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_1571079
_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
'2(C64 H86 N4 O4 P2), 2(C32 H12 B F24), 0.5(C6 H14)'
_chemical_formula_sum            'C195 H203 B2 F48 N8 O8 P4'
_chemical_formula_weight         3844.14
_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                72.2590(10)
_cell_angle_beta                 77.1930(10)
_cell_angle_gamma                89.9430(10)
_cell_formula_units_Z            1
_cell_length_a                   14.7749(2)
_cell_length_b                   16.5982(2)
_cell_length_c                   20.9941(2)
_cell_measurement_reflns_used    28614
_cell_measurement_temperature    103(5)
_cell_measurement_theta_max      74.0130
_cell_measurement_theta_min      2.8110
_cell_volume                     4769.40(10)
_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      103(5)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.963
_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    -17.00  24.00   0.50    1.36    --    0.00  38.00  60.00   82
  2  \w     50.00  88.00   0.50    1.36    --    0.00  38.00 -30.00   76
  3  \w     -8.00  19.00   0.50    1.36    --    0.00  77.00 -90.00   54
  4  \w     42.00  88.00   0.50    1.36    --    0.00  38.00  60.00   92
  5  \w     36.00  88.00   0.50    1.36    --    0.00  77.00  60.00  104
  6  \w    -18.00  31.00   0.50    1.36    --    0.00  77.00  60.00   98
  7  \w    -67.00 -27.00   0.50    1.36    --    0.00 -38.00  60.00   80
  8  \w     33.00  80.00   0.50    1.36    --    0.00  77.00 -90.00   94
  9  \w    -86.00 -59.00   0.50    1.36    --    0.00 -38.00   0.00   54
 10  \w    -17.00  16.00   0.50    1.36    --    0.00 -38.00   0.00   66
 11  \w    -16.00  28.00   0.50    1.36    --    0.00  38.00 -30.00   88
 12  \w     40.00  66.00   0.50    1.36    --    0.00  38.00 150.00   52
 13  \w     29.00  68.00   0.50    5.45    --   95.20 -30.00  30.00   78
 14  \w     68.00 126.00   0.50    5.45    --   95.20 -82.00 -30.00  116
 15  \w     92.00 180.00   0.50    5.45    --   95.20  15.00   0.00  176
 16  \w     74.00 104.00   0.50    5.45    --   95.20 -82.00-150.00   60
 17  \w      7.00  96.00   0.50    5.45    --   95.20 -61.00 120.00  178
 18  \w     21.00 111.00   0.50    5.45    --   95.20 -30.00-120.00  180
 19  \w     90.00 175.00   0.50    5.45    --   95.20  30.00-120.00  170
 20  \w     14.00 118.00   0.50    5.45    --   95.20 -61.00 -90.00  208
 21  \w     92.00 117.00   0.50    5.45    --   95.20 -82.00  30.00   50
 22  \w     26.00  85.00   0.50    5.45    --   95.20 -82.00  30.00  118
 23  \w     68.00 113.00   0.50    5.45    --   95.20 -82.00 -90.00   90
 24  \w     12.00  37.00   0.50    5.45    --   95.20 -82.00 -90.00   50
 25  \w     14.00  51.00   0.50    5.45    --   95.20 -82.00  60.00   74
 26  \w     99.00 125.00   0.50    5.45    --   95.20 -82.00  60.00   52
 27  \w      7.00 107.00   0.50    5.45    --   95.20 -30.00 150.00  200
 28  \w     13.00 127.00   0.50    5.45    --   95.20 -82.00 120.00  228
 29  \w     29.00  55.00   0.50    5.45    --   95.20 -82.00 150.00   52
 30  \w     89.00 123.00   0.50    5.45    --   95.20 -82.00 150.00   68
 31  \w     17.00 102.00   0.50    5.45    --   95.20 -82.00  49.24  170
;
_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      -0.0275418000
_diffrn_orient_matrix_UB_12      -0.0229326000
_diffrn_orient_matrix_UB_13      -0.0592869000
_diffrn_orient_matrix_UB_21      0.0463065000
_diffrn_orient_matrix_UB_22      0.0854659000
_diffrn_orient_matrix_UB_23      -0.0507563000
_diffrn_orient_matrix_UB_31      0.0926835000
_diffrn_orient_matrix_UB_32      -0.0414139000
_diffrn_orient_matrix_UB_33      -0.0135596000
_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  0.0397
_diffrn_reflns_av_unetI/netI     0.0374
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            57770
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.292
_diffrn_reflns_theta_min         2.802
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.279
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68837
_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 greenish green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.338
_exptl_crystal_description       block
_exptl_crystal_F_000             1995
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.14
_refine_diff_density_max         1.370
_refine_diff_density_min         -0.594
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1211
_refine_ls_number_reflns         18754
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0693
_refine_ls_R_factor_gt           0.0606
_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^)+(0.0808P)^2^+5.9641P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1649
_refine_ls_wR_factor_ref         0.1718
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15963
_reflns_number_total             18754
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00201f2.cif
_cod_data_source_block           3d
_cod_depositor_comments
'Adding full bibliography for 1571075--1571082.cif.'
_cod_database_code               1571079
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.841
_shelx_estimated_absorpt_t_min   0.775
_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
 Fixed Sof: C99(0.5) H99A(0.5) H99B(0.5) C97(0.5) H97A(0.5) H97B(0.5)
 H97C(0.5) C98(0.5) H98A(0.5) H98B(0.5)
3.a Ternary CH refined with riding coordinates:
 C60(H60), C22(H22), C63(H63), C34(H34), C25(H25), C48(H48), C51(H51), C37(H37)
3.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C39(H39A,H39B), C13(H13A,H13B), C40(H40A,H40B), C11(H11A,
 H11B), C8(H8A,H8B), C99(H99A,H99B), C98(H98A,H98B)
3.c Aromatic/amide H refined with riding coordinates:
 C94(H94), C86(H86), C74(H74), C92(H92), C66(H66), C84(H84), C70(H70),
 C90(H90), C78(H78), C82(H82), C76(H76), C68(H68), C55(H55), C31(H31), C19(H19),
  C29(H29), C57(H57), C56(H56), C18(H18), C17(H17), C30(H30), C45(H45),
 C43(H43), C44(H44)
3.d Idealised Me refined as rotating group:
 C59(H59A,H59B,H59C), C23(H23A,H23B,H23C), C64(H64A,H64B,H64C), C33(H33A,H33B,
 H33C), C21(H21A,H21B,H21C), C62(H62A,H62B,H62C), C49(H49A,H49B,H49C), C35(H35A,
 H35B,H35C), C61(H61A,H61B,H61C), C26(H26A,H26B,H26C), C24(H24A,H24B,H24C),
 C12(H12A,H12B,H12C), C47(H47A,H47B,H47C), C9(H9A,H9B,H9C), C52(H52A,H52B,H52C),
  C50(H50A,H50B,H50C), C36(H36A,H36B,H36C), C38(H38A,H38B,H38C), C97(H97A,H97B,
 H97C)
;
_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 3.012
_oxdiff_exptl_absorpt_empirical_full_min 0.584