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_1551493
_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         'C40 H34 Cl N2 O2, B F4'
_chemical_formula_sum            'C40 H34 B Cl F4 N2 O2'
_chemical_formula_weight         696.95
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_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                86.244(5)
_cell_angle_beta                 78.883(5)
_cell_angle_gamma                89.014(5)
_cell_formula_units_Z            2
_cell_length_a                   7.9096(4)
_cell_length_b                   13.4176(8)
_cell_length_c                   16.0932(10)
_cell_measurement_reflns_used    2910
_cell_measurement_temperature    180.01(10)
_cell_measurement_theta_max      72.8950
_cell_measurement_theta_min      4.1610
_cell_volume                     1672.27(17)
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      180.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4679
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.972
_diffrn_measured_fraction_theta_max 0.938
_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    -47.00  25.00   1.00    7.50    --  -37.69  19.00 150.00   72
  2  \w     97.00 123.00   1.00    7.50    --   37.69 178.00 -30.00   26
  3  \w    150.00 175.00   1.00   20.00    --  110.40 111.00 120.00   25
  4  \w     97.00 123.00   1.00   20.00    --  110.40  45.00  90.00   26
  5  \w     34.00 140.00   1.00   20.00    --  110.40 -45.00 120.00  106
  6  \w     82.00 115.00   1.00   20.00    --  110.40-111.00   0.00   33
  7  \w     76.00 102.00   1.00   20.00    --  110.40 -94.00 120.00   26
  8  \w     81.00 109.00   1.00   20.00    --  110.40 -94.00 150.00   28
  9  \w     27.00 129.00   1.00   20.00    --  110.40 -77.00  30.00  102
 10  \w     52.00 108.00   1.00   20.00    --  110.40-111.00 -90.00   56
 11  \w     71.00 140.00   1.00   20.00    --  110.40 -45.00-150.00   69
 12  \w    136.00 178.00   1.00   20.00    --  110.40  45.00-150.00   42
 13  \w     34.00 142.00   1.00   20.00    --  110.40 -61.00-120.00  108
 14  \w     25.00  53.00   1.00   20.00    --  110.40 -94.00 120.00   28
 15  \w     24.00  50.00   1.00   20.00    --  110.40 -94.00 150.00   26
 16  \w     19.00 172.00   1.00   20.00    --  110.40   0.00  30.00  153
 17  \w   -105.00  -5.00   1.00    7.50    --  -37.69 -57.00 -90.00  100
 18  \w   -108.00 -76.00   1.00    7.50    --  -37.69 178.00  30.00   32
 19  \w   -127.00 -37.00   1.00    7.50    --  -37.69 178.00 -60.00   90
 20  \w   -115.00  -7.00   1.00    7.50    --  -37.69 -38.00 150.00  108
;
_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      -0.0556202000
_diffrn_orient_matrix_UB_12      -0.0706156000
_diffrn_orient_matrix_UB_13      0.0796843000
_diffrn_orient_matrix_UB_21      -0.0326192000
_diffrn_orient_matrix_UB_22      0.0906673000
_diffrn_orient_matrix_UB_23      0.0550386000
_diffrn_orient_matrix_UB_31      -0.1877334000
_diffrn_orient_matrix_UB_32      0.0057354000
_diffrn_orient_matrix_UB_33      -0.0133122000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0488
_diffrn_reflns_av_unetI/netI     0.0944
_diffrn_reflns_Laue_measured_fraction_full 0.972
_diffrn_reflns_Laue_measured_fraction_max 0.938
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            10264
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.866
_diffrn_reflns_theta_min         3.301
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.536
_exptl_absorpt_correction_T_max  0.979
_exptl_absorpt_correction_T_min  0.734
_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            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.384
_exptl_crystal_description       plate
_exptl_crystal_F_000             724
_exptl_crystal_size_max          0.431
_exptl_crystal_size_mid          0.063
_exptl_crystal_size_min          0.014
_refine_diff_density_max         0.437
_refine_diff_density_min         -0.420
_refine_diff_density_rms         0.074
_refine_ls_extinction_coef       0.0013(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.097
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     454
_refine_ls_number_reflns         6353
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.1321
_refine_ls_R_factor_gt           0.0721
_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^)+(0.0555P)^2^+1.4991P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1638
_refine_ls_wR_factor_ref         0.2344
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3293
_reflns_number_total             6353
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc02127b2.cif
_cod_data_source_block           compound5
_cod_original_cell_volume        1672.26(17)
_cod_database_code               1551493
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C40 H34 B1 Cl1 F4 N2 O2'
_reflns_odcompleteness_completeness 97.41
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.29
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N41-H41
 0.86 with sigma of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C18(H18A,H18B), C42(H42A,H42B), C43(H43A,H43B)
3.b Aromatic/amide H refined with riding coordinates:
 N41(H41), C3(H3), C4(H4), C6(H6), C7(H7), C12(H12), C13(H13), C14(H14),
 C21(H21), C22(H22), C24(H24), C25(H25), C26(H26), C27(H27), C33(H33), C34(H34),
  C35(H35), C36(H36), C38(H38), C39(H39)
3.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C44(H44A,H44B,H44C)
;
_shelx_res_checksum              79681
_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 1.411
_oxdiff_exptl_absorpt_empirical_full_min 0.670