μ-Oxo-bis­{isopropoxo[2,2′-(methyl­enedithio)bis­(6-tert-butyl-4-methyl­phenolato)]titanium(IV)}

The title compound, [Ti₂(C₃H₇O)₂(C₂₃H₃₀O₂S₂)₂O], contains an O,S,S,O-tetra­dentate bis­(phenolate) ligand. It is dimeric through a μ-O atom and exhibits pseudo-C₂ symmetry. The two metal centres show a distorted octa­hedral coordination geometry.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C)= 0.005 Å
• R factor = 0.054
• wR factor = 0.139
• Data-to-parameter ratio = 21.2

checkCIF/PLATON results

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Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

µ-Oxo-bis{isopropoxo[2,2'-(methylenedithio)bis(6-tert-butyl-4- methylphenolato)]titanium(IV)}

Crystal data

[Ti2(C3H7O)2(C23H30O2S2)2O]	F(000) = 2200
Mr = 1035.15	Dx = 1.260 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 211 reflections
a = 13.809 (3) Å	θ = 3.2–20.4°
b = 22.381 (7) Å	µ = 0.49 mm^−1
c = 21.435 (7) Å	T = 173 K
β = 124.53 (2)°	Prism, yellow
V = 5458 (3) Å^3	0.38 × 0.20 × 0.13 mm
Z = 4

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	12358 independent reflections
Radiation source: fine-focus sealed tube	7100 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.063
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
φ scans, and ω scans with κ offsets	h = −17→17
Absorption correction: multi-scan (SADABS; Bruker Nonius, 2002)	k = −29→27
Tmin = 0.835, Tmax = 0.939	l = −27→27
41182 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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.139	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0655P)^2 + 1.7819P] where P = (Fo^2 + 2Fc^2)/3
12358 reflections	(Δ/σ)max = 0.001
584 parameters	Δρmax = 0.72 e Å^−3
4 restraints	Δρmin = −0.50 e Å^−3

Special details

Experimental. All operations were performed under a nitrogen atmosphere using standard Schlenk-line or glove-box techniques. Solvents were purified, dried and distilled under nitrogen using standard techniques. 2-Hydroxy-3-tert-butyl-5-methylbenzenethiol was prepared according to published procedures (Pastor & Denney, 1988). All other chemicals were commercially available and used after appropriate purification. NMR spectra were recorded on a Bruker DRX 400 spectrometer (¹H, 400 MHz; ¹³C, 101 MHz) in CDCl₃ at 298 K, unless otherwise stated. Chemical shifts for ¹H and ¹³C spectra were referenced internally using the residual protio solvent resonances and reported relative to tetramethylsilane.

The first intermediate compound, 2,2'-(methylenedithio)bis(4-methyl-6-tert-butylphenol), (II), was prepared as follows. Into a 500 ml two-necked flask equipped with magnetic stirrer and condenser were introduced sequentially 3-tert-butyl-2-hydroxy-5-methylbenzenethiol (42.09 g, 0.184 mol), methanol (80 ml) and sodium hydroxyde (7.36 g, 0.184 mol). The resulting mixture was heated [To what temperature?] under magnetic stirring until complete dissolution of the sodium hydroxyde. Dibromomethane (16.02 g, 92.2 mmol) was then added carefully and the reaction mixture kept under reflux for 2 h. The solvent was then removed under reduced pressure and the residue was extracted with diethyl ether (3 × 200 ml). The organic layers were collected, washed with water and dried over magnesium sulfate. Removal of the solvent under reduced pressure and recrystallization from acetone afforded the product as white needles (15.5 g, 36% yield). ¹H NMR (CDCl₃, 298 K, δ, p.p.m.): 1.39 (^tBu, s, 18H), 2.25 (CH₃, s, 6H), 3.92 (CH₂, s, 4H), 6.76 (OH, s, 2H), 7.11 (ArH, s, 4H); ¹³C NMR (CDCl₃, 25% C, δ, p.p.m.): 20.5 (4-CH₃), 29.2 [C(CH₃)], 34.8 [C(CH₃)], 44.6 (S—CH₂), 118.0 (C2), 128.9 (C4), 130.0(C5), 133.4 (C3), 135.9 (C6), 153.0 (C1).

The second intermediate compound, diisopropoxy[2,2'-(methylenedithio)bis(4-methyl-6-tert- butylphenolato)]titanium, (III), was prepared as follows. Compound (II) (0.63 g, 1.55 mmol), toluene (15 ml) and titanium isopropoxide (0.44 g, 1.55 mmol) were introduced sequentially into a 100 ml glass flask. The mixture was stirred magnetically for 2 h at room temperature. Removal of the solvent under vacuum and washing with pentane gave the product as a yellow powder (0.8 g, 91% yield). ¹H NMR (CDCl₃, 298 K, δ, p.p.m.): 1.18 [CH(CH₃)₂, d, 12H], 1.47 (^tBu, s, 18H), 2.22 (CH₃, s, 6H), 4.05 (CH₂, s, 4H), 4.76 [CH (CH₃)₂, m, 2H], 7.00–7.07 (ArH, m, 4H). ¹³C NMR (CDCl₃, 25% C, δ, p.p.m.): 20.6 (4-CH₃), 26.1 [CH(CH₃)₂], 29.4 [C (CH₃)₃], 35.1 [C (CH₃)₃], 51.0 (S—CH₂), 80.4 [O—CH(CH₃)₂], 122.8 (C2), 127.0 (C4), 130.1 [C5 (C3)], 131.0 [C3 (C5)], 137.1 (C6), 165.4 (C1). Attempts to crystallize (III) from hexane afforded the title complex, (I), as yellow crystals.

X-ray data were recorded at 173 K by means of an Oxford Cryostream 700 apparatus.

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	0.69566 (4)	0.26456 (2)	0.27376 (3)	0.02601 (15)
Ti2	0.88757 (4)	0.26273 (2)	0.47548 (3)	0.02561 (14)
S1	0.49118 (7)	0.29808 (3)	0.13867 (4)	0.0291 (2)
S2	0.52724 (7)	0.31532 (3)	0.29149 (4)	0.02811 (19)
S3	0.94851 (7)	0.22886 (4)	0.61727 (5)	0.0319 (2)
S4	0.70786 (7)	0.20294 (3)	0.47408 (5)	0.0296 (2)
O1	0.71460 (17)	0.34698 (9)	0.25738 (11)	0.0277 (5)
O2	0.60027 (17)	0.20093 (8)	0.26771 (11)	0.0282 (5)
O3	0.74803 (19)	0.23043 (10)	0.22399 (13)	0.0392 (6)
O4	0.81017 (16)	0.26087 (9)	0.37318 (11)	0.0320 (5)
O5	0.95788 (17)	0.18494 (9)	0.49482 (11)	0.0298 (5)
O6	0.79855 (17)	0.32180 (8)	0.48513 (11)	0.0290 (5)
O7	1.01420 (17)	0.30618 (9)	0.51142 (13)	0.0392 (6)
C1	0.6779 (2)	0.37211 (13)	0.19050 (16)	0.0242 (7)
C2	0.7457 (3)	0.41467 (13)	0.18291 (17)	0.0266 (7)
C3	0.6981 (3)	0.43675 (13)	0.11010 (18)	0.0334 (8)
H3	0.7423	0.4657	0.1040	0.033*
C4	0.5903 (3)	0.41935 (14)	0.04579 (17)	0.0344 (8)
C5	0.5244 (3)	0.37831 (13)	0.05517 (17)	0.0298 (7)
H5	0.4494	0.3663	0.0129	0.030*
C6	0.5677 (3)	0.35481 (13)	0.12625 (16)	0.0266 (7)
C7	0.8671 (3)	0.43471 (14)	0.25125 (18)	0.0334 (8)
C8	0.8532 (3)	0.46502 (16)	0.30954 (19)	0.0444 (9)
H8A	0.8149	0.4375	0.3247	0.044*
H8B	0.8050	0.5010	0.2872	0.044*
H8C	0.9308	0.4761	0.3541	0.044*
C9	0.9482 (3)	0.38024 (16)	0.28709 (19)	0.0439 (9)
H9A	0.9171	0.3532	0.3077	0.044*
H9B	1.0271	0.3935	0.3280	0.044*
H9C	0.9523	0.3592	0.2485	0.044*
C10	0.9264 (3)	0.47847 (17)	0.2280 (2)	0.0524 (10)
H10A	0.9360	0.4596	0.1906	0.052*
H10B	1.0037	0.4896	0.2727	0.052*
H10C	0.8776	0.5143	0.2059	0.052*
C11	0.5483 (3)	0.44302 (15)	−0.03136 (18)	0.0440 (9)
H11A	0.4638	0.4514	−0.0598	0.044*
H11B	0.5628	0.4131	−0.0585	0.044*
H11C	0.5908	0.4798	−0.0260	0.044*
C12	0.4451 (3)	0.33738 (14)	0.19257 (16)	0.0308 (7)
H12A	0.4549	0.3809	0.1896	0.031*
H12B	0.3606	0.3296	0.1690	0.031*
C13	0.5122 (2)	0.19467 (13)	0.27633 (15)	0.0229 (7)
C14	0.4687 (2)	0.13725 (13)	0.27596 (15)	0.0249 (7)
C15	0.3762 (3)	0.13518 (14)	0.28447 (17)	0.0325 (8)
H15	0.3456	0.0971	0.2843	0.032*
C16	0.3257 (3)	0.18535 (15)	0.29327 (19)	0.0360 (8)
C17	0.3697 (3)	0.24078 (14)	0.29378 (17)	0.0308 (7)
H17	0.3369	0.2758	0.2997	0.031*
C18	0.4624 (2)	0.24519 (13)	0.28555 (16)	0.0247 (7)
C19	0.5221 (3)	0.08122 (13)	0.26593 (17)	0.0298 (7)
C20	0.4673 (3)	0.02338 (14)	0.27034 (19)	0.0404 (9)
H20A	0.5024	−0.0109	0.2616	0.040*
H20B	0.3824	0.0240	0.2317	0.040*
H20C	0.4821	0.0201	0.3206	0.040*
C21	0.6550 (3)	0.07826 (14)	0.32870 (17)	0.0334 (8)
H21A	0.6898	0.0442	0.3194	0.033*
H21B	0.6667	0.0734	0.3780	0.033*
H21C	0.6929	0.1153	0.3286	0.033*
C22	0.5015 (3)	0.08341 (14)	0.18777 (17)	0.0374 (8)
H22A	0.5399	0.0491	0.1821	0.037*
H22B	0.5347	0.1205	0.1830	0.037*
H22C	0.4170	0.0821	0.1483	0.037*
C23	0.2244 (3)	0.17876 (18)	0.3017 (3)	0.0617 (12)
H23A	0.2317	0.1407	0.3266	0.062*
H23B	0.1500	0.1795	0.2515	0.062*
H23C	0.2261	0.2118	0.3323	0.062*
C24	0.8123 (4)	0.18753 (19)	0.2110 (3)	0.0621 (12)
H24	0.8010	0.1980	0.1620	0.062*
C25	0.7695 (4)	0.1269 (2)	0.2043 (3)	0.0824 (15)
H25A	0.6879	0.1243	0.1601	0.082*
H25B	0.7733	0.1163	0.2500	0.082*
H25C	0.8184	0.0992	0.1980	0.082*
C26	0.9402 (3)	0.1967 (2)	0.2730 (3)	0.0807 (16)
H26A	0.9649	0.2366	0.2685	0.081*
H26B	0.9873	0.1664	0.2685	0.081*
H26C	0.9519	0.1928	0.3224	0.081*
C27	1.0365 (2)	0.15640 (13)	0.55948 (16)	0.0246 (7)
C28	1.1113 (2)	0.11112 (13)	0.56304 (16)	0.0247 (7)
C29	1.1871 (2)	0.08437 (13)	0.63365 (17)	0.0281 (7)
H29	1.2372	0.0535	0.6371	0.028*
C30	1.1948 (3)	0.09929 (14)	0.69919 (17)	0.0291 (7)
C31	1.1230 (3)	0.14429 (13)	0.69443 (17)	0.0285 (7)
H31	1.1273	0.1565	0.7384	0.028*
C32	1.0445 (2)	0.17175 (13)	0.62566 (16)	0.0260 (7)
C33	1.1112 (3)	0.09474 (14)	0.49364 (17)	0.0306 (7)
C34	1.1974 (3)	0.04412 (16)	0.51056 (19)	0.0476 (10)
H34A	1.1943	0.0348	0.4648	0.048*
H34B	1.1759	0.0086	0.5269	0.048*
H34C	1.2773	0.0566	0.5509	0.048*
C35	1.1490 (3)	0.14903 (16)	0.46955 (19)	0.0420 (9)
H35A	1.1493	0.1389	0.4252	0.042*
H35B	1.2282	0.1613	0.5112	0.042*
H35C	1.0939	0.1819	0.4568	0.042*
C36	0.9883 (3)	0.07429 (15)	0.42800 (18)	0.0401 (9)
H36A	0.9897	0.0646	0.3839	0.040*
H36B	0.9317	0.1065	0.4148	0.040*
H36C	0.9651	0.0388	0.4434	0.040*
C37	1.2807 (3)	0.06718 (16)	0.77341 (18)	0.0459 (9)
H37A	1.2714	0.0823	0.8127	0.046*
H37B	1.3612	0.0745	0.7886	0.046*
H37C	1.2647	0.0242	0.7668	0.046*
C38	0.8114 (3)	0.18638 (14)	0.57367 (18)	0.0352 (8)
H38A	0.8299	0.1432	0.5796	0.035*
H38B	0.7742	0.1954	0.6008	0.035*
C39	0.7027 (2)	0.32310 (13)	0.48614 (16)	0.0238 (7)
C40	0.6562 (3)	0.37823 (13)	0.49089 (16)	0.0261 (7)
C41	0.5543 (3)	0.37524 (14)	0.48916 (17)	0.0326 (8)
H41	0.5219	0.4116	0.4923	0.033*
C42	0.4962 (3)	0.32204 (15)	0.48309 (18)	0.0344 (8)
C43	0.5440 (3)	0.26911 (14)	0.47998 (17)	0.0284 (7)
H43	0.5076	0.2322	0.4770	0.028*
C44	0.6466 (2)	0.26989 (13)	0.48121 (16)	0.0258 (7)
C45	0.7136 (3)	0.43741 (13)	0.49450 (18)	0.0341 (8)
C46	0.8438 (3)	0.43846 (16)	0.5621 (2)	0.0503 (10)
H46A	0.8800	0.4760	0.5617	0.050*
H46B	0.8852	0.4047	0.5582	0.050*
H46C	0.8488	0.4354	0.6095	0.050*
C47	0.7071 (3)	0.44559 (14)	0.42106 (19)	0.0407 (9)
H47A	0.7445	0.4835	0.4231	0.041*
H47B	0.6247	0.4460	0.3777	0.041*
H47C	0.7481	0.4125	0.4155	0.041*
C48	0.6523 (4)	0.49092 (14)	0.5025 (2)	0.0557 (11)
H48A	0.6897	0.5280	0.5021	0.056*
H48B	0.6589	0.4878	0.5504	0.056*
H48C	0.5691	0.4912	0.4603	0.056*
C49	0.3845 (3)	0.32339 (17)	0.4808 (2)	0.0540 (11)
H49A	0.3969	0.3481	0.5225	0.054*
H49B	0.3640	0.2826	0.4860	0.054*
H49C	0.3204	0.3403	0.4325	0.054*
C50A	1.1222 (7)	0.3366 (4)	0.5614 (6)	0.045 (3)*	0.398 (9)
H50A	1.1333	0.3499	0.6096	0.045*	0.398 (9)
C51A	1.2224 (9)	0.2984 (5)	0.5734 (8)	0.049 (4)*	0.398 (9)
H51A	1.2220	0.2655	0.6034	0.049*	0.398 (9)
H51B	1.2962	0.3208	0.6041	0.049*	0.398 (9)
H51C	1.2155	0.2823	0.5285	0.049*	0.398 (9)
C52A	1.1245 (8)	0.3875 (4)	0.5152 (5)	0.039 (3)*	0.398 (9)
H52A	1.0962	0.3732	0.4643	0.039*	0.398 (9)
H52B	1.2054	0.4020	0.5405	0.039*	0.398 (9)
H52C	1.0740	0.4201	0.5114	0.039*	0.398 (9)
C50B	1.1207 (5)	0.3292 (2)	0.5222 (3)	0.047 (2)*	0.602 (9)
H50B	1.1224	0.3267	0.4763	0.047*	0.602 (9)
C51B	1.2194 (5)	0.2954 (3)	0.5906 (4)	0.037 (2)*	0.602 (9)
H51D	1.2195	0.2545	0.5744	0.037*	0.602 (9)
H51E	1.2144	0.2944	0.6344	0.037*	0.602 (9)
H51F	1.2921	0.3157	0.6046	0.037*	0.602 (9)
C52B	1.1199 (8)	0.3926 (3)	0.5475 (6)	0.100 (3)*	0.602 (9)
H52D	1.0502	0.4142	0.5074	0.100*	0.602 (9)
H52E	1.1909	0.4136	0.5595	0.100*	0.602 (9)
H52F	1.1191	0.3906	0.5928	0.100*	0.602 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ti1	0.0203 (3)	0.0268 (3)	0.0319 (3)	0.0052 (2)	0.0155 (2)	0.0083 (3)
Ti2	0.0204 (3)	0.0222 (3)	0.0334 (3)	0.0036 (2)	0.0148 (2)	0.0077 (3)
S1	0.0257 (4)	0.0251 (4)	0.0304 (4)	−0.0014 (3)	0.0123 (3)	−0.0007 (3)
S2	0.0271 (4)	0.0219 (4)	0.0334 (4)	0.0005 (3)	0.0160 (4)	−0.0014 (3)
S3	0.0340 (4)	0.0277 (4)	0.0363 (5)	0.0077 (4)	0.0214 (4)	0.0030 (4)
S4	0.0314 (4)	0.0186 (4)	0.0412 (5)	0.0015 (3)	0.0221 (4)	0.0023 (4)
O1	0.0272 (11)	0.0287 (11)	0.0244 (11)	−0.0031 (9)	0.0130 (9)	0.0035 (9)
O2	0.0290 (11)	0.0205 (11)	0.0430 (13)	0.0033 (9)	0.0252 (10)	0.0027 (10)
O3	0.0384 (13)	0.0412 (14)	0.0507 (14)	0.0106 (11)	0.0329 (12)	0.0063 (12)
O4	0.0244 (11)	0.0338 (12)	0.0343 (12)	0.0069 (10)	0.0146 (10)	0.0134 (10)
O5	0.0314 (12)	0.0300 (12)	0.0279 (11)	0.0110 (10)	0.0167 (10)	0.0068 (10)
O6	0.0268 (11)	0.0185 (11)	0.0436 (13)	0.0016 (9)	0.0210 (10)	0.0056 (10)
O7	0.0215 (11)	0.0377 (13)	0.0542 (14)	−0.0031 (10)	0.0189 (11)	0.0041 (11)
C1	0.0269 (16)	0.0227 (16)	0.0233 (16)	0.0052 (13)	0.0144 (14)	0.0032 (13)
C2	0.0302 (17)	0.0227 (16)	0.0295 (17)	0.0008 (14)	0.0186 (14)	0.0014 (14)
C3	0.043 (2)	0.0220 (17)	0.046 (2)	0.0051 (15)	0.0320 (18)	0.0073 (16)
C4	0.050 (2)	0.0280 (18)	0.0284 (18)	0.0136 (16)	0.0241 (17)	0.0066 (15)
C5	0.0319 (17)	0.0272 (17)	0.0255 (16)	0.0054 (15)	0.0134 (14)	0.0012 (14)
C6	0.0277 (16)	0.0227 (16)	0.0294 (17)	0.0039 (13)	0.0161 (14)	0.0031 (14)
C7	0.0321 (18)	0.0359 (19)	0.0380 (19)	−0.0094 (15)	0.0235 (16)	−0.0038 (16)
C8	0.039 (2)	0.049 (2)	0.046 (2)	−0.0162 (18)	0.0246 (17)	−0.0175 (18)
C9	0.0275 (18)	0.058 (2)	0.044 (2)	−0.0022 (18)	0.0188 (17)	−0.0009 (19)
C10	0.047 (2)	0.061 (3)	0.054 (2)	−0.021 (2)	0.0309 (19)	−0.008 (2)
C11	0.064 (2)	0.038 (2)	0.0369 (19)	0.0111 (19)	0.0332 (19)	0.0084 (17)
C12	0.0264 (16)	0.0285 (17)	0.0371 (18)	0.0074 (14)	0.0177 (15)	0.0077 (15)
C13	0.0198 (15)	0.0265 (17)	0.0225 (15)	0.0011 (13)	0.0120 (13)	0.0019 (13)
C14	0.0227 (15)	0.0271 (17)	0.0210 (15)	−0.0017 (13)	0.0101 (13)	0.0001 (13)
C15	0.0294 (17)	0.0301 (18)	0.0361 (18)	−0.0038 (15)	0.0174 (15)	0.0031 (15)
C16	0.0277 (17)	0.045 (2)	0.042 (2)	0.0019 (16)	0.0238 (16)	0.0046 (17)
C17	0.0289 (17)	0.0318 (18)	0.0361 (18)	0.0098 (15)	0.0211 (15)	0.0034 (15)
C18	0.0224 (15)	0.0241 (16)	0.0258 (16)	−0.0001 (13)	0.0125 (13)	0.0018 (13)
C19	0.0335 (18)	0.0214 (16)	0.0316 (18)	0.0014 (14)	0.0167 (15)	0.0010 (14)
C20	0.050 (2)	0.0284 (18)	0.042 (2)	−0.0055 (17)	0.0250 (18)	−0.0058 (16)
C21	0.0405 (19)	0.0268 (17)	0.0356 (18)	0.0078 (15)	0.0230 (16)	0.0046 (15)
C22	0.041 (2)	0.0321 (19)	0.0343 (19)	0.0050 (16)	0.0189 (16)	−0.0012 (15)
C23	0.054 (2)	0.058 (3)	0.102 (3)	0.001 (2)	0.061 (3)	0.007 (2)
C24	0.055 (3)	0.060 (3)	0.084 (3)	0.014 (2)	0.047 (3)	0.012 (2)
C25	0.102 (4)	0.069 (3)	0.098 (4)	0.017 (3)	0.070 (3)	−0.012 (3)
C26	0.049 (3)	0.106 (4)	0.100 (4)	0.033 (3)	0.050 (3)	0.047 (3)
C27	0.0227 (15)	0.0207 (16)	0.0276 (16)	0.0017 (13)	0.0127 (14)	0.0048 (13)
C28	0.0199 (15)	0.0210 (16)	0.0305 (17)	0.0007 (13)	0.0127 (14)	0.0028 (14)
C29	0.0239 (16)	0.0225 (16)	0.0353 (18)	0.0069 (13)	0.0152 (14)	0.0043 (14)
C30	0.0271 (17)	0.0296 (17)	0.0282 (17)	0.0031 (14)	0.0143 (14)	0.0066 (14)
C31	0.0277 (16)	0.0341 (18)	0.0241 (16)	−0.0021 (15)	0.0150 (14)	0.0015 (14)
C32	0.0245 (16)	0.0216 (16)	0.0311 (17)	0.0020 (13)	0.0154 (14)	0.0025 (14)
C33	0.0284 (17)	0.0300 (17)	0.0302 (17)	0.0067 (14)	0.0147 (15)	0.0007 (15)
C34	0.050 (2)	0.056 (2)	0.0363 (19)	0.0267 (19)	0.0241 (18)	0.0041 (18)
C35	0.042 (2)	0.053 (2)	0.0364 (19)	0.0033 (18)	0.0256 (17)	0.0012 (17)
C36	0.041 (2)	0.036 (2)	0.0349 (18)	0.0010 (17)	0.0163 (16)	−0.0058 (16)
C37	0.048 (2)	0.050 (2)	0.036 (2)	0.0181 (19)	0.0218 (18)	0.0120 (18)
C38	0.0318 (18)	0.0307 (18)	0.049 (2)	0.0089 (15)	0.0267 (16)	0.0160 (16)
C39	0.0228 (15)	0.0211 (16)	0.0255 (16)	0.0033 (13)	0.0126 (13)	0.0032 (13)
C40	0.0302 (17)	0.0230 (16)	0.0267 (16)	0.0024 (14)	0.0171 (14)	0.0012 (13)
C41	0.043 (2)	0.0237 (17)	0.0400 (19)	0.0108 (15)	0.0288 (17)	0.0052 (15)
C42	0.0305 (18)	0.038 (2)	0.0398 (19)	0.0076 (16)	0.0229 (16)	0.0089 (16)
C43	0.0254 (16)	0.0252 (17)	0.0358 (17)	−0.0023 (14)	0.0181 (14)	0.0030 (15)
C44	0.0247 (16)	0.0193 (16)	0.0319 (17)	−0.0001 (13)	0.0151 (14)	−0.0002 (14)
C45	0.043 (2)	0.0208 (16)	0.044 (2)	−0.0001 (15)	0.0280 (17)	−0.0012 (15)
C46	0.054 (2)	0.038 (2)	0.052 (2)	−0.0201 (19)	0.026 (2)	−0.0089 (19)
C47	0.060 (2)	0.0202 (17)	0.052 (2)	0.0009 (16)	0.0374 (19)	0.0065 (16)
C48	0.088 (3)	0.0223 (18)	0.086 (3)	−0.001 (2)	0.067 (3)	−0.004 (2)
C49	0.047 (2)	0.046 (2)	0.091 (3)	0.0125 (19)	0.052 (2)	0.015 (2)

Geometric parameters (Å, º)

Ti1—O3	1.766 (2)	C24—C25	1.454 (6)
Ti1—O4	1.797 (2)	C24—C26	1.506 (6)
Ti1—O2	1.894 (2)	C24—H24	1.0000
Ti1—O1	1.923 (2)	C25—H25A	0.9800
Ti1—S1	2.7660 (13)	C25—H25B	0.9801
Ti1—S2	2.8011 (11)	C25—H25C	0.9800
Ti2—O7	1.752 (2)	C26—H26A	0.9800
Ti2—O4	1.815 (2)	C26—H26B	0.9800
Ti2—O6	1.895 (2)	C26—H26C	0.9800
Ti2—O5	1.921 (2)	C27—C32	1.402 (4)
Ti2—S3	2.7605 (14)	C27—C28	1.418 (4)
Ti2—S4	2.8046 (11)	C28—C29	1.396 (4)
S1—C6	1.766 (3)	C28—C33	1.531 (4)
S1—C12	1.829 (3)	C29—C30	1.388 (4)
S2—C18	1.776 (3)	C29—H29	0.9500
S2—C12	1.816 (3)	C30—C31	1.376 (4)
S3—C32	1.776 (3)	C30—C37	1.521 (4)
S3—C38	1.832 (3)	C31—C32	1.383 (4)
S4—C44	1.770 (3)	C31—H31	0.9500
S4—C38	1.811 (3)	C33—C35	1.524 (4)
O1—C1	1.343 (3)	C33—C34	1.531 (4)
O2—C13	1.337 (3)	C33—C36	1.537 (4)
O3—C24	1.437 (4)	C34—H34A	0.9799
O5—C27	1.342 (3)	C34—H34B	0.9800
O6—C39	1.336 (3)	C34—H34C	0.9800
O7—C50A	1.423 (9)	C35—H35A	0.9800
O7—C50B	1.447 (7)	C35—H35B	0.9800
C1—C2	1.408 (4)	C35—H35C	0.9800
C1—C6	1.409 (4)	C36—H36A	0.9800
C2—C3	1.396 (4)	C36—H36B	0.9800
C2—C7	1.541 (4)	C36—H36C	0.9800
C3—C4	1.393 (4)	C37—H37A	0.9800
C3—H3	0.9500	C37—H37B	0.9800
C4—C5	1.386 (4)	C37—H37C	0.9800
C4—C11	1.505 (4)	C38—H38A	0.9900
C5—C6	1.386 (4)	C38—H38B	0.9900
C5—H5	0.9500	C39—C44	1.392 (4)
C7—C8	1.526 (4)	C39—C40	1.421 (4)
C7—C10	1.530 (4)	C40—C41	1.389 (4)
C7—C9	1.535 (5)	C40—C45	1.523 (4)
C8—H8A	0.9800	C41—C42	1.400 (4)
C8—H8B	0.9800	C41—H41	0.9500
C8—H8C	0.9800	C42—C43	1.376 (4)
C9—H9A	0.9800	C42—C49	1.515 (4)
C9—H9B	0.9800	C43—C44	1.402 (4)
C9—H9C	0.9800	C43—H43	0.9500
C10—H10A	0.9800	C45—C48	1.531 (4)
C10—H10B	0.9800	C45—C47	1.536 (5)
C10—H10C	0.9800	C45—C46	1.542 (4)
C11—H11A	0.9800	C46—H46A	0.9800
C11—H11B	0.9800	C46—H46B	0.9800
C11—H11C	0.9800	C46—H46C	0.9800
C12—H12A	0.9900	C47—H47A	0.9800
C12—H12B	0.9900	C47—H47B	0.9800
C13—C18	1.395 (4)	C47—H47C	0.9800
C13—C14	1.417 (4)	C48—H48A	0.9800
C14—C15	1.389 (4)	C48—H48B	0.9800
C14—C19	1.530 (4)	C48—H48C	0.9800
C15—C16	1.390 (4)	C49—H49A	0.9800
C15—H15	0.9500	C49—H49B	0.9800
C16—C17	1.379 (4)	C49—H49C	0.9800
C16—C23	1.515 (4)	C50A—C51A	1.5202 (11)
C17—C18	1.390 (4)	C50A—C52A	1.5209 (11)
C17—H17	0.9500	C50A—H50A	1.0000
C19—C20	1.528 (4)	C51A—H51A	0.9800
C19—C22	1.533 (4)	C51A—H51B	0.9800
C19—C21	1.544 (4)	C51A—H51C	0.9800
C20—H20A	0.9800	C52A—H52A	0.9800
C20—H20B	0.9800	C52A—H52B	0.9800
C20—H20C	0.9800	C52A—H52C	0.9800
C21—H21A	0.9800	C50B—C51B	1.5209 (11)
C21—H21B	0.9800	C50B—C52B	1.5212 (11)
C21—H21C	0.9800	C50B—H50B	1.0000
C22—H22A	0.9800	C51B—H51D	0.9800
C22—H22B	0.9800	C51B—H51E	0.9800
C22—H22C	0.9800	C51B—H51F	0.9800
C23—H23A	0.9800	C52B—H52D	0.9800
C23—H23B	0.9800	C52B—H52E	0.9800
C23—H23C	0.9800	C52B—H52F	0.9800
O3—Ti1—O4	108.07 (10)	C28—C29—H29	117.4
O3—Ti1—O2	98.07 (10)	C31—C30—C29	117.5 (3)
O4—Ti1—O2	99.04 (9)	C31—C30—C37	121.7 (3)
O3—Ti1—O1	99.20 (10)	C29—C30—C37	120.8 (3)
O4—Ti1—O1	98.12 (9)	C30—C31—C32	120.0 (3)
O2—Ti1—O1	150.47 (9)	C30—C31—H31	120.0
O3—Ti1—S1	90.54 (8)	C32—C31—H31	120.0
O4—Ti1—S1	160.72 (8)	C31—C32—C27	122.3 (3)
O2—Ti1—S1	82.80 (7)	C31—C32—S3	121.1 (2)
O1—Ti1—S1	73.29 (6)	C27—C32—S3	116.6 (2)
O3—Ti1—S2	155.94 (8)	C35—C33—C34	107.5 (3)
O4—Ti1—S2	95.62 (8)	C35—C33—C28	109.1 (3)
O2—Ti1—S2	73.47 (6)	C34—C33—C28	112.0 (3)
O1—Ti1—S2	81.09 (7)	C35—C33—C36	109.9 (3)
S1—Ti1—S2	66.34 (3)	C34—C33—C36	107.7 (3)
O7—Ti2—O4	107.54 (11)	C28—C33—C36	110.7 (3)
O7—Ti2—O6	96.45 (10)	C33—C34—H34A	109.5
O4—Ti2—O6	100.01 (9)	C33—C34—H34B	109.5
O7—Ti2—O5	98.73 (10)	H34A—C34—H34B	109.5
O4—Ti2—O5	96.85 (9)	C33—C34—H34C	109.5
O6—Ti2—O5	152.71 (9)	H34A—C34—H34C	109.5
O7—Ti2—S3	93.61 (8)	H34B—C34—H34C	109.5
O4—Ti2—S3	157.96 (7)	C33—C35—H35A	109.5
O6—Ti2—S3	83.29 (7)	C33—C35—H35B	109.5
O5—Ti2—S3	73.27 (6)	H35A—C35—H35B	109.5
O7—Ti2—S4	157.82 (9)	C33—C35—H35C	109.4
O4—Ti2—S4	93.71 (7)	H35A—C35—H35C	109.5
O6—Ti2—S4	73.10 (7)	H35B—C35—H35C	109.5
O5—Ti2—S4	84.59 (7)	C33—C36—H36A	109.5
S3—Ti2—S4	66.19 (3)	C33—C36—H36B	109.4
C6—S1—C12	101.63 (14)	H36A—C36—H36B	109.5
C6—S1—Ti1	90.57 (10)	C33—C36—H36C	109.6
C12—S1—Ti1	89.04 (10)	H36A—C36—H36C	109.5
C18—S2—C12	101.59 (14)	H36B—C36—H36C	109.5
C18—S2—Ti1	93.19 (10)	C30—C37—H37A	109.4
C12—S2—Ti1	88.21 (10)	C30—C37—H37B	109.4
C32—S3—C38	100.05 (14)	H37A—C37—H37B	109.5
C32—S3—Ti2	93.06 (10)	C30—C37—H37C	109.6
C38—S3—Ti2	89.94 (11)	H37A—C37—H37C	109.5
C44—S4—C38	99.69 (15)	H37B—C37—H37C	109.5
C44—S4—Ti2	93.37 (10)	S4—C38—S3	113.10 (17)
C38—S4—Ti2	88.99 (10)	S4—C38—H38A	109.0
C1—O1—Ti1	126.04 (17)	S3—C38—H38A	109.0
C13—O2—Ti1	136.15 (18)	S4—C38—H38B	109.0
C24—O3—Ti1	156.2 (2)	S3—C38—H38B	109.0
Ti1—O4—Ti2	162.05 (13)	H38A—C38—H38B	107.8
C27—O5—Ti2	131.93 (18)	O6—C39—C44	119.6 (3)
C39—O6—Ti2	136.62 (18)	O6—C39—C40	120.8 (3)
C50A—O7—Ti2	162.8 (4)	C44—C39—C40	119.6 (3)
C50B—O7—Ti2	159.7 (3)	C41—C40—C39	116.6 (3)
O1—C1—C2	122.2 (3)	C41—C40—C45	122.3 (3)
O1—C1—C6	118.2 (3)	C39—C40—C45	121.1 (3)
C2—C1—C6	119.6 (3)	C40—C41—C42	124.2 (3)
C3—C2—C1	116.5 (3)	C40—C41—H41	117.9
C3—C2—C7	121.9 (3)	C42—C41—H41	117.9
C1—C2—C7	121.6 (3)	C43—C42—C41	118.1 (3)
C4—C3—C2	124.7 (3)	C43—C42—C49	121.5 (3)
C4—C3—H3	117.7	C41—C42—C49	120.3 (3)
C2—C3—H3	117.7	C42—C43—C44	119.7 (3)
C5—C4—C3	117.6 (3)	C42—C43—H43	120.1
C5—C4—C11	121.1 (3)	C44—C43—H43	120.1
C3—C4—C11	121.3 (3)	C39—C44—C43	121.7 (3)
C4—C5—C6	120.1 (3)	C39—C44—S4	117.2 (2)
C4—C5—H5	120.0	C43—C44—S4	121.0 (2)
C6—C5—H5	120.0	C40—C45—C48	112.4 (3)
C5—C6—C1	121.6 (3)	C40—C45—C47	109.0 (3)
C5—C6—S1	121.1 (2)	C48—C45—C47	107.9 (3)
C1—C6—S1	117.2 (2)	C40—C45—C46	110.9 (3)
C8—C7—C10	108.7 (3)	C48—C45—C46	107.8 (3)
C8—C7—C9	109.7 (3)	C47—C45—C46	108.7 (3)
C10—C7—C9	107.3 (3)	C45—C46—H46A	109.5
C8—C7—C2	109.5 (3)	C45—C46—H46B	109.5
C10—C7—C2	111.8 (3)	H46A—C46—H46B	109.5
C9—C7—C2	109.7 (3)	C45—C46—H46C	109.4
C7—C8—H8A	109.5	H46A—C46—H46C	109.5
C7—C8—H8B	109.4	H46B—C46—H46C	109.5
H8A—C8—H8B	109.5	C45—C47—H47A	109.5
C7—C8—H8C	109.5	C45—C47—H47B	109.5
H8A—C8—H8C	109.5	H47A—C47—H47B	109.5
H8B—C8—H8C	109.5	C45—C47—H47C	109.4
C7—C9—H9A	109.5	H47A—C47—H47C	109.5
C7—C9—H9B	109.4	H47B—C47—H47C	109.5
H9A—C9—H9B	109.5	C45—C48—H48A	109.5
C7—C9—H9C	109.5	C45—C48—H48B	109.4
H9A—C9—H9C	109.5	H48A—C48—H48B	109.5
H9B—C9—H9C	109.5	C45—C48—H48C	109.5
C7—C10—H10A	109.6	H48A—C48—H48C	109.5
C7—C10—H10B	109.4	H48B—C48—H48C	109.5
H10A—C10—H10B	109.5	C42—C49—H49A	109.5
C7—C10—H10C	109.4	C42—C49—H49B	109.4
H10A—C10—H10C	109.5	H49A—C49—H49B	109.5
H10B—C10—H10C	109.5	C42—C49—H49C	109.5
C4—C11—H11A	109.5	H49A—C49—H49C	109.5
C4—C11—H11B	109.3	H49B—C49—H49C	109.5
H11A—C11—H11B	109.5	O7—C50A—C51A	108.8 (8)
C4—C11—H11C	109.6	O7—C50A—C52A	105.5 (7)
H11A—C11—H11C	109.5	C51A—C50A—C52A	100.2 (8)
H11B—C11—H11C	109.5	O7—C50A—H50A	113.7
S2—C12—S1	113.34 (16)	C51A—C50A—H50A	113.7
S2—C12—H12A	108.9	C52A—C50A—H50A	113.7
S1—C12—H12A	108.9	O7—C50A—H52F	118.2
S2—C12—H12B	108.9	C51A—C50A—H52F	132.8
S1—C12—H12B	108.9	C52A—C50A—H52F	71.6
H12A—C12—H12B	107.7	C50A—C51A—H51A	100.9
O2—C13—C18	119.7 (3)	C50A—C51A—H51B	109.1
O2—C13—C14	120.7 (3)	H51A—C51A—H51B	109.5
C18—C13—C14	119.6 (3)	C50A—C51A—H51C	118.0
C15—C14—C13	116.6 (3)	H51A—C51A—H51C	109.5
C15—C14—C19	122.9 (3)	H51B—C51A—H51C	109.5
C13—C14—C19	120.5 (3)	C50A—C51A—H51D	121.3
C14—C15—C16	124.1 (3)	H51B—C51A—H51D	122.4
C14—C15—H15	118.0	H51C—C51A—H51D	70.8
C16—C15—H15	118.0	C50A—C51A—H51E	68.9
C17—C16—C15	118.4 (3)	H51A—C51A—H51E	45.1
C17—C16—C23	121.3 (3)	H51B—C51A—H51E	90.5
C15—C16—C23	120.4 (3)	H51C—C51A—H51E	153.2
C16—C17—C18	119.7 (3)	H51D—C51A—H51E	83.5
C16—C17—H17	120.1	C50A—C51A—H51F	112.1
C18—C17—H17	120.1	H51A—C51A—H51F	103.8
C17—C18—C13	121.6 (3)	H51C—C51A—H51F	111.2
C17—C18—S2	121.1 (2)	H51D—C51A—H51F	117.2
C13—C18—S2	117.2 (2)	H51E—C51A—H51F	87.0
C20—C19—C14	113.0 (3)	C50A—C52A—H52A	109.8
C20—C19—C22	107.6 (3)	C50A—C52A—H52B	109.0
C14—C19—C22	108.8 (2)	H52A—C52A—H52B	109.5
C20—C19—C21	107.2 (3)	C50A—C52A—H52C	109.6
C14—C19—C21	110.0 (2)	H52A—C52A—H52C	109.5
C22—C19—C21	110.2 (3)	H52B—C52A—H52C	109.5
C19—C20—H20A	109.7	C50A—C52A—H52D	98.2
C19—C20—H20B	109.4	H52A—C52A—H52D	104.8
H20A—C20—H20B	109.5	H52B—C52A—H52D	124.6
C19—C20—H20C	109.3	C50A—C52A—H52E	99.1
H20A—C20—H20C	109.5	H52A—C52A—H52E	141.5
H20B—C20—H20C	109.5	H52C—C52A—H52E	82.9
C19—C21—H21A	109.5	H52D—C52A—H52E	95.4
C19—C21—H21B	109.4	O7—C50B—C51B	104.6 (5)
H21A—C21—H21B	109.5	O7—C50B—C52B	100.2 (6)
C19—C21—H21C	109.5	C51B—C50B—C52B	107.7 (6)
H21A—C21—H21C	109.5	O7—C50B—H52A	112.2
H21B—C21—H21C	109.5	C51B—C50B—H52A	143.2
C19—C22—H22A	109.4	C52B—C50B—H52A	68.2
C19—C22—H22B	109.4	O7—C50B—H50B	114.3
H22A—C22—H22B	109.5	C51B—C50B—H50B	114.3
C19—C22—H22C	109.6	C52B—C50B—H50B	114.3
H22A—C22—H22C	109.5	H52A—C50B—H50B	47.8
H22B—C22—H22C	109.5	C50B—C51B—H51A	131.0
C16—C23—H23A	109.5	C50B—C51B—H51B	101.7
C16—C23—H23B	109.5	H51A—C51B—H51B	123.7
H23A—C23—H23B	109.5	C50B—C51B—H51C	68.9
C16—C23—H23C	109.5	H51A—C51B—H51C	98.1
H23A—C23—H23C	109.5	H51B—C51B—H51C	82.1
H23B—C23—H23C	109.5	C50B—C51B—H51D	107.6
O3—C24—C25	112.5 (3)	H51B—C51B—H51D	112.6
O3—C24—C26	106.4 (4)	H51C—C51B—H51D	56.4
C25—C24—C26	114.9 (4)	C50B—C51B—H51E	115.1
O3—C24—H24	107.6	H51A—C51B—H51E	68.1
C25—C24—H24	107.6	H51B—C51B—H51E	110.2
C26—C24—H24	107.6	H51C—C51B—H51E	165.0
C24—C25—H25A	109.3	H51D—C51B—H51E	109.5
C24—C25—H25B	109.8	C50B—C51B—H51F	105.6
H25A—C25—H25B	109.5	H51A—C51B—H51F	119.6
C24—C25—H25C	109.4	H51C—C51B—H51F	82.1
H25A—C25—H25C	109.5	H51D—C51B—H51F	109.5
H25B—C25—H25C	109.5	H51E—C51B—H51F	109.5
C24—C26—H26A	109.6	C50B—C52B—H52B	85.4
C24—C26—H26B	109.3	C50B—C52B—H52C	118.2
H26A—C26—H26B	109.5	H52B—C52B—H52C	92.0
C24—C26—H26C	109.5	C50B—C52B—H52D	110.5
H26A—C26—H26C	109.5	H52B—C52B—H52D	109.1
H26B—C26—H26C	109.5	C50B—C52B—H52E	109.5
O5—C27—C32	118.8 (3)	H52C—C52B—H52E	90.6
O5—C27—C28	122.3 (3)	H52D—C52B—H52E	109.5
C32—C27—C28	118.9 (3)	C50B—C52B—H52F	108.5
C29—C28—C27	116.1 (3)	H52B—C52B—H52F	130.5
C29—C28—C33	122.6 (3)	H52C—C52B—H52F	118.8
C27—C28—C33	121.3 (3)	H52D—C52B—H52F	109.5
C30—C29—C28	125.1 (3)	H52E—C52B—H52F	109.5
C30—C29—H29	117.4
O3—Ti1—S1—C6	−74.63 (12)	C1—C2—C7—C8	−62.7 (4)
O4—Ti1—S1—C6	90.5 (2)	C3—C2—C7—C10	−1.9 (4)
O2—Ti1—S1—C6	−172.69 (12)	C1—C2—C7—C10	176.8 (3)
O1—Ti1—S1—C6	24.82 (12)	C3—C2—C7—C9	−120.9 (3)
S2—Ti1—S1—C6	112.24 (10)	C1—C2—C7—C9	57.8 (4)
O3—Ti1—S1—C12	−176.24 (13)	C18—S2—C12—S1	−76.63 (19)
O4—Ti1—S1—C12	−11.1 (2)	Ti1—S2—C12—S1	16.26 (15)
O2—Ti1—S1—C12	85.69 (12)	C6—S1—C12—S2	−106.85 (18)
O1—Ti1—S1—C12	−76.80 (12)	Ti1—S1—C12—S2	−16.46 (15)
S2—Ti1—S1—C12	10.62 (10)	Ti1—O2—C13—C18	7.6 (4)
O3—Ti1—S2—C18	73.8 (2)	Ti1—O2—C13—C14	−172.6 (2)
O4—Ti1—S2—C18	−96.24 (12)	O2—C13—C14—C15	−179.3 (3)
O2—Ti1—S2—C18	1.54 (11)	C18—C13—C14—C15	0.5 (4)
O1—Ti1—S2—C18	166.39 (11)	O2—C13—C14—C19	0.2 (4)
S1—Ti1—S2—C18	90.81 (10)	C18—C13—C14—C19	180.0 (3)
O3—Ti1—S2—C12	−27.7 (2)	C13—C14—C15—C16	−0.1 (5)
O4—Ti1—S2—C12	162.25 (12)	C19—C14—C15—C16	−179.6 (3)
O2—Ti1—S2—C12	−99.96 (12)	C14—C15—C16—C17	−0.1 (5)
O1—Ti1—S2—C12	64.88 (12)	C14—C15—C16—C23	179.6 (3)
S1—Ti1—S2—C12	−10.70 (10)	C15—C16—C17—C18	0.0 (5)
O7—Ti2—S3—C32	−81.33 (12)	C23—C16—C17—C18	−179.7 (3)
O4—Ti2—S3—C32	82.5 (2)	C16—C17—C18—C13	0.3 (5)
O6—Ti2—S3—C32	−177.41 (11)	C16—C17—C18—S2	−176.2 (2)
O5—Ti2—S3—C32	16.71 (11)	O2—C13—C18—C17	179.2 (3)
S4—Ti2—S3—C32	108.14 (10)	C14—C13—C18—C17	−0.6 (4)
O7—Ti2—S3—C38	178.61 (13)	O2—C13—C18—S2	−4.1 (4)
O4—Ti2—S3—C38	−17.6 (2)	C14—C13—C18—S2	176.1 (2)
O6—Ti2—S3—C38	82.53 (12)	C12—S2—C18—C17	−93.6 (3)
O5—Ti2—S3—C38	−83.35 (12)	Ti1—S2—C18—C17	177.5 (2)
S4—Ti2—S3—C38	8.08 (10)	C12—S2—C18—C13	89.7 (2)
O7—Ti2—S4—C44	65.7 (2)	Ti1—S2—C18—C13	0.8 (2)
O4—Ti2—S4—C44	−97.91 (12)	C15—C14—C19—C20	−2.9 (4)
O6—Ti2—S4—C44	1.43 (11)	C13—C14—C19—C20	177.6 (3)
O5—Ti2—S4—C44	165.55 (11)	C15—C14—C19—C22	116.6 (3)
S3—Ti2—S4—C44	91.47 (10)	C13—C14—C19—C22	−62.9 (3)
O7—Ti2—S4—C38	−34.0 (2)	C15—C14—C19—C21	−122.7 (3)
O4—Ti2—S4—C38	162.45 (13)	C13—C14—C19—C21	57.8 (4)
O6—Ti2—S4—C38	−98.21 (13)	Ti1—O3—C24—C25	63.2 (7)
O5—Ti2—S4—C38	65.90 (12)	Ti1—O3—C24—C26	−63.5 (7)
S3—Ti2—S4—C38	−8.18 (11)	Ti2—O5—C27—C32	26.1 (4)
O3—Ti1—O1—C1	49.2 (2)	Ti2—O5—C27—C28	−154.2 (2)
O4—Ti1—O1—C1	159.1 (2)	O5—C27—C28—C29	−178.7 (3)
O2—Ti1—O1—C1	−75.9 (3)	C32—C27—C28—C29	1.0 (4)
S1—Ti1—O1—C1	−38.6 (2)	O5—C27—C28—C33	3.6 (4)
S2—Ti1—O1—C1	−106.4 (2)	C32—C27—C28—C33	−176.7 (3)
O3—Ti1—O2—C13	−162.2 (3)	C27—C28—C29—C30	−0.8 (4)
O4—Ti1—O2—C13	88.0 (3)	C33—C28—C29—C30	176.9 (3)
O1—Ti1—O2—C13	−36.8 (4)	C28—C29—C30—C31	−0.5 (5)
S1—Ti1—O2—C13	−72.6 (3)	C28—C29—C30—C37	180.0 (3)
S2—Ti1—O2—C13	−5.2 (2)	C29—C30—C31—C32	1.7 (4)
O4—Ti1—O3—C24	36.3 (6)	C37—C30—C31—C32	−178.8 (3)
O2—Ti1—O3—C24	−66.0 (6)	C30—C31—C32—C27	−1.5 (5)
O1—Ti1—O3—C24	138.0 (6)	C30—C31—C32—S3	178.7 (2)
S1—Ti1—O3—C24	−148.8 (6)	O5—C27—C32—C31	179.8 (3)
S2—Ti1—O3—C24	−133.2 (5)	C28—C27—C32—C31	0.1 (4)
O3—Ti1—O4—Ti2	−164.4 (4)	O5—C27—C32—S3	−0.4 (4)
O2—Ti1—O4—Ti2	−62.8 (4)	C28—C27—C32—S3	179.9 (2)
O1—Ti1—O4—Ti2	93.1 (4)	C38—S3—C32—C31	−102.4 (3)
S1—Ti1—O4—Ti2	31.2 (6)	Ti2—S3—C32—C31	167.1 (2)
S2—Ti1—O4—Ti2	11.3 (4)	C38—S3—C32—C27	77.7 (3)
O7—Ti2—O4—Ti1	−132.2 (4)	Ti2—S3—C32—C27	−12.8 (2)
O6—Ti2—O4—Ti1	−32.1 (4)	C29—C28—C33—C35	−115.6 (3)
O5—Ti2—O4—Ti1	126.4 (4)	C27—C28—C33—C35	62.1 (3)
S3—Ti2—O4—Ti1	64.8 (5)	C29—C28—C33—C34	3.3 (4)
S4—Ti2—O4—Ti1	41.4 (4)	C27—C28—C33—C34	−179.1 (3)
O7—Ti2—O5—C27	64.8 (3)	C29—C28—C33—C36	123.4 (3)
O4—Ti2—O5—C27	173.8 (2)	C27—C28—C33—C36	−58.9 (4)
O6—Ti2—O5—C27	−58.3 (3)	C44—S4—C38—S3	−80.9 (2)
S3—Ti2—O5—C27	−26.4 (2)	Ti2—S4—C38—S3	12.31 (16)
S4—Ti2—O5—C27	−93.1 (2)	C32—S3—C38—S4	−105.60 (19)
O7—Ti2—O6—C39	−162.3 (3)	Ti2—S3—C38—S4	−12.51 (17)
O4—Ti2—O6—C39	88.6 (3)	Ti2—O6—C39—C44	2.1 (4)
O5—Ti2—O6—C39	−38.7 (4)	Ti2—O6—C39—C40	−176.8 (2)
S3—Ti2—O6—C39	−69.4 (3)	O6—C39—C40—C41	178.0 (3)
S4—Ti2—O6—C39	−2.3 (2)	C44—C39—C40—C41	−0.9 (4)
O4—Ti2—O7—C50A	−178.4 (12)	O6—C39—C40—C45	0.4 (4)
O6—Ti2—O7—C50A	79.0 (12)	C44—C39—C40—C45	−178.6 (3)
O5—Ti2—O7—C50A	−78.3 (12)	C39—C40—C41—C42	0.0 (5)
S3—Ti2—O7—C50A	−4.7 (12)	C45—C40—C41—C42	177.6 (3)
S4—Ti2—O7—C50A	18.8 (13)	C40—C41—C42—C43	1.2 (5)
O4—Ti2—O7—C50B	−45.3 (7)	C40—C41—C42—C49	−179.3 (3)
O6—Ti2—O7—C50B	−148.0 (7)	C41—C42—C43—C44	−1.4 (5)
O5—Ti2—O7—C50B	54.8 (7)	C49—C42—C43—C44	179.1 (3)
S3—Ti2—O7—C50B	128.4 (7)	O6—C39—C44—C43	−178.3 (3)
S4—Ti2—O7—C50B	151.9 (6)	C40—C39—C44—C43	0.7 (4)
Ti1—O1—C1—C2	−140.1 (2)	O6—C39—C44—S4	0.2 (4)
Ti1—O1—C1—C6	39.9 (4)	C40—C39—C44—S4	179.1 (2)
O1—C1—C2—C3	179.2 (3)	C42—C43—C44—C39	0.5 (5)
C6—C1—C2—C3	−0.7 (4)	C42—C43—C44—S4	−177.8 (2)
O1—C1—C2—C7	0.5 (4)	C38—S4—C44—C39	88.4 (3)
C6—C1—C2—C7	−179.5 (3)	Ti2—S4—C44—C39	−1.2 (2)
C1—C2—C3—C4	−0.4 (5)	C38—S4—C44—C43	−93.2 (3)
C7—C2—C3—C4	178.3 (3)	Ti2—S4—C44—C43	177.3 (2)
C2—C3—C4—C5	1.7 (5)	C41—C40—C45—C48	4.7 (4)
C2—C3—C4—C11	−176.8 (3)	C39—C40—C45—C48	−177.8 (3)
C3—C4—C5—C6	−1.8 (4)	C41—C40—C45—C47	−114.8 (3)
C11—C4—C5—C6	176.7 (3)	C39—C40—C45—C47	62.7 (4)
C4—C5—C6—C1	0.7 (5)	C41—C40—C45—C46	125.5 (3)
C4—C5—C6—S1	−174.9 (2)	C39—C40—C45—C46	−56.9 (4)
O1—C1—C6—C5	−179.4 (3)	C50B—O7—C50A—C51A	−55.0 (9)
C2—C1—C6—C5	0.6 (4)	Ti2—O7—C50A—C51A	98.2 (15)
O1—C1—C6—S1	−3.6 (4)	C50B—O7—C50A—C52A	51.8 (6)
C2—C1—C6—S1	176.4 (2)	Ti2—O7—C50A—C52A	−155.0 (9)
C12—S1—C6—C5	−112.4 (3)	C50A—O7—C50B—C51B	61.0 (8)
Ti1—S1—C6—C5	158.5 (2)	Ti2—O7—C50B—C51B	−96.5 (9)
C12—S1—C6—C1	71.8 (3)	C50A—O7—C50B—C52B	−50.5 (7)
Ti1—S1—C6—C1	−17.3 (2)	Ti2—O7—C50B—C52B	152.0 (7)
C3—C2—C7—C8	118.6 (3)