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_7135137
_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         'C16 H11 N O3 S'
_chemical_formula_sum            'C16 H11 N O3 S'
_chemical_formula_weight         297.32
_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             2024-05-02
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-05-02 deposited with the CCDC.	2025-11-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.449(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.3033(2)
_cell_length_b                   16.8149(4)
_cell_length_c                   7.34640(10)
_cell_measurement_reflns_used    9188
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      68.9380
_cell_measurement_theta_min      4.2820
_cell_volume                     1271.59(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.120a 64-bit (release 16-04-2024))'
_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 0.999
_diffrn_measured_fraction_theta_max 0.990
_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    -92.00 -11.00   0.50    1.00    --  -75.43 104.00 159.00  162
  2  \w    -79.00  -3.00   0.50    1.00    --  -49.92 104.00 159.00  152
  3  \w    -55.00  -7.00   0.50    1.00    --  -75.43  61.00 120.00   96
  4  \w    -33.00  -4.00   0.50    1.00    --  -75.43  45.00-120.00   58
  5  \w    -33.00  -4.00   0.50    1.00    --  -75.43  45.00-180.00   58
  6  \w    -24.00  15.00   0.50    1.00    --   48.17 -38.00  90.00   78
  7  \w    -24.00  15.00   0.50    1.00    --   48.17 -38.00 120.00   78
  8  \w    -24.00  15.00   0.50    1.00    --   48.17 -38.00  60.00   78
  9  \w    -24.00  15.00   0.50    1.00    --   48.17 -38.00 -30.00   78
 10  \w     88.00 157.00   0.50    1.00    --   91.36 125.00-120.00  138
 11  \w    100.00 156.00   0.50    1.00    --   91.36 104.00 159.00  112
 12  \w     29.00  71.00   0.50    1.00    --   91.36 -77.00  90.00   84
 13  \w     29.00  71.00   0.50    1.00    --   91.36 -77.00 120.00   84
 14  \w     29.00  71.00   0.50    1.00    --   91.36 -77.00 150.00   84
 15  \w     29.00  71.00   0.50    1.00    --   91.36 -77.00   0.00   84
 16  \w     29.00  71.00   0.50    1.00    --   91.36 -77.00 -60.00   84
 17  \w     29.00  71.00   0.50    1.00    --   91.36 -77.00-180.00   84
 18  \w     -3.00  78.00   0.50    1.00    --   48.17-104.00  57.00  162
 19  \w     -3.00  78.00   0.50    1.00    --   48.17-104.00  57.00  162
 20  \w     29.00  92.00   0.50    1.00    --   91.36 -95.00  90.00  126
 21  \w     27.00  92.00   0.50    1.00    --   91.36-104.00  57.00  130
 22  \w     78.00 132.00   0.50    1.00    --   91.36  15.00-180.00  108
 23  \w     78.00 132.00   0.50    1.00    --   91.36  15.00-150.00  108
 24  \w     99.00 154.00   0.50    1.00    --   91.36  77.00-150.00  110
 25  \w     78.00 132.00   0.50    1.00    --   91.36  15.00 -60.00  108
 26  \w   -123.00 -75.00   0.50    1.00    --  -49.92 -38.00  60.00   96
;
_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      -0.1338880000
_diffrn_orient_matrix_UB_12      -0.0282696000
_diffrn_orient_matrix_UB_13      0.0596817000
_diffrn_orient_matrix_UB_21      -0.0561204000
_diffrn_orient_matrix_UB_22      0.0835209000
_diffrn_orient_matrix_UB_23      -0.0389276000
_diffrn_orient_matrix_UB_31      -0.0361432000
_diffrn_orient_matrix_UB_32      -0.0250068000
_diffrn_orient_matrix_UB_33      -0.1974206000
_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  0.0247
_diffrn_reflns_av_unetI/netI     0.0176
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       6
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            11803
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.185
_diffrn_reflns_theta_min         4.295
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.359
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.736
_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 pale yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   pale
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.553
_exptl_crystal_description       prism
_exptl_crystal_F_000             616
_exptl_crystal_recrystallization_method
'The material was recrystallised from DCM by slow evaporation'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.298
_refine_diff_density_min         -0.262
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.105
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     190
_refine_ls_number_reflns         2348
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.105
_refine_ls_R_factor_all          0.0297
_refine_ls_R_factor_gt           0.0283
_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^)+(0.0418P)^2^+0.4579P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0769
_refine_ls_wR_factor_ref         0.0778
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2217
_reflns_number_total             2348
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc05185a2.cif
_cod_data_source_block           2024sot0038_d1_100k_
_cod_depositor_comments
'Adding full bibliography for 7135132--7135138.cif.'
_cod_database_code               7135137
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C16H11NO3S
_chemical_oxdiff_usercomment     MEP266
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.719
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C8(H8A,H8B), C15(H15A,H15B)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C7(H7), C10(H10), C11(H11), C12(H12)
;
_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 MEP266
_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 1.637
_oxdiff_exptl_absorpt_empirical_full_min 0.641