10—C14 | 77.7 (3) | Cl2—Ti1—C14—C13 | −76.2 (3) |
N1—Ti1—C10—C11 | 122.7 (3) | O2—Ti1—C14—C13 | −145.5 (3) |
Cl1—Ti1—C10—C11 | 15.4 (3) | C11—Ti1—C14—C13 | 78.2 (3) |
Cl2—Ti1—C10—C11 | −129.1 (3) | C12—Ti1—C14—C13 | 37.1 (3) |
O2—Ti1—C10—C11 | 123.4 (3) | C10—Ti1—C14—C13 | 116.4 (4) |
C14—Ti1—C10—C11 | −114.5 (4) | N1—Ti1—C14—C10 | 52.2 (3) |
C13—Ti1—C10—C11 | −77.5 (3) | Cl1—Ti1—C14—C10 | −77.2 (3) |
C12—Ti1—C10—C11 | −36.8 (3) | Cl2—Ti1—C14—C10 | 167.4 (3) |
N1—Ti1—C10—C9 | −0.2 (4) | O2—Ti1—C14—C10 | 98.1 (3) |
Cl1—Ti1—C10—C9 | −107.6 (4) | C11—Ti1—C14—C10 | −38.2 (3) |
Cl2—Ti1—C10—C9 | 107.9 (4) | C13—Ti1—C14—C10 | −116.4 (4) |
O2—Ti1—C10—C9 | 0.4 (5) | C12—Ti1—C14—C10 | −79.3 (3) |
Experimental details
Crystal data | |
Chemical formula | [TiCl2(C15H17NO2S)] |
Mr | 394.16 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 168 |
a, b, c (Å) | 10.874 (4), 13.517 (5), 12.057 (4) |
β (°) | 101.717 (5) |
V (Å3) | 1735.4 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.93 |
Crystal size (mm) | 0.50 × 0.44 × 0.12 |
Data collection | |
Diffractometer | CCD area-detector diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.710, 0.895 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21781, 3504, 2182 |
Rint | 0.078 |
(sin θ/λ)max (Å−1) | 0.623 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.132, 1.03 |
No. of reflections | 3504 |
No. of parameters | 201 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.52, −0.41 |
Computer programs: SMART (Siemens, 1996), SMART, SAINT (Siemens, 1996) and SADABS (Sheldrick, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) based on ORTEPIIa (Johnson, 1976), CIFTAB (Sheldrick, 1997).
Ti1—N1 | 1.994 (3) | S1—O1 | 1.439 (3) |
Ti1—Cl1 | 2.2958 (16) | S1—O2 | 1.471 (3) |
Ti1—Cl2 | 2.3055 (17) | S1—N1 | 1.608 (3) |
Ti1—O2 | 2.334 (3) | S1—C1 | 1.759 (4) |
Ti1—C14 | 2.339 (5) | C8—C15B | 1.439 (16) |
Ti1—C11 | 2.361 (5) | C8—C9 | 1.456 (7) |
Ti1—C13 | 2.366 (4) | C8—C15A | 1.472 (12) |
Ti1—C12 | 2.368 (4) | C9—C10 | 1.497 (7) |
Ti1—C10 | 2.378 (4) | ||
N1—Ti1—Cl1 | 114.78 (11) | O1—S1—N1 | 115.8 (2) |
N1—Ti1—Cl2 | 115.24 (11) | O2—S1—N1 | 98.12 (18) |
Cl1—Ti1—Cl2 | 109.16 (7) | O1—S1—C1 | 107.10 (19) |
N1—Ti1—O2 | 64.50 (13) | S1—O2—Ti1 | 93.78 (15) |
Cl1—Ti1—O2 | 79.65 (10) | C15B—C8—N1 | 127.2 (8) |
Cl2—Ti1—O2 | 80.10 (9) | N1—C8—C15A | 117.9 (7) |
O1—S1—O2 | 117.5 (2) | C8—C9—C10 | 112.4 (4) |
O2—S1—N1—C8 | −179.0 (5) | S1—N1—C8—C15A | −21.5 (11) |
O2—S1—C1—C6 | 59.4 (4) | C15A—C8—C9—C10 | −155.8 (10) |
S1—N1—C8—C9 | −177.8 (4) | C8—C9—C10—C14 | 86.2 (7) |
The title compound, (I), is related to previously reported structures (Lensink, 1998; Lensink, Gainsford & Baxter, 2001; Lensink, Gainsford & Brandsma, 2001). The crystal structure consists of independent molecules (Fig. 1) of both enantantiomorphs to make a racemic crystal with one significant intermolecular contact: C11—H11····Cl2i is 2.80 Å for symmetry operation 3/2 - x, 1/2 + y, 3/2 - z. The titanium has fivefold coordination through the N and one O atom of the sulfonamide, a cyclopentadiene (assumed to occupy one coordination site) linked via an ethyl linkage to the nitrogen, and two Cl atoms. The S—O bonds [O1: 1.439 (3) Å; O2: 1.471 (3) Å] confirm the significant bonding of O2 to titanium; the Ti—Cg distance is 2.04 Å and lies within the narrow range 2.01–2.08 Å observed previously (Lensink, Gainsford & Baxter, 2001; Lensink, Gainsford & Brandsma, 2001; Allen & Kennard, 1993). The titanium coordination can best be described as being based on a tetrahedron formed by the cyclopentadiene, and the Cl1, Cl2 and N1 atoms with the Ti—O2 bond passing through the face formed by N1, Cl1 and Cl2; the angles subtended by O2 at the titanium to these three atoms are 64.50 (13), 79.65 (10) and 80.10 (9)°, respectively.