Supplementary Material (ESI) for Green Chemistry This journal is (C) The Royal Society of Chemistry 2001 data_d:_3g _database_code_CSD 167675 _journal_coden_Cambridge 1048 _publ_requested_journal 'Green Chemistry' loop_ _publ_author_name 'Correa, Waldo H.' 'Scott, Janet' _publ_contact_author_name 'Dr Janet Scott' _publ_contact_author_address ; Centre for Green Chemistry, School of Chemistry Monash University Clayton Melbourne Victoria 3800 AUSTRALIA ; _publ_contact_author_email 'JANET.SCOTT@SCI.MONASH.EDU.AU' _publ_section_title ; Efficient, solvent-free synthesis of 4-aryl-1,4-dihydropyridines ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C15 H17 N O5' _chemical_formula_weight 291.30 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0033 0.0016 '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' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M Pna2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z+1/2' '-x+1/2, y+1/2, z+1/2' 'x+1/2, -y+1/2, z' _cell_length_a 9.1435(2) _cell_length_b 27.8109(3) _cell_length_c 5.8488(10) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1487.3(3) _cell_formula_units_Z 4 _cell_measurement_temperature 123(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description plate _exptl_crystal_colour 'pale yellow' _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.25 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.301 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 616 _exptl_absorpt_coefficient_mu 0.098 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min 0.9711 _exptl_absorpt_correction_T_max 0.9759 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 123(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Enraf-nonius Kappa CCD diffractometer' _diffrn_measurement_method '1 degree, phi and omega scans' _diffrn_reflns_number 1978 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.0674 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 37 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 7 _diffrn_reflns_theta_min 2.34 _diffrn_reflns_theta_max 28.31 _reflns_number_total 1978 _reflns_number_gt 1450 _reflns_threshold_expression >2sigma(I) _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0435P)^2^+0.3463P] 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 mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.6(15) _refine_ls_number_reflns 1978 _refine_ls_number_parameters 194 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0869 _refine_ls_R_factor_gt 0.0490 _refine_ls_wR_factor_ref 0.1012 _refine_ls_wR_factor_gt 0.0883 _refine_ls_goodness_of_fit_ref 1.039 _refine_ls_restrained_S_all 1.039 _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 O5 O 0.86323(18) 0.67454(7) 0.2595(3) 0.0202(4) Uani 1 1 d . . . N2 N 0.6471(2) 0.47856(9) 0.4519(4) 0.0219(6) Uani 1 1 d . . . O4 O 0.95339(19) 0.61478(7) 0.4800(4) 0.0254(5) Uani 1 1 d . . . O2 O 0.5917(2) 0.50550(7) 0.5936(4) 0.0262(5) Uani 1 1 d . . . C1 C 0.7131(3) 0.54895(10) 0.2098(5) 0.0172(6) Uani 1 1 d . . . C2 C 0.7204(3) 0.49942(10) 0.2512(5) 0.0179(6) Uani 1 1 d . . . C9 C 0.6152(3) 0.65873(10) 0.5843(5) 0.0214(6) Uani 1 1 d . . . O1 O 0.6455(3) 0.43469(7) 0.4717(4) 0.0407(6) Uani 1 1 d . . . C5 C 0.8615(3) 0.53490(11) -0.1285(5) 0.0230(6) Uani 1 1 d . . . H5 H 0.9096 0.5472 -0.2600 0.028 Uiso 1 1 calc R . . O3 O 0.6854(2) 0.68757(7) 0.6952(4) 0.0318(5) Uani 1 1 d . . . C11 C 0.8532(3) 0.63693(9) 0.3968(5) 0.0190(6) Uani 1 1 d . . . C7 C 0.6337(3) 0.58404(10) 0.3534(5) 0.0176(6) Uani 1 1 d . . . H7 H 0.5346 0.5775 0.3908 0.021 Uiso 1 1 calc R . . C4 C 0.8688(3) 0.48626(11) -0.0793(5) 0.0229(7) Uani 1 1 d . . . H4 H 0.9230 0.4653 -0.1758 0.028 Uiso 1 1 calc R . . C3 C 0.7971(3) 0.46812(10) 0.1105(5) 0.0213(7) Uani 1 1 d . . . H3 H 0.8004 0.4347 0.1440 0.026 Uiso 1 1 calc R . . C12 C 1.0084(3) 0.69590(10) 0.1977(5) 0.0217(6) Uani 1 1 d . . . C6 C 0.7845(3) 0.56557(10) 0.0131(5) 0.0202(6) Uani 1 1 d . . . H6 H 0.7799 0.5988 -0.0239 0.024 Uiso 1 1 calc R . . C8 C 0.6935(3) 0.62446(10) 0.4334(5) 0.0184(6) Uani 1 1 d . . . C15 C 0.9642(3) 0.73889(11) 0.0543(6) 0.0342(8) Uani 1 1 d . . . H15A H 1.0520 0.7550 -0.0036 0.051 Uiso 1 1 calc R . . H15B H 0.9078 0.7614 0.1485 0.051 Uiso 1 1 calc R . . H15C H 0.9041 0.7281 -0.0745 0.051 Uiso 1 1 calc R . . C13 C 1.0864(3) 0.71169(12) 0.4136(6) 0.0294(7) Uani 1 1 d . . . H13A H 1.1188 0.6833 0.4990 0.044 Uiso 1 1 calc R . . H13B H 1.0193 0.7306 0.5086 0.044 Uiso 1 1 calc R . . H13C H 1.1714 0.7314 0.3731 0.044 Uiso 1 1 calc R . . C10 C 0.4506(3) 0.65611(12) 0.6013(6) 0.0337(8) Uani 1 1 d . . . H10A H 0.4228 0.6280 0.6923 0.051 Uiso 1 1 calc R . . H10B H 0.4087 0.6533 0.4477 0.051 Uiso 1 1 calc R . . H10C H 0.4136 0.6853 0.6751 0.051 Uiso 1 1 calc R . . C14 C 1.0947(3) 0.65969(12) 0.0590(6) 0.0341(8) Uani 1 1 d . . . H14A H 1.1200 0.6322 0.1557 0.051 Uiso 1 1 calc R . . H14B H 1.1844 0.6748 0.0020 0.051 Uiso 1 1 calc R . . H14C H 1.0355 0.6487 -0.0706 0.051 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 O5 0.0143(9) 0.0224(10) 0.0239(11) 0.0036(9) 0.0014(9) -0.0034(8) N2 0.0182(12) 0.0235(14) 0.0241(14) 0.0017(12) -0.0013(11) -0.0036(10) O4 0.0181(9) 0.0256(11) 0.0324(11) 0.0038(10) -0.0018(9) 0.0016(9) O2 0.0239(10) 0.0308(12) 0.0238(11) -0.0015(10) 0.0052(9) -0.0011(9) C1 0.0119(13) 0.0212(15) 0.0186(15) -0.0029(12) -0.0023(12) -0.0011(11) C2 0.0134(13) 0.0209(14) 0.0195(14) -0.0007(12) -0.0020(12) -0.0047(11) C9 0.0248(15) 0.0148(14) 0.0245(16) 0.0014(12) 0.0046(14) -0.0008(12) O1 0.0555(15) 0.0210(12) 0.0457(14) 0.0052(12) 0.0161(13) -0.0038(10) C5 0.0147(13) 0.0329(17) 0.0216(15) 0.0027(13) 0.0002(12) -0.0022(13) O3 0.0282(11) 0.0309(12) 0.0362(13) -0.0123(11) 0.0036(10) 0.0012(10) C11 0.0208(14) 0.0158(14) 0.0203(15) -0.0014(12) 0.0024(13) -0.0004(12) C7 0.0145(13) 0.0202(14) 0.0181(14) 0.0033(12) 0.0031(11) 0.0021(12) C4 0.0153(13) 0.0292(17) 0.0243(16) -0.0040(13) -0.0025(13) 0.0010(12) C3 0.0149(14) 0.0194(16) 0.0297(16) -0.0013(13) -0.0048(13) 0.0013(11) C12 0.0166(13) 0.0260(16) 0.0226(15) 0.0021(13) 0.0030(13) -0.0057(12) C6 0.0165(13) 0.0220(15) 0.0220(15) -0.0013(13) 0.0002(12) -0.0026(11) C8 0.0147(12) 0.0212(15) 0.0192(15) 0.0040(12) 0.0009(12) 0.0008(11) C15 0.0307(18) 0.034(2) 0.038(2) 0.0120(15) 0.0034(16) -0.0062(14) C13 0.0223(14) 0.0341(18) 0.0317(19) -0.0026(14) 0.0050(14) -0.0088(13) C10 0.0232(16) 0.0313(18) 0.047(2) -0.0050(16) 0.0088(16) 0.0015(13) C14 0.0262(16) 0.040(2) 0.036(2) -0.0073(15) 0.0116(15) -0.0040(14) _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 O5 C11 1.322(3) . ? O5 C12 1.498(3) . ? N2 O1 1.226(3) . ? N2 O2 1.227(3) . ? N2 C2 1.471(4) . ? O4 C11 1.206(3) . ? C1 C2 1.400(4) . ? C1 C6 1.401(4) . ? C1 C7 1.478(4) . ? C2 C3 1.388(4) . ? C9 O3 1.215(3) . ? C9 C8 1.483(4) . ? C9 C10 1.509(4) . ? C5 C6 1.382(4) . ? C5 C4 1.384(4) . ? C11 C8 1.516(4) . ? C7 C8 1.335(4) . ? C4 C3 1.385(4) . ? C12 C14 1.515(4) . ? C12 C15 1.515(4) . ? C12 C13 1.516(4) . ? 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 C11 O5 C12 121.4(2) . . ? O1 N2 O2 122.7(2) . . ? O1 N2 C2 118.2(2) . . ? O2 N2 C2 119.1(2) . . ? C2 C1 C6 116.4(2) . . ? C2 C1 C7 125.1(2) . . ? C6 C1 C7 118.5(2) . . ? C3 C2 C1 122.6(3) . . ? C3 C2 N2 117.1(2) . . ? C1 C2 N2 120.3(2) . . ? O3 C9 C8 119.1(2) . . ? O3 C9 C10 121.6(3) . . ? C8 C9 C10 119.3(2) . . ? C6 C5 C4 120.2(3) . . ? O4 C11 O5 126.6(2) . . ? O4 C11 C8 123.9(2) . . ? O5 C11 C8 109.5(2) . . ? C8 C7 C1 123.6(2) . . ? C5 C4 C3 120.0(3) . . ? C4 C3 C2 119.1(3) . . ? O5 C12 C14 109.1(2) . . ? O5 C12 C15 102.1(2) . . ? C14 C12 C15 111.6(3) . . ? O5 C12 C13 109.3(2) . . ? C14 C12 C13 113.2(2) . . ? C15 C12 C13 111.0(2) . . ? C5 C6 C1 121.7(3) . . ? C7 C8 C9 123.5(2) . . ? C7 C8 C11 122.5(2) . . ? C9 C8 C11 113.7(2) . . ? 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 C6 C1 C2 C3 1.8(4) . . . . ? C7 C1 C2 C3 -179.8(3) . . . . ? C6 C1 C2 N2 -179.2(2) . . . . ? C7 C1 C2 N2 -0.8(4) . . . . ? O1 N2 C2 C3 -7.0(3) . . . . ? O2 N2 C2 C3 172.2(2) . . . . ? O1 N2 C2 C1 173.9(2) . . . . ? O2 N2 C2 C1 -6.9(3) . . . . ? C12 O5 C11 O4 -2.7(4) . . . . ? C12 O5 C11 C8 178.3(2) . . . . ? C2 C1 C7 C8 129.1(3) . . . . ? C6 C1 C7 C8 -52.5(4) . . . . ? C6 C5 C4 C3 0.9(4) . . . . ? C5 C4 C3 C2 -1.0(4) . . . . ? C1 C2 C3 C4 -0.4(4) . . . . ? N2 C2 C3 C4 -179.5(2) . . . . ? C11 O5 C12 C14 65.4(3) . . . . ? C11 O5 C12 C15 -176.4(2) . . . . ? C11 O5 C12 C13 -58.8(3) . . . . ? C4 C5 C6 C1 0.6(4) . . . . ? C2 C1 C6 C5 -1.8(4) . . . . ? C7 C1 C6 C5 179.6(3) . . . . ? C1 C7 C8 C9 -177.7(2) . . . . ? C1 C7 C8 C11 -3.9(4) . . . . ? O3 C9 C8 C7 161.6(3) . . . . ? C10 C9 C8 C7 -16.8(4) . . . . ? O3 C9 C8 C11 -12.7(4) . . . . ? C10 C9 C8 C11 168.9(3) . . . . ? O4 C11 C8 C7 -66.7(4) . . . . ? O5 C11 C8 C7 112.3(3) . . . . ? O4 C11 C8 C9 107.7(3) . . . . ? O5 C11 C8 C9 -73.3(3) . . . . ? _diffrn_measured_fraction_theta_max 0.975 _diffrn_reflns_theta_full 28.31 _diffrn_measured_fraction_theta_full 0.975 _refine_diff_density_max 0.210 _refine_diff_density_min -0.307 _refine_diff_density_rms 0.057