Functionalization and solubilization of polycyclic aromatic compounds by sulfoniumization
Erchinger, Johannes E.; Okumura, Tsubasa; Nakata, Kanami; Shimizu, Daisuke; Daniliuc, Constanstin G.; Amaike, Kazuma; Glorius, Frank; Itami, Kenichiro; Ito, Hideto; Chemical Science 16 (2025) 8262–8267; doi:10.1039/D5SC01415H

data_1574397
_publ_section_title
;
 Functionalization and solubilization of polycyclic aromatic compounds by
 sulfoniumization
;
_journal_issue                   19
_journal_name_full               'Chemical Science'
_journal_page_first              8262
_journal_page_last               8267
_journal_paper_doi               10.1039/D5SC01415H
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         '2(C H Cl3), C56 H52'
_chemical_formula_sum            'C58 H54 Cl6'
_chemical_formula_weight         963.71
_chemical_name_systematic        21
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-09-17
_audit_creation_method
;
Olex2 1.5
(compiled 2024.01.12 svn.r2f8d729c for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-11-04 deposited with the CCDC.	2025-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 116.226(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   20.8136(18)
_cell_length_b                   6.0124(4)
_cell_length_c                   21.4653(18)
_cell_measurement_reflns_used    5731
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      29.3320
_cell_measurement_theta_min      2.1110
_cell_volume                     2409.6(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      123(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.815
_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    -16.00  69.00   0.50  175.00    --   -2.70  37.00 163.00  170
  2  \w    -79.00   9.00   0.50  175.00    --   -2.70 -37.00   8.00  176
  3  \w      2.00  33.00   0.50  175.00    --    3.32 -99.00   0.00   62
  4  \w     -6.00  20.00   0.50  175.00    --    3.32 -99.00 -90.00   52
  5  \w     -3.00  37.00   0.50  175.00    --    3.32 -99.00 -60.00   80
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0329961000
_diffrn_orient_matrix_UB_12      -0.0041309000
_diffrn_orient_matrix_UB_13      0.0304797000
_diffrn_orient_matrix_UB_21      0.0160572000
_diffrn_orient_matrix_UB_22      -0.0558391000
_diffrn_orient_matrix_UB_23      -0.0186671000
_diffrn_orient_matrix_UB_31      0.0099440000
_diffrn_orient_matrix_UB_32      0.1038250000
_diffrn_orient_matrix_UB_33      -0.0088193000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0582
_diffrn_reflns_av_unetI/netI     0.0599
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.815
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            21448
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.815
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         29.827
_diffrn_reflns_theta_min         1.904
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.396
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78569
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.120a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.328
_exptl_crystal_description       block
_exptl_crystal_F_000             1008
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CHCl3/hexane'
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.177
_refine_diff_density_min         -0.621
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     323
_refine_ls_number_reflns         5652
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.1094
_refine_ls_R_factor_gt           0.0735
_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^)+(0.1340P)^2^+1.1318P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2135
_refine_ls_wR_factor_ref         0.2358
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3768
_reflns_number_total             5652
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01415h2.cif
_cod_data_source_block           tbs183_quaterilene_chcl3_hex_auto
_cod_depositor_comments
'Adding full bibliography for 1574397--1574400.cif.'
_cod_database_code               1574397
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'C H Cl S'
_shelx_estimated_absorpt_t_max   0.988
_shelx_estimated_absorpt_t_min   0.908
_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
 Cl30-Cl31 \\sim Cl33-Cl34
 with sigma of 0.04
 Cl30-Cl32 \\sim Cl33-Cl35
 with sigma of 0.04
 Cl31-Cl32 \\sim Cl34-Cl35
 with sigma of 0.04
3. Others
 Sof(H29)=Sof(Cl33)=Sof(Cl34)=Sof(Cl35)=1-FVAR(1)
 Sof(Cl30)=Sof(Cl31)=Sof(Cl32)=Sof(H2A)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C29(H2A), C29(H29)
4.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C18(H18), C8(H8), C19(H19), C10(H10), C14(H14), C12(H12)
4.c Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C26(H26A,H26B,H26C), C23(H23A,H23B,
 H23C), C22(H22A,H22B,H22C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              8247
_olex2_exptl_crystal_mounting_method 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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.864
_oxdiff_exptl_absorpt_empirical_full_min 0.424