Visible-light-induced intramolecular charge transfer in the radical spirocyclisation of indole-tethered ynones
Ho, Hon Eong; Pagano, Angela; Rossi-Ashton, James A.; Donald, James R.; Epton, Ryan G.; Churchill, Jonathan C.; James, Michael J.; O'Brien, Peter; Taylor, Richard J. K.; Unsworth, William P.; Chemical Science 11 (2020) 1353–1360; doi:10.1039/C9SC05311E

data_1556721
_publ_section_title
;
 Visible-light-induced intramolecular charge transfer in the radical
 spirocyclisation of indole-tethered ynones
;
_journal_issue                   5
_journal_name_full               'Chemical Science'
_journal_page_first              1353
_journal_page_last               1360
_journal_paper_doi               10.1039/C9SC05311E
_journal_volume                  11
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C24 H19 N O S'
_chemical_formula_sum            'C24 H19 N O S'
_chemical_formula_weight         369.46
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-12-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-08-06 deposited with the CCDC.	2019-12-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.81156(11)
_cell_length_b                   17.5470(3)
_cell_length_c                   18.1227(3)
_cell_measurement_reflns_used    4053
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      70.7680
_cell_measurement_theta_min      4.8680
_cell_volume                     1848.07(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      110.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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     -8.00  41.00   1.00    2.00    --    0.00  57.00  30.00   49
  2  \w      9.00  58.00   1.00    2.00    --    0.00  74.00  50.00   49
  3  \w     -7.00  83.00   1.00    8.00    --   54.00 -77.00  90.00   90
  4  \w     23.00  65.00   1.00    8.00    --   54.00-125.00  90.00   42
  5  \w     28.00 124.00   1.00    8.00    --   54.00  77.00-150.00   96
  6  \w     55.00 109.00   1.00    8.00    --   54.00-125.00 -90.00   54
  7  \w     38.00 109.00   1.00   16.00    --  108.00 -77.00  30.00   71
  8  \w     82.00 136.00   1.00   16.00    --  108.00  37.00 -90.00   54
  9  \w     46.00 129.00   1.00   16.00    --  108.00 -37.00  30.00   83
 10  \w     54.00 115.00   1.00   16.00    --  108.00 -50.00 120.00   61
 11  \w     38.00  88.00   1.00   16.00    --  108.00-111.00 -90.00   50
 12  \w     57.00 110.00   1.00   16.00    --  108.00-111.00 -30.00   53
 13  \w     87.00 149.00   1.00   16.00    --  108.00  63.00 -30.00   62
 14  \w    127.00 153.00   1.00   16.00    --  108.00 111.00 150.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1423156000
_diffrn_orient_matrix_UB_12      -0.0250005000
_diffrn_orient_matrix_UB_13      0.0675627000
_diffrn_orient_matrix_UB_21      -0.0563949000
_diffrn_orient_matrix_UB_22      -0.0839347000
_diffrn_orient_matrix_UB_23      -0.0167141000
_diffrn_orient_matrix_UB_31      0.2164658000
_diffrn_orient_matrix_UB_32      -0.0056049000
_diffrn_orient_matrix_UB_33      -0.0488501000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0228
_diffrn_reflns_av_unetI/netI     0.0317
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            6650
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.002
_diffrn_reflns_theta_max         67.002
_diffrn_reflns_theta_min         3.506
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.649
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.736
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.328
_exptl_crystal_description       plate
_exptl_crystal_F_000             776
_exptl_crystal_recrystallization_method 'From dichloromethane/hexane'
_exptl_crystal_size_max          0.161
_exptl_crystal_size_mid          0.071
_exptl_crystal_size_min          0.035
_refine_diff_density_max         0.188
_refine_diff_density_min         -0.188
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 1220 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.016(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     248
_refine_ls_number_reflns         3220
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0285
_refine_ls_R_factor_gt           0.0273
_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^)+(0.0327P)^2^+0.3713P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0676
_refine_ls_wR_factor_ref         0.0684
_reflns_Friedel_coverage         0.674
_reflns_Friedel_fraction_full    0.952
_reflns_Friedel_fraction_max     0.952
_reflns_number_gt                3120
_reflns_number_total             3220
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc05311e2.cif
_cod_data_source_block           rjkt1805
_cod_depositor_comments
;Adding full bibliography for 1556719--1556723.cif.

 Adding full bibliography for 1556719--1556723.cif.
;
_cod_database_code               1556721
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C24 H19 N1 O1 S1'
_chemical_oxdiff_usercomment     'Hon Eong Ho heh-APG-47A'
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C3(H3A,H3B), C6(H6A,H6B)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C14(H14), C15(H15), C16(H16), C17(H17),
 C18(H18), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24)
;
_shelx_res_checksum              66199
_olex2_date_sample_data_collection 2018-12-05
_olex2_date_sample_submission    2018-11-28
_olex2_exptl_crystal_mounting_method 'oil on 200 micrometre micromount'
_olex2_submission_original_sample_id heh-AIG47
_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 1.761
_oxdiff_exptl_absorpt_empirical_full_min 0.893