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_1571077
_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         'C75 H95 N4 O2 P2 S, C32 H12 B F24'
_chemical_formula_sum            'C107 H107 B F24 N4 O2 P2 S'
_chemical_formula_weight         2041.77
_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             2022-10-25
_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                103.6170(10)
_cell_angle_beta                 108.0100(10)
_cell_angle_gamma                91.8250(10)
_cell_formula_units_Z            2
_cell_length_a                   15.1726(2)
_cell_length_b                   16.6364(2)
_cell_length_c                   21.9306(2)
_cell_measurement_reflns_used    27000
_cell_measurement_temperature    149.98(10)
_cell_measurement_theta_max      73.9890
_cell_measurement_theta_min      2.7800
_cell_volume                     5083.56(11)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.98(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.969
_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    -89.00  -2.00   0.50    5.00    --    0.00 -19.00-120.00  174
  2  \w    -29.00   8.00   0.50    5.00    --    0.00  77.00-150.00   74
  3  \w     33.00  88.00   0.50    5.00    --    0.00  77.00-150.00  110
  4  \w    -41.00 -16.00   0.50    5.00    --    0.00 -38.00-120.00   50
  5  \w    -27.00   2.00   0.50    5.00    --    0.00 -38.00 -30.00   58
  6  \w    -30.00  22.00   0.50    5.00    --    0.00 -57.00-180.00  104
  7  \w    -17.00  88.00   0.50    5.00    --    0.00  38.00-180.00  210
  8  \w    -85.00 -58.00   0.50    5.00    --    0.00 -57.00-180.00   54
  9  \w     96.00 124.00   0.50   20.00    --   95.20 -82.00 120.00   56
 10  \w     13.00 119.00   0.50   20.00    --   95.20 -61.00 -30.00  212
 11  \w      9.00  73.00   0.50   20.00    --   95.20 -82.00 120.00  128
 12  \w     24.00 107.00   0.50   20.00    --   95.20 -82.00 -90.00  166
 13  \w      6.00 118.00   0.50   20.00    --   95.20 -61.00 120.00  224
 14  \w     74.00 100.00   0.50   20.00    --   95.20 -82.00-120.00   52
 15  \w     20.00  46.00   0.50   20.00    --   95.20 -82.00  30.00   52
 16  \w     91.00 119.00   0.50   20.00    --   95.20 -82.00 150.00   56
 17  \w     72.00 127.00   0.50   20.00    --   95.20 -82.00 -30.00  110
 18  \w     72.00 152.00   0.50   20.00    --   95.20  15.00-120.00  160
 19  \w      6.00 105.00   0.50   20.00    --   95.20 -30.00 120.00  198
 20  \w      7.00  51.00   0.50   20.00    --   95.20 -82.00 -30.00   88
 21  \w     88.00 114.00   0.50   20.00    --   95.20 -45.00  60.00   52
 22  \w     66.00 107.00   0.50   20.00    --   95.20 -82.00-150.00   82
 23  \w     70.00 115.00   0.50   20.00    --   95.20 -82.00  90.00   90
 24  \w     15.00  51.00   0.50   20.00    --   95.20 -45.00  60.00   72
 25  \w     24.00 100.00   0.50   20.00    --   95.20 -45.00 -30.00  152
 26  \w     90.00 115.00   0.50   20.00    --   95.20 -82.00-180.00   50
 27  \w     13.00  91.00   0.50   20.00    --   95.20 -61.00 -90.00  156
 28  \w    135.00 176.00   0.50   20.00    --   95.20  30.00-120.00   82
 29  \w     84.00 110.00   0.50   20.00    --   95.20 -82.00  30.00   52
 30  \w     70.00 103.00   0.50   20.00    --   95.20 -30.00-150.00   66
 31  \w      8.00  42.00   0.50   20.00    --   95.20 -30.00-150.00   68
;
_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      0.0236928000
_diffrn_orient_matrix_UB_12      -0.0072431000
_diffrn_orient_matrix_UB_13      0.0719236000
_diffrn_orient_matrix_UB_21      -0.0793684000
_diffrn_orient_matrix_UB_22      -0.0715634000
_diffrn_orient_matrix_UB_23      -0.0228502000
_diffrn_orient_matrix_UB_31      0.0684582000
_diffrn_orient_matrix_UB_32      -0.0634220000
_diffrn_orient_matrix_UB_33      -0.0122603000
_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  0.0309
_diffrn_reflns_av_unetI/netI     0.0302
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            63197
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.327
_diffrn_reflns_theta_min         2.751
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.405
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87615
_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 light red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.334
_exptl_crystal_description       block
_exptl_crystal_F_000             2120
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.268
_refine_diff_density_min         -0.749
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1383
_refine_ls_number_reflns         20085
_refine_ls_number_restraints     172
_refine_ls_restrained_S_all      1.328
_refine_ls_R_factor_all          0.0906
_refine_ls_R_factor_gt           0.0779
_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^)+(0.1131P)^2^+6.1419P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2159
_refine_ls_wR_factor_ref         0.2269
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16196
_reflns_number_total             20085
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00201f2.cif
_cod_data_source_block           6
_cod_depositor_comments
'Adding full bibliography for 1571075--1571082.cif.'
_cod_database_code               1571077
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.872
_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. Rigid bond restraints
 C27, C28, F13, C89, F24, C105, F22, C105, F15, C89, F23, C105
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(F27) \\sim Ueq, Uanis(F25) \\sim Ueq, Uanis(F26) \\sim Ueq, Uanis(F30)
\\sim Ueq, Uanis(F29) \\sim Ueq, Uanis(F28) \\sim Ueq, Uanis(C104) \\sim Ueq,
Uanis(F23) \\sim Ueq, Uanis(F24) \\sim Ueq, Uanis(F22) \\sim Ueq, Uanis(F14)
\\sim Ueq, Uanis(F13) \\sim Ueq, Uanis(F15) \\sim Ueq: with sigma of 0.001 and
sigma for terminal atoms of 0.002
Uanis(F12) \\sim Ueq, Uanis(F11) \\sim Ueq, Uanis(F10) \\sim Ueq, Uanis(F9)
\\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F8) \\sim Ueq, Uanis(C27) \\sim Ueq,
Uanis(C18) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C72)
\\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C80) \\sim Ueq:
with sigma of 0.002 and sigma for terminal atoms of 0.004
4. Others
 Sof(C76)=Sof(C81)=Sof(H81)=Sof(C80)=Sof(H80)=Sof(C79)=Sof(H79)=Sof(C78)=
 Sof(H78)=Sof(C77)=Sof(H77)=1-FVAR(1)
 Sof(C70)=Sof(C75)=Sof(H75)=Sof(C74)=Sof(H74)=Sof(C73)=Sof(H73)=Sof(C72)=
 Sof(H72)=Sof(C71)=Sof(H71)=FVAR(1)
 Fixed Sof: S1(0.6) S2(0.4) F10(0.6) F8(0.6) F12(0.6) F25(0.6) F30(0.6)
 F28(0.6) F27(0.4) F9(0.4) F7(0.4) F11(0.4) F26(0.4) F29(0.4)
5.a Ternary CH refined with riding coordinates:
 C68(H68), C53(H53), C65(H65), C56(H56), C30(H30), C42(H42), C39(H39), C27(H27)
5.b Secondary CH2 refined with riding coordinates:
 C44(H44A,H44B), C45(H45A,H45B), C19(H19A,H19B), C18(H18A,H18B)
5.c Aromatic/amide H refined with riding coordinates:
 C91(H91), C107(H107), C111(H111), C93(H93), C95(H95), C99(H99), C83(H83),
 C87(H87), C60(H60), C103(H103), C109(H109), C85(H85), C101(H101), C11(H11),
 C50(H50), C62(H62), C61(H61), C22(H22), C23(H23), C10(H10), C8(H8), C24(H24),
 C12(H12), C48(H48), C49(H49), C36(H36), C9(H9), C34(H34), C35(H35), C75(H75),
 C74(H74), C73(H73), C72(H72), C71(H71), C81(H81), C80(H80), C79(H79), C78(H78),
  C77(H77)
5.d Fitted hexagon refined as free rotating group:
 C70(C75,C74,C73,C72,C71), C76(C81,C80,C79,C78,C77)
5.e Idealised Me refined as rotating group:
 C57(H57A,H57B,H57C), C66(H66A,H66B,H66C), C55(H55A,H55B,H55C), C31(H31A,H31B,
 H31C), C52(H52A,H52B,H52C), C54(H54A,H54B,H54C), C64(H64A,H64B,H64C), C69(H69A,
 H69B,H69C), C17(H17A,H17B,H17C), C67(H67A,H67B,H67C), C16(H16A,H16B,H16C),
 C15(H15A,H15B,H15C), C29(H29A,H29B,H29C), C41(H41A,H41B,H41C), C43(H43A,H43B,
 H43C), C40(H40A,H40B,H40C), C38(H38A,H38B,H38C), C28(H28A,H28B,H28C), C26(H26A,
 H26B,H26C)
;
_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 1.641
_oxdiff_exptl_absorpt_empirical_full_min 0.639