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_1576262
_publ_section_title
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 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         '3(C50 H32 O2), 4(C H2 Cl2)'
_chemical_formula_sum            'C154 H104 Cl8 O6'
_chemical_formula_weight         2333.97
_chemical_name_common            2ketones-[1,1][4]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     iterative
_audit_creation_date             2022-09-21
_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                108.872(2)
_cell_angle_beta                 94.103(3)
_cell_angle_gamma                98.397(2)
_cell_formula_units_Z            1
_cell_length_a                   10.2450(7)
_cell_length_b                   14.4312(10)
_cell_length_c                   22.1091(16)
_cell_measurement_reflns_used    9937
_cell_measurement_temperature    298.15
_cell_measurement_theta_max      65.12
_cell_measurement_theta_min      3.84
_cell_volume                     3035.2(4)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      298.15
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.942
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0424
_diffrn_reflns_av_unetI/netI     0.0408
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.942
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            49183
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.812
_diffrn_reflns_theta_min         1.501
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.246
_exptl_absorpt_correction_T_max  0.7526
_exptl_absorpt_correction_T_min  0.6310
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1232 before and 0.0557 after correction.
The Ratio of minimum to maximum transmission is 0.8384.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.277
_exptl_crystal_description       needle
_exptl_crystal_F_000             1212
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.068
_refine_diff_density_min         -0.819
_refine_diff_density_rms         0.060
_refine_ls_extinction_coef       0.025(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     840
_refine_ls_number_reflns         14931
_refine_ls_number_restraints     171
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.0805
_refine_ls_R_factor_gt           0.0657
_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^)+(0.1249P)^2^+1.0920P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1974
_refine_ls_wR_factor_ref         0.2117
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11866
_reflns_number_total             14931
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08216a2.cif
_cod_data_source_block           20220921bl_0m
_cod_database_code               1576262
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.966
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 Cl1-C76 = Cl2-C76
 1.76 with sigma of 0.02
 Cl5-C78 = Cl6-C78
 1.76 with sigma of 0.02
 C77A-Cl4A
 1.76 with sigma of 0.02
 Cl3A-C77A
 1.76 with sigma of 0.02
 C77-Cl4
 1.76 with sigma of 0.02
 Cl4A-C77A \\sim Cl3-C77
 with sigma of 0.02
 Cl4-C77 \\sim Cl3A-C77A
 with sigma of 0.02
 Cl3-Cl4 \\sim Cl4A-Cl3A
 with sigma of 0.02
 Cl1A-C76A \\sim Cl1-C76 \\sim Cl2A-C76A \\sim Cl2-C76
 with sigma of 0.02
3. Rigid bond restraints
 Cl4A, C77A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
Cl3A \\sim Cl4A \\sim C77A \\sim Cl3 \\sim Cl4 \\sim C77: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
Cl1 \\sim Cl2 \\sim C76 \\sim Cl1A \\sim Cl2A \\sim C76A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
Cl3 \\sim Cl4 \\sim C77: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Uanis(C77A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl4A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
5. Rigid body (RIGU) restrains
 Cl3A, Cl4A, C77A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 Cl1A, Cl2A, C76A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 Cl1, Cl2, C76
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 Cl3, Cl4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 Cl3, Cl4, C77
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
6. Others
 Sof(Cl1A)=Sof(Cl2A)=Sof(C76A)=Sof(H76C)=Sof(H76D)=1-FVAR(1)
 Sof(Cl1)=Sof(Cl2)=Sof(C76)=Sof(H76A)=Sof(H76B)=FVAR(1)
 Fixed Sof: Cl3A(0.25) Cl4A(0.25) C77A(0.25) H77A(0.25) H77B(0.25) Cl3(0.25)
 Cl4(0.25) C77(0.25) H77C(0.25) H77D(0.25) Cl5(0.5) Cl6(0.5) C78(0.5) H78A(0.5)
 H78B(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C77A(H77A,H77B), C77(H77C,H77D), C78(H78A,H78B), C76(H76A,H76B), C76A(H76C,
 H76D)
7.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C10(H10), C11(H11), C12(H12), C13(H13),
 C16(H16), C17(H17), C18(H18), C19(H19), C22(H22), C23(H23), C24(H24), C25(H25),
  C28(H28), C29(H29), C30(H30), C31(H31), C34(H34), C35(H35), C36(H36),
 C37(H37), C40(H40), C41(H41), C42(H42), C43(H43), C46(H46), C47(H47), C48(H48),
  C49(H49), C53(H53), C54(H54), C55(H55), C56(H56), C59(H59), C60(H60),
 C61(H61), C62(H62), C65(H65), C66(H66), C67(H67), C68(H68), C71(H71), C72(H72),
  C73(H73), C74(H74)
;
_shelx_res_checksum              86621
_olex2_submission_special_instructions 'No special instructions were received'