Rh/Ag-Mediated Peri-Selective Heteroarylation/Single Electron Transfer Annulation Cascade of 1-(Methylthio)naphthalenes and Analogues: Road Less Traveled to Benzo[de]thioacenes
Yang, Shiping; Cheng, Rui; Zhang, Min; Bin, Zhengyang; You, Jingsong; ACS Catalysis 9 (2019) 6188–; doi:10.1021/acscatal.9b01426

data_4514807
_publ_section_title
;
 Rh/Ag-Mediated Peri-Selective Heteroarylation/Single Electron Transfer
 Annulation Cascade of 1-(Methylthio)naphthalenes and Analogues: Road Less
 Traveled to Benzo[de]thioacenes
;
_journal_issue                   7
_journal_name_full               'ACS Catalysis'
_journal_page_first              6188
_journal_paper_doi               10.1021/acscatal.9b01426
_journal_volume                  9
_journal_year                    2019
_chemical_formula_moiety         'C21 H24 Cl Rh S'
_chemical_formula_sum            'C21 H24 Cl Rh S'
_chemical_formula_weight         446.82
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-12-27
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 108.015(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.74658(18)
_cell_length_b                   14.0941(3)
_cell_length_c                   9.1196(2)
_cell_measurement_reflns_used    4290
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      72.9900
_cell_measurement_theta_min      5.1090
_cell_volume                     946.87(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.989
_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    -55.00  33.00   1.00    1.00    --  -36.29  38.00 120.00   88
  2  \w   -106.00  33.00   1.00    1.00    --  -36.29   0.00 -90.00  139
  3  \w   -104.00 -20.00   1.00    1.00    --  -36.29 -57.00  90.00   84
  4  \w     20.00 104.00   1.00    1.00    --   36.29  57.00 -90.00   84
  5  \w    -31.00  53.00   1.00    1.00    --   36.29 -57.00  30.00   84
  6  \w     23.00  90.00   1.00    1.00    --   36.29-125.00-180.00   67
  7  \w     23.00  90.00   1.00    1.00    --   36.29-125.00 -90.00   67
  8  \w     23.00  90.00   1.00    1.00    --   36.29-125.00 -60.00   67
  9  \w     91.00 176.00   1.00    1.00    --  108.71  61.00 120.00   85
 10  \w     70.00 178.00   1.00    1.00    --  108.71  15.00 -30.00  108
 11  \w     91.00 176.00   1.00    1.00    --  108.71  61.00-180.00   85
 12  \w     39.00 115.00   1.00    1.00    --  108.71-111.00-180.00   76
 13  \w     82.00 176.00   1.00    1.00    --  108.71  77.00-120.00   94
 14  \w     42.00 127.00   1.00    1.00    --  108.71 -61.00 -90.00   85
 15  \w     39.00 115.00   1.00    1.00    --  108.71-111.00-120.00   76
 16  \w     39.00 109.00   1.00    1.00    --  108.71 -94.00  60.00   70
 17  \w     91.00 176.00   1.00    1.00    --  108.71  61.00 -90.00   85
 18  \w     82.00 176.00   1.00    1.00    --  108.71  77.00-150.00   94
 19  \w     87.00 137.00   1.00    1.00    --  108.71  30.00 -90.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0792169000
_diffrn_orient_matrix_UB_12      0.0007555000
_diffrn_orient_matrix_UB_13      0.1356206000
_diffrn_orient_matrix_UB_21      -0.1068088000
_diffrn_orient_matrix_UB_22      0.0909585000
_diffrn_orient_matrix_UB_23      -0.0644066000
_diffrn_orient_matrix_UB_31      -0.1613833000
_diffrn_orient_matrix_UB_32      -0.0606475000
_diffrn_orient_matrix_UB_33      -0.0950765000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0434
_diffrn_reflns_av_unetI/netI     0.0440
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            9974
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.056
_diffrn_reflns_theta_min         5.100
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.592
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.02496
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear reddish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.567
_exptl_crystal_description       plate
_exptl_crystal_F_000             456
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.000
_refine_diff_density_min         -1.017
_refine_diff_density_rms         0.143
_refine_ls_abs_structure_details
;
 Flack x determined using 1660 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.245(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     223
_refine_ls_number_reflns         3711
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0512
_refine_ls_R_factor_gt           0.0508
_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^)+(0.1090P)^2^+0.1682P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1311
_refine_ls_wR_factor_ref         0.1319
_reflns_Friedel_coverage         0.892
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.963
_reflns_number_gt                3657
_reflns_number_total             3711
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b01426_si_005.cif
_cod_data_source_block           exp_5195
_cod_original_cell_volume        946.88(4)
_cod_database_code               4514807
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
Uanis(C1) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
3.a Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C16(H16), C18(H18), C25(H25), C2AA(H2AA)
3.b Idealised Me refined as rotating group:
 C1AA(H1AA,H1AB,H1AC), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C),
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C)
;
_shelx_res_checksum              91792
_shelx_hkl_checksum              1674
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2018-12-27
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 21.775
_oxdiff_exptl_absorpt_empirical_full_min 0.463