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_4514729
_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         'C22 H22 Cl N O2 S'
_chemical_formula_sum            'C22 H22 Cl N O2 S'
_chemical_formula_weight         399.91
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-02-05
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 106.677(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.7798(3)
_cell_length_b                   11.6418(2)
_cell_length_c                   22.1990(4)
_cell_measurement_reflns_used    17213
_cell_measurement_temperature    98(2)
_cell_measurement_theta_max      30.4030
_cell_measurement_theta_min      2.6510
_cell_volume                     3906.54(13)
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  15.00   1.00   45.00    --   -9.70 -38.00 -30.00  114
  2  \w    -99.00  28.00   1.00   45.00    --   -9.70 -19.00-120.00  127
  3  \w    -99.00  15.00   1.00   45.00    --   -9.70 -38.00  90.00  114
  4  \w    -42.00  34.00   1.00   45.00    --   -9.70  72.00-120.00   76
  5  \w    -39.00  80.00   1.00   45.00    --   -9.70  57.00  30.00  119
;
_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      0.0017770000
_diffrn_orient_matrix_UB_12      -0.0497217000
_diffrn_orient_matrix_UB_13      -0.0180640000
_diffrn_orient_matrix_UB_21      -0.0468780000
_diffrn_orient_matrix_UB_22      -0.0023109000
_diffrn_orient_matrix_UB_23      -0.0099328000
_diffrn_orient_matrix_UB_31      -0.0005795000
_diffrn_orient_matrix_UB_32      0.0351483000
_diffrn_orient_matrix_UB_33      -0.0262199000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0315
_diffrn_reflns_av_unetI/netI     0.0159
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            28961
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.489
_diffrn_reflns_theta_min         2.556
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.320
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90914
_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    1.360
_exptl_crystal_description       plate
_exptl_crystal_F_000             1680
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.34
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.440
_refine_diff_density_min         -0.383
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     245
_refine_ls_number_reflns         3631
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0374
_refine_ls_R_factor_gt           0.0372
_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^)+(0.0350P)^2^+9.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0874
_refine_ls_wR_factor_ref         0.0875
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3611
_reflns_number_total             3631
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b00464_si_005.cif
_cod_data_source_block           cd1653
_cod_database_code               4514729
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.960
_shelx_estimated_absorpt_t_min   0.883
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C17(H17)
2.b Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B), C18(H18A,H18B), C20(H20A,H20B), C21(H21A,H21B), C19(H19A,H19B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C8(H8), C2(H2), C4(H4), C15(H15), C11(H11), C14(H14), C12(H12)
2.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C)
;
_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 1.111
_oxdiff_exptl_absorpt_empirical_full_min 0.880