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_7131873
_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         'C20 H12 Cl F3 N2'
_chemical_formula_sum            'C20 H12 Cl F3 N2'
_chemical_formula_weight         372.76
_space_group_crystal_system      trigonal
_space_group_IT_number           146
_space_group_name_Hall           'R 3'
_space_group_name_H-M_alt        'R 3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-06-16
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-06-16 deposited with the CCDC.	2023-07-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            18
_cell_length_a                   31.8395(3)
_cell_length_b                   31.8395(3)
_cell_length_c                   8.58300(10)
_cell_measurement_reflns_used    31048
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.4260
_cell_measurement_theta_min      4.7600
_cell_volume                     7535.33(13)
_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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4741
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_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   -102.00 -72.00   1.00    1.00    --  -40.50-161.00 130.00   30
  2  \w    -86.00  -6.00   1.00    1.00    --  -40.50 125.00 -90.00   80
  3  \w   -117.00  -9.00   1.00    1.00    --  -40.50 -19.00   0.00  108
  4  \w    -55.00  32.00   1.00    1.00    --  -40.50  37.00-180.00   87
  5  \w     55.00  92.00   1.00    1.00    --   42.79-125.00-180.00   37
  6  \w     57.00 112.00   1.00    1.00    --  111.00-125.00   0.00   55
  7  \w    100.00 176.00   1.00    1.00    --  111.00  45.00-150.00   76
  8  \w    110.00 141.00   1.00    1.00    --  111.00  77.00 -60.00   31
  9  \w     78.00 107.00   1.00    1.00    --  111.00 -94.00  90.00   29
 10  \w     82.00 107.00   1.00    1.00    --  111.00 -94.00-120.00   25
 11  \w     59.00  93.00   1.00    1.00    --  111.00 -61.00   0.00   34
 12  \w     94.00 136.00   1.00    1.00    --  111.00 -61.00   0.00   42
 13  \w     83.00 178.00   1.00    1.00    --  111.00  61.00  90.00   95
 14  \w    104.00 178.00   1.00    1.00    --  111.00  77.00 150.00   74
 15  \w    130.00 157.00   1.00    1.00    --  111.00  77.00  30.00   27
 16  \w     31.00  67.00   1.00    1.00    --  111.00 -94.00-120.00   36
 17  \w     86.00 112.00   1.00    1.00    --  111.00-125.00-180.00   26
 18  \w     40.00 110.00   1.00    1.00    --  111.00 -45.00  90.00   70
 19  \w    122.00 167.00   1.00    1.00    --  111.00 125.00 120.00   45
 20  \w     73.00 107.00   1.00    1.00    --  111.00 -94.00-180.00   34
 21  \w     57.00 103.00   1.00    1.00    --  111.00 -94.00  30.00   46
 22  \w     98.00 165.00   1.00    1.00    --  111.00 125.00  30.00   67
 23  \w     21.00  57.00   1.00    1.00    --   43.04-117.00 -78.00   36
 24  \w    124.00 157.00   1.00    1.00    --  111.00 125.00 -90.00   33
 25  \w     54.00  80.00   1.00    1.00    --  111.00-117.00 -78.00   26
 26  \w     36.00  68.00   1.00    1.00    --  111.00 -30.00 -90.00   32
 27  \w    110.00 135.00   1.00    1.00    --  111.00 -30.00 -90.00   25
 28  \w     81.00 107.00   1.00    1.00    --  111.00 -94.00 120.00   26
 29  \w     98.00 123.00   1.00    1.00    --  111.00-138.00 -17.85   25
 30  \w     64.00  90.00   1.00    1.00    --  111.00-138.00 -17.85   26
 31  \w    -54.00  15.00   1.00    1.00    --  -40.50  37.00 120.00   69
 32  \w     56.00 104.00   1.00    1.00    --   43.04  57.00  60.00   48
 33  \w     16.00  97.00   1.00    1.00    --   43.04  57.00 150.00   81
 34  \w     13.00  42.00   1.00    1.00    --   43.04  79.00  -0.66   29
 35  \w     87.00 113.00   1.00    1.00    --   43.04  57.00 -60.00   26
 36  \w     21.00  92.00   1.00    1.00    --   43.04  37.00-120.00   71
 37  \w     16.00  52.00   1.00    1.00    --   43.04  57.00  60.00   36
 38  \w     16.00  80.00   1.00    1.00    --   43.04  57.00 -60.00   64
 39  \w     10.00  42.00   1.00    1.00    --   43.04  82.00 -62.06   32
 40  \w     11.00  42.00   1.00    1.00    --   43.04  81.00 177.34   31
 41  \w     12.00  41.00   1.00    1.00    --   43.04  79.00  83.38   29
 42  \w     48.00  78.00   1.00    1.00    --   43.04-162.00 131.00   30
 43  \w     12.00  42.00   1.00    1.00    --   43.04  82.00-146.80   30
 44  \w     86.00 112.00   1.00    1.00    --  111.00  48.00 178.05   26
 45  \w     84.00 110.00   1.00    1.00    --  111.00  58.00  43.09   26
 46  \w     82.00 107.00   1.00    1.00    --  111.00  66.00  61.55   25
 47  \w    121.00 147.00   1.00    1.00    --  111.00  64.00 -14.46   26
 48  \w     83.00 108.00   1.00    1.00    --  111.00  64.00 -14.46   25
 49  \w     82.00 108.00   1.00    1.00    --  111.00  66.00  96.11   26
 50  \w     84.00 110.00   1.00    1.00    --  111.00  59.00 -18.14   26
 51  \w    153.00 178.00   1.00    1.00    --  111.00  48.00 -61.42   25
 52  \w     83.00 109.00   1.00    1.00    --  111.00  61.00 -30.00   26
 53  \w     85.00 128.00   1.00    1.00    --  111.00  55.00 141.47   43
 54  \w     83.00 109.00   1.00    1.00    --  111.00  62.00-174.04   26
 55  \w     83.00 128.00   1.00    1.00    --  111.00  61.00 150.00   45
 56  \w     87.00 113.00   1.00    1.00    --  111.00  45.00 -30.00   26
 57  \w     83.00 108.00   1.00    1.00    --  111.00  61.00  30.00   25
 58  \w     83.00 108.00   1.00    1.00    --  111.00  61.00-120.00   25
 59  \w     83.00 159.00   1.00    1.00    --  111.00  61.00   0.00   76
 60  \w     83.00 109.00   1.00    1.00    --  111.00  61.00 -60.00   26
 61  \w     86.00 140.00   1.00    1.00    --  111.00  48.00 -61.42   54
 62  \w     85.00 162.00   1.00    1.00    --  111.00  54.00 -94.92   77
 63  \w     85.00 121.00   1.00    1.00    --  111.00  56.00  58.25   36
 64  \w    150.00 177.00   1.00    1.00    --  111.00  65.00-140.52   27
 65  \w     85.00 158.00   1.00    1.00    --  111.00  55.00  21.75   73
 66  \w     83.00 109.00   1.00    1.00    --  111.00  61.00-150.00   26
 67  \w     83.00 109.00   1.00    1.00    --  111.00  61.00 120.00   26
 68  \w     83.00 109.00   1.00    1.00    --  111.00  65.00-140.52   26
 69  \w     83.00 109.00   1.00    1.00    --  111.00  61.00 -90.00   26
 70  \w     83.00 108.00   1.00    1.00    --  111.00  61.00-180.00   25
 71  \w     83.00 108.00   1.00    1.00    --  111.00  64.00-158.54   25
 72  \w     85.00 111.00   1.00    1.00    --  111.00  53.00  85.64   26
 73  \w     86.00 112.00   1.00    1.00    --  111.00  58.00 112.81   26
;
_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      -0.0456402000
_diffrn_orient_matrix_UB_12      0.0029229000
_diffrn_orient_matrix_UB_13      -0.0400281000
_diffrn_orient_matrix_UB_21      0.0311333000
_diffrn_orient_matrix_UB_22      0.0555686000
_diffrn_orient_matrix_UB_23      -0.0132225000
_diffrn_orient_matrix_UB_31      0.0081544000
_diffrn_orient_matrix_UB_32      -0.0048524000
_diffrn_orient_matrix_UB_33      -0.1744880000
_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  0.0382
_diffrn_reflns_av_unetI/netI     0.0172
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       39
_diffrn_reflns_limit_h_min       -39
_diffrn_reflns_limit_k_max       39
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            46317
_diffrn_reflns_point_group_measured_fraction_full 0.957
_diffrn_reflns_point_group_measured_fraction_max 0.944
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.470
_diffrn_reflns_theta_min         2.776
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.361
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.29508
_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    1.479
_exptl_crystal_description       plate
_exptl_crystal_F_000             3420
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.6
_exptl_crystal_size_min          0.4
_refine_diff_density_max         0.470
_refine_diff_density_min         -0.431
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Flack x determined using 3022 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.001(5)
_refine_ls_extinction_coef       0.00010(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   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     470
_refine_ls_number_reflns         6667
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0430
_refine_ls_R_factor_gt           0.0425
_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^)+(0.0647P)^2^+13.8711P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1127
_refine_ls_wR_factor_ref         0.1133
_reflns_Friedel_coverage         0.901
_reflns_Friedel_fraction_full    0.914
_reflns_Friedel_fraction_max     0.894
_reflns_number_gt                6590
_reflns_number_total             6667
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc02968a2.cif
_cod_data_source_block           exp_19124_auto
_cod_depositor_comments
;

2024-11-08
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C40 H24 Cl2 F6 N4'
_cod_original_formula_weight         745.53
_cod_original_formula_moiety         '2(C20 H12 Cl F3 N2)'
_cod_original_formula_units_Z            9
_cod_original_cell_volume        7535.33(17)
_cod_original_sg_symbol_H-M      'R 3'
_cod_database_code               7131873
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_usercomment     'C H  N Cl F'
_shelx_estimated_absorpt_t_max   0.452
_shelx_estimated_absorpt_t_min   0.254
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 N008(H008), N00A(H00A), C00F(H00F), C00I(H00I), C00Q(H00Q), C00S(H00S),
 C00U(H00U), C00V(H00V), C00Y(H00Y), C00Z(H00Z), C010(H010), C012(H012),
 C013(H013), C015(H015), C016(H016), C017(H017), C018(H018), C019(H019),
 C01A(H01A), C01B(H01B), C01C(H01C), C01E(H01E), C01F(H01F), C01G(H01G)
;
_shelx_res_checksum              6570
_shelx_hkl_checksum              54633
_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 2.139
_oxdiff_exptl_absorpt_empirical_full_min 0.605