Substrate-controlled divergent remote C-H and N-H polyfluoroarylation of 2-aminopyrimidines with polyfluoroarenes <i>via</i> Pd(II)/Pd(0) catalysis.
Das, Animesh; Maji, Biplab; Chemical communications (Cambridge, England) 60 (2024) 5630–5633; doi:10.1039/d4cc01518e

data_7132999
_publ_section_title
;
 Substrate-controlled divergent remote C-H and N-H polyfluoroarylation of
 2-aminopyrimidines with polyfluoroarenes <i>via</i> Pd(II)/Pd(0)
 catalysis.
;
_journal_issue                   43
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              5630
_journal_page_last               5633
_journal_paper_doi               10.1039/d4cc01518e
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C15 H14 F5 N3'
_chemical_formula_sum            'C15 H14 F5 N3'
_chemical_formula_weight         331.29
_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     dual
_audit_creation_date             2023-11-29
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2024-01-22 deposited with the CCDC.	2024-05-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.511(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.4951(3)
_cell_length_b                   7.6806(2)
_cell_length_c                   16.1712(5)
_cell_measurement_reflns_used    10122
_cell_measurement_temperature    100.4(9)
_cell_measurement_theta_max      67.9940
_cell_measurement_theta_min      3.7320
_cell_volume                     1471.65(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_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      100.4(9)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_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  30.00   0.50    0.30    --  -40.58  89.00 -22.00  204
  2  \w    -21.00  72.00   0.50    0.30    --   40.58 -89.00-138.00  186
  3  \w   -153.00 -78.00   0.50    1.50    --  -82.50 -89.00-138.00  150
  4  \w    -81.00 -12.00   0.50    1.50    --  -82.50  89.00 -22.00  138
  5  \w     26.00 106.00   0.50    1.50    --   96.35 -89.00-138.00  160
  6  \w    -96.00 -19.00   0.50    0.30    --  -40.58 138.00-180.00  154
  7  \w    -24.00  35.00   0.50    0.30    --  -40.58  12.00 120.00  118
  8  \w    -31.00  30.00   0.50    0.30    --  -40.58  25.00 -90.00  122
  9  \w    -25.00  43.00   0.50    0.30    --   40.58 -38.00 -60.00  136
 10  \w     22.00 107.00   0.50    0.30    --   40.58  50.00  60.00  170
 11  \w    -35.00  24.00   0.50    0.30    --   40.58 -12.00  90.00  118
 12  \w    -29.00  31.00   0.50    0.30    --   40.58 -25.00-120.00  120
 13  \w   -151.00 -61.00   0.50    1.50    --  -82.50 -59.00 150.00  180
 14  \w    -47.00 -15.00   0.50    1.50    --  -82.50  42.00 -90.00   64
 15  \w    -47.00 -15.00   0.50    1.50    --  -82.50  42.00-180.00   64
 16  \w   -156.00 -83.00   0.50    1.50    --  -82.50 -96.00  30.00  146
 17  \w    -47.00 -15.00   0.50    1.50    --  -82.50  42.00 150.00   64
 18  \w     30.00  57.00   0.50    1.50    --   96.35 -50.00  90.00   54
 19  \w     29.00  83.00   0.50    1.50    --   96.35 -68.00-120.00  108
 20  \w     30.00  57.00   0.50    1.50    --   96.35 -50.00 120.00   54
 21  \w     44.00 127.00   0.50    1.50    --   96.35-145.00-120.00  166
 22  \w     28.00  68.00   0.50    1.50    --   96.35 -59.00  30.00   80
 23  \w     30.00  57.00   0.50    1.50    --   96.35 -50.00  30.00   54
 24  \w    105.00 170.00   0.50    1.50    --   96.35  96.00   0.00  130
 25  \w     44.00 127.00   0.50    1.50    --   96.35-145.00  60.00  166
 26  \w     81.00 167.00   0.50    1.50    --   96.35  25.00 -60.00  172
 27  \w     44.00 127.00   0.50    1.50    --   96.35-145.00  90.00  166
 28  \w     33.00 110.00   0.50    1.50    --   96.35-117.00  90.00  154
 29  \w     28.00 105.00   0.50    1.50    --   96.35 -77.00 -90.00  154
 30  \w     30.00  57.00   0.50    1.50    --   96.35 -50.00 -60.00   54
 31  \w     29.00  83.00   0.50    1.50    --   96.35 -68.00  90.00  108
 32  \w    100.00 167.00   0.50    1.50    --   96.35  89.00 -22.00  134
 33  \w   -109.00 -14.00   0.50    0.30    --  -40.58 -77.00  60.00  190
 34  \w   -109.00 -14.00   0.50    0.30    --  -40.58 -77.00 120.00  190
 35  \w   -108.00 -17.00   0.50    0.30    --  -40.58 -64.00-120.00  182
 36  \w   -109.00 -14.00   0.50    0.30    --  -40.58 -77.00-180.00  190
 37  \w   -109.00 -14.00   0.50    0.30    --  -40.58 -77.00 -30.00  190
 38  \w    -25.00  43.00   0.50    0.30    --   40.58 -38.00   0.00  136
 39  \w     14.00 109.00   0.50    0.30    --   40.58  77.00  60.00  190
 40  \w     22.00 107.00   0.50    0.30    --   40.58  50.00   0.00  170
 41  \w     18.00 108.00   0.50    0.30    --   40.58  64.00-150.00  180
 42  \w     14.00 109.00   0.50    0.30    --   40.58  77.00 -90.00  190
 43  \w   -151.00 -72.00   0.50    1.50    --  -82.50 -77.00 -90.00  158
 44  \w     77.00 163.00   0.50    1.50    --   96.35  50.00-180.00  172
 45  \w     72.00 164.00   0.50    1.50    --   96.35  68.00  90.00  184
 46  \w     75.00 165.00   0.50    1.50    --   96.35  59.00 -30.00  180
 47  \w     83.00 164.00   0.50    1.50    --   96.35  33.00-120.00  162
 48  \w     80.00 164.00   0.50    1.50    --   96.35  42.00  60.00  168
 49  \w     70.00 165.00   0.50    1.50    --   96.35  77.00 120.00  190
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1245792000
_diffrn_orient_matrix_UB_12      0.0314184000
_diffrn_orient_matrix_UB_13      0.0533557000
_diffrn_orient_matrix_UB_21      0.0045820000
_diffrn_orient_matrix_UB_22      -0.1792434000
_diffrn_orient_matrix_UB_23      0.0437665000
_diffrn_orient_matrix_UB_31      0.0367369000
_diffrn_orient_matrix_UB_32      -0.0845139000
_diffrn_orient_matrix_UB_33      -0.0730836000
_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  0.0663
_diffrn_reflns_av_unetI/netI     0.0353
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            16716
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.072
_diffrn_reflns_theta_min         3.731
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.187
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65658
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.495
_exptl_crystal_description       plate
_exptl_crystal_F_000             680
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.319
_refine_diff_density_min         -0.225
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     210
_refine_ls_number_reflns         2682
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0504
_refine_ls_R_factor_gt           0.0446
_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^)+(0.0781P)^2^+0.4736P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1260
_refine_ls_wR_factor_ref         0.1326
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2323
_reflns_number_total             2682
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc01518e2.cif
_cod_data_source_block           ada_ab_272_auto_1
_cod_depositor_comments
'Adding full bibliography for 7132998--7132999.cif.'
_cod_database_code               7132999
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N F'
_chemical_oxdiff_usercomment     100K
_shelx_estimated_absorpt_t_max   0.988
_shelx_estimated_absorpt_t_min   0.797
_reflns_odcompleteness_completeness 99.96
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C11(H11)
2.b Secondary CH2 refined with riding coordinates:
 C14(H14a,H14b), C12(H12a,H12b)
2.c Aromatic/amide H refined with riding coordinates:
 N3(H3), C9(H9), C8(H8)
2.d Idealised Me refined as rotating group:
 C15(H15a,H15b,H15c), C13(H13a,H13b,H13c)
;
_shelx_res_checksum              3243
_shelx_hkl_checksum              33302
_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 1.475
_oxdiff_exptl_absorpt_empirical_full_min 0.625