Stereochemical studies of the opening of chloro vinyl epoxides: cyclic chloronium ions as intermediates.
Shemet, Andrej; Sarlah, David; Carreira, Erick M.; Organic letters 17 (2015) 1878–1881; doi:10.1021/acs.orglett.5b00558

data_1554885
_publ_section_title
;
 Stereochemical studies of the opening of chloro vinyl epoxides: cyclic
 chloronium ions as intermediates.
;
_journal_issue                   8
_journal_name_full               'Organic letters'
_journal_page_first              1878
_journal_page_last               1881
_journal_paper_doi               10.1021/acs.orglett.5b00558
_journal_volume                  17
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H20 Br2 Cl2 N2 O4'
_chemical_formula_sum            'C20 H20 Br2 Cl2 N2 O4'
_chemical_formula_weight         583.10
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-03-13
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                65.191(3)
_cell_angle_beta                 89.579(4)
_cell_angle_gamma                80.838(3)
_cell_formula_units_Z            2
_cell_length_a                   5.0746(9)
_cell_length_b                   14.828(3)
_cell_length_c                   16.699(3)
_cell_measurement_reflns_used    1034
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      20.968
_cell_measurement_theta_min      2.471
_cell_volume                     1123.5(4)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.955
_diffrn_measured_fraction_theta_max 0.955
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker Kappa Apex-II Duo'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'focusing graphite'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0652
_diffrn_reflns_av_unetI/netI     0.1401
_diffrn_reflns_Laue_measured_fraction_full 0.955
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            9967
_diffrn_reflns_point_group_measured_fraction_full 0.727
_diffrn_reflns_point_group_measured_fraction_max 0.727
_diffrn_reflns_theta_full        25.175
_diffrn_reflns_theta_max         25.175
_diffrn_reflns_theta_min         2.434
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.875
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6139
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0746 before and 0.0636 after correction.
The Ratio of minimum to maximum transmission is 0.8238.
The \l/2 correction factor is 0.0000.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.724
_exptl_crystal_description       needle
_exptl_crystal_F_000             580
_exptl_crystal_recrystallization_method 'crystallized from dichloromethane'
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.516
_refine_diff_density_min         -0.723
_refine_diff_density_rms         0.143
_refine_ls_abs_structure_details
;
 Flack x determined using 987 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.048(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.988
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     531
_refine_ls_number_reflns         5842
_refine_ls_number_restraints     579
_refine_ls_restrained_S_all      0.947
_refine_ls_R_factor_all          0.1174
_refine_ls_R_factor_gt           0.0611
_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^)+(0.0591P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1252
_refine_ls_wR_factor_ref         0.1461
_reflns_Friedel_coverage         0.523
_reflns_Friedel_fraction_full    0.499
_reflns_Friedel_fraction_max     0.499
_reflns_number_gt                3715
_reflns_number_total             5842
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b00558_si_009.cif
_cod_data_source_block           mo_ca190213_0m
_cod_original_cell_volume        1123.5(3)
_cod_database_code               1554885
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
4.a Ternary CH refined with riding coordinates:
 C11(H11), C12(H12), C24(H24), C11A(H11A), C12A(H12A), C24A(H24A)
4.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C25(H25A,H25B), C13A(H13C,H13D), C25A(H25C,H25D)
4.c Aromatic/amide H refined with riding coordinates:
 N7(H7), N17(H17), C2(H2), C3(H3), C5(H5), C6(H6), C19(H19), C20(H20),
 C22(H22), C23(H23), N7A(H7A), N17A(H17A), C2A(H2A), C3A(H3A), C5A(H5A),
 C6A(H6A), C19A(H19A), C20A(H20A), C22A(H22A), C23A(H23A)
4.d Fitted hexagon refined as free rotating group:
 C18A(C19A,C20A,C21A,C22A,C23A)
4.e Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C26A(H26D,H26E,H26F)
;
_shelx_res_checksum              4969
_shelx_hkl_checksum              40951
_shelx_shelxl_version_number     2014/7
_olex2_exptl_crystal_mounting_method tip-mounted
_olex2_submission_special_instructions 'No special instructions were received'