LED-induced Ru-photoredox Pd-catalyzed C–H arylation of (6-phenylpyridin-2-yl)pyrimidines and heteroaryl counterparts
Antoniou, Ioakeim M.; Ioannou, Natalia; Panagiotou, Nikos; Georgiades, Savvas N.; RSC Advances 14 (2024) 12179–12191; doi:10.1039/D4RA02173H

data_7248427
_publ_section_title
;
 LED-induced Ru-photoredox Pd-catalyzed C--H arylation of
 (6-phenylpyridin-2-yl)pyrimidines and heteroaryl counterparts
;
_journal_issue                   17
_journal_name_full               'RSC Advances'
_journal_page_first              12179
_journal_page_last               12191
_journal_paper_doi               10.1039/D4RA02173H
_journal_volume                  14
_journal_year                    2024
_chemical_formula_moiety         '2(C32 H23 Cl N4 O3 Pd), C H2 Cl2'
_chemical_formula_sum            'C65 H48 Cl4 N8 O6 Pd2'
_chemical_formula_weight         1391.71
_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             2023-08-16
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-11-12 deposited with the CCDC.	2024-04-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.605(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.6930(3)
_cell_length_b                   26.2789(5)
_cell_length_c                   16.4539(4)
_cell_measurement_reflns_used    9387
_cell_measurement_temperature    149.99(14)
_cell_measurement_theta_max      76.6000
_cell_measurement_theta_min      3.2970
_cell_volume                     5778.0(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.79a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.79a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.79a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      149.99(14)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_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    -62.00 -37.00   1.00    2.00    -- -105.35  57.00 150.00   25
  2  \w    -60.00 -35.00   1.00    2.00    -- -105.35  57.00  60.00   25
  3  \w    -66.00 -41.00   1.00    2.00    -- -105.35  57.00  30.00   25
  4  \w    -64.00 -36.00   1.00    2.00    -- -105.35  57.00  90.00   28
  5  \w    -43.00  20.00   1.00    0.50    --  -49.97  38.00  30.00   63
  6  \w    -65.00 -34.00   1.00    2.00    -- -105.35  57.00 -60.00   31
  7  \w    -64.00 -34.00   1.00    2.00    -- -105.35  57.00 -90.00   30
  8  \w    -65.00 -37.00   1.00    2.00    -- -105.35  57.00-120.00   28
  9  \w   -146.00-100.00   1.00    2.00    -- -105.35   0.00-120.00   46
 10  \w   -177.00-124.00   1.00    2.00    -- -105.35 -19.00-150.00   53
 11  \w   -167.00 -84.00   1.00    2.00    -- -105.35 -89.00 169.00   83
 12  \w   -175.00-106.00   1.00    2.00    -- -105.35 -38.00  90.00   69
 13  \w    -63.00  11.00   1.00    0.50    --  -49.97  89.00 -75.00   74
 14  \w    -83.00 -51.00   1.00    2.00    -- -105.35  89.00 -75.00   32
 15  \w     87.00 112.00   1.00    2.00    --  105.35   0.00 -90.00   25
 16  \w     74.00 100.00   1.00    0.50    --   49.97 125.00 150.00   26
 17  \w     74.00 104.00   1.00    0.50    --   49.97 125.00 120.00   30
 18  \w    137.00 177.00   1.00    2.00    --  105.35  89.00 -75.00   40
 19  \w     77.00 108.00   1.00    0.50    --   49.97 125.00-150.00   31
 20  \w     37.00 105.00   1.00    2.00    --  105.35 -77.00-180.00   68
 21  \w     38.00  64.00   1.00    2.00    --  105.35 -57.00-150.00   26
 22  \w     39.00  64.00   1.00    2.00    --  105.35 -57.00 -60.00   25
 23  \w     34.00  62.00   1.00    2.00    --  105.35 -57.00  90.00   28
 24  \w     43.00  68.00   1.00    2.00    --  105.35 -99.00  90.00   25
 25  \w     63.00  92.00   1.00    2.00    --  105.35 -89.00 169.00   29
 26  \w     -4.00  64.00   1.00    0.50    --   49.97 -89.00 169.00   68
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0788
_diffrn_reflns_av_unetI/netI     0.0744
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            39464
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        66.998
_diffrn_reflns_theta_max         66.998
_diffrn_reflns_theta_min         3.225
_exptl_absorpt_coefficient_mu    7.230
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89612
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.79a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.600
_exptl_crystal_description       block
_exptl_crystal_F_000             2808
_exptl_crystal_size_max          0.029
_exptl_crystal_size_mid          0.026
_exptl_crystal_size_min          0.016
_refine_diff_density_max         2.294
_refine_diff_density_min         -2.248
_refine_diff_density_rms         0.124
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     780
_refine_ls_number_reflns         10285
_refine_ls_number_restraints     55
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0762
_refine_ls_R_factor_gt           0.0549
_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^)+(0.0733P)^2^+6.2323P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1371
_refine_ls_wR_factor_ref         0.1477
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7794
_reflns_number_total             10285
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ra02173h2.cif
_cod_data_source_block           ima_3bf_orange_auto
_cod_database_code               7248427
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.893
_shelx_estimated_absorpt_t_min   0.818
_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. Restrained distances
 C79-Cl80
 1.75 with sigma of 0.005
 C79-Cl79
 1.75 with sigma of 0.005
 C80-Cl79
 1.75 with sigma of 0.005
 C80-Cl80
 1.75 with sigma of 0.005
 Cl80-Cl79
 3 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
H80A \\sim H80B \\sim C80 \\sim C79 \\sim H79A \\sim H79B \\sim Cl79 \\sim
Cl80: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within
2A
4. Others
 Sof(C80)=Sof(H80A)=Sof(H80B)=1-FVAR(1)
 Sof(C79)=Sof(H79A)=Sof(H79B)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C80(H80A,H80B), C79(H79A,H79B)
5.b Aromatic/amide H refined with riding coordinates:
 C75(H75), N12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18),
 C22(H22), C23(H23), C24(H24), C27(H27), C28(H28), C29(H29), C35(H35), C36(H36),
  C37(H37), C38(H38), C39(H39), N51(H51), C53(H53), C54(H54), C55(H55),
 C56(H56), C57(H57), C62(H62), C61(H61), C60(H60), C66(H66), C67(H67), C68(H68),
  C74(H74), C76(H76), C77(H77), C78(H78)
5.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C)
;
_shelx_res_checksum              12347
_shelx_hkl_checksum              97789
_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
;