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_1571076
_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, C2 H3 N'
_chemical_formula_sum            'C71 H93 N5 O2 P2'
_chemical_formula_weight         1110.44
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   30.4484(2)
_cell_length_b                   15.17880(10)
_cell_length_c                   14.02580(10)
_cell_measurement_reflns_used    28873
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      73.8920
_cell_measurement_theta_min      3.2600
_cell_volume                     6482.31(8)
_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 1.000
_diffrn_measured_fraction_theta_max 0.991
_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     38.00  64.00   0.50    0.50    --    0.00  38.00  90.00   52
  2  \w    -10.00  15.00   0.50    0.50    --    0.00  38.00-180.00   50
  3  \w    -23.00   2.00   0.50    0.50    --    0.00 -38.00  60.00   50
  4  \w    -88.00  17.00   0.50    0.50    --    0.00 -38.00 -60.00  210
  5  \w     -7.00  18.00   0.50    0.50    --    0.00  38.00  90.00   50
  6  \w     20.00  81.00   0.50    0.50    --    0.00  38.00-180.00  122
  7  \w    -20.00   9.00   0.50    0.50    --    0.00 -38.00 -90.00   58
  8  \w      7.00 114.00   0.50    1.64    --   95.20 -15.00 150.00  214
  9  \w     61.00  94.00   0.50    1.64    --   95.20 -30.00  30.00   66
 10  \w      8.00 115.00   0.50    1.64    --   95.20 -45.00   0.00  214
 11  \w     18.00 109.00   0.50    1.64    --   95.20 -61.00   0.00  182
 12  \w    114.00 177.00   0.50    1.64    --   95.20  30.00 -60.00  126
 13  \w    154.00 179.00   0.50    1.64    --   95.20   0.00 -30.00   50
 14  \w    154.00 184.00   0.50    1.64    --   95.20  30.00 -90.00   60
 15  \w     33.00 117.00   0.50    1.64    --   95.20   0.00 -30.00  168
 16  \w     93.00 119.00   0.50    1.64    --   95.20  30.00 120.00   52
 17  \w    133.00 159.00   0.50    1.64    --   95.20  30.00 120.00   52
 18  \w    142.00 168.00   0.50    1.64    --   95.20  30.00-180.00   52
 19  \w     60.00 110.00   0.50    1.64    --   95.20 -61.00-180.00  100
;
_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      -0.0072459000
_diffrn_orient_matrix_UB_12      0.0877708000
_diffrn_orient_matrix_UB_13      0.0527914000
_diffrn_orient_matrix_UB_21      -0.0233378000
_diffrn_orient_matrix_UB_22      0.0376372000
_diffrn_orient_matrix_UB_23      -0.0885310000
_diffrn_orient_matrix_UB_31      -0.0443108000
_diffrn_orient_matrix_UB_32      -0.0342477000
_diffrn_orient_matrix_UB_33      0.0380210000
_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  0.0382
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            44409
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.152
_diffrn_reflns_theta_min         2.903
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.967
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68263
_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    1.138
_exptl_crystal_description       block
_exptl_crystal_F_000             2400
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.377
_refine_diff_density_min         -0.271
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 5405 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.007(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     741
_refine_ls_number_reflns         12612
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0341
_refine_ls_R_factor_gt           0.0331
_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^)+(0.0525P)^2^+1.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0888
_refine_ls_wR_factor_ref         0.0895
_reflns_Friedel_coverage         0.852
_reflns_Friedel_fraction_full    0.966
_reflns_Friedel_fraction_max     0.920
_reflns_number_gt                12213
_reflns_number_total             12612
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00201f2.cif
_cod_data_source_block           2c
_cod_depositor_comments
'Adding full bibliography for 1571075--1571082.cif.'
_cod_database_code               1571076
_shelx_shelxl_version_number     2014/7
_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(C16) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
3.a Ternary CH refined with riding coordinates:
 C42(H42), C30(H30), C39(H39), C53(H53), C27(H27), C68(H68), C65(H65), C56(H56)
3.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C45(H45A,H45B), C44(H44A,H44B), C19(H19A,H19B)
3.c Aromatic/amide H refined with riding coordinates:
 C24(H24), C22(H22), C34(H34), C61(H61), C60(H60), C62(H62), C8(H8), C35(H35),
 C50(H50), C12(H12), C23(H23), C36(H36), C11(H11), C48(H48), C10(H10), C49(H49),
  C9(H9)
3.d Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C), C41(H41A,H41B,H41C), C40(H40A,H40B,H40C), C29(H29A,H29B,
 H29C), C26(H26A,H26B,H26C), C43(H43A,H43B,H43C), C54(H54A,H54B,H54C), C31(H31A,
 H31B,H31C), C67(H67A,H67B,H67C), C52(H52A,H52B,H52C), C57(H57A,H57B,H57C),
 C66(H66A,H66B,H66C), C28(H28A,H28B,H28C), C55(H55A,H55B,H55C), C64(H64A,H64B,
 H64C), C71(H71A,H71B,H71C), C17(H17A,H17B,H17C), C69(H69A,H69B,H69C), C14(H14A,
 H14B,H14C), C16(H16A,H16B,H16C)
;
_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 1.956
_oxdiff_exptl_absorpt_empirical_full_min 0.563