Steric Scale of Common Substituents from Rotational Barriers of N-(o-Substituted aryl)thiazoline-2-thione Atropisomers.
Belot, Vincent; Farran, Daniel; Jean, Marion; Albalat, Muriel; Vanthuyne, Nicolas; Roussel, Christian; The Journal of organic chemistry 82 (2017) 10188–10200; doi:10.1021/acs.joc.7b01698

data_4032889
_publ_section_title
;
 Steric Scale of Common Substituents from Rotational Barriers of
 N-(o-Substituted aryl)thiazoline-2-thione Atropisomers.
;
_journal_issue                   19
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              10188
_journal_page_last               10200
_journal_paper_doi               10.1021/acs.joc.7b01698
_journal_volume                  82
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C12 H10 Cl N S2'
_chemical_formula_sum            'C12 H10 Cl N S2'
_chemical_formula_weight         267.78
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-01-06
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5289)
;
_cell_angle_alpha                90.0
_cell_angle_beta                 90.0
_cell_angle_gamma                90.0
_cell_formula_units_Z            4
_cell_length_a                   7.40246(19)
_cell_length_b                   7.5881(2)
_cell_length_c                   21.4216(5)
_cell_measurement_reflns_used    8114
_cell_measurement_temperature    293
_cell_measurement_theta_max      66.7930
_cell_measurement_theta_min      4.1240
_cell_volume                     1203.26(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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_temperature      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3048
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -44.00 -17.00   1.00    1.00    --    0.00  77.00 -30.00   27
  2  \w     -8.00  42.00   1.00    1.00    --    0.00  77.00 -30.00   50
  3  \w     55.00 102.00   1.00    1.00    --    0.00  77.00 -30.00   47
  4  \w     97.00 137.00   1.00    2.00    --   37.69  77.00  30.00   40
  5  \w    102.00 176.00   1.00    5.00    --   75.38 104.00 -30.00   74
  6  \w    149.00 176.00   1.00   15.00    --  113.07  99.00  30.00   27
  7  \w    148.00 178.00   1.00   15.00    --  113.07  99.00  90.00   30
  8  \w    141.00 178.00   1.00   15.00    --  113.07 125.00 120.00   37
  9  \w    132.00 171.00   1.00    5.00    --   75.38  77.00 120.00   39
 10  \w    133.00 176.00   1.00   15.00    --  113.07 125.00  60.00   43
 11  \w    133.00 176.00   1.00   15.00    --  113.07  77.00  30.00   43
 12  \w    116.00 167.00   1.00   15.00    --  113.07  99.00 -90.00   51
 13  \w    138.00 174.00   1.00   15.00    --  113.07 125.00-120.00   36
 14  \w    139.00 173.00   1.00   15.00    --  113.07 125.00-180.00   34
 15  \w    144.00 176.00   1.00   15.00    --  113.07  77.00-180.00   32
 16  \w    129.00 156.00   1.00    5.00    --   90.00  68.00-149.61   27
 17  \w    102.00 129.00   1.00   15.00    --  113.07 125.00-180.00   27
 18  \w     96.00 133.00   1.00   15.00    --  113.07 125.00-120.00   37
 19  \w    101.00 142.00   1.00    5.00    --   82.00  75.00 -70.66   41
 20  \w    109.00 136.00   1.00   15.00    --  113.07  67.00 -30.00   27
 21  \w    101.00 178.00   1.00    5.00    --   82.00  73.00   7.48   77
 22  \w    114.00 141.00   1.00   15.00    --  113.07  99.00  90.00   27
 23  \w    132.00 171.00   1.00   15.00    --  113.07  99.00 150.00   39
 24  \w    101.00 134.00   1.00   15.00    --  113.07  99.00  30.00   33
 25  \w    103.00 155.00   1.00   15.00    --  113.07  99.00   0.00   52
 26  \w    100.00 177.00   1.00    5.00    --   86.00  76.00-112.65   77
 27  \w    105.00 150.00   1.00   15.00    --  113.07 178.00 -90.00   45
 28  \w     97.00 150.00   1.00   15.00    --  113.07 178.00-180.00   53
 29  \w     68.00 143.00   1.00   15.00    --  113.07 178.00 -60.00   75
 30  \w     59.00 169.00   1.00   15.00    --  113.07  77.00  60.00  110
 31  \w     79.00 106.00   1.00    5.00    --   90.00  65.00 118.78   27
 32  \w     79.00 175.00   1.00   15.00    --  113.07  77.00 120.00   96
 33  \w     57.00 144.00   1.00    5.00    --   75.38  43.00  60.00   87
 34  \w     53.00 177.00   1.00    5.00    --   78.00  75.00 159.71  124
 35  \w     53.00 175.00   1.00    5.00    --   82.00  75.00  74.41  122
 36  \w     74.00 136.00   1.00    2.00    --   37.69  57.00-150.00   62
 37  \w     54.00 143.00   1.00    5.00    --   82.00  75.00-154.61   89
 38  \w     47.00 125.00   1.00   15.00    --  113.07  77.00  30.00   78
 39  \w     49.00 150.00   1.00   15.00    --  113.07  77.00 150.00  101
 40  \w     48.00  75.00   1.00   15.00    --  113.07  77.00 120.00   27
 41  \w     47.00 173.00   1.00   15.00    --  113.07  77.00  90.00  126
 42  \w     63.00 111.00   1.00    5.00    --   75.38-104.00 -60.00   48
 43  \w     56.00 115.00   1.00   15.00    --  113.07-126.00 -79.00   59
 44  \w      9.00  62.00   1.00    5.00    --   75.38-104.00 -60.00   53
 45  \w    -32.00 113.00   1.00    5.00    --   75.38  21.00  30.00  145
 46  \w     47.00 149.00   1.00   15.00    --  113.07  77.00 -30.00  102
 47  \w     47.00 173.00   1.00   15.00    --  113.07  77.00-150.00  126
 48  \w     47.00 126.00   1.00   15.00    --  113.07  77.00   0.00   79
 49  \w     47.00 134.00   1.00   15.00    --  113.07  77.00 -90.00   87
 50  \w     48.00 175.00   1.00   15.00    --  113.07  77.00 -60.00  127
 51  \w     45.00  72.00   1.00   15.00    --  113.07  67.00 150.00   27
 52  \w     21.00  46.00   1.00    5.00    --   90.00  65.00 118.78   25
 53  \w     17.00 131.00   1.00    5.00    --   75.38  77.00 120.00  114
 54  \w     45.00  72.00   1.00   15.00    --  113.07  67.00 -30.00   27
 55  \w     30.00  76.00   1.00    5.00    --   82.00  75.00 -70.66   46
 56  \w     47.00 175.00   1.00   15.00    --  113.07  77.00-120.00  128
 57  \w     47.00 143.00   1.00   15.00    --  113.07  77.00-180.00   96
 58  \w     20.00  61.00   1.00    5.00    --   86.00  76.00-112.65   41
 59  \w     23.00  50.00   1.00    5.00    --   90.00  68.00-149.61   27
 60  \w     17.00  53.00   1.00    5.00    --   82.00  75.00-154.61   36
 61  \w     12.00  40.00   1.00    5.00    --   78.00  83.00-161.11   28
 62  \w     12.00  39.00   1.00    5.00    --   78.00  83.00 -96.50   27
 63  \w      9.00  34.00   1.00    5.00    --   75.38  86.00 -26.12   25
 64  \w     16.00  77.00   1.00    5.00    --   82.00  73.00   7.48   61
 65  \w     12.00  37.00   1.00    5.00    --   78.00  83.00  69.92   25
 66  \w     16.00  52.00   1.00    5.00    --   82.00  75.00  74.41   36
 67  \w     13.00  47.00   1.00    5.00    --   78.00  75.00 159.71   34
 68  \w     -4.00  22.00   1.00    5.00    --   66.00  97.00  80.04   26
 69  \w      1.00  27.00   1.00    5.00    --   70.00  93.00  47.81   26
 70  \w    -13.00  14.00   1.00    5.00    --   62.00 106.00 -22.64   27
 71  \w    -15.00  40.00   1.00    2.00    --   37.69  77.00  30.00   55
 72  \w     -2.00  26.00   1.00    5.00    --   75.38  43.00  60.00   28
 73  \w     -5.00  20.00   1.00    5.00    --   66.00  98.00 -84.86   25
 74  \w      1.00  26.00   1.00    5.00    --   70.00  93.00-172.70   25
 75  \w    -40.00  35.00   1.00    2.00    --   37.69  57.00-150.00   75
 76  \w    -10.00 102.00   1.00    1.00    --    0.00  77.00-180.00  112
 77  \w    -17.00  23.00   1.00    2.00    --  -37.69  77.00   0.00   40
 78  \w    -59.00 -29.00   1.00    2.00    --   46.00 156.00 100.14   30
 79  \w    -98.00 -24.00   1.00    2.00    --  -37.69  77.00   0.00   74
 80  \w    -59.00 -10.00   1.00    5.00    --  -70.50 138.00 120.00   49
 81  \w   -101.00 -64.00   1.00    5.00    --  -70.50 138.00 120.00   37
 82  \w   -102.00 -12.00   1.00    5.00    --  -70.50 138.00  90.00   90
 83  \w    -55.00 -30.00   1.00    1.00    --    0.00  77.00-180.00   25
 84  \w   -118.00  41.00   1.00    2.00    --  -37.69 -57.00-180.00  159
 85  \w    -19.00   6.00   1.00    5.00    --  -70.50 -54.00-120.00   25
 86  \w    -80.00 -41.00   1.00    5.00    --  -70.50 -54.00-120.00   39
 87  \w   -133.00-106.00   1.00    5.00    --  -70.50 -54.00-120.00   27
 88  \w   -146.00-119.00   1.00    2.00    --  -37.69 -57.00-180.00   27
 89  \w   -149.00-112.00   1.00    2.00    --  -37.69 -99.00 -60.00   37
 90  \w   -153.00 -73.00   1.00    2.00    --  -37.69-125.00 -30.00   80
 91  \w   -144.00 -93.00   1.00    2.00    --  -37.69 -99.00  60.00   51
 92  \w   -153.00  57.00   1.00    2.00    --  -37.69 -19.00 -30.00  210
 93  \w   -175.00 -84.00   1.00    5.00    --  -70.50-104.00 -30.00   91
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1115228000
_diffrn_orient_matrix_UB_12      0.0789395000
_diffrn_orient_matrix_UB_13      -0.0539231000
_diffrn_orient_matrix_UB_21      -0.1367927000
_diffrn_orient_matrix_UB_22      0.0739564000
_diffrn_orient_matrix_UB_23      0.0474185000
_diffrn_orient_matrix_UB_31      0.1101961000
_diffrn_orient_matrix_UB_32      0.1717820000
_diffrn_orient_matrix_UB_33      0.0043681000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0334
_diffrn_reflns_av_unetI/netI     0.0171
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            12817
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        66.705
_diffrn_reflns_theta_max         66.705
_diffrn_reflns_theta_min         4.127
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.797
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53845
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.478
_exptl_crystal_description       prism
_exptl_crystal_F_000             552
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.267
_refine_diff_density_min         -0.133
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 847 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.005(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     145
_refine_ls_number_reflns         2123
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0237
_refine_ls_R_factor_gt           0.0234
_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^)+(0.0362P)^2^+0.1632P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0644
_refine_ls_wR_factor_ref         0.0647
_reflns_Friedel_coverage         0.684
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                2095
_reflns_number_total             2123
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b01698_si_002.cif
_cod_data_source_block           t5cl1
_cod_depositor_comments          'Adding full bibliography for 4032889.cif.'
_cod_original_cell_volume        1203.26(6)
_cod_database_code               4032889
_shelx_shelxl_version_number     2016/4
_cell_oxdiff_angle_alpha         90.002(3)
_cell_oxdiff_angle_beta          90.033(2)
_cell_oxdiff_angle_gamma         90.013(3)
_cell_oxdiff_length_a            7.4041(2)
_cell_oxdiff_length_b            7.5889(3)
_cell_oxdiff_length_c            21.4147(6)
_cell_oxdiff_measurement_reflns_used 8114
_cell_oxdiff_volume              1203.26(7)
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11)
;
_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 1.533
_oxdiff_exptl_absorpt_empirical_full_min 0.649