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_4033490
_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
'C14 H13.98 N0.5 O S0.5, 0.53(H), 1.54(C9.1 H9.42 N0.32 O0.65 S0.32)'
_chemical_formula_sum            'C28 H29 N O2 S'
_chemical_formula_weight         443.58
_space_group_crystal_system      orthorhombic
_space_group_IT_number           55
_space_group_name_Hall           '-P 2 2ab'
_space_group_name_H-M_alt        'P b a m'
_symmetry_space_group_name_Hall  '-P 2 2ab'
_symmetry_space_group_name_H-M   'P b a m'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2016-07-20
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.16 svn.r3265 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   29.4324(13)
_cell_length_b                   26.5753(12)
_cell_length_c                   6.9714(4)
_cell_measurement_reflns_used    6103
_cell_measurement_temperature    293.59(10)
_cell_measurement_theta_max      70.6010
_cell_measurement_theta_min      3.0040
_cell_volume                     5452.9(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_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      air
_diffrn_ambient_temperature      293.59(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2195
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.004
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
  1 omega  -92.00   42.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000    0.0000 134

  2 omega  -92.00   42.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000    0.0000 134

  3 omega  -99.00  -34.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000  120.0000 65

  4 omega  -48.00   37.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -55.2002   30.0000 -150.0000 85

  5 omega -146.00  -73.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -55.2002 -125.0000 -120.0000 73

  6 omega -151.00  -80.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -55.2002  -94.0000 -180.0000 71

  7 omega -135.00  -84.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -55.2002  -94.0000  -90.0000 51

  8 omega  -93.00  -33.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -55.2002  125.0000  -90.0000 60

  9 omega   13.00   38.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       55.2002   83.0000 -166.7883 25

 10 omega   11.00   36.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       55.2002   84.0000  158.6848 25

 11 omega  115.00  143.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       55.2002  125.0000 -150.0000 28

 12 omega  103.00  137.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       55.2002   99.0000   66.0000 34

 13 omega   10.00   35.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       55.2002   85.0000   91.8852 25

 14 omega   13.00  153.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       55.2002   77.0000 -120.0000 140

 15 omega   22.00   91.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4004  -37.0000  120.0000 69

 16 omega   44.00  150.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4004  -77.0000 -120.0000 106

 17 omega   60.00  107.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4004  178.0000  120.0000 47

 18 omega   63.00   95.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4004   37.0000  -30.0000 32

 19 omega  100.00  177.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4004   50.0000  -90.0000 77

 20 omega   25.00  116.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4004 -111.0000  120.0000 91

 21 omega  123.00  149.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4004  178.0000    0.0000 26

 22 omega   66.00  153.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4004   37.0000    0.0000 87

 23 omega   21.00  154.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4004  -77.0000  120.0000 133

 24 omega   93.00  158.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4004   37.0000 -120.0000 65

 25 omega   68.00  108.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4004 -111.0000  -60.0000 40

 26 omega  105.00  154.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4004   37.0000  -30.0000 49

 27 omega   60.00  151.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4004  178.0000  150.0000 91
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0482099000
_diffrn_orient_matrix_UB_12      0.0180232000
_diffrn_orient_matrix_UB_13      -0.0520460000
_diffrn_orient_matrix_UB_21      0.0111228000
_diffrn_orient_matrix_UB_22      -0.0525290000
_diffrn_orient_matrix_UB_23      -0.0806505000
_diffrn_orient_matrix_UB_31      -0.0170826000
_diffrn_orient_matrix_UB_32      0.0166237000
_diffrn_orient_matrix_UB_33      -0.1990488000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0703
_diffrn_reflns_av_unetI/netI     0.0451
_diffrn_reflns_Laue_measured_fraction_full 1.004
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       6
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            35549
_diffrn_reflns_point_group_measured_fraction_full 1.004
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.510
_diffrn_reflns_theta_min         2.240
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.216
_exptl_absorpt_correction_T_max  0.936
_exptl_absorpt_correction_T_min  0.798
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
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 orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.081
_exptl_crystal_description
;
;
_exptl_crystal_F_000             1888
_exptl_crystal_size_max          0.327
_exptl_crystal_size_mid          0.0679
_exptl_crystal_size_min          0.0607
_refine_diff_density_max         0.805
_refine_diff_density_min         -0.315
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     610
_refine_ls_number_reflns         5734
_refine_ls_number_restraints     648
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.1208
_refine_ls_R_factor_gt           0.0905
_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^)+(0.1488P)^2^+1.9112P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2444
_refine_ls_wR_factor_ref         0.2668
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3784
_reflns_number_total             5734
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b02867_si_009.cif
_cod_data_source_block           exp_637
_cod_depositor_comments
'Adding full bibliography for 4033490--4033495.cif.'
_cod_database_code               4033490
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C28 H20 N O2 S'
_reflns_odcompleteness_completeness 99.69
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9996(3) 0.0004(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H49A,H49B} of C49, {H49C,H49D} of C49A, {H19A,H19B} of C19
 At 1.5 times of:
  All C(H,H,H) groups, {H23A,H23B} of C23, All S(H,H,H,H,H,H) groups
3. Restrained distances
 C56A-H56C = C56A-H56D
 0.96 with sigma of 0.02
 C56-H56B = C56-H56A
 0.96 with sigma of 0.002
 C50-H50A = C50-H50B
 0.96 with sigma of 0.02
 C53-H53A = C53-H53B
 0.96 with sigma of 0.02
 C50A-H50D = C50A-H50C
 0.96 with sigma of 0.02
 C53A-H53D = C53A-H53C
 0.96 with sigma of 0.02
 C23-H23B
 0.96 with sigma of 0.02
 C23-H23A
 0.96 with sigma of 0.02
 H56D-H56C
 1.57 with sigma of 0.04
 H56A-H56B
 1.57 with sigma of 0.04
 H56A-H56A_$1
 1.57 with sigma of 0.04
 H50A-H50B
 1.57 with sigma of 0.04
 H53A-H53B
 1.57 with sigma of 0.04
 H50D-H50C
 1.57 with sigma of 0.04
 H53C-H53D
 1.57 with sigma of 0.04
 H50D-C49A
 2.1 with sigma of 0.04
 H50C-C49A
 2.1 with sigma of 0.04
 H56A-H56B
 1.57 with sigma of 0.01
 C23A-C22A
 2.5 with sigma of 0.004
 C22A-C22A_$2
 2.5 with sigma of 0.004
 H23A-H23B
 1.57 with sigma of 0.04
 H23B-C21
 2.1 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
Uanis(C39A) \\sim Ueq, Uanis(C46A) \\sim Ueq, Uanis(C31A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C31, C32, C33, C34, H34, C35, C36, H36, C37, C38, H38, C39, C40, H40, C41,
 H41, C42, C43, H43, C44, C45, C46, C47, C48, C49, H49A, H49B, C50, C51, C52,
 H52A, H52B, H52C, C53, C54, C55, H55A, H55B, H55C, C56, N2, O3, O4, S2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C31A, C32A, C33A, C34A, H34A, C35A, C36A, H36A, C37A, C38A, H38A, C39A, C40A,
 H40A, C41A, H41A, C42A, C43A, H43A, C44A, C45A, C46A, C47A, C48A, C49A, H49C,
 H49D, C50A, C51A, C52A, H52D, H52E, H52F, C53A, C54A, C55A, H55D, H55E, H55F,
 C56A, N2A, O3A, O4A, S2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
{C31, C32, C33, C34, C35, C36, C37, C38, C39, C40, C41, C42, C43, C44, C45,
C46, C47, C48, C49, C50, C51, C52, C53, C54, C55, C56, N2, O3, O4, S2} sigma
for 1-2: 0.02, 1-3: 0.04
as
{C31A, C32A, C33A, C34A, C35A, C36A, C37A, C38A, C39A, C40A, C41A, C42A, C43A,
C44A, C45A, C46A, C47A, C48A, C49A, C50A, C51A, C52A, C53A, C54A, C55A, C56A,
N2A, O3A, O4A, S2A}
7. Others
 Fixed Sof: H19A(0.5) H19B(0.5) H20A(0.5) H20B(0.5) H20C(0.5) C22(0.65)
 H22A(0.65) H22B(0.65) H22C(0.65) C22A(0.35) H22D(0.35) H22E(0.35) H22F(0.35)
 C23(0.325) H23A(0.65) H23B(0.325) C23A(0.175) H(0.175) HA(0.175) HB(0.175)
 H26A(0.5) H26B(0.5) H26C(0.5) C31(0.325) C32(0.325) C33(0.325) C34(0.325)
 H34(0.325) C35(0.325) C36(0.325) H36(0.325) C37(0.325) C38(0.325) H38(0.325)
 C39(0.325) C40(0.325) H40(0.325) C41(0.325) H41(0.325) C42(0.325) C43(0.325)
 H43(0.325) C44(0.325) C45(0.325) C46(0.325) C47(0.325) C48(0.325) C49(0.325)
 H49A(0.325) H49B(0.325) C50(0.325) C51(0.325) C52(0.65) H52A(0.65) H52B(0.65)
 H52C(0.65) C53(0.325) C54(0.325) C55(0.65) H55A(0.65) H55B(0.65) H55C(0.65)
 C56(0.325) N2(0.325) O3(0.325) O4(0.325) S2(0.325) H50A(0.325) H50B(0.65)
 H53A(0.65) H53B(0.325) H56A(0.65) H56B(0.325) C31A(0.175) C32A(0.175)
 C33A(0.175) C34A(0.175) H34A(0.175) C35A(0.175) C36A(0.175) H36A(0.175)
 C37A(0.175) C38A(0.175) H38A(0.175) C39A(0.175) C40A(0.175) H40A(0.175)
 C41A(0.175) H41A(0.175) C42A(0.175) C43A(0.175) H43A(0.175) C44A(0.175)
 C45A(0.175) C46A(0.175) C47A(0.175) C48A(0.175) C49A(0.175) H49C(0.175)
 H49D(0.175) C50A(0.175) C51A(0.175) C52A(0.35) H52D(0.35) H52E(0.35)
 H52F(0.35) C53A(0.175) C54A(0.175) C55A(0.35) H55D(0.35) H55E(0.35) H55F(0.35)
 C56A(0.175) N2A(0.175) O3A(0.175) O4A(0.175) S2A(0.175) H50C(0.175) H50D(0.35)
 H53C(0.35) H53D(0.175) H56C(0.175) H56D(0.35)
8.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C49(H49A,H49B), C49A(H49C,H49D)
8.b Me refined with riding coordinates:
 C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C22A(H22D,H22E,H22F), C23A(H,HA,HB),
  C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C52(H52A,H52B,H52C), C55(H55A,H55B,
 H55C), C52A(H52D,H52E,H52F), C55A(H55D,H55E,H55F)
8.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C8(H8), C10(H10), C11(H11), C13(H13), C34(H34), C36(H36),
 C38(H38), C40(H40), C41(H41), C43(H43), C34A(H34A), C36A(H36A), C38A(H38A),
 C40A(H40A), C41A(H41A), C43A(H43A)
;
_olex2_date_sample_data_collection 2016-02-20
_olex2_submission_special_instructions 'No special instructions were received'