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Amido complexes of titanium are useful reagents in a variety of syntheses and as precursors for chemical vapour deposition of TiN. The title compound, di­chloro­bis­(di­methyl­amido)(di­methyl­amine)­titanium(IV), [TiCl2(C2H6N)2(C2H7N)], crystallizes with one mol­ecule in the asymmetric unit. The neutral complex shows an unusual fivefold coordination of the titanium centre with a distorted trigonal-bipyramidal geometry and the di­methyl­amine mol­ecule occupying an axial position.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100014773/qa0394sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100014773/qa0394Isup2.hkl
Contains datablock I

CCDC reference: 156187

Comment top

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

Experimental top

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).

Refinement top

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.

Computing details top

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.

(I) top
Crystal data top
C6H19Cl2N3TiF(000) = 528
Mr = 252.04Dx = 1.32 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 8.3083 (7) ÅCell parameters from 50 reflections
b = 11.5075 (9) Åθ = 10–12°
c = 13.360 (2) ŵ = 1.06 mm1
β = 96.034 (9)°T = 225 K
V = 1270.3 (4) Å3Irregular block, orange
Z = 40.50 × 0.20 × 0.05 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.022
θ/2θ scansθmax = 26.0°, θmin = 2.3°
Absorption correction: ψ scan
(North et al., 1968)
h = 010
Tmin = 0.799, Tmax = 0.949k = 014
2809 measured reflectionsl = 1616
2486 independent reflections3 standard reflections every 50 min
1992 reflections with I > 3σ(I) intensity decay: 0.1%
Refinement top
Refinement on F0 restraints
Least-squares matrix: fullAll 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 = 1.29Δρmax = 0.22 e Å3
1992 reflectionsΔρmin = 0.34 e Å3
185 parameters
Crystal data top
C6H19Cl2N3TiV = 1270.3 (4) Å3
Mr = 252.04Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.3083 (7) ŵ = 1.06 mm1
b = 11.5075 (9) ÅT = 225 K
c = 13.360 (2) Å0.50 × 0.20 × 0.05 mm
β = 96.034 (9)°
Data collection top
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 = 0.9493 standard reflections every 50 min
2809 measured reflections intensity decay: 0.1%
2486 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.040All H-atom parameters refined
S = 1.29Δρmax = 0.22 e Å3
1992 reflectionsΔρmin = 0.34 e Å3
185 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ti0.72390 (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)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ti0.0263 (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)
Geometric parameters (Å, º) top
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 formulaC6H19Cl2N3Ti
Mr252.04
Crystal system, space groupMonoclinic, P21/c
Temperature (K)225
a, b, c (Å)8.3083 (7), 11.5075 (9), 13.360 (2)
β (°) 96.034 (9)
V3)1270.3 (4)
Z4
Radiation typeMo Kα
µ (mm1)1.06
Crystal size (mm)0.50 × 0.20 × 0.05
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.799, 0.949
No. of measured, independent and
observed [I > 3σ(I)] reflections
2809, 2486, 1992
Rint0.022
(sin θ/λ)max1)0.616
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.040, 1.29
No. of reflections1992
No. of parameters185
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)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.

Selected geometric parameters (Å, º) top
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)
 

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