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_7135138
_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         'C22 H21 I O6'
_chemical_formula_sum            'C22 H21 I O6'
_chemical_formula_weight         508.29
_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_creation_date             2024-05-16
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-05-16 deposited with the CCDC.	2025-11-03 downloaded from the CCDC.
;
_cell_angle_alpha                73.6950(10)
_cell_angle_beta                 71.4480(10)
_cell_angle_gamma                66.600(2)
_cell_formula_units_Z            2
_cell_length_a                   9.0209(2)
_cell_length_b                   9.6030(2)
_cell_length_c                   13.9670(2)
_cell_measurement_reflns_used    17660
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      68.9150
_cell_measurement_theta_min      3.3710
_cell_volume                     1036.01(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.121a 64-bit (release 24-04-2024))'
_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 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_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 0.981
_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     42.00 121.00   0.50    1.00    --   48.17  21.00  95.00  158
  2  \w   -148.00 -69.00   0.50    1.00    --  -75.43 -21.00 -70.00  158
  3  \w   -148.00 -69.00   0.50    1.00    --  -75.43 -21.00 -70.00  158
  4  \w     86.00 149.00   0.50    1.00    --   91.36  21.00  95.00  126
  5  \w     -2.00  25.00   0.50    1.00    --    6.00  73.00-158.52   54
  6  \w     -3.00  28.00   0.50    1.00    --    6.00  72.00  16.06   62
  7  \w    -24.00  15.00   0.50    1.00    --   48.17 -38.00 150.00   78
  8  \w   -123.00 -44.00   0.50    1.00    --  -49.92 -21.00 -70.00  158
  9  \w    -23.00  24.00   0.50    1.00    --  -49.92  38.00-150.00   94
 10  \w   -123.00 -44.00   0.50    1.00    --  -49.92 -21.00 -70.00  158
 11  \w    -79.00 -13.00   0.50    1.00    --  -75.43  77.00 -90.00  132
 12  \w    -33.00  -4.00   0.50    1.00    --  -75.43  45.00 -90.00   58
 13  \w    -79.00 -13.00   0.50    1.00    --  -75.43  77.00 -90.00  132
 14  \w    -33.00  -4.00   0.50    1.00    --  -75.43  45.00 -30.00   58
 15  \w    -79.00 -13.00   0.50    1.00    --  -75.43  77.00 120.00  132
 16  \w    -92.00 -19.00   0.50    1.00    --  -82.00  95.00-159.16  146
 17  \w    -93.00 -17.00   0.50    1.00    --  -82.00 104.00   0.63  152
 18  \w    -92.00 -19.00   0.50    1.00    --  -82.00  95.00-159.16  146
 19  \w    -93.00 -19.00   0.50    1.00    --  -82.00  90.00  50.82  148
 20  \w    -97.00 -18.00   0.50    1.00    --  -82.00 114.00 151.49  158
 21  \w    -93.00 -17.00   0.50    1.00    --  -82.00 104.00   0.63  152
 22  \w    -93.00 -19.00   0.50    1.00    --  -82.00  90.00  50.82  148
 23  \w     29.00  71.00   0.50    1.00    --   91.36 -77.00-180.00   84
 24  \w     29.00  92.00   0.50    1.00    --   91.36 -95.00 120.00  126
 25  \w     29.00  92.00   0.50    1.00    --   91.36 -95.00 -90.00  126
 26  \w     29.00  92.00   0.50    1.00    --   91.36 -95.00 -90.00  126
 27  \w     99.00 154.00   0.50    1.00    --   91.36  77.00 -90.00  110
 28  \w     78.00 132.00   0.50    1.00    --   91.36  15.00-150.00  108
 29  \w     29.00  92.00   0.50    1.00    --   91.36 -95.00 150.00  126
 30  \w     29.00  92.00   0.50    1.00    --   91.36 -95.00  90.00  126
 31  \w     29.00  92.00   0.50    1.00    --   91.36 -95.00-150.00  126
 32  \w     78.00 132.00   0.50    1.00    --   91.36  15.00 -90.00  108
 33  \w     43.00  89.00   0.50    1.00    --   91.36 -95.00  60.00   92
 34  \w     38.00  90.00   0.50    1.00    --   91.36 -95.00-120.00  104
 35  \w    135.00 160.00   0.50    1.00    --   91.36  61.00 150.00   50
 36  \w     31.00  57.00   0.50    1.00    --   91.36 -77.00  60.00   52
 37  \w     86.00 119.00   0.50    1.00    --   91.36  61.00 150.00   66
 38  \w     58.00  92.00   0.50    1.00    --   91.36 -95.00 -60.00   68
 39  \w    114.00 159.00   0.50    1.00    --   91.36  45.00 150.00   90
 40  \w     31.00  64.00   0.50    1.00    --   91.36 -77.00 -90.00   66
 41  \w     29.00  56.00   0.50    1.00    --   91.36 -95.00   0.00   54
 42  \w     64.00  90.00   0.50    1.00    --   91.36 -95.00   0.00   52
 43  \w     58.00  92.00   0.50    1.00    --   91.36 -95.00 -30.00   68
 44  \w     30.00  92.00   0.50    1.00    --   91.36 -95.00  30.00  124
 45  \w     94.00 130.00   0.50    1.00    --   91.36  15.00 120.00   72
 46  \w     29.00  68.00   0.50    1.00    --   91.36-125.00   0.00   78
 47  \w    113.00 141.00   0.50    1.00    --   91.36  77.00   0.00   56
;
_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      0.1344107000
_diffrn_orient_matrix_UB_12      -0.1524212000
_diffrn_orient_matrix_UB_13      0.0314162000
_diffrn_orient_matrix_UB_21      -0.1125174000
_diffrn_orient_matrix_UB_22      -0.0899845000
_diffrn_orient_matrix_UB_23      0.0069440000
_diffrn_orient_matrix_UB_31      0.0769232000
_diffrn_orient_matrix_UB_32      -0.0148289000
_diffrn_orient_matrix_UB_33      -0.1137596000
_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  0.0212
_diffrn_reflns_av_unetI/netI     0.0118
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            18426
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.130
_diffrn_reflns_theta_min         3.392
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.455
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.29573
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.105a (Rigaku Oxford Diffraction, 2024)
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    1.629
_exptl_crystal_description       prism
_exptl_crystal_F_000             508
_exptl_crystal_recrystallization_method
'The material was recrystallised from DCM by slow evaporation'
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.416
_refine_diff_density_min         -0.419
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     266
_refine_ls_number_reflns         3788
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0172
_refine_ls_R_factor_gt           0.0172
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0244P)^2^+0.9754P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0451
_refine_ls_wR_factor_ref         0.0451
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3774
_reflns_number_total             3788
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc05185a2.cif
_cod_data_source_block           2024sot0039_d1_100k
_cod_depositor_comments
'Adding full bibliography for 7135132--7135138.cif.'
_cod_database_code               7135138
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C22H21IO6
_chemical_oxdiff_usercomment     MEP261
_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:
 C6(H6A,H6B), C7(H7A,H7B), C13(H13A,H13B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4)
2.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C)
;
_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 MEP261
_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 2.627
_oxdiff_exptl_absorpt_empirical_full_min 0.562