Sequential radical and cationic reactivity at separated sites within one molecule in solution.
Liu, Shihua; Li, Yinwu; Lin, Jieli; Ke, Zhuofeng; Grützmacher, Hansjörg; Su, Cheng-Yong; Li, Zhongshu; Chemical science 15 (2024) 5376–5384; doi:10.1039/d4sc00201f

data_1571080
_publ_section_title
;
 Sequential radical and cationic reactivity at separated sites within one
 molecule in solution.
;
_journal_issue                   14
_journal_name_full               'Chemical science'
_journal_page_first              5376
_journal_page_last               5384
_journal_paper_doi               10.1039/d4sc00201f
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         '4(C75 H95 F N4 O2 P2 S)'
_chemical_formula_sum            'C300 H380 F4 N16 O8 P8 S4'
_chemical_formula_weight         4790.18
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yac'
_space_group_name_H-M_alt        'P 1 2/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-10-25
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-10-25 deposited with the CCDC.	2024-03-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.402(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   26.0037(8)
_cell_length_b                   13.0979(3)
_cell_length_c                   40.7620(9)
_cell_measurement_reflns_used    22329
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      73.7520
_cell_measurement_theta_min      3.5510
_cell_volume                     13821.6(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.971
_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     47.00  73.00   0.50   30.00    --    0.00  38.00 -90.00   52
  2  \w     46.00  89.00   0.50   30.00    --    0.00  63.00 -21.52   86
  3  \w    -89.00 -32.00   0.50   30.00    --    0.00 -38.00   0.00  114
  4  \w    -12.00  14.00   0.50   30.00    --    0.00  38.00 -90.00   52
  5  \w    -24.00  30.00   0.50   30.00    --    0.00  63.00 -21.52  108
  6  \w      6.00 126.00   0.50  110.00    --   95.20 -82.00-120.00  240
  7  \w      6.00  94.00   0.50  110.00    --   95.20 -30.00 -90.00  176
  8  \w      9.00 111.00   0.50  110.00    --   95.20 -61.00-120.00  204
  9  \w     27.00 100.00   0.50  110.00    --   95.20 -30.00  30.00  146
 10  \w    137.00 163.00   0.50  110.00    --   95.20  15.00-150.00   52
 11  \w    150.00 176.00   0.50  110.00    --   95.20  30.00  60.00   52
 12  \w     74.00 126.00   0.50  110.00    --   95.20  15.00-150.00  104
 13  \w     80.00 110.00   0.50  110.00    --   95.20 -61.00 -60.00   60
 14  \w     85.00 111.00   0.50  110.00    --   95.20 -82.00-150.00   52
 15  \w     88.00 127.00   0.50  110.00    --   95.20 -82.00 -60.00   78
 16  \w     82.00 130.00   0.50  110.00    --   95.20  30.00  60.00   96
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0461167000
_diffrn_orient_matrix_UB_12      0.0742789000
_diffrn_orient_matrix_UB_13      -0.0018716000
_diffrn_orient_matrix_UB_21      -0.0373491000
_diffrn_orient_matrix_UB_22      -0.0900354000
_diffrn_orient_matrix_UB_23      -0.0077298000
_diffrn_orient_matrix_UB_31      -0.0043709000
_diffrn_orient_matrix_UB_32      -0.0149257000
_diffrn_orient_matrix_UB_33      0.0371058000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0798
_diffrn_reflns_av_unetI/netI     0.0844
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       49
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            85375
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.440
_diffrn_reflns_theta_min         3.541
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.235
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49652
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear reddish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.151
_exptl_crystal_description       prism
_exptl_crystal_F_000             5152
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0
_refine_diff_density_max         1.419
_refine_diff_density_min         -1.257
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1589
_refine_ls_number_reflns         27437
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0995
_refine_ls_R_factor_gt           0.0720
_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^)+(0.1283P)^2^+2.7336P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1980
_refine_ls_wR_factor_ref         0.2158
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19384
_reflns_number_total             27437
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00201f2.cif
_cod_data_source_block           7
_cod_depositor_comments
'Adding full bibliography for 1571075--1571082.cif.'
_cod_database_code               1571080
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   1.000
_shelx_estimated_absorpt_t_min   0.930
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(F2A)=1-FVAR(1)
 Sof(F2)=FVAR(1)
 Sof(F1A)=1-FVAR(2)
 Sof(F1)=FVAR(2)
3.a Ternary CH refined with riding coordinates:
 C36(H36), C62(H62), C146(H146), C149(H149), C33(H33), C134(H134), C71(H71),
 C59(H59), C120(H120), C137(H137), C45(H45), C123(H123), C107(H107), C111(H111),
  C49(H49), C74(H74)
3.b Secondary CH2 refined with riding coordinates:
 C51(H51A,H51B), C50(H50A,H50B), C24(H24A,H24B), C125(H12A,H12B), C25(H25A,
 H25B), C126(H12C,H12D), C100(H10A,H10B), C99(H99A,H99B)
3.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C56(H56), C28(H28), C12(H12), C54(H54), C29(H29), C30(H30),
 C141(H141), C142(H142), C55(H55), C143(H143), C11(H11), C9(H9), C129(H129),
 C10(H10), C117(H117), C116(H116), C87(H87), C83(H83), C115(H115), C19(H19),
 C68(H68), C23(H23), C85(H85), C130(H130), C86(H86), C20(H20), C131(H131),
 C66(H66), C67(H67), C21(H21), C40(H40), C22(H22), C84(H84), C103(H103),
 C42(H42), C105(H105), C104(H104), C41(H41), C94(H94), C98(H98), C95(H95),
 C96(H96), C97(H97)
3.d Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C61(H61A,H61B,H61C), C58(H58A,H58B,H58C), C37(H37A,H37B,
 H37C), C32(H32A,H32B,H32C), C63(H63A,H63B,H63C), C14(H14A,H14B,H14C),
 C133(H13A,H13B,H13C), C135(H13D,H13E,H13F), C34(H34A,H34B,H34C), C92(H92A,H92B,
 H92C), C16(H16A,H16B,H16C), C60(H60A,H60B,H60C), C91(H91A,H91B,H91C), C72(H72A,
 H72B,H72C), C150(H15A,H15B,H15C), C89(H89A,H89B,H89C), C17(H17A,H17B,H17C),
 C119(H11A,H11B,H11C), C145(H14D,H14E,H14F), C70(H70A,H70B,H70C), C108(H10C,
 H10D,H10E), C148(H14G,H14H,H14I), C147(H14J,H14K,H14L), C110(H11D,H11E,H11F),
 C136(H13G,H13H,H13I), C109(H10F,H10G,H10H), C121(H12E,H12F,H12G), C138(H13J,
 H13K,H13L), C44(H44A,H44B,H44C), C47(H47A,H47B,H47C), C73(H73A,H73B,H73C),
 C112(H11G,H11H,H11I), C122(H12H,H12I,H12J), C46(H46A,H46B,H46C), C124(H12K,
 H12L,H12M), C48(H48A,H48B,H48C), C75(H75A,H75B,H75C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_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 5.389
_oxdiff_exptl_absorpt_empirical_full_min 0.318