Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100014773/qa0394sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100014773/qa0394Isup2.hkl |
CCDC reference: 156187
To a solution of dimethylamine (0.50 l, 2.0 M in THF, 1.0 mol), cooled to 195 K, was added a solution of n-butyllithium (0.63 l, 1.6 M in hexane, 1.0 mol). After stirring for 30 min, the solution was warmed to room temperature and stirred an additional 1 h. After cooling to 195 K, a solution of titanium tetrachloride (0.027 l, 0.25 mol) in hexane (0.10 l) was added slowly to the solution of lithium dimethylamide. The red–brown mixture was warmed to room temperature. Volatiles were removed in vacuo and the main product tetrakis(dimethylamido)titanium(IV) (44 g, 0.20 mol) collected by distillation (343 K at 0.5 Torr; 1 Torr = 133.322 Pa). The solid residue was placed in a large sublimator. Sublimation at room temperature and 0.5 Torr yielded yellow crystals of chlorotris(dimethylamido)titanium(IV) (1.5 g, 0.01 mol). After yellow crystals no longer formed on the cold finger of the sublimator the apparatus was placed in an oil bath held at 323 K whereupon large orange crystals of dichlorobis(dimethylamido)(dimethylamine)titanium(IV) (4.6 g, 0.02 mol) formed. Further sublimation at 353 K afforded a crop of red–brown crystals of dichlorobis(dimethylamido)titanium(IV) (3.7 g, 0.02 mol).
Backgrounds were obtained from analysis of the scan profile (Blessing et al., 1974). All H atoms were refined; N—H = 0.74 (2) Å and C—H = 0.87 (2)–1.08 (3) Å.
Data collection: CAD-4 Operations Manual (Enraf-Nonius, 1977); cell refinement: CAD-4 Operations Manual; data reduction: PROCESS in MolEN (Fair, 1990); program(s) used to solve structure: Patterson and Fourier (MolEN); program(s) used to refine structure: LSFM in MolEN; software used to prepare material for publication: CIF VAX in MolEN.
C6H19Cl2N3Ti | F(000) = 528 |
Mr = 252.04 | Dx = 1.32 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.3083 (7) Å | Cell parameters from 50 reflections |
b = 11.5075 (9) Å | θ = 10–12° |
c = 13.360 (2) Å | µ = 1.06 mm−1 |
β = 96.034 (9)° | T = 225 K |
V = 1270.3 (4) Å3 | Irregular block, orange |
Z = 4 | 0.50 × 0.20 × 0.05 mm |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.022 |
θ/2θ scans | θmax = 26.0°, θmin = 2.3° |
Absorption correction: ψ scan (North et al., 1968) | h = 0→10 |
Tmin = 0.799, Tmax = 0.949 | k = 0→14 |
2809 measured reflections | l = −16→16 |
2486 independent reflections | 3 standard reflections every 50 min |
1992 reflections with I > 3σ(I) | intensity decay: 0.1% |
Refinement on F | 0 restraints |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.030 | w = 4Fo2/[σ2(Fo2) + 0.0009Fo4] |
wR(F2) = 0.040 | (Δ/σ)max = 0.001 |
S = 1.29 | Δρmax = 0.22 e Å−3 |
1992 reflections | Δρmin = −0.34 e Å−3 |
185 parameters |
C6H19Cl2N3Ti | V = 1270.3 (4) Å3 |
Mr = 252.04 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.3083 (7) Å | µ = 1.06 mm−1 |
b = 11.5075 (9) Å | T = 225 K |
c = 13.360 (2) Å | 0.50 × 0.20 × 0.05 mm |
β = 96.034 (9)° |
Enraf-Nonius CAD-4 diffractometer | 1992 reflections with I > 3σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.022 |
Tmin = 0.799, Tmax = 0.949 | 3 standard reflections every 50 min |
2809 measured reflections | intensity decay: 0.1% |
2486 independent reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.040 | All H-atom parameters refined |
S = 1.29 | Δρmax = 0.22 e Å−3 |
1992 reflections | Δρmin = −0.34 e Å−3 |
185 parameters |
x | y | z | Uiso*/Ueq | ||
Ti | 0.72390 (4) | 0.22524 (3) | 0.75747 (3) | 0.02432 (8) | |
Cl(1) | 0.67764 (7) | 0.36681 (5) | 0.88297 (4) | 0.0388 (1) | |
Cl(2) | 0.84887 (9) | 0.37154 (5) | 0.67102 (5) | 0.0524 (2) | |
N(1) | 0.8142 (2) | 0.1192 (2) | 0.8518 (1) | 0.0353 (5) | |
N(2) | 0.5096 (2) | 0.1895 (2) | 0.7165 (2) | 0.0387 (5) | |
N(3) | 0.8074 (2) | 0.1143 (2) | 0.6337 (1) | 0.0295 (4) | |
C(1) | 0.7508 (4) | 0.0191 (2) | 0.8996 (2) | 0.0569 (8) | |
C(2) | 0.9718 (3) | 0.1557 (2) | 0.8990 (2) | 0.0451 (6) | |
C(3) | 0.4305 (3) | 0.2019 (2) | 0.6145 (2) | 0.0538 (7) | |
C(4) | 0.3962 (3) | 0.1603 (3) | 0.7884 (2) | 0.0575 (8) | |
C(5) | 0.7412 (3) | −0.0047 (2) | 0.6315 (2) | 0.0431 (6) | |
C(6) | 0.9850 (3) | 0.1073 (2) | 0.6348 (2) | 0.0440 (6) | |
H(1) | 0.832 (4) | −0.048 (3) | 0.897 (2) | 0.11 (1)* | |
H(2) | 0.652 (3) | 0.002 (2) | 0.866 (2) | 0.049 (7)* | |
H(3) | 0.721 (3) | 0.039 (3) | 0.971 (2) | 0.09 (1)* | |
H(4) | 0.957 (3) | 0.182 (2) | 0.967 (2) | 0.060 (8)* | |
H(5) | 1.053 (3) | 0.100 (3) | 0.894 (2) | 0.070 (9)* | |
H(6) | 1.012 (3) | 0.222 (2) | 0.867 (2) | 0.041 (7)* | |
H(7) | 0.351 (3) | 0.259 (2) | 0.609 (2) | 0.069 (9)* | |
H(8) | 0.384 (3) | 0.128 (3) | 0.584 (2) | 0.08 (1)* | |
H(9) | 0.509 (3) | 0.223 (3) | 0.567 (2) | 0.072 (9)* | |
H(10) | 0.459 (3) | 0.161 (2) | 0.863 (2) | 0.066 (9)* | |
H(11) | 0.320 (4) | 0.224 (3) | 0.787 (3) | 0.11 (1)* | |
H(12) | 0.349 (3) | 0.085 (3) | 0.773 (2) | 0.09 (1)* | |
H(13) | 0.619 (3) | −0.005 (2) | 0.626 (2) | 0.060 (8)* | |
H(14) | 0.782 (3) | −0.040 (2) | 0.685 (2) | 0.059 (8)* | |
H(15) | 0.765 (3) | −0.049 (3) | 0.568 (2) | 0.09 (1)* | |
H(16) | 1.009 (3) | 0.063 (2) | 0.574 (2) | 0.050 (7)* | |
H(17) | 1.028 (3) | 0.062 (2) | 0.699 (2) | 0.061 (8)* | |
H(18) | 1.039 (3) | 0.192 (3) | 0.628 (2) | 0.08 (1)* | |
H(19) | 0.774 (2) | 0.146 (2) | 0.588 (2) | 0.030 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ti | 0.0263 (2) | 0.0219 (2) | 0.0245 (2) | −0.0017 (1) | 0.0016 (1) | −0.0000 (1) |
Cl(1) | 0.0483 (3) | 0.0347 (3) | 0.0334 (3) | 0.0077 (2) | 0.0044 (2) | −0.0072 (2) |
Cl(2) | 0.0846 (4) | 0.0319 (3) | 0.0446 (3) | −0.0193 (3) | 0.0255 (3) | −0.0016 (2) |
N(1) | 0.048 (1) | 0.0289 (9) | 0.0292 (9) | 0.0082 (8) | 0.0039 (8) | 0.0009 (8) |
N(2) | 0.0292 (8) | 0.036 (1) | 0.050 (1) | −0.0014 (8) | 0.0028 (8) | −0.0113 (9) |
N(3) | 0.0298 (8) | 0.0323 (9) | 0.0259 (8) | 0.0008 (7) | 0.0003 (7) | 0.0001 (7) |
C(1) | 0.081 (2) | 0.044 (1) | 0.046 (1) | 0.000 (1) | 0.009 (1) | 0.013 (1) |
C(2) | 0.050 (1) | 0.048 (1) | 0.036 (1) | 0.017 (1) | −0.002 (1) | −0.003 (1) |
C(3) | 0.041 (1) | 0.054 (2) | 0.062 (2) | 0.009 (1) | −0.014 (1) | −0.008 (1) |
C(4) | 0.039 (1) | 0.060 (2) | 0.077 (2) | −0.010 (1) | 0.017 (1) | −0.006 (2) |
C(5) | 0.052 (1) | 0.030 (1) | 0.047 (1) | −0.005 (1) | 0.004 (1) | −0.010 (1) |
C(6) | 0.035 (1) | 0.056 (1) | 0.042 (1) | 0.005 (1) | 0.007 (1) | −0.008 (1) |
Ti—Cl(1) | 2.3976 (7) | C(2)—H(4) | 0.98 (3) |
Ti—Cl(2) | 2.3449 (8) | C(2)—H(5) | 0.94 (3) |
Ti—N(1) | 1.855 (2) | C(2)—H(6) | 0.95 (2) |
Ti—N(2) | 1.853 (2) | C(3)—H(7) | 0.92 (3) |
Ti—N(3) | 2.255 (2) | C(3)—H(8) | 1.00 (3) |
N(1)—C(1) | 1.443 (3) | C(3)—H(9) | 0.99 (3) |
N(1)—C(2) | 1.455 (3) | C(4)—H(10) | 1.08 (3) |
N(2)—C(3) | 1.456 (3) | C(4)—H(11) | 0.96 (4) |
N(2)—C(4) | 1.454 (4) | C(4)—H(12) | 0.96 (3) |
N(3)—C(5) | 1.474 (3) | C(5)—H(13) | 1.01 (2) |
N(3)—C(6) | 1.476 (3) | C(5)—H(14) | 0.87 (2) |
N(3)—H(19) | 0.74 (2) | C(5)—H(15) | 1.02 (3) |
C(1)—H(1) | 1.03 (3) | C(6)—H(16) | 1.00 (2) |
C(1)—H(2) | 0.92 (2) | C(6)—H(17) | 1.03 (2) |
C(1)—H(3) | 1.04 (3) | C(6)—H(18) | 1.08 (3) |
Cl(1)—Ti—Cl(2) | 88.20 (2) | N(1)—C(2)—H(5) | 113 (2) |
Cl(1)—Ti—N(1) | 93.14 (6) | N(1)—C(2)—H(6) | 112 (1) |
Cl(1)—Ti—N(2) | 97.90 (7) | H(4)—C(2)—H(5) | 116 (2) |
Cl(1)—Ti—N(3) | 169.01 (5) | H(4)—C(2)—H(6) | 105 (2) |
Cl(2)—Ti—N(1) | 129.69 (6) | H(5)—C(2)—H(6) | 103 (2) |
Cl(2)—Ti—N(2) | 118.38 (7) | N(2)—C(3)—H(7) | 113 (2) |
Cl(2)—Ti—N(3) | 81.91 (5) | N(2)—C(3)—H(8) | 114 (2) |
N(1)—Ti—N(2) | 111.22 (9) | N(2)—C(3)—H(9) | 112 (2) |
N(1)—Ti—N(3) | 89.55 (7) | H(7)—C(3)—H(8) | 109 (2) |
N(2)—Ti—N(3) | 91.03 (8) | H(7)—C(3)—H(9) | 106 (2) |
Ti—N(1)—C(1) | 133.3 (2) | H(8)—C(3)—H(9) | 102 (2) |
Ti—N(1)—C(2) | 112.7 (1) | N(2)—C(4)—H(10) | 109 (1) |
C(1)—N(1)—C(2) | 113.1 (2) | N(2)—C(4)—H(11) | 106 (2) |
Ti—N(2)—C(3) | 125.4 (2) | N(2)—C(4)—H(12) | 110 (2) |
Ti—N(2)—C(4) | 121.7 (2) | H(10)—C(4)—H(11) | 105 (2) |
C(3)—N(2)—C(4) | 112.4 (2) | H(10)—C(4)—H(12) | 110 (2) |
Ti—N(3)—C(5) | 113.4 (1) | H(11)—C(4)—H(12) | 115 (3) |
Ti—N(3)—C(6) | 114.1 (1) | N(3)—C(5)—H(13) | 112 (2) |
Ti—N(3)—H(19) | 102 (2) | N(3)—C(5)—H(14) | 108 (2) |
C(5)—N(3)—C(6) | 108.7 (2) | N(3)—C(5)—H(15) | 112 (2) |
C(5)—N(3)—H(19) | 110 (2) | H(13)—C(5)—H(14) | 111 (2) |
C(6)—N(3)—H(19) | 109 (2) | H(13)—C(5)—H(15) | 103 (2) |
N(1)—C(1)—H(1) | 108 (2) | H(14)—C(5)—H(15) | 111 (2) |
N(1)—C(1)—H(2) | 107 (2) | N(3)—C(6)—H(16) | 108 (1) |
N(1)—C(1)—H(3) | 111 (2) | N(3)—C(6)—H(17) | 107 (1) |
H(1)—C(1)—H(2) | 112 (2) | N(3)—C(6)—H(18) | 112 (1) |
H(1)—C(1)—H(3) | 115 (2) | H(16)—C(6)—H(17) | 110 (2) |
H(2)—C(1)—H(3) | 102 (2) | H(16)—C(6)—H(18) | 106 (2) |
N(1)—C(2)—H(4) | 107 (1) | H(17)—C(6)—H(18) | 115 (2) |
Experimental details
Crystal data | |
Chemical formula | C6H19Cl2N3Ti |
Mr | 252.04 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 225 |
a, b, c (Å) | 8.3083 (7), 11.5075 (9), 13.360 (2) |
β (°) | 96.034 (9) |
V (Å3) | 1270.3 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.06 |
Crystal size (mm) | 0.50 × 0.20 × 0.05 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.799, 0.949 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 2809, 2486, 1992 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.040, 1.29 |
No. of reflections | 1992 |
No. of parameters | 185 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.22, −0.34 |
Computer programs: CAD-4 Operations Manual (Enraf-Nonius, 1977), CAD-4 Operations Manual, PROCESS in MolEN (Fair, 1990), Patterson and Fourier (MolEN), LSFM in MolEN, CIF VAX in MolEN.
Ti—Cl(1) | 2.3976 (7) | N(1)—C(2) | 1.455 (3) |
Ti—Cl(2) | 2.3449 (8) | N(2)—C(3) | 1.456 (3) |
Ti—N(1) | 1.855 (2) | N(2)—C(4) | 1.454 (4) |
Ti—N(2) | 1.853 (2) | N(3)—C(5) | 1.474 (3) |
Ti—N(3) | 2.255 (2) | N(3)—C(6) | 1.476 (3) |
N(1)—C(1) | 1.443 (3) | ||
Cl(1)—Ti—Cl(2) | 88.20 (2) | Cl(2)—Ti—N(2) | 118.38 (7) |
Cl(1)—Ti—N(1) | 93.14 (6) | Cl(2)—Ti—N(3) | 81.91 (5) |
Cl(1)—Ti—N(2) | 97.90 (7) | N(1)—Ti—N(2) | 111.22 (9) |
Cl(1)—Ti—N(3) | 169.01 (5) | N(1)—Ti—N(3) | 89.55 (7) |
Cl(2)—Ti—N(1) | 129.69 (6) | N(2)—Ti—N(3) | 91.03 (8) |
Crystals of dichlorobis(dimethylamido)(dimethylammine)titanium(IV), (I), were obtained as a side product of the synthesis of Ti(NMe2)4 from TiCl4 and LiNMe2. Sublimation of the residual solid gave crystals of (I) in a low isolated yield. \scheme