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_1571081
_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         'C68 H96 N4 O4 P2 Si, C32 H12 B F24'
_chemical_formula_sum            'C100 H108 B F24 N4 O4 P2 Si'
_chemical_formula_weight         1986.74
_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             2022-07-26
_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                87.067(2)
_cell_angle_beta                 73.300(2)
_cell_angle_gamma                89.995(2)
_cell_formula_units_Z            2
_cell_length_a                   13.4882(6)
_cell_length_b                   17.4109(7)
_cell_length_c                   22.7720(9)
_cell_measurement_reflns_used    9879
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      59.26
_cell_measurement_theta_min      2.75
_cell_volume                     5115.0(4)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_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_temperature      150.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.992
_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  0.0465
_diffrn_reflns_av_unetI/netI     0.0309
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            157333
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.137
_diffrn_reflns_theta_min         1.171
_diffrn_source_current           3.57
_diffrn_source_power             0.24954300000000001
_diffrn_source_voltage           69.9
_exptl_absorpt_coefficient_mu    0.149
_exptl_absorpt_correction_T_max  0.7516
_exptl_absorpt_correction_T_min  0.6671
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1289 before and 0.0588 after correction.
The Ratio of minimum to maximum transmission is 0.8876.
The \l/2 correction factor is Not present.
;
_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    1.290
_exptl_crystal_description       block
_exptl_crystal_F_000             2066
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.311
_refine_diff_density_min         -0.867
_refine_diff_density_rms         0.064
_refine_ls_extinction_coef       0.0056(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.080
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1275
_refine_ls_number_reflns         22499
_refine_ls_number_restraints     79
_refine_ls_restrained_S_all      1.299
_refine_ls_R_factor_all          0.0787
_refine_ls_R_factor_gt           0.0638
_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^)+(0.0918P)^2^+4.0687P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1761
_refine_ls_wR_factor_ref         0.1867
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17641
_reflns_number_total             22499
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00201f2.cif
_cod_data_source_block           8
_cod_depositor_comments
'Adding full bibliography for 1571075--1571082.cif.'
_cod_database_code               1571081
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.978
_shelx_estimated_absorpt_t_min   0.971
_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
 F13, C99, F11, C75, F12, C75, F10, C75
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(F25) \\sim Ueq, Uanis(F26) \\sim Ueq, Uanis(F27) \\sim Ueq, Uanis(F28)
\\sim Ueq, Uanis(F29) \\sim Ueq, Uanis(F24) \\sim Ueq, Uanis(F12) \\sim Ueq,
Uanis(F11) \\sim Ueq, Uanis(F10) \\sim Ueq, Uanis(F16) \\sim Ueq, Uanis(F13)
\\sim Ueq, Uanis(F9) \\sim Ueq: with sigma of 0.001 and sigma for terminal
atoms of 0.002
4. Others
 Sof(F27)=Sof(F29)=Sof(F25)=1-FVAR(1)
 Sof(F28)=Sof(F26)=Sof(F24)=FVAR(1)
 Sof(F21)=1-FVAR(2)
 Sof(F22)=FVAR(2)
 Sof(F23)=1-FVAR(3)
 Sof(F20)=FVAR(3)
 Sof(F8A)=1-FVAR(4)
 Sof(F8)=FVAR(4)
5.a Ternary CH refined with riding coordinates:
 C7(H7), C67(H67), C55(H55), C26(H26), C38(H38), C29(H29), C64(H64), C52(H52),
 C41(H41)
5.b Secondary CH2 refined with riding coordinates:
 C43(H43A,H43B), C44(H44A,H44B), C17(H17A,H17B), C18(H18A,H18B), C15(H15A,
 H15B), C12(H12A,H12B)
5.c Aromatic/amide H refined with riding coordinates:
 C82(H82), C98(H98), C86(H86), C88(H88), C59(H59), C90(H90), C21(H21),
 C78(H78), C70(H70), C94(H94), C23(H23), C60(H60), C80(H80), C74(H74), C22(H22),
  C35(H35), C33(H33), C96(H96), C61(H61), C47(H47), C49(H49), C72(H72),
 C34(H34), C48(H48)
5.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C66(H66A,H66B,H66C), C54(H54A,H54B,H54C), C68(H68A,H68B,
 H68C), C9(H9A,H9B,H9C), C39(H39A,H39B,H39C), C56(H56A,H56B,H56C), C8(H8A,H8B,
 H8C), C25(H25A,H25B,H25C), C51(H51A,H51B,H51C), C30(H30A,H30B,H30C), C53(H53A,
 H53B,H53C), C27(H27A,H27B,H27C), C63(H63A,H63B,H63C), C65(H65A,H65B,H65C),
 C37(H37A,H37B,H37C), C16(H16A,H16B,H16C), C28(H28A,H28B,H28C), C40(H40A,H40B,
 H40C), C42(H42A,H42B,H42C), C13(H13A,H13B,H13C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_olex2_submission_special_instructions 'No special instructions were received'