A transition metal- and photosensitizer-free approach for site-selective (hetero)arylation of polychlorinated heteroarenes
Cheng, Xiuliang; He, Yuhang; Song, Silin; Lin, Yu-Mei; Gong, Lei; Chemical Communications  (2023) –; doi:10.1039/D3CC02968A

data_7131870
_publ_section_title
;
 A transition metal- and photosensitizer-free approach for site-selective
 (hetero)arylation of polychlorinated heteroarenes
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC02968A
_journal_year                    2023
_chemical_formula_moiety         'C26 H19 Cl N2 O2'
_chemical_formula_sum            'C26 H19 Cl N2 O2'
_chemical_formula_weight         426.88
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-02-26
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-03-17 deposited with the CCDC.	2023-07-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 115.156(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.4970(6)
_cell_length_b                   7.6930(2)
_cell_length_c                   25.2904(7)
_cell_measurement_reflns_used    3034
_cell_measurement_temperature    233.00(10)
_cell_measurement_theta_max      74.0800
_cell_measurement_theta_min      3.8480
_cell_volume                     4138.0(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      233.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4741
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.969
_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 -28.00   1.00    1.00    --  -40.50 -37.00  90.00   82
  2  \w   -108.00 -21.00   1.00    1.00    --  -40.50 -37.00   0.00   87
  3  \w     63.00  88.00   1.00    1.00    --   43.04-125.00  30.00   25
  4  \w     37.00 103.00   1.00    1.48    --  107.03-125.00   0.00   66
  5  \w     43.00  97.00   1.00    1.48    --  107.03-125.00-150.00   54
  6  \w    151.00 177.00   1.00    1.48    --  107.03  77.00-150.00   26
  7  \w     90.00 164.00   1.00    1.48    --  107.03  45.00 -60.00   74
  8  \w     69.00 109.00   1.00    1.48    --  107.03-125.00 120.00   40
  9  \w     36.00  81.00   1.00    1.48    --  107.03 -45.00-150.00   45
 10  \w     83.00 168.00   1.00    1.48    --  107.03  30.00  30.00   85
 11  \w     72.00 109.00   1.00    1.48    --  107.03 -30.00 -60.00   37
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0579119000
_diffrn_orient_matrix_UB_12      -0.0053649000
_diffrn_orient_matrix_UB_13      -0.0137368000
_diffrn_orient_matrix_UB_21      -0.0421092000
_diffrn_orient_matrix_UB_22      0.0440076000
_diffrn_orient_matrix_UB_23      -0.0643416000
_diffrn_orient_matrix_UB_31      0.0111095000
_diffrn_orient_matrix_UB_32      0.1952064000
_diffrn_orient_matrix_UB_33      0.0141087000
_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  0.0383
_diffrn_reflns_av_unetI/netI     0.0457
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            7981
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.272
_diffrn_reflns_theta_min         3.862
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.845
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91775
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.370
_exptl_crystal_description       BAR
_exptl_crystal_F_000             1776
_exptl_crystal_recrystallization_method 'phi and omega scans'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.241
_refine_diff_density_min         -0.204
_refine_diff_density_rms         0.043
_refine_ls_extinction_coef       0.00029(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.103
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     282
_refine_ls_number_reflns         4089
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.103
_refine_ls_R_factor_all          0.0609
_refine_ls_R_factor_gt           0.0418
_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^)+(0.0336P)^2^+2.3026P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1002
_refine_ls_wR_factor_ref         0.1097
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3109
_reflns_number_total             4089
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc02968a2.cif
_cod_data_source_block           exp_18256-cxl-0224_auto
_cod_database_code               7131870
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHON
_shelx_estimated_absorpt_t_max   0.709
_shelx_estimated_absorpt_t_min   0.608
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C00S(H00A,H00B)
2.b Aromatic/amide H refined with riding coordinates:
 N005(H005), C(H), C00G(H00G), C00H(H00H), C00I(H00I), C00J(H00J), C00L(H00L),
 C00M(H00M), C00O(H00O), C00P(H00P), C00Q(H00Q), C00R(H00R), C00T(H00T),
 C00U(H00U)
2.c Idealised Me refined as rotating group:
 C00V(H00C,H00D,H00E)
;
_shelx_res_checksum              85491
_shelx_hkl_checksum              19840
_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 1.144
_oxdiff_exptl_absorpt_empirical_full_min 0.742