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_7135135
_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         'C19 H14 O5'
_chemical_formula_sum            'C19 H14 O5'
_chemical_formula_weight         322.30
_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                 97.5250(10)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   8.36270(10)
_cell_length_b                   10.98390(10)
_cell_length_c                   16.0035(2)
_cell_measurement_reflns_used    20406
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      70.0040
_cell_measurement_theta_min      4.0550
_cell_volume                     1457.34(3)
_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 0.994
_diffrn_measured_fraction_theta_max 0.994
_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    -10.00  63.00   0.50    1.00    --   50.60 -82.00  78.00  146
  2  \w    -64.00   9.00   0.50    1.00    --  -52.60  82.00-159.00  146
  3  \w    -87.00 -13.00   0.50    1.00    --  -74.99  82.00-159.00  148
  4  \w     30.00  80.00   0.50    1.00    --   90.92 -82.00  78.00  100
  5  \w    100.00 152.00   0.50    1.00    --   90.92  82.00-159.00  104
  6  \w     12.00  51.00   0.50    1.00    --   14.00  62.00   5.19   78
  7  \w     28.00  56.00   0.50    1.00    --   30.00  61.00  36.20   56
  8  \w    -20.00  15.00   0.50    1.00    --   50.60 -38.00 150.00   70
  9  \w     53.00 121.00   0.50    1.00    --   50.60  38.00 150.00  136
 10  \w    -20.00  15.00   0.50    1.00    --   50.60 -38.00-180.00   70
 11  \w    -23.00  19.00   0.50    1.00    --  -52.60  38.00   0.00   84
 12  \w   -124.00 -55.00   0.50    1.00    --  -52.60 -38.00 -30.00  138
 13  \w    -33.00  -5.00   0.50    1.00    --  -74.99  45.00 -60.00   56
 14  \w   -142.00 -86.00   0.50    1.00    --  -74.99 -61.00 150.00  112
 15  \w   -140.00 -68.00   0.50    1.00    --  -74.99 -15.00 -90.00  144
 16  \w    -33.00  -5.00   0.50    1.00    --  -74.99  45.00 -90.00   56
 17  \w    -33.00  -5.00   0.50    1.00    --  -74.99  45.00 150.00   56
 18  \w   -140.00 -68.00   0.50    1.00    --  -74.99 -15.00 -90.00  144
 19  \w     30.00  92.00   0.50    1.00    --   90.92 -95.00   0.00  124
 20  \w     30.00  71.00   0.50    1.00    --   90.92 -77.00 -90.00   82
 21  \w     27.00 100.00   0.50    1.00    --   90.92-125.00 150.00  146
 22  \w     99.00 152.00   0.50    1.00    --   90.92  77.00 -90.00  106
 23  \w     88.00 155.00   0.50    1.00    --   90.92 125.00 -30.00  134
 24  \w     88.00 158.00   0.50    1.00    --   90.92  61.00 120.00  140
 25  \w     30.00  92.00   0.50    1.00    --   90.92 -95.00 150.00  124
 26  \w     99.00 152.00   0.50    1.00    --   90.92  77.00 -30.00  106
 27  \w     30.00  92.00   0.50    1.00    --   90.92 -95.00  60.00  124
 28  \w     88.00 158.00   0.50    1.00    --   90.92  61.00 150.00  140
 29  \w     30.00  71.00   0.50    1.00    --   90.92 -77.00 150.00   82
 30  \w     30.00  71.00   0.50    1.00    --   90.92 -77.00  30.00   82
 31  \w     99.00 152.00   0.50    1.00    --   90.92  77.00-180.00  106
 32  \w     93.00 161.00   0.50    1.00    --   90.92  45.00 -30.00  136
 33  \w     30.00  92.00   0.50    1.00    --   90.92 -95.00-150.00  124
 34  \w     88.00 155.00   0.50    1.00    --   90.92 125.00-150.00  134
 35  \w     84.00 132.00   0.50    1.00    --   90.92  15.00 -60.00   96
 36  \w     30.00  71.00   0.50    1.00    --   90.92 -77.00   0.00   82
 37  \w     30.00  71.00   0.50    1.00    --   90.92 -77.00 -60.00   82
 38  \w     88.00 155.00   0.50    1.00    --   90.92 125.00 -90.00  134
 39  \w     84.00 132.00   0.50    1.00    --   90.92  15.00 150.00   96
 40  \w     30.00  92.00   0.50    1.00    --   90.92 -95.00 120.00  124
 41  \w     93.00 161.00   0.50    1.00    --   90.92  45.00-180.00  136
 42  \w     93.00 161.00   0.50    1.00    --   90.92  45.00 150.00  136
 43  \w     84.00 132.00   0.50    1.00    --   90.92  15.00  30.00   96
 44  \w     24.00  51.00   0.50    1.00    --   26.00  62.00-110.52   54
 45  \w     28.00  56.00   0.50    1.00    --   30.00  60.00 102.62   56
 46  \w     51.00 117.00   0.50    1.00    --   50.60  50.00  65.71  132
;
_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      -0.1011306000
_diffrn_orient_matrix_UB_12      -0.0923237000
_diffrn_orient_matrix_UB_13      0.0431683000
_diffrn_orient_matrix_UB_21      -0.1511672000
_diffrn_orient_matrix_UB_22      0.0790675000
_diffrn_orient_matrix_UB_23      -0.0235542000
_diffrn_orient_matrix_UB_31      -0.0378272000
_diffrn_orient_matrix_UB_32      -0.0698985000
_diffrn_orient_matrix_UB_33      -0.0837893000
_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  0.0184
_diffrn_reflns_av_unetI/netI     0.0082
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            26744
_diffrn_reflns_theta_full        70.17
_diffrn_reflns_theta_max         70.17
_diffrn_reflns_theta_min         4.90
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.889
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.659
_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    1.469
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             672
_exptl_crystal_recrystallization_method
'The material was recrystallised from DCM by slow evaporation'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.255
_refine_diff_density_min         -0.197
_refine_diff_density_rms         0.039
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     218
_refine_ls_number_reflns         2766
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0325
_refine_ls_R_factor_gt           0.0315
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0386P)^2^+0.6606P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0793
_refine_ls_wR_factor_ref         0.0801
_reflns_number_gt                2650
_reflns_number_total             2766
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d5cc05185a2.cif
_cod_data_source_block           2024sot0014_r1_100k
_cod_depositor_comments
'Adding full bibliography for 7135132--7135138.cif.'
_cod_database_code               7135135
_chemical_oxdiff_formula         C19H14O5
_chemical_oxdiff_usercomment     MEP87
_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), C19(H19A,H19B)
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:
 C18(H18A,H18B,H18C)
;
_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 MEP87
_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 1.509
_oxdiff_exptl_absorpt_empirical_full_min 0.795