Stereochemical significance of O to N atom interchanges within cationic helicenes: experimental and computational evidence of near racemization to remarkable enantiospecificity
Labrador, Geraldine M.; Besnard, Céline; Bürgi, Thomas; Poblador-Bahamonde, Amalia I.; Bosson, Johann; Lacour, Jérôme; Chemical Science  (2019) –; doi:10.1039/C9SC02127B

data_1551492
_publ_section_title
;
 Stereochemical significance of O to N atom interchanges within cationic
 helicenes: experimental and computational evidence of near racemization
 to remarkable enantiospecificity
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC02127B
_journal_year                    2019
_chemical_formula_moiety         'C32 H22 F3 N O3'
_chemical_formula_sum            'C32 H22 F3 N O3'
_chemical_formula_weight         525.50
_space_group_crystal_system      orthorhombic
_space_group_IT_number           56
_space_group_name_Hall           '-P 2ab 2ac'
_space_group_name_H-M_alt        'P c c n'
_symmetry_space_group_name_Hall  '-P 2ab 2ac'
_symmetry_space_group_name_H-M   'P c c n'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-06-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-04-05 deposited with the CCDC.    2019-06-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   8.96089(13)
_cell_length_b                   35.7856(6)
_cell_length_c                   14.92847(19)
_cell_measurement_reflns_used    15413
_cell_measurement_temperature    179.95(10)
_cell_measurement_theta_max      73.3490
_cell_measurement_theta_min      4.8950
_cell_volume                     4787.12(12)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_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    'SIR2004 (Burla et al.,  2007)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      179.95(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4679
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -100.00  -3.00   1.00    1.00    --  -38.94 -77.00  60.00   97
  2  \w   -110.00 -84.00   1.00    1.00    --  -38.94 -99.00   0.00   26
  3  \w     30.00 102.00   1.00    5.00    --  109.75 -94.00-120.00   72
  4  \w     40.00  97.00   1.00    5.00    --  109.75 -45.00-150.00   57
  5  \w     30.00  87.00   1.00    5.00    --  109.75 -30.00 -30.00   57
  6  \w     30.00  88.00   1.00    5.00    --  109.75 -30.00  30.00   58
  7  \w     31.00  72.00   1.00    5.00    --  109.75 -30.00 120.00   41
  8  \w    101.00 127.00   1.00    1.00    --   38.94 178.00 -60.00   26
  9  \w   -121.00 -81.00   1.00    1.00    --  -38.94 178.00 -60.00   40
 10  \w      5.00  67.00   1.00    1.00    --   38.94 -99.00  90.00   62
 11  \w     42.00  94.00   1.00    5.00    --  109.75 -45.00 -90.00   52
 12  \w     66.00 103.00   1.00    5.00    --  109.75 -94.00 -60.00   37
 13  \w    131.00 167.00   1.00    5.00    --  109.75 -15.00 150.00   36
 14  \w     62.00  89.00   1.00    5.00    --  109.75 -15.00 150.00   27
 15  \w   -124.00 -85.00   1.00    1.00    --  -38.94 -99.00  60.00   39
 16  \w   -120.00 -87.00   1.00    1.00    --  -38.94 -99.00  90.00   33
 17  \w   -124.00 -79.00   1.00    1.00    --  -38.94 -99.00-150.00   45
 18  \w    -86.00 -35.00   1.00    1.00    --  -38.94-178.00   0.00   51
 19  \w   -119.00 -83.00   1.00    1.00    --  -38.94 -99.00 150.00   36
 20  \w     10.00  74.00   1.00    1.00    --   38.94 -99.00 -30.00   64
 21  \w     60.00 101.00   1.00    1.00    --   38.94 178.00 -90.00   41
 22  \w     57.00 114.00   1.00    1.00    --   38.94 178.00   0.00   57
 23  \w    119.00 168.00   1.00    5.00    --  109.75  45.00 150.00   49
 24  \w     47.00  78.00   1.00    5.00    --  109.75 -45.00  90.00   31
 25  \w     41.00 105.00   1.00    5.00    --  109.75 -94.00  90.00   64
 26  \w     79.00 105.00   1.00    5.00    --  109.75  45.00 150.00   26
 27  \w     86.00 111.00   1.00    5.00    --  109.75-111.00-120.00   25
 28  \w     29.00  59.00   1.00    5.00    --  109.75-111.00-120.00   30
 29  \w    153.00 178.00   1.00    5.00    --  109.75 111.00 120.00   25
 30  \w     49.00 116.00   1.00    5.00    --  109.75-111.00  60.00   67
 31  \w     49.00  91.00   1.00    5.00    --  109.75 -94.00-180.00   42
 32  \w     96.00 156.00   1.00    5.00    --  109.75   0.00 -60.00   60
 33  \w     46.00  89.00   1.00    5.00    --  109.75   0.00 -60.00   43
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0838076000
_diffrn_orient_matrix_UB_12      -0.0375216000
_diffrn_orient_matrix_UB_13      0.0052070000
_diffrn_orient_matrix_UB_21      0.1462066000
_diffrn_orient_matrix_UB_22      -0.0209660000
_diffrn_orient_matrix_UB_23      -0.0204892000
_diffrn_orient_matrix_UB_31      0.0339030000
_diffrn_orient_matrix_UB_32      -0.0023276000
_diffrn_orient_matrix_UB_33      0.1010323000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0437
_diffrn_reflns_av_unetI/netI     0.0207
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       43
_diffrn_reflns_limit_k_min       -44
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            34874
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.338
_diffrn_reflns_theta_min         4.943
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.914
_exptl_absorpt_correction_T_max  0.955
_exptl_absorpt_correction_T_min  0.691
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.458
_exptl_crystal_description       plate
_exptl_crystal_F_000             2176
_exptl_crystal_size_max          0.631
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.170
_refine_diff_density_min         -0.234
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     353
_refine_ls_number_reflns         4778
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0415
_refine_ls_R_factor_gt           0.0369
_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^)+(0.0401P)^2^+1.9961P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0899
_refine_ls_wR_factor_ref         0.0938
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4307
_reflns_number_total             4778
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc02127b2.cif
_cod_data_source_block           compound4
_cod_original_cell_volume        4787.13(12)
_cod_database_code               1551492
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C32 H22 F3 N O3'
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Secondary CH2 refined with riding coordinates:
 C39(H39A,H39B), C38(H38A,H38B)
2.b Aromatic/amide H refined with riding coordinates:
 C21(H21), C27(H27), C36(H36), C32(H32), C33(H33), C28(H28), C35(H35),
 C30(H30), C26(H26), C31(H31), C14(H14), C13(H13), C15(H15), C25(H25), C22(H22)
2.c Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C)
;
_shelx_res_checksum              41855
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.430
_oxdiff_exptl_absorpt_empirical_full_min 0.308