CCC pincer Ru complex-catalyzed C-H vinylation/6π-E-cyclization of aldimines for constructing 4<i>H</i>-pyrido[1,2-<i>a</i>]pyrimidines.
Cai, Heng; Tu, Yong-Qiang; Niu, Qiang; Xie, Wen-Ping; Wang, Bin; Lu, Ka; Li, Zi-Hao; Zhang, Fu-Min; Zhang, Xiao-Ming; Chemical science 15 (2024) 16216–16221; doi:10.1039/d4sc05067c

data_1572486
_publ_section_title
;
 CCC pincer Ru complex-catalyzed C-H vinylation/6&#x3c0;-E-cyclization of
 aldimines for constructing 4<i>H</i>-pyrido[1,2-<i>a</i>]pyrimidines.
;
_journal_issue                   39
_journal_name_full               'Chemical science'
_journal_page_first              16216
_journal_page_last               16221
_journal_paper_doi               10.1039/d4sc05067c
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C20 H22 N2'
_chemical_formula_sum            'C20 H22 N2'
_chemical_formula_weight         290.39
_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             2023-08-03
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2024-03-18 deposited with the CCDC.	2024-09-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.3230(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.1803(2)
_cell_length_b                   12.0750(2)
_cell_length_c                   28.1968(4)
_cell_measurement_reflns_used    8230
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      76.4180
_cell_measurement_theta_min      3.1580
_cell_volume                     3106.66(10)
_computing_cell_refinement       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.931
_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 -63.00   1.00    0.50    --  -44.30 146.00 135.00   26
  2  \w   -126.00 -76.00   1.00    1.50    -- -100.00 146.00 135.00   50
  3  \w    -60.00 -35.00   1.00    1.50    -- -100.00 146.00 135.00   25
  4  \w   -112.00 -29.00   1.00    1.50    -- -100.00 125.00 120.00   83
  5  \w    -76.00 -29.00   1.00    1.50    -- -100.00 125.00   0.00   47
  6  \w   -103.00 -77.00   1.00    1.50    -- -100.00 124.00 -30.00   26
  7  \w    -90.00 -36.00   1.00    0.50    --  -44.30 124.00 -30.00   54
  8  \w    -51.00 -25.00   1.00    1.50    -- -100.00  45.00-180.00   26
  9  \w    -71.00 -30.00   1.00    1.50    -- -100.00  61.00-150.00   41
 10  \w    -52.00 -26.00   1.00    1.50    -- -100.00  45.00-150.00   26
 11  \w     68.00  94.00   1.00    1.50    --  109.64-124.00-108.00   26
 12  \w    -53.00 -26.00   1.00    1.50    -- -100.00  45.00 150.00   27
 13  \w    -53.00 -25.00   1.00    1.50    -- -100.00  45.00 120.00   28
 14  \w   -154.00 -97.00   1.00    1.50    -- -100.00-124.00-108.00   57
 15  \w   -121.00 -82.00   1.00    1.50    -- -100.00-125.00-150.00   39
 16  \w   -170.00-130.00   1.00    1.50    -- -100.00-125.00-150.00   40
 17  \w   -105.00 -78.00   1.00    0.50    --  -44.30-146.00  85.00   27
 18  \w    -19.00  20.00   1.00    0.50    --   44.30 -19.00 -30.00   39
 19  \w    -33.00  23.00   1.00    0.50    --   44.30 -19.00-120.00   56
 20  \w     -9.00  24.00   1.00    0.50    --   44.30 -19.00-180.00   33
 21  \w    -34.00  23.00   1.00    0.50    --   44.30 -19.00 120.00   57
 22  \w     42.00  67.00   1.00    1.50    --  109.64 -61.00 -90.00   25
 23  \w     67.00 101.00   1.00    1.50    --  109.64 -77.00-120.00   34
 24  \w     41.00  68.00   1.00    1.50    --  109.64 -61.00-120.00   27
 25  \w     38.00  67.00   1.00    1.50    --  109.64 -61.00 -60.00   29
 26  \w    112.00 137.00   1.00    1.50    --  109.64  30.00  60.00   25
 27  \w    150.00 175.00   1.00    1.50    --  109.64  30.00  60.00   25
 28  \w    110.00 148.00   1.00    1.50    --  109.64  30.00 -60.00   38
 29  \w     78.00 138.00   1.00    1.50    --  109.64 124.00 -30.00   60
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0238818000
_diffrn_orient_matrix_UB_12      -0.0449158000
_diffrn_orient_matrix_UB_13      -0.0497262000
_diffrn_orient_matrix_UB_21      -0.0051224000
_diffrn_orient_matrix_UB_22      0.1190531000
_diffrn_orient_matrix_UB_23      -0.0198098000
_diffrn_orient_matrix_UB_31      0.1669276000
_diffrn_orient_matrix_UB_32      0.0100730000
_diffrn_orient_matrix_UB_33      0.0126056000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0191
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.931
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            6789
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.931
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.613
_diffrn_reflns_theta_min         3.154
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.556
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58481
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.242
_exptl_crystal_description       block
_exptl_crystal_F_000             1248
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.343
_refine_diff_density_min         -0.277
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     400
_refine_ls_number_reflns         6789
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0696
_refine_ls_R_factor_gt           0.0647
_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^)+(0.0997P)^2^+2.2943P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1855
_refine_ls_wR_factor_ref         0.1892
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6160
_reflns_number_total             6789
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.9528\% 
around [0.95 -0.00 -0.32] (reciprocal) or [1.00 -0.00 -0.00] (direct)
;
_cod_data_source_file            d4sc05067c2.cif
_cod_data_source_block           caihen_0803_twin1_hklf4
_cod_depositor_comments
'Adding full bibliography for 1572486--1572491.cif.'
_cod_database_code               1572486
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.652(2)
 0.348(2)
2. 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
3.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,
 H14B), C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B),
 C34(H34A,H34B)
3.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C8(H8), C16(H16), C17(H17), C18(H18), C19(H19),
 C20(H20), C22(H22), C23(H23), C24(H24), C28(H28), C36(H36), C37(H37), C38(H38),
  C39(H39), C40(H40)
3.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C26(H26A,H26B,H26C)
;
_shelx_res_checksum              87652
_shelx_hkl_checksum              93203
_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 1.849
_oxdiff_exptl_absorpt_empirical_full_min 0.582
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2