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_7160414
_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_absolute_configuration ad
_chemical_formula_moiety         'C14 H12 Cl N O2 S'
_chemical_formula_sum            'C14 H12 Cl N O2 S'
_chemical_formula_weight         293.76
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-02-27
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-02-27 deposited with the CCDC.	2025-03-13 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   26.6824(9)
_cell_length_b                   7.1838(3)
_cell_length_c                   13.9128(4)
_cell_measurement_reflns_used    3512
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      27.34
_cell_measurement_theta_min      2.93
_cell_volume                     2666.82(16)
_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  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      100.00
_diffrn_detector                 'Photon III detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Quest'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0748
_diffrn_reflns_av_unetI/netI     0.0683
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            25468
_diffrn_reflns_theta_full        29.00
_diffrn_reflns_theta_max         29.00
_diffrn_reflns_theta_min         2.11
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           0.9
_diffrn_source_power             0.045
_diffrn_source_type              'micro-focus sealed X-ray tube'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.439
_exptl_absorpt_correction_T_max  0.6478
_exptl_absorpt_correction_T_min  0.5812
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1011 before and 0.0689 after correction.
The Ratio of minimum to maximum transmission is 0.8972.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.463
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             1216
_exptl_crystal_size_max          0.107
_exptl_crystal_size_mid          0.102
_exptl_crystal_size_min          0.015
_refine_diff_density_max         0.357
_refine_diff_density_min         -0.286
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.00(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     348
_refine_ls_number_reflns         6628
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0603
_refine_ls_R_factor_gt           0.0485
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0468P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1017
_refine_ls_wR_factor_ref         0.1095
_reflns_number_gt                5575
_reflns_number_total             6628
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d5ob00209e3.cif
_cod_data_source_block           w
_cod_depositor_comments
'Adding full bibliography for 7160414--7160418.cif.'
_cod_database_code               7160414
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.73(6)
 0.27(6)
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:
 C5(H5), C8'(H8'), C3(H3), C3'(H3'), C9'(H9'), C5'(H5'), C11'(H11'),
 C12'(H12'), C11(H11), C8(H8), C9(H9), C12(H12)
3.b Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C6(H6A,H6B,H6C), C6'(H6'A,H6'B,H6'C), C012(H01A,H01B,H01C)
;
_olex2_submission_special_instructions 'No special instructions were received'