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_1574647
_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 H68 In4 N12 O88 Ti12'
_chemical_formula_sum            'C92 H68 In4 N12 O88 Ti12'
_chemical_formula_weight         3783.66
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2023-10-16
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-11-18 deposited with the CCDC.	2025-05-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.552(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   18.8550(4)
_cell_length_b                   16.9266(2)
_cell_length_c                   31.0947(5)
_cell_measurement_reflns_used    28665
_cell_measurement_temperature    120.0(3)
_cell_measurement_theta_max      60.0240
_cell_measurement_theta_min      2.5390
_cell_volume                     9647.6(3)
_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      120.0(3)
_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 0.976
_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      4.00  83.00   0.50    1.42    --   76.66 -57.00 120.00  158
  2  \w     54.00 101.00   0.50    1.42    --   76.66  38.00  93.00   94
  3  \w     23.00  71.00   0.50    1.42    --   76.66 -38.00 -62.00   96
  4  \w     19.00  70.00   0.50    1.42    --   76.66 -38.00-180.00  102
  5  \w     67.00 117.00   0.50    1.42    --   76.66  38.00-180.00  100
  6  \w    -95.00 -30.00   0.50    1.42    --  -77.91  57.00  60.00  130
  7  \w    -71.00  -1.00   0.50    1.42    --  -77.91  38.00  93.00  140
  8  \w     14.00  60.00   0.50    0.36    --   -0.62  38.00  93.00   92
  9  \w    -71.00  -1.00   0.50    1.42    --  -77.91  38.00-120.00  140
 10  \w    -78.00  21.00   0.50    0.36    --   -0.62 -38.00 -62.00  198
 11  \w     -8.00  37.00   0.50    0.36    --   -0.62 -99.00-180.00   90
 12  \w    -46.00 -21.00   0.50    1.42    --  -77.91 125.00  90.00   50
 13  \w   -105.00 -63.00   0.50    1.42    --  -77.91 125.00  90.00   84
 14  \w   -155.00 -75.00   0.50    1.42    --  -77.91 -38.00 -62.00  160
 15  \w   -148.00-122.00   0.50    1.42    --  -77.91 -99.00  30.00   52
 16  \w   -113.00 -86.00   0.50    1.42    --  -77.91-125.00 120.00   54
;
_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      -0.0317107000
_diffrn_orient_matrix_UB_12      0.0363042000
_diffrn_orient_matrix_UB_13      0.0289154000
_diffrn_orient_matrix_UB_21      -0.0606185000
_diffrn_orient_matrix_UB_22      0.0103521000
_diffrn_orient_matrix_UB_23      -0.0319574000
_diffrn_orient_matrix_UB_31      -0.0255686000
_diffrn_orient_matrix_UB_32      -0.0695264000
_diffrn_orient_matrix_UB_33      0.0103138000
_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  0.0875
_diffrn_reflns_av_unetI/netI     0.0665
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            75300
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        53.543
_diffrn_reflns_theta_max         60.274
_diffrn_reflns_theta_min         2.181
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    5.525
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64166
_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    1.302
_exptl_crystal_description       block
_exptl_crystal_F_000             3736
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.977
_refine_diff_density_min         -1.315
_refine_diff_density_rms         0.138
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     942
_refine_ls_number_reflns         21434
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0819
_refine_ls_R_factor_gt           0.0672
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1094P)^2^+17.4244P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1920
_refine_ls_wR_factor_ref         0.2029
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16221
_reflns_number_total             21434
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4mh01920b2.cif
_cod_data_source_block           ti12in4-5no2_auto
_cod_depositor_comments
'Adding full bibliography for 1574645--1574649.cif.'
_cod_database_code               1574647
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         ' c h o n Ti In'
_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,H) groups
2. Uiso/Uaniso restraints and constraints
C20 \\sim O44 \\sim C5 \\sim O23: within 2A with sigma of 0.002 and sigma for
terminal atoms of 0.004 within 2A
3. Rigid body (RIGU) restrains
 O23, Ti3, C5
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 Ti2, O44, C20
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4.a Riding coordinates:
 C6(H6A,H6B,H6C)
4.b Rotating group:
 O15(H15A,H15B), O22(H22A,H22B)
4.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C11(H11), C12(H12), C15(H15), C16(H16), C17(H17), C22(H22), C26(H26),
 C27(H27), C30(H30), C31(H31), C32(H32), C33(H33), C38(H38), C39(H39), C40(H40),
  C43(H43), C46(H46)
4.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              61621
_shelx_fab_checksum              67726
_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 4.259
_oxdiff_exptl_absorpt_empirical_full_min 0.284