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_7135136
_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 H18 O3'
_chemical_formula_sum            'C20 H18 O3'
_chemical_formula_weight         306.34
_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
_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                77.008(2)
_cell_angle_beta                 83.439(2)
_cell_angle_gamma                81.3120(10)
_cell_formula_units_Z            2
_cell_length_a                   7.84460(10)
_cell_length_b                   8.68530(10)
_cell_length_c                   11.0599(3)
_cell_measurement_reflns_used    20856
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      68.9790
_cell_measurement_theta_min      4.1140
_cell_volume                     723.30(2)
_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 0.980
_diffrn_measured_fraction_theta_max 0.980
_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    -24.00   9.00   0.50    1.00    --   48.17 -34.00  85.00   66
  2  \w     46.00 122.00   0.50    1.00    --   48.17  34.00-116.00  152
  3  \w    -16.00  24.00   0.50    1.00    --  -49.92  34.00-116.00   80
  4  \w   -123.00 -47.00   0.50    1.00    --  -49.92 -34.00  85.00  152
  5  \w   -149.00 -73.00   0.50    1.00    --  -75.43 -34.00  85.00  152
  6  \w     89.00 164.00   0.50    1.00    --   91.36  34.00-116.00  150
  7  \w    -21.00   5.00   0.50    1.00    --    2.00  93.00-105.51   52
  8  \w      3.00  35.00   0.50    1.00    --   10.00  68.00  75.24   64
  9  \w      7.00  35.00   0.50    1.00    --   14.00  68.00  -7.81   56
 10  \w    -41.00 -15.00   0.50    1.00    --  -22.00 -68.00 -15.18   52
 11  \w    -51.00 -20.00   0.50    1.00    --  -26.00 -65.00  80.13   62
 12  \w    -56.00 -25.00   0.50    1.00    --  -30.00 -62.00 155.50   62
 13  \w    -51.00 -24.00   0.50    1.00    --  -30.00 -64.00  19.56   54
 14  \w    -62.00 -25.00   0.50    1.00    --  -30.00 -60.00-154.32   74
 15  \w    -54.00 -28.00   0.50    1.00    --  -34.00 -63.00  90.93   52
 16  \w    -62.00 -29.00   0.50    1.00    --  -34.00 -60.00 -78.68   66
 17  \w    -62.00 -30.00   0.50    1.00    --  -34.00 -57.00  46.22   64
 18  \w    -54.00 -28.00   0.50    1.00    --  -34.00 -63.00 125.03   52
 19  \w    -62.00 -33.00   0.50    1.00    --  -38.00 -59.00   1.96   58
 20  \w    -62.00 -33.00   0.50    1.00    --  -38.00 -60.00  26.94   58
 21  \w    -62.00 -33.00   0.50    1.00    --  -38.00 -58.00 179.28   58
 22  \w    -62.00 -33.00   0.50    1.00    --  -38.00 -60.00  99.47   58
 23  \w    -62.00 -34.00   0.50    1.00    --  -38.00 -57.00-109.91   56
 24  \w    -62.00 -33.00   0.50    1.00    --  -38.00 -60.00-121.28   58
 25  \w   -112.00 -39.00   0.50    1.00    --  -42.00 -52.00-157.07  146
 26  \w   -112.00 -39.00   0.50    1.00    --  -42.00 -53.00 120.98  146
 27  \w   -117.00 -44.00   0.50    1.00    --  -46.00 -47.00 -94.16  146
 28  \w   -117.00 -44.00   0.50    1.00    --  -46.00 -48.00 178.24  146
 29  \w   -116.00 -42.00   0.50    1.00    --  -46.00 -54.00 -52.41  148
 30  \w    -91.00 -16.00   0.50    1.00    --  -49.92 125.00 -60.00  150
 31  \w   -120.00 -47.00   0.50    1.00    --  -49.92 -53.00-130.74  146
 32  \w   -120.00 -47.00   0.50    1.00    --  -50.00 -52.00 -34.99  146
 33  \w   -128.00 -55.00   0.50    1.00    --  -58.00 -53.00  99.18  146
 34  \w   -128.00 -55.00   0.50    1.00    --  -58.00 -53.00 156.60  146
 35  \w   -128.00 -55.00   0.50    1.00    --  -58.00 -53.00-110.32  146
 36  \w   -129.00 -55.00   0.50    1.00    --  -58.00 -50.00 -63.58  148
 37  \w   -129.00 -55.00   0.50    1.00    --  -58.00 -49.00  66.29  148
 38  \w   -129.00 -56.00   0.50    1.00    --  -58.00 -48.00  -1.94  146
 39  \w   -132.00 -58.00   0.50    1.00    --  -62.00 -54.00  -2.86  148
 40  \w   -133.00 -59.00   0.50    1.00    --  -62.00 -50.00-143.98  148
 41  \w   -133.00 -59.00   0.50    1.00    --  -62.00 -50.00  45.35  148
 42  \w   -132.00 -58.00   0.50    1.00    --  -62.00 -54.00 -84.71  148
 43  \w   -133.00 -59.00   0.50    1.00    --  -62.00 -52.00  28.76  148
 44  \w   -132.00 -59.00   0.50    1.00    --  -62.00 -53.00 119.87  146
 45  \w   -137.00 -63.00   0.50    1.00    --  -66.00 -51.00 168.44  148
 46  \w   -137.00 -63.00   0.50    1.00    --  -66.00 -52.00-174.34  148
 47  \w   -137.00 -64.00   0.50    1.00    --  -66.00 -48.00  -9.01  146
 48  \w   -141.00 -68.00   0.50    1.00    --  -70.00 -48.00-147.56  146
 49  \w   -140.00 -66.00   0.50    1.00    --  -70.00 -53.00-156.98  148
 50  \w   -140.00 -66.00   0.50    1.00    --  -70.00 -54.00  -9.64  148
 51  \w    -91.00 -66.00   0.50    1.00    --  -70.00 -54.00 -86.61   50
 52  \w   -100.00 -71.00   0.50    1.00    --  -74.00 -49.00 133.13   58
 53  \w   -137.00 -96.00   0.50    1.00    --  -75.43-125.00  30.00   82
 54  \w    -32.00  -4.00   0.50    1.00    --  -75.43  45.00  60.00   56
 55  \w    -31.00  -6.00   0.50    1.00    --  -75.43  45.00  90.00   50
 56  \w   -100.00 -75.00   0.50    1.00    --  -78.00 -50.00 -35.75   50
 57  \w   -108.00 -83.00   0.50    1.00    --  -82.00 -52.00  68.14   50
 58  \w    -86.00 -33.00   0.50    1.00    --  -82.00  90.00 111.50  106
 59  \w   -103.00 -78.00   0.50    1.00    --  -82.00 -54.00  43.91   50
 60  \w   -104.00 -79.00   0.50    1.00    --  -82.00 -51.00 -24.29   50
 61  \w   -145.00-119.00   0.50    1.00    --  -82.00 -51.00 -24.29   52
 62  \w   -104.00 -79.00   0.50    1.00    --  -82.00 -51.00 155.79   50
 63  \w   -153.00-124.00   0.50    1.00    --  -82.00 -51.00 155.79   58
 64  \w   -106.00 -79.00   0.50    1.00    --  -82.00 -52.00 101.27   54
 65  \w   -118.00 -82.00   0.50    1.00    --  -82.00 -50.00 173.41   72
 66  \w   -105.00 -79.00   0.50    1.00    --  -82.00 -53.00 -49.37   52
 67  \w   -106.00 -80.00   0.50    1.00    --  -82.00 -52.00-158.71   52
 68  \w    -93.00 -19.00   0.50    1.00    --  -82.00  93.00-111.81  148
 69  \w   -104.00 -79.00   0.50    1.00    --  -82.00 -51.00 123.99   50
 70  \w   -153.00-128.00   0.50    1.00    --  -82.00 -51.00 123.99   50
 71  \w   -114.00 -83.00   0.50    1.00    --  -82.00 -53.00 -57.31   62
 72  \w   -115.00 -78.00   0.50    1.00    --  -82.00 -54.00 -97.63   74
 73  \w   -150.00-124.00   0.50    1.00    --  -82.00 -54.00  43.91   52
 74  \w     92.00 142.00   0.50    1.00    --   91.36  61.00   0.00  100
 75  \w     91.00 124.00   0.50    1.00    --   91.36  45.00 -60.00   66
 76  \w    126.00 157.00   0.50    1.00    --   91.36  61.00 150.00   62
 77  \w     67.00  92.00   0.50    1.00    --   91.36 -95.00  90.00   50
 78  \w     86.00 123.00   0.50    1.00    --   91.36  61.00 150.00   74
 79  \w     30.00  58.00   0.50    1.00    --   91.36 -95.00  90.00   56
 80  \w     89.00 115.00   0.50    1.00    --   91.36  61.00 -90.00   52
 81  \w     50.00 101.00   0.50    1.00    --   91.36-125.00 -30.00  102
 82  \w     68.00  98.00   0.50    1.00    --   91.36-125.00 -90.00   60
 83  \w     66.00  92.00   0.50    1.00    --   91.36 -95.00  30.00   52
 84  \w     33.00  84.00   0.50    1.00    --   91.36 -95.00   0.00  102
 85  \w     34.00  60.00   0.50    1.00    --   91.36 -95.00  30.00   52
 86  \w     34.00  60.00   0.50    1.00    --   91.36-125.00 -90.00   52
 87  \w     90.00 159.00   0.50    1.00    --   91.36  61.00 -60.00  138
 88  \w     88.00 113.00   0.50    1.00    --   91.36  61.00-120.00   50
 89  \w     33.00  68.00   0.50    1.00    --   91.36 -77.00-180.00   70
 90  \w    129.00 160.00   0.50    1.00    --   91.36  61.00 120.00   62
 91  \w     94.00 120.00   0.50    1.00    --   91.36  45.00  30.00   52
 92  \w    124.00 163.00   0.50    1.00    --   91.36  45.00 -30.00   78
 93  \w     89.00 124.00   0.50    1.00    --   91.36  61.00 120.00   70
 94  \w     98.00 123.00   0.50    1.00    --   91.36  45.00 -30.00   50
 95  \w     65.00  91.00   0.50    1.00    --   91.36 -95.00  60.00   52
 96  \w     86.00 126.00   0.50    1.00    --   91.36  61.00  30.00   80
 97  \w     34.00  60.00   0.50    1.00    --   91.36 -95.00  60.00   52
 98  \w     62.00  88.00   0.50    1.00    --   91.36 -95.00-180.00   52
 99  \w    128.00 157.00   0.50    1.00    --   91.36  61.00-150.00   58
100  \w     73.00  98.00   0.50    1.00    --   91.36-125.00   0.00   50
101  \w     34.00  60.00   0.50    1.00    --   91.36 -95.00-180.00   52
102  \w     86.00 122.00   0.50    1.00    --   91.36  61.00-150.00   72
103  \w     38.00  69.00   0.50    1.00    --   91.36-125.00   0.00   62
104  \w     86.00 150.00   0.50    1.00    --   91.36  61.00  60.00  128
105  \w     90.00 116.00   0.50    1.00    --   91.36  45.00  60.00   52
106  \w    125.00 151.00   0.50    1.00    --   91.36  61.00  90.00   52
107  \w     32.00  78.00   0.50    1.00    --   91.36 -95.00 150.00   92
108  \w     86.00 114.00   0.50    1.00    --   91.36  61.00  90.00   56
109  \w    118.00 154.00   0.50    1.00    --   91.36  77.00  30.00   72
110  \w     90.00 160.00   0.50    1.00    --   91.36  45.00 -90.00  140
111  \w     88.00 159.00   0.50    1.00    --   91.36  61.00-180.00  142
112  \w     29.00  55.00   0.50    1.00    --   91.36 -77.00  90.00   52
113  \w     36.00  63.00   0.50    1.00    --   91.36 -77.00-120.00   54
114  \w     29.00  54.00   0.50    1.00    --   91.36 -77.00 120.00   50
;
_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      -0.1500983000
_diffrn_orient_matrix_UB_12      0.1164803000
_diffrn_orient_matrix_UB_13      -0.0604920000
_diffrn_orient_matrix_UB_21      0.0851619000
_diffrn_orient_matrix_UB_22      0.1417349000
_diffrn_orient_matrix_UB_23      0.0165860000
_diffrn_orient_matrix_UB_31      0.0998081000
_diffrn_orient_matrix_UB_32      0.0067482000
_diffrn_orient_matrix_UB_33      -0.1290120000
_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  0.0156
_diffrn_reflns_av_unetI/netI     0.0075
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            24672
_diffrn_reflns_theta_full        69.13
_diffrn_reflns_theta_max         69.13
_diffrn_reflns_theta_min         4.12
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.753
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.825
_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    1.407
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             324
_exptl_crystal_recrystallization_method
'The material was recrystallised from DCM by slow evaporation'
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.268
_refine_diff_density_min         -0.208
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     210
_refine_ls_number_reflns         2653
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0319
_refine_ls_R_factor_gt           0.0312
_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^)+(0.0411P)^2^+0.3169P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0809
_refine_ls_wR_factor_ref         0.0815
_reflns_number_gt                2575
_reflns_number_total             2653
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d5cc05185a2.cif
_cod_data_source_block           2024sot0015_d1_100k
_cod_depositor_comments
'Adding full bibliography for 7135132--7135138.cif.'
_cod_database_code               7135136
_chemical_oxdiff_formula         C21h20O4
_chemical_oxdiff_usercomment     MEP257
_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:
 C14(H14A,H14B), C15(H15A,H15B), C18(H18A,H18B)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C9(H9), C10(H10), C11(H11)
2.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C20(H20A,H20B,H20C)
;
_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 MEP257
_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 1.136
_oxdiff_exptl_absorpt_empirical_full_min 0.907