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_1554898
_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         'C13 H15 Br Cl N O3'
_chemical_formula_sum            'C13 H15 Br Cl N O3'
_chemical_formula_weight         348.62
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2013-03-26
_audit_creation_method
;
  Olex2 1.2
  (compiled Dec  5 2012 16:17:34, GUI svn.r4385)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.211(9)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.929(8)
_cell_length_b                   4.841(2)
_cell_length_c                   36.446(16)
_cell_measurement_reflns_used    1418
_cell_measurement_temperature    100
_cell_measurement_theta_max      22.52
_cell_measurement_theta_min      2.50
_cell_volume                     2930(2)
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0829
_diffrn_reflns_av_unetI/netI     0.1565
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            9643
_diffrn_reflns_point_group_measured_fraction_full 0.946
_diffrn_reflns_point_group_measured_fraction_max 0.931
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.461
_diffrn_reflns_theta_min         2.279
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.991
_exptl_absorpt_correction_T_max  0.8621
_exptl_absorpt_correction_T_min  0.6570
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0826 before and 0.0612 after correction.
The Ratio of minimum to maximum transmission is 0.7621.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.581
_exptl_crystal_description       needle
_exptl_crystal_F_000             1408
_exptl_crystal_recrystallization_method
'crystallized from a dichloromethane/hexane mixture'
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.271
_refine_diff_density_min         -1.570
_refine_diff_density_rms         0.170
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.05(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     175
_refine_ls_number_reflns         6277
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.098
_refine_ls_R_factor_all          0.1440
_refine_ls_R_factor_gt           0.0989
_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^)+(0.0001P)^2^+71.4742P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2008
_refine_ls_wR_factor_ref         0.2163
_reflns_Friedel_coverage         0.691
_reflns_Friedel_fraction_full    0.884
_reflns_Friedel_fraction_max     0.862
_reflns_number_gt                4184
_reflns_number_total             6277
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b00558_si_008.cif
_cod_data_source_block           mo_ca180313_0m
_cod_database_code               1554898
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H1 of N1, H3A of C3A, H2 of C2, H3 of C3, {H8AA,H8AB} of C8A, H2A of C2A,
  {H8A,H8B} of C8, {H12C,H12D} of C12, H6A of C6A, H11 of C11, H9 of C9, H9A of
  C9A, H6 of C6, H5A of C5A, {H12A,H12B} of C12A, H10 of C10, H10A of C10A,
  H11A of C11A, H1A of N1A, H5 of C5
 At 1.5 times of:
  {H13A,H13B,H13C} of C13A, {H13D,H13E,H13F} of C13
2.a Ternary CH refined with riding coordinates:
 C9(H9), C9A(H9A), C10(H10), C10A(H10A), C11(H11), C11A(H11A)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C8A(H8AA,H8AB), C12(H12C,H12D), C12A(H12A,H12B)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1), N1A(H1A), C2(H2), C2A(H2A), C3(H3), C3A(H3A), C5(H5), C5A(H5A),
 C6(H6), C6A(H6A)
2.d Idealised Me refined as rotating group:
 C13(H13D,H13E,H13F), C13A(H13A,H13B,H13C)
;
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.646
_shelx_hkl_checksum              70769
_shelx_res_checksum              84867
_shelxl_version_number           2012-9