Synthesis and structural characterization of a dumbbell-like phenyl­phospho­nate-stabilized Ti₇–oxide cluster

In recent years, crystalline polyoxotitanium clusters (PTCs) have attracted increasing attention as a new kind of promising crystalline material. In this work, a PTC stabilized by phenyl­phospho­nate ligands, i.e. hexa-μ-isopropanolato-hexaisopropanolatodi-μ₃-oxido-hexa-μ₃-phenylphosphonato-heptatitanium tetrahydrate, [Ti₇(μ₃-O)₂(O₃P-Phen)₆(OⁱPr)₁₂]·4H₂O [PTC-54; H₂O₃P-Phen is phenyl­phospho­nic acid, C₆H₅PO(OH)₂, and HOⁱPr is iso­propanol, C₃H₇OH], was obtained successfully through a facile one-step solvothermal reaction. The dumbbell-like core structure of PTC-54 can be described as two trinuclear {Ti₃(μ₃-O)} building units combined together by six phenyl­phospho­nate ligands and one additional Ti atom, giving rise to a Ti₇ cluster. Adjacent mol­ecules of PTC-54 are further connected through π–π inter­actions between the phenyl groups to form a supra­molecular one-dimensional chain.

Computing details

Data collection: Please provide references for software used for data collection, cell refinement, data reduction, structure solution and molecular graphics; program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015).

Hexa-µ-isopropanolato-hexaisopropanolatodi-µ₃-oxido-hexa-µ₃-\ phenylphosphonato-heptatitanium tetrahydrate

Crystal data

[Ti7O2(C6H5O3P)6(C3H7O)12]·4H2O	F(000) = 4176
Mr = 2010.73	Dx = 1.319 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 23.073 (4) Å	Cell parameters from 13036 reflections
b = 12.9877 (19) Å	θ = 2.0–27.5°
c = 34.994 (5) Å	µ = 0.69 mm^−1
β = 105.158 (3)°	T = 293 K
V = 10122 (3) Å^3	Strip, colorless
Z = 4	0.5 × 0.3 × 0.25 mm

Data collection

Saturn724+ (2x2 bin mode) diffractometer	9545 reflections with I > 2σ(I)
CCD_Profile_fitting scans	Rint = 0.026
Absorption correction: multi-scan (REFERENCE?)	θmax = 27.5°, θmin = 2.0°
Tmin = 0.838, Tmax = 1.000	h = −24→29
37753 measured reflections	k = −16→16
11330 independent reflections	l = −45→45

Refinement

Refinement on F^2	452 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.067	H-atom parameters constrained
wR(F^2) = 0.235	w = 1/[σ^2(Fo^2) + (0.1774P)^2 + 10.8217P] where P = (Fo^2 + 2Fc^2)/3
S = 0.94	(Δ/σ)max = 0.004
11330 reflections	Δρmax = 1.10 e Å^−3
541 parameters	Δρmin = −0.95 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Ti1	0.2500	0.7500	0.0000	0.03929 (19)
Ti2	0.35945 (3)	0.66303 (5)	0.13197 (2)	0.05656 (19)
Ti3	0.22514 (3)	0.60260 (5)	0.11959 (2)	0.0584 (2)
Ti4	0.26528 (3)	0.83069 (5)	0.13597 (2)	0.05657 (19)
P5	0.34800 (4)	0.85942 (6)	0.07900 (2)	0.0464 (2)
P6	0.16054 (4)	0.77619 (6)	0.06246 (2)	0.0472 (2)
P7	0.29323 (4)	0.53886 (6)	0.05722 (2)	0.0468 (2)
O1	0.27758 (10)	0.70842 (16)	0.10653 (6)	0.0467 (5)
O2	0.27426 (10)	0.62259 (16)	0.02650 (6)	0.0485 (5)
O3	0.19022 (11)	0.85473 (17)	0.09434 (7)	0.0542 (5)
O4	0.35208 (11)	0.56465 (18)	0.08798 (7)	0.0548 (5)
O5	0.30948 (10)	0.82360 (17)	0.03929 (6)	0.0490 (5)
O6	0.15798 (11)	0.66969 (18)	0.08110 (8)	0.0558 (5)
O7	0.24355 (11)	0.51557 (17)	0.07827 (7)	0.0562 (6)
O8	0.31102 (11)	0.90870 (17)	0.10521 (7)	0.0535 (5)
O9	0.22152 (14)	0.7192 (2)	0.15811 (8)	0.0704 (7)
O10	0.38747 (10)	0.77219 (18)	0.10156 (7)	0.0538 (5)
O11	0.19060 (10)	0.77063 (17)	0.02888 (6)	0.0498 (5)
O12	0.25663 (15)	0.9367 (2)	0.16596 (8)	0.0774 (8)
O13	0.30742 (14)	0.5668 (2)	0.15488 (7)	0.0689 (7)
O14	0.34474 (13)	0.7739 (2)	0.16925 (7)	0.0681 (7)
C0AA	0.39677 (16)	0.9562 (3)	0.06801 (13)	0.0635 (9)
O16	0.43223 (14)	0.6211 (2)	0.15860 (8)	0.0738 (7)
C17	0.30551 (16)	0.4268 (3)	0.03063 (13)	0.0603 (8)
O18	0.18039 (15)	0.5103 (2)	0.13599 (9)	0.0781 (8)
C1AA	0.08539 (15)	0.8191 (3)	0.04023 (13)	0.0604 (8)
C2AA	0.0505 (2)	0.8644 (4)	0.06224 (18)	0.0840 (11)
H2AA	0.0671	0.8753	0.0891	0.101*
C21	0.2944 (2)	0.4291 (3)	−0.00986 (15)	0.0751 (10)
H21	0.2811	0.4893	−0.0238	0.090*
C23	0.3269 (2)	0.3351 (3)	0.05041 (17)	0.0795 (11)
H23	0.3358	0.3327	0.0779	0.095*
C24	0.3035 (2)	0.3384 (4)	−0.03022 (19)	0.0924 (13)
H24	0.2958	0.3386	−0.0577	0.111*
C27	0.3349 (2)	0.2487 (3)	0.02979 (19)	0.0870 (12)
H27	0.3485	0.1881	0.0433	0.104*
C29	0.0603 (2)	0.8049 (4)	0.00066 (16)	0.0815 (11)
H29	0.0826	0.7765	−0.0153	0.098*
C31	0.4404 (2)	1.0414 (4)	0.0211 (2)	0.0929 (12)
H31	0.4437	1.0490	−0.0046	0.111*
C33	0.4012 (2)	0.9691 (3)	0.02969 (16)	0.0779 (10)
H33	0.3778	0.9290	0.0094	0.094*
C36	0.4300 (2)	1.0176 (4)	0.09704 (19)	0.0992 (14)
H36	0.4274	1.0116	0.1230	0.119*
C3AA	−0.0075 (2)	0.8935 (4)	0.0458 (2)	0.0957 (13)
H3AA	−0.0297	0.9239	0.0615	0.115*
C2	0.3235 (2)	0.2514 (4)	−0.00936 (19)	0.0892 (12)
H2	0.3293	0.1922	−0.0229	0.107*
C3	−0.0323 (2)	0.8788 (4)	0.0077 (2)	0.0931 (13)
H3	−0.0718	0.8989	−0.0033	0.112*
C6AA	−0.0001 (2)	0.8340 (4)	−0.0156 (2)	0.1008 (15)
H6AA	−0.0181	0.8227	−0.0423	0.121*
C6	0.3852 (3)	0.8183 (6)	0.20319 (16)	0.126 (2)
H6	0.3588	0.8746	0.2066	0.151*
C7AA	0.1851 (3)	0.7216 (6)	0.18529 (16)	0.118 (2)
H7AA	0.1769	0.6492	0.1896	0.142*
C8	0.2512 (4)	1.0375 (5)	0.1791 (3)	0.165 (3)
H8	0.2631	1.0391	0.2081	0.198*
C9	0.4695 (3)	1.0923 (5)	0.0866 (2)	0.1142 (17)
H9	0.4923	1.1353	0.1061	0.137*
C11	0.3254 (4)	0.4837 (5)	0.18168 (17)	0.132 (2)
H11	0.2843	0.4651	0.1819	0.159*
C12	0.3364 (5)	0.3873 (5)	0.1626 (2)	0.160 (3)
H12A	0.3096	0.3832	0.1365	0.240*
H12B	0.3297	0.3297	0.1781	0.240*
H12C	0.3772	0.3861	0.1606	0.240*
C4AA	0.1246 (4)	0.7680 (8)	0.1672 (2)	0.158 (3)
H4AA	0.1272	0.8416	0.1697	0.238*
H4AB	0.0963	0.7425	0.1807	0.238*
H4AC	0.1116	0.7496	0.1398	0.238*
C5AA	0.1373 (5)	0.4388 (8)	0.1326 (3)	0.181 (3)
H5AA	0.1065	0.4886	0.1196	0.217*
C15	0.4324 (4)	0.8840 (7)	0.1946 (2)	0.171 (4)
H15A	0.4491	0.8506	0.1754	0.256*
H15B	0.4634	0.8954	0.2185	0.256*
H15C	0.4153	0.9489	0.1842	0.256*
C16	0.2206 (5)	0.7597 (9)	0.22503 (19)	0.192 (4)
H16A	0.2101	0.7203	0.2455	0.288*
H16B	0.2115	0.8310	0.2279	0.288*
H16C	0.2627	0.7521	0.2272	0.288*
C18	0.4911 (3)	0.5926 (7)	0.1632 (3)	0.143 (2)
C19	0.1238 (6)	0.3754 (9)	0.0980 (3)	0.225 (5)
H19A	0.1247	0.4165	0.0753	0.337*
H19B	0.0846	0.3458	0.0942	0.337*
H19C	0.1531	0.3215	0.1011	0.337*
C1	0.4736 (2)	1.1006 (4)	0.0506 (2)	0.1031 (14)
H1	0.5001	1.1484	0.0448	0.124*
C4	0.1867 (4)	1.0712 (8)	0.1642 (4)	0.220 (5)
H4A	0.1770	1.0800	0.1360	0.329*
H4B	0.1811	1.1352	0.1765	0.329*
H4C	0.1610	1.0198	0.1707	0.329*
C7	0.5222 (5)	0.6415 (10)	0.1350 (4)	0.217 (4)
H7A	0.5121	0.7133	0.1322	0.326*
H7B	0.5095	0.6083	0.1097	0.326*
H7C	0.5649	0.6341	0.1452	0.326*
C8AA	0.1101 (6)	0.4296 (10)	0.1661 (3)	0.229 (5)
H8AA	0.1377	0.3957	0.1878	0.344*
H8AB	0.0737	0.3901	0.1581	0.344*
H8AC	0.1010	0.4969	0.1743	0.344*
C10	0.2881 (5)	1.1087 (7)	0.1640 (4)	0.221 (5)
H10A	0.3234	1.0740	0.1612	0.332*
H10B	0.2995	1.1652	0.1821	0.332*
H10C	0.2657	1.1343	0.1387	0.332*
C14	0.5126 (5)	0.5001 (9)	0.1861 (4)	0.226 (5)
H14A	0.4890	0.4879	0.2045	0.339*
H14B	0.5539	0.5091	0.2003	0.339*
H14C	0.5090	0.4423	0.1685	0.339*
C5	0.3833 (6)	0.7614 (10)	0.2391 (2)	0.231 (4)
H5A	0.3831	0.8092	0.2600	0.347*
H5B	0.4179	0.7176	0.2470	0.347*
H5C	0.3475	0.7202	0.2338	0.347*
C9AA	0.3426 (6)	0.5151 (8)	0.2230 (2)	0.214 (4)
H9AA	0.3683	0.4637	0.2384	0.320*
H9AB	0.3073	0.5228	0.2323	0.320*
H9AC	0.3636	0.5796	0.2254	0.320*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ti1	0.0340 (4)	0.0370 (3)	0.0469 (4)	−0.0026 (3)	0.0107 (3)	0.0005 (3)
Ti2	0.0549 (4)	0.0545 (4)	0.0536 (3)	0.0027 (3)	0.0021 (3)	0.0064 (2)
Ti3	0.0659 (4)	0.0510 (3)	0.0640 (4)	−0.0034 (3)	0.0274 (3)	0.0113 (3)
Ti4	0.0636 (4)	0.0543 (4)	0.0533 (3)	−0.0023 (3)	0.0181 (3)	−0.0073 (2)
P5	0.0395 (4)	0.0415 (4)	0.0550 (4)	−0.0068 (3)	0.0065 (3)	−0.0027 (3)
P6	0.0413 (4)	0.0429 (4)	0.0619 (5)	−0.0026 (3)	0.0214 (4)	−0.0007 (3)
P7	0.0443 (4)	0.0352 (4)	0.0602 (4)	0.0004 (3)	0.0123 (3)	0.0041 (3)
O1	0.0487 (12)	0.0429 (10)	0.0493 (10)	−0.0010 (9)	0.0143 (9)	0.0024 (8)
O2	0.0499 (12)	0.0399 (10)	0.0551 (11)	0.0011 (9)	0.0126 (10)	0.0041 (8)
O3	0.0537 (13)	0.0487 (12)	0.0632 (13)	−0.0002 (10)	0.0208 (11)	−0.0052 (10)
O4	0.0493 (13)	0.0467 (11)	0.0639 (13)	0.0022 (9)	0.0067 (10)	0.0054 (10)
O5	0.0425 (12)	0.0494 (11)	0.0527 (11)	−0.0082 (9)	0.0081 (9)	−0.0010 (9)
O6	0.0530 (13)	0.0486 (12)	0.0714 (14)	−0.0052 (10)	0.0260 (11)	0.0048 (10)
O7	0.0594 (14)	0.0417 (11)	0.0700 (14)	−0.0048 (10)	0.0212 (12)	0.0079 (10)
O8	0.0538 (13)	0.0460 (11)	0.0593 (12)	−0.0051 (9)	0.0126 (10)	−0.0058 (9)
O9	0.088 (2)	0.0733 (17)	0.0607 (14)	−0.0024 (14)	0.0381 (14)	0.0032 (12)
O10	0.0441 (12)	0.0497 (12)	0.0625 (12)	−0.0021 (9)	0.0048 (10)	0.0012 (10)
O11	0.0410 (11)	0.0548 (12)	0.0565 (11)	0.0008 (9)	0.0176 (9)	0.0006 (9)
O12	0.095 (2)	0.0710 (17)	0.0692 (15)	0.0002 (16)	0.0274 (15)	−0.0215 (13)
O13	0.0833 (19)	0.0627 (15)	0.0597 (13)	0.0060 (13)	0.0171 (13)	0.0194 (12)
O14	0.0727 (18)	0.0764 (17)	0.0493 (12)	0.0017 (14)	0.0054 (12)	−0.0033 (11)
C0AA	0.0445 (17)	0.0461 (16)	0.099 (2)	−0.0080 (13)	0.0162 (17)	0.0051 (16)
O16	0.0657 (15)	0.0723 (16)	0.0707 (16)	0.0088 (13)	−0.0048 (13)	0.0113 (13)
C17	0.0456 (17)	0.0430 (15)	0.094 (2)	−0.0004 (13)	0.0216 (16)	−0.0038 (15)
O18	0.087 (2)	0.0673 (17)	0.0915 (19)	−0.0086 (15)	0.0437 (17)	0.0193 (15)
C1AA	0.0401 (16)	0.0490 (16)	0.095 (2)	−0.0044 (13)	0.0235 (16)	0.0014 (16)
C2AA	0.055 (2)	0.086 (2)	0.118 (3)	0.0061 (19)	0.036 (2)	−0.006 (2)
C21	0.069 (2)	0.0560 (19)	0.101 (2)	0.0030 (17)	0.022 (2)	−0.0195 (19)
C23	0.066 (2)	0.0491 (18)	0.122 (3)	0.0086 (16)	0.022 (2)	−0.0010 (19)
C24	0.082 (3)	0.080 (3)	0.115 (3)	0.003 (2)	0.027 (2)	−0.031 (2)
C27	0.070 (2)	0.0518 (19)	0.138 (3)	0.0101 (17)	0.024 (2)	−0.009 (2)
C29	0.054 (2)	0.076 (2)	0.110 (3)	0.0106 (18)	0.014 (2)	0.002 (2)
C31	0.083 (3)	0.073 (2)	0.136 (3)	−0.002 (2)	0.052 (2)	0.019 (2)
C33	0.074 (2)	0.0570 (19)	0.117 (3)	−0.0059 (17)	0.049 (2)	0.0032 (19)
C36	0.079 (3)	0.082 (3)	0.126 (3)	−0.037 (2)	0.007 (3)	0.001 (2)
C3AA	0.059 (2)	0.097 (3)	0.138 (3)	0.013 (2)	0.038 (2)	0.003 (3)
C2	0.071 (2)	0.060 (2)	0.139 (3)	0.0044 (18)	0.032 (2)	−0.030 (2)
C3	0.048 (2)	0.082 (3)	0.146 (3)	0.0045 (19)	0.020 (2)	0.009 (3)
C6AA	0.070 (3)	0.094 (3)	0.125 (3)	0.000 (2)	0.002 (3)	0.006 (3)
C6	0.136 (5)	0.148 (5)	0.073 (3)	−0.011 (4)	−0.010 (3)	−0.034 (3)
C7AA	0.140 (5)	0.149 (5)	0.093 (3)	0.005 (4)	0.079 (4)	0.011 (3)
C8	0.168 (7)	0.082 (4)	0.269 (9)	0.001 (4)	0.096 (7)	−0.069 (5)
C9	0.089 (3)	0.085 (3)	0.152 (4)	−0.036 (2)	0.001 (3)	0.005 (3)
C11	0.187 (7)	0.103 (4)	0.108 (3)	0.029 (4)	0.040 (4)	0.066 (3)
C12	0.235 (9)	0.088 (4)	0.147 (6)	0.038 (5)	0.029 (6)	0.048 (4)
C4AA	0.145 (6)	0.221 (8)	0.143 (5)	0.038 (6)	0.097 (5)	0.025 (6)
C5AA	0.211 (7)	0.187 (6)	0.174 (6)	−0.117 (5)	0.105 (5)	−0.018 (5)
C15	0.187 (8)	0.176 (7)	0.110 (5)	−0.072 (6)	−0.031 (5)	−0.015 (5)
C16	0.238 (8)	0.263 (9)	0.094 (4)	0.025 (7)	0.077 (5)	−0.005 (5)
C18	0.081 (3)	0.167 (5)	0.175 (5)	0.040 (3)	0.025 (3)	0.041 (4)
C19	0.295 (10)	0.206 (9)	0.204 (8)	−0.161 (8)	0.120 (8)	−0.065 (7)
C1	0.072 (3)	0.081 (3)	0.160 (4)	−0.019 (2)	0.037 (3)	0.015 (3)
C4	0.177 (8)	0.120 (6)	0.375 (12)	0.030 (6)	0.095 (9)	−0.038 (8)
C7	0.130 (7)	0.255 (10)	0.291 (10)	0.037 (7)	0.097 (7)	0.071 (9)
C8AA	0.284 (10)	0.239 (9)	0.219 (8)	−0.142 (8)	0.163 (8)	−0.034 (7)
C10	0.207 (9)	0.086 (5)	0.372 (12)	−0.039 (5)	0.077 (9)	−0.031 (7)
C14	0.141 (7)	0.222 (9)	0.316 (11)	0.084 (7)	0.059 (8)	0.100 (8)
C5	0.291 (8)	0.262 (8)	0.108 (5)	−0.056 (7)	−0.009 (6)	0.005 (6)
C9AA	0.312 (9)	0.194 (7)	0.109 (3)	0.025 (7)	0.010 (6)	0.053 (5)

Geometric parameters (Å, º)

Ti1—O2	1.908 (2)	P7—C17	1.790 (4)
Ti1—O2^i	1.908 (2)	O9—C7AA	1.424 (5)
Ti1—O11	1.922 (2)	O12—C8	1.404 (6)
Ti1—O11^i	1.922 (2)	O13—C11	1.419 (5)
Ti1—O5^i	1.924 (2)	O14—C6	1.427 (6)
Ti1—O5	1.924 (2)	C0AA—C36	1.360 (6)
Ti2—O16	1.780 (3)	C0AA—C33	1.382 (6)
Ti2—O1	1.957 (2)	O16—C18	1.375 (7)
Ti2—O4	1.973 (2)	C17—C21	1.373 (6)
Ti2—O10	1.980 (2)	C17—C23	1.401 (6)
Ti2—O14	2.030 (3)	O18—C5AA	1.343 (8)
Ti2—O13	2.037 (3)	C1AA—C29	1.367 (6)
Ti2—Ti4	3.1050 (10)	C1AA—C2AA	1.382 (6)
Ti2—Ti3	3.1153 (11)	C2AA—C3AA	1.366 (7)
Ti3—O18	1.773 (3)	C21—C24	1.420 (6)
Ti3—O1	1.962 (2)	C23—C27	1.372 (6)
Ti3—O7	1.967 (3)	C24—C2	1.359 (8)
Ti3—O6	1.971 (3)	C27—C2	1.326 (8)
Ti3—O13	2.030 (3)	C29—C6AA	1.412 (7)
Ti3—O9	2.043 (3)	C31—C1	1.353 (8)
Ti3—Ti4	3.1121 (10)	C31—C33	1.389 (6)
Ti4—O12	1.773 (3)	C36—C9	1.441 (8)
Ti4—O1	1.954 (2)	C3AA—C3	1.319 (8)
Ti4—O8	1.973 (2)	C3—C6AA	1.369 (8)
Ti4—O3	1.975 (3)	C6—C5	1.470 (8)
Ti4—O14	2.036 (3)	C6—C15	1.474 (8)
Ti4—O9	2.032 (3)	C7AA—C16	1.501 (7)
P5—O5	1.514 (2)	C7AA—C4AA	1.500 (7)
P5—O10	1.536 (2)	C8—C10	1.447 (13)
P5—O8	1.546 (2)	C8—C4	1.507 (8)
P5—C0AA	1.795 (4)	C9—C1	1.294 (9)
P6—O11	1.514 (2)	C11—C9AA	1.453 (7)
P6—O3	1.534 (2)	C11—C12	1.473 (7)
P6—O6	1.537 (2)	C5AA—C19	1.431 (11)
P6—C1AA	1.794 (4)	C5AA—C8AA	1.472 (7)
P7—O2	1.511 (2)	C18—C14	1.458 (8)
P7—O4	1.533 (2)	C18—C7	1.505 (8)
P7—O7	1.546 (3)
O2—Ti1—O2^i	180.0	O12—Ti4—Ti3	140.69 (11)
O2—Ti1—O11	91.39 (10)	O1—Ti4—Ti3	37.47 (6)
O2^i—Ti1—O11	88.61 (10)	O8—Ti4—Ti3	124.34 (7)
O2—Ti1—O11^i	88.61 (10)	O3—Ti4—Ti3	81.56 (7)
O2^i—Ti1—O11^i	91.39 (10)	O14—Ti4—Ti3	86.59 (9)
O11—Ti1—O11^i	180.0	O9—Ti4—Ti3	40.35 (8)
O2—Ti1—O5^i	88.87 (10)	Ti2—Ti4—Ti3	60.14 (2)
O2^i—Ti1—O5^i	91.14 (10)	O5—P5—O10	111.83 (13)
O11—Ti1—O5^i	88.37 (10)	O5—P5—O8	112.91 (13)
O11^i—Ti1—O5^i	91.63 (10)	O10—P5—O8	110.21 (14)
O2—Ti1—O5	91.13 (10)	O5—P5—C0AA	105.63 (17)
O2^i—Ti1—O5	88.87 (10)	O10—P5—C0AA	107.82 (16)
O11—Ti1—O5	91.63 (10)	O8—P5—C0AA	108.14 (16)
O11^i—Ti1—O5	88.38 (10)	O11—P6—O3	112.83 (13)
O5^i—Ti1—O5	180.00 (11)	O11—P6—O6	111.26 (13)
O16—Ti2—O1	175.56 (13)	O3—P6—O6	110.43 (14)
O16—Ti2—O4	95.01 (12)	O11—P6—C1AA	105.39 (16)
O1—Ti2—O4	87.95 (9)	O3—P6—C1AA	107.80 (16)
O16—Ti2—O10	96.00 (13)	O6—P6—C1AA	108.88 (15)
O1—Ti2—O10	87.24 (9)	O2—P7—O4	112.39 (13)
O4—Ti2—O10	91.03 (10)	O2—P7—O7	111.52 (13)
O16—Ti2—O14	100.02 (13)	O4—P7—O7	109.84 (14)
O1—Ti2—O14	76.99 (10)	O2—P7—C17	105.73 (16)
O4—Ti2—O14	164.94 (11)	O4—P7—C17	108.13 (16)
O10—Ti2—O14	88.32 (11)	O7—P7—C17	109.05 (15)
O16—Ti2—O13	100.29 (13)	Ti2—O1—Ti4	105.13 (10)
O1—Ti2—O13	76.45 (10)	Ti2—O1—Ti3	105.30 (10)
O4—Ti2—O13	88.30 (11)	Ti4—O1—Ti3	105.26 (10)
O10—Ti2—O13	163.69 (11)	P7—O2—Ti1	164.46 (15)
O14—Ti2—O13	88.13 (12)	P6—O3—Ti4	124.74 (14)
O16—Ti2—Ti4	140.06 (10)	P7—O4—Ti2	124.68 (15)
O1—Ti2—Ti4	37.40 (6)	P5—O5—Ti1	161.22 (15)
O4—Ti2—Ti4	124.80 (7)	P6—O6—Ti3	125.27 (15)
O10—Ti2—Ti4	81.54 (7)	P7—O7—Ti3	124.56 (14)
O14—Ti2—Ti4	40.28 (8)	P5—O8—Ti4	124.63 (14)
O13—Ti2—Ti4	85.48 (9)	C7AA—O9—Ti4	132.6 (4)
O16—Ti2—Ti3	139.81 (11)	C7AA—O9—Ti3	126.2 (4)
O1—Ti2—Ti3	37.42 (6)	Ti4—O9—Ti3	99.58 (11)
O4—Ti2—Ti3	81.30 (7)	P5—O10—Ti2	124.83 (15)
O10—Ti2—Ti3	123.95 (7)	P6—O11—Ti1	161.56 (15)
O14—Ti2—Ti3	86.60 (9)	C8—O12—Ti4	162.0 (5)
O13—Ti2—Ti3	39.91 (8)	C11—O13—Ti3	129.9 (4)
Ti4—Ti2—Ti3	60.04 (2)	C11—O13—Ti2	128.8 (4)
O18—Ti3—O1	174.74 (13)	Ti3—O13—Ti2	100.01 (10)
O18—Ti3—O7	96.05 (13)	C6—O14—Ti2	129.7 (4)
O1—Ti3—O7	88.08 (9)	C6—O14—Ti4	128.7 (4)
O18—Ti3—O6	95.74 (13)	Ti2—O14—Ti4	99.57 (11)
O1—Ti3—O6	87.34 (9)	C36—C0AA—C33	118.9 (4)
O7—Ti3—O6	91.95 (11)	C36—C0AA—P5	120.9 (4)
O18—Ti3—O13	100.34 (13)	C33—C0AA—P5	120.2 (3)
O1—Ti3—O13	76.49 (10)	C18—O16—Ti2	155.7 (4)
O7—Ti3—O13	88.18 (11)	C21—C17—C23	118.3 (4)
O6—Ti3—O13	163.83 (11)	C21—C17—P7	120.5 (3)
O18—Ti3—O9	99.18 (13)	C23—C17—P7	121.2 (4)
O1—Ti3—O9	76.63 (10)	C5AA—O18—Ti3	156.9 (5)
O7—Ti3—O9	164.71 (11)	C29—C1AA—C2AA	117.9 (4)
O6—Ti3—O9	87.87 (11)	C29—C1AA—P6	120.2 (3)
O13—Ti3—O9	87.78 (12)	C2AA—C1AA—P6	121.9 (4)
O18—Ti3—Ti4	138.99 (11)	C3AA—C2AA—C1AA	122.2 (5)
O1—Ti3—Ti4	37.27 (6)	C17—C21—C24	119.2 (5)
O7—Ti3—Ti4	124.84 (7)	C27—C23—C17	120.9 (5)
O6—Ti3—Ti4	81.25 (7)	C2—C24—C21	119.6 (5)
O13—Ti3—Ti4	85.41 (8)	C2—C27—C23	120.3 (5)
O9—Ti3—Ti4	40.07 (8)	C1AA—C29—C6AA	119.0 (5)
O18—Ti3—Ti2	140.15 (11)	C1—C31—C33	119.4 (6)
O1—Ti3—Ti2	37.29 (6)	C31—C33—C0AA	120.6 (5)
O7—Ti3—Ti2	81.31 (8)	C0AA—C36—C9	118.4 (6)
O6—Ti3—Ti2	124.02 (7)	C3—C3AA—C2AA	120.1 (5)
O13—Ti3—Ti2	40.08 (8)	C27—C2—C24	121.6 (4)
O9—Ti3—Ti2	86.12 (9)	C3AA—C3—C6AA	120.4 (5)
Ti4—Ti3—Ti2	59.82 (2)	C3—C6AA—C29	120.3 (6)
O12—Ti4—O1	175.76 (13)	O14—C6—C5	110.4 (7)
O12—Ti4—O8	94.78 (13)	O14—C6—C15	114.9 (5)
O1—Ti4—O8	87.57 (9)	C5—C6—C15	131.0 (7)
O12—Ti4—O3	95.80 (13)	O9—C7AA—C16	110.6 (6)
O1—Ti4—O3	87.69 (9)	O9—C7AA—C4AA	112.0 (5)
O8—Ti4—O3	90.42 (10)	C16—C7AA—C4AA	118.6 (7)
O12—Ti4—O14	99.60 (13)	O12—C8—C10	111.5 (7)
O1—Ti4—O14	76.93 (10)	O12—C8—C4	108.8 (7)
O8—Ti4—O14	88.17 (11)	C10—C8—C4	108.1 (10)
O3—Ti4—O14	164.60 (10)	C1—C9—C36	121.1 (6)
O12—Ti4—O9	100.58 (14)	O13—C11—C9AA	113.6 (6)
O1—Ti4—O9	77.10 (10)	O13—C11—C12	113.7 (5)
O8—Ti4—O9	164.64 (10)	C9AA—C11—C12	131.0 (7)
O3—Ti4—O9	88.08 (11)	O18—C5AA—C19	117.6 (7)
O14—Ti4—O9	89.23 (13)	O18—C5AA—C8AA	116.5 (7)
O12—Ti4—Ti2	139.41 (11)	C19—C5AA—C8AA	125.8 (8)
O1—Ti4—Ti2	37.47 (6)	O16—C18—C14	118.1 (7)
O8—Ti4—Ti2	81.67 (7)	O16—C18—C7	115.8 (6)
O3—Ti4—Ti2	124.51 (7)	C14—C18—C7	123.7 (8)
O14—Ti4—Ti2	40.15 (8)	C9—C1—C31	121.6 (5)
O9—Ti4—Ti2	86.60 (9)

Symmetry code: (i) −x+1/2, −y+3/2, −z.