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_4031038
_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         'C24 H21 Cl2 N O'
_chemical_formula_sum            'C24 H21 Cl2 N O'
_chemical_formula_weight         410.32
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-09-14
_audit_creation_method
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Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_audit_update_record
;
2015-03-05 deposited with the CCDC.
2015-04-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.75012(8)
_cell_length_b                   14.30489(18)
_cell_length_c                   25.1436(3)
_cell_measurement_reflns_used    8891
_cell_measurement_temperature    180(2)
_cell_measurement_theta_max      77.8160
_cell_measurement_theta_min      4.6470
_cell_volume                     2068.18(5)
_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)'
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_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
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_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_details
;
  1 omega  -47.00   26.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.6532   38.0000 -180.0000 73

  2 omega  -92.00   -1.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.6532  125.0000 -180.0000 91

  3 omega -114.00  -30.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.6532  -38.0000   90.0000 84

  4 omega -111.00  -24.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.6532  -38.0000    0.0000 87

  5 omega  -74.00  -14.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.6532  -57.0000  -90.0000 60

  6 omega   52.00   78.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000  -45.0000 -180.0000 26

  7 omega   58.00   93.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000  -45.0000    0.0000 35

  8 omega  140.00  177.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000  111.0000  120.0000 37

  9 omega   87.00  113.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000   45.0000  150.0000 26

 10 omega   42.00   96.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000  -45.0000   60.0000 54

 11 omega   37.00  115.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000 -111.0000  -30.0000 78

 12 omega   55.00  131.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000   15.0000  120.0000 76

 13 omega   85.00  114.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000   61.0000   90.0000 29

 14 omega   33.00   59.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000  -15.0000   30.0000 26

 15 omega  118.00  176.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000   61.0000  120.0000 58

 16 omega   81.00  134.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000   77.0000   90.0000 53

 17 omega   85.00  111.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000   61.0000  120.0000 26

 18 omega   64.00  172.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000  -15.0000   30.0000 108

 19 omega   90.00  134.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000   61.0000  -90.0000 44

 20 omega   85.00  174.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000   61.0000  150.0000 89

 21 omega   59.00   90.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000  -30.0000 -180.0000 31

 22 omega   81.00  108.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000   77.0000   60.0000 27

 23 omega  141.00  171.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000   77.0000   60.0000 30

 24 omega   89.00  166.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000   61.0000 -150.0000 77
;
_diffrn_measurement_device       'four-circle diffractometer'
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_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.1073577000
_diffrn_orient_matrix_UB_12      0.0290468000
_diffrn_orient_matrix_UB_13      0.0536530000
_diffrn_orient_matrix_UB_21      -0.1715494000
_diffrn_orient_matrix_UB_22      -0.0647025000
_diffrn_orient_matrix_UB_23      0.0293048000
_diffrn_orient_matrix_UB_31      0.1754635000
_diffrn_orient_matrix_UB_32      -0.0810668000
_diffrn_orient_matrix_UB_33      -0.0041740000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0304
_diffrn_reflns_av_unetI/netI     0.0272
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            16058
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.078
_diffrn_reflns_theta_min         4.683
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.926
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76376
_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.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.318
_exptl_crystal_description       block
_exptl_crystal_F_000             856
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.380
_refine_diff_density_min         -0.137
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 1700 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.003(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     257
_refine_ls_number_reflns         4392
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0357
_refine_ls_R_factor_gt           0.0339
_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^)+(0.0551P)^2^+0.2631P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0909
_refine_ls_wR_factor_ref         0.0926
_reflns_Friedel_coverage         0.715
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.982
_reflns_number_gt                4192
_reflns_number_total             4392
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo5b00848_si_003.cif
_cod_data_source_block           rr1
_cod_depositor_comments
'Adding full bibliography for 4031038--4031039.cif.'
_cod_original_cell_volume        2068.18(4)
_cod_database_code               4031038
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C20 H20 N2 O2'
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     72.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, H14 of C14, H11 of C11, H9 of C9, H24 of C24, H16 of C16,
   H22 of C22, H25 of C25, H13 of C13, H10 of C10, H17 of C17, H21 of C21, H8
  of C8, H5 of C5, H3 of C3, H12 of C12
 At 1.5 times of:
  All C(H,H,H) groups, H19 of C25
2.a Ternary CH refined with riding coordinates:
 C3(H3), C5(H5)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C16(H16),
 C17(H17), C21(H21), C22(H22), C24(H24), C25(H25)
2.c X=CH2 refined with riding coordinates:
 C1(H1A,H1B)
2.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C)
;
_olex2_submission_special_instructions 'No special instructions were received'