Macrocyclic Geminal Diols: Synthesis, Structures, Stability and Photophysical Properties
Zou, Bo; Chen, Xiaolin; Liu, Haoran; Wen, Sijie; Huang, Jieqing; Wei, Hengshan; Huang, Jinqing; Gu, Yu-Cheng; Xu, Bingjia; Fan, Jun; Jiang, Hua-Wei; Chemical Science  (2025) –; doi:10.1039/D5SC08216A

data_1576263
_publ_section_title
;
 Macrocyclic Geminal Diols: Synthesis, Structures, Stability and
 Photophysical Properties
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D5SC08216A
_journal_year                    2025
_chemical_formula_moiety         '2(C2 H6 O S), C26 H20 O4'
_chemical_formula_sum            'C30 H32 O6 S2'
_chemical_formula_weight         552.67
_chemical_name_common            2diols-[1,1][2]PCP
_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_creation_date             2022-08-11
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-08-11 deposited with the CCDC.	2025-11-12 downloaded from the CCDC.
;
_cell_angle_alpha                92.790(3)
_cell_angle_beta                 91.558(3)
_cell_angle_gamma                93.496(2)
_cell_formula_units_Z            2
_cell_length_a                   8.8569(3)
_cell_length_b                   9.1083(3)
_cell_length_c                   16.7941(6)
_cell_measurement_reflns_used    9826
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      66.8400
_cell_measurement_theta_min      4.8700
_cell_volume                     1350.06(8)
_computing_cell_refinement       'CrysAlisPro 1.171.41.119a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.119a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.119a (Rigaku OD, 2021)'
_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      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 0.966
_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     25.00  64.00   0.50    0.15    --   83.87 -57.00 120.00   78
  2  \w     54.00 101.00   0.50    0.15    --   83.87 -77.00  30.00   94
  3  \w     22.00  59.00   0.50    0.15    --   83.87 -57.00 150.00   74
  4  \w     20.00  46.00   0.50    0.15    --   83.87 -77.00  30.00   52
  5  \w     12.00  44.00   0.50    0.15    --   83.87 -38.00   0.00   64
  6  \w     14.00  42.00   0.50    0.15    --   83.87 -38.00 -30.00   56
  7  \w     82.00 156.00   0.50    0.15    --   83.87  38.00-150.00  148
  8  \w     89.00 151.00   0.50    0.15    --   83.87 107.00-148.00  124
  9  \w     12.00  37.00   0.50    0.15    --   83.87 -38.00 -60.00   50
 10  \w     25.00  62.00   0.50    0.15    --   83.87 -57.00-150.00   74
 11  \w    -48.00 -21.00   0.50    0.15    --  -86.37  77.00  90.00   54
 12  \w    -39.00 -14.00   0.50    0.15    --  -86.37  38.00 150.00   50
 13  \w    -61.00 -15.00   0.50    0.15    --  -86.37  57.00 150.00   92
 14  \w    -88.00 -58.00   0.50    0.15    --  -86.37  77.00  90.00   60
 15  \w    -41.00 -16.00   0.50    0.15    --  -86.37  38.00  30.00   50
 16  \w    -41.00 -15.00   0.50    0.15    --  -86.37  38.00 -30.00   52
 17  \w    -41.00 -16.00   0.50    0.15    --  -86.37  38.00-120.00   50
 18  \w   -118.00 -76.00   0.50    0.15    --  -86.37 -38.00 -60.00   84
 19  \w   -154.00-128.00   0.50    0.15    --  -86.37 -38.00 -60.00   52
 20  \w   -152.00 -72.00   0.50    0.15    --  -86.37 -57.00-180.00  160
 21  \w    -73.00 -34.00   0.50    0.05    --   -1.25 -57.00 -60.00   78
 22  \w    -27.00  11.00   0.50    0.05    --   -1.25 -57.00 -60.00   76
 23  \w   -103.00 -66.00   0.50    0.15    --  -86.37 107.00-148.00   74
 24  \w    -73.00 -40.00   0.50    0.05    --   -1.25 -57.00 120.00   66
 25  \w   -111.00 -85.00   0.50    0.15    --  -86.37-107.00 113.00   52
 26  \w    -15.00  24.00   0.50    0.05    --   -1.25 -99.00  30.00   78
 27  \w    -16.00  17.00   0.50    0.05    --   -1.25 -99.00-120.00   66
 28  \w    -14.00  30.00   0.50    0.05    --   -1.25 -99.00-180.00   88
 29  \w     16.00 101.00   0.50    0.15    --   83.87 -99.00 -60.00  170
 30  \w     62.00 110.00   0.50    0.15    --   83.87-125.00 -90.00   96
 31  \w     45.00  98.00   0.50    0.15    --   83.87-125.00 -60.00  106
 32  \w     20.00 106.00   0.50    0.15    --   83.87 -99.00   0.00  172
 33  \w     68.00 104.00   0.50    0.15    --   83.87-107.00 113.00   72
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0693471000
_diffrn_orient_matrix_UB_12      0.0233886000
_diffrn_orient_matrix_UB_13      0.0851313000
_diffrn_orient_matrix_UB_21      0.0995089000
_diffrn_orient_matrix_UB_22      0.1324393000
_diffrn_orient_matrix_UB_23      -0.0264679000
_diffrn_orient_matrix_UB_31      -0.1252386000
_diffrn_orient_matrix_UB_32      0.1034441000
_diffrn_orient_matrix_UB_33      0.0222406000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0258
_diffrn_reflns_av_unetI/netI     0.0282
_diffrn_reflns_Laue_measured_fraction_full 0.966
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            13412
_diffrn_reflns_point_group_measured_fraction_full 0.966
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        66.875
_diffrn_reflns_theta_max         66.875
_diffrn_reflns_theta_min         2.635
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.145
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.95428
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.119a (Rigaku Oxford Diffraction, 2021)
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    1.360
_exptl_crystal_description       block
_exptl_crystal_F_000             584
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.800
_refine_diff_density_min         -0.587
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     351
_refine_ls_number_reflns         4654
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0464
_refine_ls_R_factor_gt           0.0416
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0556P)^2^+1.1042P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1110
_refine_ls_wR_factor_ref         0.1147
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4133
_reflns_number_total             4654
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08216a2.cif
_cod_data_source_block           exp_1849_auto
_cod_database_code               1576263
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C O H'
_chemical_oxdiff_usercomment     2208016524
_shelx_estimated_absorpt_t_max   0.847
_shelx_estimated_absorpt_t_min   0.783
_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
2.a Aromatic/amide H refined with riding coordinates:
 C25(H25), C4(H4A), C3(H3A), C24(H24), C22(H22), C23(H23), C19(H19), C9(H9),
 C17(H17), C10(H10), C16(H16), C5(H5), C6(H6), C18(H18), C12(H12), C11(H11)
2.b Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C)
2.c Idealised tetrahedral OH refined as rotating group:
 O2(H2), O1(H1), O3(H3), O4(H4)
;
_shelx_res_checksum              15026
_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 1.109
_oxdiff_exptl_absorpt_empirical_full_min 0.908