Slight structural modulation around a pivotal bond: high impact on enantiomeric stability
Farran, Daniel; Vanthuyne, Nicolas; Bossa, Giulia; Belot, Vincent; Albalat, Muriel; Jean, Marion; Roussel, Christian; New Journal of Chemistry 45 (2021) 16039–16047; doi:10.1039/D1NJ03178C

data_7060872
_publ_section_title
;
 Slight structural modulation around a pivotal bond: high impact on
 enantiomeric stability
;
_journal_issue                   35
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              16039
_journal_page_last               16047
_journal_paper_doi               10.1039/D1NJ03178C
_journal_volume                  45
_journal_year                    2021
_chemical_formula_moiety         'C13 H12 Br N S2'
_chemical_formula_sum            'C13 H12 Br N S2'
_chemical_formula_weight         326.27
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-06-13
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2019-09-24 deposited with the CCDC.	2021-07-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.9970(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.52800(10)
_cell_length_b                   7.78550(10)
_cell_length_c                   15.4344(2)
_cell_measurement_reflns_used    38245
_cell_measurement_temperature    293
_cell_measurement_theta_max      70.8970
_cell_measurement_theta_min      3.8090
_cell_volume                     1383.36(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.18b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.18b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.18b (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3048
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_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   -107.00 -35.00   1.00    1.00    --  -17.77-178.00 -30.00   72
  2  \w   -107.00 -35.00   1.00    1.00    --  -17.77-178.00-120.00   72
  3  \w    -91.00  10.00   1.00    1.00    --  -17.77 -57.00 120.00  101
  4  \w     55.00 105.00   1.00    1.00    --   17.77-178.00  60.00   50
  5  \w    -10.00  91.00   1.00    1.00    --   17.77  57.00 120.00  101
  6  \w    -15.00  94.00   1.00    1.00    --   17.77  77.00-120.00  109
  7  \w     28.00 121.00   1.00    5.00    --  101.41-125.00-120.00   93
  8  \w     76.00 174.00   1.00    5.00    --  101.41  45.00-120.00   98
  9  \w     94.00 175.00   1.00    5.00    --  101.41 125.00-180.00   81
 10  \w     28.00 121.00   1.00    5.00    --  101.41-125.00  60.00   93
 11  \w     28.00 127.00   1.00    5.00    --  101.41 -45.00-180.00   99
 12  \w     94.00 175.00   1.00    5.00    --  101.41 125.00-120.00   81
 13  \w     72.00 174.00   1.00    5.00    --  101.41  61.00   0.00  102
 14  \w     72.00 174.00   1.00    5.00    --  101.41  61.00-180.00  102
 15  \w     76.00 174.00   1.00    5.00    --  101.41  45.00  60.00   98
 16  \w     29.00 130.00   1.00    5.00    --  101.41 -61.00  60.00  101
 17  \w     25.00 134.00   1.00    5.00    --  101.41 -77.00-120.00  109
 18  \w    -94.00  15.00   1.00    1.00    --  -17.77 -77.00 -60.00  109
 19  \w    -42.00  57.00   1.00    1.00    --  -17.77  38.00-150.00   99
 20  \w    -98.00  23.00   1.00    1.00    --  -17.77 -19.00 -60.00  121
 21  \w     29.00  78.00   1.00    1.00    --   17.77-133.00-126.00   49
 22  \w     57.00 107.00   1.00    1.00    --   17.77 178.00  30.00   50
 23  \w     72.00 174.00   1.00    5.00    --  101.41  61.00 -60.00  102
 24  \w     72.00 174.00   1.00    5.00    --  101.41  61.00  30.00  102
 25  \w     72.00 174.00   1.00    5.00    --  101.41  61.00 120.00  102
 26  \w     72.00 174.00   1.00    5.00    --  101.41  61.00 150.00  102
 27  \w     72.00 174.00   1.00    5.00    --  101.41  61.00 -30.00  102
 28  \w     72.00 174.00   1.00    5.00    --  101.41  61.00 -90.00  102
 29  \w     72.00 174.00   1.00    5.00    --  101.41  61.00-150.00  102
 30  \w     72.00 174.00   1.00    5.00    --  101.41  61.00  60.00  102
 31  \w     72.00 174.00   1.00    5.00    --  101.41  61.00-120.00  102
 32  \w     72.00 174.00   1.00    5.00    --  101.41  61.00  90.00  102
 33  \w    -92.00   7.00   1.00    1.00    --  -17.77 -38.00 -90.00   99
 34  \w    -98.00  23.00   1.00    1.00    --  -17.77 -19.00 120.00  121
 35  \w      1.00  59.00   1.00    1.00    --   17.77 -99.00 -60.00   58
 36  \w     30.00  80.00   1.00    1.00    --   17.77-136.00  55.00   50
 37  \w      1.00  59.00   1.00    1.00    --   17.77 -99.00 150.00   58
 38  \w     69.00 178.00   1.00    5.00    --  101.41  77.00-180.00  109
 39  \w     69.00 178.00   1.00    5.00    --  101.41  77.00 -90.00  109
 40  \w     69.00 178.00   1.00    5.00    --  101.41  77.00 -60.00  109
 41  \w     69.00 178.00   1.00    5.00    --  101.41  77.00 -30.00  109
 42  \w     69.00 178.00   1.00    5.00    --  101.41  77.00-120.00  109
 43  \w     76.00 174.00   1.00    5.00    --  101.41  45.00 150.00   98
 44  \w     69.00 178.00   1.00    5.00    --  101.41  77.00   0.00  109
 45  \w     69.00 178.00   1.00    5.00    --  101.41  77.00  60.00  109
 46  \w     69.00 178.00   1.00    5.00    --  101.41  77.00 150.00  109
 47  \w     69.00 178.00   1.00    5.00    --  101.41  77.00  90.00  109
 48  \w    -92.00   7.00   1.00    1.00    --  -17.77 -38.00 120.00   99
 49  \w    -92.00   7.00   1.00    1.00    --  -17.77 -38.00  60.00   99
 50  \w    -91.00  10.00   1.00    1.00    --  -17.77 -57.00  60.00  101
 51  \w    -98.00  23.00   1.00    1.00    --  -17.77 -19.00-120.00  121
 52  \w     -7.00  92.00   1.00    1.00    --   17.77  38.00 150.00   99
 53  \w     69.00 178.00   1.00    5.00    --  101.41  77.00  30.00  109
 54  \w     76.00 174.00   1.00    5.00    --  101.41  45.00 -60.00   98
 55  \w     69.00 178.00   1.00    5.00    --  101.41  77.00-150.00  109
 56  \w     76.00 174.00   1.00    5.00    --  101.41  45.00-150.00   98
 57  \w     76.00 174.00   1.00    5.00    --  101.41  45.00-180.00   98
 58  \w     76.00 174.00   1.00    5.00    --  101.41  45.00 -90.00   98
 59  \w     76.00 174.00   1.00    5.00    --  101.41  45.00 -30.00   98
 60  \w     76.00 174.00   1.00    5.00    --  101.41  45.00   0.00   98
 61  \w     76.00 174.00   1.00    5.00    --  101.41  45.00  90.00   98
 62  \w     69.00 178.00   1.00    5.00    --  101.41  77.00 120.00  109
 63  \w    -50.00  58.00   1.00    1.00    --  -17.77  77.00  30.00  108
 64  \w    -46.00  55.00   1.00    1.00    --  -17.77  57.00   0.00  101
 65  \w      1.00  59.00   1.00    1.00    --   17.77 -99.00  90.00   58
 66  \w     -7.00  92.00   1.00    1.00    --   17.77  38.00   0.00   99
 67  \w      1.00  59.00   1.00    1.00    --   17.77 -99.00-150.00   58
 68  \w     76.00 174.00   1.00    5.00    --  101.41  45.00 120.00   98
 69  \w     73.00 178.00   1.00    5.00    --  101.41  30.00 -60.00  105
 70  \w     76.00 174.00   1.00    5.00    --  101.41  45.00  30.00   98
 71  \w     73.00 178.00   1.00    5.00    --  101.41  30.00-120.00  105
 72  \w     73.00 178.00   1.00    5.00    --  101.41  30.00-150.00  105
 73  \w     73.00 178.00   1.00    5.00    --  101.41  30.00 150.00  105
 74  \w     73.00 178.00   1.00    5.00    --  101.41  30.00  30.00  105
 75  \w     49.00 178.00   1.00    5.00    --  101.41  15.00-150.00  129
 76  \w     49.00 167.00   1.00    5.00    --  101.41  15.00 -90.00  118
 77  \w     73.00 178.00   1.00    5.00    --  101.41  30.00  90.00  105
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1275628000
_diffrn_orient_matrix_UB_12      0.0068605000
_diffrn_orient_matrix_UB_13      0.0250952000
_diffrn_orient_matrix_UB_21      0.0044806000
_diffrn_orient_matrix_UB_22      0.1977202000
_diffrn_orient_matrix_UB_23      -0.0006688000
_diffrn_orient_matrix_UB_31      -0.0404347000
_diffrn_orient_matrix_UB_32      0.0003385000
_diffrn_orient_matrix_UB_33      -0.0967106000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0775
_diffrn_reflns_av_unetI/netI     0.0256
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            61001
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.021
_diffrn_reflns_theta_min         3.840
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.676
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45820
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.18b (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    1.567
_exptl_crystal_description       needle
_exptl_crystal_F_000             656
_exptl_crystal_size_max          0.44
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.280
_refine_diff_density_min         -0.374
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
;
 Flack x determined using 2278 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.022(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     316
_refine_ls_number_reflns         5289
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0339
_refine_ls_R_factor_gt           0.0332
_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^)+(0.0542P)^2^+0.3149P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0930
_refine_ls_wR_factor_ref         0.0941
_reflns_Friedel_coverage         0.847
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.987
_reflns_number_gt                5164
_reflns_number_total             5289
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1nj03178c2.cif
_cod_data_source_block           t6br1
_cod_depositor_comments
'Adding full bibliography for 7060869--7060872.cif.'
_cod_database_code               7060872
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         'c13 h12 Br1 n1 s2'
_diffrn_oxdiff_ac3_digest_frames
;
019ffc11be494b4f0f3f6a2e839a4e923c00030e0e1
;
_diffrn_oxdiff_ac3_digest_hkl
;
0193a07ddeeaaaa351c105601a50d7ad0cf661
;
_reflns_odcompleteness_completeness 99.96
_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, All C(H,H,H,H) groups
2. Others
 Fixed Sof: H15A(0.5) H15B(0.5) H15C(0.5) H15D(0.5) C16(0.5) H16A(0.5)
 H16B(0.5) C17(0.5) H17A(0.5) H17B(0.5) H18A(0.5) H18B(0.5) H18C(0.5) H18D(0.5)
3.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C15(H15A,H15B), C15(H15C,
 H15D), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C18(H18C,H18D),
 C19(H19A,H19B)
3.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13), C24(H24), C25(H25), C26(H26), C27(H27)
;
_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 1.919
_oxdiff_exptl_absorpt_empirical_full_min 0.516