Polycyclic Aromatic N-Ethoxycarbonyl Thioamide S-Oxides and Their Triflic Acid Promoted Cyclization to Fluorescent Thiophene Imine-Fused Arenes.
Witalewska, Marzena; Wrona-Piotrowicz, Anna; Makal, Anna; Zakrzewski, Janusz; The Journal of organic chemistry 83 (2018) 1933–1939; doi:10.1021/acs.joc.7b02867

data_4035002
_publ_section_title
;
 Polycyclic Aromatic N-Ethoxycarbonyl Thioamide S-Oxides and Their Triflic
 Acid Promoted Cyclization to Fluorescent Thiophene Imine-Fused Arenes.
;
_journal_issue                   4
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              1933
_journal_page_last               1939
_journal_paper_doi               10.1021/acs.joc.7b02867
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C20 H15 N O3 S'
_chemical_formula_sum            'C20 H15 N O3 S'
_chemical_formula_weight         349.39
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-11-28
_audit_creation_method
;
Olex2 1.2
(compiled Nov  7 2016 13:36:16 for OlexSys, GUI svn.r5261)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.330(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.2333(3)
_cell_length_b                   11.2199(3)
_cell_length_c                   29.1660(8)
_cell_measurement_reflns_used    16149
_cell_measurement_temperature    150.11(10)
_cell_measurement_theta_max      33.7720
_cell_measurement_theta_min      2.7080
_cell_volume                     3304.44(16)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43c (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43c (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43c (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      air
_diffrn_ambient_temperature      150.11(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0013
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.955
_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     49.00 108.00   1.00   30.00    --   33.41 160.00 -30.00   59
  2  \w     49.00 108.00   1.00   30.00    --   33.41 160.00-120.00   59
  3  \w      1.00 107.00   1.00   30.00    --   33.41  37.00  90.00  106
  4  \w    -20.00  78.00   1.00   30.00    --   33.41 -99.00-150.00   98
  5  \w    -20.00  78.00   1.00   30.00    --   33.41 -99.00 -60.00   98
  6  \w      1.00 107.00   1.00   30.00    --   33.41  37.00   0.00  106
  7  \w   -114.00 -21.00   1.00   30.00    --  -33.64 160.00 -30.00   93
  8  \w      0.00 106.00   1.00   30.00    --   33.41  77.00-180.00  106
  9  \w   -106.00  -1.00   1.00   30.00    --  -33.64 -77.00 -90.00  105
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0699314000
_diffrn_orient_matrix_UB_12      -0.0038903000
_diffrn_orient_matrix_UB_13      0.0024213000
_diffrn_orient_matrix_UB_21      0.0059933000
_diffrn_orient_matrix_UB_22      0.0547325000
_diffrn_orient_matrix_UB_23      0.0123361000
_diffrn_orient_matrix_UB_31      0.0017998000
_diffrn_orient_matrix_UB_32      -0.0314313000
_diffrn_orient_matrix_UB_33      0.0212050000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0211
_diffrn_reflns_av_unetI/netI     0.0174
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            35861
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         34.245
_diffrn_reflns_theta_min         2.714
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.215
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.315
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
'CrysAlisPro 1.171.38.43c (Rigaku Oxford Diffraction, 2015) Numerical absorption correction based on gaussian integration over a multifaceted crystal model Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.405
_exptl_crystal_description       block
_exptl_crystal_F_000             1456
_exptl_crystal_size_max          0.528
_exptl_crystal_size_mid          0.248
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.572
_refine_diff_density_min         -0.228
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     249
_refine_ls_number_reflns         6556
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0526
_refine_ls_R_factor_gt           0.0436
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0671P)^2^+1.9055P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1233
_refine_ls_wR_factor_ref         0.1297
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5515
_reflns_number_total             6556
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b02867_si_003.cif
_cod_data_source_block           exp_642
_cod_original_cell_volume        3304.44(15)
_cod_database_code               4035002
_chemical_oxdiff_formula         'C20 H15 N O3 S'
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     32.50
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-H1
 0.86 with sigma of 0.02
 S1-O3 \\sim S1A-O3A
 with sigma of 0.02
 S1A-C17 \\sim S1-C17
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O3A \\sim O3: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
S1A \\sim S1: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
4. Others
 Sof(S1A)=Sof(O3A)=1-FVAR(1)
 Sof(S1)=Sof(O3)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B)
5.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C3(H3), C6(H6), C7(H7), C13(H13), C10(H10), C11(H11), C8(H8), C14(H14)
5.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C)
;
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-11-25
_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 1.392
_oxdiff_exptl_absorpt_empirical_full_min 0.771