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_1576882
_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
'C72 H108 In15 N7 O45 S6, C5 H4 O2 S, 5[CH4O], 1[CH4O]'
_chemical_formula_sum            'C83 H136 In15 N7 O53 S7'
_chemical_formula_weight         4026.70
_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   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2pw2rf
_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                75.8810(10)
_cell_angle_beta                 87.5360(10)
_cell_angle_gamma                69.6850(10)
_cell_formula_units_Z            2
_cell_length_a                   15.5466(2)
_cell_length_b                   17.0764(2)
_cell_length_c                   24.2512(2)
_cell_measurement_reflns_used    62458
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.3780
_cell_measurement_theta_min      3.0080
_cell_volume                     5849.19(12)
_computing_cell_refinement       'CrysAlisPro 1.171.43.127a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.127a 64-bit (release 16-06-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.127a (Rigaku OD, 2024)'
_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(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.923
_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    113.00 175.00   0.50    0.07    --  109.44  57.00  90.00  124
  2  \w     85.00 175.00   0.50    0.07    --  109.44  78.00 -16.00  180
  3  \w     96.00 129.00   0.50    0.07    --  109.44  57.00 -60.00   66
  4  \w    140.00 173.00   0.50    0.07    --  109.44  57.00 -60.00   66
  5  \w     22.00 119.00   0.50    0.05    --   46.37  78.00 -16.00  194
  6  \w     32.00 120.00   0.50    0.05    --   46.37  38.00  90.00  176
  7  \w     40.00 106.00   0.50    0.07    --  109.44 -99.00  60.00  132
  8  \w     56.00 102.00   0.50    0.07    --  109.44 -77.00  60.00   92
  9  \w     72.00 106.00   0.50    0.07    --  109.44 -99.00  30.00   68
 10  \w     64.00  90.00   0.50    0.07    --  109.44 -99.00   0.00   52
 11  \w     37.00  62.00   0.50    0.07    --  109.44 -57.00  90.00   50
 12  \w     37.00  62.00   0.50    0.07    --  109.44 -57.00   0.00   50
 13  \w     37.00  62.00   0.50    0.07    --  109.44 -57.00-120.00   50
 14  \w     37.00 107.00   0.50    0.07    --  109.44 -78.00-141.00  140
 15  \w    -25.00  71.00   0.50    0.05    --   46.37 -78.00-141.00  192
 16  \w    -29.00  23.00   0.50    0.05    --   46.37 -19.00-120.00  104
 17  \w    -29.00  23.00   0.50    0.05    --   46.37 -19.00 -90.00  104
 18  \w    -70.00  27.00   0.50    0.05    --  -46.37  78.00 -16.00  194
 19  \w    -69.00 -24.00   0.50    0.07    --  -97.00  57.00-150.00   90
 20  \w    -29.00  29.00   0.50    0.05    --  -46.37  19.00 -90.00  116
 21  \w   -108.00 -24.00   0.50    0.07    --  -97.00  77.00 -90.00  168
 22  \w   -113.00 -24.00   0.50    0.07    --  -97.00  78.00 -16.00  178
 23  \w    -69.00 -25.00   0.50    0.07    --  -97.00  57.00 150.00   88
 24  \w   -112.00 -86.00   0.50    0.07    --  -97.00 125.00  30.00   52
 25  \w   -112.00 -27.00   0.50    0.07    --  -97.00 125.00 120.00  170
 26  \w   -127.00 -33.00   0.50    0.07    --  -97.00 146.00 115.79  188
 27  \w   -130.00 -35.00   0.50    0.07    --  -97.00 151.00 -56.34  190
 28  \w   -112.00 -27.00   0.50    0.07    --  -97.00 125.00 -60.00  170
 29  \w   -126.00 -33.00   0.50    0.07    --  -97.00 144.00-140.85  186
 30  \w   -112.00 -27.00   0.50    0.07    --  -97.00 125.00-150.00  170
 31  \w   -112.00 -27.00   0.50    0.07    --  -97.00 125.00-180.00  170
 32  \w   -170.00 -82.00   0.50    0.07    --  -97.00 -44.00  65.42  176
 33  \w   -170.00 -76.00   0.50    0.07    --  -97.00 -69.00 101.88  188
 34  \w   -170.00 -76.00   0.50    0.07    --  -97.00 -69.00 101.88  188
 35  \w   -170.00 -78.00   0.50    0.07    --  -97.00 -66.00 -61.25  184
 36  \w   -119.00 -22.00   0.50    0.05    --  -46.37 -78.00-141.00  194
 37  \w   -170.00 -73.00   0.50    0.07    --  -97.00 -78.00-141.00  194
 38  \w   -168.00 -91.00   0.50    0.07    --  -97.00 -99.00 -90.00  154
 39  \w   -167.00 -82.00   0.50    0.07    --  -97.00-125.00  30.00  170
;
_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      0.0171442000
_diffrn_orient_matrix_UB_12      -0.0333197000
_diffrn_orient_matrix_UB_13      -0.0545054000
_diffrn_orient_matrix_UB_21      -0.0880581000
_diffrn_orient_matrix_UB_22      -0.0227550000
_diffrn_orient_matrix_UB_23      0.0083595000
_diffrn_orient_matrix_UB_31      -0.0560415000
_diffrn_orient_matrix_UB_32      0.0906336000
_diffrn_orient_matrix_UB_33      -0.0354837000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0599
_diffrn_reflns_av_unetI/netI     0.0489
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.923
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            106289
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.923
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.981
_diffrn_reflns_theta_min         3.003
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    25.120
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55200
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.127a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    2.286
_exptl_crystal_description       block
_exptl_crystal_F_000             3908
_exptl_crystal_size_max          0.02
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.161
_refine_diff_density_min         -1.290
_refine_diff_density_rms         0.159
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1585
_refine_ls_number_reflns         23090
_refine_ls_number_restraints     642
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0463
_refine_ls_R_factor_gt           0.0383
_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^)+(0.0505P)^2^+12.0259P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0967
_refine_ls_wR_factor_ref         0.1023
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19461
_reflns_number_total             23090
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc00913a2.cif
_cod_data_source_block           InOC-40_auto
_cod_depositor_comments
'Adding full bibliography for 1576882--1576886.cif.'
_cod_database_code               1576882
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N In S'
_shelx_estimated_absorpt_t_max   0.787
_shelx_estimated_absorpt_t_min   0.633
_diffrn_oxdiff_ac3_digest_hkl    4110f05515b3ff4139dbc7a829aa7226318b19
_diffrn_oxdiff_digest_hkl
;
43091bd006102bbee75b2a26b7c77a483cd62b
;
_olex2_refinement_description
;
1. Restrained distances
 O61A-C62
 1.3 with sigma of 0.02
 C57-O45A
 1.3 with sigma of 0.02
 C74A-C73 = C78A-C73 = C74A-C36A
 1.4 with sigma of 0.02
 S3-C80 = S3A-C80A = S5-C1 = S5A-C1A = S4A-C23A = S4-C23 = S2-C2 = S2A-C2A =
 S7-C3 = S7A-C3A = S6A-C36A = S6-C36 = S1A-C4A = S1-C4 = S1-C55 = S1A-C53 = S3A-
 C68A = S3-C68 = S2A-C30 = S2-C29 = S7-C66 = S7A-C76 = S6A-C78A = S6-C78 = S4-
 C42 = S4A-C21 = S5A-C46 = S5-C59
 1.73 with sigma of 0.01
 S5-C59 = S5A-C46
 1.73 with sigma of 0.01
 C74A-C73 = C74A-C36A
 1.4 with sigma of 0.02
 C79A-C68A
 2.45 with sigma of 0.02
 C74A-C78A
 2.23 with sigma of 0.02
 C66-C3A
 1.4 with sigma of 0.02
 C76-C3
 1.4 with sigma of 0.02
 C76-C71 = C71-C66
 1.4 with sigma of 0.02
 C78-C73 = C74-C73 = C74-C36
 1.4 with sigma of 0.02
 C80A-C79A = C79A-C54 = C68A-C54
 1.4 with sigma of 0.02
 C36A-C78A
 2.4 with sigma of 0.02
 S2-C29 = S2A-C30
 1.73 with sigma of 0.01
 O8A-C63
 1.45 with sigma of 0.02
 In14-O8A
 2.35 with sigma of 0.02
 S5A-C46 \\sim S5-C59
 with sigma of 0.02
 S5A-C1A \\sim S5-C1
 with sigma of 0.02
 C46-C1 \\sim C59-C1A
 with sigma of 0.02
 S1A-C53 \\sim S1-C55
 with sigma of 0.02
 S1-C4 \\sim S1A-C4A
 with sigma of 0.02
 S4A-C21 \\sim S4-C42
 with sigma of 0.02
 S4-C23 \\sim S4A-C23A
 with sigma of 0.02
 C53-C4 \\sim C55-C4A
 with sigma of 0.02
 S3A-C80A \\sim S3-C80
 with sigma of 0.02
 C23-C21 \\sim C42-C23A
 with sigma of 0.02
 C72A-C51 \\sim C72-C51
 with sigma of 0.02
 O12-C72A \\sim O12-C72
 with sigma of 0.02
2. Restrained planarity
 C74A, C36A, S6A, C78A, C73
 with sigma of 0.1
 C3, C76, C71, C66, S7
 with sigma of 0.1
 C54, S3A, C68A, C79A, C80A
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
S6 \\sim C36 \\sim C74 \\sim C78 \\sim S6A \\sim C36A \\sim C74A \\sim C78A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O61A \\sim O61 \\sim C62: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C57 \\sim O45 \\sim O45A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
S3 \\sim C68 \\sim C79 \\sim C80 \\sim S3A \\sim C68A \\sim C79A \\sim C80A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C1 \\sim S5 \\sim C46 \\sim C59 \\sim C1A \\sim S5A: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C3 \\sim S7 \\sim C66 \\sim C76 \\sim C3A \\sim S7A: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
S4 \\sim C42 \\sim C23 \\sim S4A \\sim C23A \\sim C21: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
S1 \\sim C4 \\sim C53 \\sim C55 \\sim S1A \\sim C4A: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
S2 \\sim C2 \\sim C29 \\sim C30 \\sim S2A \\sim C2A: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C72A \\sim C72: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
In14 \\sim O8 \\sim O8A \\sim C63: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(S6A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C78) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(H53A)=Sof(H55A)=Sof(S1A)=Sof(C4A)=Sof(H4A)=1-FVAR(1)
 Sof(S1)=Sof(C4)=Sof(H4)=Sof(H53)=Sof(H55)=FVAR(1)
 Sof(H46A)=Sof(H59A)=Sof(C1A)=Sof(H1A)=Sof(S5A)=1-FVAR(2)
 Sof(C1)=Sof(H1)=Sof(S5)=Sof(H46)=Sof(H59)=FVAR(2)
 Sof(H21A)=Sof(H42A)=Sof(S4A)=Sof(C23A)=Sof(H23A)=1-FVAR(3)
 Sof(S4)=Sof(H21)=Sof(H42)=Sof(C23)=Sof(H23)=FVAR(3)
 Sof(H66A)=Sof(H76A)=Sof(C3A)=Sof(H3A)=Sof(S7A)=1-FVAR(4)
 Sof(C3)=Sof(H3)=Sof(S7)=Sof(H66)=Sof(H76)=FVAR(4)
 Sof(H29A)=Sof(H30A)=Sof(S2A)=Sof(C2A)=Sof(H2A)=1-FVAR(5)
 Sof(S2)=Sof(C2)=Sof(H2)=Sof(H29)=Sof(H30)=FVAR(5)
 Sof(S6A)=Sof(C36A)=Sof(H36A)=Sof(C74A)=Sof(H74A)=Sof(C78A)=Sof(H78A)=1-FVAR(6)
 Sof(S6)=Sof(C36)=Sof(H36)=Sof(C74)=Sof(H74)=Sof(C78)=Sof(H78)=FVAR(6)
 Sof(S3A)=Sof(C68A)=Sof(H68A)=Sof(C79A)=Sof(H79A)=Sof(C80A)=Sof(H80A)=1-FVAR(7)
 Sof(S3)=Sof(C68)=Sof(H68)=Sof(C79)=Sof(H79)=Sof(C80)=Sof(H80)=FVAR(7)
 Sof(H51C)=Sof(H51D)=Sof(C72A)=Sof(H72C)=Sof(H72D)=1-FVAR(8)
 Sof(H51A)=Sof(H51B)=Sof(C72)=Sof(H72A)=Sof(H72B)=FVAR(8)
 Sof(O45A)=Sof(H45C)=1-FVAR(9)
 Sof(O45)=Sof(H45)=FVAR(9)
 Sof(H63C)=Sof(H63D)=Sof(O8A)=1-FVAR(10)
 Sof(O8)=Sof(H63A)=Sof(H63B)=FVAR(10)
 Fixed Sof: O61(0.75) H61(0.75) O61A(0.25) H61A(0.25)
 Fixed X: C74A(0.696609)
5.a Ternary CH refined with riding coordinates:
 O13(H13), O19(H19), O22(H22)
5.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B),
 C13(H13A,H13B), C15(H15A,H15B), C16(H16A,H16B), C18(H18A,H18B), C19(H19A,H19B),
  C20(H20A,H20B), C22(H22A,H22B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,
 H26B), C27(H27A,H27B), C31(H31A,H31B), C33(H33A,H33B), C34(H34A,H34B),
 C35(H35A,H35B), C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B),
  C43(H43A,H43B), C44(H44A,H44B), C45(H45A,H45B), C47(H47A,H47B), C49(H49A,
 H49B), C50(H50A,H50B), C51(H51A,H51B), C51(H51C,H51D), C56(H56A,H56B),
 C58(H58A,H58B), C60(H60A,H60B), C63(H63C,H63D), C63(H63A,H63B), C64(H64A,H64B),
  C65(H65A,H65B), C69(H69A,H69B), C70(H70A,H70B), C72(H72A,H72B), C75(H75A,
 H75B), C77(H77A,H77B), C72A(H72C,H72D)
5.c Aromatic/amide H refined with riding coordinates:
 O24(H24), C1(H1), C2(H2), C3(H3), C4(H4), C21(H21), C21(H21A), C29(H29),
 C29(H29A), C30(H30), C30(H30A), C36(H36), C42(H42A), C42(H42), C46(H46),
 C46(H46A), C53(H53A), C53(H53), C55(H55A), C55(H55), C59(H59), C59(H59A),
 C66(H66A), C66(H66), C68(H68), C74(H74), C76(H76), C76(H76A), C78(H78),
 C79(H79), C80(H80), C23(H23), C4A(H4A), C1A(H1A), C23A(H23A), C3A(H3A),
 C2A(H2A), C36A(H36A), C74A(H74A), C78A(H78A), C68A(H68A), C79A(H79A),
 C80A(H80A)
5.d Tetrahedral OH refined with riding coordinates:
 O43(H43), O45(H45), O61(H61), O61A(H61A), O45A(H45C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 207 electrons were 
found in a volume of 749\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
5[CH4O], 1[CH4O] per Asymmetric Unit 
which account for 216 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              84317
_shelx_fab_checksum              30577
_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 1.995
_oxdiff_exptl_absorpt_empirical_full_min 0.531