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_4035061
_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 O3 S'
_chemical_formula_sum            'C24 H21 Br N2 O3 S'
_chemical_formula_weight         497.40
_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             2018-05-09
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_cell_angle_alpha                112.654(3)
_cell_angle_beta                 95.011(2)
_cell_angle_gamma                108.452(3)
_cell_formula_units_Z            2
_cell_length_a                   8.3367(2)
_cell_length_b                   12.4816(4)
_cell_length_c                   12.9221(4)
_cell_measurement_reflns_used    13434
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.0980
_cell_measurement_theta_min      3.7680
_cell_volume                     1142.96(7)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3829
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.981
_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      2.00  79.00   1.00    2.50    --   40.38 -99.00  90.00   77
  2  \w     41.00 115.00   1.00   10.00    --  113.00-112.00 150.00   74
  3  \w     84.00 111.00   1.00   10.00    --  113.00-112.00  90.00   27
  4  \w     83.00 115.00   1.00   10.00    --  113.00-112.00   0.00   32
  5  \w     81.00 138.00   1.00   10.00    --  113.00 -61.00 -30.00   57
  6  \w     84.00 109.00   1.00   10.00    --  113.00 -95.00-150.00   25
  7  \w     64.00 108.00   1.00   10.00    --  113.00 -95.00 -90.00   44
  8  \w     42.00 111.00   1.00   10.00    --  113.00-112.00-150.00   69
  9  \w     40.00 136.00   1.00   10.00    --  113.00 -61.00 -90.00   96
 10  \w     89.00 177.00   1.00   10.00    --  113.00  30.00  30.00   88
 11  \w    112.00 165.00   1.00   10.00    --  113.00 112.00 -90.00   53
 12  \w    109.00 166.00   1.00   10.00    --  113.00  45.00 -90.00   57
 13  \w     89.00 170.00   1.00   10.00    --  113.00  45.00 -30.00   81
 14  \w     84.00 146.00   1.00   10.00    --  113.00  30.00  90.00   62
 15  \w     61.00 136.00   1.00   10.00    --  113.00 -45.00 150.00   75
 16  \w     30.00  57.00   1.00   10.00    --  113.00 -95.00-150.00   27
 17  \w    -43.00 -16.00   1.00    2.50    --  -40.38 -77.00-150.00   27
 18  \w   -118.00 -92.00   1.00    2.50    --  -40.38 -77.00-150.00   26
 19  \w   -116.00 -14.00   1.00    2.50    --  -40.38 -38.00-150.00  102
 20  \w   -105.00 -11.00   1.00    2.50    --  -40.38 -57.00 120.00   94
 21  \w   -121.00 -39.00   1.00    2.50    --  -40.38 178.00-120.00   82
 22  \w    -70.00 -43.00   1.00    2.50    --  -40.38  96.00 108.00   27
 23  \w    -67.00 -39.00   1.00    2.50    --  -40.38 -77.00   0.00   28
 24  \w    -36.00  -7.00   1.00    2.50    --  -40.38 -77.00   0.00   29
 25  \w    -69.00  29.00   1.00    2.50    --  -40.38  57.00 -90.00   98
 26  \w   -118.00 -69.00   1.00    2.50    --  -40.38 -77.00   0.00   49
 27  \w      6.00  31.00   1.00    2.50    --   44.00  90.00-127.57   25
 28  \w     14.00  41.00   1.00    2.50    --   48.00  78.00 -20.37   27
 29  \w     17.00  42.00   1.00    2.50    --   52.00  81.00  93.66   25
 30  \w     17.00  42.00   1.00    2.50    --   52.00  82.00 125.81   25
 31  \w     19.00  45.00   1.00    2.50    --   52.00  82.00-160.59   26
 32  \w     27.00  54.00   1.00    2.50    --   60.00  75.00 -49.39   27
 33  \w     26.00  53.00   1.00    2.50    --   60.00  77.00  41.96   27
 34  \w     32.00  59.00   1.00    2.50    --   64.00  77.00  95.40   27
 35  \w     35.00  64.00   1.00    2.50    --   68.00  76.00 109.77   29
 36  \w     36.00  63.00   1.00    2.50    --   68.00  75.00-128.36   27
 37  \w     35.00  61.00   1.00    2.50    --   68.00  75.00  -9.99   26
 38  \w     35.00  65.00   1.00    2.50    --   68.00  75.00 162.89   30
 39  \w     41.00  75.00   1.00    2.50    --   72.00  77.00-106.87   34
 40  \w     46.00  72.00   1.00    2.50    --   76.00  73.00  37.32   26
 41  \w     52.00  79.00   1.00   10.00    --   84.00  74.00 -13.13   27
 42  \w     54.00  84.00   1.00   10.00    --   84.00  61.00 -48.35   30
 43  \w     53.00  82.00   1.00   10.00    --   84.00  68.00 111.09   29
 44  \w    123.00 155.00   1.00   10.00    --   84.00  61.00 -48.35   32
 45  \w     53.00  80.00   1.00   10.00    --   84.00  69.00 -48.37   27
 46  \w     52.00  78.00   1.00   10.00    --   84.00  69.00-171.14   26
 47  \w     88.00 120.00   1.00   10.00    --   84.00  61.00 -48.35   32
 48  \w    137.00 162.00   1.00   10.00    --   88.00  57.00-134.76   25
 49  \w     55.00  96.00   1.00   10.00    --   88.00  74.00  34.39   41
 50  \w     59.00  85.00   1.00   10.00    --   88.00  57.00-134.76   26
 51  \w     63.00  95.00   1.00   10.00    --   96.00  76.00  73.95   32
 52  \w     70.00  97.00   1.00   10.00    --  100.00  70.00  -8.84   27
 53  \w     67.00  97.00   1.00   10.00    --  100.00  73.00-136.71   30
 54  \w     73.00  99.00   1.00   10.00    --  104.00  75.00 158.46   26
 55  \w    136.00 174.00   1.00   10.00    --  113.00  77.00-180.00   38
 56  \w     79.00 106.00   1.00   10.00    --  113.00  77.00-180.00   27
 57  \w     87.00 174.00   1.00   10.00    --  113.00  61.00 150.00   87
 58  \w     81.00 107.00   1.00   10.00    --  113.00  77.00  60.00   26
 59  \w    123.00 150.00   1.00   10.00    --  113.00  77.00-120.00   27
 60  \w     82.00 107.00   1.00   10.00    --  113.00  71.00  95.68   25
 61  \w     86.00 139.00   1.00   10.00    --  113.00  61.00-180.00   53
 62  \w    143.00 172.00   1.00   10.00    --  113.00  77.00 120.00   29
 63  \w     79.00 112.00   1.00   10.00    --  113.00  77.00-120.00   33
 64  \w     79.00 105.00   1.00   10.00    --  113.00  77.00 120.00   26
 65  \w     79.00 105.00   1.00   10.00    --  113.00  77.00 -60.00   26
 66  \w     84.00 111.00   1.00   10.00    --  113.00  61.00 -30.00   27
 67  \w     81.00 107.00   1.00   10.00    --  113.00  68.00   4.21   26
 68  \w    115.00 141.00   1.00   10.00    --  113.00  61.00 120.00   26
 69  \w     84.00 111.00   1.00   10.00    --  113.00  61.00 120.00   27
 70  \w     80.00 105.00   1.00   10.00    --  113.00  77.00   0.00   25
 71  \w     88.00 175.00   1.00   10.00    --  113.00  61.00-150.00   87
 72  \w    113.00 171.00   1.00   10.00    --  113.00  71.00  95.68   58
 73  \w     79.00 105.00   1.00   10.00    --  113.00  77.00 -90.00   26
 74  \w    139.00 165.00   1.00   10.00    --  113.00  77.00  60.00   26
 75  \w     83.00 110.00   1.00   10.00    --  113.00  61.00 -60.00   27
 76  \w    142.00 168.00   1.00   10.00    --  113.00  77.00  30.00   26
 77  \w     79.00 105.00   1.00   10.00    --  113.00  77.00  30.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1226476000
_diffrn_orient_matrix_UB_12      0.0447099000
_diffrn_orient_matrix_UB_13      0.0731137000
_diffrn_orient_matrix_UB_21      0.1583170000
_diffrn_orient_matrix_UB_22      0.0970948000
_diffrn_orient_matrix_UB_23      0.1005232000
_diffrn_orient_matrix_UB_31      0.0119542000
_diffrn_orient_matrix_UB_32      0.0974517000
_diffrn_orient_matrix_UB_33      -0.0474316000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0324
_diffrn_reflns_av_unetI/netI     0.0203
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            21143
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.381
_diffrn_reflns_theta_min         3.817
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.535
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64306
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.445
_exptl_crystal_description       prism
_exptl_crystal_F_000             508
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.827
_refine_diff_density_min         -0.806
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     281
_refine_ls_number_reflns         4708
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0337
_refine_ls_R_factor_gt           0.0327
_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^)+(0.0320P)^2^+1.3440P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0816
_refine_ls_wR_factor_ref         0.0823
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4567
_reflns_number_total             4708
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01210_si_007.cif
_cod_data_source_block           0ver0-428-8941_sav-318
_cod_original_cell_volume        1142.95(7)
_cod_database_code               4035061
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C20
_shelx_estimated_absorpt_t_max   0.619
_shelx_estimated_absorpt_t_min   0.538
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     72.42
_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:
 C9(H9A,H9B), C7(H7A,H7B), C8(H8A,H8B)
2.b Aromatic/amide H refined with riding coordinates:
 C21(H21), C15(H15), C19(H19), C18(H18), C12(H12), C14(H14), C13(H13), C6(H6),
 C4(H4), C2(H2), C1(H1), C3(H3)
2.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C)
;
_shelx_res_checksum              3864
_shelx_hkl_checksum              19758
_shelx_fab_checksum              64293
_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 2.054
_oxdiff_exptl_absorpt_empirical_full_min 0.535