Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801005372/wn6013sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801005372/wn6013Isup2.hkl |
CCDC reference: 165625
The title compound was prepared using the method of Sullivan & Little (1967) and recrystallized from dichloromethane.
No variation in intensity was observed in the ψ scans of a number of suitable reflections and an absorption correction was therefore not applied. H atoms were placed in calculated positions and refined with a riding model.
Data collection: Nicolet P3 Software (Nicolet, 1980); cell refinement: Nicolet P3 Software; data reduction: RDNIC (Howie, 1980); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
[TiCl2(C16H22)] | F(000) = 696 |
Mr = 333.14 | Dx = 1.416 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 16.788 (13) Å | Cell parameters from 14 reflections |
b = 6.791 (7) Å | θ = 17–26° |
c = 15.814 (13) Å | µ = 0.87 mm−1 |
β = 119.89 (6)° | T = 298 K |
V = 1563 (2) Å3 | Rhomb, dark red |
Z = 4 | 0.88 × 0.30 × 0.24 mm |
Nicolet P3 diffractometer | Rint = 0.000 |
Radiation source: normal-focus sealed tube | θmax = 30.1°, θmin = 3.0° |
Graphite monochromator | h = 0→23 |
θ–2θ scans | k = 0→9 |
2207 measured reflections | l = −22→18 |
2207 independent reflections | 2 standard reflections every 50 reflections |
2147 reflections with I > 2σ(I) | intensity decay: none |
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.17 | w = 1/[σ2(Fo2) + (0.0436P)2 + 2.029P] where P = (Fo2 + 2Fc2)/3 |
2207 reflections | (Δ/σ)max < 0.001 |
90 parameters | Δρmax = 0.58 e Å−3 |
0 restraints | Δρmin = −0.66 e Å−3 |
[TiCl2(C16H22)] | V = 1563 (2) Å3 |
Mr = 333.14 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 16.788 (13) Å | µ = 0.87 mm−1 |
b = 6.791 (7) Å | T = 298 K |
c = 15.814 (13) Å | 0.88 × 0.30 × 0.24 mm |
β = 119.89 (6)° |
Nicolet P3 diffractometer | Rint = 0.000 |
2207 measured reflections | 2 standard reflections every 50 reflections |
2207 independent reflections | intensity decay: none |
2147 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.17 | Δρmax = 0.58 e Å−3 |
2207 reflections | Δρmin = −0.66 e Å−3 |
90 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. H in calculated positions and refined with a riding model. |
x | y | z | Uiso*/Ueq | ||
Ti | 0.0000 | 0.32870 (6) | 0.2500 | 0.02435 (11) | |
Cl | −0.11891 (3) | 0.09478 (8) | 0.17256 (4) | 0.04526 (15) | |
C1 | 0.03057 (13) | 0.3345 (3) | 0.42071 (13) | 0.0350 (4) | |
C2 | 0.05634 (12) | 0.5180 (3) | 0.39870 (13) | 0.0338 (3) | |
C3 | −0.02431 (13) | 0.6087 (3) | 0.32497 (14) | 0.0365 (4) | |
H3 | −0.0273 | 0.7323 | 0.2983 | 0.044* | |
C4 | −0.09917 (12) | 0.4817 (3) | 0.29856 (14) | 0.0384 (4) | |
C5 | −0.06406 (13) | 0.3115 (3) | 0.35746 (13) | 0.0370 (4) | |
H5 | −0.0984 | 0.2016 | 0.3546 | 0.044* | |
C6 | 0.09189 (19) | 0.2012 (4) | 0.50258 (15) | 0.0549 (6) | |
H6A | 0.0867 | 0.2313 | 0.5589 | 0.082* | |
H6B | 0.1543 | 0.2196 | 0.5178 | 0.082* | |
H6C | 0.0741 | 0.0669 | 0.4837 | 0.082* | |
C7 | 0.14986 (16) | 0.6088 (4) | 0.45499 (18) | 0.0538 (6) | |
H7A | 0.1544 | 0.7177 | 0.4189 | 0.081* | |
H7B | 0.1956 | 0.5123 | 0.4654 | 0.081* | |
H7C | 0.1595 | 0.6547 | 0.5168 | 0.081* | |
C8 | −0.19859 (15) | 0.5261 (5) | 0.23079 (19) | 0.0630 (7) | |
H8A | −0.2296 | 0.5397 | 0.2676 | 0.094* | |
H8B | −0.2259 | 0.4206 | 0.1847 | 0.094* | |
H8C | −0.2040 | 0.6466 | 0.1966 | 0.094* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ti | 0.02114 (17) | 0.02565 (19) | 0.02499 (19) | 0.000 | 0.01054 (14) | 0.000 |
Cl | 0.0450 (3) | 0.0472 (3) | 0.0443 (3) | −0.0206 (2) | 0.0228 (2) | −0.0136 (2) |
C1 | 0.0369 (8) | 0.0407 (9) | 0.0277 (7) | 0.0012 (7) | 0.0163 (7) | −0.0003 (7) |
C2 | 0.0311 (8) | 0.0371 (9) | 0.0317 (7) | −0.0039 (7) | 0.0143 (6) | −0.0076 (7) |
C3 | 0.0436 (9) | 0.0329 (8) | 0.0374 (8) | 0.0062 (7) | 0.0236 (8) | −0.0013 (7) |
C4 | 0.0295 (8) | 0.0510 (11) | 0.0359 (8) | 0.0071 (7) | 0.0172 (7) | −0.0045 (8) |
C5 | 0.0367 (8) | 0.0461 (10) | 0.0358 (8) | −0.0089 (7) | 0.0237 (7) | −0.0052 (7) |
C6 | 0.0662 (14) | 0.0627 (14) | 0.0334 (9) | 0.0141 (12) | 0.0231 (10) | 0.0131 (9) |
C7 | 0.0404 (11) | 0.0621 (14) | 0.0499 (12) | −0.0183 (10) | 0.0156 (9) | −0.0190 (11) |
C8 | 0.0324 (10) | 0.098 (2) | 0.0538 (13) | 0.0202 (12) | 0.0181 (9) | −0.0031 (14) |
Ti—Cl | 2.3605 (18) | C2—C7 | 1.498 (3) |
Ti—Cli | 2.3606 (18) | C3—C4 | 1.405 (3) |
Ti—C3 | 2.381 (2) | C3—H3 | 0.9300 |
Ti—C3i | 2.381 (2) | C4—C5 | 1.415 (3) |
Ti—C4i | 2.391 (2) | C4—C8 | 1.498 (3) |
Ti—C4 | 2.391 (2) | C5—H5 | 0.9300 |
Ti—C2 | 2.421 (3) | C6—H6A | 0.9600 |
Ti—C2i | 2.421 (3) | C6—H6B | 0.9600 |
Ti—C5i | 2.425 (2) | C6—H6C | 0.9600 |
Ti—C5 | 2.425 (2) | C7—H7A | 0.9600 |
Ti—C1 | 2.484 (3) | C7—H7B | 0.9600 |
Ti—C1i | 2.484 (3) | C7—H7C | 0.9600 |
C1—C5 | 1.402 (3) | C8—H8A | 0.9600 |
C1—C2 | 1.418 (3) | C8—H8B | 0.9600 |
C1—C6 | 1.493 (3) | C8—H8C | 0.9600 |
C2—C3 | 1.413 (3) | ||
Cl—Ti—Cli | 95.41 (9) | C3—Ti—C1i | 122.31 (7) |
Cl—Ti—C3 | 119.02 (7) | C3i—Ti—C1i | 55.95 (7) |
Cli—Ti—C3 | 126.13 (7) | C4i—Ti—C1i | 56.21 (8) |
Cl—Ti—C3i | 126.12 (7) | C4—Ti—C1i | 122.84 (8) |
Cli—Ti—C3i | 119.02 (7) | C2—Ti—C1i | 144.70 (8) |
C3—Ti—C3i | 74.03 (12) | C2i—Ti—C1i | 33.58 (7) |
Cl—Ti—C4i | 132.07 (7) | C5i—Ti—C1i | 33.15 (7) |
Cli—Ti—C4i | 85.11 (8) | C5—Ti—C1i | 147.01 (7) |
C3—Ti—C4i | 97.62 (9) | C1—Ti—C1i | 178.17 (9) |
C3i—Ti—C4i | 34.25 (7) | C5—C1—C2 | 107.39 (17) |
Cl—Ti—C4 | 85.11 (8) | C5—C1—C6 | 126.7 (2) |
Cli—Ti—C4 | 132.08 (7) | C2—C1—C6 | 125.67 (19) |
C3—Ti—C4 | 34.25 (7) | C5—C1—Ti | 71.09 (12) |
C3i—Ti—C4 | 97.62 (9) | C2—C1—Ti | 70.76 (10) |
C4i—Ti—C4 | 128.49 (12) | C6—C1—Ti | 127.78 (15) |
Cl—Ti—C2 | 132.95 (6) | C3—C2—C1 | 107.52 (16) |
Cli—Ti—C2 | 91.92 (9) | C3—C2—C7 | 126.9 (2) |
C3—Ti—C2 | 34.22 (7) | C1—C2—C7 | 124.98 (19) |
C3i—Ti—C2 | 88.78 (9) | C3—C2—Ti | 71.34 (12) |
C4i—Ti—C2 | 94.80 (9) | C1—C2—Ti | 75.66 (11) |
C4—Ti—C2 | 56.95 (8) | C7—C2—Ti | 125.61 (15) |
Cl—Ti—C2i | 91.92 (9) | C4—C3—C2 | 108.97 (18) |
Cli—Ti—C2i | 132.95 (6) | C4—C3—Ti | 73.25 (12) |
C3—Ti—C2i | 88.78 (10) | C2—C3—Ti | 74.44 (12) |
C3i—Ti—C2i | 34.22 (7) | C4—C3—H3 | 125.5 |
C4i—Ti—C2i | 56.95 (8) | C2—C3—H3 | 125.5 |
C4—Ti—C2i | 94.80 (9) | Ti—C3—H3 | 118.6 |
C2—Ti—C2i | 115.84 (12) | C3—C4—C5 | 106.74 (17) |
Cl—Ti—C5i | 99.19 (7) | C3—C4—C8 | 127.0 (2) |
Cli—Ti—C5i | 77.01 (7) | C5—C4—C8 | 125.8 (2) |
C3—Ti—C5i | 129.30 (8) | C3—C4—Ti | 72.50 (12) |
C3i—Ti—C5i | 56.19 (8) | C5—C4—Ti | 74.23 (11) |
C4i—Ti—C5i | 34.18 (8) | C8—C4—Ti | 124.33 (15) |
C4—Ti—C5i | 150.37 (7) | C1—C5—C4 | 109.31 (18) |
C2—Ti—C5i | 127.69 (8) | C1—C5—Ti | 75.76 (12) |
C2i—Ti—C5i | 55.94 (8) | C4—C5—Ti | 71.59 (10) |
Cl—Ti—C5 | 77.02 (7) | C1—C5—H5 | 125.3 |
Cli—Ti—C5 | 99.20 (7) | C4—C5—H5 | 125.3 |
C3—Ti—C5 | 56.19 (8) | Ti—C5—H5 | 119.0 |
C3i—Ti—C5 | 129.30 (8) | C1—C6—H6A | 109.5 |
C4i—Ti—C5 | 150.37 (7) | C1—C6—H6B | 109.5 |
C4—Ti—C5 | 34.18 (8) | H6A—C6—H6B | 109.5 |
C2—Ti—C5 | 55.94 (8) | C1—C6—H6C | 109.5 |
C2i—Ti—C5 | 127.69 (8) | H6A—C6—H6C | 109.5 |
C5i—Ti—C5 | 174.47 (10) | H6B—C6—H6C | 109.5 |
Cl—Ti—C1 | 103.76 (7) | C2—C7—H7A | 109.5 |
Cli—Ti—C1 | 77.51 (7) | C2—C7—H7B | 109.5 |
C3—Ti—C1 | 55.95 (7) | H7A—C7—H7B | 109.5 |
C3i—Ti—C1 | 122.31 (7) | C2—C7—H7C | 109.5 |
C4i—Ti—C1 | 122.84 (8) | H7A—C7—H7C | 109.5 |
C4—Ti—C1 | 56.21 (8) | H7B—C7—H7C | 109.5 |
C2—Ti—C1 | 33.58 (7) | C4—C8—H8A | 109.5 |
C2i—Ti—C1 | 144.70 (8) | C4—C8—H8B | 109.5 |
C5i—Ti—C1 | 147.01 (7) | H8A—C8—H8B | 109.5 |
C5—Ti—C1 | 33.15 (7) | C4—C8—H8C | 109.5 |
Cl—Ti—C1i | 77.51 (7) | H8A—C8—H8C | 109.5 |
Cli—Ti—C1i | 103.75 (7) | H8B—C8—H8C | 109.5 |
Cl—Ti—C1—C5 | −37.09 (13) | C5i—Ti—C3—C4 | 142.52 (12) |
Cli—Ti—C1—C5 | −129.67 (13) | C5—Ti—C3—C4 | −38.23 (12) |
C3—Ti—C1—C5 | 78.85 (13) | C1—Ti—C3—C4 | −78.45 (14) |
C3i—Ti—C1—C5 | 113.72 (13) | C1i—Ti—C3—C4 | 102.20 (14) |
C4i—Ti—C1—C5 | 154.63 (12) | Cl—Ti—C3—C2 | 124.73 (11) |
C4—Ti—C1—C5 | 37.28 (13) | Cli—Ti—C3—C2 | 2.16 (13) |
C2—Ti—C1—C5 | 117.01 (17) | C3i—Ti—C3—C2 | −112.41 (15) |
C2i—Ti—C1—C5 | 76.83 (16) | C4i—Ti—C3—C2 | −87.33 (13) |
C5i—Ti—C1—C5 | −169.86 (19) | C4—Ti—C3—C2 | 115.87 (17) |
Cl—Ti—C1—C2 | −154.10 (10) | C2i—Ti—C3—C2 | −143.75 (11) |
Cli—Ti—C1—C2 | 113.31 (12) | C5i—Ti—C3—C2 | −101.61 (13) |
C3—Ti—C1—C2 | −38.16 (12) | C5—Ti—C3—C2 | 77.64 (13) |
C3i—Ti—C1—C2 | −3.29 (13) | C1—Ti—C3—C2 | 37.42 (11) |
C4i—Ti—C1—C2 | 37.61 (13) | C1i—Ti—C3—C2 | −141.93 (11) |
C4—Ti—C1—C2 | −79.73 (13) | C2—C3—C4—C5 | 0.5 (2) |
C2i—Ti—C1—C2 | −40.2 (2) | Ti—C3—C4—C5 | 66.90 (14) |
C5i—Ti—C1—C2 | 73.12 (17) | C2—C3—C4—C8 | 173.38 (19) |
C5—Ti—C1—C2 | −117.01 (17) | Ti—C3—C4—C8 | −120.2 (2) |
Cl—Ti—C1—C6 | 85.2 (2) | C2—C3—C4—Ti | −66.43 (14) |
Cli—Ti—C1—C6 | −7.41 (19) | Cl—Ti—C4—C3 | −172.23 (11) |
C3—Ti—C1—C6 | −158.9 (2) | Cli—Ti—C4—C3 | 94.90 (14) |
C3i—Ti—C1—C6 | −124.0 (2) | C3i—Ti—C4—C3 | −46.39 (16) |
C4i—Ti—C1—C6 | −83.1 (2) | C4i—Ti—C4—C3 | −29.93 (10) |
C4—Ti—C1—C6 | 159.5 (2) | C2—Ti—C4—C3 | 37.14 (11) |
C2—Ti—C1—C6 | −120.7 (2) | C2i—Ti—C4—C3 | −80.71 (14) |
C2i—Ti—C1—C6 | −160.90 (18) | C5i—Ti—C4—C3 | −72.21 (19) |
C5i—Ti—C1—C6 | −47.6 (3) | C5—Ti—C4—C3 | 113.76 (18) |
C5—Ti—C1—C6 | 122.3 (3) | C1—Ti—C4—C3 | 77.62 (13) |
C5—C1—C2—C3 | 2.70 (19) | C1i—Ti—C4—C3 | −100.51 (13) |
C6—C1—C2—C3 | −172.03 (18) | Cl—Ti—C4—C5 | 74.01 (13) |
Ti—C1—C2—C3 | 64.72 (13) | Cli—Ti—C4—C5 | −18.86 (14) |
C5—C1—C2—C7 | 174.29 (19) | C3—Ti—C4—C5 | −113.76 (17) |
C6—C1—C2—C7 | −0.4 (3) | C3i—Ti—C4—C5 | −160.15 (11) |
Ti—C1—C2—C7 | −123.7 (2) | C4i—Ti—C4—C5 | −143.69 (12) |
C5—C1—C2—Ti | −62.03 (14) | C2—Ti—C4—C5 | −76.62 (13) |
C6—C1—C2—Ti | 123.2 (2) | C2i—Ti—C4—C5 | 165.54 (11) |
Cl—Ti—C2—C3 | −79.05 (14) | C5i—Ti—C4—C5 | 174.03 (11) |
Cli—Ti—C2—C3 | −178.26 (11) | C1—Ti—C4—C5 | −36.13 (11) |
C3i—Ti—C2—C3 | 62.74 (15) | C1i—Ti—C4—C5 | 145.73 (11) |
C4i—Ti—C2—C3 | 96.50 (14) | Cl—Ti—C4—C8 | −48.9 (2) |
C4—Ti—C2—C3 | −37.17 (12) | Cli—Ti—C4—C8 | −141.8 (2) |
C2i—Ti—C2—C3 | 41.06 (10) | C3—Ti—C4—C8 | 123.3 (3) |
C5i—Ti—C2—C3 | 106.71 (13) | C3i—Ti—C4—C8 | 76.9 (2) |
C5—Ti—C2—C3 | −78.45 (14) | C4i—Ti—C4—C8 | 93.4 (2) |
C1—Ti—C2—C3 | −114.47 (16) | C2—Ti—C4—C8 | 160.4 (2) |
C1i—Ti—C2—C3 | 64.42 (16) | C2i—Ti—C4—C8 | 42.6 (2) |
Cl—Ti—C2—C1 | 35.43 (13) | C5i—Ti—C4—C8 | 51.1 (3) |
Cli—Ti—C2—C1 | −63.78 (12) | C5—Ti—C4—C8 | −123.0 (3) |
C3—Ti—C2—C1 | 114.47 (16) | C1—Ti—C4—C8 | −159.1 (2) |
C3i—Ti—C2—C1 | 177.22 (11) | C1i—Ti—C4—C8 | 22.8 (2) |
C4i—Ti—C2—C1 | −149.03 (11) | C2—C1—C5—C4 | −2.5 (2) |
C4—Ti—C2—C1 | 77.30 (12) | C6—C1—C5—C4 | 172.21 (19) |
C2i—Ti—C2—C1 | 155.53 (12) | Ti—C1—C5—C4 | −64.27 (13) |
C5i—Ti—C2—C1 | −138.82 (11) | C2—C1—C5—Ti | 61.81 (13) |
C5—Ti—C2—C1 | 36.02 (11) | C6—C1—C5—Ti | −123.5 (2) |
C1i—Ti—C2—C1 | 178.90 (14) | C3—C4—C5—C1 | 1.2 (2) |
Cl—Ti—C2—C7 | 158.44 (16) | C8—C4—C5—C1 | −171.78 (19) |
Cli—Ti—C2—C7 | 59.23 (19) | Ti—C4—C5—C1 | 66.96 (14) |
C3—Ti—C2—C7 | −122.5 (2) | C3—C4—C5—Ti | −65.72 (13) |
C3i—Ti—C2—C7 | −59.77 (19) | C8—C4—C5—Ti | 121.3 (2) |
C4i—Ti—C2—C7 | −26.02 (19) | Cl—Ti—C5—C1 | 143.05 (13) |
C4—Ti—C2—C7 | −159.7 (2) | Cli—Ti—C5—C1 | 49.57 (13) |
C2i—Ti—C2—C7 | −81.46 (19) | C3—Ti—C5—C1 | −78.04 (12) |
C5i—Ti—C2—C7 | −15.8 (2) | C3i—Ti—C5—C1 | −90.57 (14) |
C5—Ti—C2—C7 | 159.0 (2) | C4i—Ti—C5—C1 | −46.7 (2) |
C1—Ti—C2—C7 | 123.0 (2) | C4—Ti—C5—C1 | −116.36 (18) |
C1i—Ti—C2—C7 | −58.1 (2) | C2—Ti—C5—C1 | −36.50 (12) |
C1—C2—C3—C4 | −2.0 (2) | C2i—Ti—C5—C1 | −134.69 (13) |
C7—C2—C3—C4 | −173.35 (19) | C1i—Ti—C5—C1 | −176.67 (17) |
Ti—C2—C3—C4 | 65.66 (14) | Cl—Ti—C5—C4 | −100.59 (14) |
C1—C2—C3—Ti | −67.62 (13) | Cli—Ti—C5—C4 | 165.93 (11) |
C7—C2—C3—Ti | 121.0 (2) | C3—Ti—C5—C4 | 38.32 (12) |
Cl—Ti—C3—C4 | 8.86 (13) | C3i—Ti—C5—C4 | 25.79 (15) |
Cli—Ti—C3—C4 | −113.71 (12) | C4i—Ti—C5—C4 | 69.6 (2) |
C3i—Ti—C3—C4 | 131.72 (15) | C2—Ti—C5—C4 | 79.86 (15) |
C4i—Ti—C3—C4 | 156.80 (10) | C2i—Ti—C5—C4 | −18.33 (14) |
C2—Ti—C3—C4 | −115.87 (17) | C1—Ti—C5—C4 | 116.36 (18) |
C2i—Ti—C3—C4 | 100.38 (14) | C1i—Ti—C5—C4 | −60.31 (18) |
Symmetry code: (i) −x, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [TiCl2(C16H22)] |
Mr | 333.14 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 16.788 (13), 6.791 (7), 15.814 (13) |
β (°) | 119.89 (6) |
V (Å3) | 1563 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.87 |
Crystal size (mm) | 0.88 × 0.30 × 0.24 |
Data collection | |
Diffractometer | Nicolet P3 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2207, 2207, 2147 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.705 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.100, 1.17 |
No. of reflections | 2207 |
No. of parameters | 90 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.58, −0.66 |
Computer programs: Nicolet P3 Software (Nicolet, 1980), Nicolet P3 Software, RDNIC (Howie, 1980), SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
(I) (M = Ti) | (II) (M = Zr) | ||
M—Cg | 2.102 (2) | 2.201 (8) | 2.247 (8) |
M—Cl | 2.3605 (18) | 2.439 (6) | 2.455 (7) |
Cg—M—Cgi | 133.51 (9) | 132.6 (3) | |
Cl—M—Cli | 95.41 (9) | 97.7 (2) | |
Cg—M—Cl | 104.59 (9) | 104.2 (3) | 104.8 (3) |
Cg—M—Cli | 106.22 (9) | 105.8 (3) | 106.5 (3) |
The geometric parameters are determined in terms of the centroids (Cg) of the cyclopentadienyl (Cp) rings. They are expressed in conformity with the axial molecular symmetry of (I) and hence the occurrence of entries in pairs for (II) [symmetry code: (i) -x, y, 1/2-z]. |
The molecules of the title compound, (I), are subject to the operation of a twofold crystallographic axis passing through Ti and the midpoint of the Cl—Cli vector [symmetry operation: (i) -x,y,-z + 1/2]. Therefore, the asymmetric unit consists of Ti, one Cl and one complete cylopentadienyl (hereafter Cp) ligand. The Cp ring C atoms are labelled in a manner compatible with the 1,2,4 distribution of the methyl substituents (C6, C7 and C8 respectively; see Fig. 1).
The Cp ring is itself essentially planar but the methyl substituents are displaced from the ring plane in a direction away from Ti (and the other Cp ligand) by distances of 0.174 (3), 0.123 (3) and 0.157 (3) Å for C6, C7 and C8, respectively. There is significant variation in the Ti—C distances, viz. 2.484 (3) (C1), 2.425 (2) and 2.421 (3) (C5 and C2), and 2.391 (2) and 2.381 (2) Å (C4 and C3). Small variations are also observed in the distances and angles within the Cp ring itself. Of the C—C distances which range from 1.402 (3) to 1.418 (3) Å, it is notable that whereas the longest is C1—C2, between adjacent methyl subsituted C atoms, the remaining short and intermediate C—C bonds alternate round the ring. The ring angles all differ somewhat from the ideal value of 108° and while those at C3 and C5 are greater than the ideal, those at C1, C2 and C4 are less. This variation in the angular values, although small and in which C3 and C5 are forced slightly in toward the ring centroid, is consistent with an extended scissor or lazy-tong-like effect provoked by increasing the separation of the methyl groups C6 and C7, so reducing the interaction between them.
In simple terms, Ti is in a tetrahedral environment coordinated to two Cl and to two Cp (Table 1). The Cp ligands and their methyl substituents are primarily related to one another by the operation of the crystallographic twofold axis alluded to above. The C atoms of the cyclopentadienyl rings are almost eclipsed but with a small rotation (approximately 11°) relative to one another. The distribution of the methyl substituents is more complex. Thus, while C7 of one ring almost eclipses C8 of the other, C6 of both rings tends to eclipse one or other of the Cl. This situation is much more complicated than that described by Howie et al. (1985), and references therein, for other analogous compounds.
The Cambridge Structural Database (Allen & Kennard, 1993), accessed by means of the Chemical Database Service of the EPSRC at Daresbury (Fletcher et al., 1996), includes an entry with reference code HOBYAY describing the structure of the corresponding Zr compound, (II), as determined in the space group Cc by Kimura et al. (1998). Despite the difference in space group, the structures of (I) and (II) are virtually identical (see, for example, Table 1). Thus, the compounds can reasonably be regarded as isostructural although the situation with regard to the crystallographic nature of the twofold axial molecular symmetry remains in doubt.