# Copyright The Royal Society of Chemistry, 1999 # CCDC Number: 440/114 data_mgb62 #----------------------------------------------------------------------- _audit_creation_date '1999-02-19' _audit_creation_method 'by teXsan v1.8' _audit_update_record ; 1999-04-14 acw modifies cif for journal ; #----------------------------------------------------------------------- _publ_requested_journal ' New Journal of Chemistry' _publ_requested_category ' FA ' _publ_contact_author_name ' Banwell, Martin, G. ' _publ_contact_author_address ; Research School of Chemistry, Institute of Advanced Studies Australian National University Canberra, ACT 0200 Australia ; _publ_contact_letter ; Please find here the cif for the paper First Syntheses of the Pyrroloketopiperazine Marine Natural Products (+-)-Longamide, (+-)-Longamide B Methyl Ester and (+-)-Hanishin. ; _publ_requested_coeditor_name ? _publ_contact_author_phone ' 61 2 6279 8202 ' _publ_contact_author_fax ' 61 2 6249 5995 ' _publ_contact_author_email ' mgb@rsc.anu.edu.au' loop_ _publ_author_name _publ_author_address ' Banwell, Martin, G. ' ; Research School of Chemistry, Institute of Advanced Studies Australian National University Canberra, ACT 0200 Australia ; ' Bray, Andrew M.' ; Chiron Technologies Pty Ltd 11 Duerdin St Clayton, Victoria 3168 Australia ; ' Willis, Anthony C. ' ; Research School of Chemistry, Institute of Advanced Studies Australian National University Canberra, ACT 0200 Australia ; ' Wong, David J. ' ; Research School of Chemistry, Institute of Advanced Studies Australian National University Canberra, ACT 0200 Australia ; _publ_section_title ; First Syntheses of the Pyrroloketopiperazine Marine Natural Products (+-)-Longamide, (+-)-Longamide B Methyl Ester and and (+-)-Hanishin. ; _publ_section_title_footnote ' ENTER ANY FOOTNOTES TO TITLE ' _publ_section_abstract ; ENTER ABSTRACT ; _publ_section_exptl_refinement ; ENTER EXPERIMENTAL SECTION ; _publ_section_comment ; ENTER TEXT ; _publ_section_references ; ENTER OTHER REFERENCES Molecular Structure Corporation. (1992-1997). teXsan. Single Crystal Structure Analysis Software. Version 1.7. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA. North, A.C.T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351-359. Altomare, A., Cascarano, M., Giacovazzo, C., Guagliardi, A. (1993). J. Appl. Cryst., 26, 343. ; _publ_section_acknowledgements ; ENTER ACKNOWLEDGEMENTS ; _publ_section_table_legends ; ENTER TABLE LEGENDS ; _publ_section_figure_captions ; ENTER FIGURE CAPTIONS ; #----------------------------------------------------------------------- _computing_data_collection 'MSC/AFC Diffractometer Control' _computing_cell_refinement 'MSC/AFC Diffractometer Control' _computing_data_reduction 'teXsan (MSC, 1992-1997)' _computing_structure_solution ; SIR92 (Altomare, et. al. 1993) ; _computing_structure_refinement 'teXsan (MSC, 1992-1997)' _computing_publication_material 'teXsan (MSC, 1992-1997)' #----------------------------------------------------------------------- _cell_length_a 8.168(1) _cell_length_b 9.279(2) _cell_length_c 9.875(2) _cell_angle_alpha 65.47(2) _cell_angle_beta 80.99(1) _cell_angle_gamma 67.69(1) _cell_volume 629.9(2) _cell_formula_units_Z 2 _cell_measurement_temperature 296.2 _cell_measurement_reflns_used 24 _cell_measurement_theta_min 51.9 _cell_measurement_theta_max 54.9 #----------------------------------------------------------------------- _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1 ' _symmetry_Int_Tables_number 2 _symmetry_space_group_name_Hall ? loop_ _symmetry_equiv_pos_as_xyz ' +x, +y, +z' ' -x, -y, -z' #----------------------------------------------------------------------- _publ_section_exptl_prep ; ENTER EXPERIMENTAL SECTION ; _exptl_crystal_description 'spearhead' _exptl_crystal_colour 'colourless' _exptl_crystal_size_max 0.34 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.06 _exptl_crystal_density_diffrn 1.930 _exptl_crystal_density_meas 'not measured' _chemical_formula_weight 366.01 _chemical_formula_analytical ? _chemical_formula_sum 'C10 H10 Br2 N2 O3 ' _chemical_formula_moiety 'C10 H10 Br2 N2 O3 ' _chemical_formula_structural ? _chemical_compound_source ? _chemical_name_systematic ; 6,7-dibromo-1,2,3,4-tetrahydro-1-oxo- pyrrolo[1,2-a]pyrazine-4-acetic acid, methyl ester ; _chemical_name_common ; (+-)-longamide B methyl ester ; _exptl_crystal_F_000 356.00 _exptl_absorpt_coefficient_mu 8.261 _exptl_absorpt_correction_type psi-scan _exptl_absorpt_process_details ; \y scans (North,Phillips & Matthews, 1968) ; _exptl_absorpt_correction_T_max 0.61 _exptl_absorpt_correction_T_min 0.31 _exptl_special_details ; The scan width was (1.40+0.30tan\q)\% with an \w scan speed of 32\% per minute (up to 5 scans to achieve I/\s(I) > 10). Stationary background counts were recorded at each end of the scan, and the scan time:background time ratio was 2:1. ; #----------------------------------------------------------------------- _diffrn_special_details ; ? ; _diffrn_ambient_temperature 296.2 _diffrn_radiation_wavelength 1.5418 _diffrn_radiation_type 'Cu K\a' _diffrn_radiation_source 'Rigaku rotating anode' _diffrn_radiation_monochromator graphite _diffrn_radiation_detector 'scintillation counter' _diffrn_measurement_device_type 'Rigaku AFC6R' _diffrn_measurement_method \w-2\q _diffrn_standards_number 3 _diffrn_standards_interval_count 150 _diffrn_standards_decay_% 1.16 loop_ _diffrn_standard_refln_index_h _diffrn_standard_refln_index_k _diffrn_standard_refln_index_l ? ? ? ? ? ? ? ? ? _diffrn_reflns_number 2025 _reflns_number_total 1873 _reflns_number_gt 1661 _reflns_threshold_expression I>2.00\s(I) _diffrn_reflns_av_R_equivalents 0.03682 _diffrn_reflns_av_sigmaI/netI 0.030 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 4.93 _diffrn_reflns_theta_max 60.01 _diffrn_reflns_reduction_process 'Lp corrections applied' _diffrn_orient_matrix_UB_11 0.00208 _diffrn_orient_matrix_UB_12 0.04791 _diffrn_orient_matrix_UB_13 0.07337 _diffrn_orient_matrix_UB_21 0.01388 _diffrn_orient_matrix_UB_22 -0.11216 _diffrn_orient_matrix_UB_23 0.08314 _diffrn_orient_matrix_UB_31 0.13158 _diffrn_orient_matrix_UB_32 -0.03344 _diffrn_orient_matrix_UB_33 -0.00981 #----------------------------------------------------------------------- loop_ _atom_type_symbol _atom_type_oxidation_number _atom_type_number_in_cell _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C 0 20 0.017 0.009 ;International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.1) ; H 0 20 0.000 0.000 ;International Tables for Crystallography (1992, Vol. C, Table 6.1.1.2) ; Br 0 4 -0.767 1.283 ;International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.1) ; N 0 4 0.029 0.018 ;International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.1) ; O 0 6 0.047 0.032 ;International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.1) ; #----------------------------------------------------------------------- loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_occupancy _atom_site_refinement_flags _atom_site_adp_type _atom_site_calc_flag _atom_site_calc_attached_atom Br(6) -0.19462(8) 0.22883(8) 0.93627(7) 0.0702(2) 1.000 . Uani d ? Br(7) -0.18583(9) 0.11093(8) 0.62967(7) 0.0752(2) 1.000 . Uani d ? O(1) 0.3993(5) 0.3800(5) 0.4600(4) 0.059(1) 1.000 . Uani d ? O(10) 0.2137(5) 0.3214(5) 1.1491(4) 0.077(1) 1.000 . Uani d ? O(11) 0.4801(5) 0.1322(5) 1.1475(4) 0.061(1) 1.000 . Uani d ? N(2) 0.3407(5) 0.4637(5) 0.6538(4) 0.050(1) 1.000 . Uani d ? N(5) 0.0816(5) 0.3225(4) 0.7529(4) 0.043(1) 1.000 . Uani d ? C(1) 0.3116(6) 0.3914(6) 0.5708(5) 0.045(1) 1.000 . Uani d ? C(3) 0.2166(6) 0.5053(6) 0.7664(5) 0.049(1) 1.000 . Uani d ? C(4) 0.1444(6) 0.3642(5) 0.8585(5) 0.043(1) 1.000 . Uani d ? C(6) -0.0435(6) 0.2512(6) 0.7739(5) 0.047(1) 1.000 . Uani d ? C(7) -0.0377(6) 0.2093(6) 0.6559(6) 0.051(1) 1.000 . Uani d ? C(8a) 0.1678(6) 0.3231(5) 0.6217(5) 0.043(1) 1.000 . Uani d ? C(8) 0.0953(6) 0.2541(6) 0.5592(5) 0.044(1) 1.000 . Uani d ? C(9) 0.2831(7) 0.2064(6) 0.9615(5) 0.049(1) 1.000 . Uani d ? C(10) 0.3176(6) 0.2304(6) 1.0947(5) 0.046(1) 1.000 . Uani d ? C(12) 0.5270(9) 0.1396(9) 1.2801(7) 0.083(2) 1.000 . Uani d ? H(1) 0.4341 0.4857 0.6400 0.060 1.000 . Uiso c ? H(2) 0.2754 0.5230 0.8306 0.059 1.000 . Uiso c ? H(3) 0.1208 0.6059 0.7185 0.059 1.000 . Uiso c ? H(4) 0.0474 0.4042 0.9164 0.051 1.000 . Uiso c ? H(5) 0.1288 0.2396 0.4679 0.053 1.000 . Uiso c ? H(6) 0.2422 0.1141 0.9947 0.059 1.000 . Uiso c ? H(7) 0.3903 0.1823 0.9078 0.059 1.000 . Uiso c ? H(8) 0.6451 0.0656 1.3083 0.100 1.000 . Uiso c ? H(9) 0.4489 0.1062 1.3589 0.100 1.000 . Uiso c ? H(10) 0.5176 0.2520 1.2597 0.100 1.000 . Uiso c ? loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_12 _atom_site_aniso_U_13 _atom_site_aniso_U_23 Br(6) 0.0674(4) 0.0788(5) 0.0743(4) -0.0419(3) 0.0306(3) -0.0351(3) Br(7) 0.0779(5) 0.0886(5) 0.0845(5) -0.0555(4) 0.0019(3) -0.0344(4) O(1) 0.057(2) 0.087(3) 0.055(2) -0.041(2) 0.020(2) -0.043(2) O(10) 0.068(3) 0.088(3) 0.073(3) 0.006(2) -0.005(2) -0.057(2) O(11) 0.056(2) 0.071(2) 0.053(2) -0.005(2) -0.002(2) -0.038(2) N(2) 0.053(2) 0.064(3) 0.050(2) -0.032(2) 0.015(2) -0.033(2) N(5) 0.040(2) 0.045(2) 0.045(2) -0.017(2) 0.006(2) -0.021(2) C(1) 0.044(3) 0.050(3) 0.046(3) -0.020(2) 0.005(2) -0.023(2) C(3) 0.055(3) 0.054(3) 0.045(3) -0.024(2) 0.010(2) -0.024(2) C(4) 0.046(3) 0.042(2) 0.042(2) -0.015(2) 0.004(2) -0.020(2) C(6) 0.037(3) 0.047(3) 0.055(3) -0.018(2) 0.009(2) -0.018(2) C(7) 0.048(3) 0.048(3) 0.062(3) -0.024(2) -0.002(2) -0.019(2) C(8a) 0.040(2) 0.045(2) 0.043(2) -0.014(2) 0.005(2) -0.018(2) C(8) 0.044(3) 0.046(3) 0.047(3) -0.015(2) 0.000(2) -0.022(2) C(9) 0.054(3) 0.043(2) 0.047(3) -0.010(2) 0.004(2) -0.023(2) C(10) 0.050(3) 0.042(2) 0.044(3) -0.014(2) 0.002(2) -0.019(2) C(12) 0.076(4) 0.110(5) 0.066(4) -0.011(4) -0.013(3) -0.051(4) #----------------------------------------------------------------------- _refine_special_details ; ? ; _refine_ls_structure_factor_coef F _refine_ls_matrix_type full _refine_ls_weighting_scheme 'w = 1/[\s^2^(Fo) + 0.00010|Fo|^2^]' _refine_ls_hydrogen_treatment noref _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details ? _refine_ls_abs_structure_Flack ? _refine_ls_number_reflns 1661 _refine_ls_number_parameters 154 _refine_ls_number_restraints 0 _refine_ls_number_constraints 0 _refine_ls_R_factor_all 0.0447 _refine_ls_R_factor_gt 0.0395 _refine_ls_wR_factor_all 0.0502 _refine_ls_wR_factor_ref 0.0493 _refine_ls_goodness_of_fit_all 2.512 _refine_ls_goodness_of_fit_ref 2.635 _refine_ls_shift/su_max 0.0059 _refine_ls_shift/su_mean 0.0010 _refine_diff_density_min -0.52 _refine_diff_density_max 0.70 #----------------------------------------------------------------------- _geom_special_details ; ? ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag Br(6) C(6) 1.854(5) . . yes Br(7) C(7) 1.870(5) . . yes O(1) C(1) 1.232(5) . . yes O(10) C(10) 1.188(5) . . yes O(11) C(10) 1.330(6) . . yes O(11) C(12) 1.456(7) . . yes N(2) C(1) 1.349(6) . . yes N(2) C(3) 1.455(6) . . yes N(2) H(1) 0.84 . . no N(5) C(4) 1.467(6) . . yes N(5) C(6) 1.363(6) . . yes N(5) C(8a) 1.373(6) . . yes C(1) C(8a) 1.465(6) . . yes C(3) C(4) 1.523(6) . . yes C(3) H(2) 0.95 . . no C(3) H(3) 0.95 . . no C(4) C(9) 1.525(6) . . yes C(4) H(4) 0.95 . . no C(6) C(7) 1.363(7) . . yes C(7) C(8) 1.397(7) . . yes C(8a) C(8) 1.368(7) . . yes C(8) H(5) 0.95 . . no C(9) C(10) 1.506(7) . . yes C(9) H(6) 0.95 . . no C(9) H(7) 0.95 . . no C(12) H(8) 0.95 . . no C(12) H(9) 0.95 . . no C(12) H(10) 0.95 . . no #----------------------------------------------------------------------- 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_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C(10) O(11) C(12) 116.2(4) . . . yes C(1) N(2) C(3) 122.6(4) . . . yes C(1) N(2) H(1) 118.7 . . . no C(3) N(2) H(1) 118.7 . . . no C(4) N(5) C(6) 128.5(4) . . . yes C(4) N(5) C(8a) 122.3(4) . . . yes C(6) N(5) C(8a) 108.2(4) . . . yes O(1) C(1) N(2) 123.4(4) . . . yes O(1) C(1) C(8a) 120.9(4) . . . yes N(2) C(1) C(8a) 115.7(4) . . . yes N(2) C(3) C(4) 111.6(4) . . . yes N(2) C(3) H(2) 108.9 . . . no N(2) C(3) H(3) 108.9 . . . no C(4) C(3) H(2) 108.9 . . . no C(4) C(3) H(3) 108.9 . . . no H(2) C(3) H(3) 109.5 . . . no N(5) C(4) C(3) 106.8(4) . . . yes N(5) C(4) C(9) 109.7(4) . . . yes N(5) C(4) H(4) 109.2 . . . no C(3) C(4) C(9) 112.8(4) . . . yes C(3) C(4) H(4) 109.2 . . . no C(9) C(4) H(4) 109.2 . . . no Br(6) C(6) N(5) 122.8(4) . . . yes Br(6) C(6) C(7) 128.9(4) . . . yes N(5) C(6) C(7) 108.2(4) . . . yes Br(7) C(7) C(6) 125.1(4) . . . yes Br(7) C(7) C(8) 126.7(4) . . . yes C(6) C(7) C(8) 108.2(4) . . . yes N(5) C(8a) C(1) 120.4(4) . . . yes N(5) C(8a) C(8) 108.7(4) . . . yes C(1) C(8a) C(8) 131.0(4) . . . yes C(7) C(8) C(8a) 106.7(4) . . . yes C(7) C(8) H(5) 126.7 . . . no C(8a) C(8) H(5) 126.7 . . . no C(4) C(9) C(10) 111.5(4) . . . yes C(4) C(9) H(6) 109.0 . . . no C(4) C(9) H(7) 109.0 . . . no C(10) C(9) H(6) 109.0 . . . no C(10) C(9) H(7) 109.0 . . . no H(6) C(9) H(7) 109.5 . . . no O(10) C(10) O(11) 123.6(5) . . . yes O(10) C(10) C(9) 125.3(5) . . . yes O(11) C(10) C(9) 111.0(4) . . . yes O(11) C(12) H(8) 109.5 . . . no O(11) C(12) H(9) 109.5 . . . no O(11) C(12) H(10) 109.5 . . . no H(8) C(12) H(9) 109.5 . . . no H(8) C(12) H(10) 109.5 . . . no H(9) C(12) H(10) 109.5 . . . no #----------------------------------------------------------------------- loop_ _geom_contact_atom_site_label_1 _geom_contact_atom_site_label_2 _geom_contact_distance _geom_contact_site_symmetry_1 _geom_contact_site_symmetry_2 _geom_contact_publ_flag Br(6) O(11) 3.276(4) . 1_455 no Br(7) O(1) 3.522(4) . 1_455 no O(1) N(2) 2.848(5) . 2_666 no O(1) C(12) 3.187(7) . 1_554 no O(1) O(1) 3.598(7) . 2_666 no O(10) C(4) 3.238(6) . 2_567 no O(10) C(3) 3.397(6) . 2_567 no O(11) C(9) 3.509(5) . 2_657 no C(1) C(7) 3.484(7) . 2_566 no C(8a) C(8) 3.490(6) . 2_566 no C(8a) C(8a) 3.570(9) . 2_566 no #----------------------------------------------------------------------- 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_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion _geom_torsion_publ_flag Br(6) C(6) N(5) C(4) . . . . 12.3(6) no Br(6) C(6) N(5) C(8a) . . . . -178.7(3) no Br(6) C(6) C(7) Br(7) . . . . -1.1(7) no Br(6) C(6) C(7) C(8) . . . . 178.3(3) no Br(7) C(7) C(6) N(5) . . . . -178.9(3) no Br(7) C(7) C(8) C(8a) . . . . 179.3(3) no O(1) C(1) N(2) C(3) . . . . 168.0(4) no O(1) C(1) C(8a) N(5) . . . . 174.0(4) no O(1) C(1) C(8a) C(8) . . . . -6.2(8) no O(10) C(10) O(11) C(12) . . . . 0.5(8) no O(10) C(10) C(9) C(4) . . . . 28.3(7) no O(11) C(10) C(9) C(4) . . . . -153.4(4) no N(2) C(1) C(8a) N(5) . . . . -5.3(6) no N(2) C(1) C(8a) C(8) . . . . 174.5(5) no N(2) C(3) C(4) N(5) . . . . -50.4(5) no N(2) C(3) C(4) C(9) . . . . 70.1(5) no N(5) C(4) C(9) C(10) . . . . -165.5(4) no N(5) C(6) C(7) C(8) . . . . 0.5(5) no N(5) C(8a) C(8) C(7) . . . . -0.5(5) no C(1) N(2) C(3) C(4) . . . . 42.6(6) no C(1) C(8a) N(5) C(4) . . . . -9.6(6) no C(1) C(8a) N(5) C(6) . . . . -179.4(4) no C(1) C(8a) C(8) C(7) . . . . 179.7(5) no C(3) N(2) C(1) C(8a) . . . . -12.8(7) no C(3) C(4) N(5) C(6) . . . . -155.3(4) no C(3) C(4) N(5) C(8a) . . . . 37.1(5) no C(3) C(4) C(9) C(10) . . . . 75.6(5) no C(4) N(5) C(6) C(7) . . . . -169.8(4) no C(4) N(5) C(8a) C(8) . . . . 170.6(4) no C(6) N(5) C(4) C(9) . . . . 82.1(5) no C(6) N(5) C(8a) C(8) . . . . 0.8(5) no C(6) C(7) C(8) C(8a) . . . . 0.0(5) no C(7) C(6) N(5) C(8a) . . . . -0.8(5) no C(8a) N(5) C(4) C(9) . . . . -85.4(5) no C(9) C(10) O(11) C(12) . . . . -177.8(5) no #----------------------------------------------------------------------- loop_ _geom_bond_atom_site_label_D _geom_bond_atom_site_label_H _geom_contact_atom_site_label_A _geom_bond_distance_DH _geom_contact_distance_HA _geom_contact_distance_DA _geom_angle_DHA _geom_contact_site_symmetry_A 'N(2)' 'H(1)' 'O(1)' '0.84' '2.05' '2.848(5)' '157.3' '2_666' #===END