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_7131871
_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         'C24 H17 Cl N2'
_chemical_formula_sum            'C24 H17 Cl N2'
_chemical_formula_weight         368.84
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-11-28
_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                 99.321(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.0202(6)
_cell_length_b                   7.3714(3)
_cell_length_c                   16.6190(6)
_cell_measurement_reflns_used    1892
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.8420
_cell_measurement_theta_min      3.6770
_cell_volume                     1815.76(12)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1903
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.980
_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     43.00  68.00   1.00    2.56    --    0.00  57.00 -90.00   25
  2  \w     91.00 120.00   1.00   10.25    --   56.38  87.00  50.00   29
  3  \w     94.00 130.00   1.00   10.25    --   56.38 126.00  60.00   36
  4  \w     87.00 113.00   1.00   10.25    --   56.38 126.00  90.00   26
  5  \w     79.00 177.00   1.00   10.25    --  112.76  77.00  60.00   98
  6  \w    118.00 170.00   1.00   10.25    --  112.76  64.00 -30.00   52
  7  \w    110.00 168.00   1.00   10.25    --  112.76  25.00 120.00   58
  8  \w     51.00 155.00   1.00   10.25    --  112.76 -92.00 -90.00  104
  9  \w     83.00 149.00   1.00   10.25    --  112.76  12.00-120.00   66
 10  \w     41.00  73.00   1.00   10.25    --  112.76  12.00-120.00   32
 11  \w     48.00 135.00   1.00   10.25    --  112.76 -38.00 -90.00   87
 12  \w     48.00  77.00   1.00    2.56    --    0.00 178.00  90.00   29
 13  \w    -79.00   7.00   1.00   10.25    --  -56.38  77.00  30.00   86
 14  \w   -107.00 -81.00   1.00   10.25    --  -56.38 -95.00 -60.00   26
 15  \w   -117.00 -92.00   1.00   10.25    --  -56.38 -95.00 -90.00   25
 16  \w    -86.00 -61.00   1.00   10.25    --  -56.38-152.00-116.00   25
 17  \w    -79.00 -37.00   1.00    2.56    --    0.00-178.00  60.00   42
 18  \w   -133.00 -20.00   1.00   10.25    --  -56.38 -30.00 120.00  113
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3, Ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0450868000
_diffrn_orient_matrix_UB_12      -0.1850207000
_diffrn_orient_matrix_UB_13      -0.0087217000
_diffrn_orient_matrix_UB_21      -0.0122337000
_diffrn_orient_matrix_UB_22      0.0265091000
_diffrn_orient_matrix_UB_23      -0.0931124000
_diffrn_orient_matrix_UB_31      0.0928895000
_diffrn_orient_matrix_UB_32      0.0932711000
_diffrn_orient_matrix_UB_33      0.0090259000
_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  0.0433
_diffrn_reflns_av_unetI/netI     0.0505
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            6076
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.720
_diffrn_reflns_theta_min         3.682
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.929
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59878
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.349
_exptl_crystal_description       block
_exptl_crystal_F_000             768
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.506
_refine_diff_density_min         -0.379
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     245
_refine_ls_number_reflns         3415
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0797
_refine_ls_R_factor_gt           0.0653
_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^)+(0.1281P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1760
_refine_ls_wR_factor_ref         0.2023
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2631
_reflns_number_total             3415
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc02968a2.cif
_cod_data_source_block           exp_24045cxl
_cod_database_code               7131871
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.831
_shelx_estimated_absorpt_t_min   0.831
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 N003(H003), C00E(H00E), C00F(H00F), C00G(H00G), C00H(H00H), C00I(H00I),
 C00J(H00J), C00K(H00K), C00L(H00L), C00M(H00M), C00O(H00O), C00P(H00P),
 C00Q(H00Q), C00R(H00R)
2.b Idealised Me refined as rotating group:
 C00N(H00A,H00B,H00C)
;
_shelx_res_checksum              84623
_shelx_hkl_checksum              26820
_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 1.901
_oxdiff_exptl_absorpt_empirical_full_min 0.669