Silver-mediated radical cascade trifluoromethylthiolation/cyclization of benzimidazole derivatives with AgSCF<sub>3</sub>.
Liu, Pan; Geng, Yang; Zou, Dapeng; Wu, Yangjie; Wu, Yusheng; Organic & biomolecular chemistry  (2024) –; doi:10.1039/d4ob01582g

data_7160205
_publ_section_title
;
 Silver-mediated radical cascade trifluoromethylthiolation/cyclization of
 benzimidazole derivatives with AgSCF<sub>3</sub>.
;
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_paper_doi               10.1039/d4ob01582g
_journal_year                    2024
_chemical_formula_moiety         'C13 H13 F3 N2 S'
_chemical_formula_sum            'C13 H13 F3 N2 S'
_chemical_formula_weight         286.31
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-06-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-06-04 deposited with the CCDC.	2024-10-28 downloaded from the CCDC.
;
_cell_angle_alpha                67.284(6)
_cell_angle_beta                 85.636(5)
_cell_angle_gamma                87.696(5)
_cell_formula_units_Z            4
_cell_length_a                   6.5464(4)
_cell_length_b                   13.7584(8)
_cell_length_c                   16.2007(10)
_cell_measurement_reflns_used    2645
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.7140
_cell_measurement_theta_min      3.5960
_cell_volume                     1341.98(15)
_computing_cell_refinement       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_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    -56.00  37.00   1.00    1.00    --  -33.50  37.00 -60.00   93
  2  \w   -104.00 -11.00   1.00    1.00    --  -33.50 -37.00 126.00   93
  3  \w    -52.00  35.00   1.00    1.00    --  -33.50  57.00  60.00   87
  4  \w     18.00 105.00   1.00    1.00    --   36.47  57.00   0.00   87
  5  \w    -18.00  65.00   1.00    1.00    --   36.47 -77.00   0.00   83
  6  \w    -30.00  -4.00   1.00    1.00    --   36.47 -57.00-150.00   26
  7  \w    -12.00  15.00   1.00    1.00    --   36.47 -37.00-150.00   27
  8  \w     67.00 110.00   1.00    1.00    --   36.47 178.00-180.00   43
  9  \w     38.00  64.00   1.00    1.00    --   36.47 -99.00  30.00   26
 10  \w     -5.00  21.00   1.00    1.00    --   36.47 -77.00-150.00   26
 11  \w     34.00  59.00   1.00    1.00    --   36.47 -37.00-150.00   25
 12  \w     37.00  73.00   1.00    1.00    --   36.47 -99.00-120.00   36
 13  \w      6.00  34.00   1.00    1.00    --   36.47 -99.00  30.00   28
 14  \w      7.00  74.00   1.00    1.00    --   36.47 -99.00 120.00   67
 15  \w      6.00  55.00   1.00    1.00    --   36.47 -57.00-150.00   49
 16  \w     55.00  98.00   1.00    7.50    --  108.00 -94.00-180.00   43
 17  \w     37.00  92.00   1.00    7.50    --  108.00 -30.00 -30.00   55
 18  \w    149.00 176.00   1.00    7.50    --  108.00  61.00-150.00   27
 19  \w     38.00 128.00   1.00    7.50    --  108.00 -45.00-120.00   90
 20  \w     52.00 123.00   1.00    7.50    --  108.00 -61.00 -60.00   71
 21  \w     92.00 124.00   1.00    7.50    --  108.00  61.00-150.00   32
 22  \w     74.00 100.00   1.00    7.50    --  108.00-111.00  90.00   26
 23  \w     41.00 108.00   1.00    7.50    --  108.00-111.00 120.00   67
 24  \w     62.00 117.00   1.00    7.50    --  108.00 178.00 -60.00   55
 25  \w    113.00 169.00   1.00    7.50    --  108.00  77.00  30.00   56
 26  \w     48.00  74.00   1.00    7.50    --  108.00-111.00 -30.00   26
 27  \w     42.00 119.00   1.00    7.50    --  108.00 -45.00  60.00   77
 28  \w     66.00 104.00   1.00    7.50    --  108.00 -94.00 -30.00   38
 29  \w     45.00  71.00   1.00    7.50    --  108.00 -61.00  60.00   26
 30  \w     42.00 109.00   1.00    7.50    --  108.00-111.00 -90.00   67
 31  \w     41.00 173.00   1.00    7.50    --  108.00   0.00   0.00  132
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1768513000
_diffrn_orient_matrix_UB_12      -0.0421558000
_diffrn_orient_matrix_UB_13      -0.0457434000
_diffrn_orient_matrix_UB_21      -0.1523465000
_diffrn_orient_matrix_UB_22      -0.0677461000
_diffrn_orient_matrix_UB_23      -0.0219021000
_diffrn_orient_matrix_UB_31      -0.0350024000
_diffrn_orient_matrix_UB_32      0.0914902000
_diffrn_orient_matrix_UB_33      -0.0900064000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0297
_diffrn_reflns_av_unetI/netI     0.0403
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            9426
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.078
_diffrn_reflns_theta_max         67.078
_diffrn_reflns_theta_min         3.483
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.381
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49754
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.102a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.417
_exptl_crystal_description       block
_exptl_crystal_F_000             592
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.679
_refine_diff_density_min         -0.433
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.197
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     402
_refine_ls_number_reflns         4763
_refine_ls_number_restraints     113
_refine_ls_restrained_S_all      1.283
_refine_ls_R_factor_all          0.1330
_refine_ls_R_factor_gt           0.1078
_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^)+(0.2300P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3296
_refine_ls_wR_factor_ref         0.3717
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3273
_reflns_number_total             4763
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob01582g2.cif
_cod_data_source_block           202405199b_auto
_cod_database_code               7160205
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C20H2N1O4S1F2
_shelx_estimated_absorpt_t_max   0.911
_shelx_estimated_absorpt_t_min   0.688
_reflns_odcompleteness_completeness 99.79
_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
2. Restrained distances
 C10'-C9'
 1.64 with sigma of 0.02
 C10'-C11'
 1.64 with sigma of 0.02
 C10B-C11'
 1.54 with sigma of 0.02
 C9'A-C10B
 1.54 with sigma of 0.02
 S1'A-C13B
 1.78 with sigma of 0.02
 F2'A-S1'A
 2.5 with sigma of 0.02
 C11A-C10A
 1.54 with sigma of 0.02
 S1A-C12A
 1.78 with sigma of 0.02
 C8A-C12A
 1.54 with sigma of 0.02
 C10-C9
 1.54 with sigma of 0.02
 C9A-C8A
 1.54 with sigma of 0.02
 C10A-C9A
 1.54 with sigma of 0.02
 S1A-F2A
 2.2 with sigma of 0.02
 S1A-F3A
 2.3 with sigma of 0.02
 C11A-N2
 1.45 with sigma of 0.02
 S1'A-F3'A
 2.3 with sigma of 0.02
 S1'A-F1'A
 2.3 with sigma of 0.02
 F3A-F2A
 1.8 with sigma of 0.02
 F3A-F1A
 1.8 with sigma of 0.02
 C13B-F1'A = C13B-F3'A = C13B-F2'A
 1.35 with sigma of 0.02
 C13A-F3A
 1.35 with sigma of 0.02
 C8'-C12'
 1.68 with sigma of 0.02
 C8'A-C12B
 1.54 with sigma of 0.02
 C9'-C8'
 1.78 with sigma of 0.02
 C9'A-C8'A
 1.54 with sigma of 0.02
 S1'-C12'
 1.78 with sigma of 0.02
 C7'-C8'A
 1.54 with sigma of 0.02
 F3'-F1' \\sim F3'-F2' \\sim F1'-F2'
 with sigma of 0.04
 C13'-F3' \\sim C13'-F1' \\sim C13'-F2'
 with sigma of 0.02
 F1'A-F3'A \\sim F1'A-F2'A \\sim F3'A-F2'A
 with sigma of 0.04
 C13B-F1'A \\sim C13B-F3'A \\sim C13B-F2'A
 with sigma of 0.02
 F3A-F2A \\sim F3A-F1A \\sim F2A-F1A
 with sigma of 0.04
 C13A-F3A \\sim C13A-F2A \\sim C13A-F1A
 with sigma of 0.02
 F1-F2 \\sim F1-F3 \\sim F2-F3
 with sigma of 0.04
 C13-F1 \\sim C13-F2 \\sim C13-F3
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C10B) \\sim Ueq, Uanis(C10') \\sim Ueq, Uanis(C9'A) \\sim Ueq, Uanis(C9')
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F2'A) \\sim Ueq, Uanis(F2') \\sim Ueq, Uanis(F3') \\sim Ueq, Uanis(F3'A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C8') \\sim Ueq, Uanis(C8'A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C10') = Uanis(C10B)
Uanis(C9') = Uanis(C9'A)
Uanis(C8') = Uanis(C8'A)
Uanis(C12') = Uanis(C12B)
Uanis(S1') = Uanis(S1'A)
Uanis(C13') = Uanis(C13B)
Uanis(F1') = Uanis(F1'A)
Uanis(F3') = Uanis(F3'A)
Uanis(F2') = Uanis(F2'A)
Uanis(C11) = Uanis(C11A)
Uanis(C10) = Uanis(C10A)
Uanis(C9) = Uanis(C9A)
Uanis(C8) = Uanis(C8A)
Uanis(C12) = Uanis(C12A)
Uanis(S1) = Uanis(S1A)
Uanis(C13) = Uanis(C13A)
Uanis(F3) = Uanis(F3A)
Uanis(F2) = Uanis(F2A)
Uanis(F1) = Uanis(F1A)
4. Others
 Sof(S1'A)=Sof(F1'A)=Sof(F2'A)=Sof(F3'A)=Sof(C8'A)=Sof(H8'A)=Sof(C9'A)=
 Sof(H9'C)=Sof(H9'D)=Sof(C10B)=Sof(H10G)=Sof(H10H)=Sof(H11G)=Sof(H11H)=
 Sof(C12B)=Sof(H12G)=Sof(H12H)=Sof(C13B)=1-FVAR(1)
 Sof(S1')=Sof(F1')=Sof(F2')=Sof(F3')=Sof(C8')=Sof(H8')=Sof(C9')=Sof(H9'A)=
 Sof(H9'B)=Sof(C10')=Sof(H10E)=Sof(H10F)=Sof(H11E)=Sof(H11F)=Sof(C12')=
 Sof(H12E)=Sof(H12F)=Sof(C13')=FVAR(1)
 Sof(S1A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(H9AA)=
 Sof(H9AB)=Sof(C10A)=Sof(H10C)=Sof(H10D)=Sof(C11A)=Sof(H11C)=Sof(H11D)=
 Sof(C12A)=Sof(H12C)=Sof(H12D)=Sof(C13A)=1-FVAR(2)
 Sof(S1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9A)=Sof(H9B)=
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=
 Sof(H12B)=Sof(C13)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C8(H8), C8A(H8A), C8'(H8'), C8'A(H8'A)
5.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C9A(H9AA,H9AB), C10(H10A,H10B), C10A(H10C,H10D), C11(H11A,H11B),
 C11A(H11C,H11D), C12(H12A,H12B), C12A(H12C,H12D), C9'(H9'A,H9'B), C9'A(H9'C,
 H9'D), C10'(H10E,H10F), C10B(H10G,H10H), C11'(H11E,H11F), C11'(H11G,H11H),
 C12'(H12E,H12F), C12B(H12G,H12H)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C1'(H1'), C2'(H2'), C3'(H3'), C4'(H4')
;
_shelx_res_checksum              14794
_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 1.721
_oxdiff_exptl_absorpt_empirical_full_min 0.737