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_7248429
_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(C38 H32 N4 O4), C4 H8 O2, H2 O'
_chemical_formula_sum            'C80 H74 N8 O11'
_chemical_formula_weight         1323.47
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-07-28
_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                105.4020(10)
_cell_angle_beta                 90.3540(10)
_cell_angle_gamma                107.050(2)
_cell_formula_units_Z            2
_cell_length_a                   11.6496(2)
_cell_length_b                   14.1847(2)
_cell_length_c                   22.6036(3)
_cell_measurement_reflns_used    27838
_cell_measurement_temperature    179.97(14)
_cell_measurement_theta_max      76.6020
_cell_measurement_theta_min      3.3850
_cell_volume                     3428.40(10)
_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_environment      N~2~
_diffrn_ambient_temperature      179.97(14)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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     81.00 106.00   0.50    0.80    --  106.24 -95.00-180.00   50
  2  \w     46.00  84.00   0.50    0.20    --   47.44-126.00-180.00   76
  3  \w     15.00  91.00   0.50    0.20    --   47.44-126.00 -90.00  152
  4  \w     40.00  66.00   0.50    0.80    --  106.24 -95.00-180.00   52
  5  \w     81.00 106.00   0.50    0.80    --  106.24 -95.00-120.00   50
  6  \w     49.00 113.00   0.50    0.80    --  106.24-126.00   0.00  128
  7  \w     70.00 105.00   0.50    0.80    --  106.24-126.00 150.00   70
  8  \w     34.00  95.00   0.50    0.80    --  106.24 -77.00 -30.00  122
  9  \w     48.00  86.00   0.50    0.80    --  106.24 -77.00-180.00   76
 10  \w     36.00  69.00   0.50    0.80    --  106.24 -61.00 -30.00   66
 11  \w     46.00  71.00   0.50    0.80    --  106.24 -61.00   0.00   50
 12  \w     -2.00  23.00   0.50    0.20    --   47.44 -19.00 -60.00   50
 13  \w     46.00  71.00   0.50    0.80    --  106.24 -61.00  60.00   50
 14  \w     56.00  99.00   0.50    0.80    --  106.24 -77.00 150.00   86
 15  \w    -17.00   9.00   0.50    0.20    --   47.44 -24.00 163.00   52
 16  \w     40.00  97.00   0.50    0.80    --  106.24   0.00 120.00  114
 17  \w     93.00 170.00   0.50    0.80    --  106.24  15.00  60.00  154
 18  \w    140.00 166.00   0.50    0.80    --  106.24   0.00 120.00   52
 19  \w     84.00 159.00   0.50    0.80    --  106.24  77.00  60.00  150
 20  \w     99.00 178.00   0.50    0.80    --  106.24  24.00 -32.00  158
 21  \w     36.00 122.00   0.50    0.20    --   47.44  24.00 -32.00  172
 22  \w    -68.00  19.00   0.50    0.20    --  -47.44  77.00 -30.00  174
 23  \w   -100.00 -72.00   0.50    0.80    -- -106.00  77.00-120.00   56
 24  \w    -63.00 -36.00   0.50    0.80    -- -106.00  77.00-120.00   54
 25  \w    -67.00 -33.00   0.50    0.80    -- -106.00  61.00-180.00   68
 26  \w    -71.00 -39.00   0.50    0.80    -- -106.00  61.00 -60.00   64
 27  \w    -22.00  26.00   0.50    0.20    --  -47.44  38.00  90.00   96
 28  \w    -71.00 -36.00   0.50    0.80    -- -106.00  61.00 150.00   70
 29  \w    -31.00   6.00   0.50    0.20    --  -47.44  24.00 -32.00   74
 30  \w    -61.00 -33.00   0.50    0.80    -- -106.00  61.00-120.00   56
 31  \w   -111.00 -36.00   0.50    0.80    -- -106.00 126.00-120.00  150
 32  \w   -108.00 -39.00   0.50    0.80    -- -106.00 109.00-158.37  138
 33  \w    -66.00 -40.00   0.50    0.80    -- -106.00 109.00   8.27   52
 34  \w   -108.00 -75.00   0.50    0.80    -- -106.00 109.00   8.27   66
 35  \w   -105.00 -37.00   0.50    0.80    -- -106.00 126.00  30.00  136
 36  \w   -105.00 -35.00   0.50    0.80    -- -106.00 105.00 116.26  140
 37  \w   -119.00 -35.00   0.50    0.20    --  -47.44 -24.00 163.00  168
 38  \w   -177.00-120.00   0.50    0.80    -- -106.00 -45.00  90.00  114
 39  \w   -177.00 -96.00   0.50    0.80    -- -106.00 -24.00 163.00  162
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0957092000
_diffrn_orient_matrix_UB_12      0.1053785000
_diffrn_orient_matrix_UB_13      0.0094387000
_diffrn_orient_matrix_UB_21      -0.0962789000
_diffrn_orient_matrix_UB_22      0.0536829000
_diffrn_orient_matrix_UB_23      0.0205755000
_diffrn_orient_matrix_UB_31      0.0293802000
_diffrn_orient_matrix_UB_32      0.0037193000
_diffrn_orient_matrix_UB_33      0.0672844000
_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  0.0262
_diffrn_reflns_av_unetI/netI     0.0273
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            42543
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        66.990
_diffrn_reflns_theta_max         66.990
_diffrn_reflns_theta_min         3.394
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.698
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93730
_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    1.282
_exptl_crystal_description       block
_exptl_crystal_F_000             1396
_exptl_crystal_size_max          0.54
_exptl_crystal_size_mid          0.087
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.329
_refine_diff_density_min         -0.248
_refine_diff_density_rms         0.036
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     996
_refine_ls_number_reflns         12203
_refine_ls_number_restraints     91
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0437
_refine_ls_R_factor_gt           0.0392
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0513P)^2^+0.8010P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1030
_refine_ls_wR_factor_ref         0.1058
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10828
_reflns_number_total             12203
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ra02173h2.cif
_cod_data_source_block           ima_35diome_auto
_cod_database_code               7248429
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'O N C H'
_chemical_oxdiff_usercomment     EA
_shelx_estimated_absorpt_t_max   0.946
_shelx_estimated_absorpt_t_min   0.704
_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, All O(H,H) groups
2. Restrained distances
 O93-H93G = O93-H93H
 0.87 with sigma of 0.02
 C94A-C93A
 1.35 with sigma of 0.02
 H93G-H93H
 1.38 with sigma of 0.04
 C97A-C94A
 2.35 with sigma of 0.01
 O95A-C93A
 2.39 with sigma of 0.001
 C26-C35 \\sim C26-C35A
 with sigma of 0.02
 C35-C36 \\sim C35A-C36A
 with sigma of 0.02
 C35-C40 \\sim C35A-C40A
 with sigma of 0.02
 C36-C37 \\sim C36A-C37A
 with sigma of 0.02
 C37-C38 \\sim C37A-C38A
 with sigma of 0.02
 C38-C39 \\sim C38A-C39A
 with sigma of 0.02
 C39-C40 \\sim C39A-C40A
 with sigma of 0.02
 C26-C36 \\sim C26-C36A
 with sigma of 0.04
 C26-C40 \\sim C26-C40A
 with sigma of 0.04
 C35-C37 \\sim C35A-C37A
 with sigma of 0.04
 C35-C39 \\sim C35A-C39A
 with sigma of 0.04
 C36-C38 \\sim C36A-C38A
 with sigma of 0.04
 C36-C40 \\sim C36A-C40A
 with sigma of 0.04
 C37-C39 \\sim C37A-C39A
 with sigma of 0.04
 C38-C40 \\sim C38A-C40A
 with sigma of 0.04
 O95-C94 \\sim O95A-C94A
 with sigma of 0.02
 C94-O96 \\sim C94A-O96A
 with sigma of 0.02
 C94-C93 \\sim C94A-C93A
 with sigma of 0.02
 O96-C97 \\sim O96A-C97A
 with sigma of 0.02
 C97-C98 \\sim C97A-C98A
 with sigma of 0.02
 O95-O96 \\sim O95A-O96A
 with sigma of 0.04
 O95-C93 \\sim O95A-C93A
 with sigma of 0.04
 C94-C97 \\sim C94A-C97A
 with sigma of 0.04
 O96-C93 \\sim O96A-C93A
 with sigma of 0.04
 O96-C98 \\sim O96A-C98A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C93A \\sim C94A \\sim O95A \\sim O96A \\sim C97A \\sim C98A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C93 \\sim C94 \\sim O95 \\sim O96 \\sim C97 \\sim C98: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
4. Others
 Sof(C35A)=Sof(C40A)=Sof(H40A)=Sof(C39A)=Sof(H39A)=Sof(C38A)=Sof(H38A)=
 Sof(C37A)=Sof(H37A)=Sof(C36A)=Sof(H36A)=1-FVAR(1)
 Sof(C35)=Sof(C40)=Sof(H40)=Sof(C39)=Sof(H39)=Sof(C38)=Sof(H38)=Sof(C37)=
 Sof(H37)=Sof(C36)=Sof(H36)=FVAR(1)
 Sof(C93A)=Sof(H93D)=Sof(H93E)=Sof(H93F)=Sof(C94A)=Sof(O95A)=Sof(O96A)=
 Sof(C97A)=Sof(H97C)=Sof(H97D)=Sof(C98A)=Sof(H98D)=Sof(H98E)=Sof(H98F)=1-FVAR(2)
 Sof(C93)=Sof(H93A)=Sof(H93B)=Sof(H93C)=Sof(C94)=Sof(O95)=Sof(O96)=Sof(C97)=
 Sof(H97A)=Sof(H97B)=Sof(C98)=Sof(H98A)=Sof(H98B)=Sof(H98C)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C97(H97A,H97B), C97A(H97C,H97D)
5.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), C28(H28), C40(H40), C39(H39), C38(H38), C37(H37), C36(H36),
  C40A(H40A), C39A(H39A), C38A(H38A), C37A(H37A), C36A(H36A), C42(H42),
 C43(H43), C44(H44), C45(H45), C46(H46), N58(H58), C60(H60), C61(H61), C62(H62),
  C63(H63), C64(H64), C68(H68), C69(H69), C70(H70), C74(H74), C82(H82),
 C83(H83), C84(H84), C85(H85), C86(H86), C88(H88), C89(H89), C90(H90), C91(H91),
  C92(H92)
5.c Fitted hexagon refined as free rotating group:
 C35(C40,C39,C38,C37,C36), C35A(C40A,C39A,C38A,C37A,C36A)
5.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C),
 C93(H93A,H93B,H93C), C93A(H93D,H93E,H93F), C98(H98A,H98B,H98C), C98A(H98D,H98E,
 H98F), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C78(H78A,H78B,H78C), C80(H80A,
 H80B,H80C)
;
_shelx_res_checksum              18463
_shelx_hkl_checksum              80750
_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 1.169
_oxdiff_exptl_absorpt_empirical_full_min 0.856