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_1574649
_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 H80 F12 In4 O66 Ti12, 2(C H4 O)'
_chemical_formula_sum            'C96 H87 F12 In4 O68 Ti12'
_chemical_formula_weight         3590.73
_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 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                 104.374(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.9080(4)
_cell_length_b                   22.5594(3)
_cell_length_c                   32.9320(8)
_cell_measurement_reflns_used    52165
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      31.7950
_cell_measurement_theta_min      2.0850
_cell_volume                     14327.2(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.91a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.91a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.91a (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      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.859
_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    -66.00  30.00   0.50    4.73    --   13.77 -22.00 -82.00  192
  2  \w    -16.00  93.00   0.50    4.73    --   13.77  22.00  82.00  218
  3  \w    -92.00 -41.00   0.50    4.73    --  -12.99 178.00 120.00  102
  4  \w    -91.00 -43.00   0.50    4.73    --  -12.99-178.00-150.00   96
  5  \w    -87.00  16.00   0.50    4.73    --  -12.99 -77.00 -90.00  206
  6  \w     -8.00  41.00   0.50    4.73    --   13.77  57.00 -90.00   98
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0245330000
_diffrn_orient_matrix_UB_12      -0.0092049000
_diffrn_orient_matrix_UB_13      -0.0184492000
_diffrn_orient_matrix_UB_21      -0.0263923000
_diffrn_orient_matrix_UB_22      0.0000932000
_diffrn_orient_matrix_UB_23      0.0110394000
_diffrn_orient_matrix_UB_31      -0.0074306000
_diffrn_orient_matrix_UB_32      0.0300570000
_diffrn_orient_matrix_UB_33      -0.0056765000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0500
_diffrn_reflns_av_unetI/netI     0.0582
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.859
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       48
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            197254
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.859
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.773
_diffrn_reflns_theta_min         1.700
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Mova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.363
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59403
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.91a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.665
_exptl_crystal_description       block
_exptl_crystal_F_000             7100
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_refine_diff_density_max         4.097
_refine_diff_density_min         -1.892
_refine_diff_density_rms         0.126
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1797
_refine_ls_number_reflns         41960
_refine_ls_number_restraints     1545
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.1195
_refine_ls_R_factor_gt           0.0720
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0928P)^2^+33.6251P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1870
_refine_ls_wR_factor_ref         0.2117
_reflns_Friedel_coverage         0.000
_reflns_number_gt                24557
_reflns_number_total             41960
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4mh01920b2.cif
_cod_data_source_block           ti12-5f_auto
_cod_depositor_comments
'Adding full bibliography for 1574645--1574649.cif.'
_cod_database_code               1574649
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C H O N F 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) groups, All O(H,H) groups
2. Restrained distances
 In3-O67B
 2.22 with sigma of 0.001
 O53B-C98 = O12B-C67 = O27B-C99 = O67A-C97
 1.43 with sigma of 0.01
 O67A-H67F
 0.87 with sigma of 0.01
 O12A-C67
 1.43 with sigma of 0.01
 O27A-H27C
 0.87 with sigma of 0.01
 O53A-C98
 1.43 with sigma of 0.01
 O12A-H12C
 0.87 with sigma of 0.01
 C99-H27C
 1.895715 with sigma of 0.02
 C97-H67F
 1.886266 with sigma of 0.02
 In3-H67F
 2.935845 with sigma of 0.02
 C67-H12C
 1.899967 with sigma of 0.02
 In4-H27C
 2.7867 with sigma of 0.02
 In2-H12C
 2.844474 with sigma of 0.02
 In3-O67B \\sim In3-O67A
 with sigma of 0.02
 In2-O12B \\sim In2-O12A
 with sigma of 0.02
 In4-O27B \\sim In4-O27A
 with sigma of 0.02
 In1-O53B \\sim In1-O53A
 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
O67B \\sim O67A \\sim C97: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002 within 2A
O65 \\sim C93: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004 within 2A
O27B \\sim O27A \\sim C99: within 2A with sigma of 0.002 and sigma for terminal
atoms of 0.004 within 2A
O46: within 2A with sigma of 0.002 and sigma for terminal atoms of 0.004 within
2A
O12B \\sim O12A \\sim C67: within 2A with sigma of 0.002 and sigma for terminal
atoms of 0.004 within 2A
C86 \\sim C84: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
O53B \\sim O53A \\sim C98: within 2A with sigma of 0.002 and sigma for terminal
atoms of 0.004 within 2A
Uanis(C97) \\sim Ueq, Uanis(O67B) \\sim Ueq, Uanis(O67A) \\sim Ueq: with sigma
of 0.002 and sigma for terminal atoms of 0.004
Uanis(F3) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C93, O65
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O67B, In3
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O67B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C4, C65, C99, C6, C81, C8, C57, C10, C73, C12, C89, C14, C53, C16, C61, C18,
 C69, C20, C77, C22, C85, C24, C47, C26, C51, C28, C55, C30, C59, C32, C63, C34,
  C96, C36, C71, C38, C75, C40, C79, C42, C83, C44, C87, C46, C91, C48, C97,
 C50, C25, C52, C13, C54, C27, C56, C7, C58, C29, C60, C15, C62, C31, C64, C2,
 C66, C33, C68, C17, C70, C35, C72, C9, C74, C37, C76, C19, C78, C39, C80, C5,
 C82, C41, C84, C21, C86, C43, C88, C11, C90, C45, C92, C23, C94, C98, C95, C67,
  C3, C93, C49
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 In4, O27A, C99
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 In3, O67A, C97
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O46
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O12A, In2, C67
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 In1, O53A, C98
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 In1, O53B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O27B, In4
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O12B, In2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 In2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F3, C14, C55, C37, C87, C61, C69, O31, Ti6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 F1, F9, F7, F2, F11, F3, F8, F4, F10, F5, F12, F6
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
6. Others
 Fixed Sof: O67B(0.5) H67A(0.5) H67B(0.5) O12B(0.5) H12A(0.5) H12B(0.5)
 O53B(0.5) H53A(0.5) H53B(0.5) O27B(0.5) H27A(0.5) H27B(0.5) C98(0.5) H98A(0.5)
 H98B(0.5) H98C(0.5) C97(0.5) H97A(0.5) H97B(0.5) H97C(0.5) C67(0.5) H67C(0.5)
 H67D(0.5) H67E(0.5) C99(0.5) H99A(0.5) H99B(0.5) H99C(0.5) O67A(0.5) H67F(0.5)
 O53A(0.5) H53C(0.5) O27A(0.5) H27C(0.5) O12A(0.5) H12C(0.5)
 Fixed Y: H67F(0.76424)
 Fixed Z: C97(0.60103) H67F(0.60708)
7.a Riding coordinates:
 O67B(H67A,H67B), C67(H67C,H67D,H67E), O65(H65)
7.b Rotating group:
 O4(H4A,H4B), O12B(H12A,H12B), O58(H58A,H58B), O9(H9A,H9B), O53B(H53A,H53B),
 O27B(H27A,H27B), O46(H46A,H46B)
7.c Me refined with riding coordinates:
 C99(H99A,H99B,H99C)
7.d Aromatic/amide H refined with riding coordinates:
 C4(H4), C10(H10), C22(H22), C28(H28), C32(H32), C34(H34), C42(H42), C46(H46),
 C48(H48), C54(H54), C58(H58), C62(H62), C70(H70), C74(H74), C80(H80), C82(H82),
  C86(H86), C88(H88), C95(H95), C49(H49), C25(H25), C13(H13), C55(H55),
 C57(H57), C29(H29), C15(H15), C61(H61), C2(H2), C17(H17), C69(H69), C35(H35),
 C75(H75), C77(H77), C79(H79), C83(H83), C21(H21)
7.e Fitted hexagon refined as free rotating group:
 C82(C84,C86,C88,C90,C92)
7.f Tetrahedral OH refined with riding coordinates:
 O33(H33)
7.g Idealised Me refined as rotating group:
 C78(H78A,H78B,H78C), C59(H59A,H59B,H59C), C63(H63A,H63B,H63C), C5(H5A,H5B,
 H5C), C81(H81A,H81B,H81C), C85(H85A,H85B,H85C), C89(H89A,H89B,H89C), C45(H45A,
 H45B,H45C), C47(H47A,H47B,H47C), C98(H98A,H98B,H98C), C97(H97A,H97B,H97C),
 C93(H93A,H93B,H93C)
7.h Idealised tetrahedral OH refined as rotating group:
 O53A(H53C)
;
_shelx_res_checksum              3473
_shelx_fab_checksum              72742
_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 1.742
_oxdiff_exptl_absorpt_empirical_full_min 0.549