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_1574648
_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         'C106 H114 In4 O66 Ti12'
_chemical_formula_sum            'C106 H114 In4 O66 Ti12'
_chemical_formula_weight         3478.05
_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             2023-11-23
_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                 107.4470(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.2798(2)
_cell_length_b                   20.9981(2)
_cell_length_c                   31.0613(3)
_cell_measurement_reflns_used    52722
_cell_measurement_temperature    120.0(3)
_cell_measurement_theta_max      59.7570
_cell_measurement_theta_min      2.2810
_cell_volume                     16351.9(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 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -28.00  -3.00   0.50    0.83    --   -0.62  94.00  38.00   50
  2  \w    -15.00  30.00   0.50    0.83    --   -0.62 -94.00 -71.00   90
  3  \w     84.00 123.00   0.50    3.31    --   76.66  94.00  38.00   78
  4  \w    -51.00 -25.00   0.50    3.31    --  -77.91  94.00  38.00   52
  5  \w   -132.00-106.00   0.50    3.31    --  -77.91 -94.00 -71.00   52
  6  \w   -105.00 -61.00   0.50    3.31    --  -77.91  94.00  38.00   88
  7  \w     -8.00  36.00   0.50    0.83    --   -0.62 -99.00 120.00   88
  8  \w    -20.00  72.00   0.50    0.83    --   -0.62  57.00  90.00  184
  9  \w      3.00  96.00   0.50    3.31    --   76.66 -57.00 -30.00  186
 10  \w    103.00 151.00   0.50    3.31    --   76.66  57.00   0.00   96
 11  \w     79.00 147.00   0.50    3.31    --   76.66 125.00  60.00  136
 12  \w     54.00  81.00   0.50    3.31    --   76.66 -94.00 -71.00   54
 13  \w     24.00  50.00   0.50    3.31    --   76.66 -94.00 -71.00   52
 14  \w     27.00 110.00   0.50    3.31    --   76.66-125.00 -60.00  166
 15  \w   -149.00 -70.00   0.50    3.31    --  -77.91 -38.00 -30.00  158
 16  \w    -69.00 -32.00   0.50    3.31    --  -77.91  38.00-120.00   74
 17  \w   -137.00 -82.00   0.50    3.31    --  -77.91-125.00 -30.00  110
 18  \w   -121.00 -96.00   0.50    3.31    --  -77.91 -99.00-150.00   50
;
_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      0.0067644000
_diffrn_orient_matrix_UB_12      0.0569517000
_diffrn_orient_matrix_UB_13      0.0203578000
_diffrn_orient_matrix_UB_21      -0.0340019000
_diffrn_orient_matrix_UB_22      -0.0166156000
_diffrn_orient_matrix_UB_23      0.0226580000
_diffrn_orient_matrix_UB_31      0.0406472000
_diffrn_orient_matrix_UB_32      -0.0233626000
_diffrn_orient_matrix_UB_33      0.0334035000
_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  0.0447
_diffrn_reflns_av_unetI/netI     0.0374
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            109093
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        52.931
_diffrn_reflns_theta_max         52.931
_diffrn_reflns_theta_min         2.242
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    6.404
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88084
_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    1.413
_exptl_crystal_description       block
_exptl_crystal_F_000             6952
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_refine_diff_density_max         4.774
_refine_diff_density_min         -0.743
_refine_diff_density_rms         0.103
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1780
_refine_ls_number_reflns         28871
_refine_ls_number_restraints     143
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0732
_refine_ls_R_factor_gt           0.0581
_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^)+(0.0813P)^2^+46.8228P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1573
_refine_ls_wR_factor_ref         0.1675
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22614
_reflns_number_total             28871
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4mh01920b2.cif
_cod_data_source_block           ti12in4-4ch3_auto
_cod_depositor_comments
'Adding full bibliography for 1574645--1574649.cif.'
_cod_database_code               1574648
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'c h o n Ti In'
_shelx_estimated_absorpt_t_max   0.831
_shelx_estimated_absorpt_t_min   0.831
_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, All O(H,H) groups
2. Restrained distances
 O32A-C106 = O56A-C108 = O64A-C55 = O66A-C109
 1.45 with sigma of 0.01
 O66A-H66A
 0.87 with sigma of 0.01
 O64A-H64A
 0.87 with sigma of 0.01
 O56A-H56A
 0.87 with sigma of 0.01
 O66B-C109
 1.48 with sigma of 0.01
 O32A-H32A
 0.87 with sigma of 0.01
 In4-O32B
 2.15 with sigma of 0.01
 C108-H56A
 1.937933 with sigma of 0.02
 In3-H66A
 2.862877 with sigma of 0.02
 C109-H66A
 1.926312 with sigma of 0.02
 C55-H64A
 2.017922 with sigma of 0.02
 In2-H64A
 2.758933 with sigma of 0.02
 In1-H56A
 2.814957 with sigma of 0.02
 C106-H32A
 1.958924 with sigma of 0.02
 In4-H32A
 2.770906 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O56A \\sim O56B \\sim C108: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
O66A \\sim O66B \\sim C109: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
O32A \\sim O32B \\sim C106: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
O56B \\sim C108: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
O64A \\sim O64B \\sim C55: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002 within 2A
O66B \\sim C109: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
O64B \\sim C55: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
Uanis(C109) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 In1, O56A, C108
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 In1, O56B, C108
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 In3, O66A, C109
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 In2, O64A, C55
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 In3, O66B, C109
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 In4, O32B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 In3, O66B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 In2, O64B, C55
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 In1, O56B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 In2, O64B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 In4, O32A, C106
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Others
 Fixed Sof: O32A(0.5) H32A(0.5) O32B(0.5) H32B(0.5) H32C(0.5) O56A(0.5)
 H56A(0.5) O56B(0.5) H56B(0.5) H56C(0.5) O64A(0.5) H64A(0.5) O64B(0.5)
 H64B(0.5) H64C(0.5) O66A(0.5) H66A(0.5) O66B(0.5) H66B(0.5) H66C(0.5) C55(0.5)
 H55A(0.5) H55B(0.5) H55C(0.5) C106(0.5) H10J(0.5) H10K(0.5) H10L(0.5)
 C108(0.5) H10M(0.5) H10N(0.5) H10O(0.5) C109(0.5) H10P(0.5) H10Q(0.5) H10R(0.5)
 Fixed X: O64A(0.198371) H66A(0.482459)
 Fixed Y: O66B(0.09512)
 Fixed Z: O56A(0.280399) O66A(0.160501)
6.a Riding coordinates:
 C7(H7A,H7B,H7C)
6.b Rotating group:
 O32B(H32B,H32C), O44(H44A,H44B), O47(H47A,H47B), O49(H49A,H49B), O53(H53A,
 H53B), O56B(H56B,H56C), O64B(H64B,H64C), O66B(H66B,H66C)
6.c Me refined with riding coordinates:
 C47(H47C,H47D,H47E), C76(H76A,H76B,H76C), C98(H98A,H98B,H98C), C102(H10D,H10E,
 H10F), C108(H10M,H10N,H10O)
6.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C9(H9), C13(H13), C15(H15), C17(H17), C20(H20), C21(H21),
 C28(H28), C29(H29), C35(H35), C36(H36), C43(H43), C45(H45), C48(H48), C49(H49),
  C57(H57), C62(H62), C65(H65), C66(H66), C71(H71), C72(H72), C78(H78),
 C81(H81), C83(H83), C84(H84), C85(H85), C86(H86), C88(H88), C90(H90), C91(H91),
  C93(H93), C95(H95), C107(H107)
6.e Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C33(H33A,H33B,
 H33C), C37(H37A,H37B,H37C), C41(H41A,H41B,H41C), C51(H51A,H51B,H51C), C53(H53C,
 H53D,H53E), C55(H55A,H55B,H55C), C60(H60A,H60B,H60C), C80(H80A,H80B,H80C),
 C82(H82A,H82B,H82C), C92(H92A,H92B,H92C), C94(H94A,H94B,H94C), C100(H10A,H10B,
 H10C), C104(H10G,H10H,H10I), C106(H10J,H10K,H10L), C109(H10P,H10Q,H10R)
;
_shelx_res_checksum              28571
_shelx_fab_checksum              26896
_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 2.749
_oxdiff_exptl_absorpt_empirical_full_min 0.427