Electrochemically-promoted synthesis of benzo[b]thiophene-1,1-dioxides via strained quaternary spirocyclization
Li, Rui-Tao; Yuan, Da-Fu; Ping, Meng-Qi; Zhu, Yu-Yi; Ni, Shao-Fei; Li, Ming; Wen, Li-Rong; Zhang, Lin-Bao; Chemical Science  (2022) –; doi:10.1039/D2SC01175A

data_1567395
_publ_section_title
;
 Electrochemically-promoted synthesis of benzo[b]thiophene-1,1-dioxides
 via strained quaternary spirocyclization
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC01175A
_journal_year                    2022
_chemical_formula_moiety         'C25 H23 Cl O2 S'
_chemical_formula_sum            'C25 H23 Cl O2 S'
_chemical_formula_weight         422.94
_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             2022-05-09
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-05-10 deposited with the CCDC.	2022-07-28 downloaded from the CCDC.
;
_cell_angle_alpha                87.053(2)
_cell_angle_beta                 81.996(2)
_cell_angle_gamma                86.100(2)
_cell_formula_units_Z            2
_cell_length_a                   9.2866(3)
_cell_length_b                   10.4269(3)
_cell_length_c                   11.1292(3)
_cell_measurement_reflns_used    10989
_cell_measurement_temperature    170.01(10)
_cell_measurement_theta_max      76.9320
_cell_measurement_theta_min      3.9880
_cell_volume                     1063.72(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      170.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.954
_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     95.00 122.00   0.50    0.08    --  107.36  38.00 -30.00   54
  2  \w    103.00 174.00   0.50    0.08    --  107.36  40.00 -42.47  142
  3  \w    132.00 177.00   0.50    0.08    --  107.36  38.00 -30.00   90
  4  \w     90.00 134.00   0.50    0.08    --  107.36  93.00 179.00   88
  5  \w     35.00  60.00   0.50    0.08    --  107.36 -57.00 -30.00   50
  6  \w     39.00  68.00   0.50    0.08    --  107.36 -57.00-150.00   58
  7  \w     35.00  67.00   0.50    0.08    --  107.36 -57.00-120.00   64
  8  \w     38.00  69.00   0.50    0.08    --  107.36 -57.00  60.00   62
  9  \w     36.00  69.00   0.50    0.08    --  107.36 -57.00 120.00   66
 10  \w     -5.00  29.00   0.50    0.05    --   47.70 -19.00 150.00   68
 11  \w    -18.00  45.00   0.50    0.05    --   47.70 -38.00  90.00  126
 12  \w    -24.00  66.00   0.50    0.05    --   47.70 -93.00  67.00  180
 13  \w     47.00 102.00   0.50    0.08    --  107.36 -99.00  60.00  110
 14  \w     35.00  61.00   0.50    0.08    --  107.36 -99.00   0.00   52
 15  \w     36.00  71.00   0.50    0.08    --  107.36 -99.00  30.00   70
 16  \w     56.00  97.00   0.50    0.08    --  107.36 -99.00 -30.00   82
 17  \w     75.00 106.00   0.50    0.08    --  107.36 -99.00   0.00   62
 18  \w     59.00 106.00   0.50    0.08    --  107.36 -99.00 -90.00   94
 19  \w     78.00 103.00   0.50    0.08    --  107.36 -99.00-120.00   50
 20  \w     65.00 111.00   0.50    0.08    --  107.36-125.00-150.00   92
 21  \w     46.00 111.00   0.50    0.08    --  107.36-125.00-120.00  130
 22  \w     36.00  70.00   0.50    0.08    --  107.36 -99.00-120.00   68
 23  \w     36.00  62.00   0.50    0.08    --  107.36 -93.00  67.00   52
 24  \w     69.00 105.00   0.50    0.08    --  107.36 -93.00  67.00   72
 25  \w    -20.00  20.00   0.50    0.05    --  -47.70  19.00  90.00   80
 26  \w    -60.00 -34.00   0.50    0.08    -- -104.50  57.00  90.00   52
 27  \w    -60.00 -32.00   0.50    0.08    -- -104.50  57.00  30.00   56
 28  \w    -62.00 -36.00   0.50    0.08    -- -104.50  57.00 -30.00   52
 29  \w    -18.00  17.00   0.50    0.05    --  -47.70  19.00 -30.00   70
 30  \w   -101.00 -76.00   0.50    0.08    -- -104.50  77.00-150.00   50
 31  \w   -109.00 -84.00   0.50    0.08    -- -104.50 114.00-102.06   50
 32  \w    -75.00  25.00   0.50    0.05    --  -47.70  93.00 179.00  200
 33  \w   -105.00 -80.00   0.50    0.08    -- -104.50  93.00 179.00   50
 34  \w   -167.00 -90.00   0.50    0.08    -- -104.50 -57.00  90.00  154
 35  \w   -174.00 -87.00   0.50    0.08    -- -104.50 -71.00 152.63  174
 36  \w   -171.00 -93.00   0.50    0.08    -- -104.50 -57.00 120.00  156
 37  \w   -172.00 -87.00   0.50    0.08    -- -104.50 -93.00  67.00  170
 38  \w   -118.00 -91.00   0.50    0.05    --  -47.70-125.00-120.00   54
 39  \w   -101.00 -76.00   0.50    0.05    --  -47.70-125.00-150.00   50
 40  \w   -117.00 -80.00   0.50    0.05    --  -47.70-125.00-180.00   74
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0701964000
_diffrn_orient_matrix_UB_12      0.1163594000
_diffrn_orient_matrix_UB_13      0.0712626000
_diffrn_orient_matrix_UB_21      -0.0814573000
_diffrn_orient_matrix_UB_22      0.0450794000
_diffrn_orient_matrix_UB_23      -0.1076044000
_diffrn_orient_matrix_UB_31      -0.1288716000
_diffrn_orient_matrix_UB_32      -0.0799957000
_diffrn_orient_matrix_UB_33      0.0540251000
_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  0.0222
_diffrn_reflns_av_unetI/netI     0.0197
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.954
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            12537
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.954
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.034
_diffrn_reflns_theta_min         4.015
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.647
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70667
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.121a (Rigaku Oxford Diffraction, 2021)
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    1.320
_exptl_crystal_description       block
_exptl_crystal_F_000             444
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.396
_refine_diff_density_min         -0.416
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     266
_refine_ls_number_reflns         4296
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.0351
_refine_ls_R_factor_gt           0.0343
_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^)+(0.0558P)^2^+0.3379P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0962
_refine_ls_wR_factor_ref         0.0969
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4146
_reflns_number_total             4296
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc01175a2.cif
_cod_data_source_block           tx10842_auto_pl
_cod_database_code               1567395
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHOSCl
_chemical_oxdiff_usercomment     ' '
_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.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C10(H10), C11(H11), C13(H13), C14(H14),
 C20(H20), C21(H21), C23(H23)
2.b Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C25(H25A,H25B,
 H25C)
;
_shelx_res_checksum              65746
_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 1.467
_oxdiff_exptl_absorpt_empirical_full_min 0.710