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_4033495
_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         'C15 H13 N O3 S'
_chemical_formula_sum            'C15 H13 N O3 S'
_chemical_formula_weight         287.32
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-07-04
_audit_creation_method
;
Olex2 1.2
(compiled Mar 28 2017 19:34:44 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                80.569(4)
_cell_angle_beta                 80.605(4)
_cell_angle_gamma                84.520(4)
_cell_formula_units_Z            4
_cell_length_a                   7.3734(4)
_cell_length_b                   12.7312(6)
_cell_length_c                   14.7746(7)
_cell_measurement_reflns_used    9996
_cell_measurement_temperature    295(5)
_cell_measurement_theta_max      76.3200
_cell_measurement_theta_min      3.4860
_cell_volume                     1346.45(12)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43d (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    'ShelXD (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      295(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2195
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_details
;
 ?
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1483528000
_diffrn_orient_matrix_UB_12      -0.0457885000
_diffrn_orient_matrix_UB_13      0.0608906000
_diffrn_orient_matrix_UB_21      -0.1476875000
_diffrn_orient_matrix_UB_22      -0.0061849000
_diffrn_orient_matrix_UB_23      0.0870878000
_diffrn_orient_matrix_UB_31      -0.0354062000
_diffrn_orient_matrix_UB_32      -0.1139618000
_diffrn_orient_matrix_UB_33      -0.0117748000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0179
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            17005
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.699
_diffrn_reflns_theta_min         3.067
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.202
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.641
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
'CrysAlisPro 1.171.38.43d (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    1.417
_exptl_crystal_description       block
_exptl_crystal_F_000             600
_exptl_crystal_size_max          0.223
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.095
_refine_diff_density_max         0.717
_refine_diff_density_min         -0.451
_refine_diff_density_rms         0.068
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.31(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     730
_refine_ls_number_reflns         17005
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0878
_refine_ls_R_factor_gt           0.0772
_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^)+(0.1918P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2233
_refine_ls_wR_factor_ref         0.2437
_reflns_Friedel_coverage         0.992
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.985
_reflns_number_gt                13134
_reflns_number_total             17005
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
'Component 2 rotated by 179.9606\% around [0.94 0.15 0.31] (reciprocal) or [1.00 0.00 0.00] (direct)'
_cod_data_source_file            jo7b02867_si_007.cif
_cod_data_source_block           mwit194b_v2_twin1_hklf4
_cod_depositor_comments
'Adding full bibliography for 4033490--4033495.cif.'
_cod_original_cell_volume        1346.46(11)
_cod_database_code               4033495
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C15 H15 N O3 S'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.484(2)
 0.516(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C53(H53A,H53B), C73(H73A,H73B), C33(H33A,H33B)
3.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C45(H45), C46(H46), C48(H48),
 C49(H49), C50(H50), C65(H65), C66(H66), C68(H68), C69(H69), C70(H70), C24(H24),
  C25(H25), C26(H26), C28(H28), C29(H29)
3.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C54(H54A,H54B,H54C), C55(H55A,H55B,
 H55C), C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C34(H34A,H34B,H34C), C35(H35A,
 H35B,H35C)
;
_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 3.781
_oxdiff_exptl_absorpt_empirical_full_min 0.687
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2