Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807017497/at2268sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807017497/at2268Isup2.hkl |
CCDC reference: 646634
Key indicators
- Single-crystal X-ray study
- T = 153 K
- Mean (C-C) = 0.006 Å
- R factor = 0.073
- wR factor = 0.138
- Data-to-parameter ratio = 16.2
checkCIF/PLATON results
No syntax errors found
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.745 0.939 Tmin(prime) and Tmax expected: 0.880 0.939 RR(prime) = 0.847 Please check that your absorption correction is appropriate. PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.85 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 11 N3 -TI -N2 -C6 75.70 0.80 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 16 N3 -TI -N2 -C7 -163.10 0.70 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 21 N3 -TI -N2 -C5 -45.80 0.80 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 26 N1 -TI -N3 -C8 -117.70 1.90 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 27 N4 -TI -N3 -C8 -26.10 1.90 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 28 N5 -TI -N3 -C8 156.20 1.90 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 29 CL -TI -N3 -C8 66.60 1.90 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 30 N2 -TI -N3 -C8 -59.00 2.00 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 33 N5 -TI -N4 -C12 -125.00 1.50 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 38 N5 -TI -N4 -C16 63.10 1.70 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 43 N4 -TI -N5 -C21 164.30 1.50 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 48 N4 -TI -N5 -C17 -26.30 1.70 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 66 TI -N3 -C8 -C11 -167.50 1.80 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 67 TI -N3 -C8 -C9 -47.00 2.00 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 68 TI -N3 -C8 -C10 72.00 2.00 1.555 1.555 1.555 1.555
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 17 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 15 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
To a near-frozen solution of Ti(NtBu)Cl2py3 (Mountford, 1997) (1.234 g, 2.9 mmol) in toluene (10 ml), Lidap [N,N-dimethyl-(1-Li-pyrrol-2-yl)methanamine] (376.1 mg, 2.9 mmol) in toluene (10 ml) was added dropwise. After stirring at room temperature for 12 h, the resulting solution was filtered to remove solids. Volatiles were removed from the solution under reduced pressure to yield the orange crude product, which was washed with toluene and filtered to remove a trace amount of LiCl, then recrystallized from toluene (yield 920 mg, 60%).
All H atoms were positioned geometrically and refined using a riding model (including free rotation about the ethanol C—C bond), with C—H = 0.95–0.99 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C).
Over the last two decades, the chemistry of titanium–imido complexes has received considerable attention (Wigley, 1994). It has been shown that these complexes can be utilized in a wide variety of stoichiometric and sometimes catalytic coupling reactions with unsaturated substrates. A general entry point to new titanium–imido chemistry is gained via the readily prepared synthons [Ti(NR)Cl2(py)3] (R = tBu or Aryl) (Mountford, 1997).
The title compound, (I), was prepared by combining equimolar amounts of Ti(NtBu)Cl2py3 with Lidap [N,N-dimethyl-(1-Li-pyrrol-2-yl)methanamine] in toluene. It possesses a mononuclear structure featuring a six-coordinate octahedral titanium(IV) centre.
For related literature, see: Wigley (1994); Mountford (1997).
Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids. |
[Ti(C4H9N)Cl(C5H5N)2(C7H11N2)]·C7H8 | F(000) = 1120 |
Mr = 527.98 | Dx = 1.226 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: -P 2yn | Cell parameters from 7469 reflections |
a = 10.5646 (14) Å | θ = 3.2–25.3° |
b = 15.605 (2) Å | µ = 0.42 mm−1 |
c = 17.432 (2) Å | T = 153 K |
β = 95.507 (4)° | Block, orange-yellow |
V = 2860.6 (6) Å3 | 0.30 × 0.20 × 0.15 mm |
Z = 4 |
Rigaku Mercury diffractometer | 5227 independent reflections |
Radiation source: fine-focus sealed tube | 3910 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.088 |
Detector resolution: 7.31 pixels mm-1 | θmax = 25.4°, θmin = 3.2° |
ω scans | h = −12→12 |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | k = −18→18 |
Tmin = 0.745, Tmax = 0.939 | l = −20→20 |
27774 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.073 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0334P)2 + 3.8455P] where P = (Fo2 + 2Fc2)/3 |
5227 reflections | (Δ/σ)max = 0.002 |
323 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
[Ti(C4H9N)Cl(C5H5N)2(C7H11N2)]·C7H8 | V = 2860.6 (6) Å3 |
Mr = 527.98 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.5646 (14) Å | µ = 0.42 mm−1 |
b = 15.605 (2) Å | T = 153 K |
c = 17.432 (2) Å | 0.30 × 0.20 × 0.15 mm |
β = 95.507 (4)° |
Rigaku Mercury diffractometer | 5227 independent reflections |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | 3910 reflections with I > 2σ(I) |
Tmin = 0.745, Tmax = 0.939 | Rint = 0.088 |
27774 measured reflections |
R[F2 > 2σ(F2)] = 0.073 | 0 restraints |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.14 | Δρmax = 0.37 e Å−3 |
5227 reflections | Δρmin = −0.35 e Å−3 |
323 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. |
x | y | z | Uiso*/Ueq | ||
Ti | 0.28648 (6) | 0.78065 (4) | 0.61619 (4) | 0.02125 (18) | |
Cl | 0.20129 (9) | 0.77167 (6) | 0.73991 (5) | 0.0287 (2) | |
N1 | 0.4229 (3) | 0.77268 (18) | 0.53870 (16) | 0.0208 (6) | |
N2 | 0.4963 (3) | 0.78443 (19) | 0.69666 (16) | 0.0229 (7) | |
N3 | 0.1535 (3) | 0.79291 (19) | 0.55539 (17) | 0.0249 (7) | |
N4 | 0.3083 (3) | 0.92353 (19) | 0.62425 (17) | 0.0237 (7) | |
N5 | 0.2788 (3) | 0.63571 (19) | 0.60822 (17) | 0.0235 (7) | |
C1 | 0.4128 (4) | 0.7420 (2) | 0.4639 (2) | 0.0269 (9) | |
H1 | 0.3355 | 0.7387 | 0.4313 | 0.032* | |
C2 | 0.5283 (4) | 0.7173 (2) | 0.4432 (2) | 0.0286 (9) | |
H2 | 0.5459 | 0.6947 | 0.3948 | 0.034* | |
C3 | 0.6175 (4) | 0.7320 (2) | 0.5086 (2) | 0.0272 (9) | |
H3 | 0.7063 | 0.7207 | 0.5122 | 0.033* | |
C4 | 0.5508 (3) | 0.7656 (2) | 0.5649 (2) | 0.0224 (8) | |
C5 | 0.5915 (3) | 0.8026 (2) | 0.6417 (2) | 0.0270 (9) | |
H5A | 0.6746 | 0.7780 | 0.6615 | 0.032* | |
H5B | 0.6021 | 0.8654 | 0.6369 | 0.032* | |
C6 | 0.5096 (4) | 0.8476 (3) | 0.7600 (2) | 0.0323 (9) | |
H6A | 0.5942 | 0.8424 | 0.7880 | 0.048* | |
H6B | 0.4446 | 0.8369 | 0.7953 | 0.048* | |
H6C | 0.4988 | 0.9056 | 0.7387 | 0.048* | |
C7 | 0.5217 (4) | 0.6992 (2) | 0.7319 (2) | 0.0326 (10) | |
H7A | 0.6038 | 0.7002 | 0.7631 | 0.049* | |
H7B | 0.5237 | 0.6561 | 0.6912 | 0.049* | |
H7C | 0.4543 | 0.6850 | 0.7646 | 0.049* | |
C8 | 0.0369 (3) | 0.8149 (2) | 0.5080 (2) | 0.0290 (9) | |
C9 | −0.0585 (4) | 0.8480 (3) | 0.5615 (3) | 0.0391 (11) | |
H9A | −0.0748 | 0.8034 | 0.5989 | 0.059* | |
H9B | −0.1383 | 0.8630 | 0.5310 | 0.059* | |
H9C | −0.0238 | 0.8989 | 0.5889 | 0.059* | |
C10 | 0.0665 (4) | 0.8847 (3) | 0.4507 (3) | 0.0457 (12) | |
H10A | 0.0970 | 0.9361 | 0.4790 | 0.069* | |
H10B | −0.0108 | 0.8985 | 0.4173 | 0.069* | |
H10C | 0.1323 | 0.8641 | 0.4192 | 0.069* | |
C11 | −0.0137 (4) | 0.7350 (3) | 0.4650 (2) | 0.0393 (10) | |
H11A | 0.0518 | 0.7120 | 0.4346 | 0.059* | |
H11B | −0.0894 | 0.7499 | 0.4307 | 0.059* | |
H11C | −0.0361 | 0.6918 | 0.5022 | 0.059* | |
C12 | 0.2603 (4) | 0.9699 (2) | 0.6796 (2) | 0.0281 (9) | |
H12 | 0.2242 | 0.9405 | 0.7199 | 0.034* | |
C13 | 0.2613 (4) | 1.0579 (2) | 0.6802 (2) | 0.0304 (9) | |
H13 | 0.2262 | 1.0883 | 0.7203 | 0.037* | |
C14 | 0.3131 (4) | 1.1015 (2) | 0.6226 (2) | 0.0306 (9) | |
H14 | 0.3157 | 1.1624 | 0.6226 | 0.037* | |
C15 | 0.3614 (4) | 1.0553 (2) | 0.5648 (2) | 0.0302 (9) | |
H15 | 0.3969 | 1.0837 | 0.5237 | 0.036* | |
C16 | 0.3574 (3) | 0.9673 (2) | 0.5676 (2) | 0.0270 (9) | |
H16 | 0.3909 | 0.9358 | 0.5275 | 0.032* | |
C17 | 0.3656 (4) | 0.5853 (2) | 0.5789 (2) | 0.0287 (9) | |
H17 | 0.4418 | 0.6111 | 0.5653 | 0.034* | |
C18 | 0.3502 (4) | 0.4982 (2) | 0.5674 (2) | 0.0335 (10) | |
H18 | 0.4155 | 0.4649 | 0.5481 | 0.040* | |
C19 | 0.2380 (4) | 0.4605 (3) | 0.5845 (2) | 0.0382 (10) | |
H19 | 0.2244 | 0.4008 | 0.5770 | 0.046* | |
C20 | 0.1462 (4) | 0.5112 (3) | 0.6126 (2) | 0.0361 (10) | |
H20 | 0.0679 | 0.4871 | 0.6246 | 0.043* | |
C21 | 0.1701 (4) | 0.5976 (2) | 0.6231 (2) | 0.0307 (9) | |
H21 | 0.1058 | 0.6320 | 0.6421 | 0.037* | |
C22 | 0.2942 (4) | 0.5083 (3) | 0.2703 (2) | 0.0376 (10) | |
C23 | 0.2439 (4) | 0.4756 (3) | 0.2002 (3) | 0.0394 (11) | |
H23 | 0.2702 | 0.4990 | 0.1540 | 0.047* | |
C24 | 0.1569 (4) | 0.4101 (3) | 0.1958 (3) | 0.0536 (13) | |
H24 | 0.1227 | 0.3894 | 0.1469 | 0.064* | |
C25 | 0.1191 (5) | 0.3744 (3) | 0.2618 (4) | 0.0651 (16) | |
H25 | 0.0588 | 0.3291 | 0.2588 | 0.078* | |
C26 | 0.1692 (5) | 0.4047 (4) | 0.3321 (4) | 0.0639 (16) | |
H26 | 0.1446 | 0.3797 | 0.3781 | 0.077* | |
C27 | 0.2549 (4) | 0.4711 (3) | 0.3363 (3) | 0.0490 (12) | |
H27 | 0.2879 | 0.4921 | 0.3854 | 0.059* | |
C28 | 0.3885 (5) | 0.5808 (3) | 0.2746 (3) | 0.0656 (15) | |
H28A | 0.3721 | 0.6174 | 0.2291 | 0.098* | |
H28B | 0.4749 | 0.5575 | 0.2764 | 0.098* | |
H28C | 0.3798 | 0.6146 | 0.3212 | 0.098* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ti | 0.0233 (3) | 0.0179 (3) | 0.0231 (4) | 0.0003 (3) | 0.0051 (3) | 0.0004 (3) |
Cl | 0.0340 (5) | 0.0250 (5) | 0.0285 (5) | −0.0003 (4) | 0.0115 (4) | 0.0026 (4) |
N1 | 0.0216 (15) | 0.0168 (15) | 0.0245 (16) | 0.0016 (13) | 0.0041 (13) | 0.0002 (12) |
N2 | 0.0256 (16) | 0.0201 (16) | 0.0235 (16) | −0.0006 (14) | 0.0047 (13) | −0.0001 (13) |
N3 | 0.0225 (16) | 0.0243 (17) | 0.0282 (17) | 0.0018 (14) | 0.0035 (13) | 0.0005 (13) |
N4 | 0.0266 (17) | 0.0210 (16) | 0.0233 (17) | 0.0009 (13) | 0.0023 (14) | 0.0003 (13) |
N5 | 0.0257 (17) | 0.0225 (16) | 0.0226 (17) | 0.0028 (14) | 0.0033 (13) | 0.0010 (13) |
C1 | 0.035 (2) | 0.023 (2) | 0.023 (2) | −0.0019 (17) | 0.0052 (17) | 0.0020 (15) |
C2 | 0.035 (2) | 0.022 (2) | 0.030 (2) | −0.0048 (18) | 0.0130 (17) | −0.0021 (16) |
C3 | 0.025 (2) | 0.023 (2) | 0.035 (2) | 0.0018 (17) | 0.0074 (17) | 0.0014 (17) |
C4 | 0.0185 (17) | 0.0201 (19) | 0.029 (2) | 0.0002 (15) | 0.0052 (15) | 0.0052 (15) |
C5 | 0.0227 (19) | 0.030 (2) | 0.029 (2) | −0.0041 (17) | 0.0039 (16) | −0.0007 (16) |
C6 | 0.033 (2) | 0.039 (2) | 0.025 (2) | −0.0010 (19) | 0.0017 (18) | −0.0051 (18) |
C7 | 0.031 (2) | 0.033 (2) | 0.033 (2) | 0.0028 (18) | 0.0013 (18) | 0.0073 (17) |
C8 | 0.027 (2) | 0.029 (2) | 0.031 (2) | −0.0002 (17) | 0.0038 (17) | 0.0015 (17) |
C9 | 0.026 (2) | 0.043 (3) | 0.048 (3) | 0.006 (2) | 0.0004 (19) | −0.004 (2) |
C10 | 0.037 (3) | 0.051 (3) | 0.048 (3) | −0.002 (2) | −0.004 (2) | 0.018 (2) |
C11 | 0.035 (2) | 0.046 (3) | 0.036 (2) | −0.006 (2) | −0.0017 (19) | −0.010 (2) |
C12 | 0.036 (2) | 0.022 (2) | 0.027 (2) | 0.0023 (17) | 0.0084 (17) | 0.0025 (16) |
C13 | 0.041 (2) | 0.0199 (19) | 0.031 (2) | 0.0055 (18) | 0.0044 (18) | −0.0031 (17) |
C14 | 0.034 (2) | 0.0186 (19) | 0.038 (2) | 0.0013 (17) | −0.0021 (19) | −0.0008 (17) |
C15 | 0.034 (2) | 0.022 (2) | 0.036 (2) | −0.0012 (18) | 0.0088 (18) | 0.0077 (17) |
C16 | 0.029 (2) | 0.025 (2) | 0.028 (2) | 0.0031 (17) | 0.0097 (17) | 0.0016 (16) |
C17 | 0.034 (2) | 0.020 (2) | 0.033 (2) | 0.0014 (17) | 0.0088 (18) | 0.0026 (16) |
C18 | 0.041 (2) | 0.022 (2) | 0.038 (2) | 0.0041 (19) | 0.0082 (19) | 0.0003 (17) |
C19 | 0.050 (3) | 0.021 (2) | 0.044 (3) | −0.003 (2) | 0.011 (2) | −0.0039 (18) |
C20 | 0.037 (2) | 0.029 (2) | 0.043 (3) | −0.0065 (19) | 0.008 (2) | −0.0006 (19) |
C21 | 0.034 (2) | 0.024 (2) | 0.035 (2) | −0.0006 (18) | 0.0067 (18) | 0.0039 (17) |
C22 | 0.039 (2) | 0.037 (2) | 0.037 (3) | 0.012 (2) | 0.001 (2) | 0.0002 (19) |
C23 | 0.038 (2) | 0.040 (3) | 0.041 (3) | 0.009 (2) | 0.005 (2) | −0.005 (2) |
C24 | 0.039 (3) | 0.054 (3) | 0.065 (4) | 0.014 (3) | −0.005 (3) | −0.017 (3) |
C25 | 0.032 (3) | 0.049 (3) | 0.116 (5) | 0.003 (2) | 0.014 (3) | 0.000 (3) |
C26 | 0.045 (3) | 0.074 (4) | 0.077 (4) | 0.016 (3) | 0.024 (3) | 0.030 (3) |
C27 | 0.043 (3) | 0.062 (3) | 0.041 (3) | 0.016 (3) | 0.000 (2) | 0.003 (2) |
C28 | 0.066 (4) | 0.060 (4) | 0.070 (4) | −0.011 (3) | 0.000 (3) | −0.008 (3) |
Ti—N3 | 1.687 (3) | C10—H10B | 0.9800 |
Ti—N1 | 2.071 (3) | C10—H10C | 0.9800 |
Ti—N4 | 2.245 (3) | C11—H11A | 0.9800 |
Ti—N5 | 2.267 (3) | C11—H11B | 0.9800 |
Ti—Cl | 2.4195 (11) | C11—H11C | 0.9800 |
Ti—N2 | 2.508 (3) | C12—C13 | 1.374 (5) |
N1—C1 | 1.383 (4) | C12—H12 | 0.9500 |
N1—C4 | 1.389 (4) | C13—C14 | 1.370 (5) |
N2—C6 | 1.477 (5) | C13—H13 | 0.9500 |
N2—C7 | 1.478 (5) | C14—C15 | 1.377 (5) |
N2—C5 | 1.482 (4) | C14—H14 | 0.9500 |
N3—C8 | 1.457 (5) | C15—C16 | 1.375 (5) |
N4—C12 | 1.343 (5) | C15—H15 | 0.9500 |
N4—C16 | 1.345 (4) | C16—H16 | 0.9500 |
N5—C21 | 1.341 (5) | C17—C18 | 1.381 (5) |
N5—C17 | 1.346 (5) | C17—H17 | 0.9500 |
C1—C2 | 1.361 (5) | C18—C19 | 1.381 (6) |
C1—H1 | 0.9500 | C18—H18 | 0.9500 |
C2—C3 | 1.426 (5) | C19—C20 | 1.377 (6) |
C2—H2 | 0.9500 | C19—H19 | 0.9500 |
C3—C4 | 1.367 (5) | C20—C21 | 1.380 (5) |
C3—H3 | 0.9500 | C20—H20 | 0.9500 |
C4—C5 | 1.484 (5) | C21—H21 | 0.9500 |
C5—H5A | 0.9900 | C22—C23 | 1.383 (6) |
C5—H5B | 0.9900 | C22—C27 | 1.388 (6) |
C6—H6A | 0.9800 | C22—C28 | 1.504 (6) |
C6—H6B | 0.9800 | C23—C24 | 1.372 (6) |
C6—H6C | 0.9800 | C23—H23 | 0.9500 |
C7—H7A | 0.9800 | C24—C25 | 1.371 (7) |
C7—H7B | 0.9800 | C24—H24 | 0.9500 |
C7—H7C | 0.9800 | C25—C26 | 1.373 (8) |
C8—C11 | 1.524 (5) | C25—H25 | 0.9500 |
C8—C9 | 1.528 (5) | C26—C27 | 1.373 (7) |
C8—C10 | 1.530 (5) | C26—H26 | 0.9500 |
C9—H9A | 0.9800 | C27—H27 | 0.9500 |
C9—H9B | 0.9800 | C28—H28A | 0.9800 |
C9—H9C | 0.9800 | C28—H28B | 0.9800 |
C10—H10A | 0.9800 | C28—H28C | 0.9800 |
N3—Ti—N1 | 100.75 (13) | C8—C9—H9C | 109.5 |
N3—Ti—N4 | 90.05 (13) | H9A—C9—H9C | 109.5 |
N1—Ti—N4 | 91.54 (11) | H9B—C9—H9C | 109.5 |
N3—Ti—N5 | 92.98 (13) | C8—C10—H10A | 109.5 |
N1—Ti—N5 | 85.59 (11) | C8—C10—H10B | 109.5 |
N4—Ti—N5 | 176.17 (11) | H10A—C10—H10B | 109.5 |
N3—Ti—Cl | 102.00 (11) | C8—C10—H10C | 109.5 |
N1—Ti—Cl | 156.85 (9) | H10A—C10—H10C | 109.5 |
N4—Ti—Cl | 92.66 (8) | H10B—C10—H10C | 109.5 |
N5—Ti—Cl | 89.01 (8) | C8—C11—H11A | 109.5 |
N3—Ti—N2 | 170.61 (13) | C8—C11—H11B | 109.5 |
N1—Ti—N2 | 74.53 (10) | H11A—C11—H11B | 109.5 |
N4—Ti—N2 | 82.05 (10) | C8—C11—H11C | 109.5 |
N5—Ti—N2 | 94.72 (10) | H11A—C11—H11C | 109.5 |
Cl—Ti—N2 | 83.52 (7) | H11B—C11—H11C | 109.5 |
C1—N1—C4 | 105.5 (3) | N4—C12—C13 | 122.8 (4) |
C1—N1—Ti | 129.8 (2) | N4—C12—H12 | 118.6 |
C4—N1—Ti | 120.4 (2) | C13—C12—H12 | 118.6 |
C6—N2—C7 | 106.9 (3) | C14—C13—C12 | 119.6 (4) |
C6—N2—C5 | 109.5 (3) | C14—C13—H13 | 120.2 |
C7—N2—C5 | 109.5 (3) | C12—C13—H13 | 120.2 |
C6—N2—Ti | 116.7 (2) | C13—C14—C15 | 118.5 (3) |
C7—N2—Ti | 109.0 (2) | C13—C14—H14 | 120.7 |
C5—N2—Ti | 105.1 (2) | C15—C14—H14 | 120.7 |
C8—N3—Ti | 172.1 (3) | C16—C15—C14 | 118.9 (4) |
C12—N4—C16 | 116.9 (3) | C16—C15—H15 | 120.6 |
C12—N4—Ti | 122.4 (2) | C14—C15—H15 | 120.6 |
C16—N4—Ti | 120.2 (2) | N4—C16—C15 | 123.3 (4) |
C21—N5—C17 | 116.2 (3) | N4—C16—H16 | 118.4 |
C21—N5—Ti | 117.2 (2) | C15—C16—H16 | 118.4 |
C17—N5—Ti | 125.8 (2) | N5—C17—C18 | 123.7 (4) |
C2—C1—N1 | 111.0 (3) | N5—C17—H17 | 118.1 |
C2—C1—H1 | 124.5 | C18—C17—H17 | 118.1 |
N1—C1—H1 | 124.5 | C19—C18—C17 | 118.6 (4) |
C1—C2—C3 | 106.4 (3) | C19—C18—H18 | 120.7 |
C1—C2—H2 | 126.8 | C17—C18—H18 | 120.7 |
C3—C2—H2 | 126.8 | C20—C19—C18 | 118.7 (4) |
C4—C3—C2 | 106.8 (3) | C20—C19—H19 | 120.6 |
C4—C3—H3 | 126.6 | C18—C19—H19 | 120.6 |
C2—C3—H3 | 126.6 | C19—C20—C21 | 118.8 (4) |
C3—C4—N1 | 110.3 (3) | C19—C20—H20 | 120.6 |
C3—C4—C5 | 132.3 (3) | C21—C20—H20 | 120.6 |
N1—C4—C5 | 117.0 (3) | N5—C21—C20 | 123.9 (4) |
N2—C5—C4 | 110.7 (3) | N5—C21—H21 | 118.1 |
N2—C5—H5A | 109.5 | C20—C21—H21 | 118.1 |
C4—C5—H5A | 109.5 | C23—C22—C27 | 117.3 (4) |
N2—C5—H5B | 109.5 | C23—C22—C28 | 121.2 (4) |
C4—C5—H5B | 109.5 | C27—C22—C28 | 121.4 (4) |
H5A—C5—H5B | 108.1 | C24—C23—C22 | 121.5 (5) |
N2—C6—H6A | 109.5 | C24—C23—H23 | 119.2 |
N2—C6—H6B | 109.5 | C22—C23—H23 | 119.2 |
H6A—C6—H6B | 109.5 | C25—C24—C23 | 120.2 (5) |
N2—C6—H6C | 109.5 | C25—C24—H24 | 119.9 |
H6A—C6—H6C | 109.5 | C23—C24—H24 | 119.9 |
H6B—C6—H6C | 109.5 | C24—C25—C26 | 119.4 (5) |
N2—C7—H7A | 109.5 | C24—C25—H25 | 120.3 |
N2—C7—H7B | 109.5 | C26—C25—H25 | 120.3 |
H7A—C7—H7B | 109.5 | C25—C26—C27 | 120.2 (5) |
N2—C7—H7C | 109.5 | C25—C26—H26 | 119.9 |
H7A—C7—H7C | 109.5 | C27—C26—H26 | 119.9 |
H7B—C7—H7C | 109.5 | C26—C27—C22 | 121.3 (5) |
N3—C8—C11 | 108.9 (3) | C26—C27—H27 | 119.4 |
N3—C8—C9 | 107.8 (3) | C22—C27—H27 | 119.4 |
C11—C8—C9 | 110.8 (3) | C22—C28—H28A | 109.5 |
N3—C8—C10 | 108.9 (3) | C22—C28—H28B | 109.5 |
C11—C8—C10 | 110.2 (3) | H28A—C28—H28B | 109.5 |
C9—C8—C10 | 110.2 (3) | C22—C28—H28C | 109.5 |
C8—C9—H9A | 109.5 | H28A—C28—H28C | 109.5 |
C8—C9—H9B | 109.5 | H28B—C28—H28C | 109.5 |
H9A—C9—H9B | 109.5 | ||
N3—Ti—N1—C1 | −29.6 (3) | N1—Ti—N5—C17 | 15.3 (3) |
N4—Ti—N1—C1 | −120.0 (3) | N4—Ti—N5—C17 | −26.3 (17) |
N5—Ti—N1—C1 | 62.6 (3) | Cl—Ti—N5—C17 | −142.1 (3) |
Cl—Ti—N1—C1 | 139.6 (3) | N2—Ti—N5—C17 | −58.7 (3) |
N2—Ti—N1—C1 | 158.7 (3) | C4—N1—C1—C2 | −0.4 (4) |
N3—Ti—N1—C4 | 177.3 (3) | Ti—N1—C1—C2 | −156.6 (3) |
N4—Ti—N1—C4 | 86.9 (3) | N1—C1—C2—C3 | 0.6 (4) |
N5—Ti—N1—C4 | −90.5 (3) | C1—C2—C3—C4 | −0.5 (4) |
Cl—Ti—N1—C4 | −13.5 (4) | C2—C3—C4—N1 | 0.3 (4) |
N2—Ti—N1—C4 | 5.6 (2) | C2—C3—C4—C5 | −172.2 (4) |
N3—Ti—N2—C6 | 75.7 (8) | C1—N1—C4—C3 | 0.1 (4) |
N1—Ti—N2—C6 | 136.6 (3) | Ti—N1—C4—C3 | 158.9 (2) |
N4—Ti—N2—C6 | 42.7 (3) | C1—N1—C4—C5 | 173.8 (3) |
N5—Ti—N2—C6 | −139.3 (3) | Ti—N1—C4—C5 | −27.3 (4) |
Cl—Ti—N2—C6 | −50.9 (2) | C6—N2—C5—C4 | −157.6 (3) |
N3—Ti—N2—C7 | −163.1 (7) | C7—N2—C5—C4 | 85.6 (4) |
N1—Ti—N2—C7 | −102.3 (2) | Ti—N2—C5—C4 | −31.5 (3) |
N4—Ti—N2—C7 | 163.9 (2) | C3—C4—C5—N2 | −147.3 (4) |
N5—Ti—N2—C7 | −18.2 (2) | N1—C4—C5—N2 | 40.7 (4) |
Cl—Ti—N2—C7 | 70.3 (2) | Ti—N3—C8—C11 | −167.5 (18) |
N3—Ti—N2—C5 | −45.8 (8) | Ti—N3—C8—C9 | −47 (2) |
N1—Ti—N2—C5 | 15.0 (2) | Ti—N3—C8—C10 | 72 (2) |
N4—Ti—N2—C5 | −78.8 (2) | C16—N4—C12—C13 | −0.7 (5) |
N5—Ti—N2—C5 | 99.1 (2) | Ti—N4—C12—C13 | −172.8 (3) |
Cl—Ti—N2—C5 | −172.4 (2) | N4—C12—C13—C14 | −0.1 (6) |
N1—Ti—N3—C8 | −117.7 (19) | C12—C13—C14—C15 | 0.9 (6) |
N4—Ti—N3—C8 | −26.1 (19) | C13—C14—C15—C16 | −0.9 (6) |
N5—Ti—N3—C8 | 156.2 (19) | C12—N4—C16—C15 | 0.8 (5) |
Cl—Ti—N3—C8 | 66.6 (19) | Ti—N4—C16—C15 | 173.1 (3) |
N2—Ti—N3—C8 | −59 (2) | C14—C15—C16—N4 | 0.0 (6) |
N3—Ti—N4—C12 | 92.7 (3) | C21—N5—C17—C18 | −3.1 (5) |
N1—Ti—N4—C12 | −166.5 (3) | Ti—N5—C17—C18 | −172.6 (3) |
N5—Ti—N4—C12 | −125.0 (15) | N5—C17—C18—C19 | 2.1 (6) |
Cl—Ti—N4—C12 | −9.3 (3) | C17—C18—C19—C20 | −0.3 (6) |
N2—Ti—N4—C12 | −92.4 (3) | C18—C19—C20—C21 | −0.4 (6) |
N3—Ti—N4—C16 | −79.1 (3) | C17—N5—C21—C20 | 2.3 (6) |
N1—Ti—N4—C16 | 21.6 (3) | Ti—N5—C21—C20 | 172.7 (3) |
N5—Ti—N4—C16 | 63.1 (17) | C19—C20—C21—N5 | −0.7 (6) |
Cl—Ti—N4—C16 | 178.9 (3) | C27—C22—C23—C24 | 1.1 (6) |
N2—Ti—N4—C16 | 95.8 (3) | C28—C22—C23—C24 | −179.3 (4) |
N3—Ti—N5—C21 | −53.5 (3) | C22—C23—C24—C25 | −1.0 (7) |
N1—Ti—N5—C21 | −154.1 (3) | C23—C24—C25—C26 | −0.1 (7) |
N4—Ti—N5—C21 | 164.3 (15) | C24—C25—C26—C27 | 1.0 (7) |
Cl—Ti—N5—C21 | 48.5 (3) | C25—C26—C27—C22 | −0.9 (7) |
N2—Ti—N5—C21 | 131.9 (3) | C23—C22—C27—C26 | −0.1 (6) |
N3—Ti—N5—C17 | 115.9 (3) | C28—C22—C27—C26 | −179.7 (5) |
Experimental details
Crystal data | |
Chemical formula | [Ti(C4H9N)Cl(C5H5N)2(C7H11N2)]·C7H8 |
Mr | 527.98 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 153 |
a, b, c (Å) | 10.5646 (14), 15.605 (2), 17.432 (2) |
β (°) | 95.507 (4) |
V (Å3) | 2860.6 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.42 |
Crystal size (mm) | 0.30 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Rigaku Mercury |
Absorption correction | Multi-scan (REQAB; Jacobson, 1998) |
Tmin, Tmax | 0.745, 0.939 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 27774, 5227, 3910 |
Rint | 0.088 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.073, 0.138, 1.14 |
No. of reflections | 5227 |
No. of parameters | 323 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.35 |
Computer programs: CrystalClear (Rigaku/MSC, 2005), CrystalClear, CrystalStructure (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.
Ti—N3 | 1.687 (3) | Ti—N5 | 2.267 (3) |
Ti—N1 | 2.071 (3) | Ti—Cl | 2.4195 (11) |
Ti—N4 | 2.245 (3) | Ti—N2 | 2.508 (3) |
N3—Ti—N1 | 100.75 (13) | N1—Ti—Cl | 156.85 (9) |
N3—Ti—N4 | 90.05 (13) | N4—Ti—Cl | 92.66 (8) |
N1—Ti—N4 | 91.54 (11) | N5—Ti—Cl | 89.01 (8) |
N3—Ti—N5 | 92.98 (13) | N3—Ti—N2 | 170.61 (13) |
N1—Ti—N5 | 85.59 (11) | N1—Ti—N2 | 74.53 (10) |
N4—Ti—N5 | 176.17 (11) | N4—Ti—N2 | 82.05 (10) |
N3—Ti—Cl | 102.00 (11) | N5—Ti—N2 | 94.72 (10) |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
Over the last two decades, the chemistry of titanium–imido complexes has received considerable attention (Wigley, 1994). It has been shown that these complexes can be utilized in a wide variety of stoichiometric and sometimes catalytic coupling reactions with unsaturated substrates. A general entry point to new titanium–imido chemistry is gained via the readily prepared synthons [Ti(NR)Cl2(py)3] (R = tBu or Aryl) (Mountford, 1997).
The title compound, (I), was prepared by combining equimolar amounts of Ti(NtBu)Cl2py3 with Lidap [N,N-dimethyl-(1-Li-pyrrol-2-yl)methanamine] in toluene. It possesses a mononuclear structure featuring a six-coordinate octahedral titanium(IV) centre.