Preparation of thioamides from alkyl bromides, nitriles, and hydrogen sulfide through a thio-Ritter-type reaction
Tang, Shi-Zhong; Xiang, Kai; Ye, Rui; Chen, Meng-En; Yu, Jian-Chang; He, Zhi-Juan; Zhang, Fu-Min; Chemical Communications  (2022) –; doi:10.1039/D2CC04210J

data_7130709
_publ_section_title
;
 Preparation of thioamides from alkyl bromides, nitriles, and hydrogen
 sulfide through a thio-Ritter-type reaction
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC04210J
_journal_year                    2022
_chemical_formula_moiety         'C9 H15 N S'
_chemical_formula_sum            'C9 H15 N S'
_chemical_formula_weight         169.28
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-04-26
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-04-26 deposited with the CCDC.	2022-09-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 118.687(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.6856(3)
_cell_length_b                   9.2050(2)
_cell_length_c                   10.7124(2)
_cell_measurement_reflns_used    6904
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      76.9050
_cell_measurement_theta_min      4.8120
_cell_volume                     924.35(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.960
_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    -18.00  21.00   0.50    0.05    --   47.57 -19.00  90.00   78
  2  \w     38.00  63.00   0.50    0.07    --  107.75 -57.00 150.00   50
  3  \w     76.00 101.00   0.50    0.07    --  107.75 -77.00 120.00   50
  4  \w     36.00  61.00   0.50    0.07    --  107.75 -57.00-120.00   50
  5  \w    -26.00   4.00   0.50    0.05    --   47.57 -19.00-150.00   60
  6  \w     36.00 127.00   0.50    0.07    --  107.75-149.00  35.00  182
  7  \w     86.00 111.00   0.50    0.07    --  107.75-125.00-120.00   50
  8  \w     35.00  61.00   0.50    0.07    --  107.75-125.00-120.00   52
  9  \w     -8.00  21.00   0.50    0.05    --  -47.57  77.00 -60.00   58
 10  \w    -70.00 -30.00   0.50    0.05    --  -47.57  77.00 -60.00   80
 11  \w   -154.00 -98.00   0.50    0.07    -- -100.00 -17.00 -91.00  112
 12  \w   -100.00 -74.00   0.50    0.05    --  -47.57-149.00  35.00   52
 13  \w   -172.00 -89.00   0.50    0.07    -- -100.00-111.00 100.00  166
 14  \w     98.00 171.00   0.50    0.07    --  107.75 111.00-164.00  146
 15  \w    -91.00 -34.00   0.50    0.05    --  -47.57 125.00 -60.00  114
 16  \w    -17.00   9.00   0.50    0.05    --   47.57 -19.00 -30.00   52
 17  \w    -25.00  22.00   0.50    0.05    --   47.57 -19.00  60.00   94
 18  \w    -58.00 -31.00   0.50    0.07    -- -100.00  57.00  30.00   54
 19  \w    -62.00 -28.00   0.50    0.07    -- -100.00  57.00  60.00   68
 20  \w    -69.00 -44.00   0.50    0.07    -- -100.00  57.00   0.00   50
 21  \w     35.00  60.00   0.50    0.07    --  107.75 -57.00 120.00   50
 22  \w     81.00 106.00   0.50    0.07    --  107.75 -99.00  90.00   50
 23  \w     84.00 110.00   0.50    0.07    --  107.75-125.00 -90.00   52
 24  \w     36.00  61.00   0.50    0.07    --  107.75 -57.00 -30.00   50
 25  \w     41.00 112.00   0.50    0.07    --  107.75-125.00  60.00  142
 26  \w     61.00  92.00   0.50    0.07    --  107.75-125.00 150.00   62
 27  \w     35.00  60.00   0.50    0.07    --  107.75 -57.00 -90.00   50
 28  \w     85.00 128.00   0.50    0.07    --  107.75 123.00 -80.00   86
 29  \w      3.00  34.00   0.50    0.05    --   47.57 -37.00 120.00   62
 30  \w    -20.00   7.00   0.50    0.05    --   47.57 -19.00   0.00   54
 31  \w    -11.00  15.00   0.50    0.05    --   47.57 -19.00 -90.00   52
 32  \w    -65.00 -32.00   0.50    0.07    -- -100.00  57.00 150.00   66
 33  \w    -60.00 -28.00   0.50    0.07    -- -100.00  57.00 -90.00   64
 34  \w    -55.00 -29.00   0.50    0.07    -- -100.00  57.00   0.00   52
 35  \w   -111.00 -85.00   0.50    0.07    -- -100.00 125.00-180.00   52
 36  \w    138.00 174.00   0.50    0.07    --  107.75  57.00-120.00   72
 37  \w     77.00 103.00   0.50    0.07    --  107.75 -77.00-150.00   52
 38  \w    133.00 162.00   0.50    0.07    --  107.75 123.00 -80.00   58
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1006381000
_diffrn_orient_matrix_UB_12      -0.0861150000
_diffrn_orient_matrix_UB_13      0.0381870000
_diffrn_orient_matrix_UB_21      0.0477060000
_diffrn_orient_matrix_UB_22      -0.1427155000
_diffrn_orient_matrix_UB_23      -0.0395967000
_diffrn_orient_matrix_UB_31      0.1208104000
_diffrn_orient_matrix_UB_32      -0.0152759000
_diffrn_orient_matrix_UB_33      0.1544128000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0312
_diffrn_reflns_av_unetI/netI     0.0226
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            8401
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.532
_diffrn_reflns_theta_min         4.805
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.580
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68184
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.113a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.216
_exptl_crystal_description       needle
_exptl_crystal_F_000             368
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.209
_refine_diff_density_min         -0.165
_refine_diff_density_rms         0.035
_refine_ls_extinction_coef       0.0065(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     165
_refine_ls_number_reflns         1878
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0415
_refine_ls_R_factor_gt           0.0400
_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^)+(0.0404P)^2^+0.3737P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0997
_refine_ls_wR_factor_ref         0.1007
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1788
_reflns_number_total             1878
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc04210j2.cif
_cod_data_source_block           tangshizhong1_0425_auto
_cod_original_cell_volume        924.35(4)
_cod_database_code               7130709
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 98.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Fixed Sof: S1(0.6) H1A(0.6) H1B(0.4) H4AA(0.6) H4AB(0.6) H4BC(0.4) H4BD(0.4)
 C7(0.6) H7A(0.6) H7B(0.6) C5(0.6) H5A(0.6) H5B(0.6) C6(0.6) H6(0.6) C1(0.6)
 H1(0.6) C3(0.6) H3(0.6) C2(0.6) H2A(0.6) H2B(0.6) S1B(0.4) C1B(0.4) H1BA(0.4)
 C6B(0.4) H6BA(0.4) H6BB(0.4) C3B(0.4) H3BA(0.4) H3BB(0.4) C7B(0.4) H7BA(0.4)
 H7BB(0.4) C5B(0.4) H5BA(0.4) C2B(0.4) H2BA(0.4)
3.a Ternary CH refined with riding coordinates:
 C6(H6), C1(H1), C3(H3), C1B(H1BA), C5B(H5BA), C2B(H2BA)
3.b Secondary CH2 refined with riding coordinates:
 C4(H4AA,H4AB), C4(H4BC,H4BD), C7(H7A,H7B), C5(H5A,H5B), C2(H2A,H2B), C6B(H6BA,
 H6BB), C3B(H3BA,H3BB), C7B(H7BA,H7BB)
3.c Aromatic/amide H refined with riding coordinates:
 N1(H1A), N1(H1B)
3.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C)
;
_shelx_res_checksum              72478
_shelx_hkl_checksum              22943
_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 2.380
_oxdiff_exptl_absorpt_empirical_full_min 0.381