Benzylic Thio and Seleno Newman-Kwart Rearrangements.
Eriksen, Kristina; Ulfkjær, Anne; Sølling, Theis I; Pittelkow, Michael; The Journal of organic chemistry 83 (2018) 10786–10797; doi:10.1021/acs.joc.8b01468

data_4035646
_publ_section_title
;
 Benzylic Thio and Seleno Newman-Kwart Rearrangements.
;
_journal_issue                   18
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              10786
_journal_page_last               10797
_journal_paper_doi               10.1021/acs.joc.8b01468
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C10 H12 Cl N O S'
_chemical_formula_sum            'C10 H12 Cl N O S'
_chemical_formula_weight         229.72
_chemical_name_systematic        'S-(4-chlorobenzyl) dimethylcarbamothioate'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2018-04-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.18 svn.r3501 for OlexSys, GUI svn.r5488)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.91(4)
_cell_length_b                   4.681(13)
_cell_length_c                   20.27(6)
_cell_measurement_reflns_used    7208
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.28
_cell_measurement_theta_min      3.58
_cell_volume                     1130(6)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      293.15
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1181
_diffrn_reflns_av_unetI/netI     0.0487
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            19732
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        24.905
_diffrn_reflns_theta_max         24.905
_diffrn_reflns_theta_min         3.422
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.490
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5760
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            'clear yellowish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.351
_exptl_crystal_description       needle
_exptl_crystal_F_000             480
_exptl_crystal_preparation
'Rearranged from O-(4-chlorobenzyl) dimethylcarbamothioate'
_exptl_crystal_recrystallization_method 'From dcm'
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.245
_refine_diff_density_min         -0.297
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Flack x determined using 765 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.06(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     129
_refine_ls_number_reflns         1944
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0451
_refine_ls_R_factor_gt           0.0373
_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^)+(0.0236P)^2^+1.0467P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0799
_refine_ls_wR_factor_ref         0.0840
_reflns_Friedel_coverage         0.940
_reflns_Friedel_fraction_full    0.985
_reflns_Friedel_fraction_max     0.985
_reflns_number_gt                1751
_reflns_number_total             1944
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01468_si_002.cif
_cod_data_source_block           mo_d8v3381_0mtria_a
_cod_database_code               4035646
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.953
_shelx_estimated_absorpt_t_min   0.828
_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 Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C9(H9), C10(H10)
2.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C)
;
_shelx_res_checksum              35197
_shelx_hkl_checksum              51438
_olex2_exptl_crystal_mounting_method normal
_olex2_submission_special_instructions 'No special instructions were received'