Synthesis of aminyl biradicals by base-induced Csp3‒Csp3 coupling of cationic azo dyes
Liu, Yizhu; Varava, Paul; Fabrizio, Alberto; Eymann, Léonard Y. M.; Tskhovrebov, Alexander G.; Planes, Ophélie Marie; Solari, Euro; Fadaei-Tirani, Farzaneh; Scopelliti, Rosario; Sienkiewicz, Andrzej; Corminboeuf, Clémence; Severin, Kay; Chemical Science  (2019) –; doi:10.1039/C9SC01502G

data_1550996
_publ_section_title
;
 Synthesis of aminyl biradicals by base-induced Csp3--Csp3 coupling of
 cationic azo dyes
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC01502G
_journal_year                    2019
_chemical_formula_moiety         'C60 H68 N8, C4 H8 O'
_chemical_formula_sum            'C64 H76 N8 O'
_chemical_formula_weight         973.32
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2018/3
_audit_update_record
;
2019-03-18 deposited with the CCDC.    2019-05-03 downloaded from the CCDC.
;
_cell_angle_alpha                91.897(5)
_cell_angle_beta                 104.054(6)
_cell_angle_gamma                98.399(6)
_cell_formula_units_Z            4
_cell_length_a                   12.8101(9)
_cell_length_b                   22.7080(15)
_cell_length_c                   23.9152(16)
_cell_measurement_reflns_used    3043
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      57.4440
_cell_measurement_theta_min      4.1260
_cell_volume                     6659.1(8)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Mercury 4.0.0 (CCDC, 2018)'
_computing_publication_material  'CIFTab (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      140.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2665
_diffrn_detector_type            Atlas
_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    -71.00  30.00   1.00   10.00    --  -43.01  57.00 -30.00  101
  2  \w    -72.00  -2.00   1.00   10.00    --  -43.01 125.00  60.00   70
  3  \w   -113.00 -23.00   1.00   10.00    --  -43.01 -57.00-180.00   90
  4  \w     20.00 113.00   1.00   10.00    --   43.01  37.00  90.00   93
  5  \w     69.00  96.00   1.00   10.00    --   43.01-125.00 -30.00   27
  6  \w     38.00 117.00   1.00   40.00    --  105.68-125.00 120.00   79
  7  \w     33.00  60.00   1.00   40.00    --  105.68 -61.00 150.00   27
  8  \w     34.00 119.00   1.00   40.00    --  105.68 -77.00 -60.00   85
  9  \w     43.00 119.00   1.00   40.00    --  105.68 -45.00 -60.00   76
 10  \w     60.00 131.00   1.00   40.00    --  105.68 -45.00  30.00   71
 11  \w     40.00 118.00   1.00   40.00    --  105.68-125.00 -30.00   78
 12  \w     62.00  89.00   1.00   40.00    --  105.68 -94.00-120.00   27
 13  \w    105.00 177.00   1.00   40.00    --  105.68  77.00  90.00   72
 14  \w     42.00 128.00   1.00   40.00    --  105.68 -45.00 150.00   86
 15  \w     50.00 107.00   1.00   40.00    --  105.68 -94.00 150.00   57
 16  \w     19.00 170.00   1.00   40.00    --  105.68   0.00 -90.00  151
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_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  0.0848
_diffrn_reflns_av_unetI/netI     0.1297
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            50119
_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         73.685
_diffrn_reflns_theta_min         3.603
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.450
_exptl_absorpt_correction_T_max  0.957
_exptl_absorpt_correction_T_min  0.909
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear intense red'
_exptl_crystal_density_diffrn    0.971
_exptl_crystal_description       plate
_exptl_crystal_F_000             2096
_exptl_crystal_size_max          0.247
_exptl_crystal_size_mid          0.212
_exptl_crystal_size_min          0.111
_refine_diff_density_max         0.377
_refine_diff_density_min         -0.307
_refine_diff_density_rms         0.038
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.920
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1347
_refine_ls_number_reflns         26071
_refine_ls_number_restraints     1341
_refine_ls_restrained_S_all      0.919
_refine_ls_R_factor_all          0.1845
_refine_ls_R_factor_gt           0.0764
_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^)+(0.0660P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1716
_refine_ls_wR_factor_ref         0.2388
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9330
_reflns_number_total             26071
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc01502g2.cif
_cod_data_source_block           yzl831_sq
_cod_database_code               1550996
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.897
_shelx_estimated_absorpt_t_max   0.952
_shelx_res_checksum              74563
_shelx_fab_checksum              32149