Metal carbonyl mediated rearrangement of 5-(2-oxoalkyl)-1,2,4-oxadiazoles: synthesis of fully substituted pyrimidines.
Galenko, Ekaterina E.; Zanakhov, Timur O.; Novikov, Mikhail S.; Khlebnikov, Alexander F.; Organic & biomolecular chemistry 21 (2023) 2990–3001; doi:10.1039/d3ob00148b

data_7159244
_publ_section_title
;
 Metal carbonyl mediated rearrangement of
 5-(2-oxoalkyl)-1,2,4-oxadiazoles: synthesis of fully substituted
 pyrimidines.
;
_journal_issue                   14
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2990
_journal_page_last               3001
_journal_paper_doi               10.1039/d3ob00148b
_journal_volume                  21
_journal_year                    2023
_chemical_formula_moiety         'C31 H26 N4 O2'
_chemical_formula_sum            'C31 H26 N4 O2'
_chemical_formula_weight         486.56
_chemical_name_systematic
'ethyl 2-phenyl-4-(phenyl(pyridin-2-yl)amino)-6-(p-tolyl)pyrimidine-5-carboxylate'
_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     iterative
_audit_creation_date             2022-12-08
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2023-01-17 deposited with the CCDC.	2023-03-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.459(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.0365(3)
_cell_length_b                   7.74810(10)
_cell_length_c                   20.9647(4)
_cell_measurement_reflns_used    8142
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.2220
_cell_measurement_theta_min      2.8820
_cell_volume                     2484.91(8)
_computing_cell_refinement       'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.987
_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    -25.00   0.00   0.50    4.00    --  -47.38  23.00-178.00   50
  2  \w   -121.00 -35.00   0.50    4.00    --  -47.38 -23.00  17.00  172
  3  \w     49.00 118.00   0.50    4.00    --   47.38  23.00-178.00  138
  4  \w     -3.00  23.00   0.50    4.00    --   47.38 -23.00  17.00   52
  5  \w   -158.00 -93.00   0.50   22.00    -- -105.93 -23.00  17.00  130
  6  \w     93.00 142.00   0.50   22.00    --  105.93  23.00-178.00   98
  7  \w    -19.00  26.00   0.50    4.00    --  -47.38  19.00 -30.00   90
  8  \w    -22.00  41.00   0.50    4.00    --   47.38 -37.00-120.00  126
  9  \w   -176.00-119.00   0.50   22.00    -- -105.93 -15.00  90.00  114
 10  \w    -71.00 -46.00   0.50   22.00    -- -105.93  61.00-180.00   50
 11  \w   -110.00 -62.00   0.50   22.00    -- -105.93 125.00-120.00   96
 12  \w   -173.00-119.00   0.50   22.00    -- -105.93 -30.00 -30.00  108
 13  \w     40.00  70.00   0.50   22.00    --  105.93 -61.00-120.00   60
 14  \w     34.00  70.00   0.50   22.00    --  105.93 -61.00 -60.00   72
 15  \w     35.00  66.00   0.50   22.00    --  105.93 -61.00  60.00   62
 16  \w     40.00  81.00   0.50   22.00    --  105.93 -77.00-150.00   82
 17  \w     41.00  66.00   0.50   22.00    --  105.93 -61.00  90.00   50
 18  \w     57.00 104.00   0.50   22.00    --  105.93-125.00   0.00   94
 19  \w     33.00  63.00   0.50   22.00    --  105.93 -61.00 -30.00   60
 20  \w     36.00 101.00   0.50   22.00    --  105.93 -77.00  30.00  130
 21  \w     35.00  60.00   0.50   22.00    --  105.93 -61.00-180.00   50
 22  \w     33.00  69.00   0.50   22.00    --  105.93 -61.00 -90.00   72
 23  \w     41.00  71.00   0.50   22.00    --  105.93 -61.00-150.00   60
;
_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      0.0981269000
_diffrn_orient_matrix_UB_12      -0.0101084000
_diffrn_orient_matrix_UB_13      0.0386828000
_diffrn_orient_matrix_UB_21      -0.0196111000
_diffrn_orient_matrix_UB_22      0.0608512000
_diffrn_orient_matrix_UB_23      0.0640074000
_diffrn_orient_matrix_UB_31      -0.0113979000
_diffrn_orient_matrix_UB_32      -0.1889281000
_diffrn_orient_matrix_UB_33      0.0185752000
_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  0.0417
_diffrn_reflns_av_unetI/netI     0.0393
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            16192
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.485
_diffrn_reflns_theta_min         2.889
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.661
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51948
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.115a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.301
_exptl_crystal_description       block
_exptl_crystal_F_000             1024
_exptl_crystal_preparation       'slow evaporation of MeOH solution'
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.449
_refine_diff_density_min         -0.358
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     324
_refine_ls_number_reflns         4865
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0568
_refine_ls_R_factor_gt           0.0485
_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^)+(0.0476P)^2^+1.8270P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1155
_refine_ls_wR_factor_ref         0.1200
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4290
_reflns_number_total             4865
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob00148b2.cif
_cod_data_source_block           22-172
_cod_depositor_comments
'Adding full bibliography for 7159243--7159244.cif.'
_cod_database_code               7159244
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C31H26 N4 O2'
_shelx_estimated_absorpt_t_max   0.987
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C21) = Uanis(C25)
Uanis(C24) = Uanis(C22)
3.a Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B)
3.b Aromatic/amide H refined with riding coordinates:
 C21(H21), C15(H15), C25(H25), C19(H19), C16(H16), C11(H11), C22(H22),
 C17(H17), C27(H27), C23(H23), C18(H18), C24(H24), C10(H10), C6(H6), C28(H28),
 C7(H7), C29(H29), C30(H30)
3.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C13(H13A,H13B,H13C)
;
_shelx_res_checksum              93497
_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 1.593
_oxdiff_exptl_absorpt_empirical_full_min 0.361