Metal-free aerobic oxidative direct C–H amination of electron-deficient alkenes via photoredox catalysis
Xin, Jing-Rui; He, Yan-Hong; Guan, Zhi; Organic Chemistry Frontiers 5 (2018) 1684–; doi:10.1039/C8QO00161H

data_1554279
_publ_section_title
;
 Metal-free aerobic oxidative direct C--H amination of electron-deficient
 alkenes via photoredox catalysis
;
_journal_issue                   10
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              1684
_journal_paper_doi               10.1039/C8QO00161H
_journal_volume                  5
_journal_year                    2018
_chemical_formula_moiety         'C16 H9 N5'
_chemical_formula_sum            'C16 H9 N5'
_chemical_formula_weight         271.28
_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     direct
_audit_creation_date             2017-04-20
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_audit_update_record
;
2017-06-24 deposited with the CCDC.
2018-03-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.023(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.5111(7)
_cell_length_b                   18.0998(6)
_cell_length_c                   8.8623(3)
_cell_measurement_reflns_used    5886
_cell_measurement_temperature    291.74(10)
_cell_measurement_theta_max      72.8060
_cell_measurement_theta_min      4.8770
_cell_volume                     2781.39(17)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      291.74(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0243
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.952
_diffrn_measured_fraction_theta_max 0.965
_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   -105.00 -10.00   1.00    2.86    --  -37.03 -77.00-180.00   95
  2  \w    -54.00  30.00   1.00    2.86    --  -37.03  57.00  90.00   84
  3  \w     24.00  91.00   1.00    2.86    --   37.03-126.00  30.00   67
  4  \w     24.00  91.00   1.00    2.86    --   37.03-126.00-150.00   67
  5  \w     41.00 109.00   1.00   27.82    --  110.47 -95.00-120.00   68
  6  \w     41.00 116.00   1.00   27.82    --  110.47-112.00 150.00   75
  7  \w     41.00 109.00   1.00   27.82    --  110.47 -95.00-180.00   68
  8  \w    101.00 178.00   1.00   27.82    --  110.47 112.00 150.00   77
  9  \w     92.00 177.00   1.00   27.82    --  110.47  61.00-120.00   85
 10  \w   -105.00 -10.00   1.00    2.86    --  -37.03 -77.00 -30.00   95
 11  \w    -54.00  30.00   1.00    2.86    --  -37.03  57.00 -60.00   84
 12  \w    -54.00  30.00   1.00    2.86    --  -37.03  57.00-150.00   84
 13  \w   -104.00 -20.00   1.00    2.86    --  -37.03 -57.00  60.00   84
 14  \w     41.00 132.00   1.00   27.82    --  110.47   0.00  90.00   91
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0644494000
_diffrn_orient_matrix_UB_12      0.0568541000
_diffrn_orient_matrix_UB_13      -0.0111168000
_diffrn_orient_matrix_UB_21      0.0579379000
_diffrn_orient_matrix_UB_22      -0.0501390000
_diffrn_orient_matrix_UB_23      0.0989538000
_diffrn_orient_matrix_UB_31      0.0196582000
_diffrn_orient_matrix_UB_32      -0.0386447000
_diffrn_orient_matrix_UB_33      -0.1445967000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0328
_diffrn_reflns_av_unetI/netI     0.0321
_diffrn_reflns_Laue_measured_fraction_full 0.952
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            12400
_diffrn_reflns_point_group_measured_fraction_full 0.952
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.079
_diffrn_reflns_theta_min         3.530
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.664
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.41426
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.296
_exptl_crystal_description       block
_exptl_crystal_F_000             1120
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.238
_refine_diff_density_min         -0.238
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     379
_refine_ls_number_reflns         4794
_refine_ls_number_restraints     19
_refine_ls_restrained_S_all      1.121
_refine_ls_R_factor_all          0.0739
_refine_ls_R_factor_gt           0.0585
_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^)+(0.1613P)^2^+0.1083P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2017
_refine_ls_wR_factor_ref         0.2344
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3722
_reflns_number_total             4794
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8qo00161h2.cif
_cod_data_source_block           xjr-122
_cod_original_cell_volume        2781.41(16)
_cod_database_code               1554279
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C1 H1 O1 N1 '
_reflns_odcompleteness_completeness 96.23
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Rigid bond restraints
 C5, C6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
3. Uiso/Uaniso restraints and constraints
C5 \\sim C6: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C5) \\sim Ueq, Uanis(C14) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C5) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4.a Aromatic/amide H refined with riding coordinates:
 C17(H17), C18(H18), C21(H21), C22(H22), C28(H28), C29(H29), C30(H30),
 C31(H31), C32(H32), C3(H3), C4(H4), C5(H5), C6(H6), C12(H12), C13(H13),
 C14(H14), C15(H15), C16(H16)
;
_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 3.032
_oxdiff_exptl_absorpt_empirical_full_min 0.548