An efficient pathway to high persistence length helicenes from scalable [4]-helicene synthons
Reinhard, Garrett L.; Dowling, Reed; Hewitt, Patrick; Varshney, Vikas; Simone, Davide L.; RSC Advances 15 (2025) 20935–20943; doi:10.1039/D5RA02685G

data_7250576
_publ_section_title
;
 An efficient pathway to high persistence length helicenes from scalable
 [4]-helicene synthons
;
_journal_issue                   26
_journal_name_full               'RSC Advances'
_journal_page_first              20935
_journal_page_last               20943
_journal_paper_doi               10.1039/D5RA02685G
_journal_volume                  15
_journal_year                    2025
_chemical_formula_moiety         'C58 H58 Br2 O6'
_chemical_formula_sum            'C58 H58 Br2 O6'
_chemical_formula_weight         1010.86
_chemical_name_systematic
;
11-bromo-benzophenanthren-3-yl (2-isopropyl-5-methyl-cyclohexyl) carbonate
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-05-27
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-06-03 deposited with the CCDC.	2025-06-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.4810(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.26620(10)
_cell_length_b                   8.5188(2)
_cell_length_c                   31.2770(4)
_cell_measurement_reflns_used    7571
_cell_measurement_temperature    200.00(11)
_cell_measurement_theta_max      73.3150
_cell_measurement_theta_min      4.2180
_cell_volume                     2464.35(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      200.00(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.945
_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   -114.00 -26.00   0.50   11.78    --  -47.44 -76.00-108.00  176
  2  \w    -69.00  13.00   0.50   11.78    --  -47.44  76.00  17.00  164
  3  \w     -1.00  25.00   0.50   11.78    --   47.44 -76.00-108.00   52
  4  \w     48.00  73.00   0.50   11.78    --   47.44  76.00  17.00   50
  5  \w    -84.00 -59.00   0.50   47.11    --  -91.75  76.00  17.00   50
  6  \w   -140.00-115.00   0.50   47.11    --  -91.75 -76.00-108.00   50
  7  \w     88.00 167.00   0.50   47.11    --  105.75  76.00  17.00  158
  8  \w     62.00  98.00   0.50   47.11    --  105.75 -76.00-108.00   72
  9  \w    -68.00 -17.00   0.50   11.78    --  -47.44 125.00 150.00  102
 10  \w    -51.00 -25.00   0.50   47.11    --  -91.75  45.00 -30.00   52
 11  \w    -49.00 -21.00   0.50   47.11    --  -91.75  45.00   0.00   56
 12  \w    -45.00 -20.00   0.50   47.11    --  -91.75  45.00  90.00   50
 13  \w    -49.00 -22.00   0.50   47.11    --  -91.75  45.00 150.00   54
 14  \w   -159.00-117.00   0.50   47.11    --  -91.75 -77.00 150.00   84
 15  \w    -51.00 -26.00   0.50   47.11    --  -91.75  45.00-150.00   50
 16  \w   -163.00-110.00   0.50   47.11    --  -91.75 -61.00   0.00  106
 17  \w    -68.00 -39.00   0.50   47.11    --  -91.75  61.00  90.00   58
 18  \w     41.00  71.00   0.50   47.11    --  105.75 -61.00-180.00   60
 19  \w     96.00 126.00   0.50   47.11    --  105.75 125.00-150.00   60
 20  \w     37.00  71.00   0.50   47.11    --  105.75 -61.00 150.00   68
 21  \w    135.00 160.00   0.50   47.11    --  105.75 125.00-150.00   50
 22  \w     33.00  71.00   0.50   47.11    --  105.75 -61.00 -30.00   76
 23  \w     37.00  69.00   0.50   47.11    --  105.75 -61.00-120.00   64
 24  \w     38.00 104.00   0.50   47.11    --  105.75 -77.00 -60.00  132
 25  \w     43.00  69.00   0.50   47.11    --  105.75 -61.00  30.00   52
 26  \w     38.00  70.00   0.50   47.11    --  105.75 -61.00  90.00   64
 27  \w     62.00  87.00   0.50   47.11    --  105.75 -95.00-180.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0466810000
_diffrn_orient_matrix_UB_12      -0.1061027000
_diffrn_orient_matrix_UB_13      -0.0365711000
_diffrn_orient_matrix_UB_21      -0.0816814000
_diffrn_orient_matrix_UB_22      0.1072003000
_diffrn_orient_matrix_UB_23      -0.0329465000
_diffrn_orient_matrix_UB_31      0.1374177000
_diffrn_orient_matrix_UB_32      0.0998163000
_diffrn_orient_matrix_UB_33      -0.0035157000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0328
_diffrn_reflns_av_unetI/netI     0.0388
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.945
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            18195
_diffrn_reflns_point_group_measured_fraction_full 0.794
_diffrn_reflns_point_group_measured_fraction_max 0.733
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.793
_diffrn_reflns_theta_min         4.248
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.490
_exptl_absorpt_correction_T_max  0.70548
_exptl_absorpt_correction_T_min  0.68631
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.94a (Rigaku Oxford Diffraction, 2023)
Spherical absorption correction
using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colorless'
_exptl_crystal_density_diffrn    1.362
_exptl_crystal_description       sphere
_exptl_crystal_F_000             1048
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Acetonitrile'
_exptl_crystal_size_max          0.039
_exptl_crystal_size_mid          0.009
_exptl_crystal_size_min          0.007
_exptl_crystal_size_rad          0.400
_refine_diff_density_max         0.745
_refine_diff_density_min         -0.357
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 1782 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.035(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     601
_refine_ls_number_reflns         7620
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0528
_refine_ls_R_factor_gt           0.0407
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0649P)^2^+0.4399P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1036
_refine_ls_wR_factor_ref         0.1102
_reflns_Friedel_coverage         0.450
_reflns_Friedel_fraction_full    0.556
_reflns_Friedel_fraction_max     0.489
_reflns_number_gt                6286
_reflns_number_total             7620
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ra02685g2.cif
_cod_data_source_block           4helicenementhylbromide200k_adsorpt
_cod_original_formula_sum        '2(C29 H29 Br O3)'
_cod_database_code               7250576
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C29 H28 O3 Br'
_chemical_oxdiff_usercomment     'possible debrominated product'
_diffrn_oxdiff_digest_hkl
;
0152140cfb8ff776382a6aa99a6124ac49d91c
;
_olex2_refinement_description
;
1.a Ternary CH refined with riding coordinates:
 C24(H24), C57(H57), C25(H25), C28(H28), C61(H61), C30(H30), C63(H63), C58(H58)
1.b Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B), C62(H62A,H62B), C26(H26A,H26B), C27(H27A,H27B), C60(H60A,
 H60B), C59(H59A,H59B)
1.c Aromatic/amide H refined with riding coordinates:
 C51(H51), C17(H17), C18(H18), C4(H4), C37(H37), C50(H50), C42(H42), C48(H48),
 C9(H9), C10(H10), C6(H6), C45(H45), C43(H43), C15(H15), C7(H7), C12(H12),
 C13(H13), C46(H46), C39(H39), C40(H40)
1.d Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C66(H66A,H66B,H66C), C65(H65A,H65B,H65C), C33(H33A,H33B,
 H33C), C31(H31A,H31B,H31C), C64(H64A,H64B,H64C)
;
_shelx_res_checksum              29541
_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 1.329
_oxdiff_exptl_absorpt_empirical_full_min 0.743