Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105016021/ta1483sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105016021/ta1483Isup2.hkl |
CCDC reference: 278540
Reaction of the titanium complex bearing the N-(3,5-dimethyl-2-hydroxyl-benzyl)diethanolamine Mannich base with an excess of 1.5 M aqueous NH4OH in toluene for 3 d at ambient temperature, followed by filtration to remove NH4Cl, drying over Na2SO4, elution through a basic alumina chromatography column and removal of the solvent under reduced pressure yielded yellow crystals of (I) in 58% yield.
H atoms were placed geometrically and refined with fixed individual displacement parameters [Uiso(H) = 1.5Ueq(C)] using a riding model, with C—H = 0.96 Å.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT-NT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
[Ti6(C10H15)6Cl2O10] | F(000) = 2872 |
Mr = 1377.52 | Dx = 1.378 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -p 2yn | Cell parameters from 5764 reflections |
a = 11.4724 (14) Å | θ = 2.5–25.9° |
b = 29.713 (4) Å | µ = 0.93 mm−1 |
c = 19.495 (2) Å | T = 293 K |
β = 92.090 (2)° | Prismatic, pale yellow |
V = 6641.0 (14) Å3 | 0.28 × 0.26 × 0.10 mm |
Z = 4 |
Bruker CCD area detector diffractometer | 13061 independent reflections |
Radiation source: fine-focus sealed tube | 10417 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ϕ and ω scans | θmax = 26.1°, θmin = 1.7° |
Absorption correction: multi-scan (SHELXTL; Bruker, 1997) | h = −13→14 |
Tmin = 0.781, Tmax = 0.917 | k = −33→36 |
37338 measured reflections | l = −24→13 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0707P)2 + 2.2925P] where P = (Fo2 + 2Fc2)/3 |
13061 reflections | (Δ/σ)max = 0.025 |
741 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
[Ti6(C10H15)6Cl2O10] | V = 6641.0 (14) Å3 |
Mr = 1377.52 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.4724 (14) Å | µ = 0.93 mm−1 |
b = 29.713 (4) Å | T = 293 K |
c = 19.495 (2) Å | 0.28 × 0.26 × 0.10 mm |
β = 92.090 (2)° |
Bruker CCD area detector diffractometer | 13061 independent reflections |
Absorption correction: multi-scan (SHELXTL; Bruker, 1997) | 10417 reflections with I > 2σ(I) |
Tmin = 0.781, Tmax = 0.917 | Rint = 0.026 |
37338 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.44 e Å−3 |
13061 reflections | Δρmin = −0.24 e Å−3 |
741 parameters |
x | y | z | Uiso*/Ueq | ||
Ti1 | 0.46047 (4) | 0.131198 (16) | 0.80935 (3) | 0.03300 (12) | |
Ti2 | 0.65825 (4) | 0.192381 (15) | 0.73475 (2) | 0.02873 (12) | |
Ti3 | 0.40357 (4) | 0.188854 (15) | 0.66220 (2) | 0.02974 (12) | |
Ti4 | 0.61233 (4) | 0.430223 (16) | 0.82385 (3) | 0.03380 (12) | |
Ti5 | 0.56635 (4) | 0.386734 (16) | 0.66559 (2) | 0.03226 (12) | |
Ti6 | 0.36817 (4) | 0.378985 (14) | 0.77645 (2) | 0.02737 (11) | |
Ti7 | 0.49954 (4) | 0.285904 (14) | 0.72353 (3) | 0.02983 (12) | |
Cl1 | 0.48555 (9) | 0.05966 (3) | 0.76848 (5) | 0.0649 (2) | |
Cl2 | 0.57476 (9) | 0.50473 (3) | 0.80228 (6) | 0.0728 (3) | |
O1 | 0.60384 (15) | 0.15546 (6) | 0.80270 (10) | 0.0368 (4) | |
O2 | 0.60945 (14) | 0.24876 (6) | 0.76182 (10) | 0.0347 (4) | |
O3 | 0.39368 (16) | 0.24983 (6) | 0.67900 (11) | 0.0436 (5) | |
O4 | 0.37406 (15) | 0.15968 (7) | 0.74325 (10) | 0.0402 (4) | |
O5 | 0.56177 (14) | 0.18093 (6) | 0.65929 (9) | 0.0339 (4) | |
O6 | 0.65095 (15) | 0.40690 (7) | 0.74176 (10) | 0.0414 (5) | |
O7 | 0.46679 (15) | 0.40921 (6) | 0.83698 (9) | 0.0340 (4) | |
O8 | 0.42162 (15) | 0.32011 (6) | 0.78346 (9) | 0.0331 (4) | |
O9 | 0.57357 (17) | 0.32460 (6) | 0.66805 (10) | 0.0441 (5) | |
O10 | 0.41647 (15) | 0.39644 (6) | 0.69164 (9) | 0.0355 (4) | |
C1 | 0.3138 (3) | 0.15765 (11) | 0.88104 (17) | 0.0519 (8) | |
C2 | 0.3121 (3) | 0.11145 (11) | 0.88744 (17) | 0.0525 (8) | |
C3 | 0.4207 (3) | 0.09740 (11) | 0.91794 (17) | 0.0585 (9) | |
C4 | 0.4872 (3) | 0.13727 (14) | 0.92984 (16) | 0.0576 (9) | |
C5 | 0.4205 (3) | 0.17359 (10) | 0.90622 (17) | 0.0527 (8) | |
C6 | 0.2153 (4) | 0.18615 (17) | 0.8504 (2) | 0.1000 (18) | |
H6A | 0.2436 | 0.2038 | 0.8133 | 0.150* | |
H6B | 0.1864 | 0.2058 | 0.8850 | 0.150* | |
H6C | 0.1534 | 0.1669 | 0.8335 | 0.150* | |
C7 | 0.2133 (4) | 0.07945 (18) | 0.8667 (3) | 0.1083 (19) | |
H7A | 0.1436 | 0.0964 | 0.8565 | 0.162* | |
H7B | 0.2000 | 0.0590 | 0.9037 | 0.162* | |
H7C | 0.2342 | 0.0628 | 0.8268 | 0.162* | |
C8 | 0.4538 (5) | 0.05024 (15) | 0.9388 (3) | 0.118 (2) | |
H8A | 0.4458 | 0.0468 | 0.9874 | 0.176* | |
H8B | 0.5332 | 0.0446 | 0.9275 | 0.176* | |
H8C | 0.4035 | 0.0292 | 0.9148 | 0.176* | |
C9 | 0.6077 (4) | 0.1400 (2) | 0.9626 (2) | 0.115 (2) | |
H9A | 0.6555 | 0.1591 | 0.9356 | 0.173* | |
H9B | 0.6414 | 0.1105 | 0.9651 | 0.173* | |
H9C | 0.6033 | 0.1522 | 1.0080 | 0.173* | |
C10 | 0.4569 (5) | 0.22256 (13) | 0.9100 (2) | 0.1005 (18) | |
H10A | 0.4275 | 0.2381 | 0.8697 | 0.151* | |
H10B | 0.5404 | 0.2245 | 0.9125 | 0.151* | |
H10C | 0.4257 | 0.2362 | 0.9500 | 0.151* | |
C11 | 0.8422 (2) | 0.22504 (10) | 0.71677 (18) | 0.0447 (7) | |
C12 | 0.8547 (2) | 0.19688 (11) | 0.77457 (17) | 0.0447 (7) | |
C13 | 0.8369 (2) | 0.15204 (10) | 0.75244 (17) | 0.0424 (7) | |
C14 | 0.8105 (2) | 0.15271 (10) | 0.68148 (17) | 0.0424 (7) | |
C15 | 0.8141 (2) | 0.19782 (10) | 0.65915 (17) | 0.0435 (7) | |
C16 | 0.8584 (3) | 0.27516 (11) | 0.7151 (3) | 0.0760 (13) | |
H16A | 0.9046 | 0.2831 | 0.6769 | 0.114* | |
H16B | 0.8974 | 0.2848 | 0.7570 | 0.114* | |
H16C | 0.7837 | 0.2896 | 0.7105 | 0.114* | |
C17 | 0.8799 (3) | 0.21216 (14) | 0.8473 (2) | 0.0725 (11) | |
H17A | 0.8649 | 0.1879 | 0.8783 | 0.109* | |
H17B | 0.8306 | 0.2372 | 0.8574 | 0.109* | |
H17C | 0.9601 | 0.2211 | 0.8525 | 0.109* | |
C18 | 0.8439 (3) | 0.11073 (12) | 0.7974 (2) | 0.0689 (11) | |
H18A | 0.7865 | 0.0892 | 0.7816 | 0.103* | |
H18B | 0.8292 | 0.1190 | 0.8439 | 0.103* | |
H18C | 0.9202 | 0.0977 | 0.7954 | 0.103* | |
C19 | 0.7833 (3) | 0.11266 (12) | 0.6366 (2) | 0.0692 (11) | |
H19A | 0.8543 | 0.1008 | 0.6193 | 0.104* | |
H19B | 0.7323 | 0.1216 | 0.5989 | 0.104* | |
H19C | 0.7458 | 0.0899 | 0.6630 | 0.104* | |
C20 | 0.7929 (3) | 0.21385 (14) | 0.5869 (2) | 0.0718 (11) | |
H20A | 0.7640 | 0.2442 | 0.5874 | 0.108* | |
H20B | 0.7364 | 0.1947 | 0.5640 | 0.108* | |
H20C | 0.8646 | 0.2129 | 0.5631 | 0.108* | |
C21 | 0.2611 (3) | 0.13780 (10) | 0.61476 (17) | 0.0498 (8) | |
C22 | 0.2163 (2) | 0.18225 (11) | 0.60688 (16) | 0.0446 (7) | |
C23 | 0.2883 (3) | 0.20538 (10) | 0.56213 (15) | 0.0427 (7) | |
C24 | 0.3781 (2) | 0.17571 (11) | 0.54325 (15) | 0.0459 (7) | |
C25 | 0.3609 (3) | 0.13433 (10) | 0.57593 (17) | 0.0497 (8) | |
C26 | 0.2078 (4) | 0.10166 (14) | 0.6570 (2) | 0.0920 (16) | |
H26A | 0.1624 | 0.0819 | 0.6276 | 0.138* | |
H26B | 0.1583 | 0.1151 | 0.6900 | 0.138* | |
H26C | 0.2684 | 0.0848 | 0.6805 | 0.138* | |
C27 | 0.1121 (3) | 0.20123 (16) | 0.6406 (2) | 0.0799 (13) | |
H27A | 0.1347 | 0.2119 | 0.6856 | 0.120* | |
H27B | 0.0539 | 0.1782 | 0.6441 | 0.120* | |
H27C | 0.0810 | 0.2257 | 0.6136 | 0.120* | |
C28 | 0.2714 (4) | 0.25299 (12) | 0.5378 (2) | 0.0724 (11) | |
H28A | 0.2630 | 0.2534 | 0.4887 | 0.109* | |
H28B | 0.3379 | 0.2707 | 0.5522 | 0.109* | |
H28C | 0.2025 | 0.2653 | 0.5572 | 0.109* | |
C29 | 0.4731 (3) | 0.18607 (18) | 0.4953 (2) | 0.0852 (14) | |
H29A | 0.5474 | 0.1802 | 0.5178 | 0.128* | |
H29B | 0.4687 | 0.2172 | 0.4822 | 0.128* | |
H29C | 0.4643 | 0.1675 | 0.4552 | 0.128* | |
C30 | 0.4350 (4) | 0.09287 (13) | 0.5685 (2) | 0.0908 (16) | |
H30A | 0.4332 | 0.0754 | 0.6098 | 0.136* | |
H30B | 0.5138 | 0.1016 | 0.5604 | 0.136* | |
H30C | 0.4050 | 0.0752 | 0.5305 | 0.136* | |
C31 | 0.7985 (3) | 0.40348 (12) | 0.86303 (17) | 0.0513 (8) | |
C32 | 0.7918 (3) | 0.44805 (11) | 0.8853 (2) | 0.0582 (9) | |
C33 | 0.7021 (3) | 0.45101 (12) | 0.93175 (19) | 0.0611 (10) | |
C34 | 0.6529 (3) | 0.40822 (13) | 0.93863 (16) | 0.0555 (9) | |
C35 | 0.7109 (3) | 0.37886 (10) | 0.89457 (18) | 0.0488 (8) | |
C36 | 0.8844 (3) | 0.38527 (16) | 0.8136 (2) | 0.0844 (13) | |
H36A | 0.9402 | 0.4082 | 0.8034 | 0.127* | |
H36B | 0.8437 | 0.3762 | 0.7719 | 0.127* | |
H36C | 0.9242 | 0.3598 | 0.8337 | 0.127* | |
C37 | 0.8703 (4) | 0.48653 (16) | 0.8641 (3) | 0.111 (2) | |
H37A | 0.8274 | 0.5063 | 0.8335 | 0.167* | |
H37B | 0.9364 | 0.4746 | 0.8414 | 0.167* | |
H37C | 0.8966 | 0.5029 | 0.9042 | 0.167* | |
C38 | 0.6698 (5) | 0.49221 (17) | 0.9719 (3) | 0.117 (2) | |
H38A | 0.7276 | 0.4974 | 1.0079 | 0.176* | |
H38B | 0.5952 | 0.4877 | 0.9916 | 0.176* | |
H38C | 0.6659 | 0.5178 | 0.9419 | 0.176* | |
C39 | 0.5553 (4) | 0.39496 (19) | 0.9838 (2) | 0.0996 (17) | |
H39A | 0.5840 | 0.3742 | 1.0182 | 0.149* | |
H39B | 0.4942 | 0.3809 | 0.9565 | 0.149* | |
H39C | 0.5252 | 0.4213 | 1.0056 | 0.149* | |
C40 | 0.6848 (4) | 0.32986 (12) | 0.8855 (2) | 0.0828 (14) | |
H40A | 0.7068 | 0.3205 | 0.8406 | 0.124* | |
H40B | 0.6028 | 0.3248 | 0.8902 | 0.124* | |
H40C | 0.7280 | 0.3129 | 0.9197 | 0.124* | |
C41 | 0.7073 (3) | 0.39725 (13) | 0.58077 (18) | 0.0576 (9) | |
C42 | 0.6085 (4) | 0.37819 (13) | 0.54875 (17) | 0.0610 (9) | |
C43 | 0.5171 (3) | 0.40864 (14) | 0.55218 (17) | 0.0611 (10) | |
C44 | 0.5590 (3) | 0.44782 (12) | 0.58670 (18) | 0.0584 (9) | |
C45 | 0.6778 (3) | 0.44066 (12) | 0.60400 (18) | 0.0569 (9) | |
C46 | 0.8267 (4) | 0.37556 (18) | 0.5904 (3) | 0.1014 (18) | |
H46A | 0.8187 | 0.3434 | 0.5888 | 0.152* | |
H46B | 0.8609 | 0.3843 | 0.6341 | 0.152* | |
H46C | 0.8759 | 0.3853 | 0.5545 | 0.152* | |
C47 | 0.6015 (5) | 0.33207 (16) | 0.5159 (2) | 0.1110 (19) | |
H47A | 0.6789 | 0.3204 | 0.5110 | 0.166* | |
H47B | 0.5629 | 0.3343 | 0.4715 | 0.166* | |
H47C | 0.5584 | 0.3122 | 0.5443 | 0.166* | |
C48 | 0.3936 (4) | 0.4019 (2) | 0.5237 (2) | 0.112 (2) | |
H48A | 0.3901 | 0.4091 | 0.4756 | 0.168* | |
H48B | 0.3416 | 0.4213 | 0.5474 | 0.168* | |
H48C | 0.3708 | 0.3711 | 0.5300 | 0.168* | |
C49 | 0.4905 (5) | 0.48928 (15) | 0.6018 (3) | 0.1007 (17) | |
H49A | 0.5036 | 0.4975 | 0.6490 | 0.151* | |
H49B | 0.4090 | 0.4835 | 0.5930 | 0.151* | |
H49C | 0.5150 | 0.5134 | 0.5729 | 0.151* | |
C50 | 0.7598 (4) | 0.47297 (16) | 0.6395 (2) | 0.1017 (17) | |
H50A | 0.8342 | 0.4588 | 0.6474 | 0.153* | |
H50B | 0.7289 | 0.4817 | 0.6826 | 0.153* | |
H50C | 0.7688 | 0.4991 | 0.6113 | 0.153* | |
C51 | 0.2115 (2) | 0.38909 (13) | 0.85059 (17) | 0.0519 (8) | |
C52 | 0.1852 (2) | 0.35118 (10) | 0.8078 (2) | 0.0520 (9) | |
C53 | 0.1718 (2) | 0.36773 (11) | 0.73973 (17) | 0.0439 (7) | |
C54 | 0.1875 (2) | 0.41429 (11) | 0.74202 (18) | 0.0480 (8) | |
C55 | 0.2127 (3) | 0.42708 (11) | 0.8087 (2) | 0.0520 (8) | |
C56 | 0.2312 (4) | 0.3885 (2) | 0.9269 (2) | 0.1033 (18) | |
H56A | 0.2886 | 0.4106 | 0.9400 | 0.155* | |
H56B | 0.2581 | 0.3592 | 0.9411 | 0.155* | |
H56C | 0.1593 | 0.3952 | 0.9485 | 0.155* | |
C57 | 0.1715 (3) | 0.30361 (13) | 0.8304 (3) | 0.0991 (18) | |
H57A | 0.0927 | 0.2987 | 0.8437 | 0.149* | |
H57B | 0.2241 | 0.2977 | 0.8687 | 0.149* | |
H57C | 0.1888 | 0.2838 | 0.7932 | 0.149* | |
C58 | 0.1485 (3) | 0.34001 (17) | 0.6766 (2) | 0.0896 (15) | |
H58A | 0.0662 | 0.3396 | 0.6658 | 0.134* | |
H58B | 0.1756 | 0.3098 | 0.6846 | 0.134* | |
H58C | 0.1887 | 0.3528 | 0.6389 | 0.134* | |
C59 | 0.1776 (3) | 0.44524 (16) | 0.6804 (2) | 0.0883 (15) | |
H59A | 0.0995 | 0.4567 | 0.6758 | 0.132* | |
H59B | 0.1958 | 0.4288 | 0.6398 | 0.132* | |
H59C | 0.2312 | 0.4698 | 0.6866 | 0.132* | |
C60 | 0.2369 (4) | 0.47485 (14) | 0.8322 (3) | 0.0976 (17) | |
H60A | 0.2847 | 0.4897 | 0.7997 | 0.146* | |
H60B | 0.2770 | 0.4743 | 0.8763 | 0.146* | |
H60C | 0.1647 | 0.4908 | 0.8356 | 0.146* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ti1 | 0.0336 (2) | 0.0335 (3) | 0.0321 (3) | −0.00363 (19) | 0.0029 (2) | −0.0012 (2) |
Ti2 | 0.0222 (2) | 0.0293 (2) | 0.0347 (3) | 0.00138 (17) | 0.00108 (19) | −0.0026 (2) |
Ti3 | 0.0262 (2) | 0.0328 (2) | 0.0300 (3) | 0.00063 (18) | −0.00248 (19) | −0.0052 (2) |
Ti4 | 0.0317 (2) | 0.0319 (2) | 0.0375 (3) | −0.00347 (18) | −0.0034 (2) | −0.0019 (2) |
Ti5 | 0.0318 (2) | 0.0366 (3) | 0.0287 (3) | −0.00164 (19) | 0.0058 (2) | 0.0038 (2) |
Ti6 | 0.0233 (2) | 0.0290 (2) | 0.0299 (3) | 0.00108 (17) | 0.00276 (18) | −0.00068 (19) |
Ti7 | 0.0277 (2) | 0.0266 (2) | 0.0353 (3) | 0.00143 (17) | 0.00281 (19) | −0.00390 (19) |
Cl1 | 0.0866 (6) | 0.0409 (4) | 0.0681 (6) | −0.0036 (4) | 0.0151 (5) | −0.0149 (4) |
Cl2 | 0.0843 (6) | 0.0344 (4) | 0.0984 (8) | −0.0060 (4) | −0.0159 (6) | 0.0093 (4) |
O1 | 0.0319 (9) | 0.0401 (10) | 0.0382 (11) | −0.0018 (8) | 0.0006 (8) | 0.0035 (9) |
O2 | 0.0301 (9) | 0.0319 (9) | 0.0419 (11) | 0.0023 (7) | −0.0007 (8) | −0.0048 (8) |
O3 | 0.0366 (10) | 0.0370 (10) | 0.0560 (13) | 0.0058 (8) | −0.0136 (9) | −0.0098 (9) |
O4 | 0.0318 (10) | 0.0535 (12) | 0.0353 (11) | −0.0022 (8) | 0.0008 (8) | 0.0026 (9) |
O5 | 0.0273 (9) | 0.0415 (10) | 0.0329 (10) | 0.0013 (7) | 0.0013 (8) | −0.0055 (8) |
O6 | 0.0318 (9) | 0.0563 (12) | 0.0363 (11) | −0.0051 (9) | 0.0027 (8) | −0.0007 (10) |
O7 | 0.0328 (9) | 0.0370 (10) | 0.0324 (10) | −0.0011 (8) | 0.0014 (8) | −0.0049 (8) |
O8 | 0.0321 (9) | 0.0301 (9) | 0.0375 (11) | 0.0026 (7) | 0.0075 (8) | −0.0010 (8) |
O9 | 0.0516 (12) | 0.0368 (10) | 0.0450 (12) | 0.0030 (9) | 0.0184 (10) | −0.0003 (9) |
O10 | 0.0291 (9) | 0.0452 (11) | 0.0324 (10) | 0.0020 (8) | 0.0034 (8) | 0.0069 (8) |
C1 | 0.059 (2) | 0.058 (2) | 0.0399 (18) | 0.0135 (16) | 0.0195 (15) | 0.0064 (15) |
C2 | 0.0538 (19) | 0.060 (2) | 0.0449 (19) | −0.0176 (15) | 0.0170 (15) | 0.0001 (16) |
C3 | 0.094 (3) | 0.0420 (17) | 0.0409 (19) | 0.0159 (17) | 0.0232 (18) | 0.0106 (15) |
C4 | 0.0470 (18) | 0.096 (3) | 0.0302 (17) | −0.0024 (18) | 0.0022 (14) | −0.0029 (18) |
C5 | 0.078 (2) | 0.0414 (17) | 0.0403 (18) | −0.0067 (16) | 0.0205 (17) | −0.0052 (14) |
C6 | 0.097 (3) | 0.135 (4) | 0.070 (3) | 0.069 (3) | 0.030 (3) | 0.029 (3) |
C7 | 0.098 (4) | 0.134 (4) | 0.095 (4) | −0.069 (3) | 0.038 (3) | −0.024 (3) |
C8 | 0.205 (6) | 0.068 (3) | 0.082 (3) | 0.050 (3) | 0.034 (4) | 0.035 (3) |
C9 | 0.073 (3) | 0.216 (7) | 0.056 (3) | −0.007 (3) | −0.017 (2) | −0.004 (3) |
C10 | 0.168 (5) | 0.055 (2) | 0.082 (3) | −0.040 (3) | 0.049 (3) | −0.029 (2) |
C11 | 0.0201 (12) | 0.0456 (16) | 0.069 (2) | −0.0004 (11) | 0.0072 (13) | −0.0014 (16) |
C12 | 0.0233 (13) | 0.0581 (18) | 0.0524 (19) | 0.0048 (12) | −0.0027 (13) | −0.0131 (16) |
C13 | 0.0290 (13) | 0.0455 (16) | 0.0526 (19) | 0.0109 (12) | 0.0012 (13) | 0.0014 (14) |
C14 | 0.0296 (13) | 0.0450 (16) | 0.0529 (19) | 0.0098 (12) | 0.0039 (13) | −0.0082 (14) |
C15 | 0.0244 (13) | 0.0565 (18) | 0.0500 (19) | 0.0054 (12) | 0.0085 (12) | 0.0069 (15) |
C16 | 0.0432 (19) | 0.051 (2) | 0.134 (4) | −0.0109 (15) | 0.013 (2) | −0.003 (2) |
C17 | 0.048 (2) | 0.100 (3) | 0.068 (3) | 0.0059 (19) | −0.0138 (18) | −0.026 (2) |
C18 | 0.064 (2) | 0.062 (2) | 0.080 (3) | 0.0220 (18) | −0.003 (2) | 0.018 (2) |
C19 | 0.069 (2) | 0.061 (2) | 0.077 (3) | 0.0159 (18) | −0.003 (2) | −0.028 (2) |
C20 | 0.048 (2) | 0.106 (3) | 0.062 (2) | 0.003 (2) | 0.0111 (18) | 0.022 (2) |
C21 | 0.0544 (19) | 0.0501 (18) | 0.0434 (18) | −0.0177 (15) | −0.0157 (15) | −0.0029 (15) |
C22 | 0.0273 (13) | 0.0641 (19) | 0.0419 (17) | −0.0007 (13) | −0.0062 (12) | −0.0136 (15) |
C23 | 0.0446 (16) | 0.0458 (16) | 0.0364 (16) | 0.0022 (13) | −0.0137 (13) | −0.0048 (14) |
C24 | 0.0388 (15) | 0.068 (2) | 0.0307 (15) | 0.0013 (14) | −0.0035 (12) | −0.0128 (15) |
C25 | 0.0535 (18) | 0.0465 (17) | 0.0475 (19) | 0.0094 (14) | −0.0208 (15) | −0.0207 (15) |
C26 | 0.103 (3) | 0.083 (3) | 0.087 (3) | −0.057 (3) | −0.031 (3) | 0.022 (3) |
C27 | 0.0376 (18) | 0.117 (3) | 0.084 (3) | 0.009 (2) | 0.0000 (19) | −0.027 (3) |
C28 | 0.094 (3) | 0.058 (2) | 0.063 (2) | 0.010 (2) | −0.027 (2) | 0.0061 (19) |
C29 | 0.059 (2) | 0.153 (4) | 0.044 (2) | −0.003 (3) | 0.0086 (18) | −0.011 (3) |
C30 | 0.105 (3) | 0.068 (3) | 0.096 (3) | 0.039 (2) | −0.039 (3) | −0.043 (2) |
C31 | 0.0335 (15) | 0.068 (2) | 0.052 (2) | 0.0074 (14) | −0.0081 (14) | −0.0028 (17) |
C32 | 0.0454 (18) | 0.055 (2) | 0.072 (2) | −0.0132 (15) | −0.0225 (17) | −0.0016 (18) |
C33 | 0.065 (2) | 0.060 (2) | 0.056 (2) | 0.0139 (17) | −0.0217 (18) | −0.0231 (18) |
C34 | 0.0414 (17) | 0.089 (3) | 0.0356 (17) | 0.0051 (17) | −0.0083 (14) | 0.0068 (18) |
C35 | 0.0474 (17) | 0.0435 (16) | 0.054 (2) | 0.0014 (13) | −0.0216 (15) | 0.0005 (15) |
C36 | 0.053 (2) | 0.120 (4) | 0.080 (3) | 0.027 (2) | 0.006 (2) | −0.008 (3) |
C37 | 0.074 (3) | 0.083 (3) | 0.174 (6) | −0.037 (2) | −0.038 (3) | 0.016 (3) |
C38 | 0.150 (5) | 0.103 (4) | 0.095 (4) | 0.046 (3) | −0.040 (3) | −0.059 (3) |
C39 | 0.061 (2) | 0.182 (5) | 0.056 (3) | 0.003 (3) | −0.002 (2) | 0.034 (3) |
C40 | 0.089 (3) | 0.052 (2) | 0.103 (4) | −0.003 (2) | −0.047 (3) | 0.014 (2) |
C41 | 0.0528 (19) | 0.076 (2) | 0.045 (2) | 0.0054 (17) | 0.0228 (16) | 0.0208 (18) |
C42 | 0.081 (3) | 0.072 (2) | 0.0317 (18) | −0.009 (2) | 0.0219 (17) | 0.0022 (16) |
C43 | 0.054 (2) | 0.098 (3) | 0.0310 (17) | −0.009 (2) | 0.0011 (15) | 0.0186 (19) |
C44 | 0.068 (2) | 0.064 (2) | 0.0448 (19) | 0.0107 (18) | 0.0175 (17) | 0.0255 (17) |
C45 | 0.060 (2) | 0.063 (2) | 0.049 (2) | −0.0165 (17) | 0.0163 (16) | 0.0165 (17) |
C46 | 0.070 (3) | 0.145 (4) | 0.092 (3) | 0.038 (3) | 0.048 (3) | 0.048 (3) |
C47 | 0.183 (6) | 0.091 (3) | 0.062 (3) | −0.022 (4) | 0.046 (3) | −0.022 (3) |
C48 | 0.077 (3) | 0.205 (6) | 0.053 (3) | −0.028 (3) | −0.011 (2) | 0.029 (3) |
C49 | 0.134 (4) | 0.078 (3) | 0.092 (3) | 0.046 (3) | 0.045 (3) | 0.041 (3) |
C50 | 0.110 (4) | 0.105 (4) | 0.091 (4) | −0.067 (3) | 0.011 (3) | 0.019 (3) |
C51 | 0.0289 (15) | 0.086 (2) | 0.0412 (18) | 0.0068 (15) | 0.0083 (13) | −0.0054 (17) |
C52 | 0.0236 (13) | 0.0426 (16) | 0.091 (3) | 0.0044 (12) | 0.0161 (15) | 0.0180 (17) |
C53 | 0.0200 (12) | 0.0586 (18) | 0.0531 (19) | 0.0023 (12) | 0.0011 (12) | −0.0125 (16) |
C54 | 0.0295 (14) | 0.0507 (18) | 0.064 (2) | 0.0128 (13) | 0.0045 (14) | 0.0102 (16) |
C55 | 0.0323 (15) | 0.0467 (17) | 0.078 (3) | 0.0063 (13) | 0.0098 (15) | −0.0128 (17) |
C56 | 0.064 (3) | 0.196 (6) | 0.051 (3) | 0.001 (3) | 0.019 (2) | −0.004 (3) |
C57 | 0.052 (2) | 0.059 (2) | 0.188 (6) | −0.0031 (18) | 0.032 (3) | 0.045 (3) |
C58 | 0.048 (2) | 0.125 (4) | 0.094 (3) | −0.009 (2) | −0.007 (2) | −0.051 (3) |
C59 | 0.063 (2) | 0.099 (3) | 0.103 (4) | 0.028 (2) | 0.007 (2) | 0.049 (3) |
C60 | 0.069 (3) | 0.063 (3) | 0.161 (5) | 0.008 (2) | 0.016 (3) | −0.047 (3) |
Ti1—O1 | 1.8049 (18) | C20—H20C | 0.9600 |
Ti1—O4 | 1.8073 (19) | C21—C25 | 1.399 (5) |
Ti1—Cl1 | 2.2919 (9) | C21—C22 | 1.423 (4) |
Ti1—C5 | 2.330 (3) | C21—C26 | 1.498 (5) |
Ti1—C1 | 2.361 (3) | C22—C23 | 1.403 (4) |
Ti1—C4 | 2.365 (3) | C22—C27 | 1.495 (5) |
Ti1—C2 | 2.398 (3) | C23—C24 | 1.414 (4) |
Ti1—C3 | 2.402 (3) | C23—C28 | 1.502 (4) |
Ti2—O5 | 1.8401 (18) | C24—C25 | 1.402 (5) |
Ti2—O1 | 1.8461 (19) | C24—C29 | 1.494 (5) |
Ti2—O2 | 1.8492 (18) | C25—C30 | 1.507 (4) |
Ti2—C11 | 2.360 (3) | C26—H26A | 0.9600 |
Ti2—C12 | 2.360 (3) | C26—H26B | 0.9600 |
Ti2—C15 | 2.364 (3) | C26—H26C | 0.9600 |
Ti2—C14 | 2.378 (3) | C27—H27A | 0.9600 |
Ti2—C13 | 2.389 (3) | C27—H27B | 0.9600 |
Ti3—O5 | 1.8331 (17) | C27—H27C | 0.9600 |
Ti3—O4 | 1.844 (2) | C28—H28A | 0.9600 |
Ti3—O3 | 1.8454 (19) | C28—H28B | 0.9600 |
Ti3—C24 | 2.359 (3) | C28—H28C | 0.9600 |
Ti3—C23 | 2.368 (3) | C29—H29A | 0.9600 |
Ti3—C25 | 2.373 (3) | C29—H29B | 0.9600 |
Ti3—C22 | 2.376 (3) | C29—H29C | 0.9600 |
Ti3—C21 | 2.391 (3) | C30—H30A | 0.9600 |
Ti4—O7 | 1.8095 (18) | C30—H30B | 0.9600 |
Ti4—O6 | 1.814 (2) | C30—H30C | 0.9600 |
Ti4—Cl2 | 2.2914 (10) | C31—C32 | 1.397 (5) |
Ti4—C35 | 2.323 (3) | C31—C35 | 1.403 (5) |
Ti4—C34 | 2.361 (3) | C31—C36 | 1.504 (5) |
Ti4—C31 | 2.379 (3) | C32—C33 | 1.399 (5) |
Ti4—C33 | 2.390 (3) | C32—C37 | 1.521 (5) |
Ti4—C32 | 2.403 (3) | C33—C34 | 1.400 (5) |
Ti5—O10 | 1.8334 (18) | C33—C38 | 1.507 (5) |
Ti5—O6 | 1.844 (2) | C34—C35 | 1.409 (5) |
Ti5—O9 | 1.8485 (19) | C34—C39 | 1.502 (5) |
Ti5—C43 | 2.354 (3) | C35—C40 | 1.496 (5) |
Ti5—C42 | 2.359 (3) | C36—H36A | 0.9600 |
Ti5—C41 | 2.375 (3) | C36—H36B | 0.9600 |
Ti5—C44 | 2.378 (3) | C36—H36C | 0.9600 |
Ti5—C45 | 2.399 (3) | C37—H37A | 0.9600 |
Ti6—O10 | 1.8374 (18) | C37—H37B | 0.9600 |
Ti6—O7 | 1.8389 (18) | C37—H37C | 0.9600 |
Ti6—O8 | 1.8572 (17) | C38—H38A | 0.9600 |
Ti6—C52 | 2.357 (3) | C38—H38B | 0.9600 |
Ti6—C53 | 2.362 (3) | C38—H38C | 0.9600 |
Ti6—C51 | 2.367 (3) | C39—H39A | 0.9600 |
Ti6—C55 | 2.388 (3) | C39—H39B | 0.9600 |
Ti6—C54 | 2.397 (3) | C39—H39C | 0.9600 |
Ti7—O8 | 1.8091 (18) | C40—H40A | 0.9600 |
Ti7—O9 | 1.811 (2) | C40—H40B | 0.9600 |
Ti7—O2 | 1.8157 (18) | C40—H40C | 0.9600 |
Ti7—O3 | 1.8167 (19) | C41—C42 | 1.394 (5) |
C1—C2 | 1.379 (5) | C41—C45 | 1.412 (5) |
C1—C5 | 1.386 (5) | C41—C46 | 1.520 (5) |
C1—C6 | 1.517 (5) | C42—C43 | 1.388 (5) |
C2—C3 | 1.423 (5) | C42—C47 | 1.514 (6) |
C2—C7 | 1.522 (5) | C43—C44 | 1.420 (5) |
C3—C4 | 1.424 (5) | C43—C48 | 1.516 (5) |
C3—C8 | 1.504 (5) | C44—C45 | 1.408 (5) |
C4—C5 | 1.392 (5) | C44—C49 | 1.496 (5) |
C4—C9 | 1.504 (5) | C45—C50 | 1.496 (5) |
C5—C10 | 1.515 (5) | C46—H46A | 0.9600 |
C6—H6A | 0.9600 | C46—H46B | 0.9600 |
C6—H6B | 0.9600 | C46—H46C | 0.9600 |
C6—H6C | 0.9600 | C47—H47A | 0.9600 |
C7—H7A | 0.9600 | C47—H47B | 0.9600 |
C7—H7B | 0.9600 | C47—H47C | 0.9600 |
C7—H7C | 0.9600 | C48—H48A | 0.9600 |
C8—H8A | 0.9600 | C48—H48B | 0.9600 |
C8—H8B | 0.9600 | C48—H48C | 0.9600 |
C8—H8C | 0.9600 | C49—H49A | 0.9600 |
C9—H9A | 0.9600 | C49—H49B | 0.9600 |
C9—H9B | 0.9600 | C49—H49C | 0.9600 |
C9—H9C | 0.9600 | C50—H50A | 0.9600 |
C10—H10A | 0.9600 | C50—H50B | 0.9600 |
C10—H10B | 0.9600 | C50—H50C | 0.9600 |
C10—H10C | 0.9600 | C51—C55 | 1.394 (5) |
C11—C12 | 1.407 (5) | C51—C52 | 1.427 (5) |
C11—C15 | 1.412 (4) | C51—C56 | 1.497 (5) |
C11—C16 | 1.501 (4) | C52—C53 | 1.419 (5) |
C12—C13 | 1.413 (4) | C52—C57 | 1.490 (4) |
C12—C17 | 1.506 (5) | C53—C54 | 1.395 (4) |
C13—C14 | 1.405 (4) | C53—C58 | 1.497 (5) |
C13—C18 | 1.509 (4) | C54—C55 | 1.374 (5) |
C14—C15 | 1.410 (4) | C54—C59 | 1.514 (5) |
C14—C19 | 1.503 (4) | C55—C60 | 1.514 (5) |
C15—C20 | 1.499 (5) | C56—H56A | 0.9600 |
C16—H16A | 0.9600 | C56—H56B | 0.9600 |
C16—H16B | 0.9600 | C56—H56C | 0.9600 |
C16—H16C | 0.9600 | C57—H57A | 0.9600 |
C17—H17A | 0.9600 | C57—H57B | 0.9600 |
C17—H17B | 0.9600 | C57—H57C | 0.9600 |
C17—H17C | 0.9600 | C58—H58A | 0.9600 |
C18—H18A | 0.9600 | C58—H58B | 0.9600 |
C18—H18B | 0.9600 | C58—H58C | 0.9600 |
C18—H18C | 0.9600 | C59—H59A | 0.9600 |
C19—H19A | 0.9600 | C59—H59B | 0.9600 |
C19—H19B | 0.9600 | C59—H59C | 0.9600 |
C19—H19C | 0.9600 | C60—H60A | 0.9594 |
C20—H20A | 0.9600 | C60—H60B | 0.9616 |
C20—H20B | 0.9600 | C60—H60C | 0.9585 |
O1—Ti1—O4 | 103.85 (9) | C11—C15—Ti2 | 72.47 (16) |
O1—Ti1—Cl1 | 102.67 (7) | C20—C15—Ti2 | 120.5 (2) |
O4—Ti1—Cl1 | 105.01 (7) | C11—C16—H16A | 109.5 |
O1—Ti1—C5 | 92.82 (11) | C11—C16—H16B | 109.5 |
O4—Ti1—C5 | 101.87 (11) | H16A—C16—H16B | 109.5 |
Cl1—Ti1—C5 | 144.51 (9) | C11—C16—H16C | 109.5 |
O1—Ti1—C1 | 125.50 (11) | H16A—C16—H16C | 109.5 |
O4—Ti1—C1 | 83.22 (10) | H16B—C16—H16C | 109.5 |
Cl1—Ti1—C1 | 128.01 (9) | C12—C17—H17A | 109.5 |
C5—Ti1—C1 | 34.35 (12) | C12—C17—H17B | 109.5 |
O1—Ti1—C4 | 87.43 (10) | H17A—C17—H17B | 109.5 |
O4—Ti1—C4 | 136.09 (11) | C12—C17—H17C | 109.5 |
Cl1—Ti1—C4 | 113.75 (10) | H17A—C17—H17C | 109.5 |
C5—Ti1—C4 | 34.49 (12) | H17B—C17—H17C | 109.5 |
C1—Ti1—C4 | 57.05 (12) | C13—C18—H18A | 109.5 |
O1—Ti1—C2 | 144.42 (11) | C13—C18—H18B | 109.5 |
O4—Ti1—C2 | 100.59 (11) | H18A—C18—H18B | 109.5 |
Cl1—Ti1—C2 | 95.44 (9) | C13—C18—H18C | 109.5 |
C5—Ti1—C2 | 56.78 (11) | H18A—C18—H18C | 109.5 |
C1—Ti1—C2 | 33.67 (11) | H18B—C18—H18C | 109.5 |
C4—Ti1—C2 | 57.14 (12) | C14—C19—H19A | 109.5 |
O1—Ti1—C3 | 115.67 (12) | C14—C19—H19B | 109.5 |
O4—Ti1—C3 | 135.02 (11) | H19A—C19—H19B | 109.5 |
Cl1—Ti1—C3 | 87.08 (8) | C14—C19—H19C | 109.5 |
C5—Ti1—C3 | 57.46 (11) | H19A—C19—H19C | 109.5 |
C1—Ti1—C3 | 56.98 (11) | H19B—C19—H19C | 109.5 |
C4—Ti1—C3 | 34.74 (12) | C15—C20—H20A | 109.5 |
C2—Ti1—C3 | 34.50 (12) | C15—C20—H20B | 109.5 |
O5—Ti2—O1 | 104.75 (8) | H20A—C20—H20B | 109.5 |
O5—Ti2—O2 | 102.48 (8) | C15—C20—H20C | 109.5 |
O1—Ti2—O2 | 102.69 (9) | H20A—C20—H20C | 109.5 |
O5—Ti2—C11 | 118.18 (10) | H20B—C20—H20C | 109.5 |
O1—Ti2—C11 | 132.72 (10) | C25—C21—C22 | 108.0 (3) |
O2—Ti2—C11 | 87.22 (9) | C25—C21—C26 | 127.1 (4) |
O5—Ti2—C12 | 144.35 (10) | C22—C21—C26 | 124.9 (4) |
O1—Ti2—C12 | 98.13 (10) | C25—C21—Ti3 | 72.23 (16) |
O2—Ti2—C12 | 98.64 (9) | C22—C21—Ti3 | 72.05 (16) |
C11—Ti2—C12 | 34.67 (11) | C26—C21—Ti3 | 122.0 (2) |
O5—Ti2—C15 | 87.75 (10) | C23—C22—C21 | 107.7 (3) |
O1—Ti2—C15 | 140.47 (9) | C23—C22—C27 | 125.9 (3) |
O2—Ti2—C15 | 111.08 (10) | C21—C22—C27 | 126.4 (3) |
C11—Ti2—C15 | 34.78 (11) | C23—C22—Ti3 | 72.47 (16) |
C12—Ti2—C15 | 57.75 (11) | C21—C22—Ti3 | 73.21 (16) |
O5—Ti2—C14 | 89.39 (9) | C27—C22—Ti3 | 119.6 (2) |
O1—Ti2—C14 | 106.97 (10) | C22—C23—C24 | 107.9 (3) |
O2—Ti2—C14 | 143.97 (9) | C22—C23—C28 | 125.8 (3) |
C11—Ti2—C14 | 57.57 (10) | C24—C23—C28 | 126.3 (3) |
C12—Ti2—C14 | 57.57 (10) | C22—C23—Ti3 | 73.13 (17) |
C15—Ti2—C14 | 34.61 (10) | C24—C23—Ti3 | 72.26 (16) |
O5—Ti2—C13 | 120.71 (9) | C28—C23—Ti3 | 121.1 (2) |
O1—Ti2—C13 | 84.78 (9) | C25—C24—C23 | 108.2 (3) |
O2—Ti2—C13 | 132.88 (9) | C25—C24—C29 | 125.7 (3) |
C11—Ti2—C13 | 57.36 (10) | C23—C24—C29 | 126.1 (3) |
C12—Ti2—C13 | 34.61 (10) | C25—C24—Ti3 | 73.32 (17) |
C15—Ti2—C13 | 57.30 (10) | C23—C24—Ti3 | 72.92 (16) |
C14—Ti2—C13 | 34.30 (10) | C29—C24—Ti3 | 120.9 (2) |
O5—Ti3—O4 | 100.31 (8) | C21—C25—C24 | 108.2 (3) |
O5—Ti3—O3 | 101.47 (8) | C21—C25—C30 | 126.0 (4) |
O4—Ti3—O3 | 107.16 (10) | C24—C25—C30 | 125.7 (4) |
O5—Ti3—C24 | 92.05 (9) | C21—C25—Ti3 | 73.63 (17) |
O4—Ti3—C24 | 138.09 (10) | C24—C25—Ti3 | 72.22 (17) |
O3—Ti3—C24 | 109.32 (11) | C30—C25—Ti3 | 121.6 (2) |
O5—Ti3—C23 | 121.66 (10) | C21—C26—H26A | 109.5 |
O4—Ti3—C23 | 133.54 (10) | C21—C26—H26B | 109.5 |
O3—Ti3—C23 | 84.64 (9) | H26A—C26—H26B | 109.5 |
C24—Ti3—C23 | 34.82 (10) | C21—C26—H26C | 109.5 |
O5—Ti3—C25 | 93.98 (10) | H26A—C26—H26C | 109.5 |
O4—Ti3—C25 | 104.28 (11) | H26B—C26—H26C | 109.5 |
O3—Ti3—C25 | 141.58 (10) | C22—C27—H27A | 109.5 |
C24—Ti3—C25 | 34.46 (11) | C22—C27—H27B | 109.5 |
C23—Ti3—C25 | 57.53 (10) | H27A—C27—H27B | 109.5 |
O5—Ti3—C22 | 148.76 (9) | C22—C27—H27C | 109.5 |
O4—Ti3—C22 | 99.14 (10) | H27A—C27—H27C | 109.5 |
O3—Ti3—C22 | 95.81 (10) | H27B—C27—H27C | 109.5 |
C24—Ti3—C22 | 57.49 (10) | C23—C28—H28A | 109.5 |
C23—Ti3—C22 | 34.40 (11) | C23—C28—H28B | 109.5 |
C25—Ti3—C22 | 57.47 (10) | H28A—C28—H28B | 109.5 |
O5—Ti3—C21 | 124.77 (10) | C23—C28—H28C | 109.5 |
O4—Ti3—C21 | 83.62 (10) | H28A—C28—H28C | 109.5 |
O3—Ti3—C21 | 130.23 (10) | H28B—C28—H28C | 109.5 |
C24—Ti3—C21 | 57.06 (11) | C24—C29—H29A | 109.5 |
C23—Ti3—C21 | 57.29 (11) | C24—C29—H29B | 109.5 |
C25—Ti3—C21 | 34.15 (12) | H29A—C29—H29B | 109.5 |
C22—Ti3—C21 | 34.74 (11) | C24—C29—H29C | 109.5 |
O7—Ti4—O6 | 104.44 (8) | H29A—C29—H29C | 109.5 |
O7—Ti4—Cl2 | 101.01 (7) | H29B—C29—H29C | 109.5 |
O6—Ti4—Cl2 | 104.93 (8) | C25—C30—H30A | 109.5 |
O7—Ti4—C35 | 96.95 (10) | C25—C30—H30B | 109.5 |
O6—Ti4—C35 | 98.25 (11) | H30A—C30—H30B | 109.5 |
Cl2—Ti4—C35 | 145.89 (8) | C25—C30—H30C | 109.5 |
O7—Ti4—C34 | 85.48 (10) | H30A—C30—H30C | 109.5 |
O6—Ti4—C34 | 133.19 (11) | H30B—C30—H30C | 109.5 |
Cl2—Ti4—C34 | 118.08 (10) | C32—C31—C35 | 108.0 (3) |
C35—Ti4—C34 | 34.99 (12) | C32—C31—C36 | 125.8 (4) |
O7—Ti4—C31 | 131.43 (11) | C35—C31—C36 | 126.2 (3) |
O6—Ti4—C31 | 84.86 (10) | C32—C31—Ti4 | 73.98 (17) |
Cl2—Ti4—C31 | 122.84 (9) | C35—C31—Ti4 | 70.46 (16) |
C35—Ti4—C31 | 34.70 (12) | C36—C31—Ti4 | 121.0 (2) |
C34—Ti4—C31 | 57.29 (11) | C31—C32—C33 | 108.1 (3) |
O7—Ti4—C33 | 109.57 (12) | C31—C32—C37 | 126.1 (4) |
O6—Ti4—C33 | 139.84 (11) | C33—C32—C37 | 125.8 (4) |
Cl2—Ti4—C33 | 89.08 (9) | C31—C32—Ti4 | 72.06 (17) |
C35—Ti4—C33 | 57.48 (11) | C33—C32—Ti4 | 72.49 (18) |
C34—Ti4—C33 | 34.27 (13) | C37—C32—Ti4 | 122.4 (3) |
C31—Ti4—C33 | 56.67 (12) | C32—C33—C34 | 108.3 (3) |
O7—Ti4—C32 | 141.61 (12) | C32—C33—C38 | 126.1 (4) |
O6—Ti4—C32 | 106.95 (12) | C34—C33—C38 | 125.5 (4) |
Cl2—Ti4—C32 | 91.75 (9) | C32—C33—Ti4 | 73.6 (2) |
C35—Ti4—C32 | 57.26 (11) | C34—C33—Ti4 | 71.76 (18) |
C34—Ti4—C32 | 56.85 (12) | C38—C33—Ti4 | 124.1 (3) |
C31—Ti4—C32 | 33.96 (12) | C33—C34—C35 | 107.6 (3) |
C33—Ti4—C32 | 33.93 (13) | C33—C34—C39 | 127.3 (4) |
O10—Ti5—O6 | 101.37 (9) | C35—C34—C39 | 125.0 (4) |
O10—Ti5—O9 | 101.04 (9) | C33—C34—Ti4 | 74.0 (2) |
O6—Ti5—O9 | 106.37 (10) | C35—C34—Ti4 | 71.02 (18) |
O10—Ti5—C43 | 91.21 (10) | C39—C34—Ti4 | 120.2 (2) |
O6—Ti5—C43 | 140.16 (12) | C31—C35—C34 | 107.8 (3) |
O9—Ti5—C43 | 108.03 (13) | C31—C35—C40 | 126.8 (4) |
O10—Ti5—C42 | 120.76 (12) | C34—C35—C40 | 125.3 (4) |
O6—Ti5—C42 | 133.80 (12) | C31—C35—Ti4 | 74.84 (18) |
O9—Ti5—C42 | 84.67 (11) | C34—C35—Ti4 | 73.99 (18) |
C43—Ti5—C42 | 34.26 (13) | C40—C35—Ti4 | 118.6 (2) |
O10—Ti5—C41 | 147.28 (10) | C31—C36—H36A | 109.5 |
O6—Ti5—C41 | 99.57 (11) | C31—C36—H36B | 109.5 |
O9—Ti5—C41 | 96.81 (11) | H36A—C36—H36B | 109.5 |
C43—Ti5—C41 | 57.04 (12) | C31—C36—H36C | 109.5 |
C42—Ti5—C41 | 34.25 (13) | H36A—C36—H36C | 109.5 |
O10—Ti5—C44 | 92.74 (10) | H36B—C36—H36C | 109.5 |
O6—Ti5—C44 | 106.14 (12) | C32—C37—H37A | 109.5 |
O9—Ti5—C44 | 141.20 (12) | C32—C37—H37B | 109.5 |
C43—Ti5—C44 | 34.91 (13) | H37A—C37—H37B | 109.5 |
C42—Ti5—C44 | 57.42 (13) | C32—C37—H37C | 109.5 |
C41—Ti5—C44 | 57.20 (12) | H37A—C37—H37C | 109.5 |
O10—Ti5—C45 | 123.77 (11) | H37B—C37—H37C | 109.5 |
O6—Ti5—C45 | 84.93 (11) | C33—C38—H38A | 109.5 |
O9—Ti5—C45 | 130.99 (11) | C33—C38—H38B | 109.5 |
C43—Ti5—C45 | 57.27 (13) | H38A—C38—H38B | 109.5 |
C42—Ti5—C45 | 57.12 (13) | C33—C38—H38C | 109.5 |
C41—Ti5—C45 | 34.41 (12) | H38A—C38—H38C | 109.5 |
C44—Ti5—C45 | 34.27 (12) | H38B—C38—H38C | 109.5 |
O10—Ti6—O7 | 103.94 (8) | C34—C39—H39A | 109.5 |
O10—Ti6—O8 | 102.86 (8) | C34—C39—H39B | 109.5 |
O7—Ti6—O8 | 102.65 (8) | H39A—C39—H39B | 109.5 |
O10—Ti6—C52 | 129.27 (11) | C34—C39—H39C | 109.5 |
O7—Ti6—C52 | 122.51 (11) | H39A—C39—H39C | 109.5 |
O8—Ti6—C52 | 86.88 (9) | H39B—C39—H39C | 109.5 |
O10—Ti6—C53 | 94.75 (10) | C35—C40—H40A | 109.5 |
O7—Ti6—C53 | 145.20 (9) | C35—C40—H40B | 109.5 |
O8—Ti6—C53 | 101.40 (10) | H40A—C40—H40B | 109.5 |
C52—Ti6—C53 | 34.99 (12) | C35—C40—H40C | 109.5 |
O10—Ti6—C51 | 140.76 (10) | H40A—C40—H40C | 109.5 |
O7—Ti6—C51 | 90.54 (10) | H40B—C40—H40C | 109.5 |
O8—Ti6—C51 | 109.31 (11) | C42—C41—C45 | 108.3 (3) |
C52—Ti6—C51 | 35.16 (12) | C42—C41—C46 | 126.7 (4) |
C53—Ti6—C51 | 57.71 (11) | C45—C41—C46 | 125.0 (4) |
O10—Ti6—C55 | 108.70 (11) | C42—C41—Ti5 | 72.25 (18) |
O7—Ti6—C55 | 89.25 (10) | C45—C41—Ti5 | 73.72 (18) |
O8—Ti6—C55 | 142.40 (10) | C46—C41—Ti5 | 119.4 (2) |
C52—Ti6—C55 | 57.36 (11) | C43—C42—C41 | 108.5 (3) |
C53—Ti6—C55 | 56.71 (11) | C43—C42—C47 | 125.6 (4) |
C51—Ti6—C55 | 34.10 (12) | C41—C42—C47 | 125.9 (4) |
O10—Ti6—C54 | 84.87 (10) | C43—C42—Ti5 | 72.65 (19) |
O7—Ti6—C54 | 118.13 (10) | C41—C42—Ti5 | 73.49 (19) |
O8—Ti6—C54 | 135.45 (10) | C47—C42—Ti5 | 119.8 (3) |
C52—Ti6—C54 | 57.10 (10) | C42—C43—C44 | 108.3 (3) |
C53—Ti6—C54 | 34.09 (11) | C42—C43—C48 | 126.4 (4) |
C51—Ti6—C54 | 56.44 (11) | C44—C43—C48 | 125.3 (4) |
C55—Ti6—C54 | 33.39 (12) | C42—C43—Ti5 | 73.09 (19) |
O8—Ti7—O9 | 106.42 (8) | C44—C43—Ti5 | 73.50 (19) |
O8—Ti7—O2 | 115.35 (9) | C48—C43—Ti5 | 119.8 (2) |
O9—Ti7—O2 | 107.32 (9) | C45—C44—C43 | 107.3 (3) |
O8—Ti7—O3 | 107.61 (9) | C45—C44—C49 | 126.0 (4) |
O9—Ti7—O3 | 114.14 (10) | C43—C44—C49 | 126.7 (4) |
O2—Ti7—O3 | 106.26 (8) | C45—C44—Ti5 | 73.66 (18) |
Ti1—O1—Ti2 | 128.44 (10) | C43—C44—Ti5 | 71.59 (19) |
Ti7—O2—Ti2 | 130.26 (10) | C49—C44—Ti5 | 120.5 (2) |
Ti7—O3—Ti3 | 128.29 (10) | C44—C45—C41 | 107.6 (3) |
Ti1—O4—Ti3 | 135.88 (10) | C44—C45—C50 | 126.9 (4) |
Ti3—O5—Ti2 | 121.26 (10) | C41—C45—C50 | 125.5 (4) |
Ti4—O6—Ti5 | 134.14 (10) | C44—C45—Ti5 | 72.07 (18) |
Ti4—O7—Ti6 | 128.83 (10) | C41—C45—Ti5 | 71.88 (18) |
Ti7—O8—Ti6 | 130.63 (10) | C50—C45—Ti5 | 122.3 (3) |
Ti7—O9—Ti5 | 128.90 (11) | C41—C46—H46A | 109.5 |
Ti5—O10—Ti6 | 121.44 (10) | C41—C46—H46B | 109.5 |
C2—C1—C5 | 108.9 (3) | H46A—C46—H46B | 109.5 |
C2—C1—C6 | 125.4 (4) | C41—C46—H46C | 109.5 |
C5—C1—C6 | 125.8 (4) | H46A—C46—H46C | 109.5 |
C2—C1—Ti1 | 74.61 (19) | H46B—C46—H46C | 109.5 |
C5—C1—Ti1 | 71.57 (18) | C42—C47—H47A | 109.5 |
C6—C1—Ti1 | 119.3 (2) | C42—C47—H47B | 109.5 |
C1—C2—C3 | 108.4 (3) | H47A—C47—H47B | 109.5 |
C1—C2—C7 | 127.6 (4) | C42—C47—H47C | 109.5 |
C3—C2—C7 | 124.0 (4) | H47A—C47—H47C | 109.5 |
C1—C2—Ti1 | 71.72 (18) | H47B—C47—H47C | 109.5 |
C3—C2—Ti1 | 72.91 (18) | C43—C48—H48A | 109.5 |
C7—C2—Ti1 | 121.5 (3) | C43—C48—H48B | 109.5 |
C4—C3—C2 | 106.3 (3) | H48A—C48—H48B | 109.5 |
C4—C3—C8 | 127.1 (4) | C43—C48—H48C | 109.5 |
C2—C3—C8 | 126.5 (4) | H48A—C48—H48C | 109.5 |
C4—C3—Ti1 | 71.20 (18) | H48B—C48—H48C | 109.5 |
C2—C3—Ti1 | 72.59 (18) | C44—C49—H49A | 109.5 |
C8—C3—Ti1 | 125.0 (3) | C44—C49—H49B | 109.5 |
C5—C4—C3 | 107.8 (3) | H49A—C49—H49B | 109.5 |
C5—C4—C9 | 125.8 (4) | C44—C49—H49C | 109.5 |
C3—C4—C9 | 126.4 (4) | H49A—C49—H49C | 109.5 |
C5—C4—Ti1 | 71.37 (19) | H49B—C49—H49C | 109.5 |
C3—C4—Ti1 | 74.05 (19) | C45—C50—H50A | 109.5 |
C9—C4—Ti1 | 120.7 (3) | C45—C50—H50B | 109.5 |
C1—C5—C4 | 108.7 (3) | H50A—C50—H50B | 109.5 |
C1—C5—C10 | 125.7 (4) | C45—C50—H50C | 109.5 |
C4—C5—C10 | 125.5 (4) | H50A—C50—H50C | 109.5 |
C1—C5—Ti1 | 74.08 (19) | H50B—C50—H50C | 109.5 |
C4—C5—Ti1 | 74.14 (19) | C55—C51—C52 | 107.6 (3) |
C10—C5—Ti1 | 119.8 (2) | C55—C51—C56 | 126.0 (4) |
C1—C6—H6A | 109.5 | C52—C51—C56 | 126.3 (4) |
C1—C6—H6B | 109.5 | C55—C51—Ti6 | 73.77 (18) |
H6A—C6—H6B | 109.5 | C52—C51—Ti6 | 72.05 (17) |
C1—C6—H6C | 109.5 | C56—C51—Ti6 | 121.0 (2) |
H6A—C6—H6C | 109.5 | C53—C52—C51 | 106.6 (3) |
H6B—C6—H6C | 109.5 | C53—C52—C57 | 126.6 (4) |
C2—C7—H7A | 109.5 | C51—C52—C57 | 126.8 (4) |
C2—C7—H7B | 109.5 | C53—C52—Ti6 | 72.70 (16) |
H7A—C7—H7B | 109.5 | C51—C52—Ti6 | 72.79 (16) |
C2—C7—H7C | 109.5 | C57—C52—Ti6 | 120.9 (2) |
H7A—C7—H7C | 109.5 | C54—C53—C52 | 107.7 (3) |
H7B—C7—H7C | 109.5 | C54—C53—C58 | 126.2 (4) |
C3—C8—H8A | 109.5 | C52—C53—C58 | 126.1 (3) |
C3—C8—H8B | 109.5 | C54—C53—Ti6 | 74.33 (16) |
H8A—C8—H8B | 109.5 | C52—C53—Ti6 | 72.31 (16) |
C3—C8—H8C | 109.5 | C58—C53—Ti6 | 117.9 (2) |
H8A—C8—H8C | 109.5 | C55—C54—C53 | 109.1 (3) |
H8B—C8—H8C | 109.5 | C55—C54—C59 | 126.1 (4) |
C4—C9—H9A | 109.5 | C53—C54—C59 | 124.8 (4) |
C4—C9—H9B | 109.5 | C55—C54—Ti6 | 72.92 (17) |
H9A—C9—H9B | 109.5 | C53—C54—Ti6 | 71.59 (15) |
C4—C9—H9C | 109.5 | C59—C54—Ti6 | 121.8 (2) |
H9A—C9—H9C | 109.5 | C54—C55—C51 | 108.9 (3) |
H9B—C9—H9C | 109.5 | C54—C55—C60 | 125.1 (4) |
C5—C10—H10A | 109.5 | C51—C55—C60 | 126.0 (4) |
C5—C10—H10B | 109.5 | C54—C55—Ti6 | 73.69 (17) |
H10A—C10—H10B | 109.5 | C51—C55—Ti6 | 72.13 (17) |
C5—C10—H10C | 109.5 | C60—C55—Ti6 | 120.7 (2) |
H10A—C10—H10C | 109.5 | C51—C56—H56A | 109.5 |
H10B—C10—H10C | 109.5 | C51—C56—H56B | 109.5 |
C12—C11—C15 | 108.1 (3) | H56A—C56—H56B | 109.5 |
C12—C11—C16 | 126.7 (3) | C51—C56—H56C | 109.5 |
C15—C11—C16 | 125.2 (3) | H56A—C56—H56C | 109.5 |
C12—C11—Ti2 | 72.67 (16) | H56B—C56—H56C | 109.5 |
C15—C11—Ti2 | 72.76 (16) | C52—C57—H57A | 109.5 |
C16—C11—Ti2 | 121.6 (2) | C52—C57—H57B | 109.5 |
C11—C12—C13 | 107.9 (3) | H57A—C57—H57B | 109.5 |
C11—C12—C17 | 125.8 (3) | C52—C57—H57C | 109.5 |
C13—C12—C17 | 126.3 (3) | H57A—C57—H57C | 109.5 |
C11—C12—Ti2 | 72.66 (16) | H57B—C57—H57C | 109.5 |
C13—C12—Ti2 | 73.79 (15) | C53—C58—H58A | 109.5 |
C17—C12—Ti2 | 118.3 (2) | C53—C58—H58B | 109.5 |
C14—C13—C12 | 108.1 (3) | H58A—C58—H58B | 109.5 |
C14—C13—C18 | 126.0 (3) | C53—C58—H58C | 109.5 |
C12—C13—C18 | 125.8 (3) | H58A—C58—H58C | 109.5 |
C14—C13—Ti2 | 72.43 (15) | H58B—C58—H58C | 109.5 |
C12—C13—Ti2 | 71.60 (15) | C54—C59—H59A | 109.5 |
C18—C13—Ti2 | 121.3 (2) | C54—C59—H59B | 109.5 |
C13—C14—C15 | 108.0 (3) | H59A—C59—H59B | 109.5 |
C13—C14—C19 | 126.5 (3) | C54—C59—H59C | 109.5 |
C15—C14—C19 | 125.5 (3) | H59A—C59—H59C | 109.5 |
C13—C14—Ti2 | 73.28 (16) | H59B—C59—H59C | 109.5 |
C15—C14—Ti2 | 72.16 (16) | C55—C60—H60A | 109.5 |
C19—C14—Ti2 | 120.4 (2) | C55—C60—H60B | 109.3 |
C14—C15—C11 | 107.9 (3) | H60A—C60—H60B | 109.4 |
C14—C15—C20 | 125.9 (3) | C55—C60—H60C | 109.5 |
C11—C15—C20 | 126.2 (3) | H60A—C60—H60C | 109.7 |
C14—C15—Ti2 | 73.23 (16) | H60B—C60—H60C | 109.5 |
Experimental details
Crystal data | |
Chemical formula | [Ti6(C10H15)6Cl2O10] |
Mr | 1377.52 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 11.4724 (14), 29.713 (4), 19.495 (2) |
β (°) | 92.090 (2) |
V (Å3) | 6641.0 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.93 |
Crystal size (mm) | 0.28 × 0.26 × 0.10 |
Data collection | |
Diffractometer | Bruker CCD area detector diffractometer |
Absorption correction | Multi-scan (SHELXTL; Bruker, 1997) |
Tmin, Tmax | 0.781, 0.917 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 37338, 13061, 10417 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.618 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.121, 1.02 |
No. of reflections | 13061 |
No. of parameters | 741 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.44, −0.24 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT-NT (Bruker, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
Ti1—O1 | 1.8049 (18) | Ti4—C31 | 2.379 (3) |
Ti1—O4 | 1.8073 (19) | Ti5—O10 | 1.8334 (18) |
Ti1—Cl1 | 2.2919 (9) | Ti5—O6 | 1.844 (2) |
Ti2—O5 | 1.8401 (18) | Ti5—O9 | 1.8485 (19) |
Ti2—O1 | 1.8461 (19) | Ti6—O10 | 1.8374 (18) |
Ti2—O2 | 1.8492 (18) | Ti6—O7 | 1.8389 (18) |
Ti3—O5 | 1.8331 (17) | Ti6—O8 | 1.8572 (17) |
Ti3—O4 | 1.844 (2) | Ti7—O8 | 1.8091 (18) |
Ti3—O3 | 1.8454 (19) | Ti7—O9 | 1.811 (2) |
Ti4—O7 | 1.8095 (18) | Ti7—O2 | 1.8157 (18) |
Ti4—O6 | 1.814 (2) | Ti7—O3 | 1.8167 (19) |
Ti4—Cl2 | 2.2914 (10) | ||
O1—Ti1—O4 | 103.85 (9) | O6—Ti4—C35 | 98.25 (11) |
O1—Ti1—Cl1 | 102.67 (7) | Cl2—Ti4—C31 | 122.84 (9) |
O1—Ti2—O2 | 102.69 (9) | O2—Ti7—O3 | 106.26 (8) |
O7—Ti4—O6 | 104.44 (8) | Ti7—O3—Ti3 | 128.29 (10) |
O7—Ti4—Cl2 | 101.01 (7) | Ti3—O5—Ti2 | 121.26 (10) |
O6—Ti4—Cl2 | 104.93 (8) |
In recent years, organometallic oxides have received considerable interest as hydrocarbon-soluble models for metal oxide surfaces and thus help to provide a basic understanding of catalyst-to-support interactions in heterogeneous catalytic processes (Bottomley, 1992; Pop & Müller, 1991; Bottomley & Sutin, 1988; Day & Klemperer, 1985). Previously, chain and ring polyhedral organotitanoxanes with frameworks have been well established, starting from [Cp*TiCl3] (Cp* is η5-C5H5-nRn, R is Me, SiMe3 or tBu, and n = 0, 1, 2, 3, 4, 5) (Pilar et al., 1995; Carofiglio et al., 1992; Babcock et al., 1987). However, few organotitanoxanes have been obtained from other complexes. Hence, our work has been aimed at synthesizing new polynuclear organotitanoxanes starting from some complicated complexes. We report here the synthesis and crystal structure of the first such species, (I), [(Cp*TiCl)(µ-O)2(Cp*Ti)2(µ-O)(µ-O)2]2Ti, (Cp* is η5-C5Me5).
The Ti/O/Cl core of (I), which consists of four fused Ti3O3 rings, is illustrated in Fig. 1. In the complete molecule (Fig. 2), all Ti atoms are in an approximately tetrahedral environment, with atoms Ti1–Ti6 being coordinated to η5-Cp* in a three-legged piano-stool configuration. The Ti atoms are in three distinct stereochemical environments: Ti7 is coordinated to four bridging O atoms (Ob), Ti2, Ti3, Ti5 and Ti6 are coordinated by three Ob atoms plus η5-Cp*, and Ti1 and Ti4 are coordinated by two Ob atoms, one Cl atom and one η5-Cp* ligand.
The ranges of the Ti—O and Ti—Cl bond lengths in (I) (Table 1) are 1.805 (2)–1.857 (2) and 2.291 (1)–2.2919 (1) Å, respectively, which are in the normal ranges (Reference for standard values?). However, the Ti—O distances for Ti atoms bonded to Cl and for Ti7 are somewhat shorter than those found for Ti bonded to three Ob atoms. The atoms of the individual η5-Cp* molecules are coplanar.
When viewed along the b axis, the entire molecule gives a psuedo-hexagonal impression in projection (Fig. 2). The two six-membered core rings, Ti1/Ti2/Ti3/O1/O4/O5 and Ti4/Ti5/Ti6/O6/O7/O10, are in an almost eclipsed conformation but with Ti over O, and the η5-Cp* ligands are arrayed with approximate 3 symmetry with respect to the Ti/O/Cl core. There is a distance of 9.057 (1) Å between Ti1 and Ti4.