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_1556719
_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         'C21 H19 N O S'
_chemical_formula_sum            'C21 H19 N O S'
_chemical_formula_weight         333.43
_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             2019-01-24
_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                98.564(7)
_cell_angle_beta                 100.026(7)
_cell_angle_gamma                104.633(10)
_cell_formula_units_Z            2
_cell_length_a                   7.2702(8)
_cell_length_b                   8.7819(9)
_cell_length_c                   13.6782(8)
_cell_measurement_reflns_used    1768
_cell_measurement_temperature    110.05(10)
_cell_measurement_theta_max      69.3250
_cell_measurement_theta_min      5.6720
_cell_volume                     814.84(14)
_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 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -59.00 -16.00   1.00    4.50    --    0.00 -37.00 150.00   43
  2  \w     -9.00  25.00   1.00    4.50    --    0.00 -37.00 150.00   34
  3  \w    -14.00  29.00   1.00    4.50    --    0.00  57.00 -30.00   43
  4  \w     37.00  84.00   1.00   18.00    --   54.00  57.00 -60.00   47
  5  \w     25.00  66.00   1.00   18.00    --   54.00-125.00  60.00   41
  6  \w     69.00 107.00   1.00   18.00    --   54.00-125.00  60.00   38
  7  \w     29.00  69.00   1.00   18.00    --   54.00-125.00-120.00   40
  8  \w     40.00  91.00   1.00   18.00    --   54.00  57.00 -30.00   51
  9  \w     35.00  83.00   1.00   18.00    --   54.00  65.00-110.00   48
 10  \w     31.00 122.00   1.00   18.00    --   54.00  37.00-180.00   91
 11  \w    -18.00  79.00   1.00   18.00    --   54.00 -37.00   0.00   97
 12  \w     36.00 110.00   1.00   18.00    --  108.00-111.00-180.00   74
 13  \w     90.00 149.00   1.00   18.00    --  108.00  63.00  90.00   59
 14  \w     57.00 107.00   1.00   18.00    --  108.00-111.00  90.00   50
 15  \w     38.00 142.00   1.00   18.00    --  108.00 -91.00-150.00  104
 16  \w     38.00 132.00   1.00   18.00    --  108.00 -37.00 -60.00   94
 17  \w    114.00 159.00   1.00   18.00    --  108.00  63.00   0.00   45
 18  \w     65.00 126.00   1.00   18.00    --  108.00 -50.00-180.00   61
 19  \w     86.00 158.00   1.00   18.00    --  108.00  50.00 -30.00   72
 20  \w    108.00 135.00   1.00   18.00    --  108.00 111.00 -90.00   27
 21  \w     42.00  77.00   1.00   18.00    --  108.00 -37.00 120.00   35
 22  \w     87.00 122.00   1.00   18.00    --  108.00 -37.00 120.00   35
 23  \w     73.00 108.00   1.00   18.00    --  108.00-111.00   0.00   35
 24  \w     39.00 138.00   1.00   18.00    --  108.00 -77.00   0.00   99
 25  \w    108.00 178.00   1.00   18.00    --  108.00  37.00  60.00   70
;
_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      -0.1804714000
_diffrn_orient_matrix_UB_12      -0.0516730000
_diffrn_orient_matrix_UB_13      -0.0884194000
_diffrn_orient_matrix_UB_21      0.0180494000
_diffrn_orient_matrix_UB_22      0.1777158000
_diffrn_orient_matrix_UB_23      -0.0031478000
_diffrn_orient_matrix_UB_31      0.1324261000
_diffrn_orient_matrix_UB_32      -0.0048301000
_diffrn_orient_matrix_UB_33      -0.0762432000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0232
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            4947
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.080
_diffrn_reflns_theta_max         67.080
_diffrn_reflns_theta_min         5.316
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.803
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.562
_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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.359
_exptl_crystal_description       plate
_exptl_crystal_F_000             352
_exptl_crystal_recrystallization_method
'evaporation of dichloromethane/hexane'
_exptl_crystal_size_max          0.237
_exptl_crystal_size_mid          0.121
_exptl_crystal_size_min          0.012
_refine_diff_density_max         0.269
_refine_diff_density_min         -0.394
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     235
_refine_ls_number_reflns         2912
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0559
_refine_ls_R_factor_gt           0.0436
_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^)+(0.0475P)^2^+0.4485P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1046
_refine_ls_wR_factor_ref         0.1158
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2386
_reflns_number_total             2912
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc05311e2.cif
_cod_data_source_block           rjkt1902
_cod_depositor_comments
;Adding full bibliography for 1556719--1556723.cif.

 Adding full bibliography for 1556719--1556723.cif.
;
_cod_database_code               1556719
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C21  H19 N1 O1 S1'
_chemical_oxdiff_usercomment     'Hon Eong Ho heh-APG-84'
_shelx_estimated_absorpt_t_max   0.979
_shelx_estimated_absorpt_t_min   0.675
_reflns_odcompleteness_completeness 99.73
_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. Restrained distances
 S1-C16 \\sim S1A-C16
 with sigma of 0.01
 S1-C5 \\sim S1A-C5
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C8) = Uanis(C8A)
Uanis(C7) = Uanis(C7A)
Uanis(C6A) = Uanis(C6)
Uanis(S1) = Uanis(S1A)
4. Others
 Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=1-
 FVAR(1)
 Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(C8)=Sof(H8A)=Sof(H8B)=FVAR(1)
 Sof(S1A)=1-FVAR(2)
 Sof(S1)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C6(H6), C6A(H6A)
5.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C7(H7A,H7B), C7A(H7AA,H7AB), C8(H8A,H8B), C8A(H8AA,H8AB), C9(H9A,
 H9B)
5.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C13(H13), C14(H14), C17(H17), C18(H18), C19(H19),
 C20(H20), C21(H21)
;
_shelx_res_checksum              95576
_olex2_date_sample_data_collection 2019-01-21
_olex2_date_sample_submission    2019-01-21
_olex2_exptl_crystal_mounting_method 'oil on 200 micrometre micromount'
_olex2_submission_original_sample_id heh-APG-84
_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 1.976
_oxdiff_exptl_absorpt_empirical_full_min 0.798