# Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is © The Royal Society of Chemistry 2011 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_cambridge 0177 _publ_contact_author_name 'Laszlo Parkanyi' _publ_contact_author_address ; Institute of Structural Chemistry, Chemical Research Center, Hungarian Academy of Sciences, Pusztaszeri \'ut 59, H-1025 Budapest, Hungary ; _publ_contact_author_email parka@chemres.hu _publ_contact_author_fax (36-1)438-4141/201 _publ_contact_author_phone (36-1)438-1161 _publ_contact_letter ; March 8, 2011 Please consider this CIF submission (data_ma11607, Compound 48 in the paper) for publication in Organic Biomolecular Chemistry. ; #=============================================================================== # 2. TITLE AND AUTHOR LIST _publ_section_title ; Suzuki-Miyaura Cross-coupling Reactions on Halo Derivatives on 4H-Pyrido[1,2-a]pyrimidin-4-ones ; loop_ _publ_author_name _publ_author_address 'Annamaria Molnar' ; Chemical Development, R&D, Chinoin Ltd, T\'o utca 1-5, H-1045 Budapest, Hungary, Department of Organic Chemistry & Technology, Budapest University of Technology and Economics, Budafoki \'ut 8, H-1111 Budapest, Hungary. ; 'Anita Kapros' ; Department of Organic Chemistry & Technology, Budapest University of Technology and Economics, Budafoki \'ut 8, H-1111 Budapest, Hungary. ; 'Laszlo Parkanyi' ; Institute of Structural Chemistry, Chemical Research Center, Hungarian Academy of Sciences, Pusztaszeri \'ut 59, H-1025 Budapest, Hungary ; 'Zoltan Mucsi' ; Department of Organic Chemistry & Technology, Budapest University of Technology and Economics, Budafoki \'ut 8, H-1111 Budapest, Hungary. ; 'Gabor Vlad' ; Chemical Development, R&D, Chinoin Ltd, T\'o utca 1-5, H-1045 Budapest, Hungary ; 'Istvan Hermecz' ; External Pharmaceutical Department, Budapest University of Technology and Economics, R&D, Chinoin Ltd, T\'o utca 1-5, H-1045 Budapest ; #=============================================================================== data_ma11607 _database_code_depnum_ccdc_archive 'CCDC 816421' #TrackingRef '- OBC_Molnar_Suzuki.cif' #=============================================================================== # CHEMICAL DATA _chemical_name_systematic ; 6-phenyl-4H-pyrido[1,2-a]pyrimidin-4-one ; _chemical_name_common 6-phenyl-4H-pyrido(1,2-a)pyrimidin-4-one _chemical_melting_point ? _chemical_formula_moiety 'C14 H10 N2 O' _chemical_formula_structural ? _chemical_formula_sum 'C14 H10 N2 O' _chemical_formula_iupac ? _chemical_formula_weight 222.24 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' #=============================================================================== # CRYSTAL DATA _symmetry_cell_setting Monoclinic _symmetry_space_group_name_Hall '-C 2yc' _symmetry_space_group_name_H-M 'C 2/c' _symmetry_Int_Tables_number 15 loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 x,y,z 2 -x,y,1/2-z 3 -x,-y,-z 4 x,-y,1/2+z 5 1/2+x,1/2+y,z 6 1/2-x,1/2+y,1/2-z 7 1/2-x,1/2-y,-z 8 1/2+x,1/2-y,1/2+z _cell_length_a 19.4658(4) _cell_length_b 7.8017(1) _cell_length_c 15.1530(3) _cell_angle_alpha 90 _cell_angle_beta 110.941(1) _cell_angle_gamma 90 _cell_volume 2149.23(7) _cell_formula_units_Z 8 _cell_measurement_temperature 293 _cell_measurement_reflns_used 7389 _cell_measurement_theta_min 6.51 _cell_measurement_theta_max 71.64 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.44 _exptl_crystal_size_mid 0.41 _exptl_crystal_size_min 0.39 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.374 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 928 _exptl_absorpt_coefficient_mu 0.713 _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_T_max 0.916 _exptl_absorpt_correction_T_min 0.817 _exptl_absorpt_process_details ; T.Higashi, Numerical Absorption Correction, NUMABS, 2002 ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 1.54187 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type RAXIS-RAPID _diffrn_measurement_method dtprofit.ref _diffrn_detector_area_resol_mean 10.0000 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 8822 _diffrn_reflns_av_R_equivalents 0.0262 _diffrn_reflns_av_sigmaI/netI 0.0182 _diffrn_reflns_limit_h_min -23 _diffrn_reflns_limit_h_max 23 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 7.31 _diffrn_reflns_theta_max 71.78 _diffrn_special_details ; NUMSTD=0,FUDGE=0.01,TEMP=22.0,DIRECT=0.0,SCANUM=1,XDIST=127.4,MITH=N ABSCOR=Y,DECAY=N,REDUN=Y,DECPAR=0.0,AVERAGE=N,ABSTYPE=NUM2,MODIFY=N ABSAV=0.8803,ABSMIN=0.8173,ABSMAX=0.9156,ABSLS=1.0, FACES=0,GRIDA=6,GRIDB=6,GRIDC=6,TYPE=0 Frame N=1,PHI=0.0,CHI=0.0,OMEGA=14.0,244.0,5.0,COUPLE=0.00 Frame N=2,PHI=90.0,CHI=45.0,OMEGA=10.0,185.0,5.0,COUPLE=0.00 Frame N=3,PHI=0.0,CHI=45.0,OMEGA=92.0,257.0,5.0,COUPLE=0.00 Frame N=4,PHI=180.0,CHI=45.0,OMEGA=36.0,141.0,5.0,COUPLE=0.00 U-matrix U11=-0.032558,U12=-0.025081,U13=-0.066548,U21=-0.041738, 024586,U23=0.021913,U31=-0.014949,U32=0.123271,U33=-0.009170 ; _reflns_number_total 1948 _reflns_number_gt 1575 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrystalClear (Rigaku/MSC Inc., 2006)' _computing_cell_refinement 'CrystalClear (Rigaku/MSC Inc., 2006)' _computing_data_reduction 'CrystalClear (Rigaku/MSC Inc., 2006)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Spek, A.L. (2003). J.Appl.Cryst. 36,7-13.' _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0398P)^2^+0.9412P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment noref _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.00138(15) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 1948 _refine_ls_number_parameters 155 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0438 _refine_ls_R_factor_gt 0.0342 _refine_ls_wR_factor_ref 0.0968 _refine_ls_wR_factor_gt 0.0874 _refine_ls_goodness_of_fit_ref 1.097 _refine_ls_restrained_S_all 1.097 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group O1 O 0.18513(5) 0.67308(15) 0.06846(7) 0.0534(3) Uani 1 1 d . . . N1 N 0.00367(7) 0.88609(19) -0.12432(8) 0.0548(4) Uani 1 1 d . . . C2 C 0.07127(9) 0.9165(2) -0.12664(11) 0.0570(4) Uani 1 1 d . . . H2 H 0.0745 0.9823 -0.1762 0.068 Uiso 1 1 calc R . . C3 C 0.13454(8) 0.8579(2) -0.06205(10) 0.0494(4) Uani 1 1 d . . . H3 H 0.1791 0.8846 -0.0685 0.059 Uiso 1 1 calc R . . C4 C 0.13427(7) 0.7567(2) 0.01512(10) 0.0421(4) Uani 1 1 d . . . N5 N 0.06314(6) 0.75438(15) 0.02680(8) 0.0384(3) Uani 1 1 d . . . C6 C 0.05604(7) 0.68400(19) 0.10850(9) 0.0414(3) Uani 1 1 d . . . C7 C -0.01198(8) 0.6423(2) 0.10682(11) 0.0508(4) Uani 1 1 d . . . H7 H -0.0168 0.5895 0.1593 0.061 Uiso 1 1 calc R . . C8 C -0.07555(8) 0.6771(2) 0.02750(11) 0.0537(4) Uani 1 1 d . . . H8 H -0.1215 0.6415 0.0262 0.064 Uiso 1 1 calc R . . C9 C -0.06915(8) 0.7619(2) -0.04603(11) 0.0500(4) Uani 1 1 d . . . H9 H -0.1114 0.7928 -0.0961 0.060 Uiso 1 1 calc R . . C9A C 0.00074(7) 0.8055(2) -0.04916(10) 0.0431(4) Uani 1 1 d . . . C10 C 0.12049(7) 0.6736(2) 0.19814(9) 0.0415(4) Uani 1 1 d . . . C11 C 0.16430(8) 0.8163(2) 0.23346(11) 0.0496(4) Uani 1 1 d . . . H11 H 0.1560 0.9166 0.1980 0.060 Uiso 1 1 calc R . . C12 C 0.22020(8) 0.8105(2) 0.32102(11) 0.0565(4) Uani 1 1 d . . . H12 H 0.2491 0.9068 0.3445 0.068 Uiso 1 1 calc R . . C13 C 0.23291(8) 0.6619(3) 0.37338(11) 0.0569(5) Uani 1 1 d . . . H13 H 0.2707 0.6577 0.4321 0.068 Uiso 1 1 calc R . . C14 C 0.19004(8) 0.5199(2) 0.33923(11) 0.0555(4) Uani 1 1 d . . . H14 H 0.1991 0.4195 0.3746 0.067 Uiso 1 1 calc R . . C15 C 0.13321(8) 0.5257(2) 0.25219(10) 0.0488(4) Uani 1 1 d . . . H15 H 0.1036 0.4300 0.2300 0.059 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 O1 0.0386(5) 0.0652(8) 0.0577(6) 0.0077(5) 0.0189(5) 0.0101(5) N1 0.0499(7) 0.0693(10) 0.0432(7) 0.0059(7) 0.0140(6) 0.0058(7) C2 0.0594(10) 0.0678(12) 0.0479(8) 0.0084(8) 0.0241(7) 0.0024(8) C3 0.0473(8) 0.0569(11) 0.0496(8) 0.0002(7) 0.0243(7) -0.0010(7) C4 0.0366(7) 0.0459(10) 0.0451(7) -0.0073(6) 0.0162(6) -0.0011(6) N5 0.0334(6) 0.0429(7) 0.0390(6) -0.0012(5) 0.0130(5) 0.0012(5) C6 0.0383(7) 0.0440(9) 0.0428(7) -0.0014(6) 0.0156(6) 0.0012(6) C7 0.0453(8) 0.0591(11) 0.0508(8) 0.0025(7) 0.0207(7) -0.0032(7) C8 0.0347(7) 0.0654(12) 0.0612(9) -0.0047(8) 0.0175(7) -0.0033(7) C9 0.0362(7) 0.0603(11) 0.0490(8) -0.0046(7) 0.0095(6) 0.0037(7) C9A 0.0381(7) 0.0476(10) 0.0412(7) -0.0041(6) 0.0111(6) 0.0032(6) C10 0.0377(7) 0.0479(10) 0.0412(7) 0.0005(6) 0.0171(6) 0.0029(6) C11 0.0472(8) 0.0492(10) 0.0515(8) 0.0004(7) 0.0165(7) -0.0026(7) C12 0.0453(8) 0.0675(12) 0.0551(9) -0.0124(8) 0.0161(7) -0.0096(8) C13 0.0399(8) 0.0851(14) 0.0439(8) 0.0013(8) 0.0127(6) 0.0019(8) C14 0.0497(8) 0.0671(12) 0.0513(8) 0.0134(8) 0.0198(7) 0.0079(8) C15 0.0461(8) 0.0528(10) 0.0493(8) 0.0019(7) 0.0191(7) -0.0017(7) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag O1 C4 1.2193(16) . ? N1 C9A 1.3200(19) . ? N1 C2 1.3498(19) . ? C2 C3 1.350(2) . ? C2 H2 0.9300 . ? C3 C4 1.412(2) . ? C3 H3 0.9300 . ? C4 N5 1.4573(16) . ? N5 C9A 1.3999(17) . ? N5 C6 1.4056(17) . ? C6 C7 1.3548(19) . ? C6 C10 1.4857(19) . ? C7 C8 1.409(2) . ? C7 H7 0.9300 . ? C8 C9 1.339(2) . ? C8 H8 0.9300 . ? C9 C9A 1.420(2) . ? C9 H9 0.9300 . ? C10 C15 1.386(2) . ? C10 C11 1.388(2) . ? C11 C12 1.384(2) . ? C11 H11 0.9300 . ? C12 C13 1.376(2) . ? C12 H12 0.9300 . ? C13 C14 1.372(2) . ? C13 H13 0.9300 . ? C14 C15 1.387(2) . ? C14 H14 0.9300 . ? C15 H15 0.9300 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C9A N1 C2 116.69(12) . . ? N1 C2 C3 124.55(15) . . ? N1 C2 H2 117.7 . . ? C3 C2 H2 117.7 . . ? C2 C3 C4 121.14(13) . . ? C2 C3 H3 119.4 . . ? C4 C3 H3 119.4 . . ? O1 C4 C3 127.26(13) . . ? O1 C4 N5 119.63(13) . . ? C3 C4 N5 113.10(12) . . ? C9A N5 C6 120.38(11) . . ? C9A N5 C4 118.65(11) . . ? C6 N5 C4 120.57(11) . . ? C7 C6 N5 118.71(12) . . ? C7 C6 C10 120.29(13) . . ? N5 C6 C10 120.65(11) . . ? C6 C7 C8 121.62(14) . . ? C6 C7 H7 119.2 . . ? C8 C7 H7 119.2 . . ? C9 C8 C7 119.35(13) . . ? C9 C8 H8 120.3 . . ? C7 C8 H8 120.3 . . ? C8 C9 C9A 121.43(14) . . ? C8 C9 H9 119.3 . . ? C9A C9 H9 119.3 . . ? N1 C9A N5 123.56(12) . . ? N1 C9A C9 118.71(13) . . ? N5 C9A C9 117.69(13) . . ? C15 C10 C11 119.00(13) . . ? C15 C10 C6 119.99(13) . . ? C11 C10 C6 120.70(14) . . ? C12 C11 C10 120.50(16) . . ? C12 C11 H11 119.8 . . ? C10 C11 H11 119.8 . . ? C13 C12 C11 119.89(16) . . ? C13 C12 H12 120.1 . . ? C11 C12 H12 120.1 . . ? C14 C13 C12 120.18(14) . . ? C14 C13 H13 119.9 . . ? C12 C13 H13 119.9 . . ? C13 C14 C15 120.24(16) . . ? C13 C14 H14 119.9 . . ? C15 C14 H14 119.9 . . ? C10 C15 C14 120.17(16) . . ? C10 C15 H15 119.9 . . ? C14 C15 H15 119.9 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C9A N1 C2 C3 5.9(2) . . . . no C2 N1 C9A N5 1.1(2) . . . . no C2 N1 C9A C9 -176.41(14) . . . . no C6 N5 C4 O1 12.0(2) . . . . no C6 N5 C4 C3 -169.47(13) . . . . no C9A N5 C4 O1 -160.85(14) . . . . no C9A N5 C4 C3 17.69(19) . . . . no C4 N5 C6 C7 -162.68(14) . . . . no C4 N5 C6 C10 24.1(2) . . . . no C9A N5 C6 C7 10.0(2) . . . . no C9A N5 C6 C10 -163.17(13) . . . . no C4 N5 C9A N1 -13.3(2) . . . . no C4 N5 C9A C9 164.21(13) . . . . no C6 N5 C9A N1 173.82(14) . . . . no C6 N5 C9A C9 -8.6(2) . . . . no N1 C2 C3 C4 0.1(2) . . . . no C2 C3 C4 O1 166.68(16) . . . . no C2 C3 C4 N5 -11.7(2) . . . . no N5 C6 C7 C8 -3.8(2) . . . . no C10 C6 C7 C8 169.44(14) . . . . no N5 C6 C10 C11 50.1(2) . . . . no N5 C6 C10 C15 -136.26(15) . . . . no C7 C6 C10 C11 -122.97(17) . . . . no C7 C6 C10 C15 50.6(2) . . . . no C6 C7 C8 C9 -3.8(2) . . . . no C7 C8 C9 C9A 5.1(2) . . . . no C8 C9 C9A N1 178.65(15) . . . . no C8 C9 C9A N5 1.0(2) . . . . no C6 C10 C11 C12 174.16(14) . . . . no C15 C10 C11 C12 0.5(2) . . . . no C6 C10 C15 C14 -175.20(14) . . . . no C11 C10 C15 C14 -1.5(2) . . . . no C10 C11 C12 C13 0.4(2) . . . . no C11 C12 C13 C14 -0.4(3) . . . . no C12 C13 C14 C15 -0.6(3) . . . . no C13 C14 C15 C10 1.6(2) . . . . no loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A _geom_hbond_publ_flag # Non-classical H-bond #D H A D - H H...A D...A D - H...A symm(A) # C12 H12 O1 0.9300 2.5500 3.4636(19) 169.00 6_555 yes # ----------------- Least-squares planes ----------------------------- # - 2.5637 (0.0073) x + 6.9093 (0.0014) y + 7.0159 (0.0050) z = 5.1840 (0.0012) #* 0.0566 (0.0013) N1 #* 0.0768 (0.0014) C2 #* -0.0370 (0.0013) C3 #* -0.1941 (0.0012) C4 #* 0.0544 (0.0011) N5 #* 0.1596 (0.0012) C6 #* 0.0342 (0.0013) C7 #* -0.1193 (0.0013) C8 #* -0.0657 (0.0013) C9 #* 0.0345 (0.0014) C9A # -0.5279 (0.0017) O1 # #Rms deviation of fitted atoms = 0.0987 # #- 16.4922 (0.0076) x + 2.3903 (0.0058) y + 10.7298 (0.0064) z = 1.7484 (0.0054) # #Angle to previous plane (with approximate esd) = 54.82 ( 0.05 ) # #* 0.0007 (0.0008) C10 #* -0.0017 (0.0010) C11 #* 0.0019 (0.0010) C12 #* -0.0012 (0.0012) C13 #* 0.0001 (0.0004) C14 #* 0.0001 (0.0004) C14 # #Rms deviation of fitted atoms = 0.0012 # _diffrn_measured_fraction_theta_max 0.929 _diffrn_reflns_theta_full 71.78 _diffrn_measured_fraction_theta_full 0.928 _refine_diff_density_max 0.158 _refine_diff_density_min -0.141 _refine_diff_density_rms 0.030