A novel titanium-[mu]-O-zirconium complex: bis([mu]-methyliminodiethanolato-1[kappa]³O,N,O';1:2[kappa]²O)(methyliminodiethanolato-2[kappa]³O,N,O')dipropanolato-1[kappa]O,2[kappa]O-titanium(IV)zirconium(IV)

The title compound, [TiZr(C₅H₁₁NO₂)₃(C₃H₇O)₂], contains three methyl­imino­diethano­late ligands, two in different [mu]-oxo bridging coordination modes and one bound only to the Ti atom. The Ti and Zr atoms have distorted octahedral and pentagonal-bipyramidal coordinations, respectively, which share edges. As well as some conformational disorder in the carbon chains, there is chemical disorder at one Ti site, with a mix of n- and isopropanolate ligands.

S1. Comment

The title compound, (I), was prepared as part of a study of possible precursor compounds for zirconium titanates and lead zirconate titanate (PZT). An X-ray analysis was required as the chemical structure was not unambiguously determined by other techniques (Kemmitt, Al-Salim & Gainsford, 2002). \sch

The crystal structure of (I) (Fig. 1) consists of independent [TiZr(MDEA)₃(n-propanolato)_1.6(iso-propanolato)_0.4] molecules (MDEA is methyliminodiethanolate) with only weak intermolecular contacts, e.g. C33A—H332···O22ⁱ with C···O 3.476 (9) Å [symmetry code: (i) 1/2 - x, 1/2 + y, 1/2 - z]. Within the complex, there is one weak intramolecular C15—H15B···O22 hydrogen-bond contact, with C···O 3.280 (5) Å and C—H···O 148°. For clarity, Fig. 1 shows only the major conformation rings (suffix A) and the major (60% occupancy) n-propanolate ligand bound to the Ti atom at the O41 site.

The Ti atom is in a typical distorted octahedral coordination environment, while the Zr is seven-coordinate, highly distorted from bipyramidal-pentagonal symmetry. The Ti···Zr distance of 3.459 (1) Å is considerably longer than the values of 3.413 and 3.4117 (12) Å found in the oxo-linked titanium and zirconium pinacolate complexes reported by Zechmann et al. (1998) [Cambridge Structural Database (CSD; Allen & Kennard, 1993) refcodes JARSUQ and JARWEE]. The latter are the only two µ-oxo-bridged Ti···Zr complexes found in the CSD.

Both of the MDEA ligands bound to the Zr in (I) have one O atom bridging the two metal centres. One adopts a facial conformation, as previously observed by Kemmitt, Al-Salim & Gainsford (1999), while the other is meridionally bound (see examples in Sevast'yanov et al., 2001). The latter MDEA ligand, with its flattened conformation, has Zr—N 2.397 (3) Å, which is shorter than the usual facial (twist) conformation length (Zr—N21) of 2.443 (3) Å. A comparable twist Zr—N distance of 2.427 Å is found in the complex {N,N-bis[2-(mesitylamido)ethyl]methylamine}zirconium (Schrock et al., 2000).

The Zr—O distances in (I) are similar to those found in JARSUQ and JARWEE, which have distances to the µ O atom of 2.135 (3), 2.178 (4), 2.174 (5) and 2.164 (5) Å, compared with 2.182 (2) and 2.222 (2) Å in (I). The Ti—O lengths of the bound iso-propanolate ligand in JARSUQ and JARWEE [mean 1.791 (5) Å] are identical to that for the n-propanolate ligand in (I) [1.786 (3) Å]. This suggests that the mixture of iso- and n-propanolate ligands bound to the Ti atom through oxygen (site O41) found by model trials is, structurally speaking, a reasonable possibility (see Experimental).

The third MDEA ligand is bound only to the Ti atom, adopting the facially bound conformation with a Ti—N distance of 2.346 (3) Å, slightly shorter than the values of 2.380 (3) and 2.401 (2) Å found in [Ti₃(MDEA)₂(1,3-propanolate)₄] (hereinafter KEMM1; Kemmitt, Gainsford & Robson-Marsden, 2002), and the maxiumum of 2.422 (2) Å observed in [Ti(MDEA)₂] (Kemmitt, Al-Salim et al., 1999). The folding in the MDEA is normal, with N—C—C—O dihedral angles of 44.9 (5) and 37.0 (4)° (for the A conformations), compared with means of 43.8 and 30.7° in KEMM1.

All the Ti—O(MDEA) bond lengths are similar to those found previously. The Ti—O(MDEA) mean in (I) is 1.883 (3) Å, which is comparable with the range 1.848–1.878 Å found in KEMM1, and the usually longer bridging bonds (2.014 and 2.067 Å) compare with mean values observed in related compounds of 2.107 Å (Kemmitt, Al-Salim & Gainsford, 1999) and 2.103 Å (Sevast'yanov et al., 2001).

The O atoms bound to the Ti atom (O11, O12, O21 and O31) are planar, with an average deviation of 0.024 (3) Å, and the Ti atom is 0.279 (1) Å from the plane. This plane makes an angle of 10.3 (1)° with the plane through the four approximately planar atoms O21, O31, O32 and N31 (average deviation out of the plane 0.08 Å) bound to Zr; atoms Zr and N21 are 0.022 (2) and 0.446 (5) Å, respectively, from this plane.

S2. Experimental

Titanium tetra-iso-propoxide (mass?, 21 mmol) and zirconium tetra-n-propoxide (mass?, 21 mmol) were added to N-methyldiethoxoamine (mass?, 42 mmol) in anhydrous benzene at room temperature. The mixture was stirred at 323 K under an inert atmosphere for 1 h, and the solvent was then evaporated at 323–343 K under vacuum to give a viscous material. This was dissolved in anhydrous benzene (2 ml), from which approximately cubic colourless crystals of (I) separated out (ca 30% yield).

S3. Refinement

The H atoms on atoms C31 and C34 were positionally refined. Other H atoms were placed in calculated positions, with C—H = 0.98–0.99 Å. Subsequently, all H atoms were constrained, with U_iso(H) = 1.2U_eq of their parent atom. Is this added text correct? There was conformational disorder in one methyliminodiethanolate ligand and the n-propanolate ligand bound to Zr. Chemical disorder (iso/n-propanolate) was modelled for the ligand bound to Ti; full details are given in the archived CIF. No H atoms were included for the poorly ordered iso-propanolate C atoms.

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 in WinGX (Farrugia, 1997, 1999); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. A view of the molecular structure of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms, minor conformers and the iso-propanolate ligand at O41 (see text) have been omitted for clarity.

bis(µ-methyliminodiethanolato-1κ³O,N,O';1:2κ²O)(methyliminodiethanolato- 2κ³O,N,O')dipropanolato-1κO,2κO-titanium(IV)zirconium(IV)

Crystal data

[TiZr(C5H11NO2)3(C3H7O)2]	F(000) = 2560
Mr = 608.74	Dx = 1.451 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5093 reflections
a = 31.172 (10) Å	θ = 2.6–25.8°
b = 10.407 (3) Å	µ = 0.71 mm^−1
c = 19.116 (6) Å	T = 163 K
β = 116.002 (3)°	Cubic block, colourless
V = 5574 (5) Å^3	0.30 × 0.27 × 0.25 mm
Z = 8

Data collection

Make Model CCD area-detector diffractometer	5613 independent reflections
Radiation source: fine-focus sealed tube	3723 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
Detector resolution: 8.192 pixels mm^-1	θmax = 26.4°, θmin = 2.1°
ϕ and ω scans	h = −38→35
Absorption correction: multi scan (Blessing, 1995)	k = −12→12
Tmin = 0.686, Tmax = 0.837	l = −8→23
19935 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.104	w = 1/[σ^2(Fo^2) + (0.0537P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.95	(Δ/σ)max < 0.001
5613 reflections	Δρmax = 0.60 e Å^−3
272 parameters	Δρmin = −0.59 e Å^−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00051 (7)

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. Conformational and chemical disorder was modelled as follows. The meridional MDEA ligand bound to Zr had two alternative conformations (A/B) for atoms C32, C33 and C35, with final occupancies 0.549 (3)/0.451 (3) and a common U of 0.0459 (9) Ų. The n-propanolate ligand bound to Zr was modelled in two conformations (A/B) to give final occupancies 0.641 (9)/0.359 (9) and a common U of 0.063 (1) Ų. Chemical disorder for the propanolate ligand(s) bound to Ti was finally modelled by one n-propanolate (atoms C41A, C42A and C43A, and their bound H atoms) with a common occupancy of 0.60 (1) and a common U of 0.075 (2) Ų, and iso-propanolate `atoms' (C41B, C42B, C41C, C4OC, C42C and C43C) corresponding to two conformations, with individual occupancies refined so that the total carbon occupancy for all 9 C atoms, C41A···C43C, summed to 3 (SHELXL97 SUMP); the latter six atoms had a common U which refined to 0.085 (4) Ų. The final difference map peaks (<0.59 e %A^-3) around the disorder model atoms (e.g. C41A) correspond to expected anisotropic thermal motion or unresolved H atoms.

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)
Zr	0.144893 (12)	0.16988 (3)	0.229178 (17)	0.02441 (12)
Ti	0.12749 (2)	0.05976 (6)	0.38555 (3)	0.02994 (18)
O11	0.17559 (9)	0.0289 (3)	0.48695 (13)	0.0399 (7)
O12	0.07409 (8)	−0.0297 (2)	0.38118 (13)	0.0333 (6)
O21	0.09844 (8)	0.0593 (2)	0.26841 (12)	0.0268 (6)
O22	0.16483 (8)	0.0005 (2)	0.19769 (12)	0.0293 (6)
O31	0.17928 (8)	0.1157 (2)	0.35186 (12)	0.0312 (6)
O32	0.15633 (9)	0.2626 (3)	0.14312 (13)	0.0395 (7)
O41	0.11001 (11)	0.2137 (3)	0.40551 (15)	0.0484 (7)
O51	0.10897 (9)	0.3216 (2)	0.23668 (14)	0.0385 (6)
N11	0.14742 (11)	−0.1567 (3)	0.38172 (15)	0.0336 (8)
N21	0.07596 (9)	0.0930 (3)	0.11375 (14)	0.0248 (7)
N31	0.22118 (11)	0.2733 (3)	0.29057 (16)	0.0350 (7)
C11	0.20113 (15)	−0.0867 (4)	0.5120 (2)	0.0457 (10)*
H11A	0.2101	−0.1003	0.5679	0.055*
H11B	0.2307	−0.0826	0.5050	0.055*
C12	0.17035 (15)	−0.1963 (4)	0.4650 (2)	0.0470 (11)*
H12A	0.1901	−0.2740	0.4717	0.056*
H12B	0.1457	−0.2165	0.4827	0.056*
C13	0.10037 (14)	−0.2187 (4)	0.3384 (2)	0.0455 (10)*
H13A	0.1032	−0.3126	0.3480	0.055*
H13B	0.0887	−0.2040	0.2819	0.055*
C14	0.06535 (14)	−0.1612 (4)	0.3661 (2)	0.0405 (10)*
H14B	0.0323	−0.1740	0.3256	0.049*
H14A	0.0687	−0.2058	0.4139	0.049*
C15	0.17881 (17)	−0.1859 (4)	0.3446 (2)	0.0579 (13)
H15A	0.2098	−0.1439	0.3736	0.070*
H15B	0.1642	−0.1543	0.2909	0.070*
H15C	0.1834	−0.2791	0.3446	0.070*
C21	0.04910 (12)	0.0584 (3)	0.21554 (18)	0.0288 (8)*
H21A	0.0355	0.1458	0.2105	0.035*
H21B	0.0314	−0.0001	0.2345	0.035*
C22	0.04510 (12)	0.0125 (4)	0.13766 (18)	0.0300 (9)
H22A	0.0551	−0.0785	0.1417	0.036*
H22B	0.0115	0.0185	0.0979	0.036*
C23	0.09775 (12)	0.0160 (3)	0.07250 (18)	0.0284 (8)*
H23A	0.1112	0.0740	0.0462	0.034*
H23B	0.0730	−0.0380	0.0324	0.034*
C24	0.13695 (13)	−0.0689 (4)	0.12996 (19)	0.0339 (9)
H24A	0.1226	−0.1441	0.1434	0.041*
H24B	0.1574	−0.1006	0.1060	0.041*
C25	0.04734 (13)	0.1986 (3)	0.0624 (2)	0.0343 (9)*
H25A	0.0330	0.2498	0.0896	0.041*
H25B	0.0221	0.1622	0.0149	0.041*
H25C	0.0681	0.2535	0.0487	0.041*
C31	0.22580 (17)	0.1581 (5)	0.4045 (3)	0.0467 (11)*
H31A	0.2180 (14)	0.216 (4)	0.431 (2)	0.056*
H31B	0.2433 (14)	0.086 (4)	0.418 (2)	0.056*
C34	0.19340 (18)	0.3481 (5)	0.1581 (3)	0.0528 (12)*
H34A	0.1828 (14)	0.432 (4)	0.157 (2)	0.063*
H34B	0.2105 (14)	0.331 (4)	0.125 (2)	0.063*
C32A	0.2531 (3)	0.1927 (8)	0.3558 (4)	0.0459 (8)*	0.549 (3)
H321	0.2828	0.2400	0.3882	0.055*	0.549 (3)
H322	0.2617	0.1136	0.3360	0.055*	0.549 (3)
C33A	0.2375 (3)	0.2943 (8)	0.2308 (4)	0.0459 (8)*	0.549 (3)
H331	0.2486	0.2127	0.2177	0.055*	0.549 (3)
H332	0.2641	0.3568	0.2490	0.055*	0.549 (3)
C35A	0.2156 (3)	0.4056 (7)	0.3219 (4)	0.0459 (8)*	0.549 (3)
H351	0.2028	0.3942	0.3600	0.055*	0.549 (3)
H352	0.1938	0.4589	0.2788	0.055*	0.549 (3)
H353	0.2469	0.4477	0.3469	0.055*	0.549 (3)
C41A	0.0716 (4)	0.2724 (11)	0.4108 (5)	0.075 (2)*	0.598 (12)
H411	0.0489	0.2035	0.4075	0.090*	0.598 (12)
H412	0.0555	0.3263	0.3638	0.090*	0.598 (12)
C42A	0.0784 (5)	0.3517 (12)	0.4771 (7)	0.075 (2)*	0.598 (12)
H421	0.0929	0.3024	0.5263	0.090*	0.598 (12)
H422	0.0479	0.3897	0.4714	0.090*	0.598 (12)
C43A	0.1146 (4)	0.4614 (10)	0.4735 (6)	0.075 (2)*	0.598 (12)
H431	0.1472	0.4273	0.4959	0.090*	0.598 (12)
H432	0.1134	0.5369	0.5032	0.090*	0.598 (12)
H433	0.1051	0.4859	0.4192	0.090*	0.598 (12)
C51A	0.0743 (3)	0.4172 (8)	0.2235 (5)	0.0635 (11)*	0.641 (9)
H511	0.0794	0.4573	0.2735	0.076*	0.641 (9)
H512	0.0421	0.3783	0.1999	0.076*	0.641 (9)
C52A	0.0782 (3)	0.5224 (8)	0.1670 (5)	0.0635 (11)*	0.636 (6)
H521	0.1079	0.5724	0.1948	0.076*	0.636 (6)
H522	0.0800	0.4795	0.1221	0.076*	0.636 (6)
C53A	0.0371 (3)	0.6101 (8)	0.1386 (4)	0.0635 (11)*	0.636 (6)
H531	0.0083	0.5633	0.1040	0.076*	0.636 (6)
H532	0.0427	0.6810	0.1099	0.076*	0.636 (6)
H533	0.0328	0.6444	0.1829	0.076*	0.636 (6)
C32B	0.2349 (3)	0.2871 (9)	0.3725 (5)	0.0459 (8)*	0.451 (3)
H323	0.2160	0.3565	0.3812	0.055*	0.451 (3)
H324	0.2691	0.3102	0.4001	0.055*	0.451 (3)
C33B	0.2165 (3)	0.3904 (9)	0.2463 (5)	0.0459 (8)*	0.451 (3)
H333	0.2481	0.4302	0.2611	0.055*	0.451 (3)
H334	0.1958	0.4531	0.2559	0.055*	0.451 (3)
C35B	0.2587 (3)	0.1866 (9)	0.2800 (5)	0.0459 (8)*	0.451 (3)
H354	0.2896	0.2305	0.3014	0.055*	0.451 (3)
H355	0.2483	0.1697	0.2245	0.055*	0.451 (3)
H356	0.2618	0.1051	0.3075	0.055*	0.451 (3)
C41B	0.1301 (18)	0.346 (5)	0.435 (3)	0.085 (5)*	0.163 (11)
C42B	0.0836 (17)	0.429 (4)	0.441 (3)	0.085 (5)*	0.163 (11)
C51B	0.0938 (6)	0.4480 (15)	0.2063 (9)	0.0635 (11)*	0.359 (9)
H513	0.0955	0.4567	0.1560	0.076*	0.359 (9)
H514	0.1158	0.5121	0.2428	0.076*	0.359 (9)
C52B	0.0453 (4)	0.4744 (10)	0.1949 (6)	0.0635 (11)*	0.364 (6)
H523	0.0457	0.4727	0.2469	0.076*	0.364 (6)
H524	0.0254	0.4011	0.1653	0.076*	0.364 (6)
C53B	0.0195 (4)	0.5948 (10)	0.1552 (6)	0.0635 (11)*	0.364 (6)
H534	0.0384	0.6700	0.1824	0.076*	0.364 (6)
H535	−0.0116	0.5979	0.1561	0.076*	0.364 (6)
H536	0.0150	0.5951	0.1011	0.076*	0.364 (6)
C41C	0.092 (3)	0.340 (7)	0.413 (4)	0.085 (5)*	0.115 (14)
C4OC	0.123 (2)	0.322 (5)	0.470 (3)	0.085 (5)*	0.130 (14)
C42C	0.1429 (7)	0.437 (2)	0.4515 (11)	0.085 (5)*	0.334 (14)
C43C	0.0944 (9)	0.366 (3)	0.4891 (15)	0.085 (5)*	0.307 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zr	0.0206 (2)	0.0309 (2)	0.02144 (16)	−0.00500 (17)	0.00891 (13)	−0.00285 (15)
Ti	0.0327 (4)	0.0374 (4)	0.0230 (3)	−0.0036 (3)	0.0151 (3)	−0.0058 (3)
O11	0.0433 (17)	0.0508 (18)	0.0245 (12)	−0.0131 (14)	0.0138 (12)	−0.0079 (12)
O12	0.0309 (15)	0.0438 (17)	0.0312 (13)	−0.0002 (12)	0.0191 (11)	−0.0003 (11)
O21	0.0182 (13)	0.0373 (15)	0.0236 (11)	−0.0056 (11)	0.0082 (10)	−0.0018 (10)
O22	0.0242 (14)	0.0380 (15)	0.0254 (12)	0.0012 (12)	0.0107 (11)	−0.0044 (11)
O31	0.0207 (14)	0.0444 (16)	0.0233 (11)	−0.0093 (12)	0.0050 (10)	−0.0047 (11)
O32	0.0348 (16)	0.0500 (18)	0.0323 (13)	−0.0197 (14)	0.0135 (12)	0.0016 (12)
O41	0.065 (2)	0.0452 (18)	0.0451 (15)	0.0045 (16)	0.0338 (15)	−0.0087 (13)
O51	0.0378 (16)	0.0328 (16)	0.0416 (14)	0.0037 (13)	0.0142 (12)	0.0008 (12)
N11	0.0335 (19)	0.044 (2)	0.0254 (14)	0.0055 (16)	0.0150 (14)	−0.0002 (13)
N21	0.0202 (16)	0.0328 (18)	0.0216 (13)	−0.0007 (14)	0.0093 (12)	−0.0018 (12)
N31	0.0299 (19)	0.039 (2)	0.0343 (16)	−0.0093 (16)	0.0126 (14)	−0.0060 (14)
C15	0.080 (4)	0.059 (3)	0.056 (3)	0.024 (3)	0.048 (3)	0.010 (2)
C22	0.020 (2)	0.040 (2)	0.0268 (17)	−0.0053 (17)	0.0071 (15)	−0.0056 (16)
C24	0.032 (2)	0.042 (3)	0.0300 (18)	0.0020 (19)	0.0165 (17)	−0.0038 (17)

Geometric parameters (Å, º)

Zr—O51	1.977 (3)	C24—H24B	0.9900
Zr—O22	2.046 (2)	C25—H25A	0.9800
Zr—O32	2.068 (2)	C25—H25B	0.9800
Zr—O31	2.182 (2)	C25—H25C	0.9800
Zr—O21	2.222 (2)	C31—C32A	1.554 (8)
Zr—N31	2.397 (3)	C31—C32B	1.552 (10)
Zr—N21	2.443 (3)	C31—H31A	0.89 (4)
Ti—O41	1.786 (3)	C31—H31B	0.90 (4)
Ti—O12	1.877 (2)	C34—C33A	1.569 (8)
Ti—O11	1.887 (2)	C34—C33B	1.579 (10)
Ti—O21	2.014 (2)	C34—H34A	0.93 (4)
Ti—O31	2.067 (2)	C34—H34B	1.01 (4)
Ti—N11	2.346 (3)	C32A—H321	0.9900
O11—C11	1.406 (5)	C32A—H322	0.9900
O12—C14	1.401 (4)	C33A—H331	0.9900
O21—C21	1.423 (4)	C33A—H332	0.9900
O22—C24	1.402 (4)	C35A—H351	0.9800
O31—C31	1.425 (5)	C35A—H352	0.9800
O32—C34	1.386 (5)	C35A—H353	0.9800
O41—C41A	1.386 (10)	C41A—C42A	1.449 (14)
O41—C41C	1.46 (6)	C41A—H411	0.9900
O41—C41B	1.52 (5)	C41A—H412	0.9900
O41—C4OC	1.58 (6)	C42A—C43A	1.629 (18)
O51—C51A	1.408 (9)	C42A—H421	0.9900
O51—C51B	1.432 (16)	C42A—H422	0.9900
N11—C15	1.471 (4)	C43A—H431	0.9800
N11—C13	1.479 (5)	C43A—H432	0.9800
N11—C12	1.489 (5)	C43A—H433	0.9800
N21—C23	1.481 (4)	C51A—C52A	1.580 (12)
N21—C25	1.483 (4)	C51A—H511	0.9900
N21—C22	1.491 (4)	C51A—H512	0.9900
N31—C32B	1.438 (9)	C52A—C53A	1.471 (10)
N31—C33B	1.454 (9)	C52A—H521	0.9900
N31—C33A	1.456 (7)	C52A—H522	0.9900
N31—C32A	1.470 (8)	C53A—H531	0.9800
N31—C35A	1.541 (7)	C53A—H532	0.9800
N31—C35B	1.559 (9)	C53A—H533	0.9800
C11—C12	1.508 (5)	C32B—H323	0.9900
C11—H11A	0.9900	C32B—H324	0.9900
C11—H11B	0.9900	C33B—H333	0.9900
C12—H12A	0.9900	C33B—H334	0.9900
C12—H12B	0.9900	C35B—H354	0.9800
C13—C14	1.528 (5)	C35B—H355	0.9800
C13—H13A	0.9900	C35B—H356	0.9800
C13—H13B	0.9900	C41B—C42B	1.73 (7)
C14—H14B	0.9900	C51B—C52B	1.46 (2)
C14—H14A	0.9900	C51B—H513	0.9900
C15—H15A	0.9800	C51B—H514	0.9900
C15—H15B	0.9800	C52B—C53B	1.5029
C15—H15C	0.9800	C52B—H523	0.9900
C21—C22	1.516 (4)	C52B—H524	0.9900
C21—H21A	0.9900	C53B—H534	0.9800
C21—H21B	0.9900	C53B—H535	0.9800
C22—H22A	0.9900	C53B—H536	0.9800
C22—H22B	0.9900	C41C—C4OC	1.11 (7)
C23—C24	1.518 (5)	C41C—C43C	1.45 (7)
C23—H23A	0.9900	C41C—C42C	1.74 (9)
C23—H23B	0.9900	C4OC—C43C	1.20 (6)
C24—H24A	0.9900	C4OC—C42C	1.45 (6)
O51—Zr—O22	164.68 (10)	N21—C22—H22B	109.7
O51—Zr—O32	89.19 (10)	C21—C22—H22B	109.7
O22—Zr—O32	89.27 (10)	H22A—C22—H22B	108.2
O51—Zr—O31	98.93 (10)	N21—C23—C24	110.0 (3)
O22—Zr—O31	91.39 (9)	N21—C23—H23A	109.7
O32—Zr—O31	143.18 (9)	C24—C23—H23A	109.7
O51—Zr—O21	85.16 (10)	N21—C23—H23B	109.7
O22—Zr—O21	88.84 (9)	C24—C23—H23B	109.7
O32—Zr—O21	151.06 (9)	H23A—C23—H23B	108.2
O31—Zr—O21	65.74 (8)	O22—C24—C23	110.2 (3)
O51—Zr—N31	94.46 (11)	O22—C24—H24A	109.6
O22—Zr—N31	99.61 (10)	C23—C24—H24A	109.6
O32—Zr—N31	72.55 (10)	O22—C24—H24B	109.6
O31—Zr—N31	71.05 (9)	C23—C24—H24B	109.6
O21—Zr—N31	136.14 (9)	H24A—C24—H24B	108.1
O51—Zr—N21	91.43 (10)	N21—C25—H25A	109.5
O22—Zr—N21	73.29 (9)	N21—C25—H25B	109.5
O32—Zr—N21	79.88 (9)	H25A—C25—H25B	109.5
O31—Zr—N21	135.17 (9)	N21—C25—H25C	109.5
O21—Zr—N21	71.94 (8)	H25A—C25—H25C	109.5
N31—Zr—N21	151.68 (9)	H25B—C25—H25C	109.5
O41—Ti—O12	96.12 (13)	O31—C31—C32A	107.7 (4)
O41—Ti—O11	96.46 (12)	O31—C31—C32B	107.1 (5)
O12—Ti—O11	104.55 (11)	C32A—C31—C32B	47.3 (4)
O41—Ti—O21	102.08 (11)	O31—C31—H31A	99 (3)
O12—Ti—O21	89.51 (10)	C32A—C31—H31A	123 (3)
O11—Ti—O21	155.40 (11)	O31—C31—H31B	104 (3)
O41—Ti—O31	99.61 (12)	C32B—C31—H31B	130 (3)
O12—Ti—O31	157.61 (10)	H31A—C31—H31B	133 (4)
O11—Ti—O31	89.46 (10)	O32—C34—C33A	106.3 (4)
O21—Ti—O31	71.71 (9)	O32—C34—C33B	110.4 (5)
O41—Ti—N11	167.78 (11)	O32—C34—H34A	110 (3)
O12—Ti—N11	76.37 (11)	C33A—C34—H34A	121 (3)
O11—Ti—N11	76.51 (11)	O32—C34—H34B	112 (2)
O21—Ti—N11	87.64 (9)	C33B—C34—H34B	127 (2)
O31—Ti—N11	90.41 (10)	H34A—C34—H34B	116 (3)
C11—O11—Ti	124.9 (2)	N31—C32A—C31	107.2 (5)
C14—O12—Ti	125.6 (2)	N31—C32A—H321	110.3
C21—O21—Ti	127.52 (18)	C31—C32A—H321	110.3
C21—O21—Zr	115.15 (18)	N31—C32A—H322	110.3
Ti—O21—Zr	109.39 (10)	C31—C32A—H322	110.3
C24—O22—Zr	124.8 (2)	H321—C32A—H322	108.5
C31—O31—Ti	124.0 (2)	N31—C33A—C34	106.1 (5)
C31—O31—Zr	123.2 (2)	N31—C33A—H331	110.5
Ti—O31—Zr	108.96 (10)	C34—C33A—H331	110.5
C34—O32—Zr	123.7 (2)	N31—C33A—H332	110.5
C41A—O41—Ti	139.9 (6)	C34—C33A—H332	110.5
C41B—O41—Ti	141.3 (18)	H331—C33A—H332	108.7
C4OC—O41—Ti	144 (2)	N31—C35A—H351	109.5
C51A—O51—Zr	165.0 (4)	N31—C35A—H352	109.5
C51B—O51—Zr	143.2 (7)	N31—C35A—H353	109.5
C15—N11—C13	110.2 (3)	O41—C41A—C42A	121.1 (9)
C15—N11—C12	110.5 (3)	O41—C41A—H411	107.1
C13—N11—C12	111.8 (3)	C42A—C41A—H411	107.1
C15—N11—Ti	117.1 (2)	O41—C41A—H412	107.1
C13—N11—Ti	103.0 (2)	C42A—C41A—H412	107.1
C12—N11—Ti	104.0 (2)	H411—C41A—H412	106.8
C23—N21—C25	109.3 (2)	C41A—C42A—C43A	101.5 (9)
C23—N21—C22	111.5 (3)	C41A—C42A—H421	111.5
C25—N21—C22	109.7 (3)	C43A—C42A—H421	111.5
C23—N21—Zr	103.35 (19)	C41A—C42A—H422	111.5
C25—N21—Zr	113.0 (2)	C43A—C42A—H422	111.5
C22—N21—Zr	109.72 (18)	H421—C42A—H422	109.3
C32B—N31—C33B	117.1 (6)	O51—C51A—C52A	109.2 (7)
C32B—N31—C33A	143.1 (5)	O51—C51A—H511	109.8
C33B—N31—C32A	146.1 (5)	C52A—C51A—H511	109.8
C33A—N31—C32A	114.3 (5)	O51—C51A—H512	109.8
C33A—N31—C35A	108.0 (5)	C52A—C51A—H512	109.8
C32A—N31—C35A	109.3 (4)	H511—C51A—H512	108.3
C32B—N31—C35B	108.5 (5)	C53A—C52A—C51A	111.5 (7)
C33B—N31—C35B	107.4 (5)	C53A—C52A—H521	109.3
C35A—N31—C35B	141.8 (5)	C51A—C52A—H521	109.3
C32B—N31—Zr	109.6 (4)	C53A—C52A—H522	109.3
C33B—N31—Zr	105.5 (4)	C51A—C52A—H522	109.3
C33A—N31—Zr	107.2 (3)	H521—C52A—H522	108.0
C32A—N31—Zr	108.4 (3)	N31—C32B—C31	108.9 (6)
C35A—N31—Zr	109.6 (3)	N31—C32B—H323	109.9
C35B—N31—Zr	108.4 (4)	C31—C32B—H323	109.9
O11—C11—C12	109.1 (3)	N31—C32B—H324	109.9
O11—C11—H11A	109.9	C31—C32B—H324	109.9
C12—C11—H11A	109.9	H323—C32B—H324	108.3
O11—C11—H11B	109.9	N31—C33B—C34	105.7 (6)
C12—C11—H11B	109.9	N31—C33B—H333	110.6
H11A—C11—H11B	108.3	C34—C33B—H333	110.6
N11—C12—C11	108.0 (3)	N31—C33B—H334	110.6
N11—C12—H12A	110.1	C34—C33B—H334	110.6
C11—C12—H12A	110.1	H333—C33B—H334	108.7
N11—C12—H12B	110.1	N31—C35B—H354	109.5
C11—C12—H12B	110.1	N31—C35B—H355	109.5
H12A—C12—H12B	108.4	H354—C35B—H355	109.5
N11—C13—C14	108.6 (3)	N31—C35B—H356	109.5
N11—C13—H13A	110.0	H354—C35B—H356	109.5
C14—C13—H13A	110.0	H355—C35B—H356	109.5
N11—C13—H13B	110.0	O41—C41B—C42B	105 (4)
C14—C13—H13B	110.0	O51—C51B—C52B	111.7 (13)
H13A—C13—H13B	108.3	O51—C51B—H513	109.3
O12—C14—C13	110.5 (3)	C52B—C51B—H513	109.3
O12—C14—H14B	109.5	O51—C51B—H514	109.3
C13—C14—H14B	109.5	C52B—C51B—H514	109.3
O12—C14—H14A	109.5	H513—C51B—H514	107.9
C13—C14—H14A	109.5	C51B—C52B—C53B	121.6 (8)
H14B—C14—H14A	108.1	C51B—C52B—H523	106.9
N11—C15—H15A	109.5	C53B—C52B—H523	106.9
N11—C15—H15B	109.5	C51B—C52B—H524	106.9
H15A—C15—H15B	109.5	C53B—C52B—H524	106.9
N11—C15—H15C	109.5	H523—C52B—H524	106.7
H15A—C15—H15C	109.5	C52B—C53B—H534	109.5
H15B—C15—H15C	109.5	C52B—C53B—H535	109.5
O21—C21—C22	107.3 (3)	H534—C53B—H535	109.5
O21—C21—H21A	110.3	C52B—C53B—H536	109.5
C22—C21—H21A	110.3	H534—C53B—H536	109.5
O21—C21—H21B	110.3	H535—C53B—H536	109.5
C22—C21—H21B	110.3	C43C—C41C—O41	114 (4)
H21A—C21—H21B	108.5	O41—C41C—C42C	105 (5)
N21—C22—C21	109.8 (3)	C43C—C4OC—C42C	102 (4)
N21—C22—H22A	109.7	C43C—C4OC—O41	122 (4)
C21—C22—H22A	109.7	C42C—C4OC—O41	113 (4)
O41—Ti—O11—C11	173.9 (3)	O32—Zr—N21—C25	−53.4 (2)
O12—Ti—O11—C11	75.9 (3)	O31—Zr—N21—C25	139.7 (2)
O21—Ti—O11—C11	−47.2 (4)	O21—Zr—N21—C25	120.0 (2)
O31—Ti—O11—C11	−86.5 (3)	N31—Zr—N21—C25	−66.6 (3)
N11—Ti—O11—C11	4.1 (3)	O51—Zr—N21—C22	−87.3 (2)
O41—Ti—O12—C14	179.4 (3)	O22—Zr—N21—C22	91.5 (2)
O11—Ti—O12—C14	−82.3 (3)	O32—Zr—N21—C22	−176.2 (2)
O21—Ti—O12—C14	77.3 (3)	O31—Zr—N21—C22	16.9 (3)
O31—Ti—O12—C14	44.9 (4)	O21—Zr—N21—C22	−2.9 (2)
N11—Ti—O12—C14	−10.4 (3)	N31—Zr—N21—C22	170.5 (2)
O41—Ti—O21—C21	−66.8 (3)	O51—Zr—N31—C32B	72.8 (5)
O12—Ti—O21—C21	29.4 (3)	O22—Zr—N31—C32B	−113.3 (4)
O11—Ti—O21—C21	155.2 (3)	O32—Zr—N31—C32B	160.6 (5)
O31—Ti—O21—C21	−163.0 (3)	O31—Zr—N31—C32B	−25.1 (4)
N11—Ti—O21—C21	105.8 (3)	O21—Zr—N31—C32B	−14.8 (5)
O41—Ti—O21—Zr	80.19 (13)	N21—Zr—N31—C32B	174.2 (4)
O12—Ti—O21—Zr	176.35 (11)	O51—Zr—N31—C33B	−54.1 (4)
O11—Ti—O21—Zr	−57.9 (3)	O22—Zr—N31—C33B	119.8 (4)
O31—Ti—O21—Zr	−16.06 (10)	O32—Zr—N31—C33B	33.6 (4)
N11—Ti—O21—Zr	−107.28 (11)	O31—Zr—N31—C33B	−152.0 (4)
O51—Zr—O21—C21	65.2 (2)	O21—Zr—N31—C33B	−141.8 (4)
O22—Zr—O21—C21	−100.7 (2)	N21—Zr—N31—C33B	47.3 (5)
O32—Zr—O21—C21	−14.3 (3)	O51—Zr—N31—C33A	−109.5 (4)
O31—Zr—O21—C21	167.3 (2)	O22—Zr—N31—C33A	64.4 (4)
N31—Zr—O21—C21	156.6 (2)	O32—Zr—N31—C33A	−21.8 (4)
N21—Zr—O21—C21	−27.9 (2)	O31—Zr—N31—C33A	152.6 (4)
O51—Zr—O21—Ti	−86.23 (12)	O21—Zr—N31—C33A	162.8 (3)
O22—Zr—O21—Ti	107.88 (11)	N21—Zr—N31—C33A	−8.1 (5)
O32—Zr—O21—Ti	−165.71 (16)	O51—Zr—N31—C32A	126.6 (4)
O31—Zr—O21—Ti	15.84 (10)	O22—Zr—N31—C32A	−59.5 (4)
N31—Zr—O21—Ti	5.18 (18)	O32—Zr—N31—C32A	−145.6 (4)
N21—Zr—O21—Ti	−179.33 (13)	O31—Zr—N31—C32A	28.7 (3)
O51—Zr—O22—C24	10.8 (5)	O21—Zr—N31—C32A	39.0 (4)
O32—Zr—O22—C24	−73.4 (3)	N21—Zr—N31—C32A	−132.0 (4)
O31—Zr—O22—C24	143.4 (2)	O51—Zr—N31—C35A	7.4 (3)
O21—Zr—O22—C24	77.7 (2)	O22—Zr—N31—C35A	−178.6 (3)
N31—Zr—O22—C24	−145.6 (2)	O32—Zr—N31—C35A	95.2 (3)
N21—Zr—O22—C24	6.2 (2)	O31—Zr—N31—C35A	−90.5 (3)
O41—Ti—O31—C31	75.1 (3)	O21—Zr—N31—C35A	−80.2 (3)
O12—Ti—O31—C31	−150.9 (3)	N21—Zr—N31—C35A	108.8 (4)
O11—Ti—O31—C31	−21.4 (3)	O51—Zr—N31—C35B	−168.9 (4)
O21—Ti—O31—C31	174.8 (3)	O22—Zr—N31—C35B	5.0 (4)
N11—Ti—O31—C31	−97.9 (3)	O32—Zr—N31—C35B	−81.2 (4)
O41—Ti—O31—Zr	−83.33 (13)	O31—Zr—N31—C35B	93.2 (4)
O12—Ti—O31—Zr	50.7 (3)	O21—Zr—N31—C35B	103.4 (4)
O11—Ti—O31—Zr	−179.79 (12)	N21—Zr—N31—C35B	−67.5 (4)
O21—Ti—O31—Zr	16.32 (10)	Ti—O11—C11—C12	−28.4 (4)
N11—Ti—O31—Zr	103.70 (12)	C15—N11—C12—C11	86.9 (4)
O51—Zr—O31—C31	−93.5 (3)	C13—N11—C12—C11	−150.0 (3)
O22—Zr—O31—C31	97.9 (3)	Ti—N11—C12—C11	−39.5 (3)
O32—Zr—O31—C31	7.2 (4)	O11—C11—C12—N11	44.9 (4)
O21—Zr—O31—C31	−174.0 (3)	C15—N11—C13—C14	−166.6 (3)
N31—Zr—O31—C31	−1.8 (3)	C12—N11—C13—C14	70.2 (4)
N21—Zr—O31—C31	165.3 (3)	Ti—N11—C13—C14	−40.9 (3)
O51—Zr—O31—Ti	65.15 (13)	Ti—O12—C14—C13	−10.6 (4)
O22—Zr—O31—Ti	−103.49 (12)	N11—C13—C14—O12	37.0 (4)
O32—Zr—O31—Ti	165.87 (13)	Ti—O21—C21—C22	−160.8 (2)
O21—Zr—O31—Ti	−15.38 (9)	Zr—O21—C21—C22	53.8 (3)
N31—Zr—O31—Ti	156.83 (14)	C23—N21—C22—C21	144.1 (3)
N21—Zr—O31—Ti	−36.04 (18)	C25—N21—C22—C21	−94.5 (3)
O51—Zr—O32—C34	85.0 (3)	Zr—N21—C22—C21	30.2 (3)
O22—Zr—O32—C34	−110.3 (3)	O21—C21—C22—N21	−54.0 (4)
O31—Zr—O32—C34	−18.9 (4)	C25—N21—C23—C24	165.1 (3)
O21—Zr—O32—C34	163.5 (3)	C22—N21—C23—C24	−73.3 (3)
N31—Zr—O32—C34	−9.9 (3)	Zr—N21—C23—C24	44.5 (3)
N21—Zr—O32—C34	176.6 (3)	Zr—O22—C24—C23	17.0 (4)
O12—Ti—O41—C41A	−6.2 (7)	N21—C23—C24—O22	−43.1 (4)
O11—Ti—O41—C41A	−111.7 (7)	Ti—O31—C31—C32A	−179.2 (4)
O21—Ti—O41—C41A	84.6 (7)	Zr—O31—C31—C32A	−23.7 (5)
O31—Ti—O41—C41A	157.8 (7)	Ti—O31—C31—C32B	−129.5 (4)
N11—Ti—O41—C41A	−57.5 (10)	Zr—O31—C31—C32B	25.9 (5)
O21—Ti—O41—C41B	−105 (3)	Zr—O32—C34—C33A	37.0 (5)
N11—Ti—O41—C41B	112 (3)	Zr—O32—C34—C33B	−14.3 (6)
O22—Zr—O51—C51A	−10.5 (18)	Zr—N31—C32A—C31	−49.3 (5)
O32—Zr—O51—C51A	73.8 (17)	O31—C31—C32A—N31	47.7 (6)
O31—Zr—O51—C51A	−142.3 (17)	C32B—C31—C32A—N31	−49.6 (6)
O21—Zr—O51—C51A	−77.8 (17)	C32B—N31—C33A—C34	−138.9 (8)
N31—Zr—O51—C51A	146.2 (17)	C33B—N31—C33A—C34	−51.9 (6)
N21—Zr—O51—C51A	−6.0 (17)	C32A—N31—C33A—C34	165.0 (5)
O22—Zr—O51—C51B	−86.0 (11)	C35A—N31—C33A—C34	−73.2 (6)
O32—Zr—O51—C51B	−1.7 (11)	C35B—N31—C33A—C34	145.8 (7)
O31—Zr—O51—C51B	142.3 (11)	Zr—N31—C33A—C34	44.8 (5)
O21—Zr—O51—C51B	−153.3 (11)	O32—C34—C33A—N31	−52.7 (6)
N31—Zr—O51—C51B	70.8 (11)	Ti—O41—C41A—C42A	131.0 (9)
N21—Zr—O51—C51B	−81.5 (11)	O41—C41A—C42A—C43A	58.8 (13)
O41—Ti—N11—C15	−157.2 (6)	C51B—O51—C51A—C52A	13.1 (11)
O12—Ti—N11—C15	149.8 (3)	Zr—O51—C51A—C52A	−83.0 (18)
O11—Ti—N11—C15	−101.3 (3)	O51—C51A—C52A—C53A	168.5 (6)
O21—Ti—N11—C15	59.7 (3)	C33B—N31—C32B—C31	166.2 (6)
O31—Ti—N11—C15	−11.9 (3)	C33A—N31—C32B—C31	−130.2 (8)
O41—Ti—N11—C13	81.7 (6)	C32A—N31—C32B—C31	−52.0 (6)
O12—Ti—N11—C13	28.7 (2)	C35A—N31—C32B—C31	148.3 (8)
O11—Ti—N11—C13	137.6 (2)	C35B—N31—C32B—C31	−72.1 (7)
O21—Ti—N11—C13	−61.4 (2)	Zr—N31—C32B—C31	46.1 (7)
O31—Ti—N11—C13	−133.1 (2)	O31—C31—C32B—N31	−46.7 (7)
O41—Ti—N11—C12	−35.0 (7)	C32A—C31—C32B—N31	51.8 (6)
O12—Ti—N11—C12	−88.1 (2)	C32B—N31—C33B—C34	−171.1 (6)
O11—Ti—N11—C12	20.8 (2)	C33A—N31—C33B—C34	51.3 (6)
O21—Ti—N11—C12	−178.1 (2)	C32A—N31—C33B—C34	129.9 (8)
O31—Ti—N11—C12	110.2 (2)	C35A—N31—C33B—C34	−152.7 (8)
O51—Zr—N21—C23	153.61 (19)	C35B—N31—C33B—C34	66.6 (7)
O22—Zr—N21—C23	−27.61 (18)	Zr—N31—C33B—C34	−48.9 (6)
O32—Zr—N21—C23	64.7 (2)	O32—C34—C33B—N31	43.8 (7)
O31—Zr—N21—C23	−102.2 (2)	C33A—C34—C33B—N31	−50.3 (6)
O21—Zr—N21—C23	−122.0 (2)	Ti—O41—C41B—C42B	−175.1 (15)
N31—Zr—N21—C23	51.5 (3)	Zr—O51—C51B—C52B	140.2 (8)
O51—Zr—N21—C25	35.5 (2)	O51—C51B—C52B—C53B	−173.0 (5)
O22—Zr—N21—C25	−145.7 (2)