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_1574419
_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         'C22 H32'
_chemical_formula_sum            'C22 H32'
_chemical_formula_weight         296.47
_chemical_name_systematic        compound_6c
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2mf76j
_audit_creation_date             2024-10-30
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2018.12.05 svn.r3537 for Rigaku Oxford Diffraction, GUI svn.r5625)
;
_audit_update_record
;
2025-02-21 deposited with the CCDC.	2025-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.886(8)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.5878(7)
_cell_length_b                   17.3304(17)
_cell_length_c                   20.2331(15)
_cell_measurement_reflns_used    2772
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      29.9480
_cell_measurement_theta_min      2.3430
_cell_volume                     3277.3(5)
_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 0.841
_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    -41.00  19.00   0.50  150.00    --   -2.70 -77.00-150.00  120
  2  \w    -60.00  63.00   0.50  150.00    --    3.32   0.00 -90.00  246
;
_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      0.0610811000
_diffrn_orient_matrix_UB_12      -0.0240323000
_diffrn_orient_matrix_UB_13      0.0034319000
_diffrn_orient_matrix_UB_21      0.0449078000
_diffrn_orient_matrix_UB_22      0.0320984000
_diffrn_orient_matrix_UB_23      0.0113041000
_diffrn_orient_matrix_UB_31      -0.0032617000
_diffrn_orient_matrix_UB_32      -0.0082266000
_diffrn_orient_matrix_UB_33      0.0339578000
_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  0.0881
_diffrn_reflns_av_unetI/netI     0.1010
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.841
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            10234
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.841
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         29.467
_diffrn_reflns_theta_min         2.350
_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    0.067
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.41458
_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    1.202
_exptl_crystal_description       block
_exptl_crystal_F_000             1312
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CHCl3/MeOH'
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.395
_refine_diff_density_min         -0.319
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     199
_refine_ls_number_reflns         3835
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.1014
_refine_ls_R_factor_gt           0.0720
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1226P)^2^+0.2299P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1933
_refine_ls_wR_factor_ref         0.2108
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2696
_reflns_number_total             3835
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01489a2.cif
_cod_data_source_block           hry091a_ad_biphenyl_red_chcl3_meoh_xray_auto
_cod_depositor_comments
'Adding full bibliography for 1574417--1574419.cif.'
_cod_database_code               1574419
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O'
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.984
_diffrn_oxdiff_digest_frames
;
010e4ca2ddac9212ef7e4d30797b81da1b00025e4c5
;
_diffrn_oxdiff_digest_hkl
;
016ad7067bf4750654ad37b4d1721859452dc9
;
_reflns_odcompleteness_completeness 99.42
_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:
 C2(H2), C10(H10), C9(H9), C17(H17), C11(H11), C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C4(H4A,H4B), C22(H22A,H22B), C7(H7A,H7B), C18(H18A,H18B),
 C6(H6A,H6B), C5(H5A,H5B), C19(H19A,H19B), C20(H20A,H20B), C14(H14A,H14B),
 C21(H21A,H21B), C16(H16A,H16B), C12(H12A,H12B)
;
_shelx_res_checksum              20316
_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 2.219
_oxdiff_exptl_absorpt_empirical_full_min 0.106