# Supplementary Material (ESI) for Perkin Transactions # This journal is © The Royal Society of Chemistry 2001 data_global _journal_coden_Cambridge 207 _publ_requested_journal 'J. Chem. Soc., Perkin Trans. 1' _publ_contact_letter ; ? ; _publ_contact_author ; Prof. Dr. Tomoshige Kobayashi Department of Chemistry Faculty of Science Shinshu University Asahi 3-1-1, Matsumoto, Nagano 390-8621, Japan ; _publ_contact_author_phone '+81-263-37-2470' _publ_contact_author_fax '+81-263-37-2470' _publ_contact_author_email tkobaya@gipac.shinshu-u.ac.jp _publ_section_title ; Neighboring effect of pyridazine and pyrazine rings for p-facial selectivity in the electrophilic reactions of fused isopropylidenenorbornene systems ; loop_ _publ_author_name 'Kobayashi, Tomoshige' #<--'Last name, first name' 'Miki, Kiyomi' 'Nekaeen, Behrooz' 'Ohta, Akira' #------------------------------------------------------------------------------ data_1 _database_code_CSD 158037 _chemical_name_systematic ; ???? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C20 H17 N5 O2' _chemical_formula_weight 359.39 _chemical_melting_point ? _cell_length_a 8.1189(3) _cell_length_b 10.5252(4) _cell_length_c 11.2494(3) _cell_angle_alpha 100.943(3) _cell_angle_beta 103.565(3) _cell_angle_gamma 93.725(3) _cell_volume 911.43(5) _cell_formula_units_Z 2 _cell_measurement_temperature 293 _cell_measurement_reflns_used 25 _cell_measurement_theta_min 21.25 _cell_measurement_theta_max 42.54 _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1' _symmetry_Int_Tables_number 2 _symmetry_space_group_name_Hall '-P 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' #------------------------------------------------------------------------------ _exptl_crystal_description 'plate' _exptl_crystal_colour 'colorless' _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.10 _exptl_crystal_density_diffrn 1.310 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 376 _exptl_absorpt_coefficient_mu 0.720 _exptl_absorpt_correction_type none _diffrn_ambient_temperature 293 _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type 'Cu K\a' _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Enraf-Nonius CAD4 diffractometer' _diffrn_measurement_method BISECT _diffrn_standards_number 3 _diffrn_standards_interval_count 120 _diffrn_standards_decay_% ? loop_ _diffrn_standard_refln_index_h _diffrn_standard_refln_index_k _diffrn_standard_refln_index_l 0 -3 -4 1 -8 6 7 0 -4 _diffrn_reflns_number 3977 _diffrn_reflns_av_R_equivalents 0.0094 _diffrn_reflns_av_sigmaI/netI 0.0156 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 4.14 _diffrn_reflns_theta_max 74.30 _diffrn_reflns_reduction_process 'Lp corrections applied' #------------------------------------------------------------------------------ _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _reflns_number_total 3704 _reflns_number_observed 3307 _reflns_observed_criterion 'I>2\s(I)' _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme 'calc w=1/[\s^2^(Fo^2^)+(0.0647P)^2^+0.2299P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_hydrogen_treatment refall _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0502(22) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_abs_structure_details ? _refine_ls_abs_structure_Flack ? _refine_ls_number_reflns 3704 _refine_ls_number_parameters 313 _refine_ls_number_restraints 0 _refine_ls_number_constraints 0 _refine_ls_R_factor_all 0.0475 _refine_ls_R_factor_obs 0.0424 _refine_ls_wR_factor_all 0.1185 _refine_ls_wR_factor_obs 0.1129 _refine_ls_goodness_of_fit_all 1.035 _refine_ls_goodness_of_fit_obs 1.049 _refine_ls_restrained_S_all 1.035 _refine_ls_restrained_S_obs 1.049 _refine_ls_shift/esd_max 0.000 _refine_ls_shift/esd_mean 0.000 _refine_diff_density_max 0.344 _refine_diff_density_min -0.258 _refine_diff_density_rms 0.052 _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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. ; #------------------------------------------------------------------------------ _ccdc_disorder 'none' _ccdc_comments '?' #------------------------------------------------------------------------------ _computing_data_collection 'Enraf-Nonius CAD4 Express' _computing_cell_refinement 'Enraf-Nonius CAD4 Express' _computing_data_reduction 'teXsan' _computing_structure_solution 'SHELXS-86' _computing_structure_refinement 'SHELXL-93' _publ_section_references ; SHELXS-86: G. M. Sheldrick, Acta Crystallogr., Sect. A, 46, 467 (1990). SHELXL-93: G. M. Sheldrick, SHELXL-93, Program for refinement of crystal structures, University of Gotingen, Germany, 1993. Molecular Structure Corporation, Rigaku Corporation. (1998). teXsan. Single Crystal Structure Analysis Software. Version 1.9. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA. Rigaku, 3-9-12 Akishima, Tokyo, Japan. ; #------------------------------------------------------------------------------ loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0181 0.0091 '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' 'Cl' 'Cl' 0.3639 0.7018 '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' 'O' 'O' 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' #------------------------------------------------------------------------------ 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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group C1 C 1.1872(2) 0.6860(2) 1.09527(15) 0.0479(4) Uani 1 d . . C2 C 1.0663(2) 0.74440(13) 1.14681(12) 0.0371(3) Uani 1 d . . C3 C 1.0052(2) 0.87879(12) 1.15949(13) 0.0380(3) Uani 1 d . . C4 C 1.0530(2) 0.93707(15) 1.30000(15) 0.0491(4) Uani 1 d . . C5 C 0.9623(2) 0.86759(15) 1.35361(14) 0.0484(4) Uani 1 d . . C6 C 0.8494(2) 0.75861(13) 1.25140(12) 0.0369(3) Uani 1 d . . C7 C 0.9719(2) 0.67121(12) 1.20291(11) 0.0358(3) Uani 1 d . . C8 C 1.0037(2) 0.54492(14) 1.20392(14) 0.0448(3) Uani 1 d . . C9 C 0.8107(2) 0.83705(12) 1.14462(11) 0.0334(3) Uani 1 d . . C10 C 0.7002(2) 0.94679(13) 1.16369(14) 0.0438(3) Uani 1 d . . C11 C 0.5731(3) 0.9352(2) 1.2233(2) 0.0663(5) Uani 1 d . . C12 C 0.7301(3) 1.0591(2) 1.1113(2) 0.0662(5) Uani 1 d . . C13 C 0.7330(2) 0.77645(12) 0.90909(12) 0.0348(3) Uani 1 d . . C14 C 0.5117(2) 0.62147(12) 0.88676(12) 0.0340(3) Uani 1 d . . C15 C 0.5504(2) 0.68942(13) 0.69309(13) 0.0452(3) Uani 1 d . . C16 C 0.3850(3) 0.6946(2) 0.6299(2) 0.0728(6) Uani 1 d . . C17 C 0.3494(5) 0.6849(3) 0.5000(2) 0.1027(10) Uani 1 d . . C18 C 0.4749(5) 0.6676(3) 0.4369(2) 0.1050(11) Uani 1 d . . C19 C 0.6377(4) 0.6625(3) 0.5020(2) 0.0944(8) Uani 1 d . . C20 C 0.6781(3) 0.6742(2) 0.6308(2) 0.0666(5) Uani 1 d . . N1 N 1.1260(2) 0.49283(13) 1.15484(13) 0.0552(4) Uani 1 d . . N2 N 1.2173(2) 0.56296(15) 1.10105(14) 0.0569(4) Uani 1 d . . N3 N 0.73649(13) 0.74731(10) 1.02287(9) 0.0317(2) Uani 1 d . . N4 N 0.58778(13) 0.66353(10) 1.01175(10) 0.0335(3) Uani 1 d . . N5 N 0.59167(14) 0.69841(10) 0.82532(10) 0.0351(3) Uani 1 d . . O1 O 0.82911(15) 0.85470(10) 0.88475(10) 0.0517(3) Uani 1 d . . O2 O 0.39486(12) 0.53414(10) 0.83988(9) 0.0459(3) Uani 1 d . . H1 H 1.2581(24) 0.7305(18) 1.0523(17) 0.056(5) Uiso 1 d . . H3 H 1.0336(20) 0.9330(16) 1.1036(15) 0.043(4) Uiso 1 d . . H4 H 1.1426(27) 1.0128(20) 1.3385(19) 0.070(6) Uiso 1 d . . H5 H 0.9669(23) 0.8737(18) 1.4418(18) 0.056(5) Uiso 1 d . . H6 H 0.7500(22) 0.7146(16) 1.2706(15) 0.047(4) Uiso 1 d . . H8 H 0.9377(22) 0.4886(18) 1.2416(16) 0.051(5) Uiso 1 d . . H11A H 0.4989(29) 1.0049(23) 1.2276(21) 0.077(6) Uiso 1 d . . H11B H 0.5504(35) 0.8590(28) 1.2526(25) 0.104(9) Uiso 1 d . . H12A H 0.6500(32) 1.1222(25) 1.1200(22) 0.087(7) Uiso 1 d . . H12B H 0.7403(46) 1.0349(36) 1.0227(37) 0.148(13) Uiso 1 d . . H12C H 0.8444(45) 1.1012(33) 1.1361(32) 0.131(12) Uiso 1 d . . H16 H 0.2974(28) 0.7024(22) 0.6770(21) 0.072(6) Uiso 1 d . . H17 H 0.2319(48) 0.6870(36) 0.4689(36) 0.140(12) Uiso 1 d . . H18 H 0.4480(36) 0.6526(28) 0.3394(29) 0.116(9) Uiso 1 d . . H19 H 0.7290(44) 0.6495(34) 0.4511(34) 0.137(11) Uiso 1 d . . H20 H 0.7957(32) 0.6786(24) 0.6823(24) 0.088(7) Uiso 1 d . . H4N H 0.6035(22) 0.6014(18) 1.0583(17) 0.054(5) Uiso 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 0.0354(7) 0.0576(9) 0.0487(8) 0.0058(7) 0.0098(6) 0.0089(6) C2 0.0322(6) 0.0382(7) 0.0363(6) 0.0042(5) 0.0034(5) 0.0024(5) C3 0.0369(7) 0.0322(6) 0.0432(7) 0.0061(5) 0.0095(5) -0.0010(5) C4 0.0481(8) 0.0396(7) 0.0488(8) -0.0032(6) 0.0029(6) -0.0018(6) C5 0.0564(9) 0.0464(8) 0.0353(7) -0.0025(6) 0.0068(6) 0.0055(7) C6 0.0407(7) 0.0372(7) 0.0329(6) 0.0060(5) 0.0108(5) 0.0040(5) C7 0.0354(6) 0.0361(6) 0.0319(6) 0.0052(5) 0.0020(5) 0.0037(5) C8 0.0453(8) 0.0394(7) 0.0438(7) 0.0099(6) -0.0015(6) 0.0071(6) C9 0.0358(6) 0.0292(6) 0.0345(6) 0.0037(5) 0.0101(5) 0.0032(5) C10 0.0456(7) 0.0362(7) 0.0487(8) 0.0030(6) 0.0131(6) 0.0109(6) C11 0.0597(10) 0.0531(10) 0.0973(15) 0.0137(10) 0.0398(10) 0.0198(8) C12 0.0822(14) 0.0437(9) 0.0874(14) 0.0220(9) 0.0376(11) 0.0277(9) C13 0.0375(6) 0.0312(6) 0.0366(6) 0.0091(5) 0.0099(5) 0.0026(5) C14 0.0302(6) 0.0335(6) 0.0392(6) 0.0089(5) 0.0093(5) 0.0048(5) C15 0.0620(9) 0.0358(7) 0.0345(7) 0.0114(5) 0.0033(6) 0.0029(6) C16 0.0743(13) 0.0735(12) 0.0539(10) 0.0090(9) -0.0137(9) 0.0122(10) C17 0.119(2) 0.096(2) 0.0619(14) 0.0155(12) -0.037(2) 0.005(2) C18 0.168(3) 0.092(2) 0.0401(11) 0.0220(11) -0.0015(15) -0.020(2) C19 0.139(2) 0.101(2) 0.0475(11) 0.0260(11) 0.0300(14) -0.010(2) C20 0.0854(14) 0.0762(12) 0.0457(9) 0.0240(8) 0.0237(9) 0.0026(10) N1 0.0525(8) 0.0484(7) 0.0575(8) 0.0056(6) 0.0004(6) 0.0202(6) N2 0.0460(7) 0.0614(8) 0.0590(8) 0.0033(6) 0.0079(6) 0.0217(6) N3 0.0310(5) 0.0300(5) 0.0336(5) 0.0068(4) 0.0085(4) -0.0010(4) N4 0.0314(5) 0.0327(5) 0.0374(5) 0.0094(4) 0.0103(4) -0.0012(4) N5 0.0367(6) 0.0341(5) 0.0346(5) 0.0098(4) 0.0072(4) 0.0033(4) O1 0.0615(7) 0.0469(6) 0.0464(6) 0.0134(4) 0.0161(5) -0.0149(5) O2 0.0371(5) 0.0474(6) 0.0475(6) 0.0097(4) 0.0031(4) -0.0076(4) #------------------------------------------------------------------------------ _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 N2 1.344(2) . ? C1 C2 1.374(2) . ? C1 H1 0.98(2) . ? C2 C7 1.384(2) . ? C2 C3 1.522(2) . ? C3 C4 1.529(2) . ? C3 C9 1.572(2) . ? C3 H3 0.98(2) . ? C4 C5 1.322(2) . ? C4 H4 1.00(2) . ? C5 C6 1.532(2) . ? C5 H5 0.97(2) . ? C6 C7 1.522(2) . ? C6 C9 1.567(2) . ? C6 H6 0.99(2) . ? C7 C8 1.372(2) . ? C8 N1 1.343(2) . ? C8 H8 0.99(2) . ? C9 N3 1.476(2) . ? C9 C10 1.522(2) . ? C10 C11 1.367(2) . ? C10 C12 1.449(2) . ? C11 H11A 0.98(2) . ? C11 H11B 0.95(3) . ? C12 H12A 0.97(3) . ? C12 H12B 1.00(4) . ? C12 H12C 0.96(4) . ? C13 O1 1.210(2) . ? C13 N3 1.366(2) . ? C13 N5 1.398(2) . ? C14 O2 1.221(2) . ? C14 N4 1.369(2) . ? C14 N5 1.382(2) . ? C15 C16 1.374(3) . ? C15 C20 1.383(3) . ? C15 N5 1.429(2) . ? C16 C17 1.404(3) . ? C16 H16 0.98(2) . ? C17 C18 1.375(5) . ? C17 H17 0.94(4) . ? C18 C19 1.362(5) . ? C18 H18 1.05(3) . ? C19 C20 1.388(3) . ? C19 H19 1.04(3) . ? C20 H20 0.99(3) . ? N1 N2 1.330(2) . ? N3 N4 1.4142(14) . ? N4 H4N 0.91(2) . ? #------------------------------------------------------------------------------ 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 N2 C1 C2 121.9(2) . . ? N2 C1 H1 115.1(11) . . ? C2 C1 H1 123.0(11) . . ? C1 C2 C7 117.80(13) . . ? C1 C2 C3 134.99(14) . . ? C7 C2 C3 107.20(11) . . ? C2 C3 C4 105.31(11) . . ? C2 C3 C9 98.65(10) . . ? C4 C3 C9 97.67(11) . . ? C2 C3 H3 116.8(9) . . ? C4 C3 H3 118.0(10) . . ? C9 C3 H3 117.1(10) . . ? C5 C4 C3 108.28(12) . . ? C5 C4 H4 129.8(12) . . ? C3 C4 H4 121.9(12) . . ? C4 C5 C6 107.97(13) . . ? C4 C5 H5 129.9(11) . . ? C6 C5 H5 121.9(11) . . ? C7 C6 C5 105.45(11) . . ? C7 C6 C9 99.00(10) . . ? C5 C6 C9 97.75(11) . . ? C7 C6 H6 116.6(10) . . ? C5 C6 H6 117.9(10) . . ? C9 C6 H6 117.0(10) . . ? C8 C7 C2 118.46(13) . . ? C8 C7 C6 134.73(13) . . ? C2 C7 C6 106.82(11) . . ? N1 C8 C7 121.63(15) . . ? N1 C8 H8 117.2(10) . . ? C7 C8 H8 121.2(10) . . ? N3 C9 C10 110.14(10) . . ? N3 C9 C6 110.13(10) . . ? C10 C9 C6 115.91(11) . . ? N3 C9 C3 110.32(10) . . ? C10 C9 C3 116.43(11) . . ? C6 C9 C3 92.82(10) . . ? C11 C10 C12 122.2(2) . . ? C11 C10 C9 120.31(14) . . ? C12 C10 C9 117.45(14) . . ? C10 C11 H11A 117.7(13) . . ? C10 C11 H11B 121.3(17) . . ? H11A C11 H11B 120.7(21) . . ? C10 C12 H12A 113.8(14) . . ? C10 C12 H12B 112.9(21) . . ? H12A C12 H12B 111.6(24) . . ? C10 C12 H12C 116.0(20) . . ? H12A C12 H12C 110.6(24) . . ? H12B C12 H12C 89.5(26) . . ? O1 C13 N3 127.88(12) . . ? O1 C13 N5 126.53(12) . . ? N3 C13 N5 105.58(10) . . ? O2 C14 N4 126.36(12) . . ? O2 C14 N5 127.19(12) . . ? N4 C14 N5 106.44(10) . . ? C16 C15 C20 121.2(2) . . ? C16 C15 N5 119.7(2) . . ? C20 C15 N5 119.14(15) . . ? C15 C16 C17 118.0(3) . . ? C15 C16 H16 118.7(13) . . ? C17 C16 H16 123.3(13) . . ? C18 C17 C16 121.3(3) . . ? C18 C17 H17 129.7(23) . . ? C16 C17 H17 108.9(24) . . ? C19 C18 C17 119.4(2) . . ? C19 C18 H18 118.6(16) . . ? C17 C18 H18 121.9(16) . . ? C18 C19 C20 120.9(3) . . ? C18 C19 H19 117.2(20) . . ? C20 C19 H19 121.9(20) . . ? C15 C20 C19 119.2(2) . . ? C15 C20 H20 117.2(14) . . ? C19 C20 H20 123.4(15) . . ? N2 N1 C8 120.09(13) . . ? N1 N2 C1 120.12(13) . . ? C13 N3 N4 108.83(10) . . ? C13 N3 C9 124.81(10) . . ? N4 N3 C9 117.56(9) . . ? C14 N4 N3 107.41(10) . . ? C14 N4 H4N 116.8(12) . . ? N3 N4 H4N 114.7(11) . . ? C14 N5 C13 110.25(10) . . ? C14 N5 C15 125.40(11) . . ? C13 N5 C15 123.94(11) . . ? #------------------------------------------------------------------------------ #===END