Tris(dimethyl­amido)bis­(dimethyl­amine)­titanium(IV) chlorido­bis(dimethyl­amine)[tris(penta­fluoro­phen­yl)boron–amido][tris­(penta­fluoro­phen­yl)boron–nitrido]­titanate(IV) toluene solvate

The title ionic solid, [Ti(C₂H₆N)₃(C₂H₇N)₂][Ti(C₁₈BF₁₅N)(C₁₈H₂BF₁₅N)Cl(C₂H₇N)₂]·C₇H₈, (I), comprises a cation with three dimethyl­amide ligands in the equatorial plane and two dimethyl­amine ligands positioned axially in a trigonal–bipyramidal geometry about the central Ti^IV atom. The anion has a highly distorted octa­hedral structure. The two dimethyl­amine ligands are coordinated mutually trans. The chloride is trans to the tris­(penta­fluoro­phenyl)boron–amide, while the sixth coordination site is occupied by an ortho-F atom of the tris­(penta­fluoro­phenyl)boron–amide group in a trans disposition with respect to the tris­(penta­fluoro­phenyl)boron–nitride ligand. The most significant feature of the anion is the presence of an unprecedented terminal Ti[triple bond]N moiety [1.665 (2) Å], stabilized by coordination to B(C₆F₅)₃, with a Ti[triple bond]N—B angle of 169.50 (19)°.

S1. Comment

Reaction with ammonia is employed to promote the controlled chemical deposition of the technologically important metal nitride material [TiN] from tetrakis(dimethylamido)titanium. The species formed intially is believed to be [(NMe₂)₃Ti(NH₂)] and intermediates involving NH₂, NH and N ligands have been postulated (Dubois, 1994; Hoffman, 1994; Toth, 1971; Weiller, 1996). Interest in this process has driven a number of investigations into the course of reactions between Brønsted basic group 4 metal compounds and ammonia. Typically, they react with one or more of the weakly acidic N—H groups to give polynuclear products with bridging amide, imide and nitride ligands, even where sterically demanding ancillary ligands are employed (Abarca et al., 2000; Carmalt et al., 2000; Duan & Verkade, 1996; García-Castro et al., 2006; Gómez-Sal et al., 1995; Roesky et al., 1989).

Complexation of NH₃ with a strong Lewis acid profoundly moderates its reactivity, not only by preventing it from functioning as a Lewis base and providing steric protection, but also through polarization of the N—H bonds, rendering it more Brønsted acidic (Ronan & Gilje, 1971). Tris(pentafluorophenyl)borane has proven utility as a Lewis acidic activator for polymerization catalysts and in applications as diverse as organic synthesis and materials (Erker, 2005; Piers, 2005). The ammonia adduct of tris(pentafluorophenyl)borane was amongst the first derivatives reported (Massey et al., 1963; Massey & Park, 1964; Massey & Park, 1966), but prior to our investigations its chemistry has been largely neglected.

We have recently shown that H₃N·B(C₆F₅)₃, (I), reacts with strong Brønsted bases to give complexes of the tris(pentafluorophenyl)boratoamide (amidoborate) ligand, [NH₂{B(C₆F₅)₃}]^-. For example, the reaction between (I) and (NMe₂)₄Ti yields {NH₂B(C₆F₅)₃}(NMe₂)₃Ti, (II) (Mountford, Clegg et al., 2005; Mountford et al., 2007). During the course of these investigations, we attempted to repeat the preparation of complex (II), using what appears to have been a chloride-contaminated sample of `(NMe₂)₄Ti'. Cooling the resulting solution gave a low yield of yellow plate-like crystals of the title compound, (III) (Fig. 1), and a viscous colourless oil. The low yield and adhering oil precluded satisfactory characterization by spectroscopic or elemental analysis methods.

The structure of (III) consists of the ion pair [Ti(NMe₂)₃(NMe₂H)₂]⁺[TiCl{NB(C₆F₅)₃}{NH₂B(C₆F₅)₃}(NMe₂H)₂]^-. The geometry of the cation in (III) (Fig. 2) closely resembles that of the previously reported salt [Ti(NMe₂)₃(NC₅H₅)₂]⁺[BPh₄]^-, with the amide ligands arranged in the equatorial and the amine ligands in the axial positions of a trigonal bipyramid (Boisson et al., 1997). At 1.89 Å [range 1.879 (3)–1.899 (3) Å in (I)] and 1.87 Å, respectively, the average titanium amide bond lengths in the cations of (III) and Boisson's salt are very similar.

The anion in (III) has a highly distorted octahedral structure (Fig. 2). The most significant feature of the anion is the presence of a terminal Ti≡N moiety, stabilized by coordination to B(C₆F₅)₃. The triple bond was confirmed by the short Ti1—N4 bond length of 1.665 (2) Å and approximately linear [169.50 (19)°] Ti1—N4—B2 bond angle (comparable Ti—N bond lengths have been observed for imide complexes, for example in [Ti(salophen)(═ NCPh₃)], Ti═N = 1.686 (4) Å (Franceschi et al., 1999). The B2—N4 distance of 1.532 (4) Å is significantly shorter than those observed in the amidoborate ligands of (II) and (III) [1.605 (4) and 1.575 (4) Å, respectively] and in the amidodiborate anion (1.63 Å; Lancaster et al., 2002). Terminal nitrides, with or without borane stabilization, are unprecedented for titanium. However, there are related later transition metal complexes, for example [Re{NB(C₆F₅)₃}(PMePh₂)(S₂CNEt₂)₂] [1.548 (7) Å; Doerrer et al., 1998]. The two NMe₂H ligands are mutually trans, while the Cl is located opposite the amidoborate ligand. An ortho-F of the amidoborate ligand occupies the final coordination site trans to the nitridoborate ligand. The Ti—N3 bond length in the amidoborate ligand [2.189 (2) Å] is slightly longer in the octahedral complex (III) than in the tetrahedral complex (II), presumably as a result of steric factors (Mountford et al., 2007).

The most significant cation–anion interaction in (III) is a hydrogen bond between an amino H atom on the cation and the chloride ligand of the anion (Table 1). Solid-state structures of primary amine adducts of tris(pentafluorophenyl)boron and related amidoborate complexes, such as (II), normally exhibit a bifurcated hydrogen-bonding interaction in which one N—H interacts strongly with two ortho-F, while the second N—H has only a rather longer contact to a third o-F (Mountford, Clegg et al., 2005; Mountford et al., 2007) (Fig. 3a). A similar arrangement is not possible for the amidoborate ligand in the anion of (III) because of the restraint imposed by the donor interaction between an o-F and the Ti centre. Instead, each N—H is engaged in a short-to-medium length hydrogen-bonding interaction with one o-F atom (Fig. 3b).

Whilst complex (II) can be regarded as a B(C₆F₅)₃-stabilized [(NMe₂)Ti(NH₂)], the first intermediate in the stepwise ammonolysis of [(NMe₂)₄Ti], the formation of the [N≡B(C₆F₅)₃] ligand in compound (III) formally requires three consecutive ammonia deprotonation steps. Nitridoborate ligands have been reported for later transition metals, such as the rhenium example given above. However, this is the first instance in which an [N≡B(C₆F₅)₃] ligand has been prepared by a method other than complexation between a metal nitride and B(C₆F₅)₃.

All attempts to reproduce the synthesis of (III) in order to present a full spectroscopic characterization have been hampered by ignorance of the exact composition of the `titanium amide' sample employed. Clearly, there needs to be chloride present, and the product composition corresponds precisely to that expected for the reaction of a [(NMe₂)₄ Ti]:[(Cl)(NMe₂)₃Ti]:(H₃N·B(C₆F₅)₃) as a 1:1:2 reactant mixture. However, employing the conditions used to prepare (III) and these reactants resulted only in the formation of (II), while treating (I) with [(Cl)(NMe₂)₃Ti] gave no discernible reaction.

Despite our difficulties repeating its synthesis, we consider the structural characterization of (III) to be an extremely significant result, since it demonstrates that mononuclear titanium nitrides, stabilized by B(C₆F₅)₃, are accessible. We are currently exploring means to promote consecutive deprotonation of (I) as a general route to such compounds.

Related literature

For related literature, see: Abarca et al. (2000); Boisson et al. (1997); Carmalt et al. (2000); Doerrer et al. (1998); Duan & Verkade (1996); Dubois (1994); Erker (2005); Franceschi et al. (1999); Gómez-Sal, Martin, Mena & Yélamos (1995); García-Castro, Martín, Mena, Poblet & Yélamos (2006); Hoffman (1994); Lancaster et al. (2002); Massey & Park (1964, 1966); Massey et al. (1963); Mountford et al. (2007); Mountford, Clegg, Harrington, Humphrey & Lancaster (2005); Mountford, Lancaster, Coles, Horton, Hughes, Hursthouse & Light (2005); Piers (2005); Roesky et al. (1989); Ronan & Gilje (1971); Sluis & Spek (1990); Spek (2003); Toth (1971); Weiller (1996).

S2. Experimental

All manipulations were conducted using Schlenk-line techniques under a dry nitrogen atmosphere with anhydrous solvents, following procedures described in detail elsewhere (Mountford et al., 2007). H₃N·B(C₆F₅)₃, (I), was prepared according to the literature procedure (Mountford, Lancaster et al., 2005). (NMe₂)₄Ti (0.439 g, 2.0 mmol) was added to a suspension of (I) (1.036 g, 2.0 mmol) in light petroleum (15 ml) at 253 K. The mixture was warmed to 273 K and the reactants dissolved, affording a homogeneous yellow solution. Yellow plates of (III) and a viscous oil were isolated by filtration after cooling the solution to 248 K overnight.

S3. Refinement

All H atoms were positioned using geometric constraints and refined as riding on their parent C or N atoms, with C—H_arom, C—H_sp3 and N—H distances of 0.95, 0.98 and 0.92—0.93 Å, respectively, and with U_iso(H) = 1.2 or 1.5 times U_eq(parent). [Please check added text] A toluene solvent molecule was located with crystallographic disorder refined over two sites. A large amount of residual electron density was still left unaccounted for in the lattice and was presumed to be another toluene solvent molecule, but it was too disordered to refine a chemically sensible model. The program PLATON (Spek, 2003) determined a total solvent-accessible volume of 205.5 ų for this region, which is equivalent to a solvent toluene molecule. Therefore, the SQUEEZE (van der Sluis & Spek, 1990) function of PLATON was used to eliminate the contribution of the electron density in the solvent region from the intensity data. The PLATON suite was used to generate a new reflection file, which was used for the final refinement.

Computing details

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Version 1.05; Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures

	Fig. 1. A view of the cation in (III), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A view of the anion in (III), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. A comparison between the intramolecular hydrogen-bonding arrangement in neutral amidoborate complexes such as (II) and in the anion of (III).

Tris(dimethylamido)bis(dimethylamine)titanium(IV) chlorido[tris(pentafluorophenyl)boron–amido][tris(pentafluorophenyl)boron–nitrido]bis(dimethylamine)titanate(IV) toluene solvate

Crystal data

[Ti(C2H6N)3(C2H7N)2][Ti(C18BF15N)(C18H2BF15N)Cl(C2H7N)2]·C7H8	Z = 1
Mr = 3178.95	F(000) = 1603
Triclinic, P1	Dx = 1.587 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 12.8980 (12) Å	Cell parameters from 40926 reflections
b = 14.5217 (15) Å	θ = 2.9–27.5°
c = 19.470 (2) Å	µ = 0.41 mm^−1
α = 70.482 (9)°	T = 120 K
β = 78.890 (7)°	Plate, yellow
γ = 77.513 (9)°	0.30 × 0.14 × 0.02 mm
V = 3327.1 (6) Å^3

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	15240 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	10096 reflections with I > 2σ(I)
10cm confocal mirrors monochromator	Rint = 0.071
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.9°
φ and ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −18→18
Tmin = 0.888, Tmax = 0.992	l = −25→25
61684 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.144	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0608P)^2 + 1.5269P] where P = (Fo^2 + 2Fc^2)/3
15240 reflections	(Δ/σ)max = 0.015
902 parameters	Δρmax = 0.51 e Å^−3
0 restraints	Δρmin = −0.54 e Å^−3

Special details

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. A solvent molecule was found to be present in a lattice void, which was presumably toluene, however it was too disordered to refine a chemically sensible model. The SQUEEZE (van der Sluis & Spek, 1990) function of PLATON (Spek, 2003) was used to eliminate the contribution of the electron density in the solvent region from the intensity data. PLATON determined a total solvent area volume of 205.5 Å3, which is equivalent to a solvent toluene molecule. The PLATON suite was used to generate a new reflection file, which was used for the final refinement.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1S	1.0433 (4)	0.5394 (4)	1.0426 (3)	0.0823 (15)
H1S	1.0715	0.5669	1.0715	0.099*
C2S	0.9657 (4)	0.5965 (4)	0.9990 (3)	0.0816 (15)
C3S	0.9210 (4)	0.5558 (4)	0.9561 (3)	0.0849 (15)
H3S	0.8668	0.5952	0.9269	0.102*
C4S	0.9235 (8)	0.6903 (7)	1.0042 (6)	0.082 (3)	0.50
H4S1	0.9574	0.7028	1.0405	0.123*	0.50
H4S2	0.8461	0.6950	1.0197	0.123*	0.50
H4S3	0.9373	0.7395	0.9562	0.123*	0.50
C1	0.5736 (2)	0.7990 (2)	0.21610 (18)	0.0371 (7)
H1A	0.5986	0.7274	0.2322	0.056*
H1B	0.5690	0.8255	0.2569	0.056*
H1C	0.6241	0.8308	0.1750	0.056*
C2	0.4775 (2)	0.7922 (2)	0.12369 (16)	0.0350 (7)
H2A	0.5305	0.8274	0.0868	0.052*
H2B	0.4082	0.8108	0.1049	0.052*
H2C	0.5011	0.7206	0.1341	0.052*
C3	0.2826 (3)	0.6187 (3)	0.44535 (17)	0.0438 (8)
H3A	0.2905	0.6659	0.4693	0.066*
H3B	0.3531	0.5817	0.4334	0.066*
H3C	0.2362	0.5726	0.4786	0.066*
C4	0.1254 (2)	0.7228 (2)	0.39546 (16)	0.0339 (7)
H4A	0.0846	0.6749	0.4326	0.051*
H4B	0.0897	0.7508	0.3511	0.051*
H4C	0.1293	0.7761	0.4148	0.051*
C5	0.4491 (2)	0.9048 (2)	0.37332 (14)	0.0249 (6)
C6	0.4852 (2)	0.8042 (2)	0.39633 (15)	0.0257 (6)
C7	0.5616 (2)	0.7571 (2)	0.44294 (15)	0.0278 (6)
C8	0.6067 (2)	0.8124 (2)	0.46944 (15)	0.0304 (6)
C9	0.5778 (2)	0.9135 (2)	0.44730 (16)	0.0314 (7)
C10	0.5009 (2)	0.9567 (2)	0.40094 (15)	0.0290 (6)
C11	0.3884 (2)	1.0390 (2)	0.24356 (15)	0.0300 (6)
C12	0.4919 (2)	1.0514 (2)	0.21148 (16)	0.0344 (7)
C13	0.5172 (3)	1.1165 (2)	0.14207 (18)	0.0424 (8)
C14	0.4377 (3)	1.1740 (2)	0.10256 (18)	0.0469 (9)
C15	0.3337 (3)	1.1650 (2)	0.13151 (19)	0.0469 (8)
C16	0.3114 (2)	1.0984 (2)	0.19963 (17)	0.0359 (7)
C17	0.2662 (2)	1.0240 (2)	0.37842 (16)	0.0278 (6)
C18	0.2144 (2)	0.9705 (2)	0.44372 (16)	0.0281 (6)
C19	0.1421 (2)	1.0116 (2)	0.49198 (16)	0.0319 (7)
C20	0.1190 (2)	1.1131 (2)	0.47514 (17)	0.0360 (7)
C21	0.1687 (2)	1.1702 (2)	0.41168 (18)	0.0341 (7)
C22	0.2411 (2)	1.1258 (2)	0.36597 (16)	0.0312 (6)
C23	0.1767 (2)	0.8746 (2)	0.08831 (14)	0.0255 (6)
C24	0.2293 (2)	0.9541 (2)	0.07216 (16)	0.0314 (6)
C25	0.2318 (2)	1.0292 (2)	0.00521 (17)	0.0396 (8)
C26	0.1773 (3)	1.0273 (3)	−0.04746 (16)	0.0439 (8)
C27	0.1205 (2)	0.9522 (2)	−0.03415 (16)	0.0374 (7)
C28	0.1210 (2)	0.8796 (2)	0.03248 (15)	0.0292 (6)
C29	0.2158 (2)	0.6722 (2)	0.15060 (14)	0.0252 (6)
C30	0.2053 (2)	0.5858 (2)	0.20794 (15)	0.0295 (6)
C31	0.2507 (3)	0.4915 (2)	0.20565 (18)	0.0390 (7)
C32	0.3124 (3)	0.4799 (2)	0.1421 (2)	0.0454 (8)
C33	0.3270 (3)	0.5623 (3)	0.08340 (17)	0.0400 (8)
C34	0.2791 (2)	0.6547 (2)	0.08865 (15)	0.0315 (6)
C35	0.0477 (2)	0.79652 (19)	0.20460 (14)	0.0234 (6)
C36	0.0125 (2)	0.8748 (2)	0.23366 (14)	0.0260 (6)
C37	−0.0869 (2)	0.8915 (2)	0.27289 (16)	0.0336 (7)
C38	−0.1584 (2)	0.8300 (2)	0.28341 (16)	0.0347 (7)
C39	−0.1298 (2)	0.7531 (2)	0.25378 (17)	0.0355 (7)
C40	−0.0296 (2)	0.7388 (2)	0.21490 (15)	0.0288 (6)
B1	0.3495 (2)	0.9636 (2)	0.32470 (18)	0.0265 (7)
B2	0.1727 (2)	0.7807 (2)	0.16516 (16)	0.0234 (6)
N1	0.46630 (17)	0.81909 (17)	0.19214 (12)	0.0275 (5)
H1	0.4455	0.8875	0.1790	0.033*
N2	0.23427 (18)	0.67294 (17)	0.37724 (12)	0.0264 (5)
H2	0.2212	0.6219	0.3630	0.032*
N3	0.28916 (17)	0.88953 (16)	0.31060 (12)	0.0256 (5)
H3D	0.2443	0.9304	0.2773	0.031*
H3E	0.2450	0.8695	0.3541	0.031*
N4	0.24698 (17)	0.77900 (15)	0.21834 (11)	0.0226 (5)
F1	0.44518 (12)	0.74160 (11)	0.37199 (9)	0.0313 (4)
F2	0.59174 (13)	0.65852 (12)	0.46095 (9)	0.0368 (4)
F3	0.68162 (15)	0.76959 (14)	0.51453 (11)	0.0467 (5)
F4	0.62521 (14)	0.96983 (14)	0.47061 (10)	0.0407 (4)
F5	0.47678 (13)	1.05655 (12)	0.38040 (9)	0.0341 (4)
F6	0.57656 (13)	1.00025 (13)	0.24718 (10)	0.0404 (4)
F7	0.62020 (17)	1.12314 (16)	0.11535 (11)	0.0588 (6)
F8	0.4603 (2)	1.23814 (16)	0.03608 (11)	0.0682 (7)
F9	0.2536 (2)	1.22192 (16)	0.09361 (12)	0.0687 (6)
F10	0.20662 (14)	1.09429 (13)	0.22467 (10)	0.0441 (4)
F11	0.23473 (13)	0.86945 (12)	0.46519 (9)	0.0330 (4)
F12	0.09470 (14)	0.95387 (14)	0.55430 (9)	0.0428 (4)
F13	0.04848 (15)	1.15472 (15)	0.52125 (11)	0.0528 (5)
F14	0.14781 (15)	1.26889 (13)	0.39559 (11)	0.0462 (5)
F15	0.28897 (14)	1.18870 (12)	0.30627 (10)	0.0412 (4)
F16	0.28432 (13)	0.96369 (12)	0.12136 (9)	0.0364 (4)
F17	0.28782 (16)	1.10247 (14)	−0.00681 (11)	0.0566 (6)
F18	0.18071 (17)	1.09869 (16)	−0.11268 (10)	0.0626 (6)
F19	0.06708 (16)	0.94981 (15)	−0.08616 (9)	0.0501 (5)
F20	0.06440 (13)	0.80680 (13)	0.04277 (9)	0.0369 (4)
F21	0.14980 (13)	0.59054 (12)	0.27385 (8)	0.0321 (4)
F22	0.23699 (18)	0.41238 (13)	0.26458 (11)	0.0558 (5)
F23	0.35842 (19)	0.38901 (15)	0.13795 (13)	0.0653 (6)
F24	0.38841 (17)	0.55289 (16)	0.02119 (11)	0.0581 (6)
F25	0.30112 (14)	0.73129 (13)	0.02802 (9)	0.0384 (4)
F26	0.07870 (13)	0.93986 (12)	0.22514 (9)	0.0342 (4)
F27	−0.11317 (15)	0.96775 (14)	0.30101 (11)	0.0487 (5)
F28	−0.25541 (14)	0.84372 (16)	0.32185 (11)	0.0544 (5)
F29	−0.20064 (14)	0.69273 (15)	0.26257 (12)	0.0525 (5)
F30	−0.01077 (13)	0.66249 (13)	0.18649 (10)	0.0384 (4)
Ti1	0.33593 (4)	0.75584 (3)	0.27610 (3)	0.02212 (12)
Cl1	0.43082 (6)	0.59418 (5)	0.28083 (4)	0.03547 (18)
C41	0.5941 (3)	0.3603 (3)	0.39777 (19)	0.0584 (10)
H41A	0.6515	0.3157	0.4248	0.088*
H41B	0.5501	0.3214	0.3865	0.088*
H41C	0.5494	0.4000	0.4279	0.088*
C42	0.6879 (3)	0.4991 (3)	0.3450 (2)	0.0498 (9)
H42A	0.6327	0.5367	0.3720	0.075*
H42B	0.7165	0.5445	0.2988	0.075*
H42C	0.7459	0.4647	0.3749	0.075*
C43	0.7978 (3)	0.2859 (3)	0.1061 (2)	0.0558 (10)
H43A	0.8489	0.2641	0.0681	0.084*
H43B	0.7537	0.3490	0.0833	0.084*
H43C	0.7517	0.2359	0.1318	0.084*
C44	0.9333 (3)	0.2076 (3)	0.1868 (3)	0.0690 (12)
H44A	0.8946	0.1513	0.2088	0.103*
H44B	0.9696	0.2152	0.2239	0.103*
H44C	0.9864	0.1959	0.1459	0.103*
C45	0.8892 (3)	0.2855 (3)	0.3609 (2)	0.0607 (11)
H45A	0.9504	0.2333	0.3569	0.091*
H45B	0.8252	0.2555	0.3849	0.091*
H45C	0.9042	0.3234	0.3901	0.091*
C46	0.9641 (3)	0.3995 (3)	0.2517 (2)	0.0598 (10)
H46A	0.9749	0.4410	0.2795	0.090*
H46B	0.9522	0.4408	0.2016	0.090*
H46C	1.0278	0.3490	0.2498	0.090*
C47	0.6033 (4)	0.4941 (3)	0.1372 (3)	0.0743 (13)
H47A	0.5499	0.5426	0.1555	0.112*
H47B	0.5748	0.4324	0.1497	0.112*
H47C	0.6199	0.5205	0.0837	0.112*
C48	0.7524 (4)	0.5611 (4)	0.1417 (3)	0.105 (2)
H48A	0.7758	0.5727	0.0890	0.157*
H48B	0.8148	0.5500	0.1671	0.157*
H48C	0.7023	0.6191	0.1494	0.157*
C49	0.5575 (4)	0.2641 (4)	0.2630 (3)	0.0904 (17)
H49A	0.5555	0.2265	0.2299	0.136*
H49B	0.5288	0.3340	0.2408	0.136*
H49C	0.5139	0.2379	0.3100	0.136*
C50	0.7039 (4)	0.1572 (3)	0.3239 (3)	0.0921 (18)
H50A	0.6573	0.1461	0.3710	0.138*
H50B	0.7778	0.1525	0.3320	0.138*
H50C	0.7007	0.1069	0.3014	0.138*
N5	0.6409 (2)	0.42623 (19)	0.32905 (13)	0.0349 (6)
H5	0.5823	0.4633	0.3055	0.042*
N6	0.8566 (2)	0.2989 (2)	0.15901 (16)	0.0427 (7)
H6	0.8981	0.3474	0.1320	0.051*
N7	0.8710 (2)	0.3514 (2)	0.28771 (15)	0.0395 (6)
N8	0.6997 (2)	0.4748 (2)	0.17068 (14)	0.0432 (7)
N9	0.6684 (2)	0.2548 (2)	0.27531 (17)	0.0465 (7)
Ti2	0.74757 (4)	0.35932 (4)	0.24507 (3)	0.03081 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1S	0.062 (3)	0.104 (4)	0.080 (3)	−0.016 (3)	0.016 (3)	−0.038 (3)
C2S	0.077 (3)	0.081 (4)	0.086 (3)	−0.025 (3)	0.030 (3)	−0.040 (3)
C3S	0.071 (3)	0.104 (4)	0.081 (3)	−0.022 (3)	0.017 (3)	−0.040 (3)
C4S	0.078 (6)	0.073 (7)	0.086 (7)	−0.029 (5)	−0.023 (5)	0.005 (5)
C1	0.0223 (15)	0.048 (2)	0.0428 (18)	−0.0064 (13)	0.0000 (13)	−0.0179 (15)
C2	0.0291 (15)	0.0481 (19)	0.0288 (15)	−0.0070 (13)	0.0013 (12)	−0.0154 (14)
C3	0.050 (2)	0.047 (2)	0.0286 (16)	−0.0176 (16)	−0.0076 (14)	0.0033 (14)
C4	0.0363 (16)	0.0297 (16)	0.0336 (16)	−0.0101 (13)	0.0034 (13)	−0.0083 (13)
C5	0.0196 (13)	0.0295 (15)	0.0275 (14)	−0.0068 (11)	0.0010 (11)	−0.0117 (12)
C6	0.0251 (14)	0.0272 (15)	0.0299 (14)	−0.0088 (11)	0.0010 (11)	−0.0150 (12)
C7	0.0248 (14)	0.0270 (16)	0.0313 (15)	−0.0020 (11)	−0.0006 (12)	−0.0114 (12)
C8	0.0236 (14)	0.0386 (18)	0.0307 (15)	−0.0021 (12)	−0.0069 (12)	−0.0130 (13)
C9	0.0253 (15)	0.0421 (18)	0.0367 (16)	−0.0116 (13)	0.0007 (12)	−0.0239 (14)
C10	0.0284 (15)	0.0264 (16)	0.0327 (15)	−0.0067 (12)	0.0028 (12)	−0.0122 (12)
C11	0.0359 (16)	0.0254 (15)	0.0313 (15)	−0.0083 (12)	−0.0021 (12)	−0.0115 (12)
C12	0.0397 (17)	0.0300 (16)	0.0345 (16)	−0.0083 (13)	0.0018 (14)	−0.0132 (13)
C13	0.053 (2)	0.0361 (19)	0.0396 (18)	−0.0218 (16)	0.0117 (16)	−0.0146 (15)
C14	0.073 (3)	0.0303 (18)	0.0329 (17)	−0.0168 (17)	0.0042 (17)	−0.0049 (14)
C15	0.064 (2)	0.0309 (18)	0.0405 (19)	−0.0007 (16)	−0.0127 (17)	−0.0053 (15)
C16	0.0392 (17)	0.0308 (17)	0.0378 (17)	−0.0078 (13)	−0.0035 (14)	−0.0101 (13)
C17	0.0245 (14)	0.0268 (15)	0.0350 (15)	−0.0044 (11)	−0.0044 (12)	−0.0127 (12)
C18	0.0256 (14)	0.0254 (15)	0.0367 (16)	−0.0033 (11)	−0.0075 (12)	−0.0128 (12)
C19	0.0250 (14)	0.0387 (18)	0.0366 (16)	−0.0066 (13)	−0.0025 (12)	−0.0175 (13)
C20	0.0263 (15)	0.0419 (19)	0.0453 (18)	0.0028 (13)	−0.0049 (13)	−0.0257 (15)
C21	0.0296 (15)	0.0254 (16)	0.0505 (19)	0.0029 (12)	−0.0102 (14)	−0.0177 (14)
C22	0.0284 (15)	0.0288 (16)	0.0394 (16)	−0.0041 (12)	−0.0054 (13)	−0.0141 (13)
C23	0.0238 (14)	0.0256 (15)	0.0227 (13)	0.0017 (11)	−0.0004 (11)	−0.0066 (11)
C24	0.0283 (15)	0.0313 (16)	0.0301 (15)	−0.0004 (12)	−0.0045 (12)	−0.0059 (12)
C25	0.0349 (17)	0.0332 (18)	0.0360 (17)	−0.0049 (14)	0.0011 (14)	0.0050 (13)
C26	0.0452 (19)	0.0412 (19)	0.0237 (15)	0.0064 (15)	−0.0026 (14)	0.0089 (13)
C27	0.0318 (16)	0.047 (2)	0.0248 (15)	0.0116 (14)	−0.0038 (12)	−0.0104 (13)
C28	0.0280 (15)	0.0323 (16)	0.0235 (14)	0.0018 (12)	−0.0011 (11)	−0.0090 (12)
C29	0.0218 (13)	0.0301 (15)	0.0271 (14)	−0.0028 (11)	−0.0073 (11)	−0.0118 (12)
C30	0.0301 (15)	0.0315 (16)	0.0290 (15)	−0.0059 (12)	−0.0065 (12)	−0.0101 (12)
C31	0.0504 (19)	0.0222 (16)	0.0452 (19)	−0.0055 (14)	−0.0105 (15)	−0.0094 (14)
C32	0.053 (2)	0.0324 (18)	0.057 (2)	0.0081 (15)	−0.0192 (17)	−0.0248 (17)
C33	0.0377 (17)	0.048 (2)	0.0380 (17)	0.0087 (14)	−0.0059 (14)	−0.0278 (16)
C34	0.0307 (15)	0.0336 (17)	0.0299 (15)	0.0031 (12)	−0.0071 (12)	−0.0129 (13)
C35	0.0246 (14)	0.0228 (14)	0.0196 (13)	−0.0029 (11)	−0.0065 (10)	−0.0011 (10)
C36	0.0256 (14)	0.0253 (15)	0.0256 (14)	−0.0033 (11)	−0.0061 (11)	−0.0048 (11)
C37	0.0335 (16)	0.0339 (17)	0.0277 (15)	0.0088 (13)	−0.0049 (12)	−0.0104 (13)
C38	0.0187 (14)	0.0432 (19)	0.0271 (15)	0.0038 (12)	0.0031 (11)	0.0000 (13)
C39	0.0238 (15)	0.0363 (18)	0.0381 (17)	−0.0104 (13)	−0.0073 (12)	0.0045 (13)
C40	0.0272 (15)	0.0315 (16)	0.0268 (14)	−0.0047 (12)	−0.0063 (11)	−0.0065 (12)
B1	0.0259 (16)	0.0233 (16)	0.0310 (16)	−0.0047 (13)	−0.0039 (13)	−0.0086 (13)
B2	0.0240 (15)	0.0241 (16)	0.0208 (14)	−0.0041 (12)	−0.0011 (12)	−0.0060 (12)
N1	0.0218 (11)	0.0284 (13)	0.0313 (13)	−0.0035 (9)	0.0012 (10)	−0.0108 (10)
N2	0.0343 (13)	0.0235 (12)	0.0220 (11)	−0.0087 (10)	−0.0038 (10)	−0.0050 (9)
N3	0.0236 (11)	0.0254 (12)	0.0291 (12)	−0.0038 (9)	−0.0037 (9)	−0.0101 (10)
N4	0.0239 (11)	0.0185 (11)	0.0228 (11)	−0.0045 (9)	0.0011 (9)	−0.0048 (9)
F1	0.0333 (9)	0.0253 (9)	0.0393 (9)	−0.0049 (7)	−0.0123 (7)	−0.0110 (7)
F2	0.0354 (9)	0.0310 (10)	0.0439 (10)	0.0006 (7)	−0.0127 (8)	−0.0109 (8)
F3	0.0430 (11)	0.0510 (12)	0.0542 (12)	0.0021 (9)	−0.0248 (9)	−0.0224 (9)
F4	0.0363 (10)	0.0478 (11)	0.0503 (11)	−0.0111 (8)	−0.0100 (8)	−0.0262 (9)
F5	0.0320 (9)	0.0300 (9)	0.0464 (10)	−0.0093 (7)	−0.0038 (7)	−0.0175 (8)
F6	0.0306 (9)	0.0453 (11)	0.0441 (10)	−0.0113 (8)	0.0046 (8)	−0.0143 (8)
F7	0.0609 (13)	0.0648 (14)	0.0465 (11)	−0.0307 (11)	0.0179 (10)	−0.0127 (10)
F8	0.1053 (18)	0.0499 (13)	0.0370 (11)	−0.0254 (12)	0.0071 (12)	0.0020 (9)
F9	0.0851 (17)	0.0482 (13)	0.0540 (13)	0.0035 (12)	−0.0214 (12)	0.0065 (10)
F10	0.0380 (10)	0.0384 (10)	0.0500 (11)	−0.0015 (8)	−0.0128 (8)	−0.0051 (8)
F11	0.0381 (9)	0.0271 (9)	0.0347 (9)	−0.0081 (7)	−0.0013 (7)	−0.0108 (7)
F12	0.0389 (10)	0.0517 (12)	0.0374 (10)	−0.0101 (8)	0.0079 (8)	−0.0185 (9)
F13	0.0440 (11)	0.0558 (13)	0.0592 (12)	0.0065 (9)	0.0060 (9)	−0.0348 (10)
F14	0.0500 (11)	0.0266 (10)	0.0627 (12)	0.0066 (8)	−0.0106 (9)	−0.0206 (9)
F15	0.0487 (11)	0.0228 (9)	0.0489 (11)	−0.0094 (8)	0.0022 (9)	−0.0092 (8)
F16	0.0392 (10)	0.0283 (9)	0.0383 (9)	−0.0114 (7)	−0.0087 (8)	0.0000 (7)
F17	0.0577 (13)	0.0404 (11)	0.0535 (12)	−0.0204 (10)	−0.0052 (10)	0.0160 (9)
F18	0.0643 (14)	0.0600 (14)	0.0336 (10)	−0.0015 (11)	−0.0043 (10)	0.0181 (9)
F19	0.0537 (12)	0.0615 (13)	0.0277 (9)	0.0110 (10)	−0.0167 (8)	−0.0106 (9)
F20	0.0369 (9)	0.0433 (11)	0.0323 (9)	−0.0028 (8)	−0.0101 (7)	−0.0133 (8)
F21	0.0383 (9)	0.0292 (9)	0.0267 (8)	−0.0088 (7)	−0.0016 (7)	−0.0051 (7)
F22	0.0773 (15)	0.0240 (10)	0.0590 (13)	−0.0057 (9)	−0.0106 (11)	−0.0040 (9)
F23	0.0833 (16)	0.0368 (12)	0.0802 (15)	0.0149 (11)	−0.0176 (13)	−0.0350 (11)
F24	0.0602 (13)	0.0650 (14)	0.0467 (12)	0.0175 (10)	−0.0028 (10)	−0.0338 (10)
F25	0.0400 (10)	0.0423 (10)	0.0250 (8)	0.0026 (8)	0.0013 (7)	−0.0090 (7)
F26	0.0326 (9)	0.0274 (9)	0.0454 (10)	−0.0034 (7)	−0.0050 (8)	−0.0159 (8)
F27	0.0444 (11)	0.0456 (11)	0.0528 (12)	0.0110 (9)	−0.0001 (9)	−0.0257 (9)
F28	0.0262 (9)	0.0672 (14)	0.0493 (12)	0.0028 (9)	0.0111 (8)	−0.0067 (10)
F29	0.0302 (10)	0.0530 (12)	0.0704 (13)	−0.0194 (9)	−0.0086 (9)	−0.0051 (10)
F30	0.0351 (9)	0.0384 (10)	0.0499 (11)	−0.0116 (8)	−0.0102 (8)	−0.0181 (8)
Ti1	0.0222 (2)	0.0208 (3)	0.0232 (2)	−0.00257 (19)	−0.00273 (19)	−0.00725 (19)
Cl1	0.0372 (4)	0.0272 (4)	0.0419 (4)	0.0046 (3)	−0.0109 (3)	−0.0134 (3)
C41	0.066 (2)	0.067 (3)	0.039 (2)	−0.022 (2)	0.0045 (18)	−0.0111 (18)
C42	0.059 (2)	0.045 (2)	0.054 (2)	−0.0073 (17)	−0.0068 (18)	−0.0262 (17)
C43	0.055 (2)	0.068 (3)	0.057 (2)	−0.0010 (19)	−0.0086 (18)	−0.039 (2)
C44	0.057 (2)	0.069 (3)	0.081 (3)	0.022 (2)	−0.018 (2)	−0.038 (2)
C45	0.047 (2)	0.070 (3)	0.053 (2)	−0.0136 (19)	−0.0178 (18)	0.006 (2)
C46	0.049 (2)	0.072 (3)	0.062 (2)	−0.028 (2)	−0.0100 (19)	−0.012 (2)
C47	0.083 (3)	0.066 (3)	0.083 (3)	0.024 (2)	−0.049 (3)	−0.036 (2)
C48	0.074 (3)	0.081 (4)	0.112 (4)	−0.018 (3)	−0.007 (3)	0.034 (3)
C49	0.079 (3)	0.098 (4)	0.105 (4)	−0.048 (3)	−0.040 (3)	−0.009 (3)
C50	0.054 (3)	0.036 (2)	0.172 (6)	−0.013 (2)	−0.017 (3)	−0.009 (3)
N5	0.0365 (14)	0.0350 (14)	0.0336 (13)	−0.0040 (11)	−0.0077 (11)	−0.0104 (11)
N6	0.0379 (15)	0.0402 (16)	0.0526 (17)	−0.0011 (12)	−0.0085 (13)	−0.0195 (13)
N7	0.0362 (14)	0.0417 (16)	0.0424 (15)	−0.0083 (12)	−0.0075 (12)	−0.0125 (12)
N8	0.0489 (17)	0.0415 (16)	0.0352 (14)	0.0032 (13)	−0.0090 (12)	−0.0112 (12)
N9	0.0396 (15)	0.0413 (17)	0.0639 (19)	−0.0141 (13)	−0.0023 (14)	−0.0205 (14)
Ti2	0.0301 (3)	0.0287 (3)	0.0359 (3)	−0.0039 (2)	−0.0081 (2)	−0.0113 (2)

Geometric parameters (Å, º)

C1S—C3S^i	1.351 (7)	C31—F22	1.340 (4)
C1S—C2S	1.381 (7)	C31—C32	1.376 (5)
C1S—H1S	0.9500	C32—F23	1.346 (4)
C2S—C4S	1.384 (11)	C32—C33	1.370 (5)
C2S—C3S	1.428 (7)	C33—F24	1.344 (4)
C3S—C1S^i	1.351 (7)	C33—C34	1.380 (4)
C3S—H3S	0.9500	C34—F25	1.357 (3)
C4S—H4S1	0.9800	C35—C40	1.381 (4)
C4S—H4S2	0.9800	C35—C36	1.387 (4)
C4S—H4S3	0.9800	C35—B2	1.650 (4)
C1—N1	1.484 (4)	C36—F26	1.356 (3)
C1—H1A	0.9800	C36—C37	1.378 (4)
C1—H1B	0.9800	C37—F27	1.346 (3)
C1—H1C	0.9800	C37—C38	1.361 (4)
C2—N1	1.483 (4)	C38—F28	1.341 (3)
C2—H2A	0.9800	C38—C39	1.374 (5)
C2—H2B	0.9800	C39—F29	1.349 (3)
C2—H2C	0.9800	C39—C40	1.377 (4)
C3—N2	1.475 (4)	C40—F30	1.354 (3)
C3—H3A	0.9800	B1—N3	1.575 (4)
C3—H3B	0.9800	B2—N4	1.532 (4)
C3—H3C	0.9800	N1—Ti1	2.224 (2)
C4—N2	1.471 (4)	N1—H1	0.9300
C4—H4A	0.9800	N2—Ti1	2.269 (2)
C4—H4B	0.9800	N2—H2	0.9300
C4—H4C	0.9800	N3—Ti1	2.189 (2)
C5—C6	1.378 (4)	N3—H3D	0.9200
C5—C10	1.390 (4)	N3—H3E	0.9200
C5—B1	1.652 (4)	N4—Ti1	1.665 (2)
C6—C7	1.379 (4)	F1—Ti1	2.4785 (16)
C6—F1	1.380 (3)	Ti1—Cl1	2.3820 (9)
C7—F2	1.342 (3)	C41—N5	1.467 (4)
C7—C8	1.358 (4)	C41—H41A	0.9800
C8—F3	1.339 (3)	C41—H41B	0.9800
C8—C9	1.373 (4)	C41—H41C	0.9800
C9—F4	1.348 (3)	C42—N5	1.467 (4)
C9—C10	1.375 (4)	C42—H42A	0.9800
C10—F5	1.350 (3)	C42—H42B	0.9800
C11—C12	1.382 (4)	C42—H42C	0.9800
C11—C16	1.388 (4)	C43—N6	1.471 (4)
C11—B1	1.650 (4)	C43—H43A	0.9800
C12—F6	1.351 (4)	C43—H43B	0.9800
C12—C13	1.391 (4)	C43—H43C	0.9800
C13—F7	1.342 (4)	C44—N6	1.479 (5)
C13—C14	1.359 (5)	C44—H44A	0.9800
C14—F8	1.340 (4)	C44—H44B	0.9800
C14—C15	1.368 (5)	C44—H44C	0.9800
C15—F9	1.346 (4)	C45—N7	1.456 (4)
C15—C16	1.376 (4)	C45—H45A	0.9800
C16—F10	1.352 (4)	C45—H45B	0.9800
C17—C18	1.379 (4)	C45—H45C	0.9800
C17—C22	1.390 (4)	C46—N7	1.461 (4)
C17—B1	1.670 (4)	C46—H46A	0.9800
C18—F11	1.365 (3)	C46—H46B	0.9800
C18—C19	1.380 (4)	C46—H46C	0.9800
C19—F12	1.344 (3)	C47—N8	1.447 (5)
C19—C20	1.376 (4)	C47—H47A	0.9800
C20—F13	1.344 (3)	C47—H47B	0.9800
C20—C21	1.366 (4)	C47—H47C	0.9800
C21—F14	1.338 (3)	C48—N8	1.450 (6)
C21—C22	1.373 (4)	C48—H48A	0.9800
C22—F15	1.350 (3)	C48—H48B	0.9800
C23—C24	1.381 (4)	C48—H48C	0.9800
C23—C28	1.388 (4)	C49—N9	1.467 (5)
C23—B2	1.655 (4)	C49—H49A	0.9800
C24—F16	1.354 (3)	C49—H49B	0.9800
C24—C25	1.393 (4)	C49—H49C	0.9800
C25—F17	1.344 (4)	C50—N9	1.450 (5)
C25—C26	1.361 (5)	C50—H50A	0.9800
C26—F18	1.345 (3)	C50—H50B	0.9800
C26—C27	1.370 (5)	C50—H50C	0.9800
C27—F19	1.343 (4)	N5—Ti2	2.264 (3)
C27—C28	1.372 (4)	N5—H5	0.9300
C28—F20	1.353 (3)	N6—Ti2	2.257 (3)
C29—C34	1.386 (4)	N6—H6	0.9300
C29—C30	1.385 (4)	N7—Ti2	1.899 (3)
C29—B2	1.653 (4)	N8—Ti2	1.888 (3)
C30—F21	1.360 (3)	N9—Ti2	1.879 (3)
C30—C31	1.380 (4)
C3S^i—C1S—C2S	119.8 (6)	C38—C39—C40	119.8 (3)
C3S^i—C1S—H1S	120.0	F30—C40—C39	114.9 (3)
C2S—C1S—H1S	120.1	F30—C40—C35	121.2 (2)
C1S—C2S—C4S	118.4 (7)	C39—C40—C35	123.9 (3)
C1S—C2S—C3S	120.8 (5)	N3—B1—C11	106.9 (2)
C4S—C2S—C3S	120.4 (7)	N3—B1—C5	111.8 (2)
C1S^i—C3S—C2S	119.3 (6)	C11—B1—C5	113.3 (2)
C1S^i—C3S—H3S	120.3	N3—B1—C17	108.8 (2)
C2S—C3S—H3S	120.3	C11—B1—C17	112.2 (2)
C2S—C4S—H4S1	109.5	C5—B1—C17	103.8 (2)
C2S—C4S—H4S2	109.5	N4—B2—C35	108.6 (2)
H4S1—C4S—H4S2	109.5	N4—B2—C29	102.2 (2)
C2S—C4S—H4S3	109.4	C35—B2—C29	115.1 (2)
H4S1—C4S—H4S3	109.5	N4—B2—C23	114.1 (2)
H4S2—C4S—H4S3	109.5	C35—B2—C23	104.5 (2)
N1—C1—H1A	109.5	C29—B2—C23	112.7 (2)
N1—C1—H1B	109.4	C2—N1—C1	108.8 (2)
H1A—C1—H1B	109.5	C2—N1—Ti1	112.76 (17)
N1—C1—H1C	109.4	C1—N1—Ti1	116.71 (18)
H1A—C1—H1C	109.5	C2—N1—H1	105.9
H1B—C1—H1C	109.5	C1—N1—H1	106.0
N1—C2—H2A	109.5	Ti1—N1—H1	105.9
N1—C2—H2B	109.4	C4—N2—C3	109.5 (2)
H2A—C2—H2B	109.5	C4—N2—Ti1	117.46 (17)
N1—C2—H2C	109.5	C3—N2—Ti1	119.61 (18)
H2A—C2—H2C	109.5	C4—N2—H2	102.3
H2B—C2—H2C	109.5	C3—N2—H2	102.3
N2—C3—H3A	109.4	Ti1—N2—H2	102.4
N2—C3—H3B	109.5	B1—N3—Ti1	135.93 (17)
H3A—C3—H3B	109.5	B1—N3—H3D	103.2
N2—C3—H3C	109.5	Ti1—N3—H3D	103.2
H3A—C3—H3C	109.5	B1—N3—H3E	103.2
H3B—C3—H3C	109.5	Ti1—N3—H3E	103.2
N2—C4—H4A	109.5	H3D—N3—H3E	105.2
N2—C4—H4B	109.5	B2—N4—Ti1	169.50 (19)
H4A—C4—H4B	109.5	C6—F1—Ti1	137.63 (15)
N2—C4—H4C	109.4	N4—Ti1—N3	99.60 (10)
H4A—C4—H4C	109.5	N4—Ti1—N1	96.50 (9)
H4B—C4—H4C	109.5	N3—Ti1—N1	92.24 (8)
C6—C5—C10	112.4 (3)	N4—Ti1—N2	95.92 (9)
C6—C5—B1	127.4 (2)	N3—Ti1—N2	90.09 (8)
C10—C5—B1	120.0 (2)	N1—Ti1—N2	166.79 (9)
C5—C6—C7	125.6 (3)	N4—Ti1—Cl1	104.88 (8)
C5—C6—F1	120.2 (2)	N3—Ti1—Cl1	155.19 (7)
C7—C6—F1	114.2 (2)	N1—Ti1—Cl1	88.97 (7)
F2—C7—C8	120.7 (3)	N2—Ti1—Cl1	83.53 (6)
F2—C7—C6	120.5 (2)	N4—Ti1—F1	169.90 (8)
C8—C7—C6	118.8 (3)	N3—Ti1—F1	71.18 (7)
F3—C8—C7	120.7 (3)	N1—Ti1—F1	88.15 (7)
F3—C8—C9	119.9 (3)	N2—Ti1—F1	80.31 (7)
C7—C8—C9	119.3 (3)	Cl1—Ti1—F1	84.11 (4)
F4—C9—C8	120.1 (3)	N5—C41—H41A	109.4
F4—C9—C10	120.5 (3)	N5—C41—H41B	109.5
C8—C9—C10	119.4 (3)	H41A—C41—H41B	109.5
F5—C10—C9	116.7 (2)	N5—C41—H41C	109.6
F5—C10—C5	118.8 (3)	H41A—C41—H41C	109.5
C9—C10—C5	124.4 (3)	H41B—C41—H41C	109.5
C12—C11—C16	113.3 (3)	N5—C42—H42A	109.5
C12—C11—B1	127.8 (3)	N5—C42—H42B	109.4
C16—C11—B1	118.9 (2)	H42A—C42—H42B	109.5
F6—C12—C11	121.0 (3)	N5—C42—H42C	109.5
F6—C12—C13	115.2 (3)	H42A—C42—H42C	109.5
C11—C12—C13	123.8 (3)	H42B—C42—H42C	109.5
F7—C13—C14	120.5 (3)	N6—C43—H43A	109.5
F7—C13—C12	119.5 (3)	N6—C43—H43B	109.5
C14—C13—C12	119.9 (3)	H43A—C43—H43B	109.5
F8—C14—C13	120.8 (3)	N6—C43—H43C	109.4
F8—C14—C15	120.2 (3)	H43A—C43—H43C	109.5
C13—C14—C15	118.9 (3)	H43B—C43—H43C	109.5
F9—C15—C14	119.9 (3)	N6—C44—H44A	109.5
F9—C15—C16	120.3 (3)	N6—C44—H44B	109.5
C14—C15—C16	119.8 (3)	H44A—C44—H44B	109.5
F10—C16—C15	116.3 (3)	N6—C44—H44C	109.5
F10—C16—C11	119.4 (3)	H44A—C44—H44C	109.5
C15—C16—C11	124.3 (3)	H44B—C44—H44C	109.5
C18—C17—C22	113.2 (3)	N7—C45—H45A	109.5
C18—C17—B1	119.2 (2)	N7—C45—H45B	109.4
C22—C17—B1	127.6 (3)	H45A—C45—H45B	109.5
F11—C18—C17	120.0 (2)	N7—C45—H45C	109.5
F11—C18—C19	115.2 (2)	H45A—C45—H45C	109.5
C17—C18—C19	124.7 (3)	H45B—C45—H45C	109.5
F12—C19—C20	120.3 (3)	N7—C46—H46A	109.5
F12—C19—C18	120.8 (3)	N7—C46—H46B	109.4
C20—C19—C18	118.9 (3)	H46A—C46—H46B	109.5
F13—C20—C21	121.0 (3)	N7—C46—H46C	109.5
F13—C20—C19	119.8 (3)	H46A—C46—H46C	109.5
C21—C20—C19	119.2 (3)	H46B—C46—H46C	109.5
F14—C21—C20	119.5 (3)	N8—C47—H47A	109.4
F14—C21—C22	120.8 (3)	N8—C47—H47B	109.4
C20—C21—C22	119.7 (3)	H47A—C47—H47B	109.5
F15—C22—C21	115.0 (3)	N8—C47—H47C	109.6
F15—C22—C17	120.8 (2)	H47A—C47—H47C	109.5
C21—C22—C17	124.2 (3)	H47B—C47—H47C	109.5
C24—C23—C28	113.2 (3)	N8—C48—H48A	109.6
C24—C23—B2	126.9 (2)	N8—C48—H48B	109.4
C28—C23—B2	119.8 (2)	H48A—C48—H48B	109.5
F16—C24—C23	121.5 (2)	N8—C48—H48C	109.4
F16—C24—C25	114.7 (3)	H48A—C48—H48C	109.5
C23—C24—C25	123.8 (3)	H48B—C48—H48C	109.5
F17—C25—C26	120.8 (3)	N9—C49—H49A	109.5
F17—C25—C24	120.0 (3)	N9—C49—H49B	109.3
C26—C25—C24	119.2 (3)	H49A—C49—H49B	109.5
F18—C26—C25	119.6 (3)	N9—C49—H49C	109.5
F18—C26—C27	120.4 (3)	H49A—C49—H49C	109.5
C25—C26—C27	120.0 (3)	H49B—C49—H49C	109.5
F19—C27—C26	120.1 (3)	N9—C50—H50A	109.5
F19—C27—C28	121.3 (3)	N9—C50—H50B	109.3
C26—C27—C28	118.6 (3)	H50A—C50—H50B	109.5
F20—C28—C27	116.3 (3)	N9—C50—H50C	109.6
F20—C28—C23	118.5 (2)	H50A—C50—H50C	109.5
C27—C28—C23	125.1 (3)	H50B—C50—H50C	109.5
C34—C29—C30	112.5 (3)	C41—N5—C42	109.9 (3)
C34—C29—B2	126.8 (2)	C41—N5—Ti2	119.0 (2)
C30—C29—B2	119.8 (2)	C42—N5—Ti2	113.08 (19)
F21—C30—C31	114.8 (3)	C41—N5—H5	104.3
F21—C30—C29	119.8 (2)	C42—N5—H5	104.5
C31—C30—C29	125.3 (3)	Ti2—N5—H5	104.4
F22—C31—C32	120.2 (3)	C43—N6—C44	109.6 (3)
F22—C31—C30	120.8 (3)	C43—N6—Ti2	112.8 (2)
C32—C31—C30	118.9 (3)	C44—N6—Ti2	116.1 (2)
F23—C32—C33	120.5 (3)	C43—N6—H6	105.8
F23—C32—C31	120.6 (3)	C44—N6—H6	105.9
C33—C32—C31	118.9 (3)	Ti2—N6—H6	105.9
F24—C33—C32	120.0 (3)	C45—N7—C46	110.5 (3)
F24—C33—C34	120.3 (3)	C45—N7—Ti2	122.5 (2)
C32—C33—C34	119.7 (3)	C46—N7—Ti2	126.7 (2)
F25—C34—C33	114.8 (3)	C47—N8—C48	109.5 (3)
F25—C34—C29	120.5 (3)	C47—N8—Ti2	126.3 (3)
C33—C34—C29	124.6 (3)	C48—N8—Ti2	124.1 (3)
C40—C35—C36	113.3 (2)	C50—N9—C49	110.6 (3)
C40—C35—B2	127.9 (2)	C50—N9—Ti2	123.6 (3)
C36—C35—B2	118.7 (2)	C49—N9—Ti2	125.1 (3)
F26—C36—C37	115.8 (2)	N9—Ti2—N8	117.83 (13)
F26—C36—C35	119.8 (2)	N9—Ti2—N7	121.89 (13)
C37—C36—C35	124.4 (3)	N8—Ti2—N7	120.27 (13)
F27—C37—C38	120.1 (3)	N9—Ti2—N6	92.60 (12)
F27—C37—C36	120.4 (3)	N8—Ti2—N6	89.90 (11)
C38—C37—C36	119.5 (3)	N7—Ti2—N6	88.08 (11)
F28—C38—C37	121.0 (3)	N9—Ti2—N5	89.80 (11)
F28—C38—C39	120.1 (3)	N8—Ti2—N5	88.45 (10)
C37—C38—C39	118.9 (3)	N7—Ti2—N5	91.16 (11)
F29—C39—C38	119.5 (3)	N6—Ti2—N5	177.53 (10)
F29—C39—C40	120.7 (3)

Symmetry code: (i) −x+2, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···F16	0.93	2.42	3.000 (3)	120
N2—H2···F21	0.93	2.32	3.113 (3)	143
N3—H3D···F10	0.92	2.24	2.961 (3)	135
N3—H3D···F26	0.92	2.50	3.277 (3)	143
N3—H3E···F11	0.92	2.14	2.885 (3)	137
N5—H5···Cl1	0.93	2.41	3.281 (3)	156
C1—H1B···F6	0.98	2.50	3.186 (4)	127
C2—H2B···F16	0.98	2.52	3.114 (3)	119
C42—H42B···F29^ii	0.98	2.44	3.224 (5)	136

Symmetry code: (ii) x+1, y, z.