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_1571075
_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, C3 H7'
_chemical_formula_sum            'C72 H97 N4 O2 P2'
_chemical_formula_weight         1112.47
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/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                 96.0520(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.33630(10)
_cell_length_b                   22.0219(2)
_cell_length_c                   24.3308(3)
_cell_measurement_reflns_used    18385
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      73.7240
_cell_measurement_theta_min      2.7090
_cell_volume                     6573.08(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      149.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.970
_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 -18.00   0.50    1.80    --    0.00 -38.00 150.00   58
  2  \w    -89.00  17.00   0.50    1.80    --    0.00 -19.00-150.00  212
  3  \w     -5.00  20.00   0.50    1.80    --    0.00 -57.00-180.00   50
  4  \w    -23.00  25.00   0.50    1.80    --    0.00  77.00-120.00   96
  5  \w      6.00 127.00   0.50    7.19    --   95.20 -82.00-120.00  242
  6  \w     72.00 131.00   0.50    7.19    --   95.20  61.00  30.00  118
  7  \w      6.00 117.00   0.50    7.19    --   95.20 -61.00-120.00  222
  8  \w    120.00 177.00   0.50    7.19    --   95.20  45.00  90.00  114
  9  \w     79.00 184.00   0.50    7.19    --   95.20  30.00 120.00  210
 10  \w     85.00 110.00   0.50    7.19    --   95.20  45.00  90.00   50
 11  \w     74.00 114.00   0.50    7.19    --   95.20 -45.00 -60.00   80
 12  \w     73.00 126.00   0.50    7.19    --   95.20  61.00   0.00  106
 13  \w     36.00  66.00   0.50    7.19    --   95.20 -30.00-150.00   60
;
_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      -0.0034333000
_diffrn_orient_matrix_UB_12      -0.0297858000
_diffrn_orient_matrix_UB_13      0.0570446000
_diffrn_orient_matrix_UB_21      0.0325129000
_diffrn_orient_matrix_UB_22      0.0609562000
_diffrn_orient_matrix_UB_23      0.0282689000
_diffrn_orient_matrix_UB_31      -0.1212171000
_diffrn_orient_matrix_UB_32      0.0171242000
_diffrn_orient_matrix_UB_33      -0.0009699000
_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  0.0677
_diffrn_reflns_av_unetI/netI     0.0608
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            37571
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.076
_diffrn_reflns_theta_min         2.713
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.949
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68996
_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    1.124
_exptl_crystal_description       block
_exptl_crystal_F_000             2412
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.555
_refine_diff_density_min         -0.529
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     726
_refine_ls_number_reflns         12964
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0637
_refine_ls_R_factor_gt           0.0568
_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^)+(0.0990P)^2^+2.4106P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1624
_refine_ls_wR_factor_ref         0.1688
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11163
_reflns_number_total             12964
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00201f2.cif
_cod_data_source_block           5
_cod_depositor_comments
'Adding full bibliography for 1571075--1571082.cif.'
_cod_database_code               1571075
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.911
_shelx_estimated_absorpt_t_min   0.764
_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.a Ternary CH refined with riding coordinates:
 C42(H42), C53(H53), C56(H56), C65(H65), C68(H68), C39(H39), C30(H30), C27(H27)
2.b Secondary CH2 refined with riding coordinates:
 C44(H44A,H44B), C45(H45A,H45B), C18(H18A,H18B), C19(H19A,H19B), C72(H72A,
 H72B), C71(H71A,H71B)
2.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C12(H12), C48(H48), C49(H49), C50(H50), C9(H9), C11(H11), C36(H36),
 C34(H34), C10(H10), C60(H60), C35(H35), C62(H62), C22(H22), C24(H24), C61(H61),
  C23(H23)
2.d Idealised Me refined as rotating group:
 C43(H43A,H43B,H43C), C57(H57A,H57B,H57C), C54(H54A,H54B,H54C), C55(H55A,H55B,
 H55C), C52(H52A,H52B,H52C), C41(H41A,H41B,H41C), C67(H67A,H67B,H67C), C31(H31A,
 H31B,H31C), C16(H16A,H16B,H16C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C),
 C15(H15A,H15B,H15C), C64(H64A,H64B,H64C), C38(H38A,H38B,H38C), C69(H69A,H69B,
 H69C), C17(H17A,H17B,H17C), C29(H29A,H29B,H29C), C40(H40A,H40B,H40C), C66(H66A,
 H66B,H66C), C70(H70A,H70B,H70C)
;
_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 4.086
_oxdiff_exptl_absorpt_empirical_full_min 0.519