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_7248423
_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         'C42 H32 N4 O2, C4 H8 O2'
_chemical_formula_sum            'C46 H40 N4 O4'
_chemical_formula_weight         712.82
_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             2023-08-29
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-11-12 deposited with the CCDC.	2024-04-10 downloaded from the CCDC.
;
_cell_angle_alpha                102.097(2)
_cell_angle_beta                 99.993(2)
_cell_angle_gamma                106.014(2)
_cell_formula_units_Z            2
_cell_length_a                   10.1753(2)
_cell_length_b                   10.8280(2)
_cell_length_c                   18.8802(3)
_cell_measurement_reflns_used    12952
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      76.2940
_cell_measurement_theta_min      4.3860
_cell_volume                     1894.91(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_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      180.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -89.00 -58.00   0.50    0.50    --  -47.44-151.00-110.00   62
  2  \w    -51.00 -18.00   0.50    0.50    --  -47.44 123.00 131.00   66
  3  \w   -108.00 -68.00   0.50    0.50    --  -47.44 151.00 -66.00   80
  4  \w     57.00  82.00   0.50    0.50    --   47.44 151.00 -66.00   50
  5  \w     69.00 104.00   0.50    0.50    --   47.44-151.00-110.00   70
  6  \w     25.00  91.00   0.50    0.50    --   47.44-123.00  51.00  132
  7  \w    -95.00 -56.00   0.50    2.00    -- -106.00 123.00 131.00   78
  8  \w   -125.00 -58.00   0.50    2.00    -- -106.00 151.00 -66.00  134
  9  \w   -126.00 -77.00   0.50    2.00    -- -106.00-123.00  51.00   98
 10  \w     86.00 111.00   0.50    2.00    --  106.24 151.00 -66.00   50
 11  \w     68.00  93.00   0.50    2.00    --  106.24-123.00  51.00   50
 12  \w     65.00 130.00   0.50    2.00    --  106.24-151.00-110.00  130
 13  \w    101.00 138.00   0.50    2.00    --  106.24 123.00 131.00   74
 14  \w     73.00  98.00   0.50    0.50    --   47.44 126.00  30.00   50
 15  \w    -21.00  28.00   0.50    0.50    --   47.44 -19.00 150.00   98
 16  \w    -24.00  41.00   0.50    0.50    --   47.44 -38.00 -90.00  130
 17  \w    -14.00  29.00   0.50    0.50    --   47.44 -19.00 -60.00   86
 18  \w     73.00  98.00   0.50    0.50    --   47.44 126.00   0.00   50
 19  \w    -24.00  30.00   0.50    0.50    --   47.44 -19.00-150.00  108
 20  \w   -108.00 -74.00   0.50    2.00    -- -106.00 112.00-110.98   68
 21  \w    -70.00 -45.00   0.50    2.00    -- -106.00 112.00-110.98   50
 22  \w   -107.00 -57.00   0.50    2.00    -- -106.00 126.00  90.00  100
 23  \w   -174.00 -97.00   0.50    2.00    -- -106.00 -15.00 -60.00  154
 24  \w    -97.00 -34.00   0.50    2.00    -- -106.00  77.00 -30.00  126
 25  \w    -71.00 -34.00   0.50    2.00    -- -106.00  61.00 -90.00   74
 26  \w   -100.00 -59.00   0.50    2.00    -- -106.00  77.00 -90.00   82
 27  \w   -122.00 -86.00   0.50    2.00    -- -106.00 140.00  24.48   72
 28  \w   -101.00 -40.00   0.50    2.00    -- -106.00 126.00 -60.00  122
 29  \w    105.00 162.00   0.50    2.00    --  106.24  15.00 120.00  114
 30  \w     42.00  68.00   0.50    2.00    --  106.24 -61.00-120.00   52
 31  \w     35.00  89.00   0.50    2.00    --  106.24 -77.00  30.00  108
 32  \w     35.00  70.00   0.50    2.00    --  106.24 -61.00  90.00   70
 33  \w     37.00  63.00   0.50    2.00    --  106.24 -61.00 -90.00   52
 34  \w     38.00  69.00   0.50    2.00    --  106.24 -61.00-180.00   62
 35  \w     35.00  71.00   0.50    2.00    --  106.24 -61.00 120.00   72
 36  \w     35.00  69.00   0.50    2.00    --  106.24 -61.00  30.00   68
 37  \w    101.00 178.00   0.50    2.00    --  106.24  30.00-180.00  154
 38  \w     42.00  67.00   0.50    2.00    --  106.24 -95.00  60.00   50
 39  \w     35.00  60.00   0.50    2.00    --  106.24 -77.00-120.00   50
 40  \w     96.00 170.00   0.50    2.00    --  106.24  45.00-150.00  148
 41  \w     36.00  70.00   0.50    2.00    --  106.24 -61.00  60.00   68
 42  \w    102.00 160.00   0.50    2.00    --  106.24  45.00  60.00  116
;
_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  0.0266
_diffrn_reflns_av_unetI/netI     0.0287
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            22574
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        66.992
_diffrn_reflns_theta_max         66.992
_diffrn_reflns_theta_min         4.415
_exptl_absorpt_coefficient_mu    0.641
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.99017
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.90a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.249
_exptl_crystal_description       block
_exptl_crystal_F_000             752
_exptl_crystal_size_max          0.041
_exptl_crystal_size_mid          0.031
_exptl_crystal_size_min          0.025
_refine_diff_density_max         0.290
_refine_diff_density_min         -0.190
_refine_diff_density_rms         0.033
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     547
_refine_ls_number_reflns         6736
_refine_ls_number_restraints     146
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0427
_refine_ls_R_factor_gt           0.0375
_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^)+(0.0530P)^2^+0.3423P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1012
_refine_ls_wR_factor_ref         0.1042
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5909
_reflns_number_total             6736
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ra02173h2.cif
_cod_data_source_block           ima_4-ph
_cod_original_cell_volume        1894.91(6)
_cod_database_code               7248423
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.984
_shelx_estimated_absorpt_t_min   0.974
_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
 O2-C3
 1.32 with sigma of 0.02
 O2-C7
 1.46 with sigma of 0.02
 O3-C3
 1.22 with sigma of 0.02
 C1-C3
 1.49 with sigma of 0.02
 C7-C11
 1.5 with sigma of 0.02
 O1-C1A
 1.32 with sigma of 0.02
 O1-C1B
 1.46 with sigma of 0.02
 O4-C1A
 1.22 with sigma of 0.02
 C12-C1A
 1.49 with sigma of 0.02
 C1B-C1C
 1.5 with sigma of 0.02
 O2-O3
 2.24 with sigma of 0.04
 O2-C1
 2.35 with sigma of 0.04
 O2-C11
 2.38 with sigma of 0.04
 O3-C1
 2.4 with sigma of 0.04
 O1-O4
 2.24 with sigma of 0.04
 O1-C12
 2.35 with sigma of 0.04
 O1-C1C
 2.38 with sigma of 0.04
 O4-C12
 2.4 with sigma of 0.04
 C1-C3 \\sim C7-C11
 with sigma of 0.02
 C12-C1A \\sim C1B-C1C
 with sigma of 0.02
3. Restrained planarity
 O2, O3, C1, C3, C7, C11
 with sigma of 0.1
 O1, O4, C1A, C1B, C1C, C12
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
O2 \\sim O3 \\sim C1 \\sim C3 \\sim C7 \\sim C11: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
O1 \\sim O4 \\sim C1A \\sim C1B \\sim C1C \\sim C12: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 O2, O3, C1, C3, C7, C11
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O1, O4, C1A, C1B, C1C, C12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: O2(0.5) O3(0.5) C1(0.5) H1A(0.5) H1B(0.5) H1C(0.5) C3(0.5) C7(0.5)
 H7A(0.5) H7B(0.5) C11(0.5) H11A(0.5) H11B(0.5) H11C(0.5) O1(0.5) O4(0.5)
 C1A(0.5) C1B(0.5) H1BA(0.5) H1BB(0.5) C1C(0.5) H1CA(0.5) H1CB(0.5) H1CC(0.5)
 C12(0.5) H12A(0.5) H12B(0.5) H12C(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C1B(H1BA,H1BB)
7.b Aromatic/amide H refined with riding coordinates:
 N12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C22(H22),
 C23(H23), C24(H24), C27(H27), C29(H29), C32(H32), C33(H33), C34(H34), C35(H35),
  C36(H36), C38(H38), C39(H39), C40(H40), C41(H41), C42(H42), C44(H44),
 C45(H45), C46(H46), C47(H47), C48(H48)
7.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C1(H1A,H1B,H1C), C11(H11A,H11B,H11C),
 C1C(H1CA,H1CB,H1CC), C12(H12A,H12B,H12C)
;
_shelx_res_checksum              6855
_shelx_hkl_checksum              77030
_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
;