Electronic effects in tautomeric equilibria: The case of chiral imines from D-glucamine and 2-hydroxyacetophenones
Matamoros, Esther; Cintas, Pedro; Light, Mark; Palacios, Juan C.; Organic & Biomolecular Chemistry  (2019) –; doi:10.1039/C9OB02147G

data_7157212
_publ_section_title
;
 Electronic effects in tautomeric equilibria: The case of chiral imines
 from D-glucamine and 2-hydroxyacetophenones
;
_journal_name_full               'Organic &amp; Biomolecular Chemistry'
_journal_paper_doi               10.1039/C9OB02147G
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C28 H34 Br N O13, C26 H32 Br N O12'
_chemical_formula_sum            'C54 H66 Br2 N2 O25'
_chemical_formula_weight         1302.90
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-09-23
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-09-23 deposited with the CCDC.	2019-11-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.1091(12)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.06056(13)
_cell_length_b                   8.66685(10)
_cell_length_c                   33.7640(4)
_cell_measurement_reflns_used    35897
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.6480
_cell_measurement_theta_min      2.0340
_cell_volume                     2943.99(6)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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_temperature      100(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku HG Saturn724+ (2x2 bin mode)'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.931
_diffrn_measurement_details
;
  1 omega  -96.00   39.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.0000    0.0000  120.0000 135

  2 omega  -58.00   71.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.0000   72.0000  -90.0000 129

  3 omega  -69.00   20.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.0000  -72.0000  -60.0000 89

  4 omega  -49.00  -19.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.0000   72.0000 -150.0000 30

  5 omega -109.00   71.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.0000    0.0000  -60.0000 180

  6 omega  -69.00   20.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.0000  -72.0000  -90.0000 89

  7 omega  -58.00    9.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.0000   72.0000  -30.0000 67

  8 omega  -45.00   20.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.0000   72.0000   30.0000 65
;
_diffrn_measurement_device       'four-circle \k diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroMesh'
_diffrn_orient_matrix_UB_11      -0.0206547000
_diffrn_orient_matrix_UB_12      -0.0053230000
_diffrn_orient_matrix_UB_13      0.0200258000
_diffrn_orient_matrix_UB_21      -0.0661937000
_diffrn_orient_matrix_UB_22      0.0168745000
_diffrn_orient_matrix_UB_23      -0.0058053000
_diffrn_orient_matrix_UB_31      -0.0126550000
_diffrn_orient_matrix_UB_32      -0.0799223000
_diffrn_orient_matrix_UB_33      -0.0025716000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  'Confocal mirrors, HF Varimax'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0338
_diffrn_reflns_av_unetI/netI     0.0356
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.931
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       48
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            60113
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.908
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.872
_diffrn_reflns_theta_min         2.113
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_current           55.0
_diffrn_source_power             2.475
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku FR-E+ SuperBright'
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    1.462
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93938
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.470
_exptl_crystal_description       prism
_exptl_crystal_F_000             1348
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by slow evaporation'
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.292
_refine_diff_density_min         -0.326
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Flack x determined using 6324 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.0045(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     762
_refine_ls_number_reflns         16894
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0379
_refine_ls_R_factor_gt           0.0310
_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^)+(0.0321P)^2^+0.5724P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0636
_refine_ls_wR_factor_ref         0.0662
_reflns_Friedel_coverage         0.840
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.881
_reflns_number_gt                15295
_reflns_number_total             16894
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob02147g2.cif
_cod_data_source_block           2015acc0016_k_100k
_cod_database_code               7157212
_shelx_shelxl_version_number     2016/6
_diffrn_measurement_device_type2 'Rigaku AFC12 (Right)'
_reflns_odcompleteness_completeness 93.16
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.80
_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. Rigid body (RIGU) restrains
 Br11, C101
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3.a Ternary CH refined with riding coordinates:
 C114(H114), C117(H117), C120(H120), C123(H123), C214(H214), C215(H215),
 C218(H218), C221(H221)
3.b Secondary CH2 refined with riding coordinates:
 C113(H11F,H11G), C126(H12G,H12H), C213(H21G,H21H), C224(H22G,H22H)
3.c Aromatic/amide H refined with riding coordinates:
 C102(H102), C103(H103), C106(H106), C202(H202), C203(H203), C206(H206)
3.d X=CH2 refined with riding coordinates:
 C110(H11A,H11B)
3.e Idealised Me refined as rotating group:
 C108(H10A,H10B,H10C), C112(H11C,H11D,H11E), C116(H11H,H11I,H11J), C119(H11K,
 H11L,H11M), C122(H12A,H12B,H12C), C125(H12D,H12E,H12F), C128(H12I,H12J,H12K),
 C208(H20A,H20B,H20C), C210(H21A,H21B,H21C), C212(H21D,H21E,H21F), C217(H21I,
 H21J,H21K), C220(H22A,H22B,H22C), C223(H22D,H22E,H22F), C226(H22I,H22J,H22K)
;
_shelx_res_checksum              45457
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_submission_special_instructions 'No special instructions were received'