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_4514724
_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_absolute_configuration ad
_chemical_formula_moiety         'C14 H13 N O2 S'
_chemical_formula_sum            'C14 H13 N O2 S'
_chemical_formula_weight         259.31
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-11-28
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.9497(10)
_cell_length_b                   9.3068(14)
_cell_length_c                   15.3890(17)
_cell_measurement_reflns_used    4147
_cell_measurement_temperature    98(2)
_cell_measurement_theta_max      29.6850
_cell_measurement_theta_min      2.6190
_cell_volume                     1281.8(3)
_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    -99.00  -2.00   1.00   35.00    --   -9.70 -32.00 165.00   97
  2  \w    -68.00 -42.00   1.00   35.00    --    4.20 -38.00-120.00   26
  3  \w    -33.00  15.00   1.00   35.00    --   -9.70 -38.00   0.00   48
  4  \w    -95.00 -37.00   1.00   35.00    --   -9.70 -38.00   0.00   58
;
_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      -0.0178325000
_diffrn_orient_matrix_UB_12      -0.0730071000
_diffrn_orient_matrix_UB_13      -0.0080968000
_diffrn_orient_matrix_UB_21      -0.0701044000
_diffrn_orient_matrix_UB_22      0.0211803000
_diffrn_orient_matrix_UB_23      -0.0172970000
_diffrn_orient_matrix_UB_31      0.0324480000
_diffrn_orient_matrix_UB_32      0.0053848000
_diffrn_orient_matrix_UB_33      -0.0419345000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0342
_diffrn_reflns_av_unetI/netI     0.0371
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            8472
_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         26.494
_diffrn_reflns_theta_min         2.558
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.245
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.33658
_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    1.344
_exptl_crystal_description       block
_exptl_crystal_F_000             544
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.213
_refine_diff_density_min         -0.318
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
;
 Flack x determined using 1002 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(3)
_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     164
_refine_ls_number_reflns         2659
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0343
_refine_ls_R_factor_gt           0.0333
_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^)+(0.0420P)^2^+0.2160P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0777
_refine_ls_wR_factor_ref         0.0783
_reflns_Friedel_coverage         0.721
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                2611
_reflns_number_total             2659
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b00464_si_010.cif
_cod_data_source_block           cd1631
_cod_database_code               4514724
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         S1O2NC13H20
_shelx_estimated_absorpt_t_max   0.960
_shelx_estimated_absorpt_t_min   0.923
_reflns_odcompleteness_completeness 99.88
_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 Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C10(H10), C2(H2), C12(H12), C8(H8), C7(H7), C1(H1)
2.b X=CH2 refined with riding coordinates:
 C13(H13A,H13B)
2.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C)
;
_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 1.778
_oxdiff_exptl_absorpt_empirical_full_min 0.515