Site-selective radical reactions of kinetically stable open-shell singlet diradicaloid difluorenoheteroles with tributyltin hydride and azo-based radical initiators.
Tabata, Naoki; Uchino, Takumi; Kitamura, Chitoshi; Yoshizawa, Kazunari; Shiota, Yoshihito; Kato, Shin-Ichiro; Chemical science 14 (2023) 5974–5982; doi:10.1039/d3sc00381g

data_1569179
_publ_section_title
;
 Site-selective radical reactions of kinetically stable open-shell singlet
 diradicaloid difluorenoheteroles with tributyltin hydride and azo-based
 radical initiators.
;
_journal_issue                   22
_journal_name_full               'Chemical science'
_journal_page_first              5974
_journal_page_last               5982
_journal_paper_doi               10.1039/d3sc00381g
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C52 H46 N2 S, C2 H3 N'
_chemical_formula_sum            'C54 H49 N3 S'
_chemical_formula_weight         772.02
_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             2021-01-22
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2022-12-20 deposited with the CCDC.	2023-05-15 downloaded from the CCDC.
;
_cell_angle_alpha                65.994(6)
_cell_angle_beta                 87.485(5)
_cell_angle_gamma                71.975(6)
_cell_formula_units_Z            2
_cell_length_a                   11.0183(8)
_cell_length_b                   14.4087(10)
_cell_length_c                   17.3579(9)
_cell_measurement_reflns_used    7707
_cell_measurement_temperature    113
_cell_measurement_theta_max      30.0660
_cell_measurement_theta_min      2.1760
_cell_volume                     2383.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      113
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku Saturn70 area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_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   -110.00  70.00   0.50   40.00    --  -20.00  45.00 180.00  360
  2  \w   -110.00  70.00   0.50   40.00    --  -20.00  45.00 270.00  360
  3  \w   -110.00  70.00   0.50   40.00    --  -20.00  45.00  90.00  360
  4  \w   -110.00  70.00   0.50   40.00    --  -20.00  45.00   0.00  360
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0157127000
_diffrn_orient_matrix_UB_12      -0.0412906000
_diffrn_orient_matrix_UB_13      -0.0145922000
_diffrn_orient_matrix_UB_21      -0.0144576000
_diffrn_orient_matrix_UB_22      0.0391030000
_diffrn_orient_matrix_UB_23      -0.0424712000
_diffrn_orient_matrix_UB_31      0.0645614000
_diffrn_orient_matrix_UB_32      -0.0003312000
_diffrn_orient_matrix_UB_33      -0.0014920000
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1182
_diffrn_reflns_av_unetI/netI     0.1385
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            39193
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.485
_diffrn_reflns_theta_min         1.952
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_current           16.0000
_diffrn_source_power             0.8000
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    0.104
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72482
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.076
_exptl_crystal_description       prism
_exptl_crystal_F_000             820
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.485
_refine_diff_density_min         -0.470
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.975
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     545
_refine_ls_number_reflns         10929
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.975
_refine_ls_R_factor_all          0.1642
_refine_ls_R_factor_gt           0.0884
_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^)+(0.1186P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2055
_refine_ls_wR_factor_ref         0.2488
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5540
_reflns_number_total             10929
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc00381g2.cif
_cod_data_source_block           kato2101f
_cod_depositor_comments          'Adding full bibliography for 1569179.cif.'
_cod_database_code               1569179
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_shelx_estimated_absorpt_t_max   0.998
_shelx_estimated_absorpt_t_min   0.979
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(H50A)=Sof(H50B)=Sof(H50C)=Sof(N3)=1-FVAR(1)
 Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(N2)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C18(H18), C9(H9)
3.b Aromatic/amide H refined with riding coordinates:
 C23(H23), C20(H20), C21(H21), C4(H4), C29(H29), C15(H15), C40(H40), C11(H11),
 C6(H6), C7(H7), C12(H12), C31(H31), C16(H16), C38(H38)
3.c Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C), C44(H44A,H44B,H44C), C51(H51A,H51B,H51C), C52(H52A,H52B,
 H52C), C50(H50A,H50B,H50C), C43(H43A,H43B,H43C), C35(H35A,H35B,H35C), C34(H34A,
 H34B,H34C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C42(H42A,H42B,H42C),
 C53(H53A,H53B,H53C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              78004
_shelx_fab_checksum              73755
_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 1.922
_oxdiff_exptl_absorpt_empirical_full_min 0.586