The crystal structure of the title compound, [Ti(C11H19NSi)Cl2], has been determined as part of a broad investigation of half-sandwich titanium complexes. Titanium has a pseudo-tetrahedral coordination formed by two Cl atoms [Ti—Cl = 2.2719 (4) and 2.2730 (4) Å], the N atom of the N-tert-butyl group [Ti—N = 1.9094 (12) Å] and the silyl-substituted Cp ligand [metal–Cp ring centroid distance = 2.0185 (9) Å]. The tert-butyl group was found to be disordered.
Supporting information
CCDC reference: 262237
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.002 Å
- Disorder in main residue
- R factor = 0.027
- wR factor = 0.072
- Data-to-parameter ratio = 21.0
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT213_ALERT_2_C Atom C11 has ADP max/min Ratio ............. 3.50 prolat
| Author Response:
Atom C11 (C112) belongs to disordered tert-butyl moiety. Its disorder was
described using two positions for each methyl carbon, however their ADP are
prolonged in the direction where another (much less occupied)
positions probably exist in the crystal. As the tBu moiety is not point of
interest of this study, the ADP was used to described the electron
density issuing from additional disorders.
|
PLAT213_ALERT_2_C Atom C112 has ADP max/min Ratio ............. 3.50 prolat
| Author Response:
Atom C11 (C112) belongs to disordered tert-butyl moiety. Its disorder was
described using two positions for each methyl carbon, however their ADP are
prolonged in the direction where another (much less occupied)
positions probably exist in the crystal. As the tBu moiety is not point of
interest of this study, the ADP was used to described the electron
density issuing from additional disorders.
|
PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.58 Ratio
| Author Response:
The alert is caused by large Ueq of disordered tBu
moiety.
|
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C8
| Author Response: The C8 is placed on axis of rigid body libration of tert-butyl
moiety and therefore only slightly displaced from its average position.
|
PLAT301_ALERT_3_C Main Residue Disorder ......................... 16.00 Perc.
| Author Response:
The disorder affects only methyls in tBu moiety, the other
atoms are very well resolved.
|
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
5 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
4 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
Data collection: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); cell refinement: COLLECT and DENZO; data reduction: COLLECT and DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Dichloro{(
η5,
κN)-
[(
tert-butylamido)dimethylsilyl]cyclopentadienyl}titanium(IV)
top
Crystal data top
C11H19Cl2NSiTi | Z = 2 |
Mr = 312.16 | F(000) = 324 |
Triclinic, P1 | Dx = 1.382 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.2900 (2) Å | Cell parameters from 3278 reflections |
b = 8.3810 (2) Å | θ = 1–27.5° |
c = 12.7950 (3) Å | µ = 0.98 mm−1 |
α = 73.8820 (15)° | T = 150 K |
β = 89.3720 (14)° | Plate, yellow |
γ = 62.4650 (13)° | 0.45 × 0.4 × 0.37 mm |
V = 750.07 (3) Å3 | |
Data collection top
Nonius KappaCCD area detector diffractometer | 3171 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.026 |
Graphite monochromator | θmax = 27.5°, θmin = 2.8° |
Detector resolution: 9.091 pixels mm-1 | h = −10→10 |
φ and ω scans to fill the Ewald sphere | k = −10→10 |
13385 measured reflections | l = −16→16 |
3425 independent reflections | |
Refinement top
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)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.072 | w = 1/[σ2(Fo2) + (0.0349P)2 + 0.3748P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
3425 reflections | Δρmax = 0.46 e Å−3 |
163 parameters | Δρmin = −0.43 e Å−3 |
0 restraints | Extinction correction: SHELXL (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.015 (3) |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Ti1 | 0.63696 (3) | 0.34287 (3) | 0.822662 (19) | 0.01930 (9) | |
Cl1 | 0.43897 (5) | 0.65331 (5) | 0.73810 (3) | 0.03375 (12) | |
Cl2 | 0.85502 (6) | 0.35054 (6) | 0.92425 (3) | 0.03440 (12) | |
Si1 | 0.72019 (5) | 0.03420 (5) | 0.73145 (3) | 0.02164 (11) | |
N1 | 0.75741 (15) | 0.22972 (16) | 0.71424 (9) | 0.0198 (2) | |
C1 | 0.5849 (2) | 0.0902 (2) | 0.84524 (12) | 0.0250 (3) | |
C2 | 0.6691 (2) | 0.0667 (2) | 0.94829 (12) | 0.0287 (3) | |
H2 | 0.7856 | −0.0286 | 0.9826 | 0.034* | |
C3 | 0.5477 (3) | 0.2113 (2) | 0.99043 (14) | 0.0358 (4) | |
H3 | 0.5701 | 0.2269 | 1.0570 | 0.043* | |
C4 | 0.3879 (2) | 0.3267 (2) | 0.91462 (15) | 0.0370 (4) | |
H4 | 0.2854 | 0.4327 | 0.9218 | 0.044* | |
C5 | 0.4096 (2) | 0.2541 (2) | 0.82561 (14) | 0.0310 (3) | |
H5 | 0.3232 | 0.3050 | 0.7637 | 0.037* | |
C6 | 0.9289 (2) | −0.2000 (2) | 0.77880 (15) | 0.0349 (4) | |
H6A | 0.9965 | −0.2228 | 0.7184 | 0.052* | |
H6B | 0.8939 | −0.2966 | 0.8066 | 0.052* | |
H6C | 1.0044 | −0.2018 | 0.8359 | 0.052* | |
C7 | 0.5783 (3) | 0.0498 (3) | 0.61422 (15) | 0.0395 (4) | |
H7A | 0.4745 | 0.1742 | 0.5886 | 0.059* | |
H7B | 0.5362 | −0.0420 | 0.6375 | 0.059* | |
H7C | 0.6507 | 0.0254 | 0.5558 | 0.059* | |
C8 | 0.8701 (2) | 0.2861 (2) | 0.63595 (13) | 0.0278 (3) | |
C9 | 1.0733 (4) | 0.1529 (5) | 0.6902 (4) | 0.0585 (10) | 0.70 |
H9A | 1.1527 | 0.1857 | 0.6444 | 0.088* | 0.70 |
H9B | 1.1038 | 0.0243 | 0.6988 | 0.088* | 0.70 |
H9C | 1.0887 | 0.1666 | 0.7609 | 0.088* | 0.70 |
C10 | 0.8285 (4) | 0.4891 (4) | 0.6213 (2) | 0.0363 (7) | 0.70 |
H10A | 0.8509 | 0.5015 | 0.6914 | 0.054* | 0.70 |
H10B | 0.7022 | 0.5739 | 0.5906 | 0.054* | 0.70 |
H10C | 0.9062 | 0.5195 | 0.5727 | 0.054* | 0.70 |
C11 | 0.8372 (6) | 0.2636 (6) | 0.5260 (3) | 0.0645 (12) | 0.70 |
H11A | 0.7082 | 0.3339 | 0.4993 | 0.097* | 0.70 |
H11B | 0.8804 | 0.1323 | 0.5344 | 0.097* | 0.70 |
H11C | 0.9023 | 0.3103 | 0.4745 | 0.097* | 0.70 |
C92 | 1.0472 (10) | 0.1216 (11) | 0.6276 (9) | 0.0585 (10) | 0.30 |
H92A | 1.1137 | 0.1675 | 0.5770 | 0.088* | 0.30 |
H92B | 1.0204 | 0.0379 | 0.6020 | 0.088* | 0.30 |
H92C | 1.1202 | 0.0545 | 0.6986 | 0.088* | 0.30 |
C102 | 0.9017 (11) | 0.4362 (11) | 0.6530 (7) | 0.0363 (7) | 0.30 |
H10D | 0.7860 | 0.5429 | 0.6522 | 0.054* | 0.30 |
H10E | 0.9639 | 0.4738 | 0.5955 | 0.054* | 0.30 |
H10F | 0.9759 | 0.3899 | 0.7227 | 0.054* | 0.30 |
C112 | 0.7468 (15) | 0.3753 (16) | 0.5215 (7) | 0.0645 (12) | 0.30 |
H11D | 0.6303 | 0.4773 | 0.5248 | 0.097* | 0.30 |
H11E | 0.7282 | 0.2806 | 0.5036 | 0.097* | 0.30 |
H11F | 0.8066 | 0.4225 | 0.4661 | 0.097* | 0.30 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ti1 | 0.02217 (14) | 0.01678 (14) | 0.01873 (14) | −0.00903 (10) | 0.00385 (9) | −0.00569 (10) |
Cl1 | 0.0324 (2) | 0.01926 (18) | 0.0384 (2) | −0.00611 (15) | 0.00225 (16) | −0.00377 (15) |
Cl2 | 0.0381 (2) | 0.0373 (2) | 0.0303 (2) | −0.01906 (18) | −0.00381 (16) | −0.01186 (16) |
Si1 | 0.0265 (2) | 0.02035 (19) | 0.0223 (2) | −0.01373 (16) | 0.00349 (15) | −0.00825 (15) |
N1 | 0.0212 (5) | 0.0203 (5) | 0.0201 (5) | −0.0112 (5) | 0.0042 (4) | −0.0069 (4) |
C1 | 0.0292 (7) | 0.0220 (7) | 0.0279 (7) | −0.0166 (6) | 0.0077 (6) | −0.0060 (6) |
C2 | 0.0380 (8) | 0.0236 (7) | 0.0235 (7) | −0.0165 (6) | 0.0073 (6) | −0.0027 (6) |
C3 | 0.0540 (10) | 0.0343 (8) | 0.0263 (8) | −0.0259 (8) | 0.0190 (7) | −0.0117 (7) |
C4 | 0.0369 (9) | 0.0319 (8) | 0.0447 (10) | −0.0174 (7) | 0.0227 (8) | −0.0141 (7) |
C5 | 0.0257 (7) | 0.0308 (8) | 0.0392 (9) | −0.0171 (6) | 0.0092 (6) | −0.0083 (7) |
C6 | 0.0404 (9) | 0.0225 (7) | 0.0396 (9) | −0.0116 (7) | 0.0074 (7) | −0.0126 (7) |
C7 | 0.0517 (11) | 0.0477 (10) | 0.0335 (9) | −0.0349 (9) | 0.0004 (8) | −0.0130 (8) |
C8 | 0.0303 (8) | 0.0308 (8) | 0.0335 (8) | −0.0202 (7) | 0.0166 (6) | −0.0164 (6) |
C9 | 0.0283 (12) | 0.0421 (15) | 0.108 (3) | −0.0207 (11) | 0.0250 (17) | −0.0206 (17) |
C10 | 0.050 (2) | 0.0305 (17) | 0.0351 (18) | −0.0248 (15) | 0.0199 (13) | −0.0098 (13) |
C11 | 0.112 (3) | 0.109 (3) | 0.0451 (14) | −0.093 (3) | 0.058 (2) | −0.058 (2) |
C92 | 0.0283 (12) | 0.0421 (15) | 0.108 (3) | −0.0207 (11) | 0.0250 (17) | −0.0206 (17) |
C102 | 0.050 (2) | 0.0305 (17) | 0.0351 (18) | −0.0248 (15) | 0.0199 (13) | −0.0098 (13) |
C112 | 0.112 (3) | 0.109 (3) | 0.0451 (14) | −0.093 (3) | 0.058 (2) | −0.058 (2) |
Geometric parameters (Å, º) top
Ti1—N1 | 1.9094 (12) | C7—H7B | 0.9600 |
Ti1—Cl1 | 2.2719 (4) | C7—H7C | 0.9600 |
Ti1—Cl2 | 2.2730 (4) | C8—C102 | 1.469 (9) |
Ti1—C1 | 2.2928 (14) | C8—C92 | 1.508 (7) |
Ti1—C2 | 2.3206 (15) | C8—C11 | 1.514 (3) |
Ti1—C5 | 2.3208 (16) | C8—C10 | 1.526 (3) |
Ti1—C3 | 2.4036 (16) | C8—C9 | 1.557 (4) |
Ti1—C4 | 2.4048 (16) | C8—C112 | 1.571 (10) |
Ti1—Si1 | 2.9222 (4) | C9—H9A | 0.9600 |
Si1—N1 | 1.7591 (12) | C9—H9B | 0.9600 |
Si1—C6 | 1.8535 (17) | C9—H9C | 0.9600 |
Si1—C7 | 1.8543 (17) | C10—H10A | 0.9600 |
Si1—C1 | 1.8587 (15) | C10—H10B | 0.9600 |
N1—C8 | 1.4913 (18) | C10—H10C | 0.9600 |
C1—C2 | 1.419 (2) | C11—H11A | 0.9600 |
C1—C5 | 1.426 (2) | C11—H11B | 0.9600 |
C2—C3 | 1.412 (2) | C11—H11C | 0.9600 |
C2—H2 | 0.9300 | C92—H92A | 0.9600 |
C3—C4 | 1.398 (3) | C92—H92B | 0.9600 |
C3—H3 | 0.9300 | C92—H92C | 0.9600 |
C4—C5 | 1.407 (2) | C102—H10D | 0.9600 |
C4—H4 | 0.9300 | C102—H10E | 0.9600 |
C5—H5 | 0.9300 | C102—H10F | 0.9600 |
C6—H6A | 0.9600 | C112—H11D | 0.9600 |
C6—H6B | 0.9600 | C112—H11E | 0.9600 |
C6—H6C | 0.9600 | C112—H11F | 0.9600 |
C7—H7A | 0.9600 | | |
| | | |
N1—Ti1—Cl1 | 108.67 (4) | Ti1—C3—H3 | 123.1 |
N1—Ti1—Cl2 | 106.08 (4) | C3—C4—C5 | 107.87 (15) |
Cl1—Ti1—Cl2 | 103.506 (18) | C3—C4—Ti1 | 73.05 (9) |
N1—Ti1—C1 | 74.94 (5) | C5—C4—Ti1 | 69.44 (9) |
Cl1—Ti1—C1 | 127.64 (4) | C3—C4—H4 | 126.1 |
Cl2—Ti1—C1 | 126.26 (4) | C5—C4—H4 | 126.1 |
N1—Ti1—C2 | 96.12 (5) | Ti1—C4—H4 | 123.1 |
Cl1—Ti1—C2 | 144.60 (4) | C4—C5—C1 | 109.29 (15) |
Cl2—Ti1—C2 | 92.99 (4) | C4—C5—Ti1 | 75.98 (10) |
C1—Ti1—C2 | 35.82 (5) | C1—C5—Ti1 | 70.93 (8) |
N1—Ti1—C5 | 95.70 (5) | C4—C5—H5 | 125.4 |
Cl1—Ti1—C5 | 93.40 (4) | C1—C5—H5 | 125.4 |
Cl2—Ti1—C5 | 146.08 (5) | Ti1—C5—H5 | 119.4 |
C1—Ti1—C5 | 36.00 (5) | Si1—C6—H6A | 109.5 |
C2—Ti1—C5 | 58.48 (6) | Si1—C6—H6B | 109.5 |
N1—Ti1—C3 | 130.18 (5) | H6A—C6—H6B | 109.5 |
Cl1—Ti1—C3 | 113.51 (5) | Si1—C6—H6C | 109.5 |
Cl2—Ti1—C3 | 88.85 (5) | H6A—C6—H6C | 109.5 |
C1—Ti1—C3 | 58.78 (6) | H6B—C6—H6C | 109.5 |
C2—Ti1—C3 | 34.73 (6) | Si1—C7—H7A | 109.5 |
C5—Ti1—C3 | 57.32 (6) | Si1—C7—H7B | 109.5 |
N1—Ti1—C4 | 129.75 (6) | H7A—C7—H7B | 109.5 |
Cl1—Ti1—C4 | 87.09 (4) | Si1—C7—H7C | 109.5 |
Cl2—Ti1—C4 | 116.28 (5) | H7A—C7—H7C | 109.5 |
C1—Ti1—C4 | 58.86 (6) | H7B—C7—H7C | 109.5 |
C2—Ti1—C4 | 57.51 (6) | C102—C8—N1 | 114.2 (3) |
C5—Ti1—C4 | 34.58 (6) | C102—C8—C92 | 111.3 (4) |
C3—Ti1—C4 | 33.80 (6) | N1—C8—C92 | 113.7 (3) |
N1—Ti1—Si1 | 35.45 (4) | N1—C8—C11 | 110.23 (16) |
Cl1—Ti1—Si1 | 125.559 (16) | N1—C8—C10 | 111.47 (15) |
Cl2—Ti1—Si1 | 122.257 (16) | C11—C8—C10 | 110.2 (2) |
C2—Ti1—Si1 | 65.22 (4) | N1—C8—C9 | 105.67 (17) |
C5—Ti1—Si1 | 65.29 (4) | C11—C8—C9 | 111.4 (3) |
C3—Ti1—Si1 | 96.44 (4) | C10—C8—C9 | 107.8 (2) |
C4—Ti1—Si1 | 96.43 (4) | C102—C8—C112 | 105.7 (5) |
N1—Si1—C6 | 115.25 (7) | N1—C8—C112 | 103.9 (3) |
N1—Si1—C7 | 115.09 (7) | C92—C8—C112 | 107.2 (5) |
C6—Si1—C7 | 110.90 (9) | C8—C9—H9A | 109.5 |
N1—Si1—C1 | 90.69 (6) | C8—C9—H9B | 109.5 |
C6—Si1—C1 | 111.82 (7) | C8—C9—H9C | 109.5 |
C7—Si1—C1 | 111.60 (8) | C8—C10—H10A | 109.5 |
C6—Si1—Ti1 | 124.29 (6) | C8—C10—H10B | 109.5 |
C7—Si1—Ti1 | 124.74 (7) | C8—C10—H10C | 109.5 |
C1—Si1—Ti1 | 51.67 (4) | C8—C11—H11A | 109.5 |
C8—N1—Si1 | 126.72 (9) | C8—C11—H11B | 109.5 |
C8—N1—Ti1 | 127.64 (9) | C8—C11—H11C | 109.5 |
Si1—N1—Ti1 | 105.53 (6) | C8—C92—H92A | 109.5 |
C2—C1—C5 | 105.68 (14) | C8—C92—H92B | 109.5 |
C2—C1—Si1 | 121.68 (11) | H92A—C92—H92B | 109.5 |
C5—C1—Si1 | 121.47 (11) | C8—C92—H92C | 109.5 |
C2—C1—Ti1 | 73.15 (8) | H92A—C92—H92C | 109.5 |
C5—C1—Ti1 | 73.07 (8) | H92B—C92—H92C | 109.5 |
Si1—C1—Ti1 | 88.84 (6) | C8—C102—H10D | 109.5 |
C3—C2—C1 | 109.11 (15) | C8—C102—H10E | 109.5 |
C3—C2—Ti1 | 75.85 (9) | H10D—C102—H10E | 109.5 |
C1—C2—Ti1 | 71.02 (8) | C8—C102—H10F | 109.5 |
C3—C2—H2 | 125.4 | H10D—C102—H10F | 109.5 |
C1—C2—H2 | 125.4 | H10E—C102—H10F | 109.5 |
Ti1—C2—H2 | 119.4 | C8—C112—H11D | 109.5 |
C4—C3—C2 | 108.05 (15) | C8—C112—H11E | 109.5 |
C4—C3—Ti1 | 73.14 (9) | H11D—C112—H11E | 109.5 |
C2—C3—Ti1 | 69.41 (8) | C8—C112—H11F | 109.5 |
C4—C3—H3 | 126.0 | H11D—C112—H11F | 109.5 |
C2—C3—H3 | 126.0 | H11E—C112—H11F | 109.5 |
Selected geometric parameters (Å, °). topCg1—Ti1 | 2.0185 (9) | N1-Ti1 | 1.9093 (12) |
Cl2—Ti1 | 2.2731 (6) | N1-Si1 | 1.7591 (14) |
Cl1—Ti1 | 2.2719 (5) | | |
| | | |
Cg1-Ti1-N1 | 107.12 (5) | Cl1-Ti1-Cl2 | 103.50 (2) |
Cg1-Ti1-Cl1 | 115.01 (3) | Ti1-N1-Si1 | 105.53 (7) |
Cg1-Ti1-Cl2 | 115.97 (3) | C1-Si1-N1 | 90.68 (7) |
Cg1 is the centroid of the cyclopentadienyl ring. |