Photocyclisations of <i>o</i>-iodobenzyl-indanones and tetralones infer the intermediacy of triplet aryl cations.
Powderly, Marian E.; Lindup, Toby; Jackman, Edward H.; Light, Mark E.; Legros, Julien; Chataigner, Isabelle; Harrowven, David C.; Chemical communications (Cambridge, England) 61 (2025) 19229–19232; doi:10.1039/d5cc05185a

data_7135133
_publ_section_title
;
 Photocyclisations of <i>o</i>-iodobenzyl-indanones and tetralones infer
 the intermediacy of triplet aryl cations.
;
_journal_issue                   97
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              19229
_journal_page_last               19232
_journal_paper_doi               10.1039/d5cc05185a
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C20 H16 O5'
_chemical_formula_sum            'C20 H16 O5'
_chemical_formula_weight         336.33
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-03-13
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-03-13 deposited with the CCDC.	2025-11-03 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 93.018(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   10.2969(2)
_cell_length_b                   9.8246(2)
_cell_length_c                   14.8656(3)
_cell_measurement_reflns_used    12137
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      68.9340
_cell_measurement_theta_min      4.3060
_cell_volume                     1501.76(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.109a 64-bit (release 21-02-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-1997 97-2 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_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     47.00 121.00   0.50    1.00    --   48.17  39.00 -68.00  148
  2  \w    -21.00  12.00   0.50    1.00    --   48.17 -39.00 137.00   66
  3  \w   -110.00 -85.00   0.50    1.00    --  -49.92 -39.00 137.00   50
  4  \w    -21.00  18.00   0.50    1.00    --  -49.92  39.00 -68.00   78
  5  \w   -136.00-105.00   0.50    1.00    --  -75.43 -39.00 137.00   62
  6  \w     93.00 119.00   0.50    1.00    --   91.36  39.00 -68.00   52
  7  \w    -17.00   8.00   0.50    1.00    --   48.17 -38.00   0.00   50
  8  \w    -73.00 -48.00   0.50    1.00    --  -49.92 -48.00  21.93   50
  9  \w    -72.00 -47.00   0.50    1.00    --  -49.92 -35.00   5.09   50
 10  \w    -89.00 -48.00   0.50    1.00    --  -49.92 -38.00  60.00   82
 11  \w    -22.00  16.00   0.50    1.00    --  -49.92  38.00  60.00   76
 12  \w    -77.00 -48.00   0.50    1.00    --  -50.00 -50.00 -24.38   58
 13  \w    -77.00 -51.00   0.50    1.00    --  -54.00 -53.00  16.78   52
 14  \w   -119.00 -92.00   0.50    1.00    --  -54.00 -54.00   1.87   54
 15  \w    -75.00 -50.00   0.50    1.00    --  -54.00 -54.00   1.87   50
 16  \w    -85.00 -60.00   0.50    1.00    --  -62.00 -52.00  44.68   50
 17  \w    -91.00 -65.00   0.50    1.00    --  -66.00 -51.00 -34.34   52
 18  \w    -87.00 -62.00   0.50    1.00    --  -66.00 -53.00   5.31   50
 19  \w    -91.00 -66.00   0.50    1.00    --  -70.00 -53.00  16.36   50
 20  \w    -93.00 -68.00   0.50    1.00    --  -70.00 -47.00 -21.12   50
 21  \w    -92.00 -66.00   0.50    1.00    --  -70.00 -53.00  27.07   52
 22  \w    -96.00 -71.00   0.50    1.00    --  -74.00 -52.00  64.13   50
 23  \w   -120.00 -74.00   0.50    1.00    --  -75.43 -45.00 -30.00   92
 24  \w    -30.00  -4.00   0.50    1.00    --  -75.43  45.00 120.00   52
 25  \w    -53.00 -28.00   0.50    1.00    --  -75.43  61.00  60.00   50
 26  \w    -51.00 -24.00   0.50    1.00    --  -75.43  61.00  30.00   54
 27  \w    -33.00  -5.00   0.50    1.00    --  -75.43  45.00 -90.00   56
 28  \w   -139.00 -97.00   0.50    1.00    --  -75.43-125.00  60.00   84
 29  \w    -30.00  -4.00   0.50    1.00    --  -75.43  45.00  90.00   52
 30  \w   -100.00 -75.00   0.50    1.00    --  -78.00 -52.00   4.14   50
 31  \w   -101.00 -75.00   0.50    1.00    --  -78.00 -54.00  46.93   52
 32  \w   -104.00 -79.00   0.50    1.00    --  -82.00 -52.00  -0.95   50
 33  \w   -108.00 -81.00   0.50    1.00    --  -82.00 -54.00 -14.93   54
 34  \w   -150.00-122.00   0.50    1.00    --  -82.00 -55.00  59.86   56
 35  \w     94.00 120.00   0.50    1.00    --   91.36  61.00  60.00   52
 36  \w     97.00 122.00   0.50    1.00    --   91.36  61.00 -30.00   50
 37  \w     49.00  76.00   0.50    1.00    --   91.36 -95.00   0.00   54
 38  \w     34.00  70.00   0.50    1.00    --   91.36 -77.00  60.00   72
 39  \w     40.00  69.00   0.50    1.00    --   91.36 -77.00 150.00   58
 40  \w    100.00 126.00   0.50    1.00    --   91.36  45.00  90.00   52
 41  \w     32.00  58.00   0.50    1.00    --   91.36 -95.00-150.00   52
 42  \w    122.00 158.00   0.50    1.00    --   91.36  61.00   0.00   72
 43  \w    133.00 162.00   0.50    1.00    --   91.36  45.00-150.00   58
 44  \w     86.00 160.00   0.50    1.00    --   91.36  61.00  90.00  148
 45  \w     86.00 111.00   0.50    1.00    --   91.36  61.00   0.00   50
 46  \w     91.00 157.00   0.50    1.00    --   91.36 125.00 150.00  132
 47  \w     35.00  66.00   0.50    1.00    --   91.36 -77.00-120.00   62
 48  \w    116.00 147.00   0.50    1.00    --   91.36  77.00 -60.00   62
 49  \w     94.00 120.00   0.50    1.00    --   91.36  45.00   0.00   52
 50  \w     29.00  70.00   0.50    1.00    --   91.36 -77.00 120.00   82
 51  \w     98.00 124.00   0.50    1.00    --   91.36  45.00  60.00   52
 52  \w    129.00 160.00   0.50    1.00    --   91.36  45.00  60.00   62
 53  \w     29.00  55.00   0.50    1.00    --   91.36 -77.00  90.00   52
 54  \w    127.00 152.00   0.50    1.00    --   91.36  45.00  30.00   50
 55  \w     92.00 118.00   0.50    1.00    --   91.36  45.00  30.00   52
 56  \w     95.00 124.00   0.50    1.00    --   91.36  15.00-180.00   58
 57  \w    134.00 159.00   0.50    1.00    --   91.36  61.00  30.00   50
 58  \w     39.00  76.00   0.50    1.00    --   91.36 -95.00  60.00   74
 59  \w     32.00  57.00   0.50    1.00    --   91.36 -77.00 -60.00   50
 60  \w     86.00 112.00   0.50    1.00    --   91.36  61.00  30.00   52
 61  \w     83.00 108.00   0.50    1.00    --   91.36  15.00-150.00   50
 62  \w    131.00 159.00   0.50    1.00    --   91.36  61.00 -30.00   56
 63  \w     45.00  71.00   0.50    1.00    --   91.36 -77.00 -90.00   52
 64  \w     32.00  62.00   0.50    1.00    --   91.36 -77.00-150.00   60
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1342722000
_diffrn_orient_matrix_UB_12      -0.0640483000
_diffrn_orient_matrix_UB_13      0.0228152000
_diffrn_orient_matrix_UB_21      -0.0453914000
_diffrn_orient_matrix_UB_22      -0.0441170000
_diffrn_orient_matrix_UB_23      0.0926907000
_diffrn_orient_matrix_UB_31      -0.0485702000
_diffrn_orient_matrix_UB_32      -0.1361329000
_diffrn_orient_matrix_UB_33      -0.0407585000
_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  0.0363
_diffrn_reflns_av_unetI/netI     0.0211
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            18915
_diffrn_reflns_theta_full        69.14
_diffrn_reflns_theta_max         69.14
_diffrn_reflns_theta_min         4.30
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.887
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.750
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.105a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
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    1.488
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             704
_exptl_crystal_recrystallization_method
'The material was recrystallised from DCM by slow evaporation'
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.204
_refine_diff_density_min         -0.234
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     227
_refine_ls_number_reflns         2781
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0370
_refine_ls_R_factor_gt           0.0337
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0530P)^2^+0.4804P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0915
_refine_ls_wR_factor_ref         0.0942
_reflns_number_gt                2493
_reflns_number_total             2781
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d5cc05185a2.cif
_cod_data_source_block           2024sot0033_d1_100k
_cod_depositor_comments
'Adding full bibliography for 7135132--7135138.cif.'
_cod_database_code               7135133
_chemical_oxdiff_formula         C20H16O5
_chemical_oxdiff_usercomment     MEP89
_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.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C14(H14A,H14B), C15(H15A,H15B), C20(H20A,H20B)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C6(H6), C9(H9), C10(H10), C11(H11)
2.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C)
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder with silicon oil'
_olex2_submission_original_sample_id MEP89
_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 1.685
_oxdiff_exptl_absorpt_empirical_full_min 0.652