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_7250575
_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         'C29 H31 Br O3'
_chemical_formula_sum            'C29 H31 Br O3'
_chemical_formula_weight         507.45
_chemical_name_systematic
;
(E)-6-(4-bromostyryl)-naphthalen-2-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     direct
_audit_creation_date             2025-05-21
_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                 93.2965(11)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.98182(9)
_cell_length_b                   7.54889(12)
_cell_length_c                   27.9195(4)
_cell_measurement_reflns_used    5536
_cell_measurement_temperature    200.0(3)
_cell_measurement_theta_max      76.2080
_cell_measurement_theta_min      4.7490
_cell_volume                     1258.65(3)
_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 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      200.0(3)
_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 0.916
_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    -25.00  19.00   0.50    3.67    --  -47.44  87.00-142.00   88
  2  \w     -2.00  38.00   0.50    3.67    --   47.44 -87.00  99.00   80
  3  \w   -143.00-116.00   0.50   14.68    --  -91.75 -87.00  99.00   54
  4  \w    -54.00 -22.00   0.50   14.68    --  -91.75  87.00-142.00   64
  5  \w    126.00 163.00   0.50   14.68    --  105.75  87.00-142.00   74
  6  \w     63.00 131.00   0.50   14.68    --  105.75 -87.00  99.00  136
  7  \w    -43.00  24.00   0.50    3.67    --  -47.44  38.00 -30.00  134
  8  \w    -25.00  28.00   0.50    3.67    --  -47.44  19.00-150.00  106
  9  \w    -27.00  -1.00   0.50    3.67    --   47.44 -19.00  60.00   52
 10  \w   -163.00 -81.00   0.50   14.68    --  -91.75 -30.00  90.00  164
 11  \w    -45.00 -20.00   0.50   14.68    --  -91.75  45.00 -90.00   50
 12  \w    -55.00 -25.00   0.50   14.68    --  -91.75  61.00 -60.00   60
 13  \w   -160.00-135.00   0.50   14.68    --  -91.75 -95.00  60.00   50
 14  \w    -51.00 -21.00   0.50   14.68    --  -91.75  45.00  30.00   60
 15  \w    -50.00 -21.00   0.50   14.68    --  -91.75  45.00-180.00   58
 16  \w    -70.00 -44.00   0.50   14.68    --  -91.75  61.00-150.00   52
 17  \w    -63.00 -30.00   0.50   14.68    --  -91.75  61.00  60.00   66
 18  \w    -51.00 -20.00   0.50   14.68    --  -91.75  45.00 150.00   62
 19  \w    -51.00 -21.00   0.50   14.68    --  -91.75  45.00  60.00   60
 20  \w    -48.00 -22.00   0.50   14.68    --  -91.75  45.00-120.00   52
 21  \w     38.00  64.00   0.50   14.68    --  105.75 -61.00-150.00   52
 22  \w     94.00 170.00   0.50   14.68    --  105.75  15.00-180.00  152
 23  \w     46.00  71.00   0.50   14.68    --  105.75 -61.00  60.00   50
 24  \w     37.00  69.00   0.50   14.68    --  105.75 -61.00 -60.00   64
;
_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      0.0953593000
_diffrn_orient_matrix_UB_12      0.1698848000
_diffrn_orient_matrix_UB_13      -0.0215865000
_diffrn_orient_matrix_UB_21      -0.0710840000
_diffrn_orient_matrix_UB_22      -0.0664737000
_diffrn_orient_matrix_UB_23      -0.0507673000
_diffrn_orient_matrix_UB_31      -0.2290726000
_diffrn_orient_matrix_UB_32      0.0913191000
_diffrn_orient_matrix_UB_33      0.0031963000
_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  0.0300
_diffrn_reflns_av_unetI/netI     0.0380
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.916
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            8378
_diffrn_reflns_point_group_measured_fraction_full 0.838
_diffrn_reflns_point_group_measured_fraction_max 0.754
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.507
_diffrn_reflns_theta_min         4.760
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.437
_exptl_absorpt_correction_T_max  0.53256
_exptl_absorpt_correction_T_min  0.49095
_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 yellowish'
_exptl_crystal_density_diffrn    1.339
_exptl_crystal_description       sphere
_exptl_crystal_F_000             528
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Acetonitrile'
_exptl_crystal_size_max          0.128
_exptl_crystal_size_mid          0.022
_exptl_crystal_size_min          0.005
_exptl_crystal_size_rad          0.400
_refine_diff_density_max         0.263
_refine_diff_density_min         -0.345
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1241 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.052(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     301
_refine_ls_number_reflns         4002
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0315
_refine_ls_R_factor_gt           0.0287
_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^)+(0.0372P)^2^+0.1516P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0730
_refine_ls_wR_factor_ref         0.0740
_reflns_Friedel_coverage         0.527
_reflns_Friedel_fraction_full    0.650
_reflns_Friedel_fraction_max     0.565
_reflns_number_gt                3731
_reflns_number_total             4002
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ra02685g2.cif
_cod_data_source_block           heckmenthyl_precursor200k_adsorp
_cod_database_code               7250575
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C29H31O3Br
_diffrn_oxdiff_digest_hkl
;
01c4d9a98236be6914e3625ae9c96dc855807c
;
_olex2_refinement_description
;
1.a Ternary CH refined with riding coordinates:
 C24(H24), C25(H25), C28(H28), C30(H30)
1.b Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B), C26(H26A,H26B), C27(H27A,H27B)
1.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C3(H3), C7(H7), C8(H8), C10(H10), C17(H17), C11(H11), C12(H12),
 C14(H14), C2(H2), C18(H18), C5(H5)
1.d Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C31(H31A,H31B,H31C), C33(H33A,H33B,H33C)
;
_shelx_res_checksum              88559
_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 1.863
_oxdiff_exptl_absorpt_empirical_full_min 0.524