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_1556722
_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         'C19 H15 N O'
_chemical_formula_sum            'C19 H15 N O'
_chemical_formula_weight         273.32
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-17
_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                   7.42250(12)
_cell_length_b                   9.90594(16)
_cell_length_c                   19.5109(3)
_cell_measurement_reflns_used    6762
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      70.9330
_cell_measurement_theta_min      4.5240
_cell_volume                     1434.57(4)
_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 1.001
_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     17.00  69.00   1.00    1.00    --    0.00  57.00  60.00   52
  2  \w    -61.00 -20.00   1.00    1.00    --    0.00 -57.00 -60.00   41
  3  \w     53.00  94.00   1.00    1.50    --   54.00  57.00 -90.00   41
  4  \w    -15.00  73.00   1.00    1.50    --   54.00 -57.00  60.00   88
  5  \w     28.00 112.00   1.00    1.50    --   54.00  37.00-120.00   84
  6  \w     45.00 121.00   1.00    1.50    --   54.00  57.00 -30.00   76
  7  \w     86.00 177.00   1.00    2.00    --  108.00  50.00 -60.00   91
  8  \w     68.00 135.00   1.00    2.00    --  108.00 178.00-150.00   67
  9  \w     41.00 130.00   1.00    2.00    --  108.00 -63.00 150.00   89
 10  \w     58.00 110.00   1.00    2.00    --  108.00 178.00-180.00   52
 11  \w    117.00 149.00   1.00    2.00    --  108.00 178.00-180.00   32
 12  \w     36.00 113.00   1.00    2.00    --  108.00-111.00-180.00   77
 13  \w    112.00 160.00   1.00    2.00    --  108.00  12.00  90.00   48
 14  \w    -35.00  11.00   1.00    1.00    --    0.00  99.00  46.00   46
 15  \w     23.00  68.00   1.00    1.50    --   54.40-125.00   0.00   45
 16  \w     24.00  84.00   1.00    1.50    --   54.40  77.00  30.00   60
 17  \w     14.00  40.00   1.00    1.50    --   54.40  19.00-180.00   26
 18  \w     85.00 114.00   1.00    1.50    --   54.40  19.00-180.00   29
 19  \w    -19.00  58.00   1.00    1.50    --   54.40   0.00 150.00   77
 20  \w    129.00 173.00   1.00    2.00    --  108.00 -12.00 -90.00   44
 21  \w     80.00 161.00   1.00    2.00    --  108.00  77.00 -30.00   81
 22  \w     78.00 104.00   1.00    2.00    --  108.00  77.00  60.00   26
 23  \w     86.00 112.00   1.00    2.00    --  108.00  63.00  90.00   26
 24  \w    129.00 155.00   1.00    2.00    --  108.00  63.00  90.00   26
 25  \w     79.00 105.00   1.00    2.00    --  108.00  77.00  30.00   26
 26  \w    142.00 168.00   1.00    2.00    --  108.00  77.00  30.00   26
 27  \w     78.00 104.00   1.00    2.00    --  108.00  77.00   0.00   26
 28  \w    120.00 170.00   1.00    2.00    --  108.00  77.00   0.00   50
 29  \w     84.00 110.00   1.00    2.00    --  108.00  37.00  30.00   26
 30  \w    146.00 171.00   1.00    2.00    --  108.00  37.00  30.00   25
 31  \w     86.00 112.00   1.00    2.00    --  108.00  63.00  30.00   26
 32  \w     84.00 110.00   1.00    2.00    --  108.00  37.00  90.00   26
 33  \w     86.00 120.00   1.00    2.00    --  108.00  63.00  60.00   34
 34  \w     95.00 121.00   1.00    2.00    --  108.00  50.00  90.00   26
 35  \w     86.00 118.00   1.00    2.00    --  108.00  50.00 120.00   32
 36  \w     94.00 120.00   1.00    2.00    --  108.00  50.00  30.00   26
 37  \w     95.00 121.00   1.00    2.00    --  108.00  50.00  60.00   26
 38  \w     82.00 108.00   1.00    2.00    --  108.00  37.00  60.00   26
 39  \w     85.00 111.00   1.00    2.00    --  108.00  43.00  29.76   26
 40  \w     78.00 103.00   1.00    2.00    --  108.00  77.00  56.79   25
 41  \w     79.00 104.00   1.00    2.00    --  108.00  76.00  79.73   25
;
_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      0.0696679000
_diffrn_orient_matrix_UB_12      0.0111551000
_diffrn_orient_matrix_UB_13      0.0741822000
_diffrn_orient_matrix_UB_21      0.1033955000
_diffrn_orient_matrix_UB_22      -0.1337223000
_diffrn_orient_matrix_UB_23      -0.0089103000
_diffrn_orient_matrix_UB_31      0.1658117000
_diffrn_orient_matrix_UB_32      0.0786523000
_diffrn_orient_matrix_UB_33      -0.0256210000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0227
_diffrn_reflns_av_unetI/netI     0.0168
_diffrn_reflns_Laue_measured_fraction_full 1.001
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            11327
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.058
_diffrn_reflns_theta_max         67.058
_diffrn_reflns_theta_min         4.532
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.612
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.637
_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    1.265
_exptl_crystal_description       irregular
_exptl_crystal_F_000             576
_exptl_crystal_recrystallization_method
'crystallisation from dichloromethane/hexane'
_exptl_crystal_size_max          0.217
_exptl_crystal_size_mid          0.192
_exptl_crystal_size_min          0.091
_refine_diff_density_max         0.142
_refine_diff_density_min         -0.118
_refine_diff_density_rms         0.026
_refine_ls_abs_structure_details
;
 Flack x determined using 1003 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.08(11)
_refine_ls_extinction_coef       0.0040(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.099
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     192
_refine_ls_number_reflns         2565
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.099
_refine_ls_R_factor_all          0.0257
_refine_ls_R_factor_gt           0.0243
_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^)+(0.0299P)^2^+0.1675P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0605
_refine_ls_wR_factor_ref         0.0619
_reflns_Friedel_coverage         0.709
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                2471
_reflns_number_total             2565
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc05311e2.cif
_cod_data_source_block           rjkt1905
_cod_depositor_comments
;Adding full bibliography for 1556719--1556723.cif.

 Adding full bibliography for 1556719--1556723.cif.
;
_cod_database_code               1556722
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C19 H15 N1 O1'
_chemical_oxdiff_usercomment     'Hon Eong Ho heh-JPA-569P'
_reflns_odcompleteness_completeness 99.93
_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 Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C5(H5), C6(H6), C7(H7), C14(H14), C15(H15), C16(H16),
 C17(H17), C18(H18)
2.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C)
;
_shelx_res_checksum              28265
_olex2_date_sample_data_collection 2019-05-15
_olex2_date_sample_submission    2019-05-13
_olex2_exptl_crystal_mounting_method 'oil on 200 micrometre micromount'
_olex2_submission_original_sample_id heh-jpa-569p
_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 1.169
_oxdiff_exptl_absorpt_empirical_full_min 0.864