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_1574645
_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         'C94 H92 In4 O66 Ti12, 4(C H4 O)'
_chemical_formula_sum            'C98 H104 In4 O70 Ti12'
_chemical_formula_weight         3435.89
_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
_audit_creation_date             2023-11-23
_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                   19.7706(2)
_cell_length_b                   19.7706(2)
_cell_length_c                   15.9534(2)
_cell_measurement_reflns_used    16612
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      59.1370
_cell_measurement_theta_min      2.7300
_cell_volume                     6235.81(12)
_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      100.0(3)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.987
_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     79.00 147.00   0.50    0.79    --   75.35 125.00 -30.00  136
  2  \w    -23.00  73.00   0.50    0.20    --   -1.41  57.00-180.00  192
  3  \w    -23.00  32.00   0.50    0.20    --   -1.41  57.00 -30.00  110
  4  \w     52.00 155.00   0.50    0.79    --   75.35  32.00 128.00  206
  5  \w    -23.00  76.00   0.50    0.20    --   -1.41  38.00  90.00  198
  6  \w   -107.00  -4.00   0.50    0.79    --  -78.17  77.00 -30.00  206
  7  \w     -8.00  37.00   0.50    0.20    --   -1.41 -99.00 -30.00   90
  8  \w   -150.00 -79.00   0.50    0.79    --  -78.17-125.00 109.00  142
  9  \w   -150.00 -79.00   0.50    0.79    --  -78.17-125.00  60.00  142
;
_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      0.0573655000
_diffrn_orient_matrix_UB_12      0.0313983000
_diffrn_orient_matrix_UB_13      -0.0223703000
_diffrn_orient_matrix_UB_21      -0.0357879000
_diffrn_orient_matrix_UB_22      0.0535623000
_diffrn_orient_matrix_UB_23      -0.0256956000
_diffrn_orient_matrix_UB_31      0.0047770000
_diffrn_orient_matrix_UB_32      0.0272234000
_diffrn_orient_matrix_UB_33      0.0765842000
_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  0.0580
_diffrn_reflns_av_unetI/netI     0.0410
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            32498
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        53.543
_diffrn_reflns_theta_max         60.209
_diffrn_reflns_theta_min         2.748
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    8.740
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55898
_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    1.830
_exptl_crystal_description       block
_exptl_crystal_F_000             3424
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.589
_refine_diff_density_min         -0.917
_refine_diff_density_rms         0.117
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.500(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     437
_refine_ls_number_reflns         6661
_refine_ls_number_restraints     43
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0507
_refine_ls_R_factor_gt           0.0415
_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^)+(0.0717P)^2^+2.5947P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1034
_refine_ls_wR_factor_ref         0.1090
_reflns_Friedel_coverage         0.827
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                5910
_reflns_number_total             6661
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4mh01920b2.cif
_cod_data_source_block           1-41-7_auto
_cod_depositor_comments
'Adding full bibliography for 1574645--1574649.cif.'
_cod_original_cell_volume        6235.81(15)
_cod_database_code               1574645
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C H O N In Bi Ti'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.500(12)
 0.500(12)
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) groups, All O(H,H) groups
3. Restrained distances
 O11B-H11B
 0.87 with sigma of 0.01
 O11B-C25
 1.45 with sigma of 0.01
 In1-H11B
 2.771722 with sigma of 0.02
 C25-H11B
 2.004918 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
O11B \\sim C25: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
O17 \\sim C23: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
O11B \\sim C25 \\sim O11A: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002 within 2A
5. Rigid body (RIGU) restrains
 In1, O11B, C25
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O17, C23
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O11B, C25, In1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 In1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 O11A, In1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
6. Others
 Fixed Sof: O11B(0.5) H11B(0.5) C25(0.5) H25A(0.5) H25B(0.5) H25C(0.5)
 O11A(0.5) H11A(0.5) H11C(0.5)
 Fixed X: O11B(0.574509)
 Fixed Z: O11B(0.577649)
7.a Riding coordinates:
 O17(H17A)
7.b Rotating group:
 O2(H2A,H2B), O11A(H11A,H11C)
7.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C6(H6), C7(H7), C8(H8), C10(H10), C11(H11), C12(H12), C13(H13),
 C17(H17), C18(H18), C19(H19), C21(H21)
7.d Idealised Me refined as rotating group:
 C2(H2C,H2D,H2E), C9(H9A,H9B,H9C), C25(H25A,H25B,H25C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              60332
_shelx_fab_checksum              26917
_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 2.505
_oxdiff_exptl_absorpt_empirical_full_min 0.504