Rapid and Chemodivergent Synthesis of N-Heterocyclic Sulfones and Sulfides: Mechanistic and Computational Details of the Persulfate-Initiated Catalysis
Nguyen, Viet D.; Nguyen, Vu T.; Haug, Graham C.; Dang, Hang T.; Arman, Hadi D.; Ermler, Walter C.; Larionov, Oleg V.; ACS Catalysis 9 (2019) 4015–; doi:10.1021/acscatal.9b00464

data_4514717
_publ_section_title
;
 Rapid and Chemodivergent Synthesis of N-Heterocyclic Sulfones and
 Sulfides: Mechanistic and Computational Details of the
 Persulfate-Initiated Catalysis
;
_journal_issue                   5
_journal_name_full               'ACS Catalysis'
_journal_page_first              4015
_journal_paper_doi               10.1021/acscatal.9b00464
_journal_volume                  9
_journal_year                    2019
_chemical_formula_moiety         'C18 H10 Br2 N2 O2 S'
_chemical_formula_sum            'C18 H10 Br2 N2 O2 S'
_chemical_formula_weight         478.16
_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'
_symmetry_space_group_name_Hall  '-I 2ya'
_symmetry_space_group_name_H-M   'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-06-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 105.417(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.7962(6)
_cell_length_b                   4.9199(2)
_cell_length_c                   19.1526(6)
_cell_measurement_reflns_used    7936
_cell_measurement_temperature    98(2)
_cell_measurement_theta_max      29.3560
_cell_measurement_theta_min      2.2210
_cell_volume                     1616.57(10)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28e (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28e (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28e (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      98(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -85.00  35.00   1.00   45.00    --    4.20 -59.00 152.00  120
  2  \w    -38.00  82.00   1.00   45.00    --   -7.60  59.00 -67.00  120
  3  \w    -85.00  34.00   1.00   45.00    --    4.20 -57.00 -60.00  119
  4  \w    -97.00  30.00   1.00   45.00    --   -7.60 -19.00  90.00  127
  5  \w    -32.00  82.00   1.00   45.00    --   -7.60  38.00  30.00  114
  6  \w    -32.00  45.00   1.00   45.00    --   -7.60  38.00-120.00   77
  7  \w    -32.00  82.00   1.00   45.00    --   -7.60  38.00 120.00  114
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RCD3): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0312723000
_diffrn_orient_matrix_UB_12      -0.0738898000
_diffrn_orient_matrix_UB_13      0.0073051000
_diffrn_orient_matrix_UB_21      -0.0059452000
_diffrn_orient_matrix_UB_22      -0.0685858000
_diffrn_orient_matrix_UB_23      -0.0336073000
_diffrn_orient_matrix_UB_31      0.0263791000
_diffrn_orient_matrix_UB_32      -0.1030789000
_diffrn_orient_matrix_UB_33      0.0171287000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0524
_diffrn_reflns_av_unetI/netI     0.0212
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            18018
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.984
_diffrn_reflns_theta_min         2.206
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    5.159
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.26420
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28e (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.965
_exptl_crystal_description       plate
_exptl_crystal_F_000             936
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.33
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.499
_refine_diff_density_min         -0.331
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     114
_refine_ls_number_reflns         1584
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0249
_refine_ls_R_factor_gt           0.0232
_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^)+(0.0400P)^2^+3.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0640
_refine_ls_wR_factor_ref         0.0656
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1506
_reflns_number_total             1584
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b00464_si_009.cif
_cod_data_source_block           cd1708b
_cod_database_code               4514717
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C18H10Br2SO2N2
_chemical_oxdiff_usercomment     'Oxidized sample'
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C5(H5), C7(H7), C8(H8)
;
_olex2_exptl_crystal_mounting_method 'nylon loop'
_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 2.693
_oxdiff_exptl_absorpt_empirical_full_min 0.657