All-catecholate-stabilized black titanium-oxo clusters for efficient photothermal conversion.
Hou, Jinle; Huang, Nahui; Acharya, Dinesh; Liu, Yuxin; Zhu, Jiaying; Teng, Jiaxin; Wang, Zhi; Qu, Konggang; Zhang, Xianxi; Sun, Di; Chemical science 15 (2024) 2655–2664; doi:10.1039/d3sc05617a

data_1570645
_publ_section_title
;
 All-catecholate-stabilized black titanium-oxo clusters for efficient
 photothermal conversion.
;
_journal_issue                   7
_journal_name_full               'Chemical science'
_journal_page_first              2655
_journal_page_last               2664
_journal_paper_doi               10.1039/d3sc05617a
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C72 H79 O29 Ti8'
_chemical_formula_sum            'C72 H79 O29 Ti8'
_chemical_formula_weight         1791.55
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2023-05-09
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-09-13 deposited with the CCDC.	2024-01-03 downloaded from the CCDC.
;
_cell_angle_alpha                87.685(2)
_cell_angle_beta                 89.986(2)
_cell_angle_gamma                66.441(2)
_cell_formula_units_Z            2
_cell_length_a                   13.7327(7)
_cell_length_b                   14.2235(7)
_cell_length_c                   23.4194(12)
_cell_measurement_reflns_used    9349
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      27.55
_cell_measurement_theta_min      2.39
_cell_volume                     4189.1(4)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0562
_diffrn_reflns_av_unetI/netI     0.0230
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            180993
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         2.288
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.797
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6320
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            'metallic dark red'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.420
_exptl_crystal_description       block
_exptl_crystal_F_000             1838
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.206
_refine_diff_density_min         -0.914
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1026
_refine_ls_number_reflns         14774
_refine_ls_number_restraints     158
_refine_ls_restrained_S_all      1.221
_refine_ls_R_factor_all          0.0502
_refine_ls_R_factor_gt           0.0414
_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^)+(0.0492P)^2^+8.6262P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1073
_refine_ls_wR_factor_ref         0.1147
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12739
_reflns_number_total             14774
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05617a2.cif
_cod_data_source_block           b171114f_1_0m
_cod_depositor_comments
'Adding full bibliography for 1570642--1570645.cif.'
_cod_database_code               1570645
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.961
_shelx_estimated_absorpt_t_min   0.826
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 C63A-C62A
 2.55 with sigma of 0.01
 C60-C58 = C59-C58 = C63-C61 = C62-C61 = C66-C64 = C65-C64 = C57-C55 = C56-C55
 = C68-C67 = C69-C67 = C72-C70 = C71-C70
 1.55 with sigma of 0.01
 C62A-C61 = C63A-C61
 1.55 with sigma of 0.01
3. Rigid bond restraints
 C61, O25
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
O27 \\sim C55 \\sim C56 \\sim C57: within 2A with sigma of 0.002 and sigma for
terminal atoms of 0.004 within 2A
O24 \\sim C58 \\sim C59 \\sim C60: within 2A with sigma of 0.002 and sigma for
terminal atoms of 0.004 within 2A
O26 \\sim C64 \\sim C65 \\sim C66: within 2A with sigma of 0.002 and sigma for
terminal atoms of 0.004 within 2A
C61 \\sim C62 \\sim C63 \\sim C62A \\sim C63A \\sim C76 \\sim O25: within 2A
with sigma of 0.002 and sigma for terminal atoms of 0.004 within 2A
Uanis(C64) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C65) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(C62A)=Sof(H62D)=Sof(H62E)=Sof(H62F)=Sof(C63A)=Sof(H63D)=Sof(H63E)=
 Sof(H63F)=Sof(C76)=Sof(H76)=1-FVAR(1)
 Sof(C61)=Sof(H61)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=Sof(C63)=Sof(H63A)=
 Sof(H63B)=Sof(H63C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C55(H55), C58(H58), C61(H61), C67(H67), C70(H70), C76(H76)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12),
 C15(H15), C16(H16), C17(H17), C18(H18), C20(H20), C21(H21), C22(H22), C23(H23),
  C27(H27), C28(H28A), C29(H29), C30(H30), C33(H33), C34(H34), C35(H35),
 C36(H36), C39(H39), C40(H40), C41(H41), C42(H42), C45(H45), C46(H46), C47(H47),
  C48(H48), C51(H51), C52(H52), C53(H53), C54(H54)
6.c Idealised Me refined as rotating group:
 C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C59(H59A,H59B,H59C), C60(H60A,H60B,
 H60C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C65(H65A,H65B,H65C), C66(H66A,
 H66B,H66C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C71(H71A,H71B,H71C),
 C72(H72A,H72B,H72C), C62A(H62D,H62E,H62F), C63A(H63D,H63E,H63F)
6.d Idealised tetrahedral OH refined as rotating group:
 O24(H24), O28(H28)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              73794
_shelx_hkl_checksum              82543
_shelx_fab_checksum              80708
_olex2_submission_special_instructions 'No special instructions were received'