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_7135132
_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         'C25 H19 N O5'
_chemical_formula_sum            'C25 H19 N O5'
_chemical_formula_weight         413.41
_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             2024-02-23
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-02-23 deposited with the CCDC.	2025-11-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.8665(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.51124(5)
_cell_length_b                   15.99027(9)
_cell_length_c                   12.44468(6)
_cell_measurement_reflns_used    26790
_cell_measurement_temperature    100.00(12)
_cell_measurement_theta_max      73.4870
_cell_measurement_theta_min      4.5500
_cell_volume                     1852.230(17)
_computing_cell_refinement       'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.108a 64-bit (release 14-02-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_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 1.000
_diffrn_measured_fraction_theta_max 0.981
_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     41.00 118.00   0.50    1.00    --   52.07  64.00 139.00  154
  2  \w    -14.00  63.00   0.50    1.00    --   52.07 -64.00   2.00  154
  3  \w     41.00 118.00   0.50    1.00    --   52.07  64.00 139.00  154
  4  \w    -66.00  11.00   0.50    1.00    --  -55.07  64.00 139.00  154
  5  \w    -74.00 -13.00   0.50    1.00    --  -79.34  64.00 139.00  122
  6  \w   -145.00 -68.00   0.50    1.00    --  -79.34 -64.00   2.00  154
  7  \w     18.00  78.00   0.50    1.00    --   83.39 -64.00   2.00  120
  8  \w     72.00 149.00   0.50    1.00    --   83.39  64.00 139.00  154
  9  \w    -38.00 -10.00   0.50    1.00    --    0.00 114.00  94.11   56
 10  \w      1.00  33.00   0.50    1.00    --   28.00  94.00-142.04   64
 11  \w     13.00  42.00   0.50    1.00    --   36.00  87.00-146.57   58
 12  \w     15.00  42.00   0.50    1.00    --   40.00  91.00 -64.89   54
 13  \w   -121.00 -44.00   0.50    1.00    --  -55.07 -64.00   2.00  154
 14  \w   -151.00 -72.00   0.50    1.00    --  -79.34 -37.00-150.00  158
 15  \w   -139.00 -85.00   0.50    1.00    --  -79.34 -99.00 120.00  108
 16  \w     13.00  41.00   0.50    1.00    --   83.39 -37.00  90.00   56
 17  \w     12.00  43.00   0.50    1.00    --   83.39 -37.00  30.00   62
 18  \w     12.00  43.00   0.50    1.00    --   83.39 -37.00-120.00   62
 19  \w     13.00  43.00   0.50    1.00    --   83.39 -37.00  60.00   60
 20  \w     74.00 105.00   0.50    1.00    --   83.39  57.00-120.00   62
 21  \w     12.00  37.00   0.50    1.00    --   83.39 -37.00-150.00   50
 22  \w     12.00  42.00   0.50    1.00    --   83.39 -37.00-180.00   60
 23  \w   -122.00 -78.00   0.50    1.00    --  -88.00 -31.00-100.84   88
 24  \w   -135.00 -90.00   0.50    1.00    --  -88.00-103.00 -62.92   90
 25  \w   -126.00 -78.00   0.50    1.00    --  -88.00 -50.00 -31.88   96
 26  \w   -116.00 -91.00   0.50    1.00    --  -88.00 -65.00-116.86   50
 27  \w   -142.00 -97.00   0.50    1.00    --  -88.00-120.00-175.27   90
 28  \w   -112.00 -86.00   0.50    1.00    --  -88.00-119.00  -1.76   52
 29  \w   -102.00 -76.00   0.50    1.00    --  -88.00 -78.00 -95.22   52
 30  \w   -118.00 -85.00   0.50    1.00    --  -88.00 -67.00-135.97   66
 31  \w   -152.00-127.00   0.50    1.00    --  -88.00 -67.00-135.97   50
 32  \w   -157.00 -80.00   0.50    1.00    --  -88.00 -33.00  20.75  154
 33  \w     36.00  62.00   0.50    1.00    --   92.00   9.00  76.62   52
 34  \w     33.00  70.00   0.50    1.00    --   92.00 -79.00  98.43   74
 35  \w     31.00 109.00   0.50    1.00    --   92.00 -82.00 136.71  156
 36  \w     58.00 104.00   0.50    1.00    --   92.00 -95.00  23.63   92
 37  \w     50.00  81.00   0.50    1.00    --   92.00  -2.00  31.43   62
 38  \w    123.00 149.00   0.50    1.00    --   92.00  -2.00  31.43   52
 39  \w     51.00 159.00   0.50    1.00    --   92.00  14.00 -64.86  216
 40  \w     57.00  83.00   0.50    1.00    --   92.00  15.00 -51.85   52
 41  \w     31.00  68.00   0.50    1.00    --   92.00 -83.00  80.67   74
 42  \w     31.00  72.00   0.50    1.00    --   92.00 -87.00  55.39   82
 43  \w     31.00  64.00   0.50    1.00    --   92.00 -78.00   8.95   66
 44  \w     31.00  72.00   0.50    1.00    --   92.00 -77.00 -59.31   82
 45  \w     42.00  92.00   0.50    1.00    --   92.00  12.00  33.43  100
 46  \w     32.00  88.00   0.50    1.00    --   92.00  -1.00-120.39  112
 47  \w     54.00 112.00   0.50    1.00    --   92.00  -2.00 -72.75  116
 48  \w    112.00 159.00   0.50    1.00    --   92.00   9.00  76.62   94
;
_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      0.1540264000
_diffrn_orient_matrix_UB_12      -0.0231437000
_diffrn_orient_matrix_UB_13      -0.0099538000
_diffrn_orient_matrix_UB_21      -0.0600793000
_diffrn_orient_matrix_UB_22      -0.0674920000
_diffrn_orient_matrix_UB_23      -0.0855116000
_diffrn_orient_matrix_UB_31      -0.0075660000
_diffrn_orient_matrix_UB_32      0.0647560000
_diffrn_orient_matrix_UB_33      -0.0926726000
_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  0.0152
_diffrn_reflns_av_unetI/netI     0.0061
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            33856
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.644
_diffrn_reflns_theta_min         4.564
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.854
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.701
_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    1.483
_exptl_crystal_description       prism
_exptl_crystal_F_000             864
_exptl_crystal_recrystallization_method
'The material was recrystallised from diethyl ether by slow evaporation'
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.894
_refine_diff_density_min         -0.460
_refine_diff_density_rms         0.067
_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     281
_refine_ls_number_reflns         3678
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0594
_refine_ls_R_factor_gt           0.0590
_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^)+(0.0658P)^2^+2.9060P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1458
_refine_ls_wR_factor_ref         0.1461
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3636
_reflns_number_total             3678
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc05185a2.cif
_cod_data_source_block           2024sot0018_a1_100k
_cod_depositor_comments
'Adding full bibliography for 7135132--7135138.cif.'
_cod_database_code               7135132
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C25H19N1O5
_chemical_oxdiff_usercomment     MEP272
_shelx_estimated_absorpt_t_max   0.951
_shelx_estimated_absorpt_t_min   0.772
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_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 Ternary CH refined with riding coordinates:
 C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C15(H15A,H15B), C18(H18A,H18B), C25(H25A,H25B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C6(H6), C9(H9), C10(H10), C11(H11), C21(H21), C24(H24)
2.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C)
;
_shelx_res_checksum              63537
_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 MEP272
_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 1.517
_oxdiff_exptl_absorpt_empirical_full_min 0.742