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_4033493
_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_absolute_configuration ad
_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      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2017-05-05
_audit_creation_method
;
Olex2 1.2
(compiled Mar 28 2017 19:34:44 for OlexSys, GUI svn.r5335)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   13.6323(2)
_cell_length_b                   15.09644(19)
_cell_length_c                   25.7076(3)
_cell_measurement_reflns_used    12002
_cell_measurement_temperature    185.00(10)
_cell_measurement_theta_max      27.5030
_cell_measurement_theta_min      2.0720
_cell_volume                     5290.60(12)
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      185.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0026
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.950
_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 -88.00 45.00 1.00 25.00 -- -0.08 -77.00-180.00 133 2 \w -93.00 -49.00 1.00 25.00 -- -0.08-160.00-120.00 44 3 \w 65.00 121.00 1.00 50.00 -- 28.69 160.00-180.00 56 4 \w 64.00 90.00 1.00 50.00 -- 28.69 160.00 -60.00 26 5 \w -27.00 -1.00 1.00 50.00 -- 28.69 -57.00-120.00 26 6 \w 66.00 93.00 1.00 50.00 -- 28.69 160.00 120.00 27 7 \w 19.00 71.00 1.00 50.00 -- 28.69 -57.00 60.00 52 8 \w 44.00 71.00 1.00 50.00 -- 28.69 -57.00-120.00 27 9 \w 67.00 115.00 1.00 50.00 -- 28.69 160.00 30.00 48 10 \w -65.00 90.00 1.00 50.00 -- 28.69 0.00 150.00 155'
_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      -0.0449580000
_diffrn_orient_matrix_UB_12      -0.0033689000
_diffrn_orient_matrix_UB_13      0.0137473000
_diffrn_orient_matrix_UB_21      -0.0181895000
_diffrn_orient_matrix_UB_22      -0.0295084000
_diffrn_orient_matrix_UB_23      -0.0191704000
_diffrn_orient_matrix_UB_31      0.0189118000
_diffrn_orient_matrix_UB_32      -0.0364117000
_diffrn_orient_matrix_UB_33      0.0142811000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0353
_diffrn_reflns_av_unetI/netI     0.0455
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.950
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            37702
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.894
_diffrn_reflns_theta_full        25.214
_diffrn_reflns_theta_max         27.921
_diffrn_reflns_theta_min         2.011
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.251
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.732
_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    1.443
_exptl_crystal_description       block
_exptl_crystal_F_000             2400
_exptl_crystal_recrystallization_method 'from solution: CH2Cl2/n-pentane'
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.084
_refine_diff_density_max         0.258
_refine_diff_density_min         -0.292
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Flack x determined using 3109 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.04(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     729
_refine_ls_number_reflns         11364
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0662
_refine_ls_R_factor_gt           0.0457
_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^)+(0.0364P)^2^+1.3536P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0931
_refine_ls_wR_factor_ref         0.1030
_reflns_Friedel_coverage         0.715
_reflns_Friedel_fraction_full    0.943
_reflns_Friedel_fraction_max     0.827
_reflns_number_gt                8826
_reflns_number_total             11364
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b02867_si_008.cif
_cod_data_source_block           mwit194a
_cod_depositor_comments
'Adding full bibliography for 4033490--4033495.cif.'
_cod_original_cell_volume        5290.59(12)
_cod_database_code               4033493
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C15 H13 N O3 S'
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. 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
2.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C53(H53A,H53B), C73(H73A,H73B), C33(H33A,H33B)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C44(H44), C45(H45), C46(H46),
 C48(H48), C49(H49), C64(H64), C65(H65), C66(H66), C68(H68), C69(H69), C24(H24),
  C25(H25), C26(H26), C28(H28), C29(H29)
2.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_date_sample_data_collection 2017-05-04
_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 1.239
_oxdiff_exptl_absorpt_empirical_full_min 0.806