Supplementary Material (ESI) for Perkin Transactions This journal is © The Royal Society of Chemistry 2002 data_global # *** Added by check_cif _journal_coden_Cambridge 207 _publ_requested_journal 'Perkin Transactions 1' loop_ _publ_author_name _publ_author_address 'Chris J. Hamilton' ; Division of Biological Chemistry and Molecular Microbiology School of Life Sciences, Carnelley Building University of Dundee Dundee DD1 4HN ; 'Alan H. Fairlamb' ; Division of Biological Chemistry and Molecular Microbiology School of Life Sciences, Wellcome Trust Biocentre University of Dundee Dundee DD1 5EH ; 'Ian M. Eggleston' ; Division of Biological Chemistry and Molecular Microbiology School of Life Sciences, Carnelley Building University of Dundee Dundee DD1 4HN ; _publ_contact_author_name 'Dr. Ian M. Eggleston' _publ_contact_author_address ; Division of Biological Chemistry and Molecular Microbiology School of Life Sciences, Carnelley Building University of Dundee Dundee DD1 4HN ; _publ_contact_author_email i.m.eggleston@dundee.ac.uk _publ_contact_author_fax '01382 345517' _publ_contact_author_phone '01382 344319' _publ_contact_letter ? _publ_requested_category ? #====================================================================== # TITLE AND AUTHOR LIST _publ_section_title ; Regiocontrolled synthesis of the macrocyclic polyamine alkaloid (()-Lunarine, a time-dependent inhibitor of trypanothione reductase ; #===================================================================== data_c:\jcb\data\src292\centro\src292c _database_code_CSD 174011 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C13 H10 Br N O2' _chemical_formula_weight 292.13 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' 'Br' 'Br' -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 7.5226(15) _cell_length_b 9.1659(18) _cell_length_c 9.3917(19) _cell_angle_alpha 84.65(3) _cell_angle_beta 74.43(3) _cell_angle_gamma 66.85(3) _cell_volume 573.5(2) _cell_formula_units_Z 2 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 6708 _cell_measurement_theta_min 2.25 _cell_measurement_theta_max 30.4 _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.692 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 292 _exptl_absorpt_coefficient_mu 3.571 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min 0.4138 _exptl_absorpt_correction_T_max 0.7632 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_measurement_device_type 'KappaCCD' _diffrn_measurement_device '95mm CCD camera on \k-goniostat' _diffrn_detector_area_resol_mean 9 _diffrn_radiation_monochromator 'vertically mounted graphite crystal' _computing_data_collection 'Collect (Nonius BV, 1997-2000)' _diffrn_measurement_method 'CCD' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6708 _diffrn_reflns_av_R_equivalents 0.0659 _diffrn_reflns_av_sigmaI/netI 0.0553 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 2.25 _diffrn_reflns_theta_max 30.44 _reflns_number_total 3033 _reflns_number_gt 2707 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'HKL Denzo and Scalepack (Otwinowski & Minor 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _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^)+(0.0700P)^2^+0.8005P] 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 SHELXL _refine_ls_extinction_coef 0.080(7) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 3033 _refine_ls_number_parameters 155 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0527 _refine_ls_R_factor_gt 0.0452 _refine_ls_wR_factor_ref 0.1231 _refine_ls_wR_factor_gt 0.1156 _refine_ls_goodness_of_fit_ref 1.046 _refine_ls_restrained_S_all 1.046 _refine_ls_shift/su_max 0.001 _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_symetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Br1 Br 0.22201(4) 0.69641(3) 0.28228(3) 0.02427(15) Uani 1 1 d . . . C1 C 1.0347(5) 0.1634(4) 0.0645(3) 0.0227(6) Uani 1 1 d . . . H1A H 1.1055 0.0482 0.0427 0.030 Uiso 1 1 calc R . . H1B H 0.9311 0.2063 0.0085 0.030 Uiso 1 1 calc R . . C2 C 1.1827(5) 0.2450(4) 0.0157(3) 0.0266(6) Uani 1 1 d . . . H2A H 1.2385 0.2326 -0.0927 0.035 Uiso 1 1 calc R . . H2B H 1.1120 0.3599 0.0392 0.035 Uiso 1 1 calc R . . C3 C 1.3510(5) 0.1762(4) 0.0914(3) 0.0217(6) Uani 1 1 d . . . O3 O 1.5152(4) 0.1794(3) 0.0380(3) 0.0317(5) Uani 1 1 d . . . C4 C 1.3040(4) 0.0990(4) 0.2379(3) 0.0202(6) Uani 1 1 d . . . H4A H 1.3910 0.1035 0.2986 0.026 Uiso 1 1 calc R . . H4B H 1.3337 -0.0141 0.2208 0.026 Uiso 1 1 calc R . . C4A C 1.0879(4) 0.1789(3) 0.3218(3) 0.0172(5) Uani 1 1 d . . . H4A1 H 1.0614 0.1230 0.4170 0.022 Uiso 1 1 calc R . . O5 O 1.0524(3) 0.3426(2) 0.3516(2) 0.0190(4) Uani 1 1 d . . . C5A C 0.8642(4) 0.4347(3) 0.3391(3) 0.0169(5) Uani 1 1 d . . . C6 C 0.7601(5) 0.5914(3) 0.3885(3) 0.0198(5) Uani 1 1 d . . . H6 H 0.8178 0.6440 0.4337 0.026 Uiso 1 1 calc R . . C7 C 0.5685(5) 0.6676(4) 0.3689(3) 0.0204(6) Uani 1 1 d . . . H7 H 0.4915 0.7741 0.4024 0.027 Uiso 1 1 calc R . . C8 C 0.4890(4) 0.5886(3) 0.3006(3) 0.0184(5) Uani 1 1 d . . . C9 C 0.5926(4) 0.4339(3) 0.2496(3) 0.0181(5) Uani 1 1 d . . . H9 H 0.5362 0.3820 0.2024 0.024 Uiso 1 1 calc R . . C9A C 0.7827(4) 0.3582(3) 0.2708(3) 0.0159(5) Uani 1 1 d . . . C9B C 0.9344(4) 0.1904(3) 0.2323(3) 0.0169(5) Uani 1 1 d . . . C9C C 0.8416(4) 0.0739(3) 0.2882(4) 0.0217(6) Uani 1 1 d . . . N9B N 0.7686(4) -0.0143(4) 0.3346(4) 0.0328(7) 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 Br1 0.01568(18) 0.0248(2) 0.0281(2) 0.00528(12) -0.00567(12) -0.00443(12) C1 0.0231(14) 0.0263(15) 0.0188(13) -0.0068(11) -0.0072(11) -0.0068(12) C2 0.0281(16) 0.0323(16) 0.0166(13) -0.0002(12) -0.0032(12) -0.0103(13) C3 0.0228(14) 0.0216(14) 0.0210(14) -0.0062(11) -0.0008(11) -0.0104(11) O3 0.0249(12) 0.0377(13) 0.0326(13) -0.0065(10) 0.0035(10) -0.0177(11) C4 0.0159(12) 0.0217(13) 0.0235(14) -0.0015(11) -0.0053(11) -0.0071(11) C4A 0.0185(12) 0.0158(12) 0.0187(13) -0.0013(10) -0.0071(10) -0.0062(10) O5 0.0185(9) 0.0197(10) 0.0209(10) -0.0041(8) -0.0075(8) -0.0067(8) C5A 0.0161(12) 0.0203(13) 0.0151(12) -0.0010(10) -0.0036(10) -0.0076(10) C6 0.0245(14) 0.0191(13) 0.0173(13) -0.0034(10) -0.0060(11) -0.0087(11) C7 0.0236(14) 0.0189(13) 0.0163(13) -0.0012(10) -0.0027(11) -0.0068(11) C8 0.0127(11) 0.0207(13) 0.0198(13) 0.0044(10) -0.0041(10) -0.0051(10) C9 0.0180(13) 0.0161(12) 0.0217(13) 0.0006(10) -0.0064(11) -0.0074(11) C9A 0.0164(12) 0.0147(12) 0.0161(12) -0.0010(9) -0.0042(10) -0.0053(10) C9B 0.0151(12) 0.0160(12) 0.0212(13) -0.0016(10) -0.0071(10) -0.0055(10) C9C 0.0155(12) 0.0179(13) 0.0326(16) -0.0007(11) -0.0104(11) -0.0041(10) N9B 0.0227(13) 0.0235(13) 0.055(2) 0.0057(13) -0.0142(13) -0.0101(11) _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 Br1 C8 1.906(3) . ? C1 C2 1.525(5) . ? C1 C9B 1.550(4) . ? C2 C3 1.510(5) . ? C3 O3 1.213(4) . ? C3 C4 1.508(4) . ? C4 C4A 1.511(4) . ? C4A O5 1.458(3) . ? C4A C9B 1.569(4) . ? O5 C5A 1.365(3) . ? C5A C9A 1.383(4) . ? C5A C6 1.391(4) . ? C6 C7 1.388(4) . ? C7 C8 1.389(4) . ? C8 C9 1.380(4) . ? C9 C9A 1.383(4) . ? C9A C9B 1.517(4) . ? C9B C9C 1.478(4) . ? C9C N9B 1.141(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 C2 C1 C9B 110.5(2) . . ? C3 C2 C1 111.4(3) . . ? O3 C3 C4 121.5(3) . . ? O3 C3 C2 122.9(3) . . ? C4 C3 C2 115.6(3) . . ? C3 C4 C4A 112.1(2) . . ? O5 C4A C4 107.7(2) . . ? O5 C4A C9B 105.3(2) . . ? C4 C4A C9B 114.0(2) . . ? C5A O5 C4A 107.4(2) . . ? O5 C5A C9A 113.7(2) . . ? O5 C5A C6 124.6(3) . . ? C9A C5A C6 121.8(3) . . ? C7 C6 C5A 117.2(3) . . ? C6 C7 C8 120.2(3) . . ? C9 C8 C7 122.9(3) . . ? C9 C8 Br1 118.7(2) . . ? C7 C8 Br1 118.4(2) . . ? C8 C9 C9A 116.6(3) . . ? C5A C9A C9 121.4(3) . . ? C5A C9A C9B 108.0(2) . . ? C9 C9A C9B 130.7(2) . . ? C9C C9B C9A 110.6(2) . . ? C9C C9B C1 110.3(2) . . ? C9A C9B C1 113.1(2) . . ? C9C C9B C4A 110.0(2) . . ? C9A C9B C4A 101.1(2) . . ? C1 C9B C4A 111.5(2) . . ? N9B C9C C9B 178.4(4) . . ? 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 C9B C1 C2 C3 62.7(3) . . . . ? C1 C2 C3 O3 153.8(3) . . . . ? C1 C2 C3 C4 -24.9(4) . . . . ? O3 C3 C4 C4A 148.6(3) . . . . ? C2 C3 C4 C4A -32.6(4) . . . . ? C3 C4 C4A O5 -61.7(3) . . . . ? C3 C4 C4A C9B 54.7(3) . . . . ? C4 C4A O5 C5A 143.1(2) . . . . ? C9B C4A O5 C5A 21.1(3) . . . . ? C4A O5 C5A C9A -14.2(3) . . . . ? C4A O5 C5A C6 166.1(3) . . . . ? O5 C5A C6 C7 -179.2(3) . . . . ? C9A C5A C6 C7 1.2(4) . . . . ? C5A C6 C7 C8 -0.9(4) . . . . ? C6 C7 C8 C9 0.1(5) . . . . ? C6 C7 C8 Br1 178.0(2) . . . . ? C7 C8 C9 C9A 0.5(4) . . . . ? Br1 C8 C9 C9A -177.4(2) . . . . ? O5 C5A C9A C9 179.7(3) . . . . ? C6 C5A C9A C9 -0.6(4) . . . . ? O5 C5A C9A C9B 0.6(3) . . . . ? C6 C5A C9A C9B -179.7(3) . . . . ? C8 C9 C9A C5A -0.3(4) . . . . ? C8 C9 C9A C9B 178.6(3) . . . . ? C5A C9A C9B C9C 128.4(3) . . . . ? C9 C9A C9B C9C -50.6(4) . . . . ? C5A C9A C9B C1 -107.4(3) . . . . ? C9 C9A C9B C1 73.6(4) . . . . ? C5A C9A C9B C4A 12.0(3) . . . . ? C9 C9A C9B C4A -167.1(3) . . . . ? C2 C1 C9B C9C -162.5(3) . . . . ? C2 C1 C9B C9A 73.1(3) . . . . ? C2 C1 C9B C4A -40.1(3) . . . . ? O5 C4A C9B C9C -136.6(2) . . . . ? C4 C4A C9B C9C 105.7(3) . . . . ? O5 C4A C9B C9A -19.7(3) . . . . ? C4 C4A C9B C9A -137.4(2) . . . . ? O5 C4A C9B C1 100.8(3) . . . . ? C4 C4A C9B C1 -17.0(3) . . . . ? C9A C9B C9C N9B -55(11) . . . . ? C1 C9B C9C N9B 179(100) . . . . ? C4A C9B C9C N9B 56(11) . . . . ? _diffrn_measured_fraction_theta_max 0.872 _diffrn_reflns_theta_full 30.44 _diffrn_measured_fraction_theta_full 0.872 _refine_diff_density_max 1.140 _refine_diff_density_min -1.039 _refine_diff_density_rms 0.139