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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536804031332/ya6226sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536804031332/ya6226Isup2.hkl
Contains datablock I

CCDC reference: 262237

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](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

Computing details top

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
C11H19Cl2NSiTiZ = 2
Mr = 312.16F(000) = 324
Triclinic, P1Dx = 1.382 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.2900 (2) ÅCell parameters from 3278 reflections
b = 8.3810 (2) Åθ = 1–27.5°
c = 12.7950 (3) ŵ = 0.98 mm1
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 tubeRint = 0.026
Graphite monochromatorθmax = 27.5°, θmin = 2.8°
Detector resolution: 9.091 pixels mm-1h = 1010
φ and ω scans to fill the Ewald spherek = 1010
13385 measured reflectionsl = 1616
3425 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027H-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 reflectionsΔρmax = 0.46 e Å3
163 parametersΔρmin = 0.43 e Å3
0 restraintsExtinction correction: SHELXL (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction 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
xyzUiso*/UeqOcc. (<1)
Ti10.63696 (3)0.34287 (3)0.822662 (19)0.01930 (9)
Cl10.43897 (5)0.65331 (5)0.73810 (3)0.03375 (12)
Cl20.85502 (6)0.35054 (6)0.92425 (3)0.03440 (12)
Si10.72019 (5)0.03420 (5)0.73145 (3)0.02164 (11)
N10.75741 (15)0.22972 (16)0.71424 (9)0.0198 (2)
C10.5849 (2)0.0902 (2)0.84524 (12)0.0250 (3)
C20.6691 (2)0.0667 (2)0.94829 (12)0.0287 (3)
H20.78560.02860.98260.034*
C30.5477 (3)0.2113 (2)0.99043 (14)0.0358 (4)
H30.57010.22691.05700.043*
C40.3879 (2)0.3267 (2)0.91462 (15)0.0370 (4)
H40.28540.43270.92180.044*
C50.4096 (2)0.2541 (2)0.82561 (14)0.0310 (3)
H50.32320.30500.76370.037*
C60.9289 (2)0.2000 (2)0.77880 (15)0.0349 (4)
H6A0.99650.22280.71840.052*
H6B0.89390.29660.80660.052*
H6C1.00440.20180.83590.052*
C70.5783 (3)0.0498 (3)0.61422 (15)0.0395 (4)
H7A0.47450.17420.58860.059*
H7B0.53620.04200.63750.059*
H7C0.65070.02540.55580.059*
C80.8701 (2)0.2861 (2)0.63595 (13)0.0278 (3)
C91.0733 (4)0.1529 (5)0.6902 (4)0.0585 (10)0.70
H9A1.15270.18570.64440.088*0.70
H9B1.10380.02430.69880.088*0.70
H9C1.08870.16660.76090.088*0.70
C100.8285 (4)0.4891 (4)0.6213 (2)0.0363 (7)0.70
H10A0.85090.50150.69140.054*0.70
H10B0.70220.57390.59060.054*0.70
H10C0.90620.51950.57270.054*0.70
C110.8372 (6)0.2636 (6)0.5260 (3)0.0645 (12)0.70
H11A0.70820.33390.49930.097*0.70
H11B0.88040.13230.53440.097*0.70
H11C0.90230.31030.47450.097*0.70
C921.0472 (10)0.1216 (11)0.6276 (9)0.0585 (10)0.30
H92A1.11370.16750.57700.088*0.30
H92B1.02040.03790.60200.088*0.30
H92C1.12020.05450.69860.088*0.30
C1020.9017 (11)0.4362 (11)0.6530 (7)0.0363 (7)0.30
H10D0.78600.54290.65220.054*0.30
H10E0.96390.47380.59550.054*0.30
H10F0.97590.38990.72270.054*0.30
C1120.7468 (15)0.3753 (16)0.5215 (7)0.0645 (12)0.30
H11D0.63030.47730.52480.097*0.30
H11E0.72820.28060.50360.097*0.30
H11F0.80660.42250.46610.097*0.30
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ti10.02217 (14)0.01678 (14)0.01873 (14)0.00903 (10)0.00385 (9)0.00569 (10)
Cl10.0324 (2)0.01926 (18)0.0384 (2)0.00611 (15)0.00225 (16)0.00377 (15)
Cl20.0381 (2)0.0373 (2)0.0303 (2)0.01906 (18)0.00381 (16)0.01186 (16)
Si10.0265 (2)0.02035 (19)0.0223 (2)0.01373 (16)0.00349 (15)0.00825 (15)
N10.0212 (5)0.0203 (5)0.0201 (5)0.0112 (5)0.0042 (4)0.0069 (4)
C10.0292 (7)0.0220 (7)0.0279 (7)0.0166 (6)0.0077 (6)0.0060 (6)
C20.0380 (8)0.0236 (7)0.0235 (7)0.0165 (6)0.0073 (6)0.0027 (6)
C30.0540 (10)0.0343 (8)0.0263 (8)0.0259 (8)0.0190 (7)0.0117 (7)
C40.0369 (9)0.0319 (8)0.0447 (10)0.0174 (7)0.0227 (8)0.0141 (7)
C50.0257 (7)0.0308 (8)0.0392 (9)0.0171 (6)0.0092 (6)0.0083 (7)
C60.0404 (9)0.0225 (7)0.0396 (9)0.0116 (7)0.0074 (7)0.0126 (7)
C70.0517 (11)0.0477 (10)0.0335 (9)0.0349 (9)0.0004 (8)0.0130 (8)
C80.0303 (8)0.0308 (8)0.0335 (8)0.0202 (7)0.0166 (6)0.0164 (6)
C90.0283 (12)0.0421 (15)0.108 (3)0.0207 (11)0.0250 (17)0.0206 (17)
C100.050 (2)0.0305 (17)0.0351 (18)0.0248 (15)0.0199 (13)0.0098 (13)
C110.112 (3)0.109 (3)0.0451 (14)0.093 (3)0.058 (2)0.058 (2)
C920.0283 (12)0.0421 (15)0.108 (3)0.0207 (11)0.0250 (17)0.0206 (17)
C1020.050 (2)0.0305 (17)0.0351 (18)0.0248 (15)0.0199 (13)0.0098 (13)
C1120.112 (3)0.109 (3)0.0451 (14)0.093 (3)0.058 (2)0.058 (2)
Geometric parameters (Å, º) top
Ti1—N11.9094 (12)C7—H7B0.9600
Ti1—Cl12.2719 (4)C7—H7C0.9600
Ti1—Cl22.2730 (4)C8—C1021.469 (9)
Ti1—C12.2928 (14)C8—C921.508 (7)
Ti1—C22.3206 (15)C8—C111.514 (3)
Ti1—C52.3208 (16)C8—C101.526 (3)
Ti1—C32.4036 (16)C8—C91.557 (4)
Ti1—C42.4048 (16)C8—C1121.571 (10)
Ti1—Si12.9222 (4)C9—H9A0.9600
Si1—N11.7591 (12)C9—H9B0.9600
Si1—C61.8535 (17)C9—H9C0.9600
Si1—C71.8543 (17)C10—H10A0.9600
Si1—C11.8587 (15)C10—H10B0.9600
N1—C81.4913 (18)C10—H10C0.9600
C1—C21.419 (2)C11—H11A0.9600
C1—C51.426 (2)C11—H11B0.9600
C2—C31.412 (2)C11—H11C0.9600
C2—H20.9300C92—H92A0.9600
C3—C41.398 (3)C92—H92B0.9600
C3—H30.9300C92—H92C0.9600
C4—C51.407 (2)C102—H10D0.9600
C4—H40.9300C102—H10E0.9600
C5—H50.9300C102—H10F0.9600
C6—H6A0.9600C112—H11D0.9600
C6—H6B0.9600C112—H11E0.9600
C6—H6C0.9600C112—H11F0.9600
C7—H7A0.9600
N1—Ti1—Cl1108.67 (4)Ti1—C3—H3123.1
N1—Ti1—Cl2106.08 (4)C3—C4—C5107.87 (15)
Cl1—Ti1—Cl2103.506 (18)C3—C4—Ti173.05 (9)
N1—Ti1—C174.94 (5)C5—C4—Ti169.44 (9)
Cl1—Ti1—C1127.64 (4)C3—C4—H4126.1
Cl2—Ti1—C1126.26 (4)C5—C4—H4126.1
N1—Ti1—C296.12 (5)Ti1—C4—H4123.1
Cl1—Ti1—C2144.60 (4)C4—C5—C1109.29 (15)
Cl2—Ti1—C292.99 (4)C4—C5—Ti175.98 (10)
C1—Ti1—C235.82 (5)C1—C5—Ti170.93 (8)
N1—Ti1—C595.70 (5)C4—C5—H5125.4
Cl1—Ti1—C593.40 (4)C1—C5—H5125.4
Cl2—Ti1—C5146.08 (5)Ti1—C5—H5119.4
C1—Ti1—C536.00 (5)Si1—C6—H6A109.5
C2—Ti1—C558.48 (6)Si1—C6—H6B109.5
N1—Ti1—C3130.18 (5)H6A—C6—H6B109.5
Cl1—Ti1—C3113.51 (5)Si1—C6—H6C109.5
Cl2—Ti1—C388.85 (5)H6A—C6—H6C109.5
C1—Ti1—C358.78 (6)H6B—C6—H6C109.5
C2—Ti1—C334.73 (6)Si1—C7—H7A109.5
C5—Ti1—C357.32 (6)Si1—C7—H7B109.5
N1—Ti1—C4129.75 (6)H7A—C7—H7B109.5
Cl1—Ti1—C487.09 (4)Si1—C7—H7C109.5
Cl2—Ti1—C4116.28 (5)H7A—C7—H7C109.5
C1—Ti1—C458.86 (6)H7B—C7—H7C109.5
C2—Ti1—C457.51 (6)C102—C8—N1114.2 (3)
C5—Ti1—C434.58 (6)C102—C8—C92111.3 (4)
C3—Ti1—C433.80 (6)N1—C8—C92113.7 (3)
N1—Ti1—Si135.45 (4)N1—C8—C11110.23 (16)
Cl1—Ti1—Si1125.559 (16)N1—C8—C10111.47 (15)
Cl2—Ti1—Si1122.257 (16)C11—C8—C10110.2 (2)
C2—Ti1—Si165.22 (4)N1—C8—C9105.67 (17)
C5—Ti1—Si165.29 (4)C11—C8—C9111.4 (3)
C3—Ti1—Si196.44 (4)C10—C8—C9107.8 (2)
C4—Ti1—Si196.43 (4)C102—C8—C112105.7 (5)
N1—Si1—C6115.25 (7)N1—C8—C112103.9 (3)
N1—Si1—C7115.09 (7)C92—C8—C112107.2 (5)
C6—Si1—C7110.90 (9)C8—C9—H9A109.5
N1—Si1—C190.69 (6)C8—C9—H9B109.5
C6—Si1—C1111.82 (7)C8—C9—H9C109.5
C7—Si1—C1111.60 (8)C8—C10—H10A109.5
C6—Si1—Ti1124.29 (6)C8—C10—H10B109.5
C7—Si1—Ti1124.74 (7)C8—C10—H10C109.5
C1—Si1—Ti151.67 (4)C8—C11—H11A109.5
C8—N1—Si1126.72 (9)C8—C11—H11B109.5
C8—N1—Ti1127.64 (9)C8—C11—H11C109.5
Si1—N1—Ti1105.53 (6)C8—C92—H92A109.5
C2—C1—C5105.68 (14)C8—C92—H92B109.5
C2—C1—Si1121.68 (11)H92A—C92—H92B109.5
C5—C1—Si1121.47 (11)C8—C92—H92C109.5
C2—C1—Ti173.15 (8)H92A—C92—H92C109.5
C5—C1—Ti173.07 (8)H92B—C92—H92C109.5
Si1—C1—Ti188.84 (6)C8—C102—H10D109.5
C3—C2—C1109.11 (15)C8—C102—H10E109.5
C3—C2—Ti175.85 (9)H10D—C102—H10E109.5
C1—C2—Ti171.02 (8)C8—C102—H10F109.5
C3—C2—H2125.4H10D—C102—H10F109.5
C1—C2—H2125.4H10E—C102—H10F109.5
Ti1—C2—H2119.4C8—C112—H11D109.5
C4—C3—C2108.05 (15)C8—C112—H11E109.5
C4—C3—Ti173.14 (9)H11D—C112—H11E109.5
C2—C3—Ti169.41 (8)C8—C112—H11F109.5
C4—C3—H3126.0H11D—C112—H11F109.5
C2—C3—H3126.0H11E—C112—H11F109.5
Selected geometric parameters (Å, °). top
Cg1—Ti12.0185 (9)N1-Ti11.9093 (12)
Cl2—Ti12.2731 (6)N1-Si11.7591 (14)
Cl1—Ti12.2719 (5)
Cg1-Ti1-N1107.12 (5)Cl1-Ti1-Cl2103.50 (2)
Cg1-Ti1-Cl1115.01 (3)Ti1-N1-Si1105.53 (7)
Cg1-Ti1-Cl2115.97 (3)C1-Si1-N190.68 (7)
Cg1 is the centroid of the cyclopentadienyl ring.
 

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