Electrochemical oxidative Z-selective C(sp2)–H chlorination of acrylamides
Harnedy, James; Hareram, Mishra Deepak; Tizzard, Graham J.; Coles, Simon J.; Morrill, Louis C.; Chemical Communications  (2021) –; doi:10.1039/D1CC05824J

data_7129228
_publ_section_title
;
 Electrochemical oxidative Z-selective C(sp2)--H chlorination of
 acrylamides
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC05824J
_journal_year                    2021
_chemical_formula_moiety         'C17 H16 Cl N O3 S'
_chemical_formula_sum            'C17 H16 Cl N O3 S'
_chemical_formula_weight         349.82
_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             2021-03-30
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-08-20 deposited with the CCDC.	2021-11-04 downloaded from the CCDC.
;
_cell_angle_alpha                80.648(3)
_cell_angle_beta                 88.789(3)
_cell_angle_gamma                84.471(4)
_cell_formula_units_Z            2
_cell_length_a                   8.7344(4)
_cell_length_b                   8.9409(4)
_cell_length_c                   10.7084(3)
_cell_measurement_reflns_used    10857
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      32.5040
_cell_measurement_theta_min      1.9140
_cell_volume                     821.29(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_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      100(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10
_diffrn_detector_dtime           0.000
_diffrn_detector_type            'Rigaku, HyPix 6000'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.860
_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    -99.00  22.00   0.50   25.00    --   -9.90 -60.00  30.00  242
  2  \w    -99.00  21.00   0.50   25.00    --   -9.90 -57.00 150.00  240
  3  \w    -99.00  21.00   0.50   25.00    --   -9.90 -57.00-120.00  240
  4  \w    -99.00  80.00   0.50   25.00    --   -9.90   0.00   0.00  358
  5  \w    -42.00  80.00   0.50   25.00    --   -9.90  60.00   0.00  244
  6  \w    -42.00  80.00   0.50   25.00    --   -9.90  60.00-150.00  244
  7  \w    -41.00 -10.00   0.50   25.00    --   -9.90  57.00  90.00   62
  8  \w    -41.00  80.00   0.50   25.00    --   -9.90  57.00 120.00  242
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_details 'Rigaku, AFC12 \k goniometer'
_diffrn_measurement_device_type
'Rigaku FRE+ equipped with VHF Varimax confocal mirrors and an AFC12 goniometer and HyPix 6000 detector'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroLoop'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0805959000
_diffrn_orient_matrix_UB_12      0.0001047000
_diffrn_orient_matrix_UB_13      -0.0095695000
_diffrn_orient_matrix_UB_21      -0.0099639000
_diffrn_orient_matrix_UB_22      -0.0005095000
_diffrn_orient_matrix_UB_23      -0.0654901000
_diffrn_orient_matrix_UB_31      -0.0078517000
_diffrn_orient_matrix_UB_32      0.0807584000
_diffrn_orient_matrix_UB_33      -0.0112260000
_diffrn_radiation_collimation    'Varimax focusing mirrors'
_diffrn_radiation_monochromator  'Confocal mirrors, VHF Varimax'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71075
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0763
_diffrn_reflns_av_unetI/netI     0.0475
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.860
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            24406
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.860
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.615
_diffrn_reflns_theta_min         1.927
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           55.0
_diffrn_source_power             2.475
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku FRE+'
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    0.373
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68028
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.103a (Rigaku Oxford Diffraction, 2021)
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    1.415
_exptl_crystal_description       'block (cut fragment)'
_exptl_crystal_F_000             364
_exptl_crystal_recrystallization_method 'The material was as supplied'
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.685
_refine_diff_density_min         -0.598
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     210
_refine_ls_number_reflns         5152
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0687
_refine_ls_R_factor_gt           0.0522
_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^)+(0.0746P)^2^+0.3199P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1333
_refine_ls_wR_factor_ref         0.1443
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4065
_reflns_number_total             5152
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc05824j2.cif
_cod_data_source_block           2021ncs0078z
_cod_database_code               7129228
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C17 H16 Cl N O3 S'
_chemical_oxdiff_usercomment     JRH80Product
_shelx_estimated_absorpt_t_max   0.936
_shelx_estimated_absorpt_t_min   0.912
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.64
_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.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C12(H12), C13(H13), C15(H15),
 C16(H16)
2.b Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C17(H17A,H17B,H17C)
;
_shelx_res_checksum              44667
_olex2_date_sample_data_collection 2021-03-24
_olex2_date_sample_submission    2021-02-24
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_original_sample_id JRH80Product
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 4.304
_oxdiff_exptl_absorpt_empirical_full_min 0.251