Identification of the Side Products That Diminish the Yields of the Monoamidated Product in Metal-Catalyzed C–H Amidation of 2-Phenylpyridine with Arylisocyanates
McKay, Alasdair I.; Altalhi, Weam A. O.; McInnes, Lachlan E.; Czyz, Milena L.; Canty, Allan J.; Donnelly, Paul S.; O’Hair, Richard A. J.; The Journal of Organic Chemistry  (2020) –; doi:10.1021/acs.joc.9b02831

data_4037833
_publ_section_title
;
 Identification of the Side Products That Diminish the Yields of the
 Monoamidated Product in Metal-Catalyzed C--H Amidation of
 2-Phenylpyridine with Arylisocyanates
;
_journal_name_full               'The Journal of Organic Chemistry'
_journal_paper_doi               10.1021/acs.joc.9b02831
_journal_year                    2020
_chemical_formula_moiety         'C20 H14 F3 N3 O2'
_chemical_formula_sum            'C20 H14 F3 N3 O2'
_chemical_formula_weight         385.34
_chemical_name_common            1,3,5-tri(4-fluorophenyl)biuret
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-09-10
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2019.08.16 svn.r3652 for OlexSys, GUI svn.r5895)
;
_cell_angle_alpha                94.235(3)
_cell_angle_beta                 93.075(4)
_cell_angle_gamma                113.306(5)
_cell_formula_units_Z            2
_cell_length_a                   7.7093(5)
_cell_length_b                   9.5441(5)
_cell_length_c                   12.4195(4)
_cell_measurement_reflns_used    4810
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.9250
_cell_measurement_theta_min      5.0830
_cell_volume                     833.52(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.29a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.29a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.29a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.993
_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    -24.00  14.00   0.50    0.37    --  -48.94  96.00 126.00   76
  2  \w    -77.00 -29.00   0.50    0.37    --  -48.94  96.00 126.00   96
  3  \w    -80.00 -53.00   0.50    1.47    --  -86.25  96.00 126.00   54
  4  \w     71.00 109.00   0.50    1.47    --  107.75 -96.00  17.00   76
  5  \w     40.00  69.00   0.50    1.47    --  107.75 -96.00  17.00   58
  6  \w    119.00 147.00   0.50    1.47    --  107.75  96.00 126.00   56
  7  \w   -118.00 -84.00   0.50    0.37    --  -48.94 -57.00  30.00   68
  8  \w   -119.00 -82.00   0.50    0.37    --  -48.94 -57.00   0.00   74
  9  \w    -43.00  23.00   0.50    0.37    --  -48.94  37.00 150.00  132
 10  \w    -44.00  -9.00   0.50    0.37    --  -48.94  37.00  90.00   70
 11  \w    -15.00  13.00   0.50    0.37    --  -48.94  19.00  30.00   56
 12  \w     -5.00  22.00   0.50    0.37    --  -48.94  37.00  90.00   54
 13  \w     -8.00  71.00   0.50    0.37    --   48.94 -96.00  17.00  158
 14  \w   -144.00-119.00   0.50    1.47    --  -86.25 -96.00  17.00   50
 15  \w   -155.00-107.00   0.50    1.47    --  -86.25 -77.00 120.00   96
 16  \w     36.00  88.00   0.50    1.47    --  107.75 -77.00-180.00  104
 17  \w     99.00 177.00   0.50    1.47    --  107.75  30.00   0.00  156
 18  \w     77.00 109.00   0.50    1.47    --  107.75 -94.00-180.00   64
 19  \w     35.00 117.00   0.50    1.47    --  107.75-125.00 -30.00  164
 20  \w    101.00 131.00   0.50    1.47    --  107.75 125.00-150.00   60
 21  \w     39.00  68.00   0.50    1.47    --  107.75 -61.00-150.00   58
 22  \w    139.00 167.00   0.50    1.47    --  107.75  15.00  60.00   56
 23  \w     38.00 114.00   0.50    1.47    --  107.75-125.00-180.00  152
 24  \w    100.00 132.00   0.50    1.47    --  107.75  61.00 -60.00   64
 25  \w    101.00 138.00   0.50    1.47    --  107.75  15.00  60.00   74
 26  \w     36.00  64.00   0.50    1.47    --  107.75 -61.00   0.00   56
 27  \w    137.00 174.00   0.50    1.47    --  107.75  61.00 -60.00   74
 28  \w     36.00  64.00   0.50    1.47    --  107.75 -94.00-180.00   56
 29  \w     81.00 110.00   0.50    1.47    --  107.75-125.00 -60.00   58
 30  \w    101.00 177.00   0.50    1.47    --  107.75  77.00  90.00  152
 31  \w     45.00 110.00   0.50    1.47    --  107.75-100.00   3.71  130
 32  \w     35.00  72.00   0.50    1.47    --  107.75-125.00 -60.00   74
 33  \w    146.00 178.00   0.50    1.47    --  107.75  77.00-150.00   64
 34  \w    133.00 166.00   0.50    1.47    --  107.75 125.00-150.00   66
 35  \w     41.00 108.00   0.50    1.47    --  107.75 -94.00  60.00  134
 36  \w    101.00 136.00   0.50    1.47    --  107.75  77.00-150.00   70
 37  \w     94.00 127.00   0.50    1.47    --  107.75 -77.00-180.00   66
 38  \w     38.00  69.00   0.50    1.47    --  107.75 -61.00-180.00   62
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.2025135000
_diffrn_orient_matrix_UB_12      0.0535018000
_diffrn_orient_matrix_UB_13      -0.0358199000
_diffrn_orient_matrix_UB_21      -0.0716731000
_diffrn_orient_matrix_UB_22      0.0273483000
_diffrn_orient_matrix_UB_23      -0.1114089000
_diffrn_orient_matrix_UB_31      0.0398205000
_diffrn_orient_matrix_UB_32      0.1661780000
_diffrn_orient_matrix_UB_33      0.0436349000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0317
_diffrn_reflns_av_unetI/netI     0.0306
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            9000
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.193
_diffrn_reflns_theta_min         3.583
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.063
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92169
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.29a (Rigaku Oxford Diffraction, 2018)
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    1.535
_exptl_crystal_description       prism
_exptl_crystal_F_000             396
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.262
_refine_diff_density_min         -0.292
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.113
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     253
_refine_ls_number_reflns         3412
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.113
_refine_ls_R_factor_all          0.0501
_refine_ls_R_factor_gt           0.0465
_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^)+(0.0762P)^2^+0.2798P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1284
_refine_ls_wR_factor_ref         0.1308
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3090
_reflns_number_total             3412
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02831_si_002.cif
_cod_data_source_block           9a
_cod_database_code               4037833
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C40 H28 F6 N6 O4 '
_chemical_oxdiff_usercomment     tri(4-fluorophenyl)biuret
_shelx_estimated_absorpt_t_max   0.979
_shelx_estimated_absorpt_t_min   0.910
_reflns_odcompleteness_completeness 98.14
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     75.12
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 N1(H1), N3(H3), C6(H6), C13(H13), C12(H12), C10(H10), C9(H9), C2(H2), C5(H5),
 C20(H20), C17(H17), C19(H19), C3(H3A), C16(H16)
;
_shelx_res_checksum              83447
_shelx_hkl_checksum              67293
_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 1.410
_oxdiff_exptl_absorpt_empirical_full_min 0.206