Synthesis, Resolution, Configurational Stability, and Properties of Cationic Functionalized [5]Helicenes.
Marinova, Maya; Pascal, Simon; Guénée, Laure; Besnard, Céline; Shivachev, Boris; Kostova, Kalina; Villani, Claudio; Franzini, Roberta; Dimitrov, Vladimir; Lacour, Jérôme; The Journal of organic chemistry 85 (2020) 11908–11923; doi:10.1021/acs.joc.0c01716

data_4038743
_publ_section_title
;
 Synthesis, Resolution, Configurational Stability, and Properties of
 Cationic Functionalized [5]Helicenes.
;
_journal_issue                   18
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              11908
_journal_page_last               11923
_journal_paper_doi               10.1021/acs.joc.0c01716
_journal_volume                  85
_journal_year                    2020
_chemical_absolute_configuration unk
_chemical_formula_moiety         '2(C27 H21 Br N O2), C H2 Cl2, 2(B F4)'
_chemical_formula_sum            'C55 H44 B2 Br2 Cl2 F8 N2 O4'
_chemical_formula_weight         1201.26
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2020-02-28
_audit_creation_method
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_cell_angle_alpha                104.972(5)
_cell_angle_beta                 95.439(4)
_cell_angle_gamma                94.459(4)
_cell_formula_units_Z            1
_cell_length_a                   7.7507(4)
_cell_length_b                   12.3048(5)
_cell_length_c                   13.5177(8)
_cell_measurement_reflns_used    9828
_cell_measurement_temperature    179.95(10)
_cell_measurement_theta_max      73.2340
_cell_measurement_theta_min      3.3730
_cell_volume                     1232.80(11)
_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 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (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 0.999
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measurement_details
;
  1 omega  -49.00   36.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -38.9365   38.0000  -30.0000 85

  2 omega   66.00  131.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       38.9365  178.0000 -180.0000 65

  3 omega   59.00   97.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       38.9365  178.0000 -120.0000 38

  4 omega  118.00  172.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  111.0000 -120.0000 54

  5 omega   86.00  129.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       38.9365  178.0000   30.0000 43

  6 omega  122.00  167.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000  120.0000 45

  7 omega   77.00  134.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   61.0000  -60.0000 57

  8 omega   46.00  174.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499    0.0000  -90.0000 128

  9 omega   65.00  112.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499 -111.0000  -90.0000 47

 10 omega   60.00  109.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -94.0000   30.0000 49

 11 omega   58.00  109.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -94.0000  150.0000 51

 12 omega   31.00   93.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -45.0000    0.0000 62

 13 omega   28.00  103.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -94.0000  -30.0000 75

 14 omega   30.00   83.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -30.0000   90.0000 53

 15 omega   24.00   57.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -94.0000   30.0000 33

 16 omega   26.00   63.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -94.0000 -150.0000 37

 17 omega   31.00   99.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -45.0000 -180.0000 68

 18 omega -112.00  -15.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -38.9365  -57.0000 -180.0000 97

 19 omega -119.00  -86.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -38.9365  -99.0000  -60.0000 33

 20 omega -116.00  -63.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -38.9365 -151.0000 -102.0000 53

 21 omega  -40.00   -5.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -39.0615  -77.0000 -120.0000 35

 22 omega  -70.00  -17.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -39.0615  -57.0000   60.0000 53

 23 omega  -90.00   -3.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -39.0615  -77.0000    0.0000 87

 24 omega  -51.00   -4.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -39.0615  -77.0000  120.0000 47

 25 omega  -75.00   26.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -39.0615   19.0000  -90.0000 101

 26 omega -117.00  -68.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -39.0615  -38.0000  -60.0000 49

 27 omega  -32.00   -7.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -39.0615  -57.0000 -120.0000 25

 28 omega  -77.00  -50.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -39.0615  -57.0000 -120.0000 27

 29 omega   50.00   76.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       39.0615 -125.0000 -150.0000 26

 30 omega  119.00  145.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000   90.0000 26

 31 omega  117.00  177.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000   60.0000 60

 32 omega   77.00  102.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   61.0000  -30.0000 25

 33 omega   74.00  140.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000    0.0000 66

 34 omega   74.00  100.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000  -90.0000 26

 35 omega   74.00  103.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000   60.0000 29

 36 omega   74.00  115.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000   90.0000 41

 37 omega   78.00  104.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   61.0000  -90.0000 26

 38 omega   77.00  110.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   61.0000    0.0000 33

 39 omega   74.00  125.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000  -60.0000 51

 40 omega   74.00  149.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000   30.0000 75

 41 omega   74.00  100.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000 -150.0000 26

 42 omega   77.00  111.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   61.0000  120.0000 34

 43 omega   77.00  103.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   61.0000 -120.0000 26

 44 omega   77.00  103.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   61.0000   30.0000 26

 45 omega   74.00   99.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000 -120.0000 25

 46 omega   74.00  102.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000  150.0000 28

 47 omega   77.00  109.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   61.0000   90.0000 32

 48 omega   78.00  103.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   61.0000   60.0000 25

 49 omega   74.00  123.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000  120.0000 49

 50 omega   77.00  103.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   61.0000 -180.0000 26

 51 omega   77.00  103.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   61.0000 -150.0000 26

 52 omega   74.00  101.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000 -180.0000 27

 53 omega   78.00  118.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   61.0000  150.0000 40

 54 omega   74.00  145.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000  -30.0000 71
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1992704000
_diffrn_orient_matrix_UB_12      -0.0296241000
_diffrn_orient_matrix_UB_13      -0.0193518000
_diffrn_orient_matrix_UB_21      -0.0110823000
_diffrn_orient_matrix_UB_22      0.0434806000
_diffrn_orient_matrix_UB_23      0.1165191000
_diffrn_orient_matrix_UB_31      -0.0220924000
_diffrn_orient_matrix_UB_32      0.1193043000
_diffrn_orient_matrix_UB_33      -0.0124785000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_unetI/netI     0.0331
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            15209
_diffrn_reflns_point_group_measured_fraction_full 0.908
_diffrn_reflns_point_group_measured_fraction_max 0.877
_diffrn_reflns_theta_full        67.680
_diffrn_reflns_theta_max         73.599
_diffrn_reflns_theta_min         3.409
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.787
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64059
_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.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.618
_exptl_crystal_description       plate
_exptl_crystal_F_000             606
_exptl_crystal_size_max          0.265
_exptl_crystal_size_mid          0.1635
_exptl_crystal_size_min          0.0374
_refine_diff_density_max         0.607
_refine_diff_density_min         -0.660
_refine_diff_density_rms         0.072
_refine_ls_abs_structure_details
;
rystal is a non merohedral twin. Both components were integrated into a single HKLF5 file. No attemps was made to refine the absolute structure fron the twinned data.Hooft parameter given below.
The flack parameter on the major twin refined to -0.01(5). 
;
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     761
_refine_ls_number_reflns         15209
_refine_ls_number_restraints     202
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0694
_refine_ls_R_factor_gt           0.0651
_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^)+(0.1464P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1789
_refine_ls_wR_factor_ref         0.1829
_reflns_Friedel_coverage         0.796
_reflns_Friedel_fraction_full    0.818
_reflns_Friedel_fraction_max     0.777
_reflns_number_gt                13816
_reflns_number_total             15209
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c01716_si_002.cif
_cod_data_source_block           10B
_cod_depositor_comments
'Adding full bibliography for 4038740--4038746.cif.'
_cod_original_cell_volume        1232.79(11)
_cod_database_code               4038743
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C55 H44 N2 O4 F8 B2 Br2 Cl2'
_shelx_estimated_absorpt_t_max   0.871
_shelx_estimated_absorpt_t_min   0.434
_diffrn_oxdiff_twin_integration_method simultaneous
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6504(15)
 0.3496(15)
2. 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
3. Restrained distances
 B1F-F3F \\sim B1F-F4F \\sim B1F-F2F \\sim B1F-F5F
 with sigma of 0.02
 F2F-F3F \\sim F2F-F5F \\sim F3F-F4F \\sim F3F-F5F \\sim F4F-F5F \\sim F2F-F4F
 with sigma of 0.04
 B1G-F2G \\sim B1G-F3G \\sim B1G-F4G \\sim B1G-F5G
 with sigma of 0.02
 F2G-F3G \\sim F2G-F5G \\sim F3G-F4G \\sim F3G-F5G \\sim F4G-F5G
 with sigma of 0.04
 B1I-F2I \\sim B1I-F5I \\sim B1I-F3I \\sim B1I-F4I
 with sigma of 0.02
 F2I-F3I \\sim F2I-F4I \\sim F2I-F5I \\sim F3I-F4I \\sim F3I-F5I \\sim F4I-F5I
 with sigma of 0.04
 B1H-F3H \\sim B1H-F2H \\sim B1H-F5H \\sim B1H-F4H
 with sigma of 0.02
 F3H-F2H \\sim F3H-F5H \\sim F3H-F4H \\sim F2H-F5H \\sim F2H-F4H \\sim F5H-F4H
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
Uanis(B1G) = Uanis(B1F)
Uanis(B1I) = Uanis(B1H)
5. Rigid body (RIGU) restrains
 F4G, F2G, B1G, F3G, F5G
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F2F, F3F, B1F, F4F, F5F
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F5H, F3H, B1H, F2H, F4H
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F5I, F2I, B1I, F3I, F4I
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F2G)=Sof(F3G)=Sof(B1G)=Sof(F4G)=Sof(F5G)=1-FVAR(1)
 Sof(F3F)=Sof(F4F)=Sof(B1F)=Sof(F2F)=Sof(F5F)=FVAR(1)
 Sof(F2I)=Sof(B1I)=Sof(F5I)=Sof(F3I)=Sof(F4I)=1-FVAR(2)
 Sof(F3H)=Sof(F2H)=Sof(B1H)=Sof(F5H)=Sof(F4H)=FVAR(2)
7.a Secondary CH2 refined with riding coordinates:
 C29B(H29A,H29B), C30A(H30C,H30D), C30B(H30A,H30B), C29A(H29C,H29D), C0BA(H0BA,
 H0BB)
7.b Aromatic/amide H refined with riding coordinates:
 C24B(H24B), C22B(H22B), C13B(H13B), C8B(H8B), C22A(H22A), C24A(H24A),
 C9A(H9A), C13A(H13A), C8A(H8A), C15A(H15A), C23B(H23B), C4B(H4B), C3B(H3B),
 C15B(H15B), C7B(H7B), C7A(H7A), C14B(H14B), C9B(H9B), C23A(H23A), C4A(H4A),
 C3A(H3A), C14A(H14A)
7.c Idealised Me refined as rotating group:
 C31B(H31A,H31B,H31C), C28A(H28D,H28E,H28F), C28B(H28A,H28B,H28C), C31A(H31D,
 H31E,H31F)
;
_shelx_res_checksum              26435
_shelx_hkl_checksum              51867
_olex2_submission_special_instructions 'No special instructions were received'