Ligand effect on In-Ti-oxo nanoclusters for nanolithography.
Wu, Jiao; Chen, Jiali; Wang, Liming; Ye, Yuting; Zhan, Xiaozhi; Song, Yihang; Li, Qiao-Hong; Yi, Xiaofeng; Zhang, Jian; Materials horizons 12 (2025) 6283–6290; doi:10.1039/d4mh01920b

data_1574646
_publ_section_title
;
 Ligand effect on In-Ti-oxo nanoclusters for nanolithography.
;
_journal_issue                   16
_journal_name_full               'Materials horizons'
_journal_page_first              6283
_journal_page_last               6290
_journal_paper_doi               10.1039/d4mh01920b
_journal_volume                  12
_journal_year                    2025
_chemical_formula_moiety         'C92 H88 In4 O66 Ti12, 12(H2 O)'
_chemical_formula_sum            'C92 H112 In4 O78 Ti12'
_chemical_formula_weight         3499.89
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2023-12-06
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-11-18 deposited with the CCDC.	2025-05-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   19.6806(4)
_cell_length_b                   19.6806(4)
_cell_length_c                   15.9007(4)
_cell_measurement_reflns_used    11347
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      60.0130
_cell_measurement_theta_min      3.0760
_cell_volume                     6158.8(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w      9.00  40.00   0.50    0.16    --   -0.78 -99.00 -60.00   62
  2  \w     -1.00  38.00   0.50    0.16    --   -0.78 -99.00  90.00   78
  3  \w     10.00  36.00   0.50    0.16    --   -0.78 -99.00 -90.00   52
  4  \w   -135.00-102.00   0.50    0.64    --  -78.47 -99.00-180.00   66
  5  \w   -151.00 -80.00   0.50    0.64    --  -78.47-125.00 150.00  142
  6  \w   -104.00 -59.00   0.50    0.64    --  -78.47 -71.00 103.00   90
  7  \w   -151.00-120.00   0.50    0.64    --  -78.47 -71.00 103.00   62
  8  \w   -112.00 -59.00   0.50    0.64    --  -78.47 -74.00 -17.00  106
  9  \w     83.00 147.00   0.50    0.64    --   76.91 125.00  60.00  128
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0185819000
_diffrn_orient_matrix_UB_12      -0.0384236000
_diffrn_orient_matrix_UB_13      0.0656138000
_diffrn_orient_matrix_UB_21      0.0533283000
_diffrn_orient_matrix_UB_22      -0.0408521000
_diffrn_orient_matrix_UB_23      -0.0134078000
_diffrn_orient_matrix_UB_31      0.0379695000
_diffrn_orient_matrix_UB_32      0.0385193000
_diffrn_orient_matrix_UB_33      0.0510848000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Ga K\a'
_diffrn_radiation_wavelength     1.3405
_diffrn_reflns_av_R_equivalents  0.0987
_diffrn_reflns_av_unetI/netI     0.1058
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            20463
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        53.543
_diffrn_reflns_theta_max         60.311
_diffrn_reflns_theta_min         2.761
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    8.889
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.17806
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.84a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.887
_exptl_crystal_description       block
_exptl_crystal_F_000             3496
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.01
_refine_diff_density_max         2.081
_refine_diff_density_min         -1.251
_refine_diff_density_rms         0.196
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.48(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     424
_refine_ls_number_reflns         6233
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.1069
_refine_ls_R_factor_gt           0.0797
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1378P)^2^+0.3099P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1991
_refine_ls_wR_factor_ref         0.2157
_reflns_Friedel_coverage         0.829
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                4884
_reflns_number_total             6233
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4mh01920b2.cif
_cod_data_source_block           ti12in4-24_auto
_cod_depositor_comments
'Adding full bibliography for 1574645--1574649.cif.'
_cod_original_cell_volume        6158.8(3)
_cod_database_code               1574646
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C H O Ti In'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.52(3)
 0.48(3)
2. 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,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(O20) \\sim Ueq, Uanis(O9) \\sim Ueq, Uanis(O17) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 O9, O20, O17
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Others
 Fixed Z: O20(0.211821)
6.a Riding coordinates:
 O9(H9A,H9B), O17(H17A,H17B), O20(H20A,H20B)
6.b Rotating group:
 O2(H2A,H2B), O8(H8A,H8B)
6.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C6(H6), C7(H7), C9(H9), C13(H13), C15(H15), C16(H16),
 C19(H19), C20(H20), C21(H21), C22(H22)
6.d Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C11(H11A,H11B,H11C)
;
_shelx_res_checksum              89348
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.896
_oxdiff_exptl_absorpt_empirical_full_min 0.290