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

Gao, M.-Y.; Liu, X.-X.; Fang, W.-H.; Zhang, L.; Zhang, J.

doi:10.1107/S2053229618010707

Buy article online - an online subscription or single-article purchase is required to access this article.

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

M.-Y. Gao, X.-X. Liu, W.-H. Fang, L. Zhang and J. Zhang

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.

Keywords: polyoxotitanium cluster; PTC; phenylphosphonate; crystal structure; solvothermal synthesis; SQUEEZE; optical absorption.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229618010707/jr3016sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618010707/jr3016Isup2.hkl Contains datablock I
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229618010707/jr3016sup3.pdf A packing view, PXRD pattern, FT-IR spectrum, TGA curve, UV-Vis spectrum and space-filling model, together with the full geometry

CCDC reference: 1843756

Computing details top

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 top

Crystal data top

[Ti₇O₂(C₆H₅O₃P)₆(C₃H₇O)₁₂]·4H₂O	F(000) = 4176
M_r = 2010.73	D_x = 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) Å³	Strip, colorless
Z = 4	0.5 × 0.3 × 0.25 mm

Data collection top

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

Refinement top

Refinement on F²	452 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.067	H-atom parameters constrained
wR(F²) = 0.235	w = 1/[σ²(F_o²) + (0.1774P)² + 10.8217P] where P = (F_o² + 2F_c²)/3
S = 0.94	(Δ/σ)_max = 0.004
11330 reflections	Δρ_max = 1.10 e Å⁻³
541 parameters	Δρ_min = −0.95 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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) top

Ti1—O2	1.908 (2)	P7—C17	1.790 (4)
Ti1—O2ⁱ	1.908 (2)	O9—C7AA	1.424 (5)
Ti1—O11	1.922 (2)	O12—C8	1.404 (6)
Ti1—O11ⁱ	1.922 (2)	O13—C11	1.419 (5)
Ti1—O5ⁱ	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—O2ⁱ	180.0	O12—Ti4—Ti3	140.69 (11)
O2—Ti1—O11	91.39 (10)	O1—Ti4—Ti3	37.47 (6)
O2ⁱ—Ti1—O11	88.61 (10)	O8—Ti4—Ti3	124.34 (7)
O2—Ti1—O11ⁱ	88.61 (10)	O3—Ti4—Ti3	81.56 (7)
O2ⁱ—Ti1—O11ⁱ	91.39 (10)	O14—Ti4—Ti3	86.59 (9)
O11—Ti1—O11ⁱ	180.0	O9—Ti4—Ti3	40.35 (8)
O2—Ti1—O5ⁱ	88.87 (10)	Ti2—Ti4—Ti3	60.14 (2)
O2ⁱ—Ti1—O5ⁱ	91.14 (10)	O5—P5—O10	111.83 (13)
O11—Ti1—O5ⁱ	88.37 (10)	O5—P5—O8	112.91 (13)
O11ⁱ—Ti1—O5ⁱ	91.63 (10)	O10—P5—O8	110.21 (14)
O2—Ti1—O5	91.13 (10)	O5—P5—C0AA	105.63 (17)
O2ⁱ—Ti1—O5	88.87 (10)	O10—P5—C0AA	107.82 (16)
O11—Ti1—O5	91.63 (10)	O8—P5—C0AA	108.14 (16)
O11ⁱ—Ti1—O5	88.38 (10)	O11—P6—O3	112.83 (13)
O5ⁱ—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.

Crystal data and structure refinement summary for PTC-54 top

CCDC No	1843756
Formula	C₇₂H₁₂₂O₃₆P₆Ti₇
M_r	2084.63
Crystal system	monoclinic
Space group	C2/c
a, b, c(Å)	23.073 (4), 12.9877 (19), 34.994 (5)
α, β, γ (°)	90, 105.158 (3), 90
V (Å³)	10122 (3)
Z	4
Radiation type	Mo Kα
T (K)	293 (2)
ρ_c (Mg m^-3)	1.321
µ (mm^-1)	0.688
Crystal size (mm)	0.50 × 0.30 × 0.25
Absorption correction	Multi-scan (reference?)
Tmin, Tmax	0.8381, 1.0000
Data/restraints/parameters	11330/452/541
Reflections collected	37731
Unique reflections	11327
GOF, S	0.936
R₁ [I>2σ(I)]^a	0.0673
wR₂ [I>2σ(I)]^b	0.2347

Notes: (a) R1 = Σ||F_o| - |F_c||/Σ|F_o|; (b) wR2 = {Σ[w(F_o² - F_c²)²]/Σ[w(F_o²)²]}^1/2.

Computer program(s): SHELXTL (Sheldrick, 2008); SHELXL2014 (Sheldrick, 2015).

Bond-valence-sum (BVS)^a analysis for PTC-54 top

Note: (a) V_i =ΣS_ij = Σexp[(r₀ - r_ij)/B], where r₀ is the length of a single bond (here r₀ = 1.815 Å for the Ti^iv—O bond), r_ij is the bond length between atoms i and j (expressed in Å); B is a constant, which is about 0.37 Å in this work; V_i is the sum of all bond valences of the bonds formed by a given atom i (Palenik, 2003; Brown, 2009).

Ti1	4.254		Ti2	3.921
Ti1—O2	0.729	d = 1.908 (2)	Ti2—O16	1.033	d = 1.779 (3)
Ti1—O2	0.729	d = 1.908 (2)	Ti2—O1	0.638	d = 1.957 (2)
Ti1—O11	0.700	d = 1.923 (2)	Ti2—O4	0.611	d = 1.973 (2)
Ti1—O11	0.700	d = 1.923 (2)	Ti2—O10	0.600	d = 1.980 (2)
Ti1—O5	0.698	d = 1.924 (2)	Ti2—O14	0.524	d = 2.030 (3)
Ti1—O5	0.698	d = 1.924 (2)	Ti2—O13	0.514	d = 2.037 (3)

Ti3	3.949		Ti4	3.952
Ti3—O18	1.053	d = 1.772 (3)	Ti4—O12	1.050	d = 1.773 (3)
Ti3—O1	0.630	d = 1.962 (2)	Ti4—O1	0.645	d = 1.953 (2)
Ti3—O7	0.621	d = 1.967 (3)	Ti4—O8	0.611	d = 1.973 (2)
Ti3—O6	0.615	d = 1.971 (3)	Ti4—O3	0.608	d = 1.975 (3)
Ti3—O13	0.524	d = 2.030 (3)	Ti4—O14	0.516	d = 2.036 (3)
Ti3—O9	0.506	d = 2.043 (3)	Ti4—O9	0.521	d = 2.032 (3)

Subscribe to Acta Crystallographica Section C: Structural Chemistry

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.

E-mail address*
Repeat e-mail address* (for error checking)

Format*	PDF (US $40)
	HTML (US $40)
	PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number (non-UK EC countries only)
Country*

Terms and conditions of use
Contact us

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

Supporting information

Subscribe to Acta Crystallographica Section C: Structural Chemistry

Buy online

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