[η⁵,σ-3,3-Di­methyl-1-(2,3,4,5-tetra­methyl­cyclo­penta­dienyl)­but-1-en-2-amino](η⁵-penta­methyl­cyclo­penta­dienyl)titanium

The titanocene complex [Ti(C₁₀H₁₅)(C₁₅H₂₃N)] features a penta­methyl­cyclo­penta­dienyl ligand and a substituted cyclo­penta­dienyl ligand Me₄C₅R, where R is an amino functional group which is subsequently attached to the titanium metal centre. The structure has been determined to ascertain the conformational properties of the side chain with regard to extended conjugation between the π systems and the nature of the amino interaction with the metal centre.

S1. Comment

Pentamethylcyclopentadienyl ligands (η⁵-C₅Me₅, Cp^*) are generally preferred to their cyclopentadiene analogues due to their electron richness, steric bulk and relative inertness. In turn one or more of the methyl substituents can be deprotonated to produce functionalized pendant arms which may react, or induce, other reactions at the metal, or additionally be bonded to form extended units.

The bent sandwich geometry of the title complex, (I), shown in Figure 1, is a titanocene complex featuring a pendant amino substituted pentamethylcyclopentadienyl group. The Cp^* and substituted cyclopentadienyl ligand form a staggered conformation about the Ti1 atom (viewed from above the functionalized Cp^* plane), with an acute angle between the ligands of 28.5 (5)°. The molecule possesses near crystallographic mirror symmetry through the nitrogen, metal and Cp^* ligands. The substituted Cp^* ring is unsymmetrical; there is a shorter Ti1—C1 distance of 2.312 (4) Å compared to the remaining carbon atoms in either Cp^* ligands attached to titanium [2.335 (4)–2.423 (4) Å for the functionalized Cp^*; 2.380 (4)–2.407 (4) Å for Cp^*]. A further measure of the ligand asymmetry is the ring slippage of the titanium atom relative to two Cp^* ligands; 0.13 (2) Å for the substituted ring, 0.02 (2) Å for the unsubstituted Cp^*. \sch

There is a distorted planar geometry around the titanium metal centre as shown by the angles between the centroids of the ring, titanium and nitrogen: Cg1—Ti1—Cg2 = 147.0 (5), Cg1—Ti1—N1 = 103.8 (5) and Cg2—Ti1—N1 = 109.1 (5)° [where Cg1 is the ring centroid of C1 to C5, Cg2 for C16 to C20]. These angles are in the range observed for other Cp^*₂TiL_n systems.

There is no Ti1···H1A interaction [2.47 (2) Å], since the distance exceeds the covalent radii of the relevant atoms; r_cov(Ti) = 1.47, r_cov(H) = 0.35 Å. There are no suitable N—H hydrogen bond acceptor atoms in the molecule.

The other interesting feature concerns the planar nature of the substituent at C1 of the tetramethylcyclopentadienyl ring. The hydrogen H10 on C10 and tert-butyl group at C11 are arranged in a cis configuration. The C1—C10 distance of 1.462 (5) Å has single bond characteristics whereas the inner carbon-carbon distance C10—C11 = 1.339 (6) Å is in accordance with a double bond. The nitrogen atom is near planar (Σangles = 358.8°) and connects to C11 via an intermediate length bond N1—C11 =1.393 (5) Å. This suggests a small or little delocalization of the ligand. The three atoms in the side chain, C10, C11 and N1, are all sp² hybridization as shown by their bond angles (being close to the expected 120°) and near zero torsion angles; Table 1. In this case the planarity of the pendant arm produces a more rigid group compared to those in previous studies of titanocene compounds (Beckhaus et al., 1997; Sinnema et al., 1997). The Ti1—N1 distance of 2.000 (3) Å is longer than those observed in simple titanocene amido complexes (Brady et al., 1995; Lukens et al., 1996), but is in the normal range for a Ti—N σ bond.

S2. Experimental

The complex was prepared by addition of t-C≡N (0.072 g, 0.87 mmol) to a pentane solution of [(η⁵-C₅Me₅)(Me₄C₅CH₂)Ti] (0.276 g, 0.87 mmol) at 193 K. The reaction mixture goes dark red and is warmed to room temperature. After 4 h the volatiles were removed, the residue extracted and slowly cooled to 243 K to give dark red crystals in 84% yield (Pattiasina, 1988).

S3. Refinement

All hydrogen atoms, with the exception of those on C10 and N1, were constrained and allowed to ride on their methyl carbon atoms with U_iso(H) = 1.5U_eq(C). H10 and H1A were located from a difference Fourier map and their coordinates allowed to refine with their isotropic displacement parameters constrained to U_iso(H) = 1.2U_eq(C or N); the dimensions refined to C10—H10 1.06 (4), N1—H1A 0.83 (5) Å.

Computing details

Data collection: Locally modified CAD-4 Software (Enraf-Nonius, 1989); cell refinement: SET4 (de Boer & Duisenberg, 1984); data reduction: HELENA (Spek, 1997); program(s) used to solve structure: DIRDIF96 (Beurskens et al., 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1999); software used to prepare material for publication: PLATON.

Figures

Fig. 1. Displacement ellipsoids plot (50% probability) of the complex with atom labels.

(I)

Crystal data

[Ti(C10H15)(C15H23N)]	F(000) = 1736
Mr = 400.46	Dx = 1.166 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9 reflections
a = 14.518 (9) Å	θ = 11.4–13.8°
b = 13.701 (7) Å	µ = 0.38 mm^−1
c = 23.924 (4) Å	T = 100 K
β = 106.59 (4)°	Block, brown
V = 4561 (4) Å^3	0.38 × 0.30 × 0.25 mm
Z = 8

Data collection

Enraf Nonius CAD-4F diffractometer	Rint = 0.059
Radiation source: rotating anode	θmax = 25.0°, θmin = 1.8°
Graphite monochromator	h = −17→17
ω/2θ scans	k = 0→16
4951 measured reflections	l = −28→6
4006 independent reflections	3 standard reflections every 60 min
2813 reflections with I > 2σ(I)	intensity decay: 4%

Refinement

Refinement on F^2	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.162	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0616P)^2 + 21.1265] where P = (Fo^2 + 2Fc^2)/3
4006 reflections	(Δ/σ)max = 0.001
262 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.55 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. 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 (Ų)

	x	y	z	Uiso*/Ueq
Ti1	0.22744 (5)	0.06096 (5)	0.13174 (3)	0.0116 (2)
N1	0.2565 (2)	−0.0178 (3)	0.06844 (15)	0.0143 (7)
H1A	0.267 (3)	−0.077 (3)	0.0758 (19)	0.017*
C19	0.1914 (3)	−0.0953 (3)	0.16305 (16)	0.0136 (8)
C16	0.2895 (3)	0.0073 (3)	0.23023 (16)	0.0126 (8)
C17	0.1933 (3)	0.0360 (3)	0.22343 (17)	0.0156 (9)
C11	0.2711 (3)	0.0192 (3)	0.01743 (17)	0.0149 (9)
C21	0.3770 (3)	0.0469 (3)	0.27424 (18)	0.0215 (9)
H21A	0.3594	0.1050	0.2927	0.032*
H21B	0.4255	0.0643	0.2547	0.032*
H21C	0.4031	−0.0028	0.3040	0.032*
C5	0.3103 (3)	0.1977 (3)	0.11321 (17)	0.0155 (9)
C18	0.1314 (3)	−0.0266 (3)	0.18047 (17)	0.0155 (9)
C2	0.1481 (3)	0.1813 (3)	0.06646 (18)	0.0168 (9)
C6	0.0562 (3)	0.1605 (3)	0.01976 (19)	0.0251 (10)
H6A	0.0057	0.1437	0.0379	0.038*
H6B	0.0661	0.1058	−0.0043	0.038*
H6C	0.0368	0.2185	−0.0048	0.038*
C20	0.2883 (3)	−0.0746 (3)	0.19294 (17)	0.0141 (8)
C25	0.3759 (3)	−0.1293 (3)	0.18913 (18)	0.0179 (9)
H25A	0.4010	−0.1684	0.2245	0.027*
H25B	0.4251	−0.0828	0.1854	0.027*
H25C	0.3588	−0.1724	0.1550	0.027*
C1	0.2420 (3)	0.1675 (3)	0.05978 (17)	0.0145 (8)
C10	0.2640 (3)	0.1164 (3)	0.01153 (18)	0.0161 (9)
H10	0.268 (3)	0.155 (3)	−0.0263 (19)	0.019*
C4	0.2580 (3)	0.2333 (3)	0.15124 (18)	0.0168 (9)
C3	0.1585 (3)	0.2230 (3)	0.12196 (18)	0.0177 (9)
C12	0.2905 (3)	−0.0515 (3)	−0.02726 (17)	0.0168 (9)
C22	0.1592 (3)	0.1068 (3)	0.26082 (19)	0.0212 (9)
H22A	0.1529	0.0734	0.2958	0.032*
H22B	0.0966	0.1333	0.2388	0.032*
H22C	0.2057	0.1602	0.2724	0.032*
C23	0.0243 (3)	−0.0278 (3)	0.16329 (19)	0.0222 (10)
H23A	−0.0004	−0.0468	0.1222	0.033*
H23B	0.0004	0.0373	0.1688	0.033*
H23C	0.0024	−0.0749	0.1876	0.033*
C14	0.2032 (3)	−0.1196 (3)	−0.04947 (19)	0.0218 (10)
H14A	0.1926	−0.1560	−0.0166	0.033*
H14B	0.2155	−0.1655	−0.0779	0.033*
H14C	0.1460	−0.0807	−0.0680	0.033*
C24	0.1547 (3)	−0.1810 (3)	0.12336 (18)	0.0179 (9)
H24A	0.2082	−0.2112	0.1124	0.027*
H24B	0.1062	−0.1585	0.0882	0.027*
H24C	0.1259	−0.2290	0.1437	0.027*
C15	0.3812 (3)	−0.1111 (3)	0.0012 (2)	0.0243 (10)
H15A	0.4357	−0.0669	0.0162	0.036*
H15B	0.3948	−0.1549	−0.0278	0.036*
H15C	0.3710	−0.1498	0.0334	0.036*
C7	0.0764 (3)	0.2612 (3)	0.14249 (19)	0.0256 (10)
H7A	0.0514	0.3213	0.1213	0.038*
H7B	0.0991	0.2751	0.1844	0.038*
H7C	0.0252	0.2122	0.1351	0.038*
C9	0.4171 (3)	0.1978 (3)	0.12392 (19)	0.0232 (10)
H9A	0.4372	0.2604	0.1114	0.035*
H9B	0.4354	0.1447	0.1018	0.035*
H9C	0.4486	0.1884	0.1656	0.035*
C13	0.3061 (4)	0.0035 (3)	−0.07978 (19)	0.0262 (10)
H13A	0.2495	0.0437	−0.0978	0.039*
H13B	0.3159	−0.0435	−0.1084	0.039*
H13C	0.3629	0.0455	−0.0667	0.039*
C8	0.3023 (3)	0.2856 (3)	0.20729 (19)	0.0253 (10)
H8A	0.3122	0.3543	0.1992	0.038*
H8B	0.3642	0.2555	0.2272	0.038*
H8C	0.2594	0.2813	0.2323	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ti1	0.0132 (4)	0.0093 (3)	0.0130 (4)	0.0005 (3)	0.0047 (3)	0.0005 (3)
N1	0.0220 (19)	0.0051 (16)	0.0179 (18)	−0.0004 (14)	0.0089 (15)	0.0024 (14)
C19	0.017 (2)	0.012 (2)	0.0124 (19)	−0.0005 (16)	0.0059 (16)	0.0016 (16)
C16	0.013 (2)	0.017 (2)	0.0076 (18)	−0.0011 (16)	0.0030 (15)	0.0045 (16)
C17	0.016 (2)	0.017 (2)	0.015 (2)	0.0014 (17)	0.0048 (16)	0.0050 (16)
C11	0.013 (2)	0.016 (2)	0.015 (2)	−0.0012 (16)	0.0035 (16)	0.0005 (17)
C21	0.019 (2)	0.025 (2)	0.020 (2)	−0.0009 (18)	0.0051 (17)	0.0002 (19)
C5	0.021 (2)	0.0073 (19)	0.019 (2)	0.0006 (16)	0.0077 (17)	0.0022 (16)
C18	0.016 (2)	0.017 (2)	0.016 (2)	−0.0002 (17)	0.0073 (17)	0.0041 (16)
C2	0.016 (2)	0.012 (2)	0.022 (2)	0.0037 (16)	0.0045 (17)	0.0028 (17)
C6	0.020 (2)	0.029 (3)	0.024 (2)	0.005 (2)	0.0020 (19)	0.005 (2)
C20	0.0118 (19)	0.016 (2)	0.0162 (19)	0.0035 (16)	0.0065 (16)	0.0069 (16)
C25	0.014 (2)	0.018 (2)	0.022 (2)	0.0018 (17)	0.0065 (18)	0.0041 (17)
C1	0.019 (2)	0.0053 (18)	0.020 (2)	0.0014 (16)	0.0063 (17)	0.0022 (16)
C10	0.017 (2)	0.013 (2)	0.018 (2)	0.0012 (17)	0.0061 (17)	0.0043 (17)
C4	0.023 (2)	0.007 (2)	0.020 (2)	0.0032 (16)	0.0054 (17)	0.0006 (16)
C3	0.020 (2)	0.010 (2)	0.024 (2)	0.0068 (17)	0.0086 (18)	0.0038 (17)
C12	0.019 (2)	0.014 (2)	0.019 (2)	0.0006 (17)	0.0072 (17)	−0.0014 (17)
C22	0.019 (2)	0.023 (2)	0.024 (2)	0.0019 (18)	0.0096 (19)	0.0000 (19)
C23	0.016 (2)	0.025 (2)	0.026 (2)	−0.0011 (18)	0.0064 (18)	−0.0020 (19)
C14	0.019 (2)	0.019 (2)	0.025 (2)	−0.0022 (18)	0.0021 (19)	−0.0076 (19)
C24	0.021 (2)	0.013 (2)	0.022 (2)	−0.0025 (17)	0.0093 (18)	0.0010 (17)
C15	0.020 (2)	0.025 (2)	0.031 (3)	0.0041 (19)	0.011 (2)	−0.003 (2)
C7	0.030 (3)	0.027 (2)	0.022 (2)	0.011 (2)	0.011 (2)	0.0005 (19)
C9	0.019 (2)	0.022 (2)	0.028 (2)	−0.0045 (19)	0.0067 (19)	0.0007 (19)
C13	0.039 (3)	0.025 (2)	0.018 (2)	0.000 (2)	0.014 (2)	−0.0036 (19)
C8	0.034 (3)	0.015 (2)	0.026 (2)	−0.0019 (19)	0.007 (2)	−0.0097 (19)

Geometric parameters (Å, º)

Ti1—N1	2.000 (3)	C25—H25B	0.9800
Ti1—C1	2.312 (4)	C25—H25C	0.9800
Ti1—C5	2.336 (4)	C1—C10	1.462 (6)
Ti1—C2	2.336 (4)	C10—H10	1.06 (4)
Ti1—C20	2.374 (4)	C4—C3	1.421 (6)
Ti1—C19	2.375 (4)	C4—C8	1.494 (6)
Ti1—C18	2.381 (4)	C3—C7	1.508 (6)
Ti1—C16	2.386 (4)	C12—C15	1.534 (6)
Ti1—C17	2.407 (4)	C12—C13	1.536 (6)
Ti1—C3	2.419 (4)	C12—C14	1.541 (6)
Ti1—C4	2.423 (4)	C22—H22A	0.9800
N1—C11	1.393 (5)	C22—H22B	0.9800
N1—H1A	0.83 (5)	C22—H22C	0.9800
C19—C20	1.413 (5)	C23—H23A	0.9800
C19—C18	1.423 (6)	C23—H23B	0.9800
C19—C24	1.509 (6)	C23—H23C	0.9800
C16—C17	1.414 (5)	C14—H14A	0.9800
C16—C20	1.430 (6)	C14—H14B	0.9800
C16—C21	1.501 (5)	C14—H14C	0.9800
C17—C18	1.439 (6)	C24—H24A	0.9800
C17—C22	1.497 (6)	C24—H24B	0.9800
C11—C10	1.339 (6)	C24—H24C	0.9800
C11—C12	1.527 (6)	C15—H15A	0.9800
C21—H21A	0.9800	C15—H15B	0.9800
C21—H21B	0.9800	C15—H15C	0.9800
C21—H21C	0.9800	C7—H7A	0.9800
C5—C4	1.426 (6)	C7—H7B	0.9800
C5—C1	1.437 (6)	C7—H7C	0.9800
C5—C9	1.498 (6)	C9—H9A	0.9800
C18—C23	1.491 (6)	C9—H9B	0.9800
C2—C3	1.413 (6)	C9—H9C	0.9800
C2—C1	1.429 (6)	C13—H13A	0.9800
C2—C6	1.503 (6)	C13—H13B	0.9800
C6—H6A	0.9800	C13—H13C	0.9800
C6—H6B	0.9800	C8—H8A	0.9800
C6—H6C	0.9800	C8—H8B	0.9800
C20—C25	1.501 (5)	C8—H8C	0.9800
C25—H25A	0.9800
N1—Ti1—C1	72.12 (14)	C2—C6—H6A	109.5
N1—Ti1—C5	93.31 (14)	C2—C6—H6B	109.5
C1—Ti1—C5	36.01 (14)	H6A—C6—H6B	109.5
N1—Ti1—C2	92.58 (14)	C2—C6—H6C	109.5
C1—Ti1—C2	35.82 (14)	H6A—C6—H6C	109.5
C5—Ti1—C2	59.30 (15)	H6B—C6—H6C	109.5
N1—Ti1—C20	85.59 (14)	C19—C20—C16	107.8 (3)
C1—Ti1—C20	148.88 (14)	C19—C20—C25	127.4 (4)
C5—Ti1—C20	128.57 (14)	C16—C20—C25	124.7 (4)
C2—Ti1—C20	171.97 (14)	C19—C20—Ti1	72.7 (2)
N1—Ti1—C19	82.28 (14)	C16—C20—Ti1	73.0 (2)
C1—Ti1—C19	151.51 (14)	C25—C20—Ti1	121.7 (3)
C5—Ti1—C19	162.63 (14)	C20—C25—H25A	109.5
C2—Ti1—C19	137.39 (15)	C20—C25—H25B	109.5
C20—Ti1—C19	34.62 (13)	H25A—C25—H25B	109.5
N1—Ti1—C18	112.24 (14)	C20—C25—H25C	109.5
C1—Ti1—C18	150.84 (14)	H25A—C25—H25C	109.5
C5—Ti1—C18	154.43 (14)	H25B—C25—H25C	109.5
C2—Ti1—C18	115.91 (15)	C2—C1—C5	107.5 (3)
C20—Ti1—C18	58.04 (14)	C2—C1—C10	125.6 (4)
C19—Ti1—C18	34.82 (13)	C5—C1—C10	126.1 (4)
N1—Ti1—C16	118.67 (14)	C2—C1—Ti1	73.0 (2)
C1—Ti1—C16	147.25 (14)	C5—C1—Ti1	72.9 (2)
C5—Ti1—C16	111.41 (14)	C10—C1—Ti1	111.9 (3)
C2—Ti1—C16	148.52 (14)	C11—C10—C1	114.9 (4)
C20—Ti1—C16	34.97 (13)	C11—C10—H10	124 (2)
C19—Ti1—C16	57.70 (14)	C1—C10—H10	121 (2)
C18—Ti1—C16	57.98 (14)	C3—C4—C5	107.6 (4)
N1—Ti1—C17	139.10 (14)	C3—C4—C8	127.3 (4)
C1—Ti1—C17	148.71 (14)	C5—C4—C8	124.5 (4)
C5—Ti1—C17	122.55 (14)	C3—C4—Ti1	72.8 (2)
C2—Ti1—C17	121.27 (14)	C5—C4—Ti1	69.2 (2)
C20—Ti1—C17	57.57 (13)	C8—C4—Ti1	130.4 (3)
C19—Ti1—C17	57.53 (13)	C2—C3—C4	108.9 (4)
C18—Ti1—C17	34.97 (14)	C2—C3—C7	124.3 (4)
C16—Ti1—C17	34.31 (13)	C4—C3—C7	126.3 (4)
N1—Ti1—C3	126.35 (14)	C2—C3—Ti1	69.5 (2)
C1—Ti1—C3	58.11 (14)	C4—C3—Ti1	73.1 (2)
C5—Ti1—C3	57.77 (14)	C7—C3—Ti1	129.1 (3)
C2—Ti1—C3	34.52 (14)	C11—C12—C15	109.5 (3)
C20—Ti1—C3	148.06 (14)	C11—C12—C13	111.2 (3)
C19—Ti1—C3	137.34 (14)	C15—C12—C13	108.4 (3)
C18—Ti1—C3	103.06 (14)	C11—C12—C14	109.1 (3)
C16—Ti1—C3	114.05 (14)	C15—C12—C14	110.3 (4)
C17—Ti1—C3	91.82 (14)	C13—C12—C14	108.3 (3)
N1—Ti1—C4	127.22 (14)	C17—C22—H22A	109.5
C1—Ti1—C4	58.51 (14)	C17—C22—H22B	109.5
C5—Ti1—C4	34.83 (14)	H22A—C22—H22B	109.5
C2—Ti1—C4	57.95 (14)	C17—C22—H22C	109.5
C20—Ti1—C4	128.91 (14)	H22A—C22—H22C	109.5
C19—Ti1—C4	149.57 (14)	H22B—C22—H22C	109.5
C18—Ti1—C4	119.83 (14)	C18—C23—H23A	109.5
C16—Ti1—C4	96.52 (14)	C18—C23—H23B	109.5
C17—Ti1—C4	92.14 (14)	H23A—C23—H23B	109.5
C3—Ti1—C4	34.14 (14)	C18—C23—H23C	109.5
C11—N1—Ti1	125.8 (3)	H23A—C23—H23C	109.5
C11—N1—H1A	118 (3)	H23B—C23—H23C	109.5
Ti1—N1—H1A	115 (3)	C12—C14—H14A	109.5
C20—C19—C18	108.9 (3)	C12—C14—H14B	109.5
C20—C19—C24	126.6 (4)	H14A—C14—H14B	109.5
C18—C19—C24	124.3 (4)	C12—C14—H14C	109.5
C20—C19—Ti1	72.6 (2)	H14A—C14—H14C	109.5
C18—C19—Ti1	72.8 (2)	H14B—C14—H14C	109.5
C24—C19—Ti1	125.0 (3)	C19—C24—H24A	109.5
C17—C16—C20	108.1 (3)	C19—C24—H24B	109.5
C17—C16—C21	126.2 (4)	H24A—C24—H24B	109.5
C20—C16—C21	125.3 (4)	C19—C24—H24C	109.5
C17—C16—Ti1	73.7 (2)	H24A—C24—H24C	109.5
C20—C16—Ti1	72.1 (2)	H24B—C24—H24C	109.5
C21—C16—Ti1	125.9 (3)	C12—C15—H15A	109.5
C16—C17—C18	108.1 (3)	C12—C15—H15B	109.5
C16—C17—C22	126.6 (4)	H15A—C15—H15B	109.5
C18—C17—C22	124.5 (4)	C12—C15—H15C	109.5
C16—C17—Ti1	72.0 (2)	H15A—C15—H15C	109.5
C18—C17—Ti1	71.5 (2)	H15B—C15—H15C	109.5
C22—C17—Ti1	129.9 (3)	C3—C7—H7A	109.5
C10—C11—N1	115.3 (4)	C3—C7—H7B	109.5
C10—C11—C12	125.5 (4)	H7A—C7—H7B	109.5
N1—C11—C12	119.2 (4)	C3—C7—H7C	109.5
C16—C21—H21A	109.5	H7A—C7—H7C	109.5
C16—C21—H21B	109.5	H7B—C7—H7C	109.5
H21A—C21—H21B	109.5	C5—C9—H9A	109.5
C16—C21—H21C	109.5	C5—C9—H9B	109.5
H21A—C21—H21C	109.5	H9A—C9—H9B	109.5
H21B—C21—H21C	109.5	C5—C9—H9C	109.5
C4—C5—C1	108.0 (4)	H9A—C9—H9C	109.5
C4—C5—C9	127.1 (4)	H9B—C9—H9C	109.5
C1—C5—C9	124.8 (4)	C12—C13—H13A	109.5
C4—C5—Ti1	75.9 (2)	C12—C13—H13B	109.5
C1—C5—Ti1	71.1 (2)	H13A—C13—H13B	109.5
C9—C5—Ti1	122.2 (3)	C12—C13—H13C	109.5
C19—C18—C17	107.1 (3)	H13A—C13—H13C	109.5
C19—C18—C23	126.1 (4)	H13B—C13—H13C	109.5
C17—C18—C23	126.4 (4)	C4—C8—H8A	109.5
C19—C18—Ti1	72.4 (2)	C4—C8—H8B	109.5
C17—C18—Ti1	73.5 (2)	H8A—C8—H8B	109.5
C23—C18—Ti1	125.6 (3)	C4—C8—H8C	109.5
C3—C2—C1	108.0 (4)	H8A—C8—H8C	109.5
C3—C2—C6	127.5 (4)	H8B—C8—H8C	109.5
C1—C2—C6	124.4 (4)	Cg1—Ti1—Cg2	147.0
C3—C2—Ti1	75.9 (2)	Cg1—Ti1—N1	103.8
C1—C2—Ti1	71.2 (2)	Cg2—Ti1—N1	109.1
C6—C2—Ti1	121.8 (3)
C1—Ti1—N1—C11	0.5 (3)	C3—Ti1—C2—C1	114.9 (3)
C5—Ti1—N1—C11	−29.1 (3)	C4—Ti1—C2—C1	79.3 (2)
C2—Ti1—N1—C11	30.3 (3)	N1—Ti1—C2—C6	65.3 (3)
C20—Ti1—N1—C11	−157.5 (3)	C1—Ti1—C2—C6	119.4 (4)
C19—Ti1—N1—C11	167.8 (3)	C5—Ti1—C2—C6	157.6 (4)
C18—Ti1—N1—C11	149.7 (3)	C20—Ti1—C2—C6	−11.3 (12)
C16—Ti1—N1—C11	−145.7 (3)	C19—Ti1—C2—C6	−16.1 (4)
C17—Ti1—N1—C11	178.0 (3)	C18—Ti1—C2—C6	−51.0 (4)
C3—Ti1—N1—C11	22.6 (4)	C16—Ti1—C2—C6	−121.4 (3)
C4—Ti1—N1—C11	−20.4 (4)	C17—Ti1—C2—C6	−90.5 (3)
N1—Ti1—C19—C20	93.4 (2)	C3—Ti1—C2—C6	−125.7 (4)
C1—Ti1—C19—C20	119.3 (3)	C4—Ti1—C2—C6	−161.3 (4)
C5—Ti1—C19—C20	17.2 (6)	C18—C19—C20—C16	0.8 (4)
C2—Ti1—C19—C20	178.8 (2)	C24—C19—C20—C16	−173.9 (4)
C18—Ti1—C19—C20	−116.8 (3)	Ti1—C19—C20—C16	65.0 (3)
C16—Ti1—C19—C20	−37.7 (2)	C18—C19—C20—C25	178.6 (4)
C17—Ti1—C19—C20	−78.6 (2)	C24—C19—C20—C25	4.0 (6)
C3—Ti1—C19—C20	−129.2 (3)	Ti1—C19—C20—C25	−117.1 (4)
C4—Ti1—C19—C20	−73.5 (3)	C18—C19—C20—Ti1	−64.3 (3)
N1—Ti1—C19—C18	−149.8 (2)	C24—C19—C20—Ti1	121.1 (4)
C1—Ti1—C19—C18	−123.8 (3)	C17—C16—C20—C19	0.5 (4)
C5—Ti1—C19—C18	134.0 (4)	C21—C16—C20—C19	173.4 (4)
C2—Ti1—C19—C18	−64.4 (3)	Ti1—C16—C20—C19	−64.9 (3)
C20—Ti1—C19—C18	116.8 (3)	C17—C16—C20—C25	−177.5 (3)
C16—Ti1—C19—C18	79.1 (2)	C21—C16—C20—C25	−4.6 (6)
C17—Ti1—C19—C18	38.2 (2)	Ti1—C16—C20—C25	117.2 (4)
C3—Ti1—C19—C18	−12.4 (3)	C17—C16—C20—Ti1	65.4 (3)
C4—Ti1—C19—C18	43.3 (4)	C21—C16—C20—Ti1	−121.7 (4)
N1—Ti1—C19—C24	−29.5 (3)	N1—Ti1—C20—C19	−82.8 (2)
C1—Ti1—C19—C24	−3.6 (5)	C1—Ti1—C20—C19	−126.4 (3)
C5—Ti1—C19—C24	−105.7 (5)	C5—Ti1—C20—C19	−173.5 (2)
C2—Ti1—C19—C24	55.9 (4)	C2—Ti1—C20—C19	−5.7 (11)
C20—Ti1—C19—C24	−122.9 (4)	C18—Ti1—C20—C19	36.9 (2)
C18—Ti1—C19—C24	120.3 (4)	C16—Ti1—C20—C19	115.5 (3)
C16—Ti1—C19—C24	−160.7 (4)	C17—Ti1—C20—C19	78.5 (2)
C17—Ti1—C19—C24	158.4 (4)	C3—Ti1—C20—C19	97.1 (3)
C3—Ti1—C19—C24	107.9 (3)	C4—Ti1—C20—C19	141.4 (2)
C4—Ti1—C19—C24	163.5 (3)	N1—Ti1—C20—C16	161.7 (2)
N1—Ti1—C16—C17	−136.6 (2)	C1—Ti1—C20—C16	118.1 (3)
C1—Ti1—C16—C17	121.6 (3)	C5—Ti1—C20—C16	71.0 (3)
C5—Ti1—C16—C17	116.8 (2)	C2—Ti1—C20—C16	−121.2 (10)
C2—Ti1—C16—C17	51.0 (4)	C19—Ti1—C20—C16	−115.5 (3)
C20—Ti1—C16—C17	−115.8 (3)	C18—Ti1—C20—C16	−78.6 (2)
C19—Ti1—C16—C17	−78.4 (2)	C17—Ti1—C20—C16	−37.0 (2)
C18—Ti1—C16—C17	−37.0 (2)	C3—Ti1—C20—C16	−18.4 (4)
C3—Ti1—C16—C17	53.7 (3)	C4—Ti1—C20—C16	25.9 (3)
C4—Ti1—C16—C17	84.2 (2)	N1—Ti1—C20—C25	41.0 (3)
N1—Ti1—C16—C20	−20.9 (3)	C1—Ti1—C20—C25	−2.7 (5)
C1—Ti1—C16—C20	−122.6 (3)	C5—Ti1—C20—C25	−49.7 (4)
C5—Ti1—C16—C20	−127.4 (2)	C2—Ti1—C20—C25	118.1 (10)
C2—Ti1—C16—C20	166.8 (3)	C19—Ti1—C20—C25	123.8 (4)
C19—Ti1—C16—C20	37.4 (2)	C18—Ti1—C20—C25	160.7 (4)
C18—Ti1—C16—C20	78.7 (2)	C16—Ti1—C20—C25	−120.7 (4)
C17—Ti1—C16—C20	115.8 (3)	C17—Ti1—C20—C25	−157.7 (4)
C3—Ti1—C16—C20	169.5 (2)	C3—Ti1—C20—C25	−139.1 (3)
C4—Ti1—C16—C20	−160.0 (2)	C4—Ti1—C20—C25	−94.8 (3)
N1—Ti1—C16—C21	100.2 (3)	C3—C2—C1—C5	2.4 (4)
C1—Ti1—C16—C21	−1.5 (5)	C6—C2—C1—C5	178.6 (4)
C5—Ti1—C16—C21	−6.4 (4)	Ti1—C2—C1—C5	−65.3 (3)
C2—Ti1—C16—C21	−72.2 (4)	C3—C2—C1—C10	172.7 (4)
C20—Ti1—C16—C21	121.0 (4)	C6—C2—C1—C10	−11.1 (7)
C19—Ti1—C16—C21	158.4 (4)	Ti1—C2—C1—C10	105.1 (4)
C18—Ti1—C16—C21	−160.2 (4)	C3—C2—C1—Ti1	67.6 (3)
C17—Ti1—C16—C21	−123.2 (4)	C6—C2—C1—Ti1	−116.2 (4)
C3—Ti1—C16—C21	−69.5 (4)	C4—C5—C1—C2	−2.2 (4)
C4—Ti1—C16—C21	−38.9 (3)	C9—C5—C1—C2	−178.1 (4)
C20—C16—C17—C18	−1.5 (4)	Ti1—C5—C1—C2	65.3 (3)
C21—C16—C17—C18	−174.3 (4)	C4—C5—C1—C10	−172.6 (4)
Ti1—C16—C17—C18	62.8 (3)	C9—C5—C1—C10	11.6 (6)
C20—C16—C17—C22	168.9 (4)	Ti1—C5—C1—C10	−105.0 (4)
C21—C16—C17—C22	−3.9 (6)	C4—C5—C1—Ti1	−67.6 (3)
Ti1—C16—C17—C22	−126.8 (4)	C9—C5—C1—Ti1	116.6 (4)
C20—C16—C17—Ti1	−64.3 (3)	N1—Ti1—C1—C2	121.8 (3)
C21—C16—C17—Ti1	122.9 (4)	C5—Ti1—C1—C2	−115.0 (3)
N1—Ti1—C17—C16	66.9 (3)	C20—Ti1—C1—C2	168.2 (3)
C1—Ti1—C17—C16	−117.5 (3)	C19—Ti1—C1—C2	94.8 (3)
C5—Ti1—C17—C16	−80.4 (3)	C18—Ti1—C1—C2	18.1 (4)
C2—Ti1—C17—C16	−151.7 (2)	C16—Ti1—C1—C2	−122.7 (3)
C20—Ti1—C17—C16	37.7 (2)	C17—Ti1—C1—C2	−55.1 (4)
C19—Ti1—C17—C16	79.0 (2)	C3—Ti1—C1—C2	−37.2 (2)
C18—Ti1—C17—C16	117.0 (3)	C4—Ti1—C1—C2	−77.6 (2)
C3—Ti1—C17—C16	−132.6 (2)	N1—Ti1—C1—C5	−123.2 (3)
C4—Ti1—C17—C16	−98.4 (2)	C2—Ti1—C1—C5	115.0 (3)
N1—Ti1—C17—C18	−50.0 (3)	C20—Ti1—C1—C5	−76.8 (3)
C1—Ti1—C17—C18	125.5 (3)	C19—Ti1—C1—C5	−150.2 (3)
C5—Ti1—C17—C18	162.6 (2)	C18—Ti1—C1—C5	133.1 (3)
C2—Ti1—C17—C18	91.4 (3)	C16—Ti1—C1—C5	−7.7 (4)
C20—Ti1—C17—C18	−79.3 (3)	C17—Ti1—C1—C5	59.9 (4)
C19—Ti1—C17—C18	−38.0 (2)	C3—Ti1—C1—C5	77.7 (2)
C16—Ti1—C17—C18	−117.0 (3)	C4—Ti1—C1—C5	37.4 (2)
C3—Ti1—C17—C18	110.4 (2)	N1—Ti1—C1—C10	−0.4 (3)
C4—Ti1—C17—C18	144.6 (2)	C5—Ti1—C1—C10	122.7 (4)
N1—Ti1—C17—C22	−170.0 (3)	C2—Ti1—C1—C10	−122.3 (4)
C1—Ti1—C17—C22	5.5 (5)	C20—Ti1—C1—C10	45.9 (4)
C5—Ti1—C17—C22	42.6 (4)	C19—Ti1—C1—C10	−27.5 (5)
C2—Ti1—C17—C22	−28.6 (4)	C18—Ti1—C1—C10	−104.2 (4)
C20—Ti1—C17—C22	160.7 (4)	C16—Ti1—C1—C10	115.1 (3)
C19—Ti1—C17—C22	−158.0 (4)	C17—Ti1—C1—C10	−177.4 (3)
C18—Ti1—C17—C22	−120.0 (5)	C3—Ti1—C1—C10	−159.5 (3)
C16—Ti1—C17—C22	123.0 (5)	C4—Ti1—C1—C10	160.1 (3)
C3—Ti1—C17—C22	−9.6 (4)	N1—C11—C10—C1	0.0 (6)
C4—Ti1—C17—C22	24.6 (4)	C12—C11—C10—C1	178.1 (3)
Ti1—N1—C11—C10	−0.4 (5)	C2—C1—C10—C11	−83.9 (5)
Ti1—N1—C11—C12	−178.7 (3)	C5—C1—C10—C11	84.7 (5)
N1—Ti1—C5—C4	167.9 (2)	Ti1—C1—C10—C11	0.4 (5)
C1—Ti1—C5—C4	115.0 (3)	C1—C5—C4—C3	1.3 (4)
C2—Ti1—C5—C4	76.9 (3)	C9—C5—C4—C3	177.0 (4)
C20—Ti1—C5—C4	−105.1 (3)	Ti1—C5—C4—C3	−63.1 (3)
C19—Ti1—C5—C4	−117.5 (5)	C1—C5—C4—C8	−170.1 (4)
C18—Ti1—C5—C4	−9.5 (4)	C9—C5—C4—C8	5.6 (7)
C16—Ti1—C5—C4	−69.5 (3)	Ti1—C5—C4—C8	125.5 (4)
C17—Ti1—C5—C4	−32.8 (3)	C1—C5—C4—Ti1	64.4 (3)
C3—Ti1—C5—C4	36.2 (2)	C9—C5—C4—Ti1	−119.9 (4)
N1—Ti1—C5—C1	52.9 (2)	N1—Ti1—C4—C3	101.9 (3)
C2—Ti1—C5—C1	−38.1 (2)	C1—Ti1—C4—C3	78.4 (3)
C20—Ti1—C5—C1	139.9 (2)	C5—Ti1—C4—C3	117.1 (3)
C19—Ti1—C5—C1	127.5 (4)	C2—Ti1—C4—C3	36.0 (2)
C18—Ti1—C5—C1	−124.4 (3)	C20—Ti1—C4—C3	−138.8 (2)
C16—Ti1—C5—C1	175.5 (2)	C19—Ti1—C4—C3	−94.4 (3)
C17—Ti1—C5—C1	−147.8 (2)	C18—Ti1—C4—C3	−67.6 (3)
C3—Ti1—C5—C1	−78.8 (2)	C16—Ti1—C4—C3	−124.2 (2)
C4—Ti1—C5—C1	−115.0 (3)	C17—Ti1—C4—C3	−90.1 (2)
N1—Ti1—C5—C9	−66.8 (3)	N1—Ti1—C4—C5	−15.2 (3)
C1—Ti1—C5—C9	−119.8 (4)	C1—Ti1—C4—C5	−38.7 (2)
C2—Ti1—C5—C9	−157.9 (4)	C2—Ti1—C4—C5	−81.1 (3)
C20—Ti1—C5—C9	20.2 (4)	C20—Ti1—C4—C5	104.0 (3)
C19—Ti1—C5—C9	7.7 (7)	C19—Ti1—C4—C5	148.5 (3)
C18—Ti1—C5—C9	115.8 (4)	C18—Ti1—C4—C5	175.3 (2)
C16—Ti1—C5—C9	55.8 (4)	C16—Ti1—C4—C5	118.6 (2)
C17—Ti1—C5—C9	92.4 (3)	C17—Ti1—C4—C5	152.8 (2)
C3—Ti1—C5—C9	161.4 (4)	C3—Ti1—C4—C5	−117.1 (3)
C4—Ti1—C5—C9	125.3 (4)	N1—Ti1—C4—C8	−133.4 (4)
C20—C19—C18—C17	−1.7 (4)	C1—Ti1—C4—C8	−156.9 (4)
C24—C19—C18—C17	173.1 (3)	C5—Ti1—C4—C8	−118.2 (5)
Ti1—C19—C18—C17	−65.8 (3)	C2—Ti1—C4—C8	160.7 (4)
C20—C19—C18—C23	−174.3 (4)	C20—Ti1—C4—C8	−14.1 (5)
C24—C19—C18—C23	0.5 (6)	C19—Ti1—C4—C8	30.3 (5)
Ti1—C19—C18—C23	121.6 (4)	C18—Ti1—C4—C8	57.1 (4)
C20—C19—C18—Ti1	64.2 (3)	C16—Ti1—C4—C8	0.5 (4)
C24—C19—C18—Ti1	−121.0 (4)	C17—Ti1—C4—C8	34.6 (4)
C16—C17—C18—C19	2.0 (4)	C3—Ti1—C4—C8	124.7 (5)
C22—C17—C18—C19	−168.7 (4)	C1—C2—C3—C4	−1.6 (5)
Ti1—C17—C18—C19	65.1 (3)	C6—C2—C3—C4	−177.7 (4)
C16—C17—C18—C23	174.5 (4)	Ti1—C2—C3—C4	62.8 (3)
C22—C17—C18—C23	3.9 (6)	C1—C2—C3—C7	171.4 (4)
Ti1—C17—C18—C23	−122.3 (4)	C6—C2—C3—C7	−4.6 (7)
C16—C17—C18—Ti1	−63.1 (3)	Ti1—C2—C3—C7	−124.1 (4)
C22—C17—C18—Ti1	126.2 (4)	C1—C2—C3—Ti1	−64.5 (3)
N1—Ti1—C18—C19	32.6 (3)	C6—C2—C3—Ti1	119.5 (4)
C1—Ti1—C18—C19	125.6 (3)	C5—C4—C3—C2	0.2 (5)
C5—Ti1—C18—C19	−150.2 (3)	C8—C4—C3—C2	171.2 (4)
C2—Ti1—C18—C19	137.3 (2)	Ti1—C4—C3—C2	−60.6 (3)
C20—Ti1—C18—C19	−36.7 (2)	C5—C4—C3—C7	−172.6 (4)
C16—Ti1—C18—C19	−78.2 (2)	C8—C4—C3—C7	−1.6 (7)
C17—Ti1—C18—C19	−114.5 (3)	Ti1—C4—C3—C7	126.5 (4)
C3—Ti1—C18—C19	171.4 (2)	C5—C4—C3—Ti1	60.8 (3)
C4—Ti1—C18—C19	−156.4 (2)	C8—C4—C3—Ti1	−128.2 (4)
N1—Ti1—C18—C17	147.2 (2)	N1—Ti1—C3—C2	13.8 (3)
C1—Ti1—C18—C17	−119.9 (3)	C1—Ti1—C3—C2	38.7 (2)
C5—Ti1—C18—C17	−35.6 (4)	C5—Ti1—C3—C2	81.5 (3)
C2—Ti1—C18—C17	−108.2 (2)	C20—Ti1—C3—C2	−166.1 (3)
C20—Ti1—C18—C17	77.8 (2)	C19—Ti1—C3—C2	−109.8 (3)
C19—Ti1—C18—C17	114.5 (3)	C18—Ti1—C3—C2	−117.0 (2)
C16—Ti1—C18—C17	36.3 (2)	C16—Ti1—C3—C2	−177.5 (2)
C3—Ti1—C18—C17	−74.1 (2)	C17—Ti1—C3—C2	−150.5 (2)
C4—Ti1—C18—C17	−41.9 (3)	C4—Ti1—C3—C2	118.4 (4)
N1—Ti1—C18—C23	−89.5 (4)	N1—Ti1—C3—C4	−104.6 (3)
C1—Ti1—C18—C23	3.4 (5)	C1—Ti1—C3—C4	−79.7 (3)
C5—Ti1—C18—C23	87.7 (5)	C5—Ti1—C3—C4	−36.9 (2)
C2—Ti1—C18—C23	15.1 (4)	C2—Ti1—C3—C4	−118.4 (4)
C20—Ti1—C18—C23	−158.9 (4)	C20—Ti1—C3—C4	75.5 (4)
C19—Ti1—C18—C23	−122.2 (5)	C19—Ti1—C3—C4	131.8 (3)
C16—Ti1—C18—C23	159.6 (4)	C18—Ti1—C3—C4	124.6 (2)
C17—Ti1—C18—C23	123.3 (5)	C16—Ti1—C3—C4	64.1 (3)
C3—Ti1—C18—C23	49.2 (4)	C17—Ti1—C3—C4	91.1 (2)
C4—Ti1—C18—C23	81.4 (4)	N1—Ti1—C3—C7	131.9 (4)
N1—Ti1—C2—C3	−169.0 (2)	C1—Ti1—C3—C7	156.9 (4)
C1—Ti1—C2—C3	−114.9 (3)	C5—Ti1—C3—C7	−160.4 (4)
C5—Ti1—C2—C3	−76.6 (3)	C2—Ti1—C3—C7	118.2 (5)
C20—Ti1—C2—C3	114.4 (10)	C20—Ti1—C3—C7	−47.9 (5)
C19—Ti1—C2—C3	109.7 (3)	C19—Ti1—C3—C7	8.4 (5)
C18—Ti1—C2—C3	74.8 (3)	C18—Ti1—C3—C7	1.2 (4)
C16—Ti1—C2—C3	4.4 (4)	C16—Ti1—C3—C7	−59.3 (4)
C17—Ti1—C2—C3	35.2 (3)	C17—Ti1—C3—C7	−32.3 (4)
C4—Ti1—C2—C3	−35.6 (2)	C4—Ti1—C3—C7	−123.4 (5)
N1—Ti1—C2—C1	−54.0 (2)	C10—C11—C12—C15	122.6 (5)
C5—Ti1—C2—C1	38.3 (2)	N1—C11—C12—C15	−59.4 (5)
C20—Ti1—C2—C1	−130.6 (10)	C10—C11—C12—C13	2.8 (6)
C19—Ti1—C2—C1	−135.4 (2)	N1—C11—C12—C13	−179.2 (3)
C18—Ti1—C2—C1	−170.3 (2)	C10—C11—C12—C14	−116.6 (5)
C16—Ti1—C2—C1	119.3 (3)	N1—C11—C12—C14	61.4 (5)
C17—Ti1—C2—C1	150.1 (2)