An oxo-bridged centrosymmetric tetranuclear titanium compound

The title compound, octa-tert-butoxybis­[[mu]₃-2,2'-(N-methyl­imino)­diethanolato]­di-[mu]-oxo-tetratitanium(IV), [Ti₂O{(OCH₂CH₂)₂(NCH₃)}{(CH₃)₃CO}₄]₂ or [Ti₄(C₅H₁₁NO₂)₂(C₄H₉O)₈O₂], lies about an inversion centre, and displays the less usual zigzag configuration. One O atom of the N-methyl­diethoxo­amine ligand bridges the symmetry-related Ti atoms, while the other bridges the two independent Ti atoms, with the N atom binding to give a facial configuration. Four ^tBuO^- ligands and a bridging oxide complete the respective five- and sixfold coordination of the two Ti atoms. The Ti-O bond lengths range in a self-consistent fashion from 1.7624 (17) to 2.0878 (18) Å, while the Ti-N bond length is 2.374 (2) Å.

S1. Comment

This study is part of a programme aimed at modifying metal alkoxides as precursors to high-tech oxides. A recent review (Hubert-Pfalzgraf, 2003) discusses many structural features and applications of this class of compound. The varied coordination chemistry of N-methyldiethoxoamine (MDEA) has been of great interest to us in forming volatile complexes (Sevast'yanov et al., 2001; Kemmitt et al., 2003), mixed metal alkoxides (Gainsford et al., 2002a,b), an oxoalkoxide structure, (Kemmitt Al-Salim & Gainsford, 1999) and other complexes with different metal:ligand ratios (Kemmitt Al-Salim Gainsford & Henderson, 1999; Kemmitt Al-Salim & Gainsford, 2002; Kemmitt Gainsford & Robson-Marsden, 2002). Aminoalkoxide ligands influence the formation of partial hydrolysis condensates, as noted by the contrasting structures observed in cyclic hexanuclear MDEA oxotitanate (Kemmitt Al-Salim & Gainsford, 1999), dimethylaminoethoxide (DMAE) oxotitanate, which forms a Ti₄O₄ cluster core (Johnson et al., 2001), and the isolated linear oxo-bridges observed in triethanolaminotitanates (Kemmitt et al., 2000). In the current structure, the title titanium complex, (I), has fewer amine functions and retains some alkoxide ligands, resulting in a new structural type for partial hydrolysis condensates. \sch

The crystal structure of (I) consists of independent centrosymmetric [Ti₂O(N-methyldiethoxoamine)(t-butoxide)₄]₂ complexes (Fig 1). There are a few weak intermolecular contacts, e.g. C13—H13A···H13A(1 − x, 1 − y, −z) 2.22 Å. The four Ti atoms are arranged in the less usual zigzag configuration, Ti1—Ti2—Ti2ⁱ 117.40 (2)° [symmetry code: (i) −x, −y, 1 − z]. The terminal Ti1 atoms are pentacoordinate, while the linking Ti2 atoms are hexacoordinate.

The Ti1 stereochemistry can best be described as distorted bipyramidal, with apical atoms O1 and O7 of the MDEA bridging ligand and one t-butoxide, and equatorial atoms O5, O6 and O3 from two t-butoxides and the bridging oxide, respectively (mean O—Ti—O 118.4°).

The hexacoordinate Ti2 stereochemistry approaches a trigonal antiprism arrangement. One trigonal face of the antiprism is occupied by the three coordinating atoms of the MDEA ligand, O1, O2 and N1, where atom O2 bridges the two symmetry-related Ti2 atoms and atom O1 bridges the two independent atoms Ti1 and Ti2. The other face of the antiprism is occupied by atoms O3, O4 and O2 from the bridging oxide, a t-butoxide and the arm of the symmetry-related MDEA ligand, respectively. The Ti—O(bridging) [1.7624 (17)–2.0878 (18) Å] and Ti—N [2.374 (2) Å] bond lengths are within the normal ranges for this type of complex.

The Ti1···Ti2 and Ti2···Ti2ⁱ distances of 3.0459 (7) and 3.3101 (10) Å compare with the values of 3.307 (3) and 3.242 (4) Å in the similar zigzag Ti₄ structure [Ti₄(OⁱPr)₈(µ,η²-OCH₂CH═CHCH₂O)₂ (µ₃,η²-OCH₂CH ═CHCH₂O)₂] found by Miele-Pajot et al. (1999). The shorter Ti1···Ti2 distance in (I) is expected from the smaller less constrained bridging between atoms Ti1 and Ti2. Ti···Ti distances in the range 2.952–3.570 Å are observed in other Ti—O—Ti bridged complexes.

Tetratitanium oxygen-bridged complexes adopt eight different configurations, as observed in a search of the Cambridge Structural Database (CSD, July, 2003 update; Allen, 2002). A previous analysis of multititanium oxygen-bridged compounds was given by Boyle et al. (1997). In the following list, the items are `type' followed by, in brackets, the numbers found, an example CSD code and the reference for that example: square (13, RONBUR; Troyanov & Gorbenko, 1997), cube (10, GOXMUB; Guerrero et al., 1999), capped parallelogram (10, NEMBIQ; Weymann-Schildknetch & Henry, 2001), butterfly (1, GOMVIN; Boyle et al., 1998), planar linear (2, JUKQUB; Franceschi et al., 1999) planar with µ₃-O—Ti bridge (3, NOCYOT; Moran et al., 1998), bowed linear or plate (1, FETMIA; Pedersen et al., 1987) and zigzag [2, (I) and WOGLEJ; Miele-Pajot et al., 1999]. In most cases (except the last two), the Ti atoms are six-coordinate. It is noted that the zigzag configuration is found in a related Zr₄ compound, [Zr₂(µ₂-O,µ₂-O'-methyliminodiethanolate) (µ₂-O-n-propanolate)₃(n-propanolate)₃]₂, and an analogous TiZr₂Ti compound, but with the MDEA ligands adopting planar meridional binding conformations around the Zr atoms (Gainsford et al., 2002b,c).

S2. Experimental

Crystals of the title compound were isolated from liquid Ti₂(MDEA)(O^tBu)₆, prepared by the addition of Ti(t-butoxide)₄ (27.2 g, 0.08 mol) to a solution of MDEA (4.76 g, 0.04 mol) in anhydrous toluene (100 ml) at room temperature. After stirring for 4 h, the solvent was distilled off, leaving the crude product as a mobile oil. The extremely moisture-sensitive liquid was briefly exposed to atmospheric air and then stored in an airtight flask. Within minutes, feathery crystals of (I) appeared around the neck of the flask. X-ray quality crystals grew slowly in the liquid over several months.

S3. Refinement

All non-methyl and methyl H atoms were constrained to U_iso(H) = 1.2 or 1.3 times, respectively, U_eq of their parent atom. Atom C21 was disordered over two sites and given a common isotropic displacement parameter. All non-H atoms were refined with anisotropic displacement parameters.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996) and SADABS (Sheldrick, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms have been omitted for clarity.

octa-tert-butoxy-bis[µ₃-2,2'-(N-methylimino)diethanolato]di-µ-oxo- tetratitanium(IV)

Crystal data

[Ti4O2(C5H11NO2)2(C4H9O)8]	F(000) = 1120
Mr = 1042.79	Dx = 1.223 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5496 reflections
a = 9.2937 (10) Å	θ = 2.3–23.8°
b = 23.058 (3) Å	µ = 0.60 mm^−1
c = 13.5360 (16) Å	T = 163 K
β = 102.436 (2)°	Block, colourless
V = 2832.7 (6) Å^3	0.36 × 0.15 × 0.15 mm
Z = 2

Data collection

Siemens SMART CCD area-detector diffractometer	5693 independent reflections
Radiation source: fine-focus sealed tube	3634 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.081
Detector resolution: 8.192 pixels mm^-1	θmax = 26.4°, θmin = 1.8°
ϕ and ω scans	h = −11→6
Absorption correction: multi-scan (Blessing, 1995)	k = −28→28
Tmin = 0.678, Tmax = 0.914	l = −16→16
33365 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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0351P)^2 + 1.5206P] where P = (Fo^2 + 2Fc^2)/3
5693 reflections	(Δ/σ)max = 0.001
291 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Special details

Experimental. Crystal decay was monitored by repeating the initial 10 frames at the end of the data collection and analyzing duplicate reflections. The standard 0.8 mm diameter collimator was used.

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	Occ. (<1)
Ti1	0.19063 (6)	0.11133 (2)	0.72467 (4)	0.02662 (14)
Ti2	0.06662 (5)	−0.00141 (2)	0.62365 (3)	0.02170 (12)
O1	0.26024 (19)	0.02810 (8)	0.69609 (13)	0.0273 (4)
O2	0.10824 (18)	0.02296 (7)	0.48488 (12)	0.0215 (4)
O3	0.01569 (19)	0.06678 (7)	0.66401 (13)	0.0254 (4)
O4	0.0217 (2)	−0.05266 (8)	0.71304 (13)	0.0306 (5)
O5	0.2957 (2)	0.10188 (9)	0.85277 (14)	0.0424 (5)
O6	0.3001 (2)	0.14026 (8)	0.64192 (14)	0.0334 (5)
O7	0.0833 (2)	0.17403 (8)	0.74002 (16)	0.0403 (5)
N1	0.2475 (2)	−0.06676 (9)	0.58990 (17)	0.0278 (5)
C1	0.3960 (3)	−0.00117 (12)	0.7124 (2)	0.0341 (7)
H1A	0.4468	0.0016	0.7845	0.041*
H1B	0.4601	0.0163	0.6708	0.041*
C2	0.3645 (3)	−0.06397 (12)	0.6831 (2)	0.0360 (7)
H2A	0.4551	−0.0828	0.6713	0.043*
H2B	0.3325	−0.0849	0.7385	0.043*
C3	0.1901 (3)	−0.12633 (11)	0.5731 (2)	0.0378 (8)
H3A	0.2697	−0.1524	0.5645	0.049*
H3B	0.1111	−0.1274	0.5121	0.049*
H3C	0.1513	−0.1388	0.6315	0.049*
C4	0.2998 (3)	−0.04625 (12)	0.4991 (2)	0.0312 (7)
H4A	0.2563	−0.0708	0.4402	0.037*
H4B	0.4084	−0.0501	0.5115	0.037*
C5	0.2569 (3)	0.01648 (12)	0.4757 (2)	0.0286 (7)
H5A	0.3219	0.0425	0.5237	0.034*
H5B	0.2664	0.0264	0.4062	0.034*
C6	−0.0165 (4)	−0.06348 (13)	0.8084 (2)	0.0407 (8)
C7	0.1252 (5)	−0.0738 (2)	0.8855 (3)	0.0832 (14)
H7A	0.1795	−0.1058	0.8628	0.108*
H7B	0.1023	−0.0837	0.9508	0.108*
H7C	0.1855	−0.0386	0.8928	0.108*
C8	−0.1102 (5)	−0.11798 (15)	0.7954 (3)	0.0664 (11)
H8A	−0.2034	−0.1104	0.7474	0.086*
H8B	−0.1303	−0.1294	0.8608	0.086*
H8C	−0.0574	−0.1493	0.7695	0.086*
C9	−0.1012 (5)	−0.01290 (15)	0.8362 (3)	0.0683 (12)
H9A	−0.0393	0.0219	0.8433	0.089*
H9B	−0.1299	−0.0209	0.9004	0.089*
H9C	−0.1897	−0.0066	0.7830	0.089*
C10	0.4068 (4)	0.12584 (15)	0.9310 (2)	0.0465 (9)
C11	0.5510 (4)	0.1253 (2)	0.8959 (3)	0.0855 (15)
H11A	0.5767	0.0853	0.8824	0.111*
H11B	0.6289	0.1420	0.9486	0.111*
H11C	0.5405	0.1483	0.8338	0.111*
C12	0.3681 (5)	0.18700 (19)	0.9538 (4)	0.0972 (17)
H12A	0.3591	0.2108	0.8928	0.126*
H12B	0.4458	0.2029	1.0077	0.126*
H12C	0.2743	0.1871	0.9758	0.126*
C13	0.4170 (5)	0.0874 (2)	1.0225 (3)	0.0826 (14)
H13A	0.3215	0.0866	1.0422	0.107*
H13B	0.4923	0.1026	1.0786	0.107*
H13C	0.4437	0.0479	1.0062	0.107*
C14	0.3188 (3)	0.18807 (12)	0.5788 (2)	0.0367 (7)
C15	0.4486 (4)	0.17289 (14)	0.5318 (3)	0.0504 (9)
H15A	0.5322	0.1607	0.5850	0.066*
H15B	0.4765	0.2070	0.4969	0.066*
H15C	0.4206	0.1412	0.4831	0.066*
C16	0.1810 (4)	0.19426 (16)	0.4978 (3)	0.0600 (10)
H16A	0.1587	0.1573	0.4621	0.078*
H16B	0.1956	0.2243	0.4497	0.078*
H16C	0.0988	0.2052	0.5287	0.078*
C17	0.3512 (5)	0.24201 (15)	0.6429 (3)	0.0658 (12)
H17A	0.2697	0.2494	0.6766	0.086*
H17B	0.3623	0.2751	0.5998	0.086*
H17C	0.4425	0.2365	0.6938	0.086*
C18	−0.0382 (4)	0.20265 (14)	0.7673 (3)	0.0469 (9)
C19	−0.0596 (5)	0.17745 (17)	0.8669 (3)	0.0752 (13)
H19A	−0.0748	0.1355	0.8598	0.098*
H19B	−0.1458	0.1954	0.8852	0.098*
H19C	0.0281	0.1852	0.9200	0.098*
C20	−0.0022 (4)	0.26684 (14)	0.7769 (3)	0.0582 (10)
H20A	0.0883	0.2726	0.8285	0.076*
H20B	−0.0835	0.2877	0.7966	0.076*
H20C	0.0118	0.2817	0.7117	0.076*
C21A	−0.1768 (9)	0.1844 (5)	0.7017 (8)	0.0527 (14)*	0.517 (15)
H21A	−0.1848	0.1421	0.7034	0.068*	0.517 (15)
H21B	−0.1793	0.1971	0.6323	0.068*	0.517 (15)
H21C	−0.2594	0.2019	0.7254	0.068*	0.517 (15)
C21B	−0.1675 (10)	0.2019 (5)	0.6695 (8)	0.0527 (14)*	0.483 (15)
H21D	−0.2012	0.1619	0.6546	0.068*	0.483 (15)
H21E	−0.1316	0.2176	0.6120	0.068*	0.483 (15)
H21F	−0.2495	0.2257	0.6814	0.068*	0.483 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ti1	0.0263 (3)	0.0264 (3)	0.0277 (3)	−0.0055 (2)	0.0069 (2)	−0.0063 (2)
Ti2	0.0202 (3)	0.0204 (2)	0.0234 (2)	0.0000 (2)	0.00230 (19)	−0.0006 (2)
O1	0.0177 (11)	0.0288 (10)	0.0321 (10)	0.0031 (8)	−0.0018 (8)	−0.0021 (8)
O2	0.0159 (11)	0.0218 (9)	0.0268 (10)	−0.0011 (7)	0.0044 (8)	−0.0013 (8)
O3	0.0207 (11)	0.0252 (10)	0.0293 (10)	−0.0005 (8)	0.0035 (8)	−0.0036 (8)
O4	0.0343 (12)	0.0302 (11)	0.0273 (10)	−0.0024 (9)	0.0066 (9)	0.0032 (8)
O5	0.0413 (14)	0.0511 (14)	0.0309 (11)	−0.0171 (11)	−0.0008 (10)	−0.0075 (10)
O6	0.0319 (12)	0.0292 (11)	0.0420 (12)	−0.0029 (9)	0.0147 (10)	0.0021 (9)
O7	0.0342 (13)	0.0327 (11)	0.0572 (14)	−0.0061 (9)	0.0167 (11)	−0.0196 (10)
N1	0.0226 (14)	0.0240 (12)	0.0346 (13)	0.0038 (10)	0.0012 (11)	0.0001 (10)
C1	0.0252 (17)	0.0399 (17)	0.0327 (15)	0.0037 (14)	−0.0035 (13)	−0.0028 (14)
C2	0.0285 (18)	0.0348 (17)	0.0397 (17)	0.0134 (13)	−0.0037 (14)	0.0012 (14)
C3	0.038 (2)	0.0231 (16)	0.0508 (19)	0.0049 (13)	0.0068 (16)	−0.0029 (13)
C4	0.0232 (17)	0.0350 (16)	0.0352 (16)	0.0043 (13)	0.0056 (13)	−0.0071 (13)
C5	0.0188 (16)	0.0350 (17)	0.0323 (15)	−0.0009 (12)	0.0064 (13)	−0.0018 (12)
C6	0.051 (2)	0.0405 (19)	0.0332 (17)	−0.0046 (16)	0.0139 (16)	0.0090 (14)
C7	0.080 (3)	0.130 (4)	0.033 (2)	0.000 (3)	0.000 (2)	0.025 (2)
C8	0.084 (3)	0.054 (2)	0.073 (3)	−0.014 (2)	0.042 (2)	0.010 (2)
C9	0.110 (4)	0.053 (2)	0.057 (2)	0.001 (2)	0.051 (2)	−0.0007 (18)
C10	0.042 (2)	0.058 (2)	0.0338 (17)	−0.0164 (17)	−0.0032 (15)	−0.0068 (16)
C11	0.044 (3)	0.136 (4)	0.072 (3)	−0.032 (3)	0.003 (2)	−0.008 (3)
C12	0.097 (4)	0.077 (3)	0.100 (4)	−0.019 (3)	−0.018 (3)	−0.043 (3)
C13	0.080 (3)	0.118 (4)	0.042 (2)	−0.027 (3)	−0.005 (2)	0.011 (2)
C14	0.039 (2)	0.0260 (16)	0.0482 (19)	−0.0033 (14)	0.0162 (16)	0.0028 (14)
C15	0.047 (2)	0.050 (2)	0.062 (2)	0.0045 (17)	0.0277 (19)	0.0106 (18)
C16	0.046 (2)	0.050 (2)	0.080 (3)	0.0045 (18)	0.006 (2)	0.023 (2)
C17	0.091 (3)	0.038 (2)	0.079 (3)	−0.021 (2)	0.040 (2)	−0.0108 (19)
C18	0.036 (2)	0.0420 (19)	0.065 (2)	−0.0012 (15)	0.0168 (18)	−0.0250 (17)
C19	0.085 (3)	0.055 (2)	0.105 (3)	−0.002 (2)	0.063 (3)	−0.006 (2)
C20	0.073 (3)	0.041 (2)	0.065 (2)	0.0068 (18)	0.024 (2)	−0.0121 (18)

Geometric parameters (Å, º)

Ti1—O7	1.794 (2)	C9—H9A	0.9800
Ti1—O6	1.7957 (19)	C9—H9B	0.9800
Ti1—O5	1.810 (2)	C9—H9C	0.9800
Ti1—O3	1.9488 (18)	C10—C12	1.504 (5)
Ti1—O1	2.0878 (18)	C10—C13	1.511 (5)
Ti1—Ti2	3.0459 (7)	C10—C11	1.515 (5)
Ti2—O3	1.7624 (17)	C11—H11A	0.9800
Ti2—O4	1.8034 (18)	C11—H11B	0.9800
Ti2—O1	1.9755 (18)	C11—H11C	0.9800
Ti2—O2^i	2.0044 (17)	C12—H12A	0.9800
Ti2—O2	2.0751 (17)	C12—H12B	0.9800
Ti2—N1	2.374 (2)	C12—H12C	0.9800
Ti2—Ti2^i	3.3101 (10)	C13—H13A	0.9800
O1—C1	1.406 (3)	C13—H13B	0.9800
O2—C5	1.422 (3)	C13—H13C	0.9800
O4—C6	1.433 (3)	C14—C16	1.503 (4)
O5—C10	1.422 (3)	C14—C17	1.509 (4)
O6—C14	1.429 (3)	C14—C15	1.521 (4)
O7—C18	1.423 (3)	C15—H15A	0.9800
N1—C3	1.473 (3)	C15—H15B	0.9800
N1—C2	1.479 (3)	C15—H15C	0.9800
N1—C4	1.493 (3)	C16—H16A	0.9800
C1—C2	1.513 (4)	C16—H16B	0.9800
C1—H1A	0.9900	C16—H16C	0.9800
C1—H1B	0.9900	C17—H17A	0.9800
C2—H2A	0.9900	C17—H17B	0.9800
C2—H2B	0.9900	C17—H17C	0.9800
C3—H3A	0.9800	C18—C21A	1.460 (8)
C3—H3B	0.9800	C18—C20	1.517 (4)
C3—H3C	0.9800	C18—C19	1.520 (5)
C4—C5	1.516 (4)	C18—C21B	1.585 (9)
C4—H4A	0.9900	C19—H19A	0.9800
C4—H4B	0.9900	C19—H19B	0.9800
C5—H5A	0.9900	C19—H19C	0.9800
C5—H5B	0.9900	C20—H20A	0.9800
C6—C9	1.499 (5)	C20—H20B	0.9800
C6—C7	1.512 (5)	C20—H20C	0.9800
C6—C8	1.517 (4)	C21A—H21A	0.9800
C7—H7A	0.9800	C21A—H21B	0.9800
C7—H7B	0.9800	C21A—H21C	0.9800
C7—H7C	0.9800	C21B—H21D	0.9800
C8—H8A	0.9800	C21B—H21E	0.9800
C8—H8B	0.9800	C21B—H21F	0.9800
C8—H8C	0.9800
O7—Ti1—O6	100.17 (9)	H7A—C7—H7B	109.5
O7—Ti1—O5	100.64 (10)	C6—C7—H7C	109.5
O6—Ti1—O5	112.40 (9)	H7A—C7—H7C	109.5
O7—Ti1—O3	92.27 (8)	H7B—C7—H7C	109.5
O6—Ti1—O3	117.79 (8)	C6—C8—H8A	109.5
O5—Ti1—O3	124.68 (9)	C6—C8—H8B	109.5
O7—Ti1—O1	164.71 (8)	H8A—C8—H8B	109.5
O6—Ti1—O1	89.21 (8)	C6—C8—H8C	109.5
O5—Ti1—O1	86.68 (8)	H8A—C8—H8C	109.5
O3—Ti1—O1	72.61 (7)	H8B—C8—H8C	109.5
O7—Ti1—Ti2	125.02 (7)	C6—C9—H9A	109.5
O6—Ti1—Ti2	104.32 (6)	C6—C9—H9B	109.5
O5—Ti1—Ti2	113.65 (7)	H9A—C9—H9B	109.5
O3—Ti1—Ti2	32.89 (5)	C6—C9—H9C	109.5
O1—Ti1—Ti2	40.06 (5)	H9A—C9—H9C	109.5
O3—Ti2—O4	105.07 (9)	H9B—C9—H9C	109.5
O3—Ti2—O1	79.37 (8)	O5—C10—C12	110.5 (3)
O4—Ti2—O1	102.15 (8)	O5—C10—C13	106.8 (3)
O3—Ti2—O2^i	102.64 (8)	C12—C10—C13	110.9 (3)
O4—Ti2—O2^i	93.50 (8)	O5—C10—C11	108.3 (3)
O1—Ti2—O2^i	163.18 (7)	C12—C10—C11	109.8 (3)
O3—Ti2—O2	98.85 (8)	C13—C10—C11	110.5 (3)
O4—Ti2—O2	154.15 (8)	C10—C11—H11A	109.5
O1—Ti2—O2	91.64 (7)	C10—C11—H11B	109.5
O2^i—Ti2—O2	71.54 (8)	H11A—C11—H11B	109.5
O3—Ti2—N1	150.98 (8)	C10—C11—H11C	109.5
O4—Ti2—N1	89.37 (8)	H11A—C11—H11C	109.5
O1—Ti2—N1	72.97 (8)	H11B—C11—H11C	109.5
O2^i—Ti2—N1	101.40 (7)	C10—C12—H12A	109.5
O2—Ti2—N1	73.74 (7)	C10—C12—H12B	109.5
O3—Ti2—Ti1	36.90 (6)	H12A—C12—H12B	109.5
O4—Ti2—Ti1	112.20 (6)	C10—C12—H12C	109.5
O1—Ti2—Ti1	42.86 (5)	H12A—C12—H12C	109.5
O2^i—Ti2—Ti1	135.17 (5)	H12B—C12—H12C	109.5
O2—Ti2—Ti1	92.81 (5)	C10—C13—H13A	109.5
N1—Ti2—Ti1	114.39 (6)	C10—C13—H13B	109.5
O3—Ti2—Ti2^i	103.24 (6)	H13A—C13—H13B	109.5
O4—Ti2—Ti2^i	126.95 (6)	C10—C13—H13C	109.5
O1—Ti2—Ti2^i	126.70 (6)	H13A—C13—H13C	109.5
O2^i—Ti2—Ti2^i	36.49 (5)	H13B—C13—H13C	109.5
O2—Ti2—Ti2^i	35.06 (5)	O6—C14—C16	108.4 (2)
N1—Ti2—Ti2^i	86.80 (6)	O6—C14—C17	109.1 (3)
Ti1—Ti2—Ti2^i	117.40 (2)	C16—C14—C17	112.0 (3)
C1—O1—Ti2	127.12 (16)	O6—C14—C15	106.4 (2)
C1—O1—Ti1	135.69 (16)	C16—C14—C15	110.2 (3)
Ti2—O1—Ti1	97.07 (8)	C17—C14—C15	110.6 (3)
C5—O2—Ti2^i	124.03 (15)	C14—C15—H15A	109.5
C5—O2—Ti2	115.15 (15)	C14—C15—H15B	109.5
Ti2^i—O2—Ti2	108.46 (8)	H15A—C15—H15B	109.5
Ti2—O3—Ti1	110.21 (9)	C14—C15—H15C	109.5
C6—O4—Ti2	148.97 (18)	H15A—C15—H15C	109.5
C10—O5—Ti1	145.2 (2)	H15B—C15—H15C	109.5
C14—O6—Ti1	144.92 (18)	C14—C16—H16A	109.5
C18—O7—Ti1	153.6 (2)	C14—C16—H16B	109.5
C3—N1—C2	110.3 (2)	H16A—C16—H16B	109.5
C3—N1—C4	109.9 (2)	C14—C16—H16C	109.5
C2—N1—C4	112.2 (2)	H16A—C16—H16C	109.5
C3—N1—Ti2	111.93 (17)	H16B—C16—H16C	109.5
C2—N1—Ti2	103.28 (16)	C14—C17—H17A	109.5
C4—N1—Ti2	109.10 (15)	C14—C17—H17B	109.5
O1—C1—C2	107.6 (2)	H17A—C17—H17B	109.5
O1—C1—H1A	110.2	C14—C17—H17C	109.5
C2—C1—H1A	110.2	H17A—C17—H17C	109.5
O1—C1—H1B	110.2	H17B—C17—H17C	109.5
C2—C1—H1B	110.2	O7—C18—C21A	110.7 (4)
H1A—C1—H1B	108.5	O7—C18—C20	107.6 (3)
N1—C2—C1	109.3 (2)	C21A—C18—C20	118.8 (5)
N1—C2—H2A	109.8	O7—C18—C19	108.4 (3)
C1—C2—H2A	109.8	C21A—C18—C19	99.4 (6)
N1—C2—H2B	109.8	C20—C18—C19	111.5 (3)
C1—C2—H2B	109.8	O7—C18—C21B	106.2 (4)
H2A—C2—H2B	108.3	C20—C18—C21B	101.3 (5)
N1—C3—H3A	109.5	C19—C18—C21B	121.1 (6)
N1—C3—H3B	109.5	C18—C19—H19A	109.5
H3A—C3—H3B	109.5	C18—C19—H19B	109.5
N1—C3—H3C	109.5	H19A—C19—H19B	109.5
H3A—C3—H3C	109.5	C18—C19—H19C	109.5
H3B—C3—H3C	109.5	H19A—C19—H19C	109.5
N1—C4—C5	110.9 (2)	H19B—C19—H19C	109.5
N1—C4—H4A	109.5	C18—C20—H20A	109.5
C5—C4—H4A	109.5	C18—C20—H20B	109.5
N1—C4—H4B	109.5	H20A—C20—H20B	109.5
C5—C4—H4B	109.5	C18—C20—H20C	109.5
H4A—C4—H4B	108.0	H20A—C20—H20C	109.5
O2—C5—C4	107.4 (2)	H20B—C20—H20C	109.5
O2—C5—H5A	110.2	C18—C21A—H21A	109.5
C4—C5—H5A	110.2	C18—C21A—H21B	109.5
O2—C5—H5B	110.2	H21A—C21A—H21B	109.5
C4—C5—H5B	110.2	C18—C21A—H21C	109.5
H5A—C5—H5B	108.5	H21A—C21A—H21C	109.5
O4—C6—C9	109.6 (2)	H21B—C21A—H21C	109.5
O4—C6—C7	107.5 (3)	C18—C21B—H21D	109.5
C9—C6—C7	112.1 (3)	C18—C21B—H21E	109.5
O4—C6—C8	106.7 (3)	H21D—C21B—H21E	109.5
C9—C6—C8	110.8 (3)	C18—C21B—H21F	109.5
C7—C6—C8	110.0 (3)	H21D—C21B—H21F	109.5
C6—C7—H7A	109.5	H21E—C21B—H21F	109.5
C6—C7—H7B	109.5
O7—Ti1—Ti2—O3	−5.76 (13)	Ti2^i—Ti2—O3—Ti1	−118.30 (7)
O6—Ti1—Ti2—O3	−119.42 (12)	O7—Ti1—O3—Ti2	175.28 (10)
O5—Ti1—Ti2—O3	117.82 (12)	O6—Ti1—O3—Ti2	72.55 (12)
O1—Ti1—Ti2—O3	169.59 (12)	O5—Ti1—O3—Ti2	−80.12 (13)
O7—Ti1—Ti2—O4	−91.41 (11)	O1—Ti1—O3—Ti2	−7.00 (8)
O6—Ti1—Ti2—O4	154.92 (9)	O3—Ti2—O4—C6	−14.4 (4)
O5—Ti1—Ti2—O4	32.16 (10)	O1—Ti2—O4—C6	67.7 (4)
O3—Ti1—Ti2—O4	−85.66 (12)	O2^i—Ti2—O4—C6	−118.5 (4)
O1—Ti1—Ti2—O4	83.93 (10)	O2—Ti2—O4—C6	−171.6 (3)
O7—Ti1—Ti2—O1	−175.35 (12)	N1—Ti2—O4—C6	140.1 (4)
O6—Ti1—Ti2—O1	70.99 (10)	Ti1—Ti2—O4—C6	23.9 (4)
O5—Ti1—Ti2—O1	−51.77 (11)	Ti2^i—Ti2—O4—C6	−134.4 (3)
O3—Ti1—Ti2—O1	−169.59 (12)	O7—Ti1—O5—C10	−67.1 (4)
O7—Ti1—Ti2—O2^i	28.86 (12)	O6—Ti1—O5—C10	38.7 (4)
O6—Ti1—Ti2—O2^i	−84.80 (10)	O3—Ti1—O5—C10	−167.4 (3)
O5—Ti1—Ti2—O2^i	152.43 (10)	O1—Ti1—O5—C10	126.5 (4)
O3—Ti1—Ti2—O2^i	34.62 (12)	Ti2—Ti1—O5—C10	156.9 (3)
O1—Ti1—Ti2—O2^i	−155.79 (11)	O7—Ti1—O6—C14	−11.3 (3)
O7—Ti1—Ti2—O2	95.27 (10)	O5—Ti1—O6—C14	−117.3 (3)
O6—Ti1—Ti2—O2	−18.40 (8)	O3—Ti1—O6—C14	86.8 (3)
O5—Ti1—Ti2—O2	−141.16 (9)	O1—Ti1—O6—C14	156.6 (3)
O3—Ti1—Ti2—O2	101.03 (11)	Ti2—Ti1—O6—C14	119.1 (3)
O1—Ti1—Ti2—O2	−89.38 (9)	O6—Ti1—O7—C18	163.1 (5)
O7—Ti1—Ti2—N1	168.68 (10)	O5—Ti1—O7—C18	−81.6 (5)
O6—Ti1—Ti2—N1	55.01 (9)	O3—Ti1—O7—C18	44.3 (5)
O5—Ti1—Ti2—N1	−67.75 (10)	O1—Ti1—O7—C18	36.0 (7)
O3—Ti1—Ti2—N1	174.43 (11)	Ti2—Ti1—O7—C18	47.5 (5)
O1—Ti1—Ti2—N1	−15.98 (10)	O3—Ti2—N1—C3	168.17 (18)
O7—Ti1—Ti2—Ti2^i	69.12 (9)	O4—Ti2—N1—C3	47.07 (18)
O6—Ti1—Ti2—Ti2^i	−44.54 (7)	O1—Ti2—N1—C3	149.98 (19)
O5—Ti1—Ti2—Ti2^i	−167.30 (8)	O2^i—Ti2—N1—C3	−46.37 (19)
O3—Ti1—Ti2—Ti2^i	74.88 (10)	O2—Ti2—N1—C3	−113.10 (19)
O1—Ti1—Ti2—Ti2^i	−115.53 (8)	Ti1—Ti2—N1—C3	161.27 (16)
O3—Ti2—O1—C1	177.1 (2)	Ti2^i—Ti2—N1—C3	−80.00 (18)
O4—Ti2—O1—C1	73.8 (2)	O3—Ti2—N1—C2	49.5 (3)
O2^i—Ti2—O1—C1	−84.3 (3)	O4—Ti2—N1—C2	−71.61 (17)
O2—Ti2—O1—C1	−84.2 (2)	O1—Ti2—N1—C2	31.30 (16)
N1—Ti2—O1—C1	−11.7 (2)	O2^i—Ti2—N1—C2	−165.06 (16)
Ti1—Ti2—O1—C1	−176.5 (2)	O2—Ti2—N1—C2	128.22 (17)
Ti2^i—Ti2—O1—C1	−84.2 (2)	Ti1—Ti2—N1—C2	42.59 (17)
O3—Ti2—O1—Ti1	−6.34 (8)	Ti2^i—Ti2—N1—C2	161.32 (16)
O4—Ti2—O1—Ti1	−109.65 (8)	O3—Ti2—N1—C4	−70.0 (2)
O2^i—Ti2—O1—Ti1	92.2 (3)	O4—Ti2—N1—C4	168.87 (17)
O2—Ti2—O1—Ti1	92.36 (7)	O1—Ti2—N1—C4	−88.21 (17)
N1—Ti2—O1—Ti1	164.80 (9)	O2^i—Ti2—N1—C4	75.43 (17)
Ti2^i—Ti2—O1—Ti1	92.33 (7)	O2—Ti2—N1—C4	8.71 (16)
O7—Ti1—O1—C1	−169.4 (3)	Ti1—Ti2—N1—C4	−76.92 (17)
O6—Ti1—O1—C1	62.4 (2)	Ti2^i—Ti2—N1—C4	41.81 (16)
O5—Ti1—O1—C1	−50.1 (2)	Ti2—O1—C1—C2	−11.1 (3)
O3—Ti1—O1—C1	−178.0 (2)	Ti1—O1—C1—C2	173.83 (18)
Ti2—Ti1—O1—C1	176.1 (3)	C3—N1—C2—C1	−166.6 (2)
O7—Ti1—O1—Ti2	14.6 (4)	C4—N1—C2—C1	70.6 (3)
O6—Ti1—O1—Ti2	−113.63 (9)	Ti2—N1—C2—C1	−46.8 (3)
O5—Ti1—O1—Ti2	133.88 (9)	O1—C1—C2—N1	40.6 (3)
O3—Ti1—O1—Ti2	5.90 (7)	C3—N1—C4—C5	139.3 (2)
O3—Ti2—O2—C5	115.59 (16)	C2—N1—C4—C5	−97.6 (3)
O4—Ti2—O2—C5	−86.7 (2)	Ti2—N1—C4—C5	16.2 (3)
O1—Ti2—O2—C5	36.10 (16)	Ti2^i—O2—C5—C4	−81.6 (2)
O2^i—Ti2—O2—C5	−143.95 (19)	Ti2—O2—C5—C4	56.0 (2)
N1—Ti2—O2—C5	−35.63 (16)	N1—C4—C5—O2	−44.1 (3)
Ti1—Ti2—O2—C5	78.98 (15)	Ti2—O4—C6—C9	30.3 (5)
Ti2^i—Ti2—O2—C5	−143.95 (19)	Ti2—O4—C6—C7	−91.7 (4)
O3—Ti2—O2—Ti2^i	−100.46 (9)	Ti2—O4—C6—C8	150.3 (3)
O4—Ti2—O2—Ti2^i	57.2 (2)	Ti1—O5—C10—C12	54.9 (5)
O1—Ti2—O2—Ti2^i	−179.95 (8)	Ti1—O5—C10—C13	175.7 (3)
O2^i—Ti2—O2—Ti2^i	0.0	Ti1—O5—C10—C11	−65.3 (5)
N1—Ti2—O2—Ti2^i	108.32 (9)	Ti1—O6—C14—C16	−59.6 (4)
Ti1—Ti2—O2—Ti2^i	−137.07 (7)	Ti1—O6—C14—C17	62.6 (4)
O4—Ti2—O3—Ti1	107.04 (10)	Ti1—O6—C14—C15	−178.1 (2)
O1—Ti2—O3—Ti1	7.18 (9)	Ti1—O7—C18—C21A	−64.4 (8)
O2^i—Ti2—O3—Ti1	−155.77 (8)	Ti1—O7—C18—C20	164.2 (3)
O2—Ti2—O3—Ti1	−82.83 (9)	Ti1—O7—C18—C19	43.6 (6)
N1—Ti2—O3—Ti1	−10.5 (2)	Ti1—O7—C18—C21B	−88.0 (7)

Symmetry code: (i) −x, −y, −z+1.