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_1572491
_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         'C27 H22 N2'
_chemical_formula_sum            'C27 H22 N2'
_chemical_formula_weight         374.46
_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             2023-11-29
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-03-18 deposited with the CCDC.	2024-09-03 downloaded from the CCDC.
;
_cell_angle_alpha                109.707(2)
_cell_angle_beta                 101.745(2)
_cell_angle_gamma                98.816(2)
_cell_formula_units_Z            2
_cell_length_a                   9.0020(2)
_cell_length_b                   10.8545(2)
_cell_length_c                   12.0854(2)
_cell_measurement_reflns_used    7863
_cell_measurement_temperature    301.84(10)
_cell_measurement_theta_max      75.4870
_cell_measurement_theta_min      4.0330
_cell_volume                     1056.44(4)
_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 (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      air
_diffrn_ambient_temperature      301.84(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.946
_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 -53.00   0.50    0.05    --  -46.54 125.00  90.00   56
  2  \w    -60.00 -29.00   0.50    0.05    -- -102.00  61.00 -90.00   62
  3  \w    -21.00   6.00   0.50    0.05    --  -46.54  21.00 -44.00   54
  4  \w    -27.00  17.00   0.50    0.05    --   46.54 -21.00 149.00   88
  5  \w    -18.00   9.00   0.50    0.05    --   46.54 -77.00  60.00   54
  6  \w     17.00  61.00   0.50    0.05    --   46.54 -77.00  60.00   88
  7  \w    -21.00  27.00   0.50    0.05    --   46.54 -19.00   0.00   96
  8  \w    -25.00  42.00   0.50    0.05    --   46.54 -37.00 -90.00  134
  9  \w     38.00 105.00   0.50    0.05    --  104.27 -94.00-180.00  134
 10  \w     44.00  78.00   0.50    0.05    --  104.27 -94.00-150.00   68
 11  \w     34.00  77.00   0.50    0.05    --  104.27 -94.00  30.00   86
 12  \w     38.00 108.00   0.50    0.05    --  104.27-106.00 120.68  140
 13  \w     71.00  97.00   0.50    0.05    --  104.27 -94.00 120.00   52
 14  \w     44.00  69.00   0.50    0.05    --  104.27 -94.00 120.00   50
 15  \w     32.00  73.00   0.50    0.05    --  104.27 -61.00 -60.00   82
 16  \w     33.00  95.00   0.50    0.05    --  104.27 -77.00 -90.00  124
 17  \w     40.00  70.00   0.50    0.05    --  104.27 -61.00   0.00   60
 18  \w     42.00  92.00   0.50    0.05    --   46.54  21.00 -44.00  100
 19  \w     92.00 176.00   0.50    0.05    --  104.27  45.00  30.00  168
 20  \w     93.00 167.00   0.50    0.05    --  104.27  21.00 -44.00  148
 21  \w    108.00 143.00   0.50    0.05    --  104.27  30.00   0.00   70
 22  \w    130.00 172.00   0.50    0.05    --  104.27  30.00  60.00   84
 23  \w    146.00 172.00   0.50    0.05    --  104.27  30.00   0.00   52
 24  \w   -130.00 -57.00   0.50    0.05    -- -102.00 151.00  -1.05  146
 25  \w   -112.00 -52.00   0.50    0.05    -- -102.00 125.00-150.00  120
 26  \w   -106.00 -80.00   0.50    0.05    -- -102.00 125.00 -30.00   52
 27  \w   -109.00 -58.00   0.50    0.05    -- -102.00 125.00 -90.00  102
 28  \w    -62.00 -33.00   0.50    0.05    -- -102.00 125.00 -30.00   58
 29  \w    -57.00 -32.00   0.50    0.05    -- -102.00 125.00  30.00   50
 30  \w    -73.00 -44.00   0.50    0.05    -- -102.00 125.00 120.00   58
 31  \w   -111.00 -85.00   0.50    0.05    -- -102.00 125.00 120.00   52
 32  \w    -70.00 -34.00   0.50    0.05    --  -46.54 -21.00 149.00   72
 33  \w   -121.00 -76.00   0.50    0.05    --  -46.54 -21.00 149.00   90
 34  \w   -170.00 -89.00   0.50    0.05    -- -102.00 -21.00 149.00  162
 35  \w   -171.00 -90.00   0.50    0.05    -- -102.00 -45.00 120.00  162
 36  \w   -135.00 -93.00   0.50    0.05    -- -102.00 -45.00-150.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0952153000
_diffrn_orient_matrix_UB_12      0.1115868000
_diffrn_orient_matrix_UB_13      -0.0271349000
_diffrn_orient_matrix_UB_21      0.1183346000
_diffrn_orient_matrix_UB_22      -0.0861762000
_diffrn_orient_matrix_UB_23      -0.0297167000
_diffrn_orient_matrix_UB_31      -0.0967681000
_diffrn_orient_matrix_UB_32      -0.0651806000
_diffrn_orient_matrix_UB_33      -0.1349328000
_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  0.0256
_diffrn_reflns_av_unetI/netI     0.0271
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.946
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            11830
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.035
_diffrn_reflns_theta_min         4.041
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.528
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55941
_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 light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.177
_exptl_crystal_description       block
_exptl_crystal_F_000             396
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.113
_refine_diff_density_min         -0.137
_refine_diff_density_rms         0.029
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     308
_refine_ls_number_reflns         4181
_refine_ls_number_restraints     60
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0543
_refine_ls_R_factor_gt           0.0461
_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^)+(0.0739P)^2^+0.0504P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1288
_refine_ls_wR_factor_ref         0.1368
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3366
_reflns_number_total             4181
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05067c2.cif
_cod_data_source_block           caiheng1626-tyq_1128_auto
_cod_depositor_comments
'Adding full bibliography for 1572486--1572491.cif.'
_cod_original_cell_volume        1056.43(4)
_cod_database_code               1572491
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.939
_shelx_estimated_absorpt_t_min   0.916
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C26) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C29)
\\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C25) \\sim Ueq,
Uanis(C31) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C7) \\sim Ueq: with sigma of
0.004 and sigma for terminal atoms of 0.002
3. Others
 Fixed Sof: C3(0.4) H3(0.4) C7(0.7) H7(0.7) C13(0.4) H13(0.4) C25(0.4)
 H25(0.4) C26(0.4) H26(0.4) C29(0.6) H29(0.6) C30(0.6) H30(0.6) C31(0.6)
 H31(0.6) C28(0.6) H28(0.6) C32(0.3) H32(0.3)
4.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C7(H7), C8(H8), C11(H11), C13(H13), C14(H14), C15(H15),
 C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C23(H23), C24(H24),
  C25(H25), C26(H26), C27(H27), C29(H29), C30(H30), C31(H31), C28(H28), C32(H32)
4.b Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C)
;
_shelx_res_checksum              42907
_shelx_hkl_checksum              78347
_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 2.183
_oxdiff_exptl_absorpt_empirical_full_min 0.649