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_7135134
_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 O6, C0.5 H0.98 Cl'
_chemical_formula_sum            'C20.5 H16.98 Cl O6'
_chemical_formula_weight         394.77
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/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                 100.6850(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.9727(3)
_cell_length_b                   8.12080(10)
_cell_length_c                   20.9626(2)
_cell_measurement_reflns_used    21711
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.8320
_cell_measurement_theta_min      4.2480
_cell_volume                     3508.34(8)
_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 0.997
_diffrn_measured_fraction_theta_max 0.945
_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     11.00  91.00   0.50    1.00    --   50.60-126.00-106.00  160
  2  \w    -93.00 -17.00   0.50    1.00    --  -52.60 126.00 -29.00  152
  3  \w   -100.00 -17.00   0.50    1.00    --  -74.99 126.00 -29.00  166
  4  \w   -140.00 -93.00   0.50    1.00    --  -74.99-126.00-106.00   94
  5  \w     26.00 100.00   0.50    1.00    --   90.92-126.00-106.00  148
  6  \w     88.00 156.00   0.50    1.00    --   90.92 126.00 -29.00  136
  7  \w     19.00  45.00   0.50    1.00    --   22.00  65.00 157.08   52
  8  \w    -17.00  41.00   0.50    1.00    --   50.60 -57.00 -90.00  116
  9  \w    -20.00  15.00   0.50    1.00    --   50.60 -38.00 -30.00   70
 10  \w    -17.00  41.00   0.50    1.00    --   50.60 -57.00  60.00  116
 11  \w    -23.00  19.00   0.50    1.00    --  -52.60  38.00 150.00   84
 12  \w    -61.00   9.00   0.50    1.00    --  -52.60  77.00 -90.00  140
 13  \w    -23.00  19.00   0.50    1.00    --  -52.60  38.00-150.00   84
 14  \w    -23.00  19.00   0.50    1.00    --  -52.60  38.00  90.00   84
 15  \w    -33.00  -5.00   0.50    1.00    --  -74.99  45.00-150.00   56
 16  \w   -146.00 -75.00   0.50    1.00    --  -74.99 -30.00  60.00  142
 17  \w    -33.00  -5.00   0.50    1.00    --  -74.99  45.00 -30.00   56
 18  \w    -93.00 -22.00   0.50    1.00    --  -82.00  98.00 108.73  142
 19  \w    -92.00 -21.00   0.50    1.00    --  -82.00 100.00-109.29  142
 20  \w    -93.00 -20.00   0.50    1.00    --  -82.00  91.00  33.91  146
 21  \w    -97.00 -20.00   0.50    1.00    --  -82.00 114.00 -46.58  154
 22  \w    -92.00 -20.00   0.50    1.00    --  -82.00  93.00 -34.48  144
 23  \w     30.00  92.00   0.50    1.00    --   90.92 -95.00 -60.00  124
 24  \w     30.00  92.00   0.50    1.00    --   90.92 -95.00 150.00  124
 25  \w     30.00  92.00   0.50    1.00    --   90.92 -95.00 150.00  124
 26  \w     84.00 132.00   0.50    1.00    --   90.92  15.00  30.00   96
 27  \w     38.00  92.00   0.50    1.00    --   90.92 -95.00  60.00  108
 28  \w    105.00 160.00   0.50    1.00    --   90.92  45.00 -60.00  110
 29  \w     64.00  92.00   0.50    1.00    --   90.92 -95.00-120.00   56
 30  \w     30.00  59.00   0.50    1.00    --   90.92 -95.00-120.00   58
 31  \w     66.00  92.00   0.50    1.00    --   90.92 -95.00 -90.00   52
 32  \w     30.00  88.00   0.50    1.00    --   90.92 -95.00  30.00  116
 33  \w     99.00 124.00   0.50    1.00    --   90.92  77.00  90.00   50
 34  \w     31.00  92.00   0.50    1.00    --   90.92 -95.00-180.00  122
 35  \w     32.00  61.00   0.50    1.00    --   90.92 -95.00 -90.00   58
 36  \w     31.00  63.00   0.50    1.00    --   90.92 -77.00 -30.00   64
 37  \w     58.00  84.00   0.50    1.00    --   90.92 -95.00 -30.00   52
 38  \w     96.00 142.00   0.50    1.00    --   90.92  45.00-120.00   92
 39  \w     30.00  56.00   0.50    1.00    --   90.92 -95.00 -30.00   52
 40  \w    108.00 150.00   0.50    1.00    --   90.92  77.00  30.00   84
 41  \w     37.00  89.00   0.50    1.00    --   90.92 -95.00 120.00  104
 42  \w     85.00 129.00   0.50    1.00    --   90.92  15.00  90.00   88
 43  \w     44.00  91.00   0.50    1.00    --   90.92 -95.00  90.00   94
 44  \w     30.00  55.00   0.50    1.00    --   90.92 -77.00 -90.00   50
 45  \w     30.00  55.00   0.50    1.00    --   90.92 -77.00  30.00   50
 46  \w     89.00 115.00   0.50    1.00    --   90.92  15.00   0.00   52
 47  \w     99.00 124.00   0.50    1.00    --   90.92  77.00 120.00   50
 48  \w     99.00 151.00   0.50    1.00    --   90.92  77.00  60.00  104
 49  \w     41.00  92.00   0.50    1.00    --   98.00 -99.00   7.54  102
;
_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      0.0400859000
_diffrn_orient_matrix_UB_12      0.0710056000
_diffrn_orient_matrix_UB_13      -0.0481564000
_diffrn_orient_matrix_UB_21      0.0207329000
_diffrn_orient_matrix_UB_22      -0.1754606000
_diffrn_orient_matrix_UB_23      -0.0153050000
_diffrn_orient_matrix_UB_31      -0.0595403000
_diffrn_orient_matrix_UB_32      -0.0132646000
_diffrn_orient_matrix_UB_33      -0.0551699000
_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  0.0217
_diffrn_reflns_av_unetI/netI     0.0113
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.945
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            31217
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.945
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.664
_diffrn_reflns_theta_min         4.291
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.262
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.547
_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    1.495
_exptl_crystal_description       prism
_exptl_crystal_F_000             1640
_exptl_crystal_recrystallization_method
'The material was recrystallised from DCM by'
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.231
_refine_diff_density_min         -0.257
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     261
_refine_ls_number_reflns         3327
_refine_ls_number_restraints     240
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0347
_refine_ls_R_factor_gt           0.0332
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0391P)^2^+3.9881P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0839
_refine_ls_wR_factor_ref         0.0849
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3137
_reflns_number_total             3327
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc05185a2.cif
_cod_data_source_block           2024sot0017_d1_100k
_cod_depositor_comments
'Adding full bibliography for 7135132--7135138.cif.'
_cod_original_formula_sum        'C20.50 H16.98 Cl O6'
_cod_database_code               7135134
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C20H18O6
_chemical_oxdiff_usercomment     MEP283
_shelx_estimated_absorpt_t_max   0.840
_shelx_estimated_absorpt_t_min   0.613
_reflns_odcompleteness_completeness 99.31
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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. Restrained distances
 Cl1A-C21 = Cl1B-C21
 1.7 with sigma of 0.02
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(H21A)=Sof(H21B)=Sof(Cl1B)=1-FVAR(1)
 Sof(Cl1A)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C18(H18A,H18B), C21(H21A,H21B)
5.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C7(H7), C9(H9), C10(H10), C12(H12), C15(H15)
5.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              9471
_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 MEP283
_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 1.223
_oxdiff_exptl_absorpt_empirical_full_min 0.811