Di-μ-chlorido-bis­[dichlorido(N,N-diethyl­acetamidinato)(N,N-diethyl­acetamidine)titanium(IV)] acetonitrile disolvate

Straessler, N.A.; Caudle, M.T.; Groy, T.L.

doi:10.1107/S1600536807062022

metal-organic compounds

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Volume 64| Part 1| January 2008| Page m20

https://doi.org/10.1107/S1600536807062022

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Di-μ-chlorido-bis[dichlorido(N,N-diethylacetamidinato)(N,N-diethylacetamidine)titanium(IV)] acetonitrile disolvate

Nicholas A. Straessler,^a M. Tyler Caudle ^b and Thomas L. Groy ^c ^*

^aATK Launch Systems, Brigham City, UT 84302, USA, ^bBASF Catalysts LLC, Iselin, NJ 08830, USA, and ^cDepartment of Chemistry and Biochemistry, Arizona State University, Tempe, AZ 85287, USA
^*Correspondence e-mail: tgroy@asu.edu

(Received 16 November 2007; accepted 22 November 2007; online 6 December 2007)

In the centrosymmetric title compound [Ti₂Cl₆(C₆H₁₃N₂)₂(C₆H₁₄N₂)₂]·2C₂H₃N, an inversion center relates the two Ti atoms which display a distorted octahedral coordination geometry. There are two uncoordinated acetonitrile solvent molecules per molecule of title compound in the crystal structure.

Related literature

For the structure, see: Dunn et al. (1994 ); Guiducci et al. (2001 ); Lewkebandara et al. (1994 ); Nielson et al. (2001 ). For the reaction mechanism, see: Bradley & Ganorkar (1968 ); Chandra et al. (1970 ); Forsberg et al. (1987 ); Maresca et al. (1986 ); Rouschias & Wilkinson (1968 ).

Experimental

Crystal data

[Ti₂Cl₆(C₆H₁₃N₂)₂(C₆H₁₄N₂)₂]·2C₂H₃N
M_r = 845.36
Triclinic, $[P \overline 1]$
a = 9.6217 (6) Å
b = 11.1812 (7) Å
c = 11.2298 (8) Å
α = 95.680 (1)°
β = 105.192 (1)°
γ = 106.938 (1)°
V = 1095.03 (12) Å³
Z = 1
Mo Kα radiation
μ = 0.76 mm⁻¹
T = 298 (2) K
0.30 × 0.15 × 0.15 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003a ) T_min = 0.870, T_max = 0.890
8928 measured reflections
3871 independent reflections
2999 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.134
S = 1.02
3871 reflections
215 parameters
H-atom parameters constrained
Δρ_max = 0.82 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: SMART (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2003b ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807062022/lx2036sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807062022/lx2036Isup2.hkl

checkCIF report

Comment top

The structure of title compound, (I) was solved as part of an investigation into the effects of nitriles on N,N-dialkylamido titanium(IV) complexes. Compound (I) is a dimeric molecule in which two symmetrically equivalent titanium atoms are each coordinated by one anionic diethylacetamidino group (N1), one neutral diethylacetamidine ligand (N3), two terminal chlorides (Cl2 and Cl3), and two equivalent bridging chlorides (Cl1). This gives a pseudo–octahedral configuration about each titanium center. The acetamidine and acetamidino ligands are oriented in cis coordination positions.

The Ti₂Cl₂ unit of (I) is distorted such that the Ti1—Cl1 bond that is trans to the diethylacetamidino ligand is significantly longer than the Ti—Cl1 bond that is trans to Cl3 (2.7002 (8) Å versus. 2.4557 (8) Å). This is consistent with the greater sigma-electron donating ability of the acetamidino ligand relative to the Cl^-. The Ti—Cl1—Ti bond angle is 102.96 (3)°, similar to that of other dichloro-bridged Ti⁴⁺ compounds (Nielson et al., 2001). The terminal titanium–chloride bond lengths (Ti—Cl2 = 2.3882 (8) Å and Ti—Cl3 = 2.3511 (9) Å) are shorter than the bridging Ti—Cl1 bonds, and are within the normal range for such linkages.

In general, the ligands in (I) bend away from the diethylacetamidino group resulting in bond angles greater than the ideal 90° for octahedral complexes {N1—Ti—Cl3 = 101.24 (9)°, N1—Ti—Cl1 = 95.57 (9)°, N1—Ti—Cl2 = 95.51 (8)°, N1—Ti—N3 = 94.42 (10)°}. This can be attributed to electrostatic repulsion caused by substantial pi–electron donation from the diethylacetamidino nitrogen to the empty 3 d orbitals on Ti⁴⁺. The approximately linear Ti—N1—C1 bond angle (165.7 (2)°) and the short Ti—N1 bond length (1.751 (2) Å) indicate significant Ti—N1 multiple–bond character analogous to those observed in titanium(IV) imides (Guiducci et al., 2001; Lewkebandara et al., 1994; Dunn et al., 1994). The Ti—N3 acetamidine bond length is 2.130 (2) Å, which is 0.379 Å longer than the Ti—N1 acetamidino bond length at 1.751 (2) Å, clearly supporting multiple–bond character in the Ti—N1 bond.

Formation of metal–amidine complexes has been shown to occur by two different mechanisms: (1) acetonitrile insertion into metal–amide bonds (Bradley & Ganorkar, 1968; Chandra et al., 1970); (2) nucleophilic attack by free amine on coordinated nitriles in the presence of metal ions (Forsberg et al., 1987; Rouschias & Wilkinson, 1968; Maresca et al., 1986). However, secondary amines such as diethylamine do not react with nitriles in the absence of metal ions. The addition of TiCl₄ to acetonitrile results in a yellow solvate formed by coordination of CH₃CN to the titanium atom. We speculate that (I) then most likely forms via mechanism 2 because the metal-nitrogen linkage to the nitrile is established before addition of diethylamine. Furthermore, direct insertion of CH₃CN has been reported to only occur slowly (Bradley & Ganorkar, 1968), whereas we observe reaction of diethylamine with the TiCl₄–acetonitrile solvate to occur immediately.

Related literature top

For the structure, see: Dunn et al. (1994); Guiducci et al. (2001); Lewkebandara et al. (1994); Nielson et al. (2001). For the reaction mechanism, see: Bradley & Ganorkar (1968); Chandra et al. (1970); Forsberg et al. (1987); Maresca et al. (1986); Rouschias & Wilkinson (1968).

Experimental top

While stirring under an atmosphere of nitrogen, 2 ml (18.24 mmol) of TiCl₄ were added to approximately 50 ml of anhydrous acetonitrile in a Schlenk flask. To the resulting bright yellow solution was added 5.66 ml (54.71 mmol) of diethylamine. The exothermic reaction turned dark orange and white solid began to precipitate immediately. After twelve hours of stirring, solid white diethylammonium chloride was removed by filtration under nitrogen, and the filtrate was concentrated by intermittent evaporation with a stream of nitrogen over a period of four days. Removal of almost half of the solvent yielded X-ray quality crystals of I.

Structure description top

For the structure, see: Dunn et al. (1994); Guiducci et al. (2001); Lewkebandara et al. (1994); Nielson et al. (2001). For the reaction mechanism, see: Bradley & Ganorkar (1968); Chandra et al. (1970); Forsberg et al. (1987); Maresca et al. (1986); Rouschias & Wilkinson (1968).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAIN(Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2003b); software used to prepare material for publication: SHELXTL (Sheldrick, 2003b).

Figures top

Fig. 1. Thermal ellipsoid plot of centrosymmetric title compund shown at the 30% probability level. Solvent molecules and hydrogen atoms omitted for clarity. Only unique atoms are labeled.

Di-µ-chlorido-bis[dichlorido(N,N-diethylacetamidinato)(N,N- diethylacetamidine)titanium(IV)] acetonitrile disolvate top

Crystal data top

[Ti₂Cl₆(C₆H₁₃N₂)₂(C₆H₁₄N₂)₂]·2C₂H₃N	Z = 1
M_r = 845.36	F(000) = 444
Triclinic, P1	D_x = 1.282 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.6217 (6) Å	Cell parameters from 5597 reflections
b = 11.1812 (7) Å	θ = 4.7–55.0°
c = 11.2298 (8) Å	µ = 0.76 mm⁻¹
α = 95.680 (1)°	T = 298 K
β = 105.192 (1)°	Block, orange
γ = 106.938 (1)°	0.30 × 0.15 × 0.15 mm
V = 1095.03 (12) Å³

Data collection top

Bruker SMART APEX diffractometer	3871 independent reflections
Radiation source: fine-focus sealed tube	2999 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
ω scan	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003a)	h = −11→11
T_min = 0.870, T_max = 0.890	k = −13→13
8928 measured reflections	l = −13→13

Refinement top

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0851P)²] where P = (F_o² + 2F_c²)/3
3871 reflections	(Δ/σ)_max < 0.001
215 parameters	Δρ_max = 0.82 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[Ti₂Cl₆(C₆H₁₃N₂)₂(C₆H₁₄N₂)₂]·2C₂H₃N	γ = 106.938 (1)°
M_r = 845.36	V = 1095.03 (12) Å³
Triclinic, P1	Z = 1
a = 9.6217 (6) Å	Mo Kα radiation
b = 11.1812 (7) Å	µ = 0.76 mm⁻¹
c = 11.2298 (8) Å	T = 298 K
α = 95.680 (1)°	0.30 × 0.15 × 0.15 mm
β = 105.192 (1)°

Data collection top

Bruker SMART APEX diffractometer	3871 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003a)	2999 reflections with I > 2σ(I)
T_min = 0.870, T_max = 0.890	R_int = 0.045
8928 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.134	H-atom parameters constrained
S = 1.02	Δρ_max = 0.82 e Å⁻³
3871 reflections	Δρ_min = −0.28 e Å⁻³
215 parameters

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	U_iso*/U_eq
Ti	0.68333 (5)	0.53749 (4)	0.65286 (4)	0.04665 (18)
Cl1	0.62466 (7)	0.54169 (6)	0.42723 (6)	0.0509 (2)
Cl2	0.65097 (9)	0.31620 (6)	0.60603 (8)	0.0697 (3)
Cl3	0.66161 (11)	0.52732 (8)	0.85562 (7)	0.0787 (3)
N1	0.8818 (3)	0.5903 (2)	0.6847 (2)	0.0596 (6)
C1	1.0294 (5)	0.6394 (3)	0.6804 (3)	0.0803 (10)
C2	1.0542 (5)	0.7145 (5)	0.5730 (5)	0.135 (2)
H2A	1.1219	0.6877	0.5358	0.203*
H2B	1.0979	0.8041	0.6073	0.203*
H2C	0.9579	0.6978	0.5101	0.203*
N2	1.1381 (3)	0.6309 (3)	0.7609 (3)	0.0836 (9)
C3	1.1039 (5)	0.5546 (4)	0.8621 (4)	0.0909 (12)
H3A	1.1916	0.5854	0.9371	0.109*
H3B	1.0184	0.5697	0.8837	0.109*
C4	1.0682 (6)	0.4183 (5)	0.8236 (5)	0.136 (2)
H4A	1.0827	0.3799	0.8967	0.204*
H4B	1.1345	0.4034	0.7774	0.204*
H4C	0.9641	0.3815	0.7714	0.204*
C5	1.2977 (4)	0.6763 (4)	0.7612 (4)	0.0981 (14)
H5A	1.3002	0.6815	0.6760	0.118*
H5B	1.3466	0.6153	0.7897	0.118*
C6	1.3848 (5)	0.8030 (5)	0.8434 (5)	0.132 (2)
H6A	1.4855	0.8319	0.8353	0.198*
H6B	1.3917	0.7964	0.9292	0.198*
H6C	1.3334	0.8626	0.8189	0.198*
N3	0.6676 (3)	0.72414 (19)	0.66808 (19)	0.0484 (5)
H3C	0.5873	0.7282	0.6148	0.058*
C7	0.7531 (3)	0.8339 (2)	0.7406 (2)	0.0480 (6)
C8	0.8672 (3)	0.8363 (3)	0.8616 (3)	0.0621 (8)
H8A	0.8564	0.7507	0.8738	0.093*
H8B	0.8499	0.8823	0.9300	0.093*
H8C	0.9684	0.8776	0.8584	0.093*
N4	0.7431 (3)	0.9462 (2)	0.7128 (2)	0.0579 (6)
C9	0.8370 (4)	1.0706 (3)	0.7955 (3)	0.0731 (9)
H9A	0.8673	1.1323	0.7443	0.088*
H9B	0.9289	1.0624	0.8501	0.088*
C10	0.7545 (5)	1.1182 (4)	0.8737 (4)	0.1025 (14)
H10A	0.8175	1.2011	0.9222	0.154*
H10B	0.7312	1.0608	0.9293	0.154*
H10C	0.6615	1.1237	0.8203	0.154*
C11	0.6473 (4)	0.9544 (3)	0.5929 (3)	0.0742 (10)
H11A	0.6273	1.0346	0.6006	0.089*
H11B	0.5503	0.8862	0.5705	0.089*
C12	0.7191 (6)	0.9456 (5)	0.4896 (4)	0.1124 (16)
H12A	0.6590	0.9637	0.4153	0.169*
H12B	0.7236	0.8612	0.4721	0.169*
H12C	0.8204	1.0061	0.5157	0.169*
N5	0.7942 (7)	0.9547 (5)	0.1738 (6)	0.175 (2)
C13	0.7192 (6)	0.8570 (5)	0.1685 (5)	0.1060 (14)
C14	0.6195 (7)	0.7345 (5)	0.1617 (6)	0.1335 (18)
H14A	0.5241	0.7402	0.1683	0.200*
H14B	0.6639	0.6977	0.2293	0.200*
H14C	0.6025	0.6819	0.0828	0.200*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ti	0.0470 (3)	0.0384 (3)	0.0445 (3)	0.0127 (2)	−0.0004 (2)	0.0059 (2)
Cl1	0.0511 (4)	0.0509 (4)	0.0447 (4)	0.0153 (3)	0.0081 (3)	0.0041 (3)
Cl2	0.0661 (5)	0.0421 (4)	0.0841 (6)	0.0206 (4)	−0.0059 (4)	0.0067 (4)
Cl3	0.0915 (6)	0.0739 (5)	0.0456 (4)	0.0040 (5)	0.0037 (4)	0.0171 (4)
N1	0.0457 (14)	0.0528 (14)	0.0677 (15)	0.0153 (11)	0.0003 (11)	0.0041 (11)
C1	0.076 (2)	0.073 (2)	0.081 (2)	0.032 (2)	0.008 (2)	−0.0126 (18)
C2	0.079 (3)	0.152 (5)	0.187 (5)	0.022 (3)	0.055 (3)	0.099 (4)
N2	0.0541 (17)	0.082 (2)	0.097 (2)	0.0180 (15)	0.0127 (16)	−0.0198 (17)
C3	0.083 (3)	0.103 (3)	0.084 (3)	0.041 (2)	0.006 (2)	0.027 (2)
C4	0.126 (4)	0.097 (4)	0.134 (4)	0.023 (3)	−0.022 (3)	0.010 (3)
C5	0.051 (2)	0.118 (3)	0.113 (3)	0.027 (2)	0.022 (2)	−0.027 (3)
C6	0.058 (2)	0.137 (4)	0.159 (5)	−0.001 (3)	0.030 (3)	−0.046 (4)
N3	0.0502 (13)	0.0409 (12)	0.0443 (12)	0.0163 (10)	−0.0014 (9)	0.0029 (9)
C7	0.0476 (15)	0.0463 (15)	0.0444 (14)	0.0132 (12)	0.0093 (12)	0.0026 (11)
C8	0.0627 (19)	0.0536 (17)	0.0512 (17)	0.0114 (15)	−0.0018 (13)	0.0011 (13)
N4	0.0654 (16)	0.0363 (12)	0.0557 (14)	0.0118 (11)	0.0013 (11)	−0.0024 (10)
C9	0.083 (2)	0.0399 (16)	0.072 (2)	0.0089 (16)	0.0028 (17)	−0.0060 (14)
C10	0.134 (4)	0.077 (3)	0.090 (3)	0.044 (3)	0.022 (3)	−0.013 (2)
C11	0.093 (2)	0.0432 (16)	0.070 (2)	0.0233 (16)	−0.0030 (18)	0.0061 (14)
C12	0.150 (4)	0.106 (3)	0.071 (3)	0.026 (3)	0.029 (3)	0.032 (2)
N5	0.170 (5)	0.122 (4)	0.249 (6)	0.012 (3)	0.132 (5)	0.038 (4)
C13	0.102 (3)	0.101 (3)	0.132 (4)	0.028 (3)	0.069 (3)	0.031 (3)
C14	0.144 (5)	0.101 (4)	0.162 (5)	0.029 (3)	0.065 (4)	0.041 (3)

Geometric parameters (Å, º) top

Ti—N1	1.751 (2)	N3—C7	1.307 (3)
Ti—N3	2.130 (2)	N3—H3C	0.8600
Ti—Cl3	2.3511 (9)	C7—N4	1.348 (3)
Ti—Cl2	2.3882 (8)	C7—C8	1.498 (4)
Ti—Cl1	2.4557 (8)	C8—H8A	0.9600
Ti—Cl1ⁱ	2.7002 (8)	C8—H8B	0.9600
Cl1—Tiⁱ	2.7002 (8)	C8—H8C	0.9600
N1—C1	1.381 (4)	N4—C11	1.447 (4)
C1—N2	1.225 (4)	N4—C9	1.478 (3)
C1—C2	1.566 (6)	C9—C10	1.484 (5)
C2—H2A	0.9600	C9—H9A	0.9700
C2—H2B	0.9600	C9—H9B	0.9700
C2—H2C	0.9600	C10—H10A	0.9600
N2—C5	1.469 (4)	C10—H10B	0.9600
N2—C3	1.534 (5)	C10—H10C	0.9600
C3—C4	1.454 (6)	C11—C12	1.506 (5)
C3—H3A	0.9700	C11—H11A	0.9700
C3—H3B	0.9700	C11—H11B	0.9700
C4—H4A	0.9600	C12—H12A	0.9600
C4—H4B	0.9600	C12—H12B	0.9600
C4—H4C	0.9600	C12—H12C	0.9600
C5—C6	1.485 (6)	N5—C13	1.106 (6)
C5—H5A	0.9700	C13—C14	1.406 (7)
C5—H5B	0.9700	C14—H14A	0.9600
C6—H6A	0.9600	C14—H14B	0.9600
C6—H6B	0.9600	C14—H14C	0.9600
C6—H6C	0.9600

N1—Ti—N3	94.42 (10)	C5—C6—H6C	109.5
N1—Ti—Cl3	101.24 (9)	H6A—C6—H6C	109.5
N3—Ti—Cl3	90.72 (6)	H6B—C6—H6C	109.5
N1—Ti—Cl2	95.51 (8)	C7—N3—Ti	134.05 (18)
N3—Ti—Cl2	168.45 (6)	C7—N3—H3C	113.0
Cl3—Ti—Cl2	93.10 (3)	Ti—N3—H3C	113.0
N1—Ti—Cl1	95.57 (9)	N3—C7—N4	123.2 (2)
N3—Ti—Cl1	84.04 (6)	N3—C7—C8	119.0 (2)
Cl3—Ti—Cl1	162.74 (4)	N4—C7—C8	117.8 (2)
Cl2—Ti—Cl1	89.15 (3)	C7—C8—H8A	109.5
N1—Ti—Cl1ⁱ	172.61 (9)	C7—C8—H8B	109.5
N3—Ti—Cl1ⁱ	84.93 (6)	H8A—C8—H8B	109.5
Cl3—Ti—Cl1ⁱ	86.13 (3)	C7—C8—H8C	109.5
Cl2—Ti—Cl1ⁱ	84.46 (3)	H8A—C8—H8C	109.5
Cl1—Ti—Cl1ⁱ	77.04 (3)	H8B—C8—H8C	109.5
Ti—Cl1—Tiⁱ	102.96 (3)	C7—N4—C11	121.7 (2)
C1—N1—Ti	165.7 (2)	C7—N4—C9	123.6 (2)
N2—C1—N1	121.7 (4)	C11—N4—C9	114.5 (2)
N2—C1—C2	120.8 (4)	N4—C9—C10	112.4 (3)
N1—C1—C2	117.4 (3)	N4—C9—H9A	109.1
C1—C2—H2A	109.5	C10—C9—H9A	109.1
C1—C2—H2B	109.5	N4—C9—H9B	109.1
H2A—C2—H2B	109.5	C10—C9—H9B	109.1
C1—C2—H2C	109.5	H9A—C9—H9B	107.9
H2A—C2—H2C	109.5	C9—C10—H10A	109.5
H2B—C2—H2C	109.5	C9—C10—H10B	109.5
C1—N2—C5	125.3 (4)	H10A—C10—H10B	109.5
C1—N2—C3	117.5 (3)	C9—C10—H10C	109.5
C5—N2—C3	116.9 (3)	H10A—C10—H10C	109.5
C4—C3—N2	113.5 (4)	H10B—C10—H10C	109.5
C4—C3—H3A	108.9	N4—C11—C12	112.4 (3)
N2—C3—H3A	108.9	N4—C11—H11A	109.1
C4—C3—H3B	108.9	C12—C11—H11A	109.1
N2—C3—H3B	108.9	N4—C11—H11B	109.1
H3A—C3—H3B	107.7	C12—C11—H11B	109.1
C3—C4—H4A	109.5	H11A—C11—H11B	107.9
C3—C4—H4B	109.5	C11—C12—H12A	109.5
H4A—C4—H4B	109.5	C11—C12—H12B	109.5
C3—C4—H4C	109.5	H12A—C12—H12B	109.5
H4A—C4—H4C	109.5	C11—C12—H12C	109.5
H4B—C4—H4C	109.5	H12A—C12—H12C	109.5
N2—C5—C6	112.4 (3)	H12B—C12—H12C	109.5
N2—C5—H5A	109.1	N5—C13—C14	178.0 (6)
C6—C5—H5A	109.1	C13—C14—H14A	109.5
N2—C5—H5B	109.1	C13—C14—H14B	109.5
C6—C5—H5B	109.1	H14A—C14—H14B	109.5
H5A—C5—H5B	107.9	C13—C14—H14C	109.5
C5—C6—H6A	109.5	H14A—C14—H14C	109.5
C5—C6—H6B	109.5	H14B—C14—H14C	109.5
H6A—C6—H6B	109.5

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Ti₂Cl₆(C₆H₁₃N₂)₂(C₆H₁₄N₂)₂]·2C₂H₃N
M_r	845.36
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	9.6217 (6), 11.1812 (7), 11.2298 (8)
α, β, γ (°)	95.680 (1), 105.192 (1), 106.938 (1)
V (Å³)	1095.03 (12)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.76
Crystal size (mm)	0.30 × 0.15 × 0.15

Data collection
Diffractometer	Bruker SMART APEX
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003a)
T_min, T_max	0.870, 0.890
No. of measured, independent and observed [I > 2σ(I)] reflections	8928, 3871, 2999
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.134, 1.02
No. of reflections	3871
No. of parameters	215
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.82, −0.28

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAIN(Bruker, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2003b).

Acknowledgements

We express our gratitude to the National Science Foundation for their contribution toward the purchase of the single-crystal instrumentation used in this study through Award No. CHE-9808440.

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