The role of titanium-oxo clusters in the sulfate process for TiO<sub>2</sub> production.
Kozma, Karoly; Wang, Maoyu; Molina, Pedro I.; Martin, Nicolas P.; Feng, Zhenxing; Nyman, May; Dalton transactions (Cambridge, England : 2003) 48 (2019) 11086–11093; doi:10.1039/c9dt01337g

data_7700329
_publ_section_title
;
 The role of titanium-oxo clusters in the sulfate process for
 TiO<sub>2</sub> production.
;
_journal_issue                   29
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              11086
_journal_page_last               11093
_journal_paper_doi               10.1039/c9dt01337g
_journal_volume                  48
_journal_year                    2019
_chemical_formula_moiety
'2(O89.5 S9.17 Ti18), 10(Cl), 0.67(O4 S), 26(O), 10(C16 H36 N), 2(C15 H34 N)'
_chemical_formula_sum            'C190 H428 Cl10 N12 O207.66 S19 Ti36'
_chemical_formula_weight         8892.02
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-06-14 deposited with the CCDC.    2019-06-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.136(2)
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   18.2006(7)
_cell_length_b                   17.8315(7)
_cell_length_c                   30.6879(14)
_cell_measurement_reflns_used    7575
_cell_measurement_temperature    173.15
_cell_measurement_theta_max      49.03
_cell_measurement_theta_min      2.43
_cell_volume                     9957.6(7)
_computing_cell_refinement       'Bruker Saint'
_computing_data_collection       'Bruker Apex2'
_computing_data_reduction        'Bruker Saint'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      173.15
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.959
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0749
_diffrn_reflns_av_unetI/netI     0.1049
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.959
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            50933
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        49.904
_diffrn_reflns_theta_max         49.904
_diffrn_reflns_theta_min         2.428
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    8.153
_exptl_absorpt_correction_T_max  0.4513
_exptl_absorpt_correction_T_min  0.3349
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.1007 before and 0.0800 after correction. The Ratio of minimum to maximum transmission is 0.7421. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.483
_exptl_crystal_description       prism
_exptl_crystal_F_000             4579
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.104
_refine_diff_density_min         -0.582
_refine_diff_density_rms         0.128
_refine_ls_abs_structure_details
;
 Flack x determined using 5500 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.111(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2076
_refine_ls_number_reflns         19697
_refine_ls_number_restraints     420
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.1097
_refine_ls_R_factor_gt           0.0856
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1199P)^2^+79.4467P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2186
_refine_ls_wR_factor_ref         0.2391
_reflns_Friedel_coverage         0.913
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.951
_reflns_number_gt                15506
_reflns_number_total             19697
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt01337g2.cif
_cod_data_source_block           cu_may336a_0m
_cod_depositor_comments          'Adding full bibliography for 7700329.cif.'
_cod_database_code               7700329
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.854
_shelx_estimated_absorpt_t_min   0.562
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.906(2)
 0.094(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C14B-C15B
 1.5 with sigma of 0.02
 S4-O78
 1.5 with sigma of 0.02
 S10B-O64 \\sim S10B-O92B \\sim S10B-O94B \\sim S10B-O93B \\sim S10A-O63 \\sim
S10A-O90A \\sim S10A-
 O89A \\sim S10A-O91A \\sim S10C-O91C \\sim S10C-O95C \\sim S10C-O96C \\sim
S10C-O97C
 with sigma of 0.02
 C8D-C7D \\sim C7D-C6D \\sim C9D-C8D
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uiso(Cl6) = Uiso(O78)
5. Rigid body (RIGU) restrains
 C16B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A, C10A, C11A, C12A, C13A, C14A, C15A,
 C16A, C17A, C2B, C3B, C4B, C5B, C6B, C7B, C8B, C9B, C10B, C11B, C12B, C13B,
 C14B, C15B, C16B, C2C, C3C, C4C, C5C, C6C, C7C, C8C, C9C, C10C, C11C, C12C,
 C13C, C14C, C15C, C16C, C17C, C2D, C3D, C4D, C5D, C6D, C7D, C8D, C9D, C10D,
 C11D, C12D, C13D, C14D, C15D, C16D, C17D, C2E, C3E, C4E, C5E, C6E, C7E, C8E,
 C9E, C10E, C11E, C12E, C13E, C14E, C15E, C16E, C17E, C2F, C3F, C4F, C5F, C6F,
 C7F, C8F, C9F, C10F, C11F, C12F, C13F, C14F, C15F, C16F, C050
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 Fixed Sof: Cl5(0.5) Cl6(0.5) S4(0.5) S10A(0.33333) S10B(0.33333)
 S10C(0.33333) O14W(0.5) O77(0.5) O79(0.5) O89A(0.33333) O90A(0.333)
 O91A(0.333) O92B(0.33333) O93B(0.33333) O94B(0.33333) O95C(0.333)
 O96C(0.33333) O97C(0.33333) O6W(0.5) O78(0.5) O91C(0.333)
7.a Secondary CH2 refined with riding coordinates:
 C2A(H2AA,H2AB), C3A(H3AA,H3AB), C4A(H4AA,H4AB), C6A(H6AA,H6AB), C7A(H7AA,
 H7AB), C8A(H8AA,H8AB), C10A(H10A,H10B), C11A(H11A,H11B), C12A(H12A,H12B),
 C14A(H14A,H14B), C15A(H15A,H15B), C16A(H16A,H16B), C2B(H2BA,H2BB), C3B(H3BA,
 H3BB), C4B(H4BA,H4BB), C6B(H6BA,H6BB), C7B(H7BA,H7BB), C8B(H8BA,H8BB),
 C10B(H10K,H10L), C11B(H11K,H11L), C12B(H12K,H12L), C14B(H14K,H14L), C15B(H15K,
 H15L), C2C(H2CA,H2CB), C3C(H3CA,H3CB), C4C(H4CA,H4CB), C6C(H6CA,H6CB),
 C7C(H7CA,H7CB), C8C(H8CA,H8CB), C10C(H10C,H10D), C11C(H11C,H11D), C12C(H12C,
 H12D), C14C(H14C,H14D), C15C(H15C,H15D), C16C(H16C,H16D), C2D(H2DA,H2DB),
 C3D(H3DA,H3DB), C4D(H4DA,H4DB), C6D(H6DA,H6DB), C7D(H7DA,H7DB), C8D(H8DA,H8DB),
  C10D(H10E,H10F), C11D(H11E,H11F), C12D(H12E,H12F), C14D(H14E,H14F), C15D(H15E,
 H15F), C16D(H16E,H16F), C2E(H2EA,H2EB), C3E(H3EA,H3EB), C4E(H4EA,H4EB),
 C6E(H6EA,H6EB), C7E(H7EA,H7EB), C8E(H8EA,H8EB), C10E(H10G,H10H), C11E(H11G,
 H11H), C12E(H12G,H12H), C14E(H14G,H14H), C15E(H15G,H15H), C16E(H16G,H16H),
 C2F(H2FA,H2FB), C3F(H3FA,H3FB), C4F(H4FA,H4FB), C6F(H6FA,H6FB), C7F(H7FA,H7FB),
  C8F(H8FA,H8FB), C10F(H10I,H10J), C11F(H11I,H11J), C12F(H12I,H12J), C13F(H13M,
 H13N), C14F(H14I,H14J), C15F(H15I,H15J)
7.b Me refined with riding coordinates:
 C5A(H5AA,H5AB,H5AC), C9A(H9AA,H9AB,H9AC), C13A(H13A,H13B,H13C), C17A(H17A,
 H17B,H17C), C5B(H5BA,H5BB,H5BC), C9B(H9BA,H9BB,H9BC), C13B(H13O,H13P,H13Q),
 C16B(H16L,H16M,H16N), C5C(H5CA,H5CB,H5CC), C9C(H9CA,H9CB,H9CC), C13C(H13D,H13E,
 H13F), C17C(H17D,H17E,H17F), C5D(H5DA,H5DB,H5DC), C9D(H9DA,H9DB,H9DC),
 C13D(H13G,H13H,H13I), C17D(H17G,H17H,H17I), C5E(H5EA,H5EB,H5EC), C9E(H9EA,H9EB,
 H9EC), C13E(H13J,H13K,H13L), C17E(H17J,H17K,H17L), C5F(H5FA,H5FB,H5FC),
 C9F(H9FA,H9FB,H9FC), C16F(H16I,H16J,H16K), C050(H05A,H05B,H05C)
;
_shelx_res_checksum              5315
_olex2_submission_special_instructions 'No special instructions were received'