Base-controlled regioselectivity <i>via</i> distinct mechanisms during C-H thionation of azinium salts with elemental sulfur.
Kositova, Olga A.; Bugaenko, Dmitry I.; Goncharenko, Victoria E.; Nechaev, Mikhail S.; Karchava, Alexander V.; Organic & biomolecular chemistry 23 (2025) 3547–3552; doi:10.1039/d5ob00209e

data_7160416
_publ_section_title
;
 Base-controlled regioselectivity <i>via</i> distinct mechanisms during
 C-H thionation of azinium salts with elemental sulfur.
;
_journal_issue                   15
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3547
_journal_page_last               3552
_journal_paper_doi               10.1039/d5ob00209e
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C10 H9 N S'
_chemical_formula_sum            'C10 H9 N S'
_chemical_formula_weight         175.24
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2m74vw
_audit_creation_date             2023-11-09
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.17 svn.r577a77a9 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-01-28 deposited with the CCDC.	2025-03-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   15.077(3)
_cell_length_b                   7.584(2)
_cell_length_c                   28.746(7)
_cell_measurement_reflns_used    1416
_cell_measurement_temperature    110.00
_cell_measurement_theta_max      26.84
_cell_measurement_theta_min      2.79
_cell_volume                     3286.9(13)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      110.00
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker D8 Quest with Photon III Detector'
_diffrn_measurement_method       '\f and \w shutterless scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1275
_diffrn_reflns_av_unetI/netI     0.1502
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            21752
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        24.995
_diffrn_reflns_theta_max         24.995
_diffrn_reflns_theta_min         2.686
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.327
_exptl_absorpt_correction_T_max  0.6471
_exptl_absorpt_correction_T_min  0.4691
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1733 before and 0.0813 after correction.
The Ratio of minimum to maximum transmission is 0.7249.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.416
_exptl_crystal_description       needle
_exptl_crystal_F_000             1472
_exptl_crystal_size_max          0.108
_exptl_crystal_size_mid          0.018
_exptl_crystal_size_min          0.013
_refine_diff_density_max         1.519
_refine_diff_density_min         -0.332
_refine_diff_density_rms         0.117
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.4(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.008
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     438
_refine_ls_number_reflns         5748
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.008
_refine_ls_R_factor_all          0.1513
_refine_ls_R_factor_gt           0.0867
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1223P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2013
_refine_ls_wR_factor_ref         0.2392
_reflns_Friedel_coverage         0.949
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                3470
_reflns_number_total             5748
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00209e2.cif
_cod_data_source_block           q
_cod_depositor_comments
'Adding full bibliography for 7160414--7160418.cif.'
_cod_original_cell_volume        3287.0(14)
_cod_database_code               7160416
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6(3)
 0.4(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3.a Aromatic/amide H refined with riding coordinates:
 C26(H26), C6(H6), C7(H7), C22(H22), C32(H32), C21(H21), C8(H8), C31(H31),
 C27(H27), C2(H2), C25(H25), C36(H36), C1(H1), C28(H28), C12(H12), C17(H17),
 C5(H5), C35(H35), C11(H11), C18(H18), C37(H37), C38(H38), C16(H16), C15(H15)
3.b Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C20(H20A,H20B,H20C), C30(H30A,H30B,H30C), C40(H40A,H40B,
 H40C)
;
_shelx_res_checksum              21390
_olex2_submission_special_instructions 'No special instructions were received'