Functionalized cationic [4]helicenes with unique tuning of absorption, fluorescence and chiroptical properties up to the far-red range
Delgado, I. Hernández; Pascal, S.; Wallabregue, A.; Duwald, R.; Besnard, C.; Guénée, L.; Nançoz, C.; Vauthey, E.; Tovar, R. C.; Lunkley, J. L.; Muller, G.; Lacour, J.; Chem. Sci. 7 (2016) 4685–; doi:10.1039/C6SC00614K

data_1543068
_publ_section_title
;
 Functionalized cationic [4]helicenes with unique tuning of absorption,
 fluorescence and chiroptical properties up to the far-red range
;
_journal_issue                   7
_journal_name_full               'Chem. Sci.'
_journal_page_first              4685
_journal_paper_doi               10.1039/C6SC00614K
_journal_volume                  7
_journal_year                    2016
_chemical_formula_moiety         'C28 H29 N2 O3, B F4'
_chemical_formula_sum            'C28 H29 B F4 N2 O3'
_chemical_formula_weight         528.34
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P -2ac -2n'
_space_group_name_H-M_alt        'P n 21 a'
_symmetry_space_group_name_Hall  'P -2ac -2n'
_symmetry_space_group_name_H-M   'P n 21 a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2015-06-05
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-12-21 deposited with the CCDC.
2016-04-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   22.69881(19)
_cell_length_b                   21.08434(17)
_cell_length_c                   10.59460(9)
_cell_measurement_reflns_used    20139
_cell_measurement_temperature    180.00(14)
_cell_measurement_theta_max      73.3440
_cell_measurement_theta_min      3.8690
_cell_volume                     5070.46(7)
_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, 2008)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      180.00(14)
_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 0.994
_diffrn_measurement_details
;
  1 omega  -60.00    5.00   1.0000    3.4950
omega____ theta____ kappa____ phi______ frames
    -      -38.9365   77.0000   30.0000 65

  2 omega   21.00   71.00   1.0000    3.4950
omega____ theta____ kappa____ phi______ frames
    -       38.9365   77.0000   90.0000 50

  3 omega   85.00  177.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000    0.0000 92

  4 omega  118.00  156.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000   90.0000 38

  5 omega  129.00  169.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000  120.0000 40

  6 omega   79.00  166.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000  -60.0000 87

  7 omega  107.00  160.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000 -120.0000 53

  8 omega   75.00  166.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000  -90.0000 91

  9 omega   74.00  106.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000  120.0000 32

 10 omega  -65.00   45.00   1.0000    3.4950
omega____ theta____ kappa____ phi______ frames
    -      -38.9365   77.0000 -150.0000 110

 11 omega -117.00  -87.00   1.0000    3.4950
omega____ theta____ kappa____ phi______ frames
    -      -38.9365  -99.0000   30.0000 30

 12 omega -120.00  -94.00   1.0000    3.4950
omega____ theta____ kappa____ phi______ frames
    -      -38.9365  -99.0000  120.0000 26

 13 omega -121.00  -84.00   1.0000    3.4950
omega____ theta____ kappa____ phi______ frames
    -      -38.9365  -99.0000 -120.0000 37

 14 omega  -96.00   -8.00   1.0000    3.4950
omega____ theta____ kappa____ phi______ frames
    -      -38.9365  -38.0000   60.0000 88

 15 omega -124.00  -80.00   1.0000    3.4950
omega____ theta____ kappa____ phi______ frames
    -      -38.9365  -99.0000 -180.0000 44

 16 omega   99.00  132.00   1.0000    3.4950
omega____ theta____ kappa____ phi______ frames
    -       38.9365  178.0000 -150.0000 33

 17 omega   56.00  125.00   1.0000    3.4950
omega____ theta____ kappa____ phi______ frames
    -       38.9365 -178.0000   30.0000 69

 18 omega   77.00  138.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -77.0000 -120.0000 61

 19 omega   46.00   72.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -77.0000 -120.0000 26

 20 omega   28.00   73.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -94.0000 -150.0000 45

 21 omega   38.00   72.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -30.0000 -180.0000 34

 22 omega  109.00  136.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   45.0000 -180.0000 27

 23 omega   67.00  102.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -94.0000 -180.0000 35

 24 omega   46.00   72.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499 -111.0000  -30.0000 26

 25 omega   89.00  116.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499 -111.0000  -30.0000 27

 26 omega   39.00  113.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499 -111.0000  120.0000 74

 27 omega   84.00  109.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -94.0000 -150.0000 25

 28 omega   52.00   87.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -30.0000  -30.0000 35

 29 omega   58.00  144.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  178.0000  150.0000 86

 30 omega  147.00  174.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  111.0000  -90.0000 27
;
_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      0.0290317000
_diffrn_orient_matrix_UB_12      -0.0228415000
_diffrn_orient_matrix_UB_13      -0.1233042000
_diffrn_orient_matrix_UB_21      -0.0396400000
_diffrn_orient_matrix_UB_22      -0.0593068000
_diffrn_orient_matrix_UB_23      0.0006223000
_diffrn_orient_matrix_UB_31      -0.0468212000
_diffrn_orient_matrix_UB_32      0.0360656000
_diffrn_orient_matrix_UB_33      -0.0770407000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0313
_diffrn_reflns_av_unetI/netI     0.0234
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            38343
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.680
_diffrn_reflns_theta_max         73.413
_diffrn_reflns_theta_min         3.895
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.919
_exptl_absorpt_correction_T_max  0.962
_exptl_absorpt_correction_T_min  0.806
_exptl_absorpt_correction_type   gaussian
_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)
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            'dark red'
_exptl_crystal_density_diffrn    1.384
_exptl_crystal_description       plate
_exptl_crystal_F_000             2208
_exptl_crystal_size_max          0.4285
_exptl_crystal_size_mid          0.1339
_exptl_crystal_size_min          0.0652
_refine_diff_density_max         0.686
_refine_diff_density_min         -0.403
_refine_diff_density_rms         0.048
_refine_ls_abs_structure_details
;

The space-.group is non centrosymmetric but contains symmetry element of the second kind.

 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.5(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     713
_refine_ls_number_reflns         9318
_refine_ls_number_restraints     84
_refine_ls_restrained_S_all      1.164
_refine_ls_R_factor_all          0.0546
_refine_ls_R_factor_gt           0.0510
_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^)+(0.1043P)^2^+1.0712P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1480
_refine_ls_wR_factor_ref         0.1533
_reflns_Friedel_coverage         0.945
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                8670
_reflns_number_total             9318
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6sc00614k2.cif
_cod_data_source_block           ih346
_cod_depositor_comments
'Adding full bibliography for 1543067--1543076.cif.'
_cod_database_code               1543068
_chemical_oxdiff_formula         'C28 H29 N2 O3'
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5(2) 0.5(2)
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
 F10B-B6 \\sim F10-B6 \\sim F9B-B6 \\sim F9-B6
 with sigma of 0.02
 F10B-F7 \\sim F10B-F8 \\sim F10B-F9B \\sim F9B-F7 \\sim F9B-F8
 with sigma of 0.04
 F10-F7 \\sim F10-F8 \\sim F10-F9B \\sim F9-F7 \\sim F9-F8
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
F10 \\sim F10B: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
5. Rigid body (RIGU) restrains
 F7, F8, B6, F9B, F10B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F7, F8, B6, F9, F10
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F9)=Sof(F10)=1-FVAR(1)
 Sof(F9B)=Sof(F10B)=FVAR(1)
7.a Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C15(H15A,H15B), C16(H16A,H16B), C31A(H31A,H31B), C10(H10A,
 H10B), C28A(H28A,H28B), C29A(H29A,H29B), C32A(H32A,H32B)
7.b Aromatic/amide H refined with riding coordinates:
 C2A(H2A), C4A(H4A), C5A(H5A), C11(H11), C13(H13), C14(H14), C16A(H16C),
 C17(H17), C18A(H18A), C2AB(H2AB), C4AB(H4AB), C5AB(H5AB), C7(H7), C8(H8),
 C17A(H17A), C25A(H25A), C26A(H26A), C27A(H27A)
7.c Idealised Me refined as rotating group:
 C1A(H1AA,H1AB,H1AC), C19(H19A,H19B,H19C), C22A(H22A,H22B,H22C), C33A(H33A,
 H33B,H33C), C1B(H1BA,H1BB,H1BC), C18(H18B,H18C,H18D), C21A(H21A,H21B,H21C),
 C30A(H30A,H30B,H30C)
;
_shelx_shelxl_version_number     2014/7