A double-helical S,C-bridged tetraphenyl-<i>para</i>-phenylenediamine and its persistent radical cation.
Harada, Kaho; Hasegawa, Chika; Matsumoto, Taisuke; Sugishita, Hiroki; Kitamura, Chitoshi; Higashibayashi, Shuhei; Hasegawa, Masashi; Suzuki, Shuichi; Kato, Shin-Ichiro; Chemical communications (Cambridge, England) 59 (2023) 1301–1304; doi:10.1039/d2cc06144a

data_7131152
_publ_section_title
;
 A double-helical S,C-bridged tetraphenyl-<i>para</i>-phenylenediamine and
 its persistent radical cation.
;
_journal_issue                   10
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              1301
_journal_page_last               1304
_journal_paper_doi               10.1039/d2cc06144a
_journal_volume                  59
_journal_year                    2023
_chemical_formula_moiety         'C36 H28 N2 S2, C2 F6 N O4 S2, C0.5 H2 Cl'
_chemical_formula_sum            'C38.5 H30 Cl F6 N3 O4 S4'
_chemical_formula_weight         876.34
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-02-01
_audit_creation_method
;
Olex2 1.5-ac5-020
(compiled 2021.11.16 svn.r5db059d7 for Rigaku Oxford Diffraction, GUI svn.r6430)
;
_audit_update_record
;
2022-06-13 deposited with the CCDC.	2022-12-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 116.638(6)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   31.1922(15)
_cell_length_b                   9.4751(3)
_cell_length_c                   28.2134(13)
_cell_measurement_reflns_used    10105
_cell_measurement_temperature    100.06(10)
_cell_measurement_theta_max      75.6240
_cell_measurement_theta_min      3.2070
_cell_volume                     7453.4(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.41a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.41a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.41a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-ac5-020 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-020 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.06(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.976
_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     99.00 150.00   0.50    0.05    --  107.00  30.00  90.00  102
  2  \w    104.00 176.00   0.50    0.05    --  107.00  45.00 150.00  144
  3  \w    108.00 157.00   0.50    0.05    --  107.00  30.00 120.00   98
  4  \w    102.00 128.00   0.50    0.05    --  107.00  15.00  60.00   52
  5  \w     99.00 127.00   0.50    0.05    --  107.00  15.00 -30.00   56
  6  \w    100.00 167.00   0.50    0.05    --  107.00  30.00-120.00  134
  7  \w    110.00 136.00   0.50    0.05    --  107.00 125.00 120.00   52
  8  \w    146.00 172.00   0.50    0.05    --  107.00 125.00 120.00   52
  9  \w    -29.00  -4.00   0.50    0.05    --   44.35 -38.00-180.00   50
 10  \w     33.00  74.00   0.50    0.05    --  107.00 -77.00-180.00   82
 11  \w     43.00  68.00   0.50    0.05    --  107.00 -77.00 -30.00   50
 12  \w     39.00  77.00   0.50    0.05    --  107.00 -77.00 120.00   76
 13  \w     68.00  94.00   0.50    0.05    --  107.00 -88.00  90.88   52
 14  \w     44.00  84.00   0.50    0.05    --  107.00 -94.00  60.00   80
 15  \w     42.00  94.00   0.50    0.05    --  107.00 -98.00  94.99  104
 16  \w     70.00  95.00   0.50    0.05    --  107.00 -90.00 120.75   50
 17  \w     63.00  95.00   0.50    0.05    --  107.00 -90.00 101.34   64
 18  \w     33.00  59.00   0.50    0.05    --  107.00 -90.00 101.34   52
 19  \w     40.00  66.00   0.50    0.05    --  107.00 -90.00 120.75   52
 20  \w     37.00  69.00   0.50    0.05    --  107.00-125.00-120.00   64
 21  \w     48.00  83.00   0.50    0.05    --  107.00 -94.00-120.00   70
 22  \w     65.00  91.00   0.50    0.05    --  107.00 -94.00-180.00   52
 23  \w   -126.00-100.00   0.50    0.05    -- -104.00 -15.00  90.00   52
 24  \w   -126.00-100.00   0.50    0.05    -- -104.00 -30.00 150.00   52
 25  \w   -159.00-133.00   0.50    0.05    -- -104.00 -30.00 150.00   52
 26  \w   -143.00-108.00   0.50    0.05    -- -104.00 -77.00 -90.00   70
 27  \w    -95.00 -64.00   0.50    0.05    -- -104.00  91.00 162.12   62
 28  \w    -64.00 -10.00   0.50    0.05    --  -44.35  77.00  60.00  108
 29  \w    -11.00  27.00   0.50    0.05    --  -44.35  38.00 120.00   76
 30  \w    -16.00  28.00   0.50    0.05    --  -44.35  38.00  90.00   88
 31  \w    -17.00  32.00   0.50    0.05    --  -44.35  38.00 -30.00   98
 32  \w    -15.00  27.00   0.50    0.05    --  -44.35  38.00-150.00   84
 33  \w    -17.00  30.00   0.50    0.05    --  -44.35  38.00-180.00   94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0533909000
_diffrn_orient_matrix_UB_12      0.0066288000
_diffrn_orient_matrix_UB_13      0.0403560000
_diffrn_orient_matrix_UB_21      -0.0139225000
_diffrn_orient_matrix_UB_22      -0.0074643000
_diffrn_orient_matrix_UB_23      0.0458710000
_diffrn_orient_matrix_UB_31      0.0028103000
_diffrn_orient_matrix_UB_32      -0.1622865000
_diffrn_orient_matrix_UB_33      -0.0004820000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0771
_diffrn_reflns_av_unetI/netI     0.0718
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            27685
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.771
_diffrn_reflns_theta_min         3.170
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.684
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.96322
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.41a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.562
_exptl_crystal_description       plate
_exptl_crystal_F_000             3592
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.039
_exptl_crystal_size_min          0.019
_refine_diff_density_max         0.332
_refine_diff_density_min         -0.632
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     524
_refine_ls_number_reflns         7571
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0730
_refine_ls_R_factor_gt           0.0452
_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^)+(0.0401P)^2^+7.6756P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1007
_refine_ls_wR_factor_ref         0.1111
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5441
_reflns_number_total             7571
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc06144a2.cif
_cod_data_source_block           ks2201d_auto
_cod_depositor_comments
'Adding full bibliography for 7131149--7131152.cif.'
_cod_original_formula_sum        'C38.50 H30 Cl F6 N3 O4 S4'
_cod_database_code               7131152
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.343
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(H57C)=Sof(H57D)=Sof(Cl)=1-FVAR(1)
 Sof(Cl56)=Sof(H57A)=Sof(H57B)=FVAR(1)
3.a Secondary CH2 refined with riding coordinates:
 C57(H57A,H57B), C57(H57C,H57D)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C32(H32), C17(H17), C9(H9), C31(H31), C23(H23), C38(H38), C6(H6),
 C29(H29), C37(H37), C36(H36), C8(H8), C25(H25), C7(H7), C30(H30), C24(H24)
3.c Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C34(H34A,H34B,H34C), C39(H39A,H39B,H39C), C40(H40A,H40B,
 H40C)
;
_shelx_res_checksum              14798
_shelx_hkl_checksum              19657
_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 1.261
_oxdiff_exptl_absorpt_empirical_full_min 0.815