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_1556723
_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_formula_moiety         'C25 H21 N O S'
_chemical_formula_sum            'C25 H21 N O S'
_chemical_formula_weight         383.49
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-12-13
_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                81.846(4)
_cell_angle_beta                 74.281(5)
_cell_angle_gamma                81.076(5)
_cell_formula_units_Z            2
_cell_length_a                   8.7543(5)
_cell_length_b                   9.9710(6)
_cell_length_c                   11.6327(6)
_cell_measurement_reflns_used    7579
_cell_measurement_temperature    110.05(10)
_cell_measurement_theta_max      70.7950
_cell_measurement_theta_min      3.9550
_cell_volume                     960.27(10)
_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      110.05(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 0.981
_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    -72.00  26.00   1.00    1.00    --    0.00 -37.00-120.00   98
  2  \w    -21.00  69.00   1.00    1.00    --    0.00  57.00  30.00   90
  3  \w     23.00 111.00   1.00    1.00    --   54.00-125.00-180.00   88
  4  \w     28.00 126.00   1.00    1.00    --   54.00  37.00 -30.00   98
  5  \w     10.00 127.00   1.00    1.00    --   54.00  19.00 -90.00  117
  6  \w    -18.00  80.00   1.00    1.00    --   54.00 -37.00  90.00   98
  7  \w    -15.00  75.00   1.00    1.00    --   54.00 -57.00   0.00   90
  8  \w     33.00 123.00   1.00    1.00    --   54.00  57.00-120.00   90
  9  \w      1.00  96.00   1.00    1.00    --   54.00 -99.00 -30.00   95
 10  \w     36.00 113.00   1.00    1.00    --  108.00-111.00-150.00   77
 11  \w     86.00 176.00   1.00    1.00    --  108.00  63.00-150.00   90
 12  \w     86.00 176.00   1.00    1.00    --  108.00  63.00  90.00   90
 13  \w     40.00 130.00   1.00    1.00    --  108.00 -63.00 -60.00   90
 14  \w     40.00 130.00   1.00    1.00    --  108.00 -63.00-180.00   90
 15  \w     36.00 134.00   1.00    1.00    --  108.00 -37.00  90.00   98
 16  \w     36.00 113.00   1.00    1.00    --  108.00-111.00 -30.00   77
 17  \w     36.00 113.00   1.00    1.00    --  108.00-111.00  60.00   77
 18  \w     82.00 178.00   1.00    1.00    --  108.00  37.00 -90.00   96
 19  \w     38.00 130.00   1.00    1.00    --  108.00 -50.00  60.00   92
 20  \w     35.00 178.00   1.00    1.00    --  108.00 -12.00-120.00  143
 21  \w     36.00 113.00   1.00    1.00    --  108.00-111.00-180.00   77
 22  \w     36.00 113.00   1.00    1.00    --  108.00-111.00 120.00   77
 23  \w    -21.00  69.00   1.00    1.00    --    0.00  57.00-150.00   90
 24  \w    -69.00  21.00   1.00    1.00    --    0.00 -57.00 -30.00   90
 25  \w    -15.00  75.00   1.00    1.00    --   54.00 -57.00-150.00   90
 26  \w     24.00 124.00   1.00    1.00    --   54.00  77.00 -30.00  100
 27  \w     24.00 124.00   1.00    1.00    --   54.00  77.00-180.00  100
 28  \w     24.00 124.00   1.00    1.00    --   54.00  77.00  60.00  100
 29  \w     24.00 124.00   1.00    1.00    --   54.00  77.00-120.00  100
 30  \w     24.00 124.00   1.00    1.00    --   54.00  77.00 -60.00  100
 31  \w     24.00 124.00   1.00    1.00    --   54.00  77.00 120.00  100
 32  \w     24.00 124.00   1.00    1.00    --   54.00  77.00   0.00  100
 33  \w     74.00 136.00   1.00    1.00    --  108.00  25.00-180.00   62
 34  \w     86.00 178.00   1.00    1.00    --  108.00  50.00  60.00   92
 35  \w     78.00 178.00   1.00    1.00    --  108.00  77.00 -60.00  100
 36  \w     74.00 178.00   1.00    1.00    --  108.00  25.00  30.00  104
;
_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      -0.0286799000
_diffrn_orient_matrix_UB_12      0.0588785000
_diffrn_orient_matrix_UB_13      0.1206137000
_diffrn_orient_matrix_UB_21      0.1812858000
_diffrn_orient_matrix_UB_22      -0.0226316000
_diffrn_orient_matrix_UB_23      -0.0109531000
_diffrn_orient_matrix_UB_31      0.0155755000
_diffrn_orient_matrix_UB_32      0.1440618000
_diffrn_orient_matrix_UB_33      -0.0668677000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0214
_diffrn_reflns_av_unetI/netI     0.0175
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            14054
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.048
_diffrn_reflns_theta_min         3.970
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.605
_exptl_absorpt_correction_T_max  0.882
_exptl_absorpt_correction_T_min  0.640
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.326
_exptl_crystal_description       block
_exptl_crystal_F_000             404
_exptl_crystal_recrystallization_method DCM/Et2O/hexane
_exptl_crystal_size_max          0.49
_exptl_crystal_size_mid          0.281
_exptl_crystal_size_min          0.124
_refine_diff_density_max         0.292
_refine_diff_density_min         -0.284
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     258
_refine_ls_number_reflns         3652
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0334
_refine_ls_R_factor_gt           0.0318
_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^)+(0.0376P)^2^+0.4785P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0796
_refine_ls_wR_factor_ref         0.0808
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3469
_reflns_number_total             3652
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc05311e2.cif
_cod_data_source_block           rjkt1804
_cod_depositor_comments
;Adding full bibliography for 1556719--1556723.cif.

 Adding full bibliography for 1556719--1556723.cif.
;
_cod_database_code               1556723
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C25 H21 N O S'
_chemical_oxdiff_usercomment     'Hon Eong Ho heh-APG-37 (A)'
_shelx_estimated_absorpt_t_max   0.826
_shelx_estimated_absorpt_t_min   0.507
_reflns_odcompleteness_completeness 99.97
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C18(H18)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C13(H13), C14(H14), C15(H15),
 C16(H16), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25)
2.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C)
;
_olex2_date_sample_data_collection 2018-12-04
_olex2_date_sample_submission    2018-11-28
_olex2_exptl_crystal_mounting_method 'oil on micromount'
_olex2_submission_original_sample_id heh-APG-37
_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 1.364
_oxdiff_exptl_absorpt_empirical_full_min 0.675