Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052725/sj2384sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052725/sj2384Isup2.hkl |
CCDC reference: 667238
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.036
- wR factor = 0.085
- Data-to-parameter ratio = 16.8
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT220_ALERT_2_B Large Non-Solvent C Ueq(max)/Ueq(min) ... 4.02 Ratio PLAT222_ALERT_3_B Large Non-Solvent H Ueq(max)/Ueq(min) ... 4.04 Ratio
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.672 1.000 Tmin(prime) and Tmax expected: 0.770 0.926 RR(prime) = 0.808 Please check that your absorption correction is appropriate. PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.80 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.93 PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.70 mm PLAT230_ALERT_2_C Hirshfeld Test Diff for N2 - C41 .. 6.73 su PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C37 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C44 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C5 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C35 PLAT331_ALERT_2_C Small Average Phenyl C-C Dist. C35 -C40 1.37 Ang.
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.926 Tmax scaled 0.926 Tmin scaled 0.622 REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 26.03 From the CIF: _reflns_number_total 8479 Count of symmetry unique reflns 4765 Completeness (_total/calc) 177.94% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 3714 Fraction of Friedel pairs measured 0.779 Are heavy atom types Z>Si present yes PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2 = . R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3 = . R PLAT794_ALERT_5_G Check Predicted Bond Valency for Ti (9) 4.14
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 10 ALERT level C = Check and explain 7 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 7 ALERT type 2 Indicator that the structure model may be wrong or deficient 5 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
To a solution of Ti(TADDOLate)Cl2(AcOEt)2 (1.55 g, 2.00 mmol) (Shao & Gau, 1998) in 5 ml CH2Cl2 at 298 K, N,N'-dibenzylideneethane-1,2-diamine (0.470 g, 2.00 mmol) in 5 ml CH2Cl2 was added. The solution was stirred for 12 h and the sovlent was removed. The resulted yellow solid was dissolved in 5 ml CH2Cl2 followed by a slow addition of 5 ml hexane. The two-layered solution was allowed to stand for 12 h at 298 K to give colorless crystals (0.917 g, 55.0%). 1H NMR (300 MHz, CDCl3): δ9.00 (s, 2H, N=CH), 7.77–7.12 (m, 30H, Ph), 5.60 (s, 2H, OCH), 4.13 (m, 4H, NCH2), 0.56 (s, 6H, CH3) p.p.m.. 13C{1H} NMR (75 MHz, CDCl3): δ166.77, 144.90, 143.70, 131.66, 131.52, 130.33, 129.78, 128.73, 128.18, 127.52, 127.45, 127.32, 127.03, 126.95, 111.35, 99.99, 80.26, 51.70, 27.38 p.p.m..
All H atoms were treated as riding, with C—H = 0.93–0.98 Å, and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C). Higher Ueq values are observed for C6, C7, C17, C18, C36, C37, C38, C39, C44 and C45 due to vibrations of peripheral methyl or phenyl groups away from the Ti metal center.
Titanium(IV) complexes of 2,2-dimethyl-α,α,α',α'-tetraaryl-1,3-dioxolane- 4,5-dimethanolates (TADDOLs) have been reported to be excellent catalysts in a variety of asymmetric reactions such as ethylation (Shao & Gau, 1998), arylation (Weber & Seebach, 1994), Diels-Alder (Narasaka et al., 1989), and fluorination reactions (Hintermann & Togni, 2000). In these studies, molecular structures of both four-coordinate Ti(TADDOLate)2 (Seebach et al., 1992) and six-coordinate Ti(TADDOLate)Cl2L2 (Gothelf et al., 1995) complexes were reported. For six-coordinate complexes, the two chloride ligands are invariably trans to each other and L2 could be two neutral monodentate ligands, such as tetrahydrofuran (Shao et al., 2001) or acetonitrile (Hintermann & Togni, 2000). L2 could also be a neutral bidentate like bipyridine or a 1,10-phenathroline. Recently, the molecular structure of an aluminium(III)-TADDOLate complex has been reported (Chen et al., 2007).
The molecular structure of (I) has a distorted octahedral geometry about the titanium(IV) metal center with Ti—O(TADDOLate) bond lengths of 1.7797 (16)and 1.7855 (14) Å which are nearly identical to those in Ti(TADDOLate)Cl2(CH3CN)2 (II) (Hintermann & Togni, 2000) and Ti(TADDOLate)Cl2(bipyridine) (III) (Sheen & Gau, 2004). However, these Ti—O bond lengths are slightly longer than those of 1.752 (5) and 1.765 (5)Å in Ti(TADDOLate)Cl2(MeOCH2CH2OMe) (Hintermann & Togni, 2000). The weakest Ti—N(imine) bonds are trans to the strongest Ti—O bonds (Gau et al., 1996) where the bond lengths are found to be 2.246 (2) and 2.2476 (17) Å. These are slightly shorter than the Ti—N distances to the monodentate CH3CN ligands in (II), 2.264 (4) and 2.283 (4) Å but are somewhat longer than those of 2.229 (5) and 2.232 (5) Å in the bidentate bipyridine complex (III). The N—Ti—N bond angle in the five-membered chelate ring 73.90 (7)° is close to that of 72.0 (2)° in (III). However, this angle is ~10° smaller than the 83.24 (14)° observed in (II) with two monodentate nitrogen donors. In terms of Ti—Cl bond lengths and O—Ti—O angles, relatively small variations are observed in these structures. The Ti—Cl bonds bend away from the Ti—O bonds with a Cl—Ti—Cl angle of 163.96 (3)°.
For general background, see: Chen et al. (2007); Gau et al. (1996); Narasaka et al. (1989); Seebach et al. (1992); Shao & Gau (1998); Weber & Seebach (1994). For related structures, see: Hintermann & Togni (2000); Gothelf et al. (1995); Shao et al. (2001); Sheen & Gau (2004).
Data collection: SMART (Siemens 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).
Fig. 1. The molecular structure of (I), with atom-numbering scheme. Displacement ellipsoids are drawn at the 20% probability level. All except tertiary H atoms have been omitted for clarity. |
[TiCl2(C31H28O4)(C16H16N2)] | F(000) = 1712 |
Mr = 819.64 | Dx = 1.256 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 7794 reflections |
a = 9.9044 (9) Å | θ = 2.3–26.0° |
b = 18.8261 (17) Å | µ = 0.37 mm−1 |
c = 23.238 (2) Å | T = 293 K |
V = 4332.9 (7) Å3 | Block, colorless |
Z = 4 | 0.70 × 0.59 × 0.21 mm |
Bruker SMART 1000 CCD diffractometer | 8479 independent reflections |
Radiation source: fine-focus sealed tube | 6464 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
φ and ω scans | θmax = 26.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→12 |
Tmin = 0.672, Tmax = 1.000 | k = −23→23 |
24512 measured reflections | l = −28→23 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.085 | w = 1/[σ2(Fo2) + (0.0439P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.95 | (Δ/σ)max = 0.001 |
8479 reflections | Δρmax = 0.25 e Å−3 |
505 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 3731 Friedel pairs |
0 constraints | Absolute structure parameter: −0.03 (2) |
Primary atom site location: structure-invariant direct methods |
[TiCl2(C31H28O4)(C16H16N2)] | V = 4332.9 (7) Å3 |
Mr = 819.64 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 9.9044 (9) Å | µ = 0.37 mm−1 |
b = 18.8261 (17) Å | T = 293 K |
c = 23.238 (2) Å | 0.70 × 0.59 × 0.21 mm |
Bruker SMART 1000 CCD diffractometer | 8479 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 6464 reflections with I > 2σ(I) |
Tmin = 0.672, Tmax = 1.000 | Rint = 0.042 |
24512 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.085 | Δρmax = 0.25 e Å−3 |
S = 0.95 | Δρmin = −0.23 e Å−3 |
8479 reflections | Absolute structure: Flack (1983), 3731 Friedel pairs |
505 parameters | Absolute structure parameter: −0.03 (2) |
0 restraints |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Ti | 0.01130 (4) | 0.890362 (18) | 0.017317 (17) | 0.03442 (10) | |
Cl1 | −0.19289 (6) | 0.87499 (4) | −0.03230 (3) | 0.05223 (17) | |
Cl2 | 0.22879 (6) | 0.87341 (3) | 0.05768 (3) | 0.05237 (17) | |
O1 | 0.04561 (15) | 0.97815 (7) | −0.00782 (7) | 0.0376 (4) | |
O2 | −0.10731 (18) | 1.13265 (8) | 0.05941 (7) | 0.0518 (4) | |
O3 | −0.0431 (2) | 1.08799 (9) | 0.14664 (7) | 0.0556 (5) | |
O4 | −0.06491 (15) | 0.91234 (8) | 0.08435 (7) | 0.0378 (4) | |
N1 | 0.09409 (19) | 0.83911 (10) | −0.06252 (9) | 0.0423 (5) | |
N2 | −0.00005 (18) | 0.77257 (9) | 0.03233 (9) | 0.0390 (4) | |
C1 | 0.0141 (2) | 1.05209 (10) | −0.00378 (10) | 0.0382 (5) | |
C2 | −0.0782 (2) | 1.05946 (11) | 0.04940 (10) | 0.0372 (5) | |
H2A | −0.1630 | 1.0343 | 0.0419 | 0.045* | |
C3 | −0.0195 (2) | 1.03286 (11) | 0.10639 (10) | 0.0380 (5) | |
H3A | 0.0781 | 1.0262 | 0.1020 | 0.046* | |
C4 | −0.0835 (2) | 0.96249 (12) | 0.12945 (10) | 0.0371 (5) | |
C5 | −0.0873 (4) | 1.15128 (14) | 0.11801 (12) | 0.0625 (8) | |
C6 | −0.2193 (5) | 1.1747 (2) | 0.14401 (18) | 0.1215 (18) | |
H6A | −0.2845 | 1.1372 | 0.1403 | 0.182* | |
H6B | −0.2512 | 1.2162 | 0.1243 | 0.182* | |
H6C | −0.2062 | 1.1854 | 0.1840 | 0.182* | |
C7 | 0.0228 (5) | 1.20642 (17) | 0.12197 (15) | 0.1091 (16) | |
H7A | 0.1036 | 1.1884 | 0.1045 | 0.164* | |
H7B | 0.0400 | 1.2172 | 0.1617 | 0.164* | |
H7C | −0.0053 | 1.2488 | 0.1023 | 0.164* | |
C8 | −0.0567 (3) | 1.07213 (12) | −0.06015 (11) | 0.0445 (6) | |
C9 | 0.0162 (4) | 1.06813 (15) | −0.11071 (11) | 0.0632 (8) | |
H9A | 0.1066 | 1.0549 | −0.1095 | 0.076* | |
C10 | −0.0427 (5) | 1.0834 (2) | −0.16289 (14) | 0.0867 (11) | |
H10A | 0.0078 | 1.0800 | −0.1965 | 0.104* | |
C11 | −0.1747 (5) | 1.1035 (2) | −0.16552 (15) | 0.0887 (11) | |
H11A | −0.2146 | 1.1133 | −0.2009 | 0.106* | |
C12 | −0.2486 (4) | 1.10906 (18) | −0.11572 (15) | 0.0794 (10) | |
H12A | −0.3381 | 1.1239 | −0.1173 | 0.095* | |
C13 | −0.1903 (3) | 1.09274 (14) | −0.06321 (12) | 0.0586 (7) | |
H13A | −0.2415 | 1.0957 | −0.0298 | 0.070* | |
C14 | 0.1464 (3) | 1.09407 (12) | 0.00229 (11) | 0.0460 (6) | |
C15 | 0.1502 (3) | 1.16627 (14) | −0.01034 (14) | 0.0635 (8) | |
H15A | 0.0730 | 1.1891 | −0.0236 | 0.076* | |
C16 | 0.2688 (4) | 1.20430 (17) | −0.00315 (17) | 0.0898 (12) | |
H16A | 0.2707 | 1.2525 | −0.0118 | 0.108* | |
C17 | 0.3823 (4) | 1.1718 (2) | 0.0165 (2) | 0.1116 (16) | |
H17A | 0.4611 | 1.1979 | 0.0214 | 0.134* | |
C18 | 0.3811 (3) | 1.10086 (19) | 0.0291 (2) | 0.1041 (15) | |
H18A | 0.4592 | 1.0787 | 0.0422 | 0.125* | |
C19 | 0.2627 (3) | 1.06186 (15) | 0.02209 (16) | 0.0702 (9) | |
H19A | 0.2620 | 1.0137 | 0.0309 | 0.084* | |
C20 | −0.2338 (2) | 0.97070 (13) | 0.14184 (11) | 0.0437 (6) | |
C21 | −0.3293 (3) | 0.94547 (16) | 0.10358 (14) | 0.0606 (8) | |
H21A | −0.3018 | 0.9228 | 0.0700 | 0.073* | |
C22 | −0.4658 (3) | 0.9538 (2) | 0.11499 (17) | 0.0855 (11) | |
H22A | −0.5296 | 0.9361 | 0.0893 | 0.103* | |
C23 | −0.5063 (4) | 0.9878 (2) | 0.16382 (19) | 0.0984 (13) | |
H23A | −0.5979 | 0.9936 | 0.1711 | 0.118* | |
C24 | −0.4135 (4) | 1.0133 (2) | 0.20214 (17) | 0.0826 (11) | |
H24A | −0.4418 | 1.0371 | 0.2351 | 0.099* | |
C25 | −0.2781 (3) | 1.00354 (17) | 0.19176 (13) | 0.0613 (8) | |
H25A | −0.2152 | 1.0192 | 0.2186 | 0.074* | |
C26 | −0.0096 (3) | 0.93361 (12) | 0.18191 (10) | 0.0430 (6) | |
C27 | 0.1065 (3) | 0.96223 (18) | 0.20453 (13) | 0.0652 (8) | |
H27A | 0.1421 | 1.0035 | 0.1887 | 0.078* | |
C28 | 0.1710 (4) | 0.9303 (2) | 0.25059 (16) | 0.0865 (11) | |
H28A | 0.2483 | 0.9509 | 0.2659 | 0.104* | |
C29 | 0.1224 (4) | 0.8686 (2) | 0.27395 (16) | 0.0933 (12) | |
H29A | 0.1682 | 0.8462 | 0.3038 | 0.112* | |
C30 | 0.0059 (4) | 0.84082 (18) | 0.25278 (15) | 0.0860 (10) | |
H30A | −0.0298 | 0.7998 | 0.2691 | 0.103* | |
C31 | −0.0595 (3) | 0.87281 (16) | 0.20752 (13) | 0.0633 (8) | |
H31A | −0.1393 | 0.8530 | 0.1938 | 0.076* | |
C32 | 0.1284 (3) | 0.76385 (13) | −0.05528 (13) | 0.0516 (7) | |
H32A | 0.2164 | 0.7595 | −0.0373 | 0.062* | |
H32B | 0.1321 | 0.7408 | −0.0926 | 0.062* | |
C33 | 0.0228 (2) | 0.72842 (11) | −0.01819 (11) | 0.0456 (6) | |
H33A | −0.0605 | 0.7230 | −0.0397 | 0.055* | |
H33B | 0.0536 | 0.6817 | −0.0066 | 0.055* | |
C34 | 0.0898 (3) | 0.86842 (14) | −0.11157 (12) | 0.0544 (7) | |
H34A | 0.0754 | 0.9172 | −0.1109 | 0.065* | |
C35 | 0.1041 (3) | 0.83741 (17) | −0.16978 (13) | 0.0639 (8) | |
C36 | 0.0207 (5) | 0.7833 (2) | −0.18752 (18) | 0.1132 (15) | |
H36A | −0.0416 | 0.7635 | −0.1623 | 0.136* | |
C37 | 0.0307 (7) | 0.7587 (3) | −0.2438 (2) | 0.149 (2) | |
H37A | −0.0269 | 0.7230 | −0.2564 | 0.179* | |
C38 | 0.1227 (8) | 0.7859 (3) | −0.2800 (2) | 0.145 (2) | |
H38A | 0.1303 | 0.7679 | −0.3171 | 0.174* | |
C39 | 0.2044 (7) | 0.8395 (3) | −0.2628 (2) | 0.1272 (18) | |
H39A | 0.2678 | 0.8586 | −0.2879 | 0.153* | |
C40 | 0.1926 (5) | 0.8654 (2) | −0.20779 (15) | 0.0912 (12) | |
H40A | 0.2469 | 0.9032 | −0.1964 | 0.109* | |
C41 | −0.0077 (3) | 0.74781 (12) | 0.08336 (12) | 0.0497 (6) | |
H41A | −0.0180 | 0.7821 | 0.1118 | 0.060* | |
C42 | −0.0030 (3) | 0.67446 (13) | 0.10504 (12) | 0.0559 (7) | |
C43 | 0.0597 (5) | 0.6663 (2) | 0.15814 (16) | 0.0970 (12) | |
H43A | 0.0924 | 0.7060 | 0.1775 | 0.116* | |
C44 | 0.0734 (6) | 0.6011 (3) | 0.1818 (2) | 0.1319 (19) | |
H44A | 0.1147 | 0.5964 | 0.2176 | 0.158* | |
C45 | 0.0277 (6) | 0.5429 (2) | 0.1541 (2) | 0.1213 (18) | |
H45A | 0.0416 | 0.4981 | 0.1700 | 0.146* | |
C46 | −0.0396 (4) | 0.54923 (17) | 0.10223 (18) | 0.0899 (12) | |
H46A | −0.0740 | 0.5091 | 0.0841 | 0.108* | |
C47 | −0.0557 (3) | 0.61513 (14) | 0.07746 (13) | 0.0614 (7) | |
H47A | −0.1013 | 0.6199 | 0.0427 | 0.074* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ti | 0.0350 (2) | 0.02628 (18) | 0.0420 (2) | −0.00081 (16) | −0.00169 (19) | 0.00011 (18) |
Cl1 | 0.0408 (3) | 0.0585 (4) | 0.0573 (4) | −0.0036 (3) | −0.0117 (3) | −0.0018 (3) |
Cl2 | 0.0378 (3) | 0.0460 (3) | 0.0734 (5) | 0.0010 (3) | −0.0125 (3) | −0.0005 (3) |
O1 | 0.0435 (8) | 0.0278 (7) | 0.0415 (9) | −0.0019 (6) | 0.0009 (7) | 0.0017 (7) |
O2 | 0.0807 (12) | 0.0317 (9) | 0.0430 (10) | 0.0127 (8) | −0.0082 (9) | −0.0038 (8) |
O3 | 0.0897 (14) | 0.0405 (9) | 0.0366 (9) | 0.0029 (9) | −0.0097 (10) | −0.0058 (8) |
O4 | 0.0397 (8) | 0.0322 (8) | 0.0414 (9) | 0.0012 (6) | 0.0002 (7) | 0.0008 (7) |
N1 | 0.0446 (11) | 0.0327 (10) | 0.0495 (13) | −0.0039 (8) | 0.0038 (10) | −0.0033 (10) |
N2 | 0.0373 (10) | 0.0319 (9) | 0.0477 (12) | −0.0014 (9) | −0.0028 (10) | 0.0020 (8) |
C1 | 0.0501 (13) | 0.0247 (10) | 0.0398 (13) | −0.0003 (10) | −0.0036 (12) | 0.0011 (9) |
C2 | 0.0463 (13) | 0.0255 (11) | 0.0396 (14) | 0.0036 (10) | −0.0077 (11) | −0.0001 (10) |
C3 | 0.0454 (14) | 0.0331 (11) | 0.0355 (13) | −0.0031 (10) | −0.0037 (12) | −0.0016 (9) |
C4 | 0.0404 (13) | 0.0362 (12) | 0.0348 (13) | 0.0003 (10) | −0.0023 (11) | 0.0027 (10) |
C5 | 0.110 (2) | 0.0364 (15) | 0.0408 (16) | 0.0089 (15) | 0.0019 (16) | −0.0042 (13) |
C6 | 0.183 (4) | 0.102 (3) | 0.080 (3) | 0.080 (3) | 0.048 (3) | 0.017 (2) |
C7 | 0.205 (5) | 0.0591 (19) | 0.063 (2) | −0.045 (3) | −0.028 (3) | −0.0087 (16) |
C8 | 0.0658 (17) | 0.0300 (12) | 0.0376 (14) | 0.0014 (11) | −0.0076 (13) | 0.0013 (11) |
C9 | 0.084 (2) | 0.0637 (17) | 0.0421 (16) | 0.0067 (17) | −0.0015 (17) | −0.0005 (13) |
C10 | 0.122 (3) | 0.097 (3) | 0.0403 (18) | 0.005 (2) | −0.003 (2) | 0.0060 (17) |
C11 | 0.131 (3) | 0.085 (3) | 0.050 (2) | 0.001 (2) | −0.035 (2) | 0.0054 (19) |
C12 | 0.090 (2) | 0.080 (2) | 0.068 (2) | 0.0131 (19) | −0.033 (2) | 0.008 (2) |
C13 | 0.0700 (19) | 0.0585 (17) | 0.0475 (17) | 0.0083 (14) | −0.0117 (15) | 0.0039 (14) |
C14 | 0.0562 (15) | 0.0346 (13) | 0.0471 (15) | −0.0092 (11) | −0.0033 (12) | 0.0060 (11) |
C15 | 0.085 (2) | 0.0376 (14) | 0.068 (2) | −0.0114 (13) | −0.0020 (17) | 0.0054 (14) |
C16 | 0.115 (3) | 0.0517 (19) | 0.103 (3) | −0.040 (2) | 0.006 (3) | 0.0117 (19) |
C17 | 0.096 (3) | 0.088 (3) | 0.151 (4) | −0.059 (2) | −0.024 (3) | 0.021 (3) |
C18 | 0.068 (2) | 0.082 (2) | 0.162 (4) | −0.0383 (18) | −0.029 (2) | 0.038 (3) |
C19 | 0.0597 (17) | 0.0520 (16) | 0.099 (3) | −0.0181 (14) | −0.0094 (19) | 0.0205 (18) |
C20 | 0.0413 (13) | 0.0447 (14) | 0.0451 (16) | 0.0037 (11) | 0.0010 (12) | 0.0046 (12) |
C21 | 0.0425 (15) | 0.074 (2) | 0.065 (2) | −0.0023 (14) | −0.0021 (15) | −0.0006 (16) |
C22 | 0.0391 (18) | 0.122 (3) | 0.095 (3) | −0.0071 (17) | 0.0012 (18) | −0.002 (2) |
C23 | 0.0468 (19) | 0.141 (4) | 0.108 (3) | 0.020 (2) | 0.023 (2) | 0.022 (3) |
C24 | 0.070 (2) | 0.102 (3) | 0.075 (2) | 0.020 (2) | 0.028 (2) | 0.002 (2) |
C25 | 0.0572 (18) | 0.077 (2) | 0.0495 (17) | 0.0089 (15) | 0.0052 (15) | −0.0011 (16) |
C26 | 0.0468 (14) | 0.0466 (13) | 0.0357 (13) | 0.0078 (12) | 0.0028 (13) | 0.0047 (11) |
C27 | 0.0593 (18) | 0.079 (2) | 0.0575 (19) | −0.0028 (16) | −0.0138 (16) | 0.0208 (17) |
C28 | 0.069 (2) | 0.116 (3) | 0.074 (2) | 0.006 (2) | −0.0251 (19) | 0.027 (2) |
C29 | 0.107 (3) | 0.108 (3) | 0.065 (2) | 0.031 (3) | −0.016 (2) | 0.031 (2) |
C30 | 0.108 (3) | 0.080 (2) | 0.070 (2) | 0.008 (2) | 0.002 (2) | 0.0425 (19) |
C31 | 0.0731 (19) | 0.0586 (18) | 0.0583 (18) | −0.0017 (15) | 0.0010 (15) | 0.0180 (15) |
C32 | 0.0552 (15) | 0.0364 (13) | 0.0631 (18) | 0.0042 (11) | 0.0051 (14) | −0.0063 (13) |
C33 | 0.0485 (14) | 0.0309 (11) | 0.0573 (16) | −0.0029 (10) | 0.0022 (14) | −0.0023 (11) |
C34 | 0.0719 (18) | 0.0418 (14) | 0.0494 (16) | 0.0023 (13) | −0.0019 (14) | −0.0019 (13) |
C35 | 0.087 (2) | 0.0554 (17) | 0.0497 (18) | 0.0106 (16) | −0.0036 (17) | −0.0048 (15) |
C36 | 0.134 (4) | 0.121 (3) | 0.085 (3) | −0.029 (3) | −0.002 (3) | −0.040 (3) |
C37 | 0.206 (6) | 0.146 (5) | 0.095 (4) | −0.036 (5) | −0.007 (4) | −0.054 (4) |
C38 | 0.238 (7) | 0.130 (5) | 0.067 (3) | 0.032 (5) | −0.002 (4) | −0.037 (3) |
C39 | 0.210 (6) | 0.107 (3) | 0.065 (3) | 0.014 (4) | 0.040 (3) | −0.005 (3) |
C40 | 0.139 (3) | 0.077 (2) | 0.057 (2) | 0.001 (2) | 0.022 (2) | 0.0007 (19) |
C41 | 0.0539 (16) | 0.0373 (13) | 0.0578 (17) | 0.0028 (12) | −0.0058 (15) | −0.0011 (12) |
C42 | 0.0623 (16) | 0.0463 (14) | 0.0591 (17) | 0.0063 (14) | 0.0016 (16) | 0.0147 (13) |
C43 | 0.143 (3) | 0.071 (2) | 0.077 (3) | 0.012 (2) | −0.027 (3) | 0.018 (2) |
C44 | 0.199 (5) | 0.103 (4) | 0.094 (3) | 0.045 (4) | −0.035 (3) | 0.037 (3) |
C45 | 0.185 (5) | 0.071 (3) | 0.108 (4) | 0.049 (3) | 0.017 (4) | 0.043 (3) |
C46 | 0.123 (3) | 0.0464 (18) | 0.101 (3) | 0.0019 (19) | 0.036 (3) | 0.0079 (19) |
C47 | 0.0687 (17) | 0.0444 (15) | 0.0712 (19) | 0.0004 (14) | 0.0115 (15) | 0.0087 (15) |
Ti—O4 | 1.7797 (16) | C19—H19A | 0.9300 |
Ti—O1 | 1.7855 (14) | C20—C21 | 1.382 (4) |
Ti—N1 | 2.246 (2) | C20—C25 | 1.386 (4) |
Ti—N2 | 2.2476 (17) | C21—C22 | 1.387 (4) |
Ti—Cl1 | 2.3459 (7) | C21—H21A | 0.9300 |
Ti—Cl2 | 2.3710 (7) | C22—C23 | 1.363 (5) |
O1—C1 | 1.430 (2) | C22—H22A | 0.9300 |
O2—C5 | 1.420 (3) | C23—C24 | 1.367 (5) |
O2—C2 | 1.427 (3) | C23—H23A | 0.9300 |
O3—C3 | 1.417 (3) | C24—C25 | 1.375 (5) |
O3—C5 | 1.433 (3) | C24—H24A | 0.9300 |
O4—C4 | 1.422 (3) | C25—H25A | 0.9300 |
N1—C34 | 1.267 (3) | C26—C27 | 1.374 (4) |
N1—C32 | 1.467 (3) | C26—C31 | 1.382 (4) |
N2—C41 | 1.276 (3) | C27—C28 | 1.384 (4) |
N2—C33 | 1.456 (3) | C27—H27A | 0.9300 |
C1—C8 | 1.533 (3) | C28—C29 | 1.368 (5) |
C1—C14 | 1.537 (3) | C28—H28A | 0.9300 |
C1—C2 | 1.543 (3) | C29—C30 | 1.359 (5) |
C2—C3 | 1.531 (3) | C29—H29A | 0.9300 |
C2—H2A | 0.9800 | C30—C31 | 1.374 (4) |
C3—C4 | 1.563 (3) | C30—H30A | 0.9300 |
C3—H3A | 0.9800 | C31—H31A | 0.9300 |
C4—C26 | 1.522 (3) | C32—C33 | 1.510 (3) |
C4—C20 | 1.525 (3) | C32—H32A | 0.9700 |
C5—C6 | 1.505 (5) | C32—H32B | 0.9700 |
C5—C7 | 1.508 (5) | C33—H33A | 0.9700 |
C6—H6A | 0.9600 | C33—H33B | 0.9700 |
C6—H6B | 0.9600 | C34—C35 | 1.480 (4) |
C6—H6C | 0.9600 | C34—H34A | 0.9300 |
C7—H7A | 0.9600 | C35—C40 | 1.351 (5) |
C7—H7B | 0.9600 | C35—C36 | 1.374 (5) |
C7—H7C | 0.9600 | C36—C37 | 1.390 (6) |
C8—C13 | 1.381 (4) | C36—H36A | 0.9300 |
C8—C9 | 1.381 (4) | C37—C38 | 1.341 (7) |
C9—C10 | 1.376 (4) | C37—H37A | 0.9300 |
C9—H9A | 0.9300 | C38—C39 | 1.354 (8) |
C10—C11 | 1.362 (5) | C38—H38A | 0.9300 |
C10—H10A | 0.9300 | C39—C40 | 1.372 (6) |
C11—C12 | 1.373 (5) | C39—H39A | 0.9300 |
C11—H11A | 0.9300 | C40—H40A | 0.9300 |
C12—C13 | 1.384 (4) | C41—C42 | 1.471 (3) |
C12—H12A | 0.9300 | C41—H41A | 0.9300 |
C13—H13A | 0.9300 | C42—C47 | 1.390 (4) |
C14—C19 | 1.381 (4) | C42—C43 | 1.390 (4) |
C14—C15 | 1.391 (4) | C43—C44 | 1.352 (5) |
C15—C16 | 1.386 (4) | C43—H43A | 0.9300 |
C15—H15A | 0.9300 | C44—C45 | 1.351 (6) |
C16—C17 | 1.359 (5) | C44—H44A | 0.9300 |
C16—H16A | 0.9300 | C45—C46 | 1.382 (6) |
C17—C18 | 1.367 (5) | C45—H45A | 0.9300 |
C17—H17A | 0.9300 | C46—C47 | 1.377 (4) |
C18—C19 | 1.393 (4) | C46—H46A | 0.9300 |
C18—H18A | 0.9300 | C47—H47A | 0.9300 |
O4—Ti—O1 | 98.73 (7) | C17—C18—C19 | 119.8 (3) |
O4—Ti—N1 | 167.86 (7) | C17—C18—H18A | 120.1 |
O1—Ti—N1 | 93.32 (7) | C19—C18—H18A | 120.1 |
O4—Ti—N2 | 94.15 (7) | C14—C19—C18 | 120.7 (3) |
O1—Ti—N2 | 166.79 (7) | C14—C19—H19A | 119.7 |
N1—Ti—N2 | 73.90 (7) | C18—C19—H19A | 119.7 |
O4—Ti—Cl1 | 95.35 (6) | C21—C20—C25 | 118.4 (2) |
O1—Ti—Cl1 | 96.75 (5) | C21—C20—C4 | 120.8 (2) |
N1—Ti—Cl1 | 81.71 (5) | C25—C20—C4 | 120.8 (2) |
N2—Ti—Cl1 | 84.92 (5) | C20—C21—C22 | 120.4 (3) |
O4—Ti—Cl2 | 94.04 (6) | C20—C21—H21A | 119.8 |
O1—Ti—Cl2 | 94.65 (5) | C22—C21—H21A | 119.8 |
N1—Ti—Cl2 | 86.40 (6) | C23—C22—C21 | 119.9 (4) |
N2—Ti—Cl2 | 81.44 (5) | C23—C22—H22A | 120.0 |
Cl1—Ti—Cl2 | 163.96 (3) | C21—C22—H22A | 120.0 |
C1—O1—Ti | 146.95 (14) | C22—C23—C24 | 120.6 (3) |
C5—O2—C2 | 111.52 (18) | C22—C23—H23A | 119.7 |
C3—O3—C5 | 110.67 (17) | C24—C23—H23A | 119.7 |
C4—O4—Ti | 148.64 (14) | C23—C24—C25 | 119.6 (3) |
C34—N1—C32 | 122.1 (2) | C23—C24—H24A | 120.2 |
C34—N1—Ti | 122.94 (17) | C25—C24—H24A | 120.2 |
C32—N1—Ti | 113.87 (17) | C24—C25—C20 | 121.0 (3) |
C41—N2—C33 | 123.35 (19) | C24—C25—H25A | 119.5 |
C41—N2—Ti | 120.50 (16) | C20—C25—H25A | 119.5 |
C33—N2—Ti | 115.48 (14) | C27—C26—C31 | 117.4 (2) |
O1—C1—C8 | 106.47 (17) | C27—C26—C4 | 124.6 (2) |
O1—C1—C14 | 108.70 (18) | C31—C26—C4 | 117.9 (2) |
C8—C1—C14 | 109.99 (19) | C26—C27—C28 | 120.7 (3) |
O1—C1—C2 | 105.63 (16) | C26—C27—H27A | 119.6 |
C8—C1—C2 | 113.03 (19) | C28—C27—H27A | 119.6 |
C14—C1—C2 | 112.66 (19) | C29—C28—C27 | 120.9 (4) |
O2—C2—C3 | 104.57 (18) | C29—C28—H28A | 119.6 |
O2—C2—C1 | 109.70 (18) | C27—C28—H28A | 119.6 |
C3—C2—C1 | 116.00 (19) | C30—C29—C28 | 118.8 (3) |
O2—C2—H2A | 108.8 | C30—C29—H29A | 120.6 |
C3—C2—H2A | 108.8 | C28—C29—H29A | 120.6 |
C1—C2—H2A | 108.8 | C29—C30—C31 | 120.6 (3) |
O3—C3—C2 | 105.59 (17) | C29—C30—H30A | 119.7 |
O3—C3—C4 | 109.11 (18) | C31—C30—H30A | 119.7 |
C2—C3—C4 | 114.82 (18) | C30—C31—C26 | 121.6 (3) |
O3—C3—H3A | 109.1 | C30—C31—H31A | 119.2 |
C2—C3—H3A | 109.1 | C26—C31—H31A | 119.2 |
C4—C3—H3A | 109.1 | N1—C32—C33 | 109.4 (2) |
O4—C4—C26 | 106.91 (18) | N1—C32—H32A | 109.8 |
O4—C4—C20 | 109.42 (19) | C33—C32—H32A | 109.8 |
C26—C4—C20 | 110.8 (2) | N1—C32—H32B | 109.8 |
O4—C4—C3 | 104.92 (17) | C33—C32—H32B | 109.8 |
C26—C4—C3 | 112.47 (19) | H32A—C32—H32B | 108.2 |
C20—C4—C3 | 112.02 (19) | N2—C33—C32 | 108.40 (18) |
O2—C5—O3 | 106.40 (19) | N2—C33—H33A | 110.0 |
O2—C5—C6 | 109.6 (3) | C32—C33—H33A | 110.0 |
O3—C5—C6 | 108.8 (3) | N2—C33—H33B | 110.0 |
O2—C5—C7 | 109.2 (3) | C32—C33—H33B | 110.0 |
O3—C5—C7 | 108.9 (3) | H33A—C33—H33B | 108.4 |
C6—C5—C7 | 113.7 (3) | N1—C34—C35 | 130.3 (3) |
C5—C6—H6A | 109.5 | N1—C34—H34A | 114.8 |
C5—C6—H6B | 109.5 | C35—C34—H34A | 114.8 |
H6A—C6—H6B | 109.5 | C40—C35—C36 | 118.9 (3) |
C5—C6—H6C | 109.5 | C40—C35—C34 | 120.4 (3) |
H6A—C6—H6C | 109.5 | C36—C35—C34 | 120.6 (3) |
H6B—C6—H6C | 109.5 | C35—C36—C37 | 119.1 (5) |
C5—C7—H7A | 109.5 | C35—C36—H36A | 120.5 |
C5—C7—H7B | 109.5 | C37—C36—H36A | 120.5 |
H7A—C7—H7B | 109.5 | C38—C37—C36 | 120.7 (5) |
C5—C7—H7C | 109.5 | C38—C37—H37A | 119.6 |
H7A—C7—H7C | 109.5 | C36—C37—H37A | 119.6 |
H7B—C7—H7C | 109.5 | C37—C38—C39 | 120.4 (5) |
C13—C8—C9 | 118.2 (3) | C37—C38—H38A | 119.8 |
C13—C8—C1 | 123.5 (2) | C39—C38—H38A | 119.8 |
C9—C8—C1 | 118.3 (2) | C38—C39—C40 | 119.2 (5) |
C10—C9—C8 | 121.1 (3) | C38—C39—H39A | 120.4 |
C10—C9—H9A | 119.4 | C40—C39—H39A | 120.4 |
C8—C9—H9A | 119.4 | C35—C40—C39 | 121.7 (4) |
C11—C10—C9 | 120.3 (4) | C35—C40—H40A | 119.1 |
C11—C10—H10A | 119.9 | C39—C40—H40A | 119.1 |
C9—C10—H10A | 119.9 | N2—C41—C42 | 131.2 (2) |
C10—C11—C12 | 119.7 (3) | N2—C41—H41A | 114.4 |
C10—C11—H11A | 120.2 | C42—C41—H41A | 114.4 |
C12—C11—H11A | 120.2 | C47—C42—C43 | 119.3 (3) |
C11—C12—C13 | 120.3 (3) | C47—C42—C41 | 125.8 (3) |
C11—C12—H12A | 119.9 | C43—C42—C41 | 114.9 (3) |
C13—C12—H12A | 119.9 | C44—C43—C42 | 120.4 (4) |
C8—C13—C12 | 120.5 (3) | C44—C43—H43A | 119.8 |
C8—C13—H13A | 119.8 | C42—C43—H43A | 119.8 |
C12—C13—H13A | 119.8 | C45—C44—C43 | 120.6 (4) |
C19—C14—C15 | 118.5 (2) | C45—C44—H44A | 119.7 |
C19—C14—C1 | 121.1 (2) | C43—C44—H44A | 119.7 |
C15—C14—C1 | 120.4 (2) | C44—C45—C46 | 120.5 (3) |
C16—C15—C14 | 120.2 (3) | C44—C45—H45A | 119.8 |
C16—C15—H15A | 119.9 | C46—C45—H45A | 119.8 |
C14—C15—H15A | 119.9 | C47—C46—C45 | 119.9 (4) |
C17—C16—C15 | 120.6 (3) | C47—C46—H46A | 120.1 |
C17—C16—H16A | 119.7 | C45—C46—H46A | 120.1 |
C15—C16—H16A | 119.7 | C46—C47—C42 | 119.2 (3) |
C16—C17—C18 | 120.4 (3) | C46—C47—H47A | 120.4 |
C16—C17—H17A | 119.8 | C42—C47—H47A | 120.4 |
C18—C17—H17A | 119.8 |
Experimental details
Crystal data | |
Chemical formula | [TiCl2(C31H28O4)(C16H16N2)] |
Mr | 819.64 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 9.9044 (9), 18.8261 (17), 23.238 (2) |
V (Å3) | 4332.9 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.37 |
Crystal size (mm) | 0.70 × 0.59 × 0.21 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.672, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24512, 8479, 6464 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.085, 0.95 |
No. of reflections | 8479 |
No. of parameters | 505 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.23 |
Absolute structure | Flack (1983), 3731 Friedel pairs |
Absolute structure parameter | −0.03 (2) |
Computer programs: SMART (Siemens 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000).
Ti—O4 | 1.7797 (16) | Ti—N2 | 2.2476 (17) |
Ti—O1 | 1.7855 (14) | Ti—Cl1 | 2.3459 (7) |
Ti—N1 | 2.246 (2) | Ti—Cl2 | 2.3710 (7) |
O4—Ti—O1 | 98.73 (7) | Cl1—Ti—Cl2 | 163.96 (3) |
N1—Ti—N2 | 73.90 (7) |
Titanium(IV) complexes of 2,2-dimethyl-α,α,α',α'-tetraaryl-1,3-dioxolane- 4,5-dimethanolates (TADDOLs) have been reported to be excellent catalysts in a variety of asymmetric reactions such as ethylation (Shao & Gau, 1998), arylation (Weber & Seebach, 1994), Diels-Alder (Narasaka et al., 1989), and fluorination reactions (Hintermann & Togni, 2000). In these studies, molecular structures of both four-coordinate Ti(TADDOLate)2 (Seebach et al., 1992) and six-coordinate Ti(TADDOLate)Cl2L2 (Gothelf et al., 1995) complexes were reported. For six-coordinate complexes, the two chloride ligands are invariably trans to each other and L2 could be two neutral monodentate ligands, such as tetrahydrofuran (Shao et al., 2001) or acetonitrile (Hintermann & Togni, 2000). L2 could also be a neutral bidentate like bipyridine or a 1,10-phenathroline. Recently, the molecular structure of an aluminium(III)-TADDOLate complex has been reported (Chen et al., 2007).
The molecular structure of (I) has a distorted octahedral geometry about the titanium(IV) metal center with Ti—O(TADDOLate) bond lengths of 1.7797 (16)and 1.7855 (14) Å which are nearly identical to those in Ti(TADDOLate)Cl2(CH3CN)2 (II) (Hintermann & Togni, 2000) and Ti(TADDOLate)Cl2(bipyridine) (III) (Sheen & Gau, 2004). However, these Ti—O bond lengths are slightly longer than those of 1.752 (5) and 1.765 (5)Å in Ti(TADDOLate)Cl2(MeOCH2CH2OMe) (Hintermann & Togni, 2000). The weakest Ti—N(imine) bonds are trans to the strongest Ti—O bonds (Gau et al., 1996) where the bond lengths are found to be 2.246 (2) and 2.2476 (17) Å. These are slightly shorter than the Ti—N distances to the monodentate CH3CN ligands in (II), 2.264 (4) and 2.283 (4) Å but are somewhat longer than those of 2.229 (5) and 2.232 (5) Å in the bidentate bipyridine complex (III). The N—Ti—N bond angle in the five-membered chelate ring 73.90 (7)° is close to that of 72.0 (2)° in (III). However, this angle is ~10° smaller than the 83.24 (14)° observed in (II) with two monodentate nitrogen donors. In terms of Ti—Cl bond lengths and O—Ti—O angles, relatively small variations are observed in these structures. The Ti—Cl bonds bend away from the Ti—O bonds with a Cl—Ti—Cl angle of 163.96 (3)°.