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_1574417
_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         'C24 H26'
_chemical_formula_sum            'C24 H26'
_chemical_formula_weight         314.4694
_chemical_name_systematic        7k
_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     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2l6tzm
_audit_creation_date             2024-09-07
_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                84.768(3)
_cell_angle_beta                 83.360(3)
_cell_angle_gamma                85.557(3)
_cell_formula_units_Z            4
_cell_length_a                   8.7615(3)
_cell_length_b                   10.5013(3)
_cell_length_c                   17.8315(6)
_cell_measurement_reflns_used    9394
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      30.1090
_cell_measurement_theta_min      2.1850
_cell_volume                     1619.11(9)
_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 1.000
_diffrn_measured_fraction_theta_max 0.827
_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    -11.00  32.00   0.50    1.50    --    3.48 -99.00 -30.00   86
  2  \w      1.00  38.00   0.50    1.50    --    3.48 -99.00-120.00   74
  3  \w      8.00  38.00   0.50    1.50    --    3.48 -99.00-180.00   60
  4  \w     37.00  70.00   0.50    1.50    --   -2.85  57.00-120.00   66
  5  \w    -19.00  23.00   0.50    1.50    --   -2.85  57.00-120.00   84
  6  \w    -15.00  29.00   0.50    1.50    --   -2.85  57.00  30.00   88
  7  \w     42.00  68.00   0.50    1.50    --   -2.85  57.00  30.00   52
  8  \w     -2.00  73.00   0.50    1.50    --   -2.85  37.00 -30.00  150
  9  \w    -61.00 -28.00   0.50    1.50    --   -2.85 -77.00  30.00   66
 10  \w    -13.00  19.00   0.50    1.50    --   -2.85 -77.00  30.00   64
;
_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      0.0047078000
_diffrn_orient_matrix_UB_12      -0.0519111000
_diffrn_orient_matrix_UB_13      0.0282036000
_diffrn_orient_matrix_UB_21      0.0126543000
_diffrn_orient_matrix_UB_22      -0.0435846000
_diffrn_orient_matrix_UB_23      -0.0285799000
_diffrn_orient_matrix_UB_31      0.0805671000
_diffrn_orient_matrix_UB_32      0.0052152000
_diffrn_orient_matrix_UB_33      -0.0016147000
_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  0.0382
_diffrn_reflns_av_unetI/netI     0.0416
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.827
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            22243
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.827
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         29.807
_diffrn_reflns_theta_min         1.952
_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    0.072
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78990
_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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.290
_exptl_crystal_description       block
_exptl_crystal_F_000             680
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane'
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.435
_refine_diff_density_min         -0.295
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.103
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     433
_refine_ls_number_reflns         7678
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.103
_refine_ls_R_factor_all          0.0561
_refine_ls_R_factor_gt           0.0456
_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^)+(0.0692P)^2^+0.2305P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1274
_refine_ls_wR_factor_ref         0.1334
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6208
_reflns_number_total             7678
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01489a2.cif
_cod_data_source_block           toy2127_hexane_xray_auto
_cod_depositor_comments
'Adding full bibliography for 1574417--1574419.cif.'
_cod_database_code               1574417
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H'
_shelx_estimated_absorpt_t_max   0.989
_shelx_estimated_absorpt_t_min   0.958
_diffrn_oxdiff_digest_frames
;
012e3598fe0f2579736dcf657163f845890002612f4
;
_diffrn_oxdiff_digest_hkl
;
01e9136d1680d3fe34e775bce4a27948eb10ff
;
_reflns_odcompleteness_completeness 99.98
_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 Ternary CH refined with riding coordinates:
 C40(H00H), C22(H00F), C37(H00K), C19(H00M), C16(H00N), C43(H00O), C46(H00Q),
 C13(H00R)
2.b Secondary CH2 refined with riding coordinates:
 C15(H00A,H00B), C36(H00L,H00P), C48(H00S,H00T), C35(H00V,H00W), C38(H00Y,H),
 C17(H00C,H00D), C11(H00E,H00G), C14(H01A,H01B), C41(H01O,H01P), C47(H01Q,H01R),
  C20(H01C,H01D), C42(H01S,H01T), C24(H01E,H01F), C12(H01G,H01H), C44(H01U,
 H01V), C39(H01W,H01X), C45(H01Y,HA), C21(H01I,H01J), C23(H01K,H01L), C18(H01M,
 H01N)
2.c Aromatic/amide H refined with riding coordinates:
 C30(H00I), C29(H00J), C6(H00U), C5(H00X)
;
_shelx_res_checksum              25244
_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 2.260
_oxdiff_exptl_absorpt_empirical_full_min 0.380