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_7160415
_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         'C13 H10 N2 S'
_chemical_formula_sum            'C13 H10 N2 S'
_chemical_formula_weight         226.29
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_block_doi                 10.5517/ccdc.csd.cc2m74rs
_audit_creation_date             2025-01-27
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-01-28 deposited with the CCDC.	2025-03-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.194(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.7446(7)
_cell_length_b                   14.6012(9)
_cell_length_c                   7.0569(6)
_cell_measurement_reflns_used    3407
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      26.94
_cell_measurement_theta_min      2.38
_cell_volume                     1051.76(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      100.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker D8 Quest with Photon III detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0439
_diffrn_reflns_av_unetI/netI     0.0416
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            11353
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.526
_diffrn_reflns_theta_min         1.995
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           0.9
_diffrn_source_power             0.045
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.276
_exptl_absorpt_correction_T_max  0.6471
_exptl_absorpt_correction_T_min  0.3683
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1511 before and 0.0560 after correction.
The Ratio of minimum to maximum transmission is 0.5692.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.429
_exptl_crystal_description       block
_exptl_crystal_F_000             472
_exptl_crystal_size_max          0.098
_exptl_crystal_size_mid          0.087
_exptl_crystal_size_min          0.076
_refine_diff_density_max         0.494
_refine_diff_density_min         -0.282
_refine_diff_density_rms         0.070
_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     146
_refine_ls_number_reflns         3202
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0597
_refine_ls_R_factor_gt           0.0478
_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^)+(0.0778P)^2^+0.1359P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1257
_refine_ls_wR_factor_ref         0.1341
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2581
_reflns_number_total             3202
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00209e2.cif
_cod_data_source_block           w
_cod_depositor_comments
'Adding full bibliography for 7160414--7160418.cif.'
_cod_database_code               7160415
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
C1: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
S1 \\sim C1: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
Uanis(C1) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
3.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C8(H8), C3(H3), C6(H6), C5(H5), C10(H10), C9(H9)
3.b Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C)
;
_shelx_res_checksum              74494
_olex2_submission_special_instructions 'No special instructions were received'