Counteranion-Stabilized Titanium(IV) Isopolyoxocationic Clusters Isolated from Water.
Zhang, Guanyun; Hou, Jie; Li, Mingzhong; Tung, Chen-Ho; Wang, Yifeng; Inorganic chemistry 55 (2016) 4704–4709; doi:10.1021/acs.inorgchem.5b01901

data_4346659
_publ_section_title
;
 Counteranion-Stabilized Titanium(IV) Isopolyoxocationic Clusters Isolated
 from Water.
;
_journal_issue                   10
_journal_name_full               'Inorganic chemistry'
_journal_page_first              4704
_journal_page_last               4709
_journal_paper_doi               10.1021/acs.inorgchem.5b01901
_journal_volume                  55
_journal_year                    2016
_chemical_formula_moiety         'H40 O28 Ti6, 6(C16 H36 N), 14(Cl), 4(O)'
_chemical_formula_sum            'C96 H256 Cl14 N6 O32 Ti6'
_chemical_formula_weight         2790.75
_space_group_crystal_system      tetragonal
_space_group_IT_number           114
_space_group_name_Hall           'P -4 2n'
_space_group_name_H-M_alt        'P -4 21 c'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2015-06-26
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   33.2861(14)
_cell_length_b                   33.2861(14)
_cell_length_c                   56.069(2)
_cell_measurement_temperature    173.15
_cell_volume                     62122(4)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_diffrn_ambient_temperature      173.15
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1014
_diffrn_reflns_av_unetI/netI     0.0592
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       62
_diffrn_reflns_limit_l_min       -65
_diffrn_reflns_number            323135
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        25.214
_diffrn_reflns_theta_max         24.411
_diffrn_reflns_theta_min         0.864
_exptl_absorpt_coefficient_mu    0.594
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.194
_exptl_crystal_description       block
_exptl_crystal_F_000             24000
_refine_diff_density_max         1.011
_refine_diff_density_min         -0.439
_refine_diff_density_rms         0.133
_refine_ls_abs_structure_details
;
 Flack x determined using 12357 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -1.347(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2812
_refine_ls_number_reflns         50441
_refine_ls_number_restraints     300
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.1435
_refine_ls_R_factor_gt           0.1059
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1749P)^2^+68.4160P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2696
_refine_ls_wR_factor_ref         0.3191
_reflns_Friedel_coverage         0.891
_reflns_Friedel_fraction_full    0.889
_reflns_Friedel_fraction_max     0.975
_reflns_number_gt                33833
_reflns_number_total             50441
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b01901_si_004.cif
_cod_data_source_block           p
_cod_original_cell_volume        62122(6)
_cod_database_code               4346659
_shelxl_version_number           2013-4
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C129-N9
 1.55 with sigma of 0.01
 C133-N9
 1.55 with sigma of 0.01
 C141-N9
 1.55 with sigma of 0.01
 N9-C137
 1.55 with sigma of 0.01
 N9-C141
 1.55 with sigma of 0.01
 C137-C138 = C137-N9
 1.55 with sigma of 0.01
 N9-C133
 1.55 with sigma of 0.01
 C29-N2
 1.55 with sigma of 0.01
 N5-C65
 1.55 with sigma of 0.01
 N5-C69
 1.55 with sigma of 0.01
 N5-C73
 1.55 with sigma of 0.01
 C77-N5
 1.55 with sigma of 0.01
 N1-C9
 1.55 with sigma of 0.021
 N1-C1
 1.55 with sigma of 0.021
 N1-C5
 1.55 with sigma of 0.021
 N5_$1-C73_$1
 1.55 with sigma of 0.021
 N5_$1-C69_$1
 1.55 with sigma of 0.021
 C77_$1-N5_$1
 1.55 with sigma of 0.021
 N12-C177
 1.55 with sigma of 0.01
 N12-C181
 1.55 with sigma of 0.01
 C165-N11
 1.55 with sigma of 0.01
 N11-C169
 1.55 with sigma of 0.01
 N11-C173
 1.55 with sigma of 0.01
 N11-C161
 1.55 with sigma of 0.01
 N7-C97
 1.55 with sigma of 0.01
 N7-C109
 1.55 with sigma of 0.01
 C105-N7
 1.55 with sigma of 0.01
 C29_$1-N2_$1
 1.55 with sigma of 0.01
 C95-C96
 1.5 with sigma of 0.02
 C94-C96
 2.4 with sigma of 0.02
 C144-C143
 1.5 with sigma of 0.02
 C142-C143
 2.4 with sigma of 0.02
 C136-C134
 2.4 with sigma of 0.02
 C135-C136
 1.5 with sigma of 0.02
 C100-C99
 1.5 with sigma of 0.02
 C100-C98
 2.4 with sigma of 0.02
 C123-C124
 1.5 with sigma of 0.02
 C122-C124
 2.4 with sigma of 0.02
 C181-C182
 1.5 with sigma of 0.02
 C182-C183
 1.5 with sigma of 0.02
 N12-C182
 2.4 with sigma of 0.02
 C173-C174
 1.5 with sigma of 0.02
 C174-C175
 1.5 with sigma of 0.02
 C175-C176
 1.5 with sigma of 0.02
 C161-C162
 1.5 with sigma of 0.02
 C162-C163
 1.5 with sigma of 0.02
 C164-C163
 1.5 with sigma of 0.02
 C165-C166
 1.5 with sigma of 0.02
 C166-C167
 1.5 with sigma of 0.02
 C167-C168
 1.5 with sigma of 0.02
 C169-C170
 1.5 with sigma of 0.02
 C170-C171
 1.5 with sigma of 0.02
 C171-C172
 1.5 with sigma of 0.02
 N11-C162
 2.4 with sigma of 0.02
 C161-C163
 2.4 with sigma of 0.02
 C162-C164
 2.4 with sigma of 0.02
 N11-C174
 2.4 with sigma of 0.02
 C173-C175
 2.4 with sigma of 0.02
 C174-C176
 2.4 with sigma of 0.02
 N11-C166
 2.4 with sigma of 0.02
 C165-C167
 2.4 with sigma of 0.02
 C166-C168
 2.4 with sigma of 0.02
 N11-C170
 2.4 with sigma of 0.02
 C169-C171
 2.4 with sigma of 0.02
 C170-C172
 2.4 with sigma of 0.02
 C181-C182
 1.5 with sigma of 0.02
 C182-C183
 1.5 with sigma of 0.02
 C183-C184
 1.5 with sigma of 0.02
 N12-C182
 2.4 with sigma of 0.02
 C181-C183
 2.4 with sigma of 0.02
 C182-C184
 2.4 with sigma of 0.02
 C67-C68
 1.5 with sigma of 0.02
 C66-C68
 2.4 with sigma of 0.02
 C185-C186
 1.5 with sigma of 0.02
 C186-C187
 1.5 with sigma of 0.02
 C187-C188
 1.5 with sigma of 0.02
 C185-C187
 2.4 with sigma of 0.02
 C186-C188
 2.4 with sigma of 0.02
 N12-C186
 2.4 with sigma of 0.02
 C151-C152
 1.5 with sigma of 0.02
 C150-C152
 2.4 with sigma of 0.02
 C189-C190
 1.5 with sigma of 0.02
 N12-C190
 2.4 with sigma of 0.02
 C190-C191
 1.5 with sigma of 0.02
 C189-C191
 2.4 with sigma of 0.02
 C192-C191
 1.5 with sigma of 0.02
 C190-C192
 2.4 with sigma of 0.02
 C71-C72
 1.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
N12 \\sim C177 \\sim C178 \\sim C179 \\sim C180 \\sim C181 \\sim C182 \\sim
C183 \\sim C184: within 1.7A with sigma of 0.004 and sigma for terminal atoms
of 0.08
N12 \\sim C177 \\sim C178 \\sim C179 \\sim C180 \\sim C181 \\sim C182 \\sim
C183 \\sim C184 \\sim C185 \\sim C186 \\sim C187 \\sim C188 \\sim C189: within
1.7A with sigma of 0.004 and sigma for terminal atoms of 0.08
N11 \\sim C161 \\sim C162 \\sim C163 \\sim C164 \\sim C165 \\sim C166 \\sim
C167 \\sim C168 \\sim C169 \\sim C170 \\sim C171 \\sim C172 \\sim C173 \\sim
C174 \\sim C175 \\sim C176: within 1.7A with sigma of 0.004 and sigma for
terminal atoms of 0.08
C149 \\sim C150 \\sim C151 \\sim C152: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 C187, C188
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C3, C4
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C134, C135
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C122, C123
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C135, C136
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C134, C135
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C175, C176
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C66, C67
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C121, C122
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C131, C132
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: H96A(0.5) H96B(0.5) H96C(0.5) H96D(0.5) H96E(0.5) H96F(0.5)
 H18C(0.5) H18D(0.5) H18E(0.5) H18F(0.5) H18G(0.5) H18H(0.5) H14J(0.5)
 H14K(0.5) H14L(0.5) H14M(0.5) H14N(0.5) H14O(0.5) H12N(0.5) H12O(0.5)
 H12P(0.5) H12Q(0.5) H12R(0.5) H12S(0.5) H56A(0.5) H56B(0.5) H56C(0.5)
 H56D(0.5) H56E(0.5) H56F(0.5) H15G(0.5) H15H(0.5) H15I(0.5) H15J(0.5)
 H15K(0.5) H15L(0.5) H16U(0.5) H16V(0.5) H16W(0.5) H16X(0.5) H16Y(0.5) HG(0.5)
 Cl1(0.33333) Cl7A(0.66667)
6.a Rotating group:
 O1(H1A,H1B), O2(H2A,H2B), O3(H3A,H3B), O4(H4A,H4B), O5(H5A,H5B), O6(H6A,H6B),
 O7(H7A,H7B), O8(H8A,H8B), O9(H9A,H9B), O10(H10A,H10B), O11(H11A,H11B),
 O12(H12A,H12B), O13(H13A,H13B), O14(H14A,H14B), O15(H15A,H15B), O16(H16A,H16B),
  O17(H17A,H17B), O18(H18A,H18B), O19(H19A,H19B), O20(H20A,H20B), O36(H36D,
 H36E), O37(H37C,H37D), O39(H39C,H39D), O40(H40D,H40E), O41(H41C,H41D),
 O44(H44D,H44E), O45(H45C,H45D), O46(H46C,H46D), O48(H48D,H48E), O49(H49C,H49D),
  O29(H29C,H29D), O30(H30C,H30D), O31(H31C,H31D), O34(H34C,H34D), O35(H35C,
 H35D), O50(H50C,H50D), O52(H52D,H52E), O53(H53C,H53D), O55(H55C,H55D),
 O56(H56G,H56H)
6.b Secondary CH2 refined with riding coordinates:
 C81(H81A,H81B), C82(H82A,H82B), C83(H83A,H83B), C85(H85A,H85B), C86(H86A,
 H86B), C87(H87A,H87B), C89(H89A,H89B), C90(H90A,H90B), C91(H91A,H91B),
 C93(H93A,H93B), C94(H94A,H94B), C95(H95A,H95B), C177(H17C,H17D), C178(H17E,
 H17F), C179(H17G,H17H), C181(H18I,H18J), C182(H18K,H18L), C183(H18M,H18N),
 C185(H18R,H18S), C186(H18T,H18U), C187(H18V,H18W), C189(H18Z,HA), C190(H19C,
 H19D), C191(H19E,H19F), C129(H12C,H12D), C130(H13C,H13D), C131(H13E,H13F),
 C133(H13J,H13K), C134(H13L,H13M), C135(H13N,H13O), C137(H13S,H13T), C138(H13U,
 H13V), C139(H13W,H13X), C141(H14F,H14G), C142(H14H,H14I), C144(H14P,H14Q),
 C113(H11C,H11D), C114(H11E,H11F), C115(H11G,H11H), C117(H11L,H11M), C118(H11N,
 H11O), C119(H11P,H11Q), C121(H12H,H12I), C122(H12J,H12K), C123(H12L,H12M),
 C125(H12T,H12U), C126(H12V,H12W), C127(H12X,H12Y), C49(H49A,H49B), C50(H50A,
 H50B), C51(H51A,H51B), C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B),
 C57(H57A,H57B), C58(H58A,H58B), C59(H59A,H59B), C61(H61A,H61B), C62(H62A,H62B),
  C63(H63A,H63B), C145(H14R,H14S), C146(H14T,H14U), C147(H14V,H14W), C149(H14Z,
 HE), C150(H15C,H15D), C151(H15E,H15F), C153(H15M,H15N), C154(H15O,H15P),
 C155(H15Q,H15R), C157(H15V,H15W), C158(H15X,H15Y), C159(H15Z,HF), C161(H16F,
 H16G), C162(H16H,H16I), C163(H16J,H16K), C165(H16O,H16P), C166(H16Q,H16R),
 C167(H16S,H16T), C169(H16Z,HH), C170(H17I,H17J), C171(H17K,H17L), C173(H17P,
 H17Q), C174(H17R,H17S), C175(H17T,H17U), C17(H17Y,HI), C18(H18,HJ), C19(H19J,
 H19K), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C25(H25A,H25B),
 C26(H26A,H26B), C27(H27A,H27B), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B),
  C65(H65A,H65B), C66(H66A,H66B), C67(H67A,H67B), C69(H69A,H69B), C70(H70A,
 H70B), C71(H71A,H71B), C73(H73A,H73B), C74(H74A,H74B), C75(H75A,H75B),
 C77(H77A,H77B), C78(H78A,H78B), C79(H79A,H79B), C1(H1C,H1D), C2(H2C,H2D),
 C3(H3C,H3D), C5(H5C,H5D), C6(H6C,H6D), C7(H7C,H7D), C9(H9C,H9D), C10(H10C,
 H10D), C11(H11R,H11S), C13(H13Y,HM), C14(H14,HN), C15(H15,HO), C33(H33A,H33B),
 C34(H34A,H34B), C35(H35A,H35B), C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B),
  C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B), C45(H45A,H45B), C46(H46A,
 H46B), C47(H47A,H47B), C97(H97A,H97B), C98(H98A,H98B), C99(H99A,H99B),
 C101(H10H,H10I), C102(H10J,H10K), C103(H10L,H10M), C105(H10Q,H10R), C106(H10S,
 H10T), C107(H10U,H10V), C109(H10Z,HR), C110(H11T,H11U), C111(H11V,H11W)
6.c Disordered Me refined with riding coordinates:
 C96(H96A,H96B,H96C,H96D,H96E,H96F), C180(H18C,H18D,H18E,H18F,H18G,H18H),
 C143(H14J,H14K,H14L,H14M,H14N,H14O), C124(H12N,H12O,H12P,H12Q,H12R,H12S),
 C56(H56A,H56B,H56C,H56D,H56E,H56F), C152(H15G,H15H,H15I,H15J,H15K,H15L),
 C168(H16U,H16V,H16W,H16X,H16Y,HG)
6.d Idealised Me refined as rotating group:
 C84(H84A,H84B,H84C), C88(H88A,H88B,H88C), C92(H92A,H92B,H92C), C184(H18O,H18P,
 H18Q), C188(H18X,H18Y,H), C192(H19G,H19H,H19I), C132(H13G,H13H,H13I),
 C136(H13P,H13Q,H13R), C140(H14C,H14D,H14E), C116(H11I,H11J,H11K), C120(H12E,
 H12F,H12G), C128(H12Z,HB,HC), C52(H52A,H52B,H52C), C60(H60A,H60B,H60C),
 C64(H64A,H64B,H64C), C148(H14X,H14Y,HD), C156(H15S,H15T,H15U), C160(H16C,H16D,
 H16E), C164(H16L,H16M,H16N), C172(H17M,H17N,H17O), C176(H17V,H17W,H17X),
 C20(H20C,H20D,H20E), C24(H24A,H24B,H24C), C28(H28A,H28B,H28C), C32(H32A,H32B,
 H32C), C68(H68A,H68B,H68C), C72(H72A,H72B,H72C), C76(H76A,H76B,H76C), C80(H80A,
 H80B,H80C), C4(H4C,H4D,H4E), C8(H8C,H8D,H8E), C12(H12,HK,HL), C16(H16,HP,HQ),
 C36(H36A,H36B,H36C), C40(H40A,H40B,H40C), C44(H44A,H44B,H44C), C48(H48A,H48B,
 H48C), C100(H10E,H10F,H10G), C104(H10N,H10O,H10P), C108(H10W,H10X,H10Y),
 C112(H11X,H11Y,HS)
;
_shelx_res_checksum              16828
_shelx_hkl_checksum              16259
_olex2_submission_special_instructions 'No special instructions were received'