Solvent-induced structural transformation in luminescence-enhanced polymorphic ionic HOFs.
Yang, Yi; Zhou, Bin; Dai, Yu-Ying; Cao, Li-Hui; Chemical communications (Cambridge, England) 62 (2026) 5691–5695; doi:10.1039/d6cc00927a

data_7135464
_publ_section_title
;
 Solvent-induced structural transformation in luminescence-enhanced
 polymorphic ionic HOFs.
;
_journal_issue                   20
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              5691
_journal_page_last               5695
_journal_paper_doi               10.1039/d6cc00927a
_journal_volume                  62
_journal_year                    2026
_chemical_formula_moiety
'C34 H36 N10, C26 H16 O12 S4, C4 H9 N O, 2(C H4 O), H2 O'
_chemical_formula_sum            'C66 H71 N11 O16 S4'
_chemical_formula_weight         1402.57
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2026-02-03
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2026-02-04 deposited with the CCDC.	2026-02-20 downloaded from the CCDC.
;
_cell_angle_alpha                72.997(2)
_cell_angle_beta                 71.086(2)
_cell_angle_gamma                88.933(2)
_cell_formula_units_Z            2
_cell_length_a                   13.6618(3)
_cell_length_b                   14.7540(3)
_cell_length_c                   19.1796(5)
_cell_measurement_reflns_used    18236
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.6440
_cell_measurement_theta_min      3.1250
_cell_volume                     3484.94(15)
_computing_cell_refinement       'CrysAlisPro 1.171.43.106a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.106a 64-bit (release 01-02-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.106a (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 2025/1 (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 0.966
_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    -29.00  43.00   0.50    0.08    --  -39.20  19.00 150.00  144
  2  \w    -36.00  30.00   0.50    0.08    --  -52.00  30.00  30.00  132
  3  \w    -25.00  28.00   0.50    0.08    --  -52.00  15.00 -60.00  106
  4  \w     21.00  89.00   0.50    0.08    --   39.20-113.00 -43.00  136
  5  \w     36.00  63.00   0.50    0.30    --  111.82-111.00-180.00   54
  6  \w     83.00 108.00   0.50    0.30    --  111.82-111.00-180.00   50
  7  \w     63.00 108.00   0.50    0.30    --  111.82-113.00 -43.00   90
  8  \w     74.00  99.00   0.50    0.30    --  111.82-111.00-120.00   50
  9  \w     81.00 108.00   0.50    0.30    --  111.82-111.00  30.00   54
 10  \w     37.00  75.00   0.50    0.30    --  111.82-111.00  30.00   76
 11  \w     36.00 107.00   0.50    0.30    --  111.82-111.00   0.00  142
 12  \w     35.00 107.00   0.50    0.30    --  111.82-111.00 -90.00  144
 13  \w     32.00  61.00   0.50    0.30    --  111.82 -94.00-120.00   58
 14  \w     76.00 105.00   0.50    0.30    --  111.82 -94.00  30.00   58
 15  \w     33.00  92.00   0.50    0.30    --  111.82 -94.00  90.00  118
 16  \w     35.00 102.00   0.50    0.30    --  111.82-111.00 150.00  134
 17  \w     52.00 102.00   0.50    0.30    --  111.82 -94.00 150.00  100
 18  \w     77.00 103.00   0.50    0.30    --  111.82-111.00 120.00   52
 19  \w     36.00  78.00   0.50    0.30    --  111.82 -94.00 -90.00   84
 20  \w     32.00 105.00   0.50    0.30    --  111.82 -94.00-180.00  146
 21  \w     36.00  73.00   0.50    0.30    --  111.82 -94.00  30.00   74
 22  \w     38.00  91.00   0.50    0.30    --  111.82 -77.00  30.00  106
 23  \w     41.00  67.00   0.50    0.30    --  111.82 -77.00  90.00   52
 24  \w     38.00  64.00   0.50    0.30    --  111.82 -77.00 -60.00   52
 25  \w     38.00  63.00   0.50    0.30    --  111.82 -61.00 -90.00   50
 26  \w     38.00  64.00   0.50    0.30    --  111.82 -61.00-180.00   52
 27  \w     39.00  64.00   0.50    0.30    --  111.82 -61.00 -60.00   50
 28  \w     43.00  68.00   0.50    0.30    --  111.82 -61.00 150.00   50
 29  \w    -17.00   9.00   0.50    0.08    --   39.20 -19.00  60.00   52
 30  \w   -114.00 -67.00   0.50    0.08    --  -39.20 -57.00-120.00   94
 31  \w   -120.00 -88.00   0.50    0.08    --  -52.00 -94.00-120.00   64
 32  \w   -122.00 -88.00   0.50    0.08    --  -39.20-179.00 -90.00   68
 33  \w    -73.00 -48.00   0.50    0.08    --  -39.20-179.00 -90.00   50
 34  \w   -126.00 -87.00   0.50    0.08    --  -52.00 -94.00  90.00   78
 35  \w   -132.00 -95.00   0.50    0.08    --  -52.00 -94.00   0.00   74
 36  \w    -43.00 -18.00   0.50    0.08    --  -39.20 -57.00-120.00   50
 37  \w    -97.00 -67.00   0.50    0.08    --  -52.00 111.00 150.00   60
 38  \w    -56.00 -13.00   0.50    0.08    --  -52.00 111.00 150.00   86
 39  \w   -111.00 -70.00   0.50    0.08    --  -39.20 179.00  60.00   82
 40  \w    -77.00 -50.00   0.50    0.08    --  -52.00 113.00  48.00   54
 41  \w    -53.00 -17.00   0.50    0.08    --  -39.20 113.00  48.00   72
 42  \w    121.00 174.00   0.50    0.30    --  111.82  77.00-180.00  106
 43  \w    132.00 163.00   0.50    0.30    --  111.82  61.00-150.00   62
 44  \w     87.00 116.00   0.50    0.30    --  111.82  61.00-150.00   58
 45  \w    110.00 151.00   0.50    0.30    --  111.82  45.00 -90.00   82
 46  \w     91.00 171.00   0.50    0.30    --  111.82  15.00-150.00  160
 47  \w     27.00  70.00   0.50    0.30    --  111.82   0.00   0.00   86
 48  \w     81.00 156.00   0.50    0.30    --  111.82   0.00   0.00  150
 49  \w     75.00 175.00   0.50    0.30    --  111.82  30.00 120.00  200
 50  \w     90.00 174.00   0.50    0.30    --  111.82  45.00 150.00  168
 51  \w     92.00 149.00   0.50    0.30    --  111.82 113.00  48.00  114
 52  \w    130.00 155.00   0.50    0.30    --  111.82 111.00 120.00   50
 53  \w    107.00 141.00   0.50    0.30    --  111.82 111.00 150.00   68
;
_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      0.0182857000
_diffrn_orient_matrix_UB_12      0.0361037000
_diffrn_orient_matrix_UB_13      -0.0875076000
_diffrn_orient_matrix_UB_21      0.0145565000
_diffrn_orient_matrix_UB_22      -0.1021432000
_diffrn_orient_matrix_UB_23      -0.0045821000
_diffrn_orient_matrix_UB_31      -0.1173198000
_diffrn_orient_matrix_UB_32      -0.0164527000
_diffrn_orient_matrix_UB_33      0.0160725000
_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  0.1040
_diffrn_reflns_av_unetI/netI     0.0720
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            38633
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.069
_diffrn_reflns_theta_min         2.555
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.872
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53895
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.106a (Rigaku Oxford Diffraction, 2024)
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    1.337
_exptl_crystal_description       needle
_exptl_crystal_F_000             1472
_exptl_crystal_recrystallization_method
'The crystals were growth by means of evaporation of a mixture of DMA, MeOH and H2O at RT.'
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.989
_refine_diff_density_min         -0.781
_refine_diff_density_rms         0.119
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1027
_refine_ls_number_reflns         14092
_refine_ls_number_restraints     453
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.1131
_refine_ls_R_factor_gt           0.0985
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1596P)^2^+6.6491P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2522
_refine_ls_wR_factor_ref         0.2629
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11779
_reflns_number_total             14092
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cc00927a2.cif
_cod_data_source_block           7101-clh-zb-3
_cod_depositor_comments
'Adding full bibliography for 7135464--7135465.cif.'
_cod_original_cell_volume        3484.95(15)
_cod_database_code               7135464
_shelx_shelxl_version_number     2025/1
_shelx_estimated_absorpt_t_max   0.706
_shelx_estimated_absorpt_t_min   0.454
_exptl_crystal_mounting_method
;
 Crystals were removed from the crystallisation vial and immediately coated
 with PDMS (polydimethylsiloxane/Dimethicone, CAS: 9006-65-9 on a glass slide.
 A suitable single crystal was selected and mounted on a glass fiber using
 vacuum silicone grease as adhesive. The glass fiber with single crystal was
 mounted on copper pin with solid paraffin. Operator: DJ_Tokyo.
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,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
 O15-C62 = O15A-C62A = O15B-C62B = O15C-C62C
 1.43 with sigma of 0.01
 C61-O14 = C61A-O14A
 1.43 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O15 \\sim C62 \\sim O15A \\sim C62A \\sim O15B \\sim C62B \\sim O15C \\sim
C62C: within 3A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
3A
C47 \\sim N7 \\sim N8 \\sim C48 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim
C53 \\sim N7A \\sim N8A \\sim C48A \\sim C49A \\sim C50A \\sim C51A \\sim C52A
\\sim C53A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
O14A \\sim C61A \\sim O14 \\sim C61: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(O15) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(O15A) \\sim Ueq, Uanis(C62A)
\\sim Ueq, Uanis(O15B) \\sim Ueq, Uanis(C62B) \\sim Ueq, Uanis(O15C) \\sim Ueq,
Uanis(C62C) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Same fragment restrains
{C47, N7A, N8A, C48A, C49A, C50A, C51A, C52A, C53A} sigma for 1-2: 0.01, 1-3:
0.01
as in
{C47, N7, N8, C48, C49, C50, C51, C52, C53}
5. Others
 1*[Sof(O15)+Sof(C62)]+1*[Sof(O15A)+Sof(C62A)]+1*[Sof(O15B)+Sof(C62B)]+1*
 [Sof(O15C)+Sof(C62C)]=1 with esd of 0
 Sof(O15)=Sof(C62)=FVAR(1)
 Sof(O15A)=Sof(C62A)=FVAR(2)
 Sof(N7A)=Sof(H7AA)=Sof(H7AB)=Sof(N8A)=Sof(H8AA)=Sof(H8AB)=Sof(C48A)=Sof(H48A)=
 Sof(C49A)=Sof(H49A)=Sof(C50A)=Sof(C51A)=Sof(H51A)=Sof(C52A)=Sof(H52A)=
 Sof(C53A)=1-FVAR(3)
 Sof(N7)=Sof(H7A)=Sof(H7B)=Sof(N8)=Sof(H8A)=Sof(H8B)=Sof(C48)=Sof(H48)=
 Sof(C49)=Sof(H49)=Sof(C50)=Sof(C51)=Sof(H51)=Sof(C52)=Sof(H52)=Sof(C53)=FVAR(3)
 Sof(O14A)=Sof(C61A)=1-FVAR(4)
 Sof(O14)=Sof(H14A)=Sof(C61)=FVAR(4)
 Sof(O15B)=Sof(C62B)=FVAR(5)
 Sof(O15C)=Sof(C62C)=FVAR(6)
6.a Riding coordinates:
 O13(H13A,H13B), O14(H14A)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C10(H10), C11(H11), C13(H13), C14(H14),
 C16(H16), C17(H17), C19(H19), C20(H20), C22(H22), C23(H23), C25(H25), C26(H26),
  C28(H28), C29(H29), C31(H31), C32(H32), C34(H34), C35(H35), C38(H38),
 C39(H39), C41(H41), C42(H42), C45(H45), C46(H46), C48(H48), C49(H49), C51(H51),
  C52(H52), C55(H55), C56(H56), C58(H58), C59(H59), C48A(H48A), C49A(H49A),
 C51A(H51A), C52A(H52A)
6.c X=CH2 refined with riding coordinates:
 N2(H2A,H2B), N3(H3A,H3B), N4(H4A,H4B), N5(H5A,H5B), N9(H9A,H9B), N10(H10A,
 H10B), N7(H7A,H7B), N8(H8A,H8B), N7A(H7AA,H7AB), N8A(H8AA,H8AB)
6.d Idealised Me refined as rotating group:
 C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C)
;
_shelx_res_checksum              58286
_shelx_hkl_checksum              53278
_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 3.585
_oxdiff_exptl_absorpt_empirical_full_min 0.213