Rh-catalyzed mechanochemical transfer hydrogenation for the synthesis of periphery-hydrogenated polycyclic aromatic compounds
Toyama, Yoshifumi; Nakamura, Takumu; Horikawa, Yushin; Morinaka, Yuta; Ono, Yohei; Yagi, Akiko; Itami, Kenichiro; Ito, Hideto; Chemical Science 16 (2025) 9117–9124; doi:10.1039/D5SC01489A

data_1574418
_publ_section_title
;
 Rh-catalyzed mechanochemical transfer hydrogenation for the synthesis of
 periphery-hydrogenated polycyclic aromatic compounds
;
_journal_issue                   21
_journal_name_full               'Chemical Science'
_journal_page_first              9117
_journal_page_last               9124
_journal_paper_doi               10.1039/D5SC01489A
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C42 H36'
_chemical_formula_sum            'C42 H36'
_chemical_formula_weight         540.7464
_chemical_name_systematic        7e
_space_group_crystal_system      orthorhombic
_space_group_IT_number           68
_space_group_name_Hall           '-C 2a 2ac'
_space_group_name_H-M_alt        'C c c a :2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2l6v0p
_audit_creation_date             2024-08-26
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2018.12.05 svn.r3537 for Rigaku Oxford Diffraction, GUI svn.r5625)
;
_audit_update_record
;
2024-10-10 deposited with the CCDC.	2025-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.7173(12)
_cell_length_b                   13.4757(6)
_cell_length_c                   8.5134(4)
_cell_measurement_reflns_used    4611
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      29.4650
_cell_measurement_theta_min      2.9210
_cell_volume                     2950.4(2)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_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 0.998
_diffrn_measured_fraction_theta_max 0.868
_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     -6.00  26.00   0.50  120.00    --   -2.54 -87.00 115.00   64
  2  \w     14.00  46.00   0.50  120.00    --    3.16  57.00 -90.00   64
  3  \w    -13.00  69.00   0.50  120.00    --    3.16  57.00 -30.00  164
  4  \w      3.00  38.00   0.50  120.00    --    3.16 -99.00 -60.00   70
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0041695000
_diffrn_orient_matrix_UB_12      0.0221610000
_diffrn_orient_matrix_UB_13      -0.0745103000
_diffrn_orient_matrix_UB_21      0.0270610000
_diffrn_orient_matrix_UB_22      -0.0092238000
_diffrn_orient_matrix_UB_23      0.0069866000
_diffrn_orient_matrix_UB_31      -0.0033655000
_diffrn_orient_matrix_UB_32      -0.0468330000
_diffrn_orient_matrix_UB_33      -0.0366178000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0301
_diffrn_reflns_av_unetI/netI     0.0238
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.868
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            8767
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.868
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         29.557
_diffrn_reflns_theta_min         2.939
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.069
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65322
_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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.217
_exptl_crystal_description       plate
_exptl_crystal_F_000             1152
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CHCl3/pentane'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.350
_refine_diff_density_min         -0.189
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     96
_refine_ls_number_reflns         1797
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0466
_refine_ls_R_factor_gt           0.0387
_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^)+(0.0578P)^2^+1.6299P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1035
_refine_ls_wR_factor_ref         0.1089
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1523
_reflns_number_total             1797
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01489a2.cif
_cod_data_source_block
toy2011a_hydrogenated-ruburene_chcl3-pentane_xray_auto
_cod_depositor_comments
'Adding full bibliography for 1574417--1574419.cif.'
_cod_original_sg_symbol_Hall     '-C 2b 2bc'
_cod_original_sg_symbol_H-M      'C c c e'
_cod_database_code               1574418
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H Cl'
_shelx_estimated_absorpt_t_max   0.999
_shelx_estimated_absorpt_t_min   0.993
_diffrn_oxdiff_digest_frames
;
0157a7e0762ce4822625fc3f3800e3b1ee000250ab9
;
_diffrn_oxdiff_digest_hkl
;
010905d7a748f4b8756d30f356e6c735c1f45b
;
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C4(H00A,H00B), C5(H00C,H00D)
2.b Aromatic/amide H refined with riding coordinates:
 C7(H006), C11(H007), C10(H009), C8(H00E), C9(H00F)
;
_shelx_res_checksum              49069
_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 1.582
_oxdiff_exptl_absorpt_empirical_full_min 0.742