Rare Medium-Sized Rings Prepared via Hydrolytic Imidazoline Ring Expansion (HIRE).
Osipyan, Angelina; Sapegin, Alexander; Novikov, Alexander S.; Krasavin, Mikhail; The Journal of organic chemistry 83 (2018) 9707–9717; doi:10.1021/acs.joc.8b01210

data_4035056
_publ_section_title
;
 Rare Medium-Sized Rings Prepared via Hydrolytic Imidazoline Ring
 Expansion (HIRE).
;
_journal_issue                   17
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              9707
_journal_page_last               9717
_journal_paper_doi               10.1021/acs.joc.8b01210
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'Br, C24 H21 N2 O2 S'
_chemical_formula_sum            'C24 H21 Br N2 O2 S'
_chemical_formula_weight         481.40
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_cell_angle_alpha                62.156(3)
_cell_angle_beta                 85.674(2)
_cell_angle_gamma                71.169(2)
_cell_formula_units_Z            2
_cell_length_a                   8.2753(2)
_cell_length_b                   12.7887(4)
_cell_length_c                   12.9785(4)
_cell_measurement_reflns_used    8191
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      71.7060
_cell_measurement_theta_min      3.7990
_cell_volume                     1144.82(7)
_computing_cell_refinement       'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_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      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix3000
_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    -81.00 -55.00   0.50    0.20    --  -41.35-157.00 159.00   52
  2  \w    -30.00  -4.00   0.50    0.20    --  -41.35 118.00  40.00   52
  3  \w    -91.00 -65.00   0.50    0.20    --  -41.35 157.00-165.00   52
  4  \w     56.00  93.00   0.50    0.20    --   41.35 157.00-165.00   74
  5  \w     65.00 106.00   0.50    0.20    --   41.35-157.00 159.00   82
  6  \w      6.00  43.00   0.50    0.20    --   41.35-118.00 -45.00   74
  7  \w     54.00  80.00   0.50    0.20    --   41.35-118.00 -45.00   52
  8  \w     43.00 116.00   0.50    0.20    --  101.00-118.00 -45.00  146
  9  \w     64.00  89.00   0.50    0.20    --  101.00-157.00 159.00   50
 10  \w    109.00 135.00   0.50    0.20    --  101.00 118.00  40.00   52
 11  \w    -14.00  11.00   0.50    0.20    --  -41.35  77.00  90.00   50
 12  \w    -87.00 -61.00   0.50    0.20    --  -41.35 -65.00-180.00   52
 13  \w   -104.00 -78.00   0.50    0.20    --  -41.35 -77.00-180.00   52
 14  \w    -62.00 -29.00   0.50    0.20    --  -41.35 -43.00  90.00   66
 15  \w    -52.00 -17.00   0.50    0.20    --  -41.35 -77.00-180.00   70
 16  \w    -61.00 -32.00   0.50    0.20    --  -41.35  65.00   0.00   58
 17  \w   -105.00 -69.00   0.50    0.20    --  -41.35 -77.00 120.00   72
 18  \w    -64.00 -16.00   0.50    0.20    --  -41.35 -77.00 120.00   96
 19  \w    -25.00  11.00   0.50    0.20    --  -41.35  65.00   0.00   72
 20  \w    -58.00 -33.00   0.50    0.20    --  -41.35 -65.00-180.00   50
 21  \w    -64.00 -17.00   0.50    0.20    --  -41.35  77.00  90.00   94
 22  \w     31.00  98.00   0.50    0.20    --   41.35  54.00 -90.00  134
 23  \w     34.00  62.00   0.50    0.20    --   41.35  65.00  30.00   56
 24  \w     78.00 104.00   0.50    0.20    --   41.35  43.00   0.00   52
 25  \w     69.00  95.00   0.50    0.20    --   41.35  65.00  30.00   52
 26  \w     78.00 105.00   0.50    0.20    --   41.35  65.00-150.00   54
 27  \w     -9.00  16.00   0.50    0.20    --   41.35 -21.00 -90.00   50
 28  \w     24.00  66.00   0.50    0.20    --   41.35  65.00-150.00   84
 29  \w     32.00  73.00   0.50    0.20    --   41.35  43.00   0.00   82
 30  \w     36.00 129.00   0.50    0.20    --  101.00 -87.00 -60.00  186
 31  \w     94.00 124.00   0.50    0.20    --  101.00  25.00  90.00   60
 32  \w    129.00 157.00   0.50    0.20    --  101.00  68.00  30.00   56
 33  \w    104.00 129.00   0.50    0.20    --  101.00 -87.00-120.00   50
 34  \w     38.00 122.00   0.50    0.20    --  101.00-133.00-180.00  168
 35  \w    103.00 129.00   0.50    0.20    --  101.00  77.00  90.00   52
 36  \w     89.00 132.00   0.50    0.20    --  101.00  42.00  30.00   86
 37  \w     92.00 124.00   0.50    0.20    --  101.00 -77.00  90.00   64
 38  \w     65.00 111.00   0.50    0.20    --  101.00 -77.00   0.00   92
 39  \w     53.00 123.00   0.50    0.20    --  101.00-133.00 -60.00  140
 40  \w     46.00 120.00   0.50    0.20    --  101.00 -68.00   0.00  148
 41  \w     38.00 114.00   0.50    0.20    --  101.00 -42.00   0.00  152
 42  \w     83.00 119.00   0.50    0.20    --  101.00  68.00  30.00   72
 43  \w    108.00 151.00   0.50    0.20    --  101.00  77.00 -60.00   86
 44  \w     72.00 107.00   0.50    0.20    --  101.00   8.00-120.00   70
 45  \w    100.00 157.00   0.50    0.20    --  101.00  33.00-120.00  114
 46  \w     73.00  99.00   0.50    0.20    --  101.00 -68.00  90.00   52
 47  \w     38.00  63.00   0.50    0.20    --  101.00 -68.00  90.00   50
 48  \w     63.00 113.00   0.50    0.20    --  101.00 -59.00 -90.00  100
 49  \w     57.00  87.00   0.50    0.20    --  101.00 -59.00 150.00   60
 50  \w     40.00 110.00   0.50    0.20    --  101.00 -33.00-150.00  140
 51  \w     41.00 113.00   0.50    0.20    --  101.00 -42.00 120.00  144
 52  \w     76.00 106.00   0.50    0.20    --  101.00 -25.00  90.00   60
 53  \w    104.00 130.00   0.50    0.20    --  101.00  68.00 -30.00   52
 54  \w    123.00 148.00   0.50    0.20    --  101.00   8.00-120.00   50
 55  \w     35.00  61.00   0.50    0.20    --  101.00 -25.00  90.00   52
 56  \w     40.00 111.00   0.50    0.20    --  101.00-111.00-180.00  142
 57  \w     87.00 112.00   0.50    0.20    --  101.00  68.00 -90.00   50
 58  \w    100.00 152.00   0.50    0.20    --  101.00  42.00  90.00  104
 59  \w     42.00  91.00   0.50    0.20    --  101.00-133.00  30.00   98
 60  \w     37.00  62.00   0.50    0.20    --  101.00 -87.00-120.00   50
 61  \w    100.00 128.00   0.50    0.20    --  101.00 -87.00 120.00   56
 62  \w    113.00 154.00   0.50    0.20    --  101.00  33.00 -60.00   82
 63  \w     87.00 112.00   0.50    0.20    --  101.00  59.00 -90.00   50
 64  \w     85.00 110.00   0.50    0.20    --  101.00-111.00  60.00   50
 65  \w     85.00 153.00   0.50    0.20    --  101.00  50.00   0.00  136
 66  \w    104.00 129.00   0.50    0.20    --  101.00 157.00-165.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0281115000
_diffrn_orient_matrix_UB_12      -0.0846601000
_diffrn_orient_matrix_UB_13      0.1334728000
_diffrn_orient_matrix_UB_21      -0.1480139000
_diffrn_orient_matrix_UB_22      -0.0458720000
_diffrn_orient_matrix_UB_23      -0.0061627000
_diffrn_orient_matrix_UB_31      0.1276904000
_diffrn_orient_matrix_UB_32      -0.1072272000
_diffrn_orient_matrix_UB_33      -0.0177640000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0322
_diffrn_reflns_av_unetI/netI     0.0339
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            12053
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.844
_diffrn_reflns_theta_min         3.868
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.476
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78637
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.35a (Rigaku Oxford Diffraction, 2017)
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    1.397
_exptl_crystal_description       prism
_exptl_crystal_F_000             492
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.444
_refine_diff_density_min         -0.596
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     272
_refine_ls_number_reflns         4465
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0292
_refine_ls_R_factor_gt           0.0276
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0361P)^2^+0.4817P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0717
_refine_ls_wR_factor_ref         0.0729
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4188
_reflns_number_total             4465
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01210_si_006.cif
_cod_data_source_block           428-9075-sav-928
_cod_database_code               4035056
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C24 H21 N2 O2 S Br2'
_shelx_estimated_absorpt_t_max   0.529
_shelx_estimated_absorpt_t_min   0.477
_reflns_odcompleteness_completeness 99.13
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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:
 C2(H2A,H2B), C18(H18A,H18B), C3(H3A,H3B)
2.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C12(H12), C5(H5), C8(H8), C6(H6), C20(H20), C24(H24),
 C7(H7), C21(H21), C22(H22), C23(H23)
2.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C)
;
_shelx_res_checksum              48831
_shelx_hkl_checksum              84625
_shelx_fab_checksum              73423
_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 1.581
_oxdiff_exptl_absorpt_empirical_full_min 0.696