Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2003 data_global _journal_coden_Cambridge 177 loop_ _publ_author_name 'Colin Gibson' 'Gilles Argouarch' 'Alan R. Kennedy' 'David C. Sherrington' 'Graham Stones' _publ_contact_author_name 'Dr Colin Gibson' _publ_contact_author_address ; Pure & Applied Chemistry University of Strathclyde 295 Cathedral Street Glasgow G1 1XL UNITED KINGDOM ; _publ_contact_author_email C.L.GIBSON@STRATH.AC.UK _publ_requested_journal 'Organic & Biomolecular Chemistry' _publ_section_title ; Bifurcated, Modular Syntheses of Chiral Annulet Triazacyclononanes ; data_sota _database_code_CSD 219446 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C13 H31 Br2 N3' _chemical_formula_weight 389.23 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source Br Br -0.2901 2.4595 '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' 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' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M P212121 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' _cell_length_a 7.5110(2) _cell_length_b 12.0412(5) _cell_length_c 19.5980(7) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1772.47(11) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 3844 _cell_measurement_theta_min 2.68 _cell_measurement_theta_max 27.85 _exptl_crystal_description tabular _exptl_crystal_colour colourless _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.459 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 800 _exptl_absorpt_coefficient_mu 4.565 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; SORTAV - Blessing Acta Cryst A (1995), 51, 33-38. ; _exptl_absorpt_correction_T_min 0.48 _exptl_absorpt_correction_T_max 0.79 _exptl_special_details ; Run at EPSRC Southampton service. ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Nonius rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Enraf Nonius CCD' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 15649 _diffrn_reflns_av_R_equivalents 0.0578 _diffrn_reflns_av_sigmaI/netI 0.0553 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 25 _diffrn_reflns_theta_min 2.68 _diffrn_reflns_theta_max 27.85 _reflns_number_total 3844 _reflns_number_gt 3241 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect & Denzo' _computing_cell_refinement ? _computing_data_reduction ? _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 w=1/[\s^2^(Fo^2^)+(0.0325P)^2^+0.0000P] 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 -0.030(11) _refine_ls_number_reflns 3844 _refine_ls_number_parameters 177 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0526 _refine_ls_R_factor_gt 0.0349 _refine_ls_wR_factor_ref 0.0685 _refine_ls_wR_factor_gt 0.0639 _refine_ls_goodness_of_fit_ref 1.039 _refine_ls_restrained_S_all 1.039 _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_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Br1 Br 0.61808(5) 0.33952(3) 0.174186(18) 0.02659(10) Uani 1 d . . . Br2 Br 1.08781(4) 0.25333(3) 0.364279(19) 0.03030(10) Uani 1 d . . . N1 N 0.1503(4) 0.5148(2) 0.06826(14) 0.0213(6) Uani 1 d . . . N2 N 0.0886(4) 0.5363(2) 0.21309(15) 0.0218(6) Uani 1 d . . . H2N H 0.045(5) 0.576(3) 0.1804(19) 0.020(9) Uiso 1 d . . . N3 N 0.3455(4) 0.6772(2) 0.12775(14) 0.0175(6) Uani 1 d . . . H3N H 0.239(5) 0.673(3) 0.1222(18) 0.022(10) Uiso 1 d . . . C1 C 0.0713(5) 0.4233(3) 0.10657(18) 0.0285(9) Uani 1 d . . . H1A H 0.1075 0.3520 0.0856 0.034 Uiso 1 calc R . . H1B H -0.0600 0.4286 0.1039 0.034 Uiso 1 calc R . . C2 C 0.1282(5) 0.4243(3) 0.18115(17) 0.0262(8) Uani 1 d . . . H2A H 0.0637 0.3654 0.2063 0.031 Uiso 1 calc R . . H2B H 0.2573 0.4087 0.1844 0.031 Uiso 1 calc R . . C3 C 0.2479(5) 0.5971(3) 0.24320(16) 0.0203(8) Uani 1 d . . . H3 H 0.2067 0.6715 0.2594 0.024 Uiso 1 calc R . . C4 C 0.3960(5) 0.6150(3) 0.19172(15) 0.0194(7) Uani 1 d . . . H4A H 0.4936 0.6560 0.2145 0.023 Uiso 1 calc R . . H4B H 0.4434 0.5415 0.1783 0.023 Uiso 1 calc R . . C5 C 0.4221(5) 0.6236(3) 0.06499(16) 0.0206(7) Uani 1 d . . . H5A H 0.5531 0.6185 0.0695 0.025 Uiso 1 calc R . . H5B H 0.3952 0.6701 0.0246 0.025 Uiso 1 calc R . . C6 C 0.3441(4) 0.5067(3) 0.05464(17) 0.0185(7) Uani 1 d . . . H6 H 0.3969 0.4572 0.0903 0.022 Uiso 1 calc R . . C7 C 0.0443(5) 0.5526(4) 0.0105(2) 0.0339(10) Uani 1 d . . . H7A H 0.0334 0.4924 -0.0229 0.051 Uiso 1 calc R . . H7B H 0.1026 0.6165 -0.0108 0.051 Uiso 1 calc R . . H7C H -0.0744 0.5742 0.0264 0.051 Uiso 1 calc R . . C8 C -0.0626(5) 0.5291(3) 0.26335(19) 0.0323(9) Uani 1 d . . . H8A H -0.1693 0.5013 0.2402 0.049 Uiso 1 calc R . . H8B H -0.0867 0.6030 0.2821 0.049 Uiso 1 calc R . . H8C H -0.0303 0.4784 0.3004 0.049 Uiso 1 calc R . . C9 C 0.3265(5) 0.5354(3) 0.30369(18) 0.0311(9) Uani 1 d . . . H9A H 0.3800 0.4658 0.2880 0.047 Uiso 1 calc R . . H9B H 0.2321 0.5192 0.3368 0.047 Uiso 1 calc R . . H9C H 0.4179 0.5816 0.3253 0.047 Uiso 1 calc R . . C10 C 0.3927(5) 0.7971(3) 0.13269(18) 0.0242(7) Uani 1 d . . . H10A H 0.5225 0.8052 0.1327 0.036 Uiso 1 calc R . . H10B H 0.3441 0.8279 0.1750 0.036 Uiso 1 calc R . . H10C H 0.3426 0.8371 0.0936 0.036 Uiso 1 calc R . . C11 C 0.5985(5) 0.4608(3) -0.02468(18) 0.0308(8) Uani 1 d . . . H11A H 0.6547 0.4247 0.0146 0.046 Uiso 1 calc R . . H11B H 0.6401 0.5378 -0.0280 0.046 Uiso 1 calc R . . H11C H 0.6303 0.4207 -0.0664 0.046 Uiso 1 calc R . . C12 C 0.3971(5) 0.4596(3) -0.01575(16) 0.0227(7) Uani 1 d . . . H12 H 0.3428 0.5073 -0.0520 0.027 Uiso 1 calc R . . C13 C 0.3282(5) 0.3413(3) -0.02447(19) 0.0312(8) Uani 1 d . . . H13A H 0.3611 0.3137 -0.0698 0.047 Uiso 1 calc R . . H13B H 0.1983 0.3408 -0.0198 0.047 Uiso 1 calc R . . H13C H 0.3810 0.2935 0.0106 0.047 Uiso 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 Br1 0.03018(18) 0.02185(18) 0.02774(18) 0.00496(16) 0.00000(16) 0.00705(16) Br2 0.02608(17) 0.0241(2) 0.0407(2) 0.00165(18) -0.00031(16) -0.00745(17) N1 0.0157(14) 0.0242(16) 0.0238(15) -0.0040(12) -0.0026(12) -0.0019(12) N2 0.0268(16) 0.0165(15) 0.0221(15) -0.0002(12) 0.0010(14) -0.0016(14) N3 0.0203(16) 0.0126(15) 0.0196(15) -0.0001(12) -0.0005(12) 0.0023(12) C1 0.0228(19) 0.032(2) 0.031(2) -0.0091(16) 0.0040(16) -0.0080(17) C2 0.032(2) 0.0157(17) 0.0305(19) -0.0041(15) 0.0079(18) -0.0040(15) C3 0.0294(18) 0.0147(19) 0.0169(17) -0.0007(14) -0.0006(14) -0.0011(15) C4 0.0240(16) 0.0147(16) 0.0193(17) 0.0019(12) -0.0031(14) -0.0021(15) C5 0.0238(17) 0.0199(18) 0.0180(17) 0.0004(13) 0.0012(14) -0.0002(15) C6 0.0152(16) 0.0200(19) 0.0205(17) 0.0016(14) 0.0009(13) -0.0020(14) C7 0.030(2) 0.036(2) 0.036(2) -0.0082(19) -0.0132(17) 0.0056(17) C8 0.037(2) 0.033(2) 0.027(2) -0.0024(17) 0.0118(17) -0.0035(18) C9 0.042(2) 0.030(2) 0.0205(19) 0.0033(16) -0.0005(16) -0.0009(18) C10 0.0317(18) 0.0129(16) 0.0281(18) 0.0023(14) -0.0030(19) -0.0057(16) C11 0.0263(19) 0.039(2) 0.0273(19) -0.0053(16) 0.0062(17) -0.0014(19) C12 0.0253(18) 0.0231(18) 0.0196(17) -0.0024(14) -0.0033(16) 0.0002(17) C13 0.035(2) 0.029(2) 0.0295(19) -0.0120(18) -0.0007(15) 0.0009(18) _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 N1 C7 1.456(4) . ? N1 C1 1.459(4) . ? N1 C6 1.483(4) . ? N2 C8 1.506(5) . ? N2 C2 1.516(4) . ? N2 C3 1.522(4) . ? N2 H2N 0.87(4) . ? N3 C10 1.490(4) . ? N3 C5 1.503(4) . ? N3 C4 1.509(4) . ? N3 H3N 0.81(4) . ? C1 C2 1.523(5) . ? C1 H1A 0.9900 . ? C1 H1B 0.9900 . ? C2 H2A 0.9900 . ? C2 H2B 0.9900 . ? C3 C4 1.517(5) . ? C3 C9 1.518(5) . ? C3 H3 1.0000 . ? C4 H4A 0.9900 . ? C4 H4B 0.9900 . ? C5 C6 1.538(5) . ? C5 H5A 0.9900 . ? C5 H5B 0.9900 . ? C6 C12 1.544(5) . ? C6 H6 1.0000 . ? C7 H7A 0.9800 . ? C7 H7B 0.9800 . ? C7 H7C 0.9800 . ? C8 H8A 0.9800 . ? C8 H8B 0.9800 . ? C8 H8C 0.9800 . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C10 H10A 0.9800 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? C11 C12 1.523(5) . ? C11 H11A 0.9800 . ? C11 H11B 0.9800 . ? C11 H11C 0.9800 . ? C12 C13 1.525(5) . ? C12 H12 1.0000 . ? C13 H13A 0.9800 . ? C13 H13B 0.9800 . ? C13 H13C 0.9800 . ? 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 C7 N1 C1 114.4(3) . . ? C7 N1 C6 114.7(3) . . ? C1 N1 C6 116.2(3) . . ? C8 N2 C2 111.6(3) . . ? C8 N2 C3 111.5(3) . . ? C2 N2 C3 115.7(3) . . ? C8 N2 H2N 103(2) . . ? C2 N2 H2N 105(2) . . ? C3 N2 H2N 108(2) . . ? C10 N3 C5 112.2(3) . . ? C10 N3 C4 111.5(3) . . ? C5 N3 C4 111.8(2) . . ? C10 N3 H3N 108(3) . . ? C5 N3 H3N 104(3) . . ? C4 N3 H3N 109(3) . . ? N1 C1 C2 111.9(3) . . ? N1 C1 H1A 109.2 . . ? C2 C1 H1A 109.2 . . ? N1 C1 H1B 109.2 . . ? C2 C1 H1B 109.2 . . ? H1A C1 H1B 107.9 . . ? N2 C2 C1 110.4(3) . . ? N2 C2 H2A 109.6 . . ? C1 C2 H2A 109.6 . . ? N2 C2 H2B 109.6 . . ? C1 C2 H2B 109.6 . . ? H2A C2 H2B 108.1 . . ? C4 C3 C9 107.7(3) . . ? C4 C3 N2 112.8(3) . . ? C9 C3 N2 111.9(3) . . ? C4 C3 H3 108.1 . . ? C9 C3 H3 108.1 . . ? N2 C3 H3 108.1 . . ? N3 C4 C3 116.0(3) . . ? N3 C4 H4A 108.3 . . ? C3 C4 H4A 108.3 . . ? N3 C4 H4B 108.3 . . ? C3 C4 H4B 108.3 . . ? H4A C4 H4B 107.4 . . ? N3 C5 C6 110.7(3) . . ? N3 C5 H5A 109.5 . . ? C6 C5 H5A 109.5 . . ? N3 C5 H5B 109.5 . . ? C6 C5 H5B 109.5 . . ? H5A C5 H5B 108.1 . . ? N1 C6 C5 106.9(3) . . ? N1 C6 C12 116.0(3) . . ? C5 C6 C12 110.9(3) . . ? N1 C6 H6 107.6 . . ? C5 C6 H6 107.6 . . ? C12 C6 H6 107.6 . . ? N1 C7 H7A 109.5 . . ? N1 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? N1 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? N2 C8 H8A 109.5 . . ? N2 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? N2 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C3 C9 H9A 109.5 . . ? C3 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C3 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? N3 C10 H10A 109.5 . . ? N3 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? N3 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? C12 C11 H11A 109.5 . . ? C12 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C12 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C11 C12 C13 109.4(3) . . ? C11 C12 C6 110.8(3) . . ? C13 C12 C6 110.9(3) . . ? C11 C12 H12 108.6 . . ? C13 C12 H12 108.6 . . ? C6 C12 H12 108.6 . . ? C12 C13 H13A 109.5 . . ? C12 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C12 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? 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 C7 N1 C1 C2 -151.5(3) . . . . ? C6 N1 C1 C2 71.3(4) . . . . ? C8 N2 C2 C1 109.3(3) . . . . ? C3 N2 C2 C1 -121.8(3) . . . . ? N1 C1 C2 N2 54.1(4) . . . . ? C8 N2 C3 C4 -174.7(3) . . . . ? C2 N2 C3 C4 56.4(4) . . . . ? C8 N2 C3 C9 63.7(4) . . . . ? C2 N2 C3 C9 -65.2(4) . . . . ? C10 N3 C4 C3 97.4(3) . . . . ? C5 N3 C4 C3 -136.1(3) . . . . ? C9 C3 C4 N3 -179.0(3) . . . . ? N2 C3 C4 N3 57.0(4) . . . . ? C10 N3 C5 C6 -169.8(3) . . . . ? C4 N3 C5 C6 64.1(3) . . . . ? C7 N1 C6 C5 83.6(3) . . . . ? C1 N1 C6 C5 -139.2(3) . . . . ? C7 N1 C6 C12 -40.5(4) . . . . ? C1 N1 C6 C12 96.6(3) . . . . ? N3 C5 C6 N1 43.0(3) . . . . ? N3 C5 C6 C12 170.3(3) . . . . ? N1 C6 C12 C11 177.3(3) . . . . ? C5 C6 C12 C11 55.2(4) . . . . ? N1 C6 C12 C13 -61.0(4) . . . . ? C5 C6 C12 C13 176.9(3) . . . . ? _diffrn_measured_fraction_theta_max 0.941 _diffrn_reflns_theta_full 27.85 _diffrn_measured_fraction_theta_full 0.941 _refine_diff_density_max 0.407 _refine_diff_density_min -0.657 _refine_diff_density_rms 0.094