Record-Large Indium-Oxo Clusters: Synthesis, Hierarchical Assembly, and Efficient Optical Limiting
Wang, Xiuzhen; Chen, Yian; Yi, Xiaofeng; Chen, Shumei; Zhang, Jian; Chemical Science  (2026) –; doi:10.1039/D6SC00913A

data_1576884
_publ_section_title
;
 Record-large indium-oxo clusters: synthesis, hierarchical assembly, and
 efficient optical limiting.
;
_journal_issue                   18
_journal_name_full               'Chemical science'
_journal_page_first              9256
_journal_page_last               9263
_journal_paper_doi               10.1039/d6sc00913a
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety
'C84.95 H115.9 F6 In15 N7 O45, C7 H5 F O2, 1.05(H2 O), 3[CH4O], 5[CH4O]'
_chemical_formula_sum            'C99.95 H155 F7 In15 N7 O56.05'
_chemical_formula_weight         4206.80
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2pw2vj
_audit_creation_date             2026-03-03
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2026-03-05 deposited with the CCDC.	2026-03-16 downloaded from the CCDC.
;
_cell_angle_alpha                105.2860(10)
_cell_angle_beta                 96.3120(10)
_cell_angle_gamma                103.5060(10)
_cell_formula_units_Z            2
_cell_length_a                   15.3911(2)
_cell_length_b                   17.1544(2)
_cell_length_c                   26.9239(3)
_cell_measurement_reflns_used    76001
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      30.9190
_cell_measurement_theta_min      1.8050
_cell_volume                     6555.04(15)
_computing_cell_refinement       'CrysAlisPro 1.171.43.101a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.43.101a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.43.101a (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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(11)
_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 0.825
_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  62.00   0.50    2.21    --   -5.79   0.00 120.00  282
  2  \w    -79.00  62.00   0.50    2.21    --   -5.79   0.00 120.00  282
  3  \w    -20.00  68.00   0.50    2.21    --   -5.79  38.00 -30.00  176
  4  \w     -9.00  40.00   0.50    2.21    --    6.02 -99.00 -30.00   98
  5  \w    -79.00   9.00   0.50    2.21    --   -5.79 -38.00  30.00  176
  6  \w    -79.00  10.00   0.50    2.21    --   -5.79 -57.00 150.00  178
  7  \w    -18.00  28.00   0.50    2.21    --   -5.79 -99.00 120.00   92
;
_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      -0.0395612000
_diffrn_orient_matrix_UB_12      -0.0344128000
_diffrn_orient_matrix_UB_13      -0.0069258000
_diffrn_orient_matrix_UB_21      0.0076335000
_diffrn_orient_matrix_UB_22      -0.0114437000
_diffrn_orient_matrix_UB_23      -0.0261215000
_diffrn_orient_matrix_UB_31      0.0264711000
_diffrn_orient_matrix_UB_32      -0.0259053000
_diffrn_orient_matrix_UB_33      0.0064330000
_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  0.0392
_diffrn_reflns_av_unetI/netI     0.0375
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.825
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            147095
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.825
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.802
_diffrn_reflns_theta_min         1.698
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Mova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.685
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94425
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.101a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    2.131
_exptl_crystal_description       block
_exptl_crystal_F_000             4100
_exptl_crystal_size_max          0.0165
_exptl_crystal_size_mid          0.01554
_exptl_crystal_size_min          0.0143
_refine_diff_density_max         1.845
_refine_diff_density_min         -1.610
_refine_diff_density_rms         0.142
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.011
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1848
_refine_ls_number_reflns         33896
_refine_ls_number_restraints     1374
_refine_ls_restrained_S_all      1.010
_refine_ls_R_factor_all          0.0557
_refine_ls_R_factor_gt           0.0368
_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^)+(0.0298P)^2^+26.8738P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0799
_refine_ls_wR_factor_ref         0.0886
_reflns_Friedel_coverage         0.000
_reflns_number_gt                25892
_reflns_number_total             33896
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc00913a2.cif
_cod_data_source_block           InOC-39_auto
_cod_depositor_comments
'Adding full bibliography for 1576882--1576886.cif.'
_cod_original_cell_volume        6555.04(14)
_cod_database_code               1576884
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N F In'
_cell_oxdiff_angle_alpha         105.2857(9)
_cell_oxdiff_angle_beta          96.3120(8)
_cell_oxdiff_angle_gamma         103.5060(9)
_cell_oxdiff_length_a            15.39109(15)
_cell_oxdiff_length_b            17.15439(18)
_cell_oxdiff_length_c            26.9239(3)
_cell_oxdiff_measurement_reflns_used 76001
_cell_oxdiff_volume              6555.04(11)
_shelx_estimated_absorpt_t_max   0.963
_shelx_estimated_absorpt_t_min   0.957
_diffrn_oxdiff_digest_hkl
;
012439abf12fcdf27b707f750e0e5d44d58700
;
_olex2_refinement_description
;
1. Restrained distances
 O35-C67A = O47B-C67B = O35-C67A
 1.2 with sigma of 0.02
 O44A-C24A = O38A-C16A
 1.25 with sigma of 0.02
 O31A-C16A = O45A-C24A = O47A-C67A = O35A-C67B
 1.3 with sigma of 0.02
 O32-C73A = O23-C75A = O14-C5A
 1.35 with sigma of 0.02
 F7A-C22A = F5A-C83A
 1.38 with sigma of 0.02
 F4A-C80A = C91A-F6A
 1.4 with sigma of 0.02
 N7-C18A = N7-C74A = N7-C81A
 1.45 with sigma of 0.02
 C58A-C24A = C67A-C49A = C88A-C27 = C46A-C16A = C74A-C73A = C81A-C75A = C5A-C18A
 1.5 with sigma of 0.02
 C85A-C67A \\sim C82A-C67A
 with sigma of 0.02
 F4A-C94A \\sim F4A-C78A
 with sigma of 0.02
2. Restrained planarity
 F7A, C24A, O44A, O45A, C58A, C23A, C59A, C61A, C60A, C22A
 with sigma of 0.1
 F5A, O31A, C16A, O38A, C46A, C62A, C71A, C77A, C86A, C83A
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
O31 \\sim O38 \\sim C16 \\sim F5 \\sim C46 \\sim C62 \\sim C71 \\sim C77 \\sim
C83 \\sim C86 \\sim O31A \\sim O38A \\sim C16A \\sim F5A \\sim C46A \\sim C62A
\\sim C71A \\sim C77A \\sim C83A \\sim C86A: within 2A with sigma of 0.005 and
sigma for terminal atoms of 0.01 within 2A
O45 \\sim O45A \\sim C24 \\sim C24A \\sim O44 \\sim O44A \\sim C58 \\sim C59
\\sim C60 \\sim C22 \\sim C61 \\sim C23 \\sim F7 \\sim C58A \\sim C23A \\sim
C59A \\sim C60A \\sim C61A \\sim C22A \\sim F7A: within 2A with sigma of 0.005
and sigma for terminal atoms of 0.01 within 2A
O35 \\sim C49A \\sim C85A \\sim C78A \\sim C80A \\sim C94A \\sim C82A \\sim
O47A \\sim C67A \\sim O35A \\sim F4B \\sim C49B \\sim C85B \\sim C78B \\sim
C80B \\sim C94B \\sim C82B \\sim O47B \\sim C67B \\sim F4A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
N7 \\sim C5 \\sim C18 \\sim C73 \\sim C74 \\sim C75 \\sim C81 \\sim C73A \\sim
C74A \\sim C81A \\sim C75A \\sim C5A \\sim C18A \\sim O14 \\sim O32 \\sim O23:
within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
F6 \\sim C87 \\sim C88 \\sim C89 \\sim C90 \\sim C91 \\sim C1 \\sim F6A \\sim
C87A \\sim C89A \\sim C90A \\sim C91A \\sim C1A \\sim C88A \\sim C27: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Others
 Sof(F6A)=Sof(C87A)=Sof(H87A)=Sof(C88A)=Sof(C89A)=Sof(H89A)=Sof(C90A)=
 Sof(H90A)=Sof(C91A)=Sof(C1A)=Sof(H1A)=1-FVAR(1)
 Sof(F6)=Sof(C87)=Sof(H87)=Sof(C88)=Sof(C89)=Sof(H89)=Sof(C90)=Sof(H90)=
 Sof(C91)=Sof(C1)=Sof(H1)=FVAR(1)
 Sof(C73A)=Sof(H73E)=Sof(H73F)=Sof(C74A)=Sof(H74A)=Sof(H74B)=Sof(C81A)=
 Sof(H81C)=Sof(H81D)=Sof(C75A)=Sof(H75C)=Sof(H75D)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=
 Sof(C18A)=Sof(H18C)=Sof(H18D)=1-FVAR(2)
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(C73)=Sof(H73A)=
 Sof(H73B)=Sof(C74)=Sof(H73C)=Sof(H73D)=Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(C81)=
 Sof(H81A)=Sof(H81B)=FVAR(2)
 Sof(O31A)=Sof(O38A)=Sof(C16A)=Sof(F5A)=Sof(C46A)=Sof(C71A)=Sof(H71A)=
 Sof(C86A)=Sof(H86A)=Sof(C83A)=Sof(C77A)=Sof(H77A)=Sof(C62A)=Sof(H62A)=1-FVAR(3)
 Sof(O31)=Sof(O38)=Sof(C16)=Sof(F5)=Sof(C46)=Sof(C62)=Sof(H62)=Sof(C71)=
 Sof(H71)=Sof(C77)=Sof(H77)=Sof(C83)=Sof(C86)=Sof(H86)=FVAR(3)
 Sof(C24A)=Sof(O44A)=Sof(O45A)=Sof(C58A)=Sof(C59A)=Sof(H59A)=Sof(C60A)=
 Sof(H60A)=Sof(C22A)=Sof(C61A)=Sof(H61A)=Sof(C23A)=Sof(H23A)=Sof(F7A)=1-FVAR(4)
 Sof(O44)=Sof(O45)=Sof(C24)=Sof(C58)=Sof(C59)=Sof(H59)=Sof(C60)=Sof(H60)=
 Sof(C22)=Sof(C61)=Sof(H61)=Sof(C23)=Sof(H23)=Sof(F7)=FVAR(4)
 Sof(O35A)=Sof(H35C)=Sof(F4B)=Sof(C49B)=Sof(C85B)=Sof(H85B)=Sof(C78B)=
 Sof(H78B)=Sof(C80B)=Sof(C94B)=Sof(H94B)=Sof(C82B)=Sof(H82B)=Sof(O47B)=
 Sof(C67B)=1-FVAR(5)
 Sof(O35)=Sof(F4A)=Sof(C49A)=Sof(C85A)=Sof(H85A)=Sof(C78A)=Sof(H78A)=Sof(C80A)=
 Sof(C94A)=Sof(H94A)=Sof(C82A)=Sof(H82A)=Sof(O47A)=Sof(H47C)=Sof(C67A)=FVAR(5)
 Fixed Sof: H19(0.55) H21(0.5) C92(0.5) H92A(0.5) H92B(0.5) H92C(0.5)
 C57(0.45) H57A(0.45) H57B(0.45) H57C(0.45) O93(0.55) H93A(0.55) H93B(0.55)
 O95(0.5) H95A(0.5) H95B(0.5)
 Fixed X: O35(0.12251) C5A(0.562428)
5.a Riding coordinates:
 O19(H19), O21(H21), O93(H93A,H93B), O95(H95A,H95B)
5.b Ternary CH refined with riding coordinates:
 O22(H22)
5.c Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,
 H10B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B),
 C15(H15A,H15B), C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B),
  C26(H26A,H26B), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B), C32(H32A,
 H32B), C33(H33A,H33B), C35(H35A,H35B), C37(H37A,H37B), C39(H39A,H39B),
 C40(H40A,H40B), C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B), C44(H44A,H44B),
  C45(H45A,H45B), C47(H47A,H47B), C50(H50A,H50B), C52(H52A,H52B), C53(H53A,
 H53B), C55(H55A,H55B), C56(H56A,H56B), C63(H63A,H63B), C69(H69A,H69B),
 C73(H73A,H73B), C74(H73C,H73D), C75(H75A,H75B), C81(H81A,H81B), C73A(H73E,
 H73F), C74A(H74A,H74B), C81A(H81C,H81D), C75A(H75C,H75D), C5A(H5AA,H5AB),
 C18A(H18C,H18D)
5.d Aromatic/amide H refined with riding coordinates:
 O10(H10), C3(H3), C25(H25), C36(H36), C48(H48), C51(H51), C54(H54), C59(H59),
 C60(H60), C61(H61), C23(H23), C62(H62), C64(H64), C66(H66), C68(H68), C71(H71),
  C72(H72), C76(H76), C77(H77), C84(H84), C86(H86), C87(H87), C89(H89),
 C90(H90), C1(H1), C87A(H87A), C89A(H89A), C90A(H90A), C1A(H1A), C85A(H85A),
 C78A(H78A), C94A(H94A), C82A(H82A), C71A(H71A), C86A(H86A), C77A(H77A),
 C62A(H62A), C59A(H59A), C60A(H60A), C61A(H61A), C23A(H23A), C85B(H85B),
 C78B(H78B), C94B(H94B), C82B(H82B)
5.e Fitted hexagon refined as free rotating group:
 C58(C59,C60,C22,C61,C23), C87(C88,C89,C90,C91,C1), C87A(C88A,C89A,C90A,C91A,
 C1A), C49A(C85A,C78A,C80A,C94A,C82A), C46A(C71A,C86A,C83A,C77A,C62A),
 C58A(C59A,C60A,C22A,C61A,C23A), C49B(C85B,C78B,C80B,C94B,C82B)
5.f Tetrahedral OH refined with riding coordinates:
 O43(H43), O46(H46), O47A(H47C), O35A(H35C)
5.g Idealised Me refined as rotating group:
 C92(H92A,H92B,H92C), C57(H57A,H57B,H57C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 290 electrons were 
found in a volume of 1105\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
3[CH4O], 5[CH4O] per Asymmetric Unit 
which account for 288 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              71230
_shelx_fab_checksum              10161
_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 1.111
_oxdiff_exptl_absorpt_empirical_full_min 0.924