Multi-hydrophilic groups synergistic assembly ionic HOFs with multiple-water clusters and superprotonic single-crystal conductivity.
Li, Shu-Hui; Cao, Li-Hui; Zhang, Wenmin; Bai, Xiang-Tian; Chen, Xu-Yong; Chemical communications (Cambridge, England) 61 (2025) 4034–4037; doi:10.1039/d4cc06654e

data_7134248
_publ_section_title
;
 Multi-hydrophilic groups synergistic assembly ionic HOFs with
 multiple-water clusters and superprotonic single-crystal conductivity.
;
_journal_issue                   20
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              4034
_journal_page_last               4037
_journal_paper_doi               10.1039/d4cc06654e
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety
'4(C10 H6 O8 S2), C10 H5 O8 S2, C10 H8 O9 S2, 62(H2 O), H O, 4(C21 H24 N7)'
_chemical_formula_sum            'C144 H258 N28 O112 S12'
_chemical_formula_weight         4558.49
_chemical_name_systematic        iHOF
_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
_audit_creation_date             2024-10-18
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-11-29 deposited with the CCDC.	2025-02-09 downloaded from the CCDC.
;
_cell_angle_alpha                82.4312(11)
_cell_angle_beta                 76.3819(11)
_cell_angle_gamma                78.0115(11)
_cell_formula_units_Z            2
_cell_length_a                   15.89692(19)
_cell_length_b                   24.3336(3)
_cell_length_c                   31.3004(4)
_cell_measurement_reflns_used    45626
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      75.7120
_cell_measurement_theta_min      2.2350
_cell_volume                     11467.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.89a (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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_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 0.972
_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    -58.00 -23.00   0.50    0.32    --  -39.45 106.00 -58.00   70
  2  \w      5.00  84.00   0.50    0.32    --   39.45-106.00-157.00  158
  3  \w    -53.00 -28.00   0.50    0.32    --  -52.00 106.00 -58.00   50
  4  \w     81.00 107.00   0.50    1.28    --  111.82-106.00-157.00   52
  5  \w     86.00 145.00   0.50    1.28    --  111.82 106.00 -58.00  118
  6  \w   -106.00 -59.00   0.50    0.32    --  -39.45 -57.00 -90.00   94
  7  \w    -54.00 -22.00   0.50    0.32    --  -39.45 -57.00 -90.00   64
  8  \w    -28.00  42.00   0.50    0.32    --  -39.45  19.00  30.00  140
  9  \w     62.00 121.00   0.50    0.32    --   39.45 179.00-120.00  118
 10  \w     73.00 122.00   0.50    0.32    --   39.45 179.00 120.00   98
 11  \w     49.00 121.00   0.50    0.32    --   39.45 179.00   0.00  144
 12  \w     61.00  97.00   0.50    0.32    --   39.45 179.00-180.00   72
 13  \w   -129.00 -88.00   0.50    0.32    --  -52.00 -94.00  90.00   82
 14  \w    -30.00  -4.00   0.50    0.32    --  -52.00  30.00 -90.00   52
 15  \w    -26.00  31.00   0.50    0.32    --  -52.00  15.00-180.00  114
 16  \w      3.00  29.00   0.50    0.32    --  -52.00  30.00 -90.00   52
 17  \w   -132.00 -93.00   0.50    0.32    --  -52.00 -94.00 -30.00   78
 18  \w    -38.00  30.00   0.50    0.32    --  -52.00  30.00 120.00  136
 19  \w   -132.00 -87.00   0.50    0.32    --  -52.00 -94.00-120.00   90
 20  \w     33.00  70.00   0.50    1.28    --  111.82 -94.00-150.00   74
 21  \w     82.00 108.00   0.50    1.28    --  111.82-111.00-180.00   52
 22  \w     38.00  63.00   0.50    1.28    --  111.82 -61.00 -30.00   50
 23  \w     83.00 108.00   0.50    1.28    --  111.82-111.00  90.00   50
 24  \w     39.00  68.00   0.50    1.28    --  111.82 -77.00  30.00   58
 25  \w     81.00 135.00   0.50    1.28    --  111.82  77.00 -90.00  108
 26  \w     42.00  68.00   0.50    1.28    --  111.82-111.00  90.00   52
 27  \w     38.00 103.00   0.50    1.28    --  111.82 -77.00 120.00  130
 28  \w     78.00 103.00   0.50    1.28    --  111.82 -77.00  30.00   50
 29  \w     44.00 107.00   0.50    1.28    --  111.82-111.00  30.00  126
 30  \w     84.00 175.00   0.50    1.28    --  111.82  61.00-180.00  182
 31  \w     37.00  63.00   0.50    1.28    --  111.82-111.00-180.00   52
 32  \w     41.00  70.00   0.50    1.28    --  111.82 -94.00-120.00   58
 33  \w     33.00 100.00   0.50    1.28    --  111.82 -94.00  30.00  134
 34  \w     53.00  80.00   0.50    1.28    --  111.82-111.00 -90.00   54
 35  \w     83.00 108.00   0.50    1.28    --  111.82-111.00 -90.00   50
 36  \w    119.00 166.00   0.50    1.28    --  111.82   0.00  30.00   94
 37  \w     33.00  85.00   0.50    1.28    --  111.82 -94.00 -90.00  104
 38  \w    106.00 173.00   0.50    1.28    --  111.82  45.00-150.00  134
 39  \w     53.00 110.00   0.50    1.28    --  111.82   0.00  30.00  114
 40  \w     38.00  68.00   0.50    1.28    --  111.82 -61.00 -60.00   60
 41  \w     80.00 106.00   0.50    1.28    --  111.82  30.00 150.00   52
 42  \w     36.00 108.00   0.50    1.28    --  111.82-111.00 150.00  144
 43  \w     97.00 163.00   0.50    1.28    --  111.82  61.00  60.00  132
 44  \w    109.00 171.00   0.50    1.28    --  111.82  30.00 150.00  124
 45  \w     82.00 108.00   0.50    1.28    --  111.82-111.00 120.00   52
 46  \w     36.00  61.00   0.50    1.28    --  111.82-111.00 120.00   50
 47  \w     77.00 103.00   0.50    1.28    --  111.82-111.00   0.00   52
 48  \w     33.00  78.00   0.50    1.28    --  111.82 -94.00 -30.00   90
 49  \w     77.00 102.00   0.50    1.28    --  111.82 -94.00-120.00   50
 50  \w     75.00 162.00   0.50    1.28    --  111.82  30.00 120.00  174
 51  \w     39.00  64.00   0.50    1.28    --  111.82 -61.00 -90.00   50
 52  \w     40.00  66.00   0.50    1.28    --  111.82 -61.00-120.00   52
 53  \w     38.00  63.00   0.50    1.28    --  111.82 -61.00   0.00   50
 54  \w     71.00 100.00   0.50    1.28    --  111.82 -94.00-180.00   58
 55  \w     72.00 108.00   0.50    1.28    --  111.82-111.00 -30.00   72
 56  \w     83.00 154.00   0.50    1.28    --  111.82  45.00-120.00  142
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0142781000
_diffrn_orient_matrix_UB_12      0.0544623000
_diffrn_orient_matrix_UB_13      0.0151369000
_diffrn_orient_matrix_UB_21      -0.0515445000
_diffrn_orient_matrix_UB_22      -0.0150682000
_diffrn_orient_matrix_UB_23      0.0468465000
_diffrn_orient_matrix_UB_31      0.0861861000
_diffrn_orient_matrix_UB_32      -0.0320583000
_diffrn_orient_matrix_UB_33      0.0126701000
_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  0.0657
_diffrn_reflns_av_unetI/netI     0.0596
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            137872
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.957
_diffrn_reflns_theta_min         2.264
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.947
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72436
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.89a (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    1.320
_exptl_crystal_description       'rect. Prism'
_exptl_crystal_F_000             4812
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.44
_refine_diff_density_max         0.096
_refine_diff_density_min         -0.033
_refine_diff_density_rms         0.008
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   2.320
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2882
_refine_ls_number_reflns         46475
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      57.547
_refine_ls_R_factor_all          0.2090
_refine_ls_R_factor_gt           0.1938
_refine_ls_shift/su_max          13.207
_refine_ls_shift/su_mean         0.071
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.5088
_refine_ls_wR_factor_ref         0.5198
_reflns_Friedel_coverage         0.000
_reflns_number_gt                38728
_reflns_number_total             46475
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc06654e2.cif
_cod_data_source_block           7325-clh-2b-1-100k_autored
_cod_depositor_comments
'Adding full bibliography for 7134247--7134248.cif.'
_cod_database_code               7134248
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.481
_shelx_estimated_absorpt_t_min   0.305
_olex2_refinement_description
;
1. Restrained distances
 H59B-H5B_$2
 2.1 with sigma of 0.01
 H73A-H10L
 2.1 with sigma of 0.01
 H87A-H10O_$6
 2.1 with sigma of 0.01
 H29A-H11D_$2
 2.15 with sigma of 0.01
 H9B-H10I_$1
 2.15 with sigma of 0.01
 H27B-H55A_$3
 2.15 with sigma of 0.01
 H87B-H10O_$6
 2.15 with sigma of 0.01
 H29B-O29
 2.15 with sigma of 0.01
 H23D-O23
 2.15 with sigma of 0.01
 H59B-H57A_$1
 2.15 with sigma of 0.01
 H19A-H3D_$4
 2.15 with sigma of 0.01
 H57B-H8C_$5
 2.15 with sigma of 0.01
 H21A-H85A
 2.15 with sigma of 0.01
 H10C-H11N
 2.15 with sigma of 0.01
 H59A-H5B_$2
 2.15 with sigma of 0.01
2. Others
 Fixed Sof: O5(0.5) H5C(0.5) H5D(0.5) O41(0.5) H41A(0.5) H41B(0.5)
3.a Free rotating group:
 O2(H2A,H2B), O3(H3C,H3D), O5(H5C,H5D), O9(H9C,H9D), O11(H11C,H11D), O13(H13C,
 H13D), O15(H15C,H15D), O17(H17C,H17D), O19(H19C,H19D), O21(H21A,H21B),
 O23(H23C,H23D), O25(H25C,H25D), O27(H27C,H27D), O29(H29A,H29B), O31(H31A,H31B),
  O33(H33A,H33B), O35(H35A,H35B), O37(H37A,H37B), O39(H39A,H39B), O41(H41A,
 H41B), O43(H43A,H43B), O45(H45A,H45B), O47(H47A,H47B), O49(H49A,H49B),
 O51(H51A,H51B), O53(H53A,H53B), O55(H55A,H55B), O57(H57A,H57B), O59(H59A,H59B),
  O61(H61A,H61B), O63(H63A,H63B), O65(H65A,H65B), O67(H67A,H67B), O69(H69A,
 H69B), O71(H71A,H71B), O73(H73A,H73B), O75(H75A,H75B), O77(H77A,H77B),
 O81(H81A,H81B), O83(H83A,H83B), O85(H85A,H85B), O87(H87A,H87B), O89(H89A,H89B),
  O91(H91A,H91B), O93(H93A,H93B), O95(H95A,H95B), O97(H97A,H97B), O98(H98A,
 H98B), O99(H99A,H99B), O100(H10C,H10D), O101(H10U), O102(H10E,H10F), O103(H10G,
 H10H), O104(H10I,H10J), O105(H10K,H10L), O106(H10M,H10N), O107(H10O,H10P),
 O108(H10Q,H10R), O109(H10S,H10T), O110(H11E,H11F), O111(H11G,H11H), O112(H11I,
 H11J), O113(H11K,H11L), O114(H11M,H11N), O115(H11O,H11P)
3.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C8(H8C), C10(H10), C14(H14C), C41(H41), C43(H43), C89(H89), C91(H91),
 C106(H106), C110(H110), C114(H114), C120(H120), C47(H47), C93(H93), C99(H99),
 C101(H101), C22(H22C), C26(H26), C30(H30), C34(H34), C44(H44), C52(H52),
 C54(H54), C58(H58), C66(H66), C68(H68), C70(H70), C72(H72), C74(H74), C76(H76),
  C78(H78), C80(H80), C82(H82), C88(H88), C94(H94), C98(H98), C15(H15),
 C27(H27), C53(H53), C55(H55), C59(H59), C103(H103), C107(H107), C111(H111),
 C113(H113), C115(H115), C117(H117), C119(H119), C2(H2), C31(H31), C33(H33),
 C67(H67), C123(H123), C125(H125), C129(H129), C133(H133), C135(H135),
 C137(H137), C139(H139), C141(H141), C9(H9), C39(H39), C75(H75), C77(H77),
 C79(H79), C124(H124), C128(H128), C130(H130), C132(H132), C136(H136),
 C142(H142), C144(H144)
3.c X=CH2 refined with riding coordinates:
 N4(H4A,H4B), N6(H6A,H6B), N8(H8A,H8B), N10(H10A,H10B), N12(H12A,H12B),
 N14(H14A,H14B), N5(H5A,H5B), N7(H7A,H7B), N9(H9A,H9B), N15(H15A,H15B),
 N17(H17A,H17B), N19(H19A,H19B), N3(H3A,H3B), N11(H11A,H11B), N13(H13A,H13B),
 N23(H23A,H23B), N25(H25A,H25B), N27(H27A,H27B), N18(H18A,H18B), N20(H20A,H20B),
  N22(H22A,H22B), N24(H24A,H24B), N26(H26A,H26B), N28(H28A,H28B)
3.d Idealised tetrahedral OH refined as rotating group:
 O8(H8), O14(H14), O66(H66A), O70(H70A), O50(H50), O82(H82A), O92(H92),
 O18(H18), O22(H22), O40(H40), O48(H48)
;
_shelx_res_checksum              65763
_shelx_hkl_checksum              89939
_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 1.435
_oxdiff_exptl_absorpt_empirical_full_min 0.309