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_1572487
_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_absolute_configuration ad
_chemical_formula_moiety         'C20 H22 N2'
_chemical_formula_sum            'C20 H22 N2'
_chemical_formula_weight         290.39
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.02211(19)
_cell_length_b                   10.3152(2)
_cell_length_c                   16.3908(3)
_cell_measurement_reflns_used    8931
_cell_measurement_temperature    303.64(10)
_cell_measurement_theta_max      76.1740
_cell_measurement_theta_min      2.6780
_cell_volume                     1694.48(6)
_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      air
_diffrn_ambient_temperature      303.64(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.970
_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  25.00   0.50    0.05    --   46.61 -19.00  30.00  100
  2  \w     33.00  66.00   0.50    0.05    --  104.21 -61.00 -60.00   66
  3  \w     45.00  71.00   0.50    0.05    --  104.21 -61.00   0.00   52
  4  \w     33.00  58.00   0.50    0.05    --  104.21 -61.00  90.00   50
  5  \w     35.00  80.00   0.50    0.05    --  104.21-125.00  47.00   90
  6  \w     84.00 112.00   0.50    0.05    --  104.21-125.00  47.00   56
  7  \w     38.00  70.00   0.50    0.05    --   46.61-125.00  47.00   64
  8  \w   -121.00 -37.00   0.50    0.05    --  -46.61  -9.00 128.00  168
  9  \w   -175.00 -84.00   0.50    0.05    -- -102.00  -9.00 128.00  182
 10  \w   -128.00 -30.00   0.50    0.05    -- -102.00 149.00-160.00  196
 11  \w   -168.00-123.00   0.50    0.05    -- -102.00-125.00  47.00   90
 12  \w     -6.00  25.00   0.50    0.05    --  -46.61  37.00  90.00   62
 13  \w    -18.00  20.00   0.50    0.05    --  -46.61  19.00 -30.00   76
 14  \w    -37.00 -10.00   0.50    0.05    --  -46.61  37.00  90.00   54
 15  \w   -114.00 -87.00   0.50    0.05    -- -102.00 -94.00 -90.00   54
 16  \w    -65.00 -39.00   0.50    0.05    -- -102.00  61.00 -60.00   52
 17  \w   -163.00-130.00   0.50    0.05    -- -102.00 -94.00 -90.00   66
 18  \w   -148.00 -96.00   0.50    0.05    -- -102.00 -77.00  60.00  104
 19  \w     71.00 111.00   0.50    0.05    --  104.21-125.00   0.00   80
 20  \w     78.00 104.00   0.50    0.05    --  104.21 -94.00  60.00   52
 21  \w     32.00  59.00   0.50    0.05    --  104.21 -94.00  60.00   54
 22  \w     34.00  73.00   0.50    0.05    --  104.21 -61.00-120.00   78
;
_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      -0.0077028000
_diffrn_orient_matrix_UB_12      -0.0141009000
_diffrn_orient_matrix_UB_13      0.0933713000
_diffrn_orient_matrix_UB_21      -0.1531474000
_diffrn_orient_matrix_UB_22      -0.0105265000
_diffrn_orient_matrix_UB_23      -0.0053849000
_diffrn_orient_matrix_UB_31      0.0115673000
_diffrn_orient_matrix_UB_32      -0.1483435000
_diffrn_orient_matrix_UB_33      -0.0085157000
_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  0.0281
_diffrn_reflns_av_unetI/netI     0.0252
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            10954
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.733
_diffrn_reflns_theta_min         5.066
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.510
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61276
_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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.138
_exptl_crystal_description       block
_exptl_crystal_F_000             624
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.136
_refine_diff_density_min         -0.142
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 1254 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     203
_refine_ls_number_reflns         3369
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0444
_refine_ls_R_factor_gt           0.0427
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0712P)^2^+0.0875P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1116
_refine_ls_wR_factor_ref         0.1138
_reflns_Friedel_coverage         0.719
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.938
_reflns_number_gt                3169
_reflns_number_total             3369
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05067c2.cif
_cod_data_source_block           caiheng_0803_auto
_cod_depositor_comments
'Adding full bibliography for 1572486--1572491.cif.'
_cod_database_code               1572487
_shelx_shelxl_version_number     2018/3
_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.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C7(H7), C14(H14), C16(H16), C17(H17), C18(H18),
 C19(H19), C20(H20)
2.b Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,H13C)
;
_shelx_res_checksum              64472
_shelx_hkl_checksum              37584
_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 1.450
_oxdiff_exptl_absorpt_empirical_full_min 0.542