Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026761/om2129sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026761/om2129Isup2.hkl |
CCDC reference: 654707
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.004 Å
- R factor = 0.040
- wR factor = 0.127
- Data-to-parameter ratio = 14.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.25 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.71 Ratio PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C3 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C1
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Ti1 (4) 4.30
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
To a solution of Ti(acac)2Cl2 (0.225 g, 0.71 mmol) in CH3CN (15 ml), a mixture of diol (0.181 g, 0.71 mmol) and sodium acetate (0.116 g, 1.42 mmol) in the same solvent (15 ml) was added dropwise at 300 K and the mixture was refluxed for 8 h. The reaction mixture was cooled to room temperature and filtered through celite. The filtrate was concentrated to a small volume (3 ml) and hexane was added (2 ml). Storage of the solution at 263 K yielded dark red blocks of the title compound (0.237 g, 67%; m.p.: 419–421 K). Analysis, calculated for C27H32O6Ti: C 64.77, H 6.45; found: C 64.62, H 6.46%. Spectroscopic analysis: 1H NMR (300 MHz, 298 K, CDCl3, δ, p.p.m.): 7.12–7.26 (m, 4 H, phenyl), 5.95 (s, 1 H, CH, acac), 4.41 (s, 2 H, CH2), 2.08 (m, 6 H, CH3), 1.42 (s, 18 H, tert-butyl).
H atoms were placed in calculated positions (C—H = 0.95–0.98 Å) and included as riding contributions with isotropic displacement parameters 1.2–1.5 times those of the attached carbon atoms.
Titanium complexes containing aryloxides with bulky substituents are of interest in homogeneous catalysis, particularly in relation to polymerization processes (Priya et al., 2004; Fokken et al.,1996; Groysman et al., 2003). When bulky phenolate ligands are employed instead of metallocenes better results were obtained in polymerization of olefins (Hanava et al., 2003). The utility of titanium aryloxides in catalytic reactions such as olefin polymerization, oxidation, epoxidation and carbon-carbon coupling reactions are well documented (Chuck et al., 2006). Here, we report the mixed ligand complex [(–OC(CH3)CHC(CH3)O–)2Ti{(–OC6H2(Me)2)(µ-CH2) ((Me)2C6H2O–)}].
The coordination about the titanium(IV) center is distorted octahedral (Table 1). The acetylacetonate ligands are planar within 0.01 Å but are not coplanar with the metal. Instead, the O1, O2, C1, C2, C3 plane makes a dihedral angle of 16.1 (2)° with the Ti1 O1 O2 plane while the corresponding angle for the other acetylacetonate ligand is 14.0 (1)°. The bisphenoxo ligand adopts a open book conformation with the dihedral angle between the two aromatic rings being 106.79 (8)°. The two Ti—O—C angles associated with this ligand differ significantly (Table 1). This is attributed to packing considerations since the rings containing C20 through C26 in two adjacent molecules are parallel, partially interleaved and separated by 3.74 Å while C12 and C13 in the other ring make contacts, respectively, with H8 (2.88 Å) and H10B (2.89 Å) in the molecule at x,-1 + y,z. The former interaction tends to open up the Ti—O6—C20 angle while the latter acts to decrease the Ti—O5—C11 angle.
For related literature, see: Chuck et al. (2006); Fokken et al. (1996); Groysman et al. (2003); Hanava et al. (2003); Priya et al. (2004).
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
Fig. 1. Perspective view of the title compound. Displacement ellipsoids are drawn at the 50% level and H-atoms are drawn as spheres of arbitrary radius. |
[Ti(C5H7O2)2(C17H18O2)] | Z = 2 |
Mr = 500.43 | F(000) = 528 |
Triclinic, P1 | Dx = 1.272 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.3605 (9) Å | Cell parameters from 25 reflections |
b = 9.3419 (7) Å | θ = 18.2–23.1° |
c = 17.652 (1) Å | µ = 0.37 mm−1 |
α = 92.472 (5)° | T = 298 K |
β = 95.599 (7)° | Block, red |
γ = 107.209 (7)° | 0.46 × 0.40 × 0.26 mm |
V = 1306.9 (2) Å3 |
Enraf–Nonius CAD-4 diffractometer | 3123 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.021 |
Graphite monochromator | θmax = 25.1°, θmin = 2.3° |
θ/2θ scans | h = 0→9 |
Absorption correction: empirical (using intensity measurements) ψ scans (North et al., 1968) | k = −11→10 |
Tmin = 0.850, Tmax = 0.911 | l = −21→20 |
4973 measured reflections | 2 standard reflections every 2 min |
4628 independent reflections | intensity decay: <1% |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.063P)2 + 0.4456P] where P = (Fo2 + 2Fc2)/3 |
4628 reflections | (Δ/σ)max = 0.001 |
314 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
[Ti(C5H7O2)2(C17H18O2)] | γ = 107.209 (7)° |
Mr = 500.43 | V = 1306.9 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.3605 (9) Å | Mo Kα radiation |
b = 9.3419 (7) Å | µ = 0.37 mm−1 |
c = 17.652 (1) Å | T = 298 K |
α = 92.472 (5)° | 0.46 × 0.40 × 0.26 mm |
β = 95.599 (7)° |
Enraf–Nonius CAD-4 diffractometer | 3123 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) ψ scans (North et al., 1968) | Rint = 0.021 |
Tmin = 0.850, Tmax = 0.911 | 2 standard reflections every 2 min |
4973 measured reflections | intensity decay: <1% |
4628 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.23 e Å−3 |
4628 reflections | Δρmin = −0.34 e Å−3 |
314 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-atoms were placed in calculated positions (C—H = 0.95 - 0.98 Å) and included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached carbon atoms. |
x | y | z | Uiso*/Ueq | ||
Ti1 | 0.83024 (6) | 0.95224 (5) | 0.68559 (3) | 0.04474 (16) | |
O1 | 0.7004 (3) | 0.8836 (2) | 0.57985 (11) | 0.0600 (5) | |
O2 | 1.0249 (2) | 0.9282 (2) | 0.63419 (10) | 0.0541 (5) | |
O3 | 0.8816 (2) | 1.1664 (2) | 0.65189 (10) | 0.0516 (5) | |
O4 | 0.6234 (2) | 0.9907 (2) | 0.71662 (11) | 0.0531 (5) | |
O5 | 0.7537 (2) | 0.7554 (2) | 0.70880 (10) | 0.0508 (5) | |
O6 | 0.9587 (2) | 1.02024 (19) | 0.77511 (10) | 0.0476 (4) | |
C1 | 0.7354 (5) | 0.8132 (4) | 0.52428 (17) | 0.0732 (10) | |
C2 | 0.5923 (6) | 0.7500 (6) | 0.4607 (2) | 0.1285 (19) | |
H2A | 0.5136 | 0.6618 | 0.4762 | 0.193* | |
H2B | 0.6367 | 0.7243 | 0.4156 | 0.193* | |
H2C | 0.5361 | 0.8241 | 0.4499 | 0.193* | |
C3 | 0.8900 (5) | 0.7935 (5) | 0.5200 (2) | 0.0895 (12) | |
H3 | 0.9025 | 0.7357 | 0.4780 | 0.107* | |
C4 | 1.0287 (4) | 0.8529 (4) | 0.57311 (17) | 0.0637 (8) | |
C5 | 1.1956 (5) | 0.8313 (5) | 0.5618 (2) | 0.0929 (13) | |
H5A | 1.2845 | 0.9137 | 0.5879 | 0.111* | |
H5B | 1.2076 | 0.8273 | 0.5083 | 0.111* | |
H5C | 1.2015 | 0.7390 | 0.5820 | 0.111* | |
C6 | 0.8209 (3) | 1.2722 (3) | 0.67020 (15) | 0.0481 (6) | |
C7 | 0.9100 (4) | 1.4253 (3) | 0.64689 (19) | 0.0692 (9) | |
H7A | 1.0217 | 1.4601 | 0.6736 | 0.083* | |
H7B | 0.8488 | 1.4937 | 0.6593 | 0.083* | |
H7C | 0.9164 | 1.4201 | 0.5929 | 0.083* | |
C8 | 0.6801 (3) | 1.2504 (3) | 0.70863 (16) | 0.0529 (7) | |
H8 | 0.6478 | 1.3342 | 0.7224 | 0.063* | |
C9 | 0.5848 (3) | 1.1124 (3) | 0.72778 (14) | 0.0477 (6) | |
C10 | 0.4241 (4) | 1.0942 (4) | 0.76311 (19) | 0.0669 (9) | |
H10A | 0.3294 | 1.0519 | 0.7251 | 0.080* | |
H10B | 0.4213 | 1.1906 | 0.7830 | 0.080* | |
H10C | 0.4191 | 1.0286 | 0.8038 | 0.080* | |
C11 | 0.7272 (3) | 0.6725 (3) | 0.77042 (14) | 0.0434 (6) | |
C12 | 0.5619 (3) | 0.5910 (3) | 0.78049 (16) | 0.0507 (7) | |
C13 | 0.5362 (4) | 0.5020 (3) | 0.84165 (17) | 0.0552 (7) | |
H13 | 0.4264 | 0.4485 | 0.8488 | 0.066* | |
C14 | 0.6676 (4) | 0.4898 (3) | 0.89250 (16) | 0.0499 (6) | |
C15 | 0.8289 (3) | 0.5727 (3) | 0.88113 (15) | 0.0466 (6) | |
H15 | 0.9186 | 0.5661 | 0.9149 | 0.056* | |
C16 | 0.8635 (3) | 0.6658 (3) | 0.82145 (14) | 0.0414 (6) | |
C17 | 0.4165 (4) | 0.6007 (4) | 0.7242 (2) | 0.0755 (10) | |
H17A | 0.3135 | 0.5307 | 0.7356 | 0.113* | |
H17B | 0.4368 | 0.5769 | 0.6733 | 0.113* | |
H17C | 0.4074 | 0.7008 | 0.7282 | 0.113* | |
C18 | 0.6375 (5) | 0.3883 (4) | 0.9572 (2) | 0.0732 (9) | |
H18A | 0.7436 | 0.3836 | 0.9814 | 0.088* | |
H18B | 0.5694 | 0.2893 | 0.9376 | 0.088* | |
H18C | 0.5804 | 0.4274 | 0.9938 | 0.088* | |
C19 | 1.0431 (3) | 0.7572 (3) | 0.81441 (15) | 0.0432 (6) | |
H19A | 1.0531 | 0.7811 | 0.7618 | 0.052* | |
H19B | 1.1177 | 0.6977 | 0.8278 | 0.052* | |
C20 | 1.0499 (3) | 1.0264 (3) | 0.84343 (13) | 0.0397 (5) | |
C21 | 1.0956 (3) | 1.1597 (3) | 0.89035 (15) | 0.0439 (6) | |
C22 | 1.1872 (3) | 1.1633 (3) | 0.96104 (15) | 0.0480 (6) | |
H22 | 1.2159 | 1.2506 | 0.9933 | 0.058* | |
C23 | 1.2369 (3) | 1.0433 (3) | 0.98512 (14) | 0.0470 (6) | |
C24 | 1.1904 (3) | 0.9132 (3) | 0.93643 (15) | 0.0448 (6) | |
H24 | 1.2227 | 0.8309 | 0.9519 | 0.054* | |
C25 | 1.0974 (3) | 0.9015 (3) | 0.86565 (14) | 0.0399 (5) | |
C26 | 1.0431 (4) | 1.2922 (3) | 0.86477 (19) | 0.0668 (9) | |
H26A | 1.0880 | 1.3752 | 0.9026 | 0.080* | |
H26B | 0.9223 | 1.2659 | 0.8582 | 0.080* | |
H26C | 1.0855 | 1.3202 | 0.8172 | 0.080* | |
C27 | 1.3356 (4) | 1.0516 (4) | 1.06257 (16) | 0.0612 (8) | |
H27A | 1.3620 | 1.1512 | 1.0867 | 0.073* | |
H27B | 1.4381 | 1.0282 | 1.0565 | 0.073* | |
H27C | 1.2693 | 0.9807 | 1.0937 | 0.073* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ti1 | 0.0526 (3) | 0.0502 (3) | 0.0340 (3) | 0.0202 (2) | 0.00336 (19) | 0.00056 (19) |
O1 | 0.0672 (13) | 0.0742 (14) | 0.0399 (11) | 0.0279 (11) | −0.0059 (9) | 0.0002 (10) |
O2 | 0.0589 (12) | 0.0664 (12) | 0.0435 (11) | 0.0275 (10) | 0.0117 (9) | 0.0018 (9) |
O3 | 0.0589 (12) | 0.0553 (11) | 0.0485 (11) | 0.0248 (9) | 0.0173 (9) | 0.0113 (9) |
O4 | 0.0501 (11) | 0.0556 (11) | 0.0554 (12) | 0.0167 (9) | 0.0127 (9) | 0.0044 (9) |
O5 | 0.0581 (11) | 0.0503 (11) | 0.0426 (10) | 0.0164 (9) | −0.0002 (8) | 0.0008 (8) |
O6 | 0.0576 (11) | 0.0481 (10) | 0.0382 (10) | 0.0195 (9) | 0.0016 (8) | −0.0011 (8) |
C1 | 0.097 (3) | 0.085 (2) | 0.0383 (17) | 0.036 (2) | −0.0102 (16) | −0.0087 (16) |
C2 | 0.140 (4) | 0.160 (5) | 0.075 (3) | 0.055 (4) | −0.043 (3) | −0.050 (3) |
C3 | 0.111 (3) | 0.123 (3) | 0.0485 (19) | 0.062 (3) | 0.0014 (19) | −0.024 (2) |
C4 | 0.083 (2) | 0.074 (2) | 0.0461 (17) | 0.0388 (18) | 0.0187 (16) | 0.0100 (15) |
C5 | 0.102 (3) | 0.126 (3) | 0.075 (2) | 0.065 (3) | 0.031 (2) | 0.004 (2) |
C6 | 0.0546 (16) | 0.0529 (16) | 0.0370 (14) | 0.0190 (13) | −0.0016 (11) | 0.0021 (11) |
C7 | 0.082 (2) | 0.0534 (18) | 0.072 (2) | 0.0177 (16) | 0.0174 (18) | 0.0075 (15) |
C8 | 0.0530 (16) | 0.0559 (17) | 0.0537 (17) | 0.0238 (14) | 0.0055 (13) | −0.0030 (13) |
C9 | 0.0443 (15) | 0.0617 (17) | 0.0366 (14) | 0.0184 (13) | −0.0010 (11) | −0.0065 (12) |
C10 | 0.0517 (18) | 0.082 (2) | 0.069 (2) | 0.0227 (16) | 0.0139 (15) | −0.0076 (17) |
C11 | 0.0513 (15) | 0.0360 (13) | 0.0438 (14) | 0.0165 (12) | 0.0031 (12) | −0.0059 (11) |
C12 | 0.0463 (15) | 0.0465 (15) | 0.0566 (17) | 0.0128 (12) | 0.0025 (12) | −0.0093 (13) |
C13 | 0.0477 (16) | 0.0434 (15) | 0.070 (2) | 0.0061 (12) | 0.0136 (14) | −0.0020 (14) |
C14 | 0.0574 (17) | 0.0361 (13) | 0.0533 (16) | 0.0089 (12) | 0.0107 (13) | −0.0006 (12) |
C15 | 0.0558 (16) | 0.0381 (13) | 0.0475 (15) | 0.0187 (12) | 0.0019 (12) | −0.0026 (11) |
C16 | 0.0461 (14) | 0.0336 (12) | 0.0456 (14) | 0.0146 (11) | 0.0073 (11) | −0.0060 (10) |
C17 | 0.0539 (19) | 0.081 (2) | 0.086 (3) | 0.0190 (17) | −0.0121 (17) | 0.0027 (19) |
C18 | 0.084 (2) | 0.0562 (18) | 0.077 (2) | 0.0113 (17) | 0.0199 (19) | 0.0170 (16) |
C19 | 0.0445 (14) | 0.0425 (14) | 0.0461 (14) | 0.0189 (11) | 0.0053 (11) | 0.0003 (11) |
C20 | 0.0351 (13) | 0.0477 (14) | 0.0355 (13) | 0.0114 (11) | 0.0056 (10) | −0.0013 (11) |
C21 | 0.0365 (13) | 0.0457 (14) | 0.0484 (15) | 0.0122 (11) | 0.0043 (11) | −0.0039 (12) |
C22 | 0.0387 (14) | 0.0526 (16) | 0.0483 (15) | 0.0096 (12) | 0.0030 (11) | −0.0118 (12) |
C23 | 0.0361 (13) | 0.0606 (17) | 0.0400 (14) | 0.0088 (12) | 0.0048 (11) | −0.0011 (12) |
C24 | 0.0378 (13) | 0.0491 (15) | 0.0480 (15) | 0.0127 (11) | 0.0056 (11) | 0.0090 (12) |
C25 | 0.0342 (13) | 0.0448 (14) | 0.0414 (13) | 0.0112 (11) | 0.0100 (10) | 0.0027 (11) |
C26 | 0.0651 (19) | 0.0509 (17) | 0.081 (2) | 0.0219 (15) | −0.0137 (16) | −0.0161 (16) |
C27 | 0.0547 (18) | 0.075 (2) | 0.0468 (16) | 0.0123 (15) | −0.0026 (13) | 0.0025 (15) |
Ti1—O6 | 1.798 (2) | C11—C16 | 1.400 (4) |
Ti1—O5 | 1.839 (2) | C12—C13 | 1.386 (4) |
Ti1—O4 | 1.989 (2) | C12—C17 | 1.520 (4) |
Ti1—O2 | 2.002 (2) | C13—C14 | 1.385 (4) |
Ti1—O1 | 2.040 (2) | C13—H13 | 0.9300 |
Ti1—O3 | 2.046 (2) | C14—C15 | 1.381 (4) |
O1—C1 | 1.263 (4) | C14—C18 | 1.508 (4) |
O2—C4 | 1.270 (3) | C15—C16 | 1.393 (4) |
O3—C6 | 1.280 (3) | C15—H15 | 0.9300 |
O4—C9 | 1.283 (3) | C16—C19 | 1.512 (4) |
O5—C11 | 1.360 (3) | C17—H17A | 0.9600 |
O6—C20 | 1.352 (3) | C17—H17B | 0.9600 |
C1—C3 | 1.367 (5) | C17—H17C | 0.9600 |
C1—C2 | 1.518 (5) | C18—H18A | 0.9600 |
C2—H2A | 0.9600 | C18—H18B | 0.9600 |
C2—H2B | 0.9600 | C18—H18C | 0.9600 |
C2—H2C | 0.9600 | C19—C25 | 1.515 (3) |
C3—C4 | 1.376 (5) | C19—H19A | 0.9700 |
C3—H3 | 0.9300 | C19—H19B | 0.9700 |
C4—C5 | 1.499 (5) | C20—C21 | 1.396 (3) |
C5—H5A | 0.9600 | C20—C25 | 1.398 (3) |
C5—H5B | 0.9600 | C21—C22 | 1.392 (4) |
C5—H5C | 0.9600 | C21—C26 | 1.504 (4) |
C6—C8 | 1.383 (4) | C22—C23 | 1.376 (4) |
C6—C7 | 1.500 (4) | C22—H22 | 0.9300 |
C7—H7A | 0.9600 | C23—C24 | 1.390 (4) |
C7—H7B | 0.9600 | C23—C27 | 1.513 (4) |
C7—H7C | 0.9600 | C24—C25 | 1.388 (3) |
C8—C9 | 1.376 (4) | C24—H24 | 0.9300 |
C8—H8 | 0.9300 | C26—H26A | 0.9600 |
C9—C10 | 1.503 (4) | C26—H26B | 0.9600 |
C10—H10A | 0.9600 | C26—H26C | 0.9600 |
C10—H10B | 0.9600 | C27—H27A | 0.9600 |
C10—H10C | 0.9600 | C27—H27B | 0.9600 |
C11—C12 | 1.399 (4) | C27—H27C | 0.9600 |
O6—Ti1—O5 | 95.80 (8) | C12—C11—C16 | 120.8 (2) |
O6—Ti1—O4 | 96.15 (8) | C13—C12—C11 | 118.5 (3) |
O5—Ti1—O4 | 90.98 (8) | C13—C12—C17 | 121.9 (3) |
O6—Ti1—O2 | 92.84 (8) | C11—C12—C17 | 119.6 (3) |
O5—Ti1—O2 | 95.41 (8) | C14—C13—C12 | 122.5 (3) |
O4—Ti1—O2 | 168.39 (8) | C14—C13—H13 | 118.7 |
O6—Ti1—O1 | 175.50 (9) | C12—C13—H13 | 118.7 |
O5—Ti1—O1 | 87.13 (8) | C15—C14—C13 | 117.4 (3) |
O4—Ti1—O1 | 87.20 (8) | C15—C14—C18 | 120.9 (3) |
O2—Ti1—O1 | 83.46 (8) | C13—C14—C18 | 121.7 (3) |
O6—Ti1—O3 | 90.75 (8) | C14—C15—C16 | 123.0 (3) |
O5—Ti1—O3 | 171.80 (8) | C14—C15—H15 | 118.5 |
O4—Ti1—O3 | 83.40 (8) | C16—C15—H15 | 118.5 |
O2—Ti1—O3 | 89.17 (8) | C15—C16—C11 | 117.7 (2) |
O1—Ti1—O3 | 86.64 (8) | C15—C16—C19 | 119.9 (2) |
C1—O1—Ti1 | 129.8 (2) | C11—C16—C19 | 122.4 (2) |
C4—O2—Ti1 | 130.9 (2) | C12—C17—H17A | 109.5 |
C6—O3—Ti1 | 130.3 (2) | C12—C17—H17B | 109.5 |
C9—O4—Ti1 | 132.1 (2) | H17A—C17—H17B | 109.5 |
C11—O5—Ti1 | 140.2 (2) | C12—C17—H17C | 109.5 |
C20—O6—Ti1 | 162.5 (2) | H17A—C17—H17C | 109.5 |
O1—C1—C3 | 123.7 (3) | H17B—C17—H17C | 109.5 |
O1—C1—C2 | 115.3 (3) | C14—C18—H18A | 109.5 |
C3—C1—C2 | 121.1 (3) | C14—C18—H18B | 109.5 |
C1—C2—H2A | 109.5 | H18A—C18—H18B | 109.5 |
C1—C2—H2B | 109.5 | C14—C18—H18C | 109.5 |
H2A—C2—H2B | 109.5 | H18A—C18—H18C | 109.5 |
C1—C2—H2C | 109.5 | H18B—C18—H18C | 109.5 |
H2A—C2—H2C | 109.5 | C16—C19—C25 | 111.9 (2) |
H2B—C2—H2C | 109.5 | C16—C19—H19A | 109.2 |
C1—C3—C4 | 124.9 (3) | C25—C19—H19A | 109.2 |
C1—C3—H3 | 117.6 | C16—C19—H19B | 109.2 |
C4—C3—H3 | 117.6 | C25—C19—H19B | 109.2 |
O2—C4—C3 | 123.2 (3) | H19A—C19—H19B | 107.9 |
O2—C4—C5 | 115.7 (3) | O6—C20—C21 | 118.5 (2) |
C3—C4—C5 | 121.1 (3) | O6—C20—C25 | 120.1 (2) |
C4—C5—H5A | 109.5 | C21—C20—C25 | 121.4 (2) |
C4—C5—H5B | 109.5 | C22—C21—C20 | 117.8 (2) |
H5A—C5—H5B | 109.5 | C22—C21—C26 | 122.1 (2) |
C4—C5—H5C | 109.5 | C20—C21—C26 | 120.1 (2) |
H5A—C5—H5C | 109.5 | C23—C22—C21 | 122.8 (2) |
H5B—C5—H5C | 109.5 | C23—C22—H22 | 118.6 |
O3—C6—C8 | 123.4 (3) | C21—C22—H22 | 118.6 |
O3—C6—C7 | 116.4 (3) | C22—C23—C24 | 117.7 (2) |
C8—C6—C7 | 120.3 (3) | C22—C23—C27 | 121.1 (3) |
C6—C7—H7A | 109.5 | C24—C23—C27 | 121.2 (3) |
C6—C7—H7B | 109.5 | C25—C24—C23 | 122.4 (2) |
H7A—C7—H7B | 109.5 | C25—C24—H24 | 118.8 |
C6—C7—H7C | 109.5 | C23—C24—H24 | 118.8 |
H7A—C7—H7C | 109.5 | C24—C25—C20 | 118.0 (2) |
H7B—C7—H7C | 109.5 | C24—C25—C19 | 121.7 (2) |
C9—C8—C6 | 124.0 (3) | C20—C25—C19 | 120.3 (2) |
C9—C8—H8 | 118.0 | C21—C26—H26A | 109.5 |
C6—C8—H8 | 118.0 | C21—C26—H26B | 109.5 |
O4—C9—C8 | 123.6 (2) | H26A—C26—H26B | 109.5 |
O4—C9—C10 | 115.0 (3) | C21—C26—H26C | 109.5 |
C8—C9—C10 | 121.4 (3) | H26A—C26—H26C | 109.5 |
C9—C10—H10A | 109.5 | H26B—C26—H26C | 109.5 |
C9—C10—H10B | 109.5 | C23—C27—H27A | 109.5 |
H10A—C10—H10B | 109.5 | C23—C27—H27B | 109.5 |
C9—C10—H10C | 109.5 | H27A—C27—H27B | 109.5 |
H10A—C10—H10C | 109.5 | C23—C27—H27C | 109.5 |
H10B—C10—H10C | 109.5 | H27A—C27—H27C | 109.5 |
O5—C11—C12 | 118.7 (2) | H27B—C27—H27C | 109.5 |
O5—C11—C16 | 120.4 (2) |
Experimental details
Crystal data | |
Chemical formula | [Ti(C5H7O2)2(C17H18O2)] |
Mr | 500.43 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 8.3605 (9), 9.3419 (7), 17.652 (1) |
α, β, γ (°) | 92.472 (5), 95.599 (7), 107.209 (7) |
V (Å3) | 1306.9 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.37 |
Crystal size (mm) | 0.46 × 0.40 × 0.26 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | Empirical (using intensity measurements) ψ scans (North et al., 1968) |
Tmin, Tmax | 0.850, 0.911 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4973, 4628, 3123 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.127, 1.02 |
No. of reflections | 4628 |
No. of parameters | 314 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.34 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1989), CAD-4 Software, XCAD4 (Harms, 1996), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
Ti1—O6 | 1.798 (2) | Ti1—O2 | 2.002 (2) |
Ti1—O5 | 1.839 (2) | Ti1—O1 | 2.040 (2) |
Ti1—O4 | 1.989 (2) | Ti1—O3 | 2.046 (2) |
O6—Ti1—O5 | 95.80 (8) | O4—Ti1—O1 | 87.20 (8) |
O6—Ti1—O4 | 96.15 (8) | O2—Ti1—O1 | 83.46 (8) |
O5—Ti1—O4 | 90.98 (8) | O6—Ti1—O3 | 90.75 (8) |
O6—Ti1—O2 | 92.84 (8) | O5—Ti1—O3 | 171.80 (8) |
O5—Ti1—O2 | 95.41 (8) | O4—Ti1—O3 | 83.40 (8) |
O4—Ti1—O2 | 168.39 (8) | O2—Ti1—O3 | 89.17 (8) |
O6—Ti1—O1 | 175.50 (9) | O1—Ti1—O3 | 86.64 (8) |
O5—Ti1—O1 | 87.13 (8) |
Titanium complexes containing aryloxides with bulky substituents are of interest in homogeneous catalysis, particularly in relation to polymerization processes (Priya et al., 2004; Fokken et al.,1996; Groysman et al., 2003). When bulky phenolate ligands are employed instead of metallocenes better results were obtained in polymerization of olefins (Hanava et al., 2003). The utility of titanium aryloxides in catalytic reactions such as olefin polymerization, oxidation, epoxidation and carbon-carbon coupling reactions are well documented (Chuck et al., 2006). Here, we report the mixed ligand complex [(–OC(CH3)CHC(CH3)O–)2Ti{(–OC6H2(Me)2)(µ-CH2) ((Me)2C6H2O–)}].
The coordination about the titanium(IV) center is distorted octahedral (Table 1). The acetylacetonate ligands are planar within 0.01 Å but are not coplanar with the metal. Instead, the O1, O2, C1, C2, C3 plane makes a dihedral angle of 16.1 (2)° with the Ti1 O1 O2 plane while the corresponding angle for the other acetylacetonate ligand is 14.0 (1)°. The bisphenoxo ligand adopts a open book conformation with the dihedral angle between the two aromatic rings being 106.79 (8)°. The two Ti—O—C angles associated with this ligand differ significantly (Table 1). This is attributed to packing considerations since the rings containing C20 through C26 in two adjacent molecules are parallel, partially interleaved and separated by 3.74 Å while C12 and C13 in the other ring make contacts, respectively, with H8 (2.88 Å) and H10B (2.89 Å) in the molecule at x,-1 + y,z. The former interaction tends to open up the Ti—O6—C20 angle while the latter acts to decrease the Ti—O5—C11 angle.