Nitrogen Stereodynamics and Complexation Phenomena as Key Factors in the Deprotonative Dynamic Resolution of Alkylideneaziridines: A Spectroscopic and Computational Study.
Degennaro, Leonardo; Pisano, Luisa; Parisi, Giovanna; Mansueto, Rosmara; Clarkson, Guy J.; Shipman, Michael; Luisi, Renzo; The Journal of organic chemistry 80 (2015) 6411–6418; doi:10.1021/acs.joc.5b00848

data_4031039
_publ_section_title
;
 Nitrogen Stereodynamics and Complexation Phenomena as Key Factors in the
 Deprotonative Dynamic Resolution of Alkylideneaziridines: A Spectroscopic
 and Computational Study.
;
_journal_issue                   12
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              6411
_journal_page_last               6418
_journal_paper_doi               10.1021/acs.joc.5b00848
_journal_volume                  80
_journal_year                    2015
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C25 H23 Cl2 N O'
_chemical_formula_sum            'C25 H23 Cl2 N O'
_chemical_formula_weight         424.34
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-09-15
_audit_creation_method
;
Olex2 1.2
(compiled 2014.08.28 svn.r2986 for OlexSys, GUI svn.r4874)
;
_audit_update_record
;
2015-03-05 deposited with the CCDC.
2015-04-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.7987(12)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.11584(8)
_cell_length_b                   7.91067(11)
_cell_length_c                   22.5849(3)
_cell_measurement_reflns_used    6022
_cell_measurement_temperature    180(2)
_cell_measurement_theta_max      77.9000
_cell_measurement_theta_min      5.5800
_cell_volume                     1090.27(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      180(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1417
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_details
;
  1 omega  -83.00   26.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.7109   19.0000   90.0000 109

  2 omega  -22.00   33.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.7109   38.0000  120.0000 55

  3 omega  -48.00   25.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.7109   38.0000  -30.0000 73

  4 omega   46.00   87.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       41.7109 -123.0000   53.0000 41

  5 omega   49.00   83.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       41.7109 -125.0000 -120.0000 34

  6 omega   19.00   46.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       41.7109 -125.0000 -120.0000 27

  7 omega   89.00  177.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000   45.0000    0.0000 88

  8 omega  108.00  174.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000   45.0000 -150.0000 66

  9 omega   41.00   98.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -45.0000 -150.0000 57

 10 omega   47.00  147.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -77.0000   30.0000 100

 11 omega   31.00  109.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -94.0000  -30.0000 78

 12 omega   36.00  105.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -94.0000 -120.0000 69

 13 omega  100.00  132.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  111.0000   30.0000 32

 14 omega   90.00  139.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000   61.0000 -120.0000 49

 15 omega   41.00   95.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -45.0000  -60.0000 54

 16 omega   46.00  132.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000 -149.0000 -110.0000 86

 17 omega   38.00   88.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -30.0000   30.0000 50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1338835000
_diffrn_orient_matrix_UB_12      0.0110350000
_diffrn_orient_matrix_UB_13      -0.0601137000
_diffrn_orient_matrix_UB_21      -0.0266482000
_diffrn_orient_matrix_UB_22      -0.1936375000
_diffrn_orient_matrix_UB_23      -0.0005414000
_diffrn_orient_matrix_UB_31      -0.2123604000
_diffrn_orient_matrix_UB_32      0.0173383000
_diffrn_orient_matrix_UB_33      0.0325656000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0287
_diffrn_reflns_av_unetI/netI     0.0319
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            7141
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.206
_diffrn_reflns_theta_min         5.891
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.792
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.35240
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
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    1.293
_exptl_crystal_description       block
_exptl_crystal_F_000             444
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.335
_refine_diff_density_min         -0.174
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 1996 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).

Flack parameter refined to 0.003(5) so you can be confident in the 
assignment of the chirality but the molecule already contains an 
known chiral centre unchanging during the synthesis 
;
_refine_ls_abs_structure_Flack   0.003(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     267
_refine_ls_number_reflns         4487
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0338
_refine_ls_R_factor_gt           0.0336
_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^)+(0.0631P)^2^+0.0819P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0890
_refine_ls_wR_factor_ref         0.0892
_reflns_Friedel_coverage         0.826
_reflns_Friedel_fraction_full    0.987
_reflns_Friedel_fraction_max     0.940
_reflns_number_gt                4451
_reflns_number_total             4487
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo5b00848_si_002.cif
_cod_data_source_block           rr2
_cod_depositor_comments
'Adding full bibliography for 4031038--4031039.cif.'
_cod_original_cell_volume        1090.27(2)
_cod_database_code               4031039
_shelxl_version_number           2014-2
_chemical_oxdiff_formula         'C20 H20 N2 O2 Cl2'
_reflns_odcompleteness_completeness 99.74
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     72.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups, H20 of C26
 At 1.2 times of:
  H6 of C6, H4 of C4, H2 of C2, H18 of C18, H17 of C17, H15 of C15, H14 of
  C14, H13 of C13, H12 of C12, H11 of C11, H10 of C10, H9 of C9, H26 of C26,
  H25 of C25, H23 of C23, H22 of C22
2.a Ternary CH refined with riding coordinates:
 C4(H4), C6(H6)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15),
 C17(H17), C18(H18), C22(H22), C23(H23), C25(H25), C26(H26)
2.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C7(H7A,H7B,H7C)
;
_olex2_submission_special_instructions 'No special instructions were received'