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_1543076
_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         'C27 H28 N3 O4, H N O3, N O3'
_chemical_formula_sum            'C27 H29 N5 O10'
_chemical_formula_weight         583.55
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2015-02-24
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2016-03-22 deposited with the CCDC.
2016-04-08 downloaded from the CCDC.
;
_cell_angle_alpha                78.648(4)
_cell_angle_beta                 84.294(4)
_cell_angle_gamma                66.016(5)
_cell_formula_units_Z            4
_cell_length_a                   11.8159(7)
_cell_length_b                   14.3381(7)
_cell_length_c                   17.9959(9)
_cell_measurement_reflns_used    18201
_cell_measurement_temperature    179(2)
_cell_measurement_theta_max      73.7220
_cell_measurement_theta_min      3.3620
_cell_volume                     2730.4(3)
_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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      179(2)
_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 0.982
_diffrn_measurement_details
;
  1 omega -112.00  -41.60   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865  -57.0000 -180.0000 88

  2 omega -127.00  -33.40   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865  178.0000  -90.0000 117

  3 omega -112.00   -6.40   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865  -37.0000  -60.0000 132

  4 omega  -34.00   -2.80   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865  -77.0000   90.0000 39

  5 omega  -47.00    4.20   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865   37.0000  -60.0000 64

  6 omega  -93.00  -41.80   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865  -77.0000   90.0000 64

  7 omega  -38.00   -6.80   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865  -57.0000 -180.0000 39

  8 omega   61.00  127.40   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -       37.6865 -178.0000  -90.0000 83

  9 omega   -3.00   22.60   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -       40.0000   96.0000 -121.4006 32

 10 omega   11.00   35.80   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -       48.0000   83.0000   65.2612 31

 11 omega   15.00   42.20   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   82.0000  -13.4253 34

 12 omega   96.00  122.40   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   82.0000  133.9326 33

 13 omega   20.00   45.60   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   79.0000 -163.8674 32

 14 omega   31.00   60.60   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   77.0000   -4.7761 37

 15 omega   30.00   67.60   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   76.0000   44.6165 47

 16 omega   93.00  147.40   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   77.0000   -4.7761 68

 17 omega   28.00   56.00   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   76.0000  -98.4675 35

 18 omega   32.00   56.80   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   77.0000 -171.9023 31

 19 omega  119.00  146.20   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   77.0000  -75.7706 34

 20 omega   32.00   69.60   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   77.0000  -75.7706 47

 21 omega   32.00   59.20   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   76.0000 -131.3169 34

 22 omega   32.00  151.20   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   77.0000   84.3788 149

 23 omega   33.00   73.00   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   76.0000  126.8296 50

 24 omega   96.00  124.00   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   77.0000 -171.9023 35

 25 omega   75.00  150.20   0.8000    0.8000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   76.0000 -131.3169 94

 26 omega  123.00  150.20   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000   90.0000 34

 27 omega   74.00  101.20   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000   90.0000 34

 28 omega   23.00  109.40   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  -94.0000   30.0000 108

 29 omega   74.00  168.40   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000 -150.0000 118

 30 omega   80.00  119.20   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000  120.0000 49

 31 omega  135.00  161.40   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000  120.0000 33

 32 omega   80.00  107.20   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000    0.0000 34

 33 omega   80.00  163.20   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000  -60.0000 104

 34 omega   74.00  113.20   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000  120.0000 49

 35 omega   37.00  109.00   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  -94.0000 -180.0000 90

 36 omega   81.00  116.20   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000   90.0000 44

 37 omega   77.00  105.00   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000  -30.0000 35

 38 omega   74.00  176.40   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000    0.0000 128

 39 omega   74.00   99.60   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000  -90.0000 32

 40 omega   78.00  178.00   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000 -180.0000 125

 41 omega  101.00  176.20   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  111.0000   90.0000 94

 42 omega   78.00  163.60   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000  -90.0000 107

 43 omega   74.00  141.20   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000  150.0000 84

 44 omega   74.00   99.60   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000 -180.0000 32

 45 omega   41.00  105.80   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  -94.0000   90.0000 81

 46 omega   77.00  104.20   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000  150.0000 34

 47 omega  118.00  178.00   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000   60.0000 75

 48 omega   75.00  100.60   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000   60.0000 32

 49 omega   57.00  114.60   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999 -111.0000  -60.0000 72

 50 omega   32.00   99.20   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  -45.0000   60.0000 84

 51 omega  112.00  174.40   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000  -30.0000 78

 52 omega   74.00  122.00   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000 -120.0000 60

 53 omega   74.00  173.20   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000   30.0000 124

 54 omega   79.00  104.60   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000 -150.0000 32

 55 omega   74.00  106.00   0.8000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000  -30.0000 40
;
_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      -0.0812806000
_diffrn_orient_matrix_UB_12      -0.0389944000
_diffrn_orient_matrix_UB_13      -0.0365107000
_diffrn_orient_matrix_UB_21      0.0362852000
_diffrn_orient_matrix_UB_22      -0.0971533000
_diffrn_orient_matrix_UB_23      0.0622036000
_diffrn_orient_matrix_UB_31      -0.1115800000
_diffrn_orient_matrix_UB_32      0.0573777000
_diffrn_orient_matrix_UB_33      0.0492457000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0260
_diffrn_reflns_av_unetI/netI     0.0186
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            42101
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.680
_diffrn_reflns_theta_max         73.845
_diffrn_reflns_theta_min         3.425
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.930
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62641
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.420
_exptl_crystal_description       block
_exptl_crystal_F_000             1224
_exptl_crystal_size_max          0.4757
_exptl_crystal_size_mid          0.3328
_exptl_crystal_size_min          0.1608
_refine_diff_density_max         0.528
_refine_diff_density_min         -0.308
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     773
_refine_ls_number_reflns         10854
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0466
_refine_ls_R_factor_gt           0.0407
_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^)+(0.0685P)^2^+0.6780P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1164
_refine_ls_wR_factor_ref         0.1227
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9411
_reflns_number_total             10854
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6sc00614k2.cif
_cod_data_source_block           reduced
_cod_depositor_comments
'Adding full bibliography for 1543067--1543076.cif.'
_cod_database_code               1543076
_chemical_oxdiff_formula         'C27 H29 N5 O10'
_reflns_odcompleteness_completeness 99.91
_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. Restrained distances
 O12-H12
 0.8 with sigma of 0.02
 O4-H4
 0.8 with sigma of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C28B(H28A,H28B), C29B(H29A,H29B), C31B(H31A,H31B), C32B(H32A,H32B), C28A(H28C,
 H28D), C29A(H29C,H29D), C31A(H31C,H31D), C32A(H32C,H32D)
3.b Aromatic/amide H refined with riding coordinates:
 C4B(H4B), C5B(H5B), C13B(H13B), C14B(H14B), C15B(H15B), C22B(H22B),
 C23B(H23B), C24B(H24B), C4A(H4A), C5A(H5A), C13A(H13A), C14A(H14A), C15A(H15A),
  C22A(H22A), C23A(H23A), C24A(H24A)
3.c Idealised Me refined as rotating group:
 C18B(H18A,H18B,H18C), C27B(H27A,H27B,H27C), C30B(H30A,H30B,H30C), C33B(H33A,
 H33B,H33C), C18A(H18D,H18E,H18F), C27A(H27D,H27E,H27F), C30A(H30D,H30E,H30F),
 C33A(H33D,H33E,H33F)
;
_shelx_shelxl_version_number     2014/7