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_1571078
_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         'C69 H90 N4 O2 P2, C32 H12 B F24'
_chemical_formula_sum            'C101 H102 B F24 N4 O2 P2'
_chemical_formula_weight         1932.61
_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
_audit_creation_date             2020-12-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-10-25 deposited with the CCDC.	2024-03-01 downloaded from the CCDC.
;
_cell_angle_alpha                106.472(2)
_cell_angle_beta                 101.180(2)
_cell_angle_gamma                96.412(2)
_cell_formula_units_Z            2
_cell_length_a                   12.9969(5)
_cell_length_b                   20.0236(7)
_cell_length_c                   20.1523(7)
_cell_measurement_reflns_used    9559
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.8360
_cell_measurement_theta_min      2.7120
_cell_volume                     4855.8(3)
_computing_cell_refinement       'SAINT V8.40A (?, 2016)'
_computing_data_reduction        'SAINT V8.40A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.0
_diffrn_measured_fraction_theta_full 0.980
_diffrn_measured_fraction_theta_max 0.950
_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  0.0901
_diffrn_reflns_av_unetI/netI     0.0924
_diffrn_reflns_Laue_measured_fraction_full 0.980
_diffrn_reflns_Laue_measured_fraction_max 0.950
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            92619
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.950
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.143
_diffrn_reflns_theta_min         1.077
_exptl_absorpt_coefficient_mu    0.141
_exptl_absorpt_correction_T_max  0.7516
_exptl_absorpt_correction_T_min  0.6873
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1557 before and 0.0637 after correction.
The Ratio of minimum to maximum transmission is 0.9144.
The \l/2 correction factor is Not present.
;
_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    1.322
_exptl_crystal_description       plate
_exptl_crystal_F_000             2006
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.381
_refine_diff_density_min         -0.320
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1511
_refine_ls_number_reflns         20436
_refine_ls_number_restraints     258
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.1929
_refine_ls_R_factor_gt           0.0890
_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^)+(0.0723P)^2^+7.8025P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1776
_refine_ls_wR_factor_ref         0.2327
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9837
_reflns_number_total             20436
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00201f2.cif
_cod_data_source_block           3c
_cod_depositor_comments
'Adding full bibliography for 1571075--1571082.cif.'
_cod_database_code               1571078
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   73.8190
_shelx_estimated_absorpt_t_min   2.7080
_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. Uiso/Uaniso restraints and constraints
Uanis(F16) \\sim Ueq, Uanis(F17) \\sim Ueq, Uanis(F18) \\sim Ueq, Uanis(F19)
\\sim Ueq, Uanis(F21) \\sim Ueq, Uanis(F22) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(F25) \\sim Ueq, Uanis(F28) \\sim Ueq, Uanis(F31) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C42) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C38)
\\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C35) \\sim Ueq,
Uanis(C39) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C57)
\\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C73) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(F24) \\sim Ueq, Uanis(F27) \\sim Ueq, Uanis(F30) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(F26) \\sim Ueq, Uanis(F23) \\sim Ueq, Uanis(F29) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C56) \\sim Ueq, Uanis(C52) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(N2) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C59)
\\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(F35) \\sim Ueq, Uanis(F40) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F11) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F33) \\sim Ueq, Uanis(F39)
\\sim Ueq, Uanis(F36) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C59) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=
 Sof(C43)=Sof(H43)=Sof(C36)=Sof(H36)=Sof(C35)=Sof(C58)=Sof(C39)=Sof(C38)=
 Sof(H38)=Sof(C37)=Sof(H37)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=Sof(C55)=
 Sof(H55A)=Sof(H55B)=Sof(H55C)=Sof(C57)=Sof(H57)=1-FVAR(1)
 Sof(C46)=Sof(C48)=Sof(C40)=Sof(H40)=Sof(C51)=Sof(H51)=Sof(C47)=Sof(C50)=
 Sof(H50)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=Sof(C54)=Sof(H54)=Sof(C49)=
 Sof(H49)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C52)=Sof(H52A)=Sof(H52B)=
 Sof(H52C)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=FVAR(1)
 Sof(F17)=Sof(F19)=Sof(F22)=1-FVAR(2)
 Sof(F16)=Sof(F18)=Sof(F21)=FVAR(2)
 Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(C73)=Sof(H73A)=Sof(H73B)=1-FVAR(3)
 Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(C71)=Sof(H71A)=Sof(H71B)=FVAR(3)
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(C19)=Sof(H19A)=Sof(H19B)=1-FVAR(4)
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(C18)=Sof(H18A)=Sof(H18B)=FVAR(4)
 Sof(N3)=1-FVAR(5)
 Sof(N2)=FVAR(5)
 Fixed Sof: F33(0.33333) F31(0.33333) F25(0.33333) F36(0.33333) F39(0.33333)
 F28(0.33333) F27(0.33333) F30(0.33333) F24(0.33333) F26(0.33333) F29(0.33333)
 F23(0.33333) F38(0.33333) F34(0.33333) F35(0.33333) F40(0.33333) F32(0.33333)
 F37(0.33333)
4.a Ternary CH refined with riding coordinates:
 C23(H23), C85(H85), C76(H76), C32(H32), C70(H70), C60(H60), C40(H40),
 C54(H54), C43(H43), C57(H57)
4.b Secondary CH2 refined with riding coordinates:
 C74(H74A,H74B), C20(H20A,H20B), C71(H71A,H71B), C18(H18A,H18B), C72(H72A,
 H72B), C73(H73A,H73B), C21(H21A,H21B), C19(H19A,H19B)
4.c Aromatic/amide H refined with riding coordinates:
 C91(H91), C100(H100), C104(H104), C108(H108), C89(H89), C116(H116),
 C112(H112), C106(H106), C96(H96), C30(H30), C114(H114), C82(H82), C13(H13),
 C87(H87), C29(H29), C98(H98), C80(H80), C81(H81), C28(H28), C14(H14), C66(H66),
  C17(H17), C16(H16), C64(H64), C15(H15), C65(H65), C51(H51), C50(H50),
 C49(H49), C36(H36), C38(H38), C37(H37)
4.d Fitted hexagon refined as free rotating group:
 C36(C35,C58,C39,C38,C37)
4.e Idealised Me refined as rotating group:
 C84(H84A,H84B,H84C), C83(H83A,H83B,H83C), C75(H75A,H75B,H75C), C24(H24A,H24B,
 H24C), C10(H10A,H10B,H10C), C22(H22A,H22B,H22C), C69(H69A,H69B,H69C), C77(H77A,
 H77B,H77C), C31(H31A,H31B,H31C), C8(H8A,H8B,H8C), C33(H33A,H33B,H33C),
 C11(H11A,H11B,H11C), C45(H45A,H45B,H45C), C68(H68A,H68B,H68C), C59(H59A,H59B,
 H59C), C61(H61A,H61B,H61C), C41(H41A,H41B,H41C), C52(H52A,H52B,H52C), C56(H56A,
 H56B,H56C), C44(H44A,H44B,H44C), C42(H42A,H42B,H42C), C53(H53A,H53B,H53C),
 C55(H55A,H55B,H55C)
;
_olex2_submission_special_instructions 'No special instructions were received'