Unexpected formation of [5]helicenes from hexaarylbenzenes containing pyrrole moieties
Ammon, Felix; Sauer, Stephanie Theresia; Lippert, Rainer; Lungerich, Dominik; Reger, David; Hampel, Frank; Jux, Norbert; Organic Chemistry Frontiers 4 (2017) 861–; doi:10.1039/C7QO00112F

data_1553743
_publ_section_title
;
 Unexpected formation of [5]helicenes from hexaarylbenzenes containing
 pyrrole moieties
;
_journal_issue                   5
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              861
_journal_paper_doi               10.1039/C7QO00112F
_journal_volume                  4
_journal_year                    2017
_chemical_formula_moiety         'C66 H63 N O2 S, 1.5(C H2 Cl2)'
_chemical_formula_sum            'C67.5 H66 Cl3 N O2 S'
_chemical_formula_weight         1061.62
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_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             2016-09-14
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_audit_update_record
;
2017-01-12 deposited with the CCDC.
2017-03-23 downloaded from the CCDC.
;
_cell_angle_alpha                109.303(4)
_cell_angle_beta                 105.791(4)
_cell_angle_gamma                106.459(5)
_cell_formula_units_Z            2
_cell_length_a                   14.0225(7)
_cell_length_b                   15.4902(10)
_cell_length_c                   15.6494(5)
_cell_measurement_reflns_used    7577
_cell_measurement_temperature    152.7(10)
_cell_measurement_theta_max      56.5370
_cell_measurement_theta_min      3.7480
_cell_volume                     2814.2(3)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      152.7(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6144
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.709
_diffrn_measured_fraction_theta_max 0.961
_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     52.00 149.00   1.00   11.97    --   72.75  77.00  60.00   97
  2  \w     32.00 152.00   1.00   11.97    --   72.75  19.00  30.00  120
  3  \w     34.00 111.00   1.00   11.97    --   72.75 -99.00 120.00   77
  4  \w     36.00 120.00   1.00   11.97    --   72.75-125.00  60.00   84
  5  \w      1.00 105.00   1.00   11.97    --   72.75 -77.00-120.00  104
  6  \w     -2.00  97.00   1.00   11.97    --   72.75 -38.00  90.00   99
  7  \w    -76.00  33.00   1.00    2.99    --    0.00 -77.00  60.00  109
;
_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      0.1164151000
_diffrn_orient_matrix_UB_12      0.0829147000
_diffrn_orient_matrix_UB_13      0.0582537000
_diffrn_orient_matrix_UB_21      0.0455082000
_diffrn_orient_matrix_UB_22      -0.0803298000
_diffrn_orient_matrix_UB_23      -0.0052202000
_diffrn_orient_matrix_UB_31      0.0078850000
_diffrn_orient_matrix_UB_32      -0.0058610000
_diffrn_orient_matrix_UB_33      -0.0978922000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0257
_diffrn_reflns_av_unetI/netI     0.0357
_diffrn_reflns_Laue_measured_fraction_full 0.709
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            11987
_diffrn_reflns_point_group_measured_fraction_full 0.709
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         56.723
_diffrn_reflns_theta_min         3.593
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.173
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83739
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dull brownish yellow'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.253
_exptl_crystal_description       block
_exptl_crystal_F_000             1122
_exptl_crystal_recrystallization_method 'crystallized from DCM/EtOH'
_exptl_crystal_size_max          0.181
_exptl_crystal_size_mid          0.128
_exptl_crystal_size_min          0.071
_refine_diff_density_max         1.591
_refine_diff_density_min         -0.768
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     700
_refine_ls_number_reflns         7226
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0797
_refine_ls_R_factor_gt           0.0729
_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^)+(0.1319P)^2^+4.0495P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1995
_refine_ls_wR_factor_ref         0.2094
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6344
_reflns_number_total             7226
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7qo00112f2.cif
_cod_data_source_block           16jux_fa02_2
_cod_original_formula_sum        'C67.50 H66 Cl3 N O2 S'
_cod_database_code               1553743
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'C66 H63 N O2 S'
_reflns_odcompleteness_completeness 98.51
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     55.03
_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
 Cl21-C200 \\sim Cl22-C200
 with sigma of 0.02
 Cl22-C200 \\sim Cl21-C200
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Cl21 \\sim Cl22: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
Cl11 \\sim Cl12: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
4. Others
 Fixed Sof: Cl11(0.75) Cl12(0.75) Cl22(0.75) Cl21(0.75) C200(0.75) H20A(0.75)
 H20B(0.75) C100(0.75) H10A(0.75) H10B(0.75)
5.a Secondary CH2 refined with riding coordinates:
 C200(H20A,H20B), C100(H10A,H10B)
5.b Aromatic/amide H refined with riding coordinates:
 C22(H22), C21(H21), C27(H27), C53(H53), C59(H59), C42(H42), C36(H36),
 C20(H20), C66(H66), C73(H73), C33(H33), C71(H71), C64(H64), C16(H16), C12(H12),
  C13(H13), C15(H15), C14(H14)
5.c Idealised Me refined as rotating group:
 C75(H75A,H75B,H75C), C76(H76A,H76B,H76C), C77(H77A,H77B,H77C), C56(H56A,H56B,
 H56C), C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C68(H68A,H68B,H68C), C58(H58A,
 H58B,H58C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C),
 C57(H57A,H57B,H57C), C40(H40A,H40B,H40C), C39(H39A,H39B,H39C), C41(H41A,H41B,
 H41C)
;
_olex2_date_sample_data_collection 2016-08-30
_olex2_exptl_crystal_mounting_method 'mounted on a loop'
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.361
_oxdiff_exptl_absorpt_empirical_full_min 0.719