# Supplementary Material (ESI) for ChemComm # This journal is © The Royal Society of Chemistry 2000 # CCDC Number: 182/1797 data_global _publ_contact_author_name 'C L Raston' _publ_contact_author_address ; Centre for Green Chemistry, School of Chemistry, Monash University, Clayton, Melbourne, Victoria, 3800, Australia ; _publ_reqested_journal 'Chemical Communications' _publ_section_title ;Toward benign syntheses of pyridines involving sequential solvent free Aldol Michael addition reactions ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ; 4'-(4-octyloxyphenyl)-4,2': 6',4''-terpyridine ; _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C116 H124 N12 O4' _chemical_formula_weight 1750.27 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 monoclinic _symmetry_space_group_name_H-M C2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 19.7473(3) _cell_length_b 10.8189(3) _cell_length_c 23.8391(7) _cell_angle_alpha 90.00 _cell_angle_beta 114.0330(10) _cell_angle_gamma 90.00 _cell_volume 4651.6(2) _cell_formula_units_Z 2 _cell_measurement_temperature 123(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description prim _exptl_crystal_colour yellow _exptl_crystal_size_max 0.18 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.250 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1872 _exptl_absorpt_coefficient_mu 0.076 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _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 CCD _diffrn_measurement_method 'Phi and Omega scan ' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 28604 _diffrn_reflns_av_R_equivalents 0.053 _diffrn_reflns_av_sigmaI/netI 0.0660 _diffrn_reflns_limit_h_min -25 _diffrn_reflns_limit_h_max 26 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 0 _diffrn_reflns_limit_l_min -31 _diffrn_reflns_limit_l_max 31 _diffrn_reflns_theta_min 1.87 _diffrn_reflns_theta_max 28.17 _reflns_number_total 5661 _reflns_number_gt 3759 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Enraf-Nonius) ' _computing_cell_refinement DENZO _computing_data_reduction DENZO _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics X-Seed _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^)+(0.1001P)^2^+1.0504P] 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_number_reflns 5661 _refine_ls_number_parameters 422 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1116 _refine_ls_R_factor_gt 0.0625 _refine_ls_wR_factor_ref 0.1848 _refine_ls_wR_factor_gt 0.1456 _refine_ls_goodness_of_fit_ref 1.089 _refine_ls_restrained_S_all 1.089 _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 C1 C 0.45784(12) 0.76501(18) 0.13272(9) 0.0229(5) Uani 1 1 d . . . H1 H 0.5315(11) 0.458(2) 0.0798(9) 0.026(5) Uiso 1 1 d . . . C2 C 0.46185(12) 0.89226(19) 0.13251(10) 0.0277(5) Uani 1 1 d . . . H2 H 0.3896(11) 0.061(2) 0.3346(10) 0.027(6) Uiso 1 1 d . . . N3 N 0.43818(10) 0.96692(15) 0.16557(8) 0.0283(4) Uani 1 1 d . . . H3 H 0.2885(14) -0.031(2) 0.5926(12) 0.048(7) Uiso 1 1 d . . . C4 C 0.40870(12) 0.90948(18) 0.20009(11) 0.0283(5) Uani 1 1 d . . . H4 H 0.2516(13) -0.125(2) 0.5372(11) 0.034(6) Uiso 1 1 d . . . C5 C 0.40270(11) 0.78336(17) 0.20368(10) 0.0234(5) Uani 1 1 d . . . H5 H 0.2505(14) 0.352(2) 0.3202(11) 0.045(7) Uiso 1 1 d . . . C6 C 0.42843(10) 0.70678(16) 0.16973(8) 0.0175(4) Uani 1 1 d . . . H6 H 0.1665(13) -0.003(2) 0.5937(11) 0.041(7) Uiso 1 1 d . . . C7 C 0.42482(10) 0.56971(16) 0.17239(8) 0.0162(4) Uani 1 1 d . . . H7 H 0.1379(16) -0.118(2) 0.5477(13) 0.056(8) Uiso 1 1 d . . . C8 C 0.40098(10) 0.51039(16) 0.21281(9) 0.0179(4) Uani 1 1 d . . . H8 H 0.4828(13) 0.927(2) 0.1047(11) 0.041(7) Uiso 1 1 d . . . C9 C 0.39708(10) 0.38170(17) 0.21325(8) 0.0170(4) Uani 1 1 d . . . H9 H 0.4085(12) 0.1540(18) 0.0803(10) 0.027(6) Uiso 1 1 d . . . C10 C 0.41809(10) 0.31695(17) 0.17229(8) 0.0173(4) Uani 1 1 d . . . H10 H 0.5667(15) 0.347(2) 0.0090(12) 0.048(7) Uiso 1 1 d . . . C11 C 0.44255(10) 0.38241(16) 0.13350(8) 0.0168(4) Uani 1 1 d . . . H11 H 0.4506(11) 0.059(2) 0.0116(9) 0.026(5) Uiso 1 1 d . . . N12 N 0.44639(9) 0.50657(13) 0.13356(7) 0.0183(4) Uani 1 1 d . . . H12 H 0.2304(14) -0.242(2) 0.6244(11) 0.045(7) Uiso 1 1 d . . . C13 C 0.46543(10) 0.31774(16) 0.08884(8) 0.0173(4) Uani 1 1 d . . . H13 H 0.4735(13) 0.721(2) 0.1105(11) 0.032(6) Uiso 1 1 d . . . C14 C 0.44183(11) 0.19839(17) 0.06801(9) 0.0214(4) Uani 1 1 d . . . H14 H 0.1229(13) -0.140(2) 0.6615(11) 0.040(7) Uiso 1 1 d . . . C15 C 0.46563(12) 0.14299(18) 0.02704(9) 0.0249(5) Uani 1 1 d . . . H15 H 0.1028(15) -0.253(2) 0.6161(13) 0.053(8) Uiso 1 1 d . . . N16 N 0.51089(10) 0.19652(16) 0.00495(8) 0.0276(4) Uani 1 1 d . . . H16 H 0.4351(12) 0.1633(18) 0.2707(9) 0.022(5) Uiso 1 1 d . . . C17 C 0.53310(13) 0.3115(2) 0.02513(10) 0.0289(5) Uani 1 1 d . . . H17 H 0.4163(11) 0.2289(19) 0.1699(9) 0.022(5) Uiso 1 1 d . . . C18 C 0.51224(12) 0.37463(18) 0.06611(10) 0.0243(5) Uani 1 1 d . . . H18 H 0.3898(14) 0.958(2) 0.2206(12) 0.046(7) Uiso 1 1 d . . . C19 C 0.36971(10) 0.31721(16) 0.25501(8) 0.0177(4) Uani 1 1 d . . . H19 H 0.3118(13) -0.033(2) 0.3694(11) 0.037(7) Uiso 1 1 d . . . C20 C 0.39603(11) 0.20102(17) 0.27913(9) 0.0197(4) Uani 1 1 d . . . H20 H 0.1683(16) 0.044(2) 0.4795(13) 0.059(8) Uiso 1 1 d . . . C21 C 0.36895(11) 0.13950(18) 0.31699(9) 0.0219(4) Uani 1 1 d . . . H21 H 0.3821(12) 0.7519(18) 0.2288(10) 0.022(5) Uiso 1 1 d . . . C22 C 0.31440(11) 0.19468(18) 0.33129(9) 0.0227(4) Uani 1 1 d . . . H22 H 0.2954(14) -0.089(2) 0.4592(11) 0.041(6) Uiso 1 1 d . . . C23 C 0.28854(11) 0.31193(18) 0.30857(9) 0.0232(4) Uani 1 1 d . . . H23 H 0.2982(11) 0.4514(19) 0.2554(9) 0.019(5) Uiso 1 1 d . . . C24 C 0.31573(11) 0.37179(18) 0.27114(9) 0.0217(4) Uani 1 1 d . . . H24 H 0.3707(13) 0.0489(19) 0.4288(10) 0.032(6) Uiso 1 1 d . . . O25 O 0.28235(8) 0.14192(12) 0.36667(7) 0.0299(4) Uani 1 1 d . . . H25 H 0.3247(16) 0.102(2) 0.5130(13) 0.062(9) Uiso 1 1 d . . . C26 C 0.31464(13) 0.0304(2) 0.39878(11) 0.0281(5) Uani 1 1 d . . . H26 H 0.1618(14) -0.268(2) 0.6870(12) 0.049(7) Uiso 1 1 d . . . C27 C 0.27118(13) -0.00806(19) 0.43581(10) 0.0264(5) Uani 1 1 d . . . H27 H 0.2215(14) -0.028(2) 0.4088(11) 0.036(6) Uiso 1 1 d . . . C28 C 0.27011(17) 0.0873(2) 0.48169(12) 0.0400(6) Uani 1 1 d . . . H28 H 0.2501(16) -0.125(2) 0.6708(14) 0.066(9) Uiso 1 1 d . . . C29 C 0.21796(16) 0.0549(2) 0.51231(12) 0.0364(6) Uani 1 1 d . . . H29 H 0.2546(16) 0.168(3) 0.4614(14) 0.067(9) Uiso 1 1 d . . . C30 C 0.24061(13) -0.0543(2) 0.55565(11) 0.0303(5) Uani 1 1 d . . . H30 H 0.3875(12) 0.5594(19) 0.2412(10) 0.033(6) Uiso 1 1 d . . . C31 C 0.18345(13) -0.0847(2) 0.58111(10) 0.0288(5) Uani 1 1 d . . . H31 H 0.2154(16) 0.130(3) 0.5374(13) 0.060(8) Uiso 1 1 d . . . C32 C 0.20843(14) -0.1732(2) 0.63442(11) 0.0330(5) Uani 1 1 d . . . C33 C 0.14657(15) -0.2123(2) 0.65232(12) 0.0360(6) Uani 1 1 d . . . 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 C1 0.0301(11) 0.0216(10) 0.0214(11) -0.0009(8) 0.0148(9) -0.0006(8) C2 0.0329(12) 0.0233(11) 0.0301(12) 0.0038(9) 0.0160(10) -0.0030(9) N3 0.0339(10) 0.0201(9) 0.0323(11) 0.0022(7) 0.0148(9) -0.0011(7) C4 0.0356(13) 0.0206(10) 0.0346(13) -0.0031(9) 0.0202(11) 0.0027(9) C5 0.0277(11) 0.0216(10) 0.0280(12) 0.0014(8) 0.0185(10) -0.0002(8) C6 0.0172(10) 0.0172(9) 0.0175(10) 0.0000(7) 0.0065(8) -0.0008(7) C7 0.0158(9) 0.0171(9) 0.0161(9) -0.0006(7) 0.0069(8) -0.0012(7) C8 0.0200(10) 0.0176(9) 0.0174(10) -0.0021(7) 0.0092(8) -0.0009(7) C9 0.0163(9) 0.0197(9) 0.0145(9) 0.0002(7) 0.0057(8) -0.0012(7) C10 0.0197(10) 0.0147(9) 0.0180(10) 0.0003(7) 0.0081(8) -0.0011(7) C11 0.0183(10) 0.0168(9) 0.0154(9) 0.0004(7) 0.0070(8) -0.0006(7) N12 0.0205(9) 0.0173(8) 0.0176(8) 0.0004(6) 0.0084(7) -0.0002(6) C13 0.0216(10) 0.0174(9) 0.0132(9) 0.0025(7) 0.0074(8) 0.0021(7) C14 0.0287(11) 0.0182(10) 0.0196(10) 0.0011(8) 0.0123(9) -0.0025(8) C15 0.0339(12) 0.0218(11) 0.0212(11) -0.0037(8) 0.0135(10) -0.0018(9) N16 0.0336(10) 0.0307(10) 0.0237(10) -0.0035(7) 0.0170(8) -0.0005(8) C17 0.0344(12) 0.0317(12) 0.0293(12) -0.0028(9) 0.0220(11) -0.0061(10) C18 0.0300(11) 0.0222(10) 0.0251(11) -0.0026(8) 0.0158(10) -0.0046(9) C19 0.0214(10) 0.0184(9) 0.0145(9) -0.0019(7) 0.0084(8) -0.0046(7) C20 0.0198(10) 0.0201(10) 0.0209(10) -0.0015(8) 0.0100(9) -0.0017(8) C21 0.0246(11) 0.0201(10) 0.0209(10) 0.0030(8) 0.0091(9) -0.0003(8) C22 0.0228(10) 0.0273(11) 0.0204(10) 0.0020(8) 0.0111(9) -0.0044(8) C23 0.0237(11) 0.0266(11) 0.0239(11) 0.0003(8) 0.0144(9) 0.0017(8) C24 0.0247(11) 0.0194(10) 0.0235(11) 0.0021(8) 0.0124(9) 0.0016(8) O25 0.0311(8) 0.0326(8) 0.0344(9) 0.0136(6) 0.0220(7) 0.0047(6) C26 0.0327(13) 0.0278(11) 0.0282(12) 0.0078(10) 0.0171(11) 0.0016(9) C27 0.0284(12) 0.0290(12) 0.0245(12) 0.0023(9) 0.0136(10) -0.0036(9) C28 0.0635(19) 0.0292(13) 0.0386(15) -0.0038(11) 0.0323(14) -0.0145(12) C29 0.0577(17) 0.0284(12) 0.0351(14) 0.0001(10) 0.0311(14) -0.0017(11) C30 0.0309(13) 0.0354(13) 0.0279(13) 0.0023(10) 0.0154(11) -0.0021(10) C31 0.0301(12) 0.0337(12) 0.0252(12) 0.0014(9) 0.0139(10) 0.0016(10) C32 0.0337(13) 0.0375(13) 0.0329(13) 0.0059(11) 0.0187(11) 0.0066(11) C33 0.0381(14) 0.0465(15) 0.0311(14) 0.0092(12) 0.0219(12) 0.0062(12) _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 C1 C2 1.379(3) . ? C1 C6 1.389(3) . ? C2 N3 1.339(3) . ? N3 C4 1.339(3) . ? C4 C5 1.375(3) . ? C5 C6 1.391(3) . ? C6 C7 1.487(3) . ? C7 N12 1.351(2) . ? C7 C8 1.390(3) . ? C8 C9 1.395(3) . ? C9 C10 1.395(3) . ? C9 C19 1.486(3) . ? C10 C11 1.398(3) . ? C11 N12 1.345(2) . ? C11 C13 1.490(3) . ? C13 C18 1.391(3) . ? C13 C14 1.394(3) . ? C14 C15 1.381(3) . ? C15 N16 1.340(3) . ? N16 C17 1.342(3) . ? C17 C18 1.385(3) . ? C19 C20 1.392(3) . ? C19 C24 1.402(3) . ? C20 C21 1.392(3) . ? C21 C22 1.390(3) . ? C22 O25 1.368(2) . ? C22 C23 1.392(3) . ? C23 C24 1.376(3) . ? O25 C26 1.432(2) . ? C26 C27 1.518(3) . ? C27 C28 1.510(3) . ? C28 C29 1.526(3) . ? C29 C30 1.512(3) . ? C30 C31 1.519(3) . ? C31 C32 1.505(3) . ? C32 C33 1.509(3) . ? 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 C2 C1 C6 119.6(2) . . ? N3 C2 C1 124.5(2) . . ? C2 N3 C4 115.17(18) . . ? N3 C4 C5 124.7(2) . . ? C4 C5 C6 119.58(19) . . ? C1 C6 C5 116.47(17) . . ? C1 C6 C7 121.26(17) . . ? C5 C6 C7 122.27(17) . . ? N12 C7 C8 122.13(16) . . ? N12 C7 C6 116.17(15) . . ? C8 C7 C6 121.70(16) . . ? C7 C8 C9 120.09(17) . . ? C8 C9 C10 117.58(17) . . ? C8 C9 C19 120.66(17) . . ? C10 C9 C19 121.74(16) . . ? C9 C10 C11 119.34(17) . . ? N12 C11 C10 122.66(17) . . ? N12 C11 C13 115.88(16) . . ? C10 C11 C13 121.47(16) . . ? C11 N12 C7 118.18(15) . . ? C18 C13 C14 116.74(17) . . ? C18 C13 C11 120.91(16) . . ? C14 C13 C11 122.35(17) . . ? C15 C14 C13 119.56(18) . . ? N16 C15 C14 124.32(18) . . ? C15 N16 C17 115.66(17) . . ? N16 C17 C18 124.2(2) . . ? C17 C18 C13 119.51(18) . . ? C20 C19 C24 117.68(17) . . ? C20 C19 C9 121.62(17) . . ? C24 C19 C9 120.70(16) . . ? C21 C20 C19 121.50(18) . . ? C22 C21 C20 119.63(18) . . ? O25 C22 C21 124.83(17) . . ? O25 C22 C23 115.56(17) . . ? C21 C22 C23 119.62(18) . . ? C24 C23 C22 120.19(19) . . ? C23 C24 C19 121.36(18) . . ? C22 O25 C26 117.64(15) . . ? O25 C26 C27 107.92(17) . . ? C28 C27 C26 114.30(18) . . ? C27 C28 C29 113.6(2) . . ? C30 C29 C28 115.9(2) . . ? C29 C30 C31 112.4(2) . . ? C32 C31 C30 115.70(19) . . ? C31 C32 C33 113.1(2) . . ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 28.17 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.366 _refine_diff_density_min -0.451 _refine_diff_density_rms 0.103