# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2008 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Yoshio Hisaeda' _publ_contact_author_email YHISATCM@MBOX.NC.KYUSHU-U.AC.JP _publ_section_title ; Photophysical and Photosensitizing Properties of Brominated Porphycenes ; loop_ _publ_author_name 'Yoshio Hisaeda' 'Chihaya Adachi' 'Isao Aritome' 'Tatsushi Baba' 'Ayataka Endo' 'Yusuke Iseki' ; H.Shimakoshi ; # Attachment 'Monobromoprphycene__2_rev.cif' data_Monobromoporphycene _database_code_depnum_ccdc_archive 'CCDC 677018' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common 3-bromo-2,7,12,17-tetra-n-propylporphycene _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C32 H37 Br N4' _chemical_formula_weight 557.57 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' 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 P1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' _cell_length_a 5.0446(6) _cell_length_b 11.5130(14) _cell_length_c 11.8712(14) _cell_angle_alpha 101.158(3) _cell_angle_beta 93.095(3) _cell_angle_gamma 93.654(2) _cell_volume 673.50(14) _cell_formula_units_Z 1 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 1850 _cell_measurement_theta_min 2.76 _cell_measurement_theta_max 29.54 _exptl_crystal_description prism _exptl_crystal_colour violet _exptl_crystal_size_max 0.29 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 1.375 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 292 _exptl_absorpt_coefficient_mu 1.554 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.6613 _exptl_absorpt_correction_T_max 0.8601 _exptl_absorpt_process_details 'SADABS; Sheldrick, 1996' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(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 area detector' _diffrn_measurement_method '\p and \w scans' _diffrn_detector_area_resol_mean 8.366 _diffrn_standards_number 64 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 594 _diffrn_standards_decay_% 0 _diffrn_reflns_number 5068 _diffrn_reflns_av_R_equivalents 0.0229 _diffrn_reflns_av_sigmaI/netI 0.0578 _diffrn_reflns_limit_h_min -6 _diffrn_reflns_limit_h_max 6 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -9 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 1.75 _diffrn_reflns_theta_max 28.28 _reflns_number_total 4014 _reflns_number_gt 3636 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker, 2001)' _computing_cell_refinement 'SMART (Bruker, 2001)' _computing_data_reduction 'SAINT (Bruker, 2001)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL (Bruker, 2001)' _computing_publication_material 'SHELXTL (Bruker, 2001)' _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. Disorder was found for Br atom. The total occupancy at each atom site was kept as 1 during the refinement. The largest peak on the difference Fourier map corresponds to a disorder in the C3 bromine group. ; _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^)+(0.1326P)^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 constr _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 0.293(14) _refine_ls_number_reflns 4014 _refine_ls_number_parameters 356 _refine_ls_number_restraints 3 _refine_ls_R_factor_all 0.0730 _refine_ls_R_factor_gt 0.0628 _refine_ls_wR_factor_ref 0.1816 _refine_ls_wR_factor_gt 0.1636 _refine_ls_goodness_of_fit_ref 1.074 _refine_ls_restrained_S_all 1.074 _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 Br1A Br -0.29425(11) 0.48188(7) 1.09494(7) 0.0259(2) Uani 0.80 1 d P A 1 Br1B Br 0.038(2) 0.3461(8) 1.0713(8) 0.048(2) Uani 0.10 1 d P A 2 Br1C Br 0.4265(11) 0.5116(5) 0.2370(5) 0.0152(10) Uani 0.10 1 d P A 3 C1 C -0.3646(12) 0.6325(5) 0.8147(6) 0.0162(12) Uani 1 1 d . A . C2 C -0.4491(10) 0.6188(5) 0.9285(5) 0.0159(11) Uani 1 1 d . A . C3 C -0.2965(11) 0.5314(5) 0.9557(5) 0.0160(11) Uani 1 1 d . . . H3 H -0.2986 0.5018 1.0249 0.019 Uiso 0.20 1 calc PR A 1 C4 C -0.1338(11) 0.4928(5) 0.8619(5) 0.0155(11) Uani 1 1 d . A . C5 C 0.0488(10) 0.4025(5) 0.8475(5) 0.0145(10) Uani 1 1 d . . . C6 C 0.1213(11) 0.3236(5) 0.9210(5) 0.0174(11) Uani 1 1 d . A . H6 H 0.0527 0.3195 0.9932 0.021 Uiso 0.90 1 calc PR B 2 C7 C 0.3082(11) 0.2550(5) 0.8681(5) 0.0181(11) Uani 1 1 d . . . C8 C 0.3534(12) 0.2916(6) 0.7603(6) 0.0161(13) Uani 1 1 d . A . C9 C 0.5344(12) 0.2495(5) 0.6804(6) 0.0189(11) Uani 1 1 d . . . H9 H 0.6349 0.1886 0.7007 0.023 Uiso 1 1 calc R A . C10 C 0.5938(12) 0.2794(5) 0.5788(6) 0.0176(12) Uani 1 1 d . A . H10 H 0.7317 0.2373 0.5421 0.021 Uiso 1 1 calc R . . C11 C 0.4864(11) 0.3627(5) 0.5173(5) 0.0157(11) Uani 1 1 d . . . C12 C 0.5665(13) 0.3818(6) 0.4063(7) 0.0192(14) Uani 1 1 d . A . C13 C 0.4242(11) 0.4704(5) 0.3808(6) 0.0192(11) Uani 1 1 d . . . H13 H 0.4336 0.5042 0.3140 0.023 Uiso 0.90 1 calc PR A 3 C14 C 0.2557(10) 0.5037(5) 0.4743(5) 0.0137(10) Uani 1 1 d . A . C15 C 0.0746(11) 0.5908(5) 0.4867(5) 0.0162(11) Uani 1 1 d . . . C16 C 0.0038(13) 0.6715(5) 0.4146(6) 0.0170(13) Uani 1 1 d . A . H16 H 0.0745 0.6760 0.3428 0.020 Uiso 1 1 calc R . . C17 C -0.1827(11) 0.7412(5) 0.4661(5) 0.0167(11) Uani 1 1 d . . . C18 C -0.2332(11) 0.7039(5) 0.5713(5) 0.0152(11) Uani 1 1 d . A . C19 C -0.4171(11) 0.7459(5) 0.6516(5) 0.0173(11) Uani 1 1 d . . . H19 H -0.5196 0.8061 0.6314 0.021 Uiso 1 1 calc R A . C20 C -0.4746(11) 0.7147(5) 0.7551(5) 0.0165(10) Uani 1 1 d . A . H20 H -0.6127 0.7560 0.7925 0.020 Uiso 1 1 calc R . . C21 C -0.6396(12) 0.6863(5) 0.9997(5) 0.0198(11) Uani 1 1 d . . . H21A H -0.7194 0.6355 1.0494 0.024 Uiso 1 1 calc R A . H21B H -0.7849 0.7056 0.9486 0.024 Uiso 1 1 calc R . . C22 C -0.5145(11) 0.8013(5) 1.0756(6) 0.0218(12) Uani 1 1 d . A . H22A H -0.3705 0.7824 1.1276 0.026 Uiso 1 1 calc R . . H22B H -0.4343 0.8524 1.0264 0.026 Uiso 1 1 calc R . . C23 C -0.7173(14) 0.8686(6) 1.1470(6) 0.0326(15) Uani 1 1 d . . . H23A H -0.8485 0.8959 1.0960 0.049 Uiso 1 1 calc R A . H23B H -0.6265 0.9372 1.2001 0.049 Uiso 1 1 calc R . . H23C H -0.8078 0.8162 1.1911 0.049 Uiso 1 1 calc R . . C24 C 0.4409(12) 0.1573(5) 0.9108(6) 0.0216(12) Uani 1 1 d . A . H24A H 0.3965 0.1592 0.9913 0.026 Uiso 1 1 calc R . . H24B H 0.6361 0.1734 0.9113 0.026 Uiso 1 1 calc R . . C25 C 0.3640(13) 0.0314(5) 0.8403(6) 0.0272(13) Uani 1 1 d . . . H25A H 0.4145 0.0280 0.7603 0.033 Uiso 1 1 calc R A . H25B H 0.4670 -0.0260 0.8733 0.033 Uiso 1 1 calc R . . C26 C 0.0716(14) -0.0056(6) 0.8380(8) 0.0397(18) Uani 1 1 d . A . H26A H 0.0181 0.0010 0.9169 0.060 Uiso 1 1 calc R . . H26B H 0.0377 -0.0881 0.7967 0.060 Uiso 1 1 calc R . . H26C H -0.0310 0.0461 0.7987 0.060 Uiso 1 1 calc R . . C27 C 0.7675(12) 0.3140(6) 0.3354(6) 0.0196(13) Uani 1 1 d . . . H27A H 0.9099 0.2940 0.3875 0.023 Uiso 1 1 calc R A . H27B H 0.8502 0.3650 0.2866 0.023 Uiso 1 1 calc R . . C28 C 0.6394(12) 0.1993(5) 0.2583(6) 0.0241(12) Uani 1 1 d . A . H28A H 0.5568 0.1481 0.3070 0.029 Uiso 1 1 calc R . . H28B H 0.4971 0.2191 0.2061 0.029 Uiso 1 1 calc R . . C29 C 0.8419(13) 0.1322(6) 0.1879(6) 0.0327(16) Uani 1 1 d . . . H29A H 0.9448 0.1865 0.1496 0.049 Uiso 1 1 calc R A . H29B H 0.7500 0.0680 0.1298 0.049 Uiso 1 1 calc R . . H29C H 0.9623 0.0985 0.2385 0.049 Uiso 1 1 calc R . . C30 C -0.3154(11) 0.8386(5) 0.4203(6) 0.0204(12) Uani 1 1 d . A . H30A H -0.5108 0.8225 0.4188 0.025 Uiso 1 1 calc R . . H30B H -0.2682 0.8356 0.3400 0.025 Uiso 1 1 calc R . . C31 C -0.2398(12) 0.9639(5) 0.4896(6) 0.0263(13) Uani 1 1 d . . . H31A H -0.3415 1.0210 0.4558 0.032 Uiso 1 1 calc R A . H31B H -0.2918 0.9680 0.5694 0.032 Uiso 1 1 calc R . . C32 C 0.0520(13) 1.0002(6) 0.4926(8) 0.0364(17) Uani 1 1 d . A . H32A H 0.1507 0.9584 0.5439 0.055 Uiso 1 1 calc R . . H32B H 0.0820 1.0860 0.5211 0.055 Uiso 1 1 calc R . . H32C H 0.1137 0.9798 0.4149 0.055 Uiso 1 1 calc R . . N1 N -0.1793(11) 0.5579(4) 0.7787(5) 0.0152(11) Uani 1 1 d . . . H1 H -0.1012 0.5520 0.7135 0.018 Uiso 0.10 1 calc PR A . N2 N 0.1870(9) 0.3803(4) 0.7528(4) 0.0160(9) Uani 1 1 d . A . H2 H 0.1730 0.4171 0.6946 0.019 Uiso 0.90 1 calc PR . . N3 N 0.2977(9) 0.4382(4) 0.5545(4) 0.0165(9) Uani 1 1 d . A . H3A H 0.2182 0.4430 0.6193 0.020 Uiso 0.10 1 calc PR . . N4 N -0.0717(9) 0.6149(4) 0.5810(4) 0.0140(9) Uani 1 1 d . A . H4 H -0.0631 0.5784 0.6395 0.017 Uiso 0.90 1 calc PR . . 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 Br1A 0.0346(4) 0.0280(4) 0.0188(3) 0.0091(3) 0.0078(3) 0.0110(3) Br1B 0.068(5) 0.050(5) 0.032(4) 0.017(4) 0.010(4) 0.010(4) Br1C 0.021(2) 0.018(2) 0.009(2) 0.0053(19) 0.0038(19) 0.0075(19) C1 0.020(3) 0.011(3) 0.018(3) 0.003(2) 0.005(2) 0.001(2) C2 0.017(2) 0.016(3) 0.015(3) 0.003(2) 0.003(2) -0.002(2) C3 0.021(3) 0.015(3) 0.013(3) 0.003(2) 0.005(2) 0.000(2) C4 0.019(3) 0.013(2) 0.014(3) 0.002(2) -0.002(2) 0.004(2) C5 0.018(2) 0.010(2) 0.016(3) 0.003(2) 0.002(2) 0.0027(19) C6 0.022(3) 0.015(3) 0.016(3) 0.005(2) 0.002(2) 0.003(2) C7 0.023(3) 0.012(2) 0.022(3) 0.010(2) 0.001(2) 0.004(2) C8 0.016(3) 0.014(3) 0.019(3) 0.003(2) 0.002(2) 0.003(2) C9 0.027(3) 0.009(2) 0.021(3) 0.006(2) -0.005(2) 0.001(2) C10 0.018(3) 0.013(3) 0.022(3) 0.002(2) 0.004(2) 0.005(2) C11 0.020(2) 0.011(2) 0.015(3) 0.000(2) 0.002(2) 0.0029(19) C12 0.016(3) 0.023(3) 0.017(3) -0.001(3) 0.000(2) 0.002(2) C13 0.020(3) 0.017(3) 0.021(3) 0.002(2) 0.006(2) 0.002(2) C14 0.014(2) 0.013(2) 0.015(3) 0.003(2) 0.002(2) 0.0014(19) C15 0.019(3) 0.013(3) 0.017(3) 0.004(2) -0.002(2) 0.001(2) C16 0.024(3) 0.014(3) 0.015(3) 0.008(2) 0.000(2) 0.002(2) C17 0.016(2) 0.015(3) 0.019(3) 0.003(2) 0.003(2) 0.005(2) C18 0.018(3) 0.014(3) 0.014(3) 0.005(2) -0.002(2) 0.001(2) C19 0.020(3) 0.012(2) 0.021(3) 0.004(2) 0.004(2) 0.008(2) C20 0.019(2) 0.012(2) 0.019(3) 0.002(2) 0.006(2) 0.0051(19) C21 0.024(3) 0.018(3) 0.016(3) 0.001(2) 0.001(2) 0.001(2) C22 0.018(3) 0.019(3) 0.026(3) -0.004(2) 0.003(2) 0.006(2) C23 0.031(3) 0.031(3) 0.033(4) -0.006(3) 0.010(3) 0.014(3) C24 0.022(3) 0.022(3) 0.024(3) 0.011(2) 0.003(2) 0.007(2) C25 0.033(3) 0.013(3) 0.036(4) 0.005(3) 0.001(3) 0.008(2) C26 0.033(4) 0.027(3) 0.060(5) 0.009(3) -0.003(3) 0.007(3) C27 0.019(3) 0.018(3) 0.021(3) -0.001(3) 0.007(2) 0.006(2) C28 0.025(3) 0.022(3) 0.023(3) -0.003(2) 0.000(2) 0.007(2) C29 0.031(3) 0.025(3) 0.037(4) -0.010(3) 0.009(3) 0.010(3) C30 0.024(3) 0.015(3) 0.025(3) 0.009(2) -0.001(2) 0.007(2) C31 0.026(3) 0.021(3) 0.035(4) 0.011(3) 0.003(3) 0.009(2) C32 0.029(3) 0.022(3) 0.056(5) 0.004(3) -0.002(3) 0.004(3) N1 0.022(3) 0.011(2) 0.015(3) 0.0055(19) 0.006(2) 0.0024(19) N2 0.018(2) 0.013(2) 0.019(2) 0.0064(18) 0.0036(18) 0.0049(17) N3 0.022(2) 0.011(2) 0.017(2) 0.0034(18) 0.0028(19) 0.0037(17) N4 0.020(2) 0.0076(19) 0.015(2) 0.0040(17) 0.0006(18) 0.0047(17) _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 Br1A C3 1.850(5) . ? Br1B C6 1.829(11) . ? Br1C C13 1.858(9) . ? C1 N1 1.341(9) . ? C1 C20 1.410(8) . ? C1 C2 1.472(8) . ? C2 C3 1.380(8) . ? C2 C21 1.473(8) . ? C3 C4 1.437(8) . ? C3 H3 0.9500 . ? C4 N1 1.369(8) . ? C4 C5 1.424(8) . ? C5 N2 1.346(7) . ? C5 C6 1.427(7) . ? C6 C7 1.369(8) . ? C6 H6 0.9500 . ? C7 C8 1.448(9) . ? C7 C24 1.500(7) . ? C8 N2 1.375(8) . ? C8 C9 1.393(10) . ? C9 C10 1.361(9) . ? C9 H9 0.9500 . ? C10 C11 1.428(8) . ? C10 H10 0.9500 . ? C11 N3 1.364(7) . ? C11 C12 1.452(10) . ? C12 C13 1.355(10) . ? C12 C27 1.512(10) . ? C13 C14 1.443(8) . ? C13 H13 0.9500 . ? C14 N3 1.341(7) . ? C14 C15 1.391(8) . ? C15 N4 1.367(8) . ? C15 C16 1.429(8) . ? C16 C17 1.368(9) . ? C16 H16 0.9500 . ? C17 C18 1.427(8) . ? C17 C30 1.514(7) . ? C18 N4 1.367(7) . ? C18 C19 1.406(8) . ? C19 C20 1.385(8) . ? C19 H19 0.9500 . ? C20 H20 0.9500 . ? C21 C22 1.527(8) . ? C21 H21A 0.9900 . ? C21 H21B 0.9900 . ? C22 C23 1.519(8) . ? C22 H22A 0.9900 . ? C22 H22B 0.9900 . ? C23 H23A 0.9800 . ? C23 H23B 0.9800 . ? C23 H23C 0.9800 . ? C24 C25 1.542(9) . ? C24 H24A 0.9900 . ? C24 H24B 0.9900 . ? C25 C26 1.506(9) . ? C25 H25A 0.9900 . ? C25 H25B 0.9900 . ? C26 H26A 0.9800 . ? C26 H26B 0.9800 . ? C26 H26C 0.9800 . ? C27 C28 1.536(8) . ? C27 H27A 0.9900 . ? C27 H27B 0.9900 . ? C28 C29 1.511(9) . ? C28 H28A 0.9900 . ? C28 H28B 0.9900 . ? C29 H29A 0.9800 . ? C29 H29B 0.9800 . ? C29 H29C 0.9800 . ? C30 C31 1.530(9) . ? C30 H30A 0.9900 . ? C30 H30B 0.9900 . ? C31 C32 1.501(9) . ? C31 H31A 0.9900 . ? C31 H31B 0.9900 . ? C32 H32A 0.9800 . ? C32 H32B 0.9800 . ? C32 H32C 0.9800 . ? N1 H1 0.8800 . ? N2 H2 0.8800 . ? N3 H3A 0.8800 . ? N4 H4 0.8800 . ? 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 N1 C1 C20 126.8(6) . . ? N1 C1 C2 111.4(5) . . ? C20 C1 C2 121.8(5) . . ? C3 C2 C1 103.4(5) . . ? C3 C2 C21 128.0(5) . . ? C1 C2 C21 128.6(5) . . ? C2 C3 C4 108.8(5) . . ? C2 C3 Br1A 124.1(4) . . ? C4 C3 Br1A 127.0(4) . . ? C2 C3 H3 125.6 . . ? C4 C3 H3 125.6 . . ? Br1A C3 H3 3.1 . . ? N1 C4 C5 121.1(6) . . ? N1 C4 C3 108.9(5) . . ? C5 C4 C3 129.9(5) . . ? N2 C5 C4 121.1(5) . . ? N2 C5 C6 108.6(5) . . ? C4 C5 C6 130.3(5) . . ? C7 C6 C5 107.2(5) . . ? C7 C6 Br1B 128.5(5) . . ? C5 C6 Br1B 122.3(5) . . ? C7 C6 H6 126.4 . . ? C5 C6 H6 126.4 . . ? Br1B C6 H6 12.8 . . ? C6 C7 C8 107.6(5) . . ? C6 C7 C24 127.1(5) . . ? C8 C7 C24 125.2(6) . . ? N2 C8 C9 125.9(6) . . ? N2 C8 C7 106.5(5) . . ? C9 C8 C7 127.6(6) . . ? C10 C9 C8 131.8(6) . . ? C10 C9 H9 114.1 . . ? C8 C9 H9 114.1 . . ? C9 C10 C11 131.7(6) . . ? C9 C10 H10 114.2 . . ? C11 C10 H10 114.2 . . ? N3 C11 C10 125.5(5) . . ? N3 C11 C12 109.4(5) . . ? C10 C11 C12 125.0(6) . . ? C13 C12 C11 106.1(6) . . ? C13 C12 C27 128.2(7) . . ? C11 C12 C27 125.7(6) . . ? C12 C13 C14 106.9(6) . . ? C12 C13 Br1C 121.4(6) . . ? C14 C13 Br1C 130.8(5) . . ? C12 C13 H13 126.5 . . ? C14 C13 H13 126.5 . . ? Br1C C13 H13 9.3 . . ? N3 C14 C15 121.9(5) . . ? N3 C14 C13 110.1(5) . . ? C15 C14 C13 128.0(5) . . ? N4 C15 C14 122.3(5) . . ? N4 C15 C16 106.5(5) . . ? C14 C15 C16 131.2(6) . . ? C17 C16 C15 108.6(6) . . ? C17 C16 H16 125.7 . . ? C15 C16 H16 125.7 . . ? C16 C17 C18 107.2(5) . . ? C16 C17 C30 126.9(6) . . ? C18 C17 C30 125.9(5) . . ? N4 C18 C19 124.4(5) . . ? N4 C18 C17 107.4(5) . . ? C19 C18 C17 128.1(5) . . ? C20 C19 C18 131.1(5) . . ? C20 C19 H19 114.4 . . ? C18 C19 H19 114.4 . . ? C19 C20 C1 131.4(5) . . ? C19 C20 H20 114.3 . . ? C1 C20 H20 114.3 . . ? C2 C21 C22 113.6(5) . . ? C2 C21 H21A 108.9 . . ? C22 C21 H21A 108.9 . . ? C2 C21 H21B 108.9 . . ? C22 C21 H21B 108.9 . . ? H21A C21 H21B 107.7 . . ? C23 C22 C21 112.0(5) . . ? C23 C22 H22A 109.2 . . ? C21 C22 H22A 109.2 . . ? C23 C22 H22B 109.2 . . ? C21 C22 H22B 109.2 . . ? H22A C22 H22B 107.9 . . ? C22 C23 H23A 109.5 . . ? C22 C23 H23B 109.5 . . ? H23A C23 H23B 109.5 . . ? C22 C23 H23C 109.5 . . ? H23A C23 H23C 109.5 . . ? H23B C23 H23C 109.5 . . ? C7 C24 C25 115.1(5) . . ? C7 C24 H24A 108.5 . . ? C25 C24 H24A 108.5 . . ? C7 C24 H24B 108.5 . . ? C25 C24 H24B 108.5 . . ? H24A C24 H24B 107.5 . . ? C26 C25 C24 113.4(6) . . ? C26 C25 H25A 108.9 . . ? C24 C25 H25A 108.9 . . ? C26 C25 H25B 108.9 . . ? C24 C25 H25B 108.9 . . ? H25A C25 H25B 107.7 . . ? C25 C26 H26A 109.5 . . ? C25 C26 H26B 109.5 . . ? H26A C26 H26B 109.5 . . ? C25 C26 H26C 109.5 . . ? H26A C26 H26C 109.5 . . ? H26B C26 H26C 109.5 . . ? C12 C27 C28 111.9(5) . . ? C12 C27 H27A 109.2 . . ? C28 C27 H27A 109.2 . . ? C12 C27 H27B 109.2 . . ? C28 C27 H27B 109.2 . . ? H27A C27 H27B 107.9 . . ? C29 C28 C27 111.5(5) . . ? C29 C28 H28A 109.3 . . ? C27 C28 H28A 109.3 . . ? C29 C28 H28B 109.3 . . ? C27 C28 H28B 109.3 . . ? H28A C28 H28B 108.0 . . ? C28 C29 H29A 109.5 . . ? C28 C29 H29B 109.5 . . ? H29A C29 H29B 109.5 . . ? C28 C29 H29C 109.5 . . ? H29A C29 H29C 109.5 . . ? H29B C29 H29C 109.5 . . ? C17 C30 C31 114.5(5) . . ? C17 C30 H30A 108.6 . . ? C31 C30 H30A 108.6 . . ? C17 C30 H30B 108.6 . . ? C31 C30 H30B 108.6 . . ? H30A C30 H30B 107.6 . . ? C32 C31 C30 113.2(6) . . ? C32 C31 H31A 108.9 . . ? C30 C31 H31A 108.9 . . ? C32 C31 H31B 108.9 . . ? C30 C31 H31B 108.9 . . ? H31A C31 H31B 107.7 . . ? C31 C32 H32A 109.5 . . ? C31 C32 H32B 109.5 . . ? H32A C32 H32B 109.5 . . ? C31 C32 H32C 109.5 . . ? H32A C32 H32C 109.5 . . ? H32B C32 H32C 109.5 . . ? C1 N1 C4 107.5(6) . . ? C1 N1 H1 126.3 . . ? C4 N1 H1 126.3 . . ? C5 N2 C8 110.1(5) . . ? C5 N2 H2 125.0 . . ? C8 N2 H2 125.0 . . ? C14 N3 C11 107.4(5) . . ? C14 N3 H3A 126.3 . . ? C11 N3 H3A 126.3 . . ? C18 N4 C15 110.3(5) . . ? C18 N4 H4 124.8 . . ? C15 N4 H4 124.8 . . ? _diffrn_measured_fraction_theta_max 0.987 _diffrn_reflns_theta_full 28.28 _diffrn_measured_fraction_theta_full 0.987 _refine_diff_density_max 1.517 _refine_diff_density_min -0.706 _refine_diff_density_rms 0.189 # Attachment 'Dibromoporphycene_3_.cif' data_Dibromoporphycene _database_code_depnum_ccdc_archive 'CCDC 677019' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common H2(Br2TPrPc) _chemical_melting_point ? _chemical_formula_moiety 'C32 H36 Br2 N4' _chemical_formula_sum 'C32 H36 Br2 N4' _chemical_formula_weight 636.47 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' 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 5.2634(3) _cell_length_b 10.5871(6) _cell_length_c 13.0516(8) _cell_angle_alpha 72.8090(10) _cell_angle_beta 83.9900(10) _cell_angle_gamma 81.2080(10) _cell_volume 685.27(7) _cell_formula_units_Z 1 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 3241 _cell_measurement_theta_min 2.95 _cell_measurement_theta_max 30.45 _exptl_crystal_description prism _exptl_crystal_colour purple _exptl_crystal_size_max 0.34 _exptl_crystal_size_mid 0.11 _exptl_crystal_size_min 0.11 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 1.542 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 326 _exptl_absorpt_coefficient_mu 2.987 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.4299 _exptl_absorpt_correction_T_max 0.7347 _exptl_absorpt_process_details 'SADABS; Sheldrick 1996' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(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 area detector' _diffrn_measurement_method '\p and \w scans' _diffrn_detector_area_resol_mean 8.366 _diffrn_standards_number 115 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 294 _diffrn_standards_decay_% 0 _diffrn_reflns_number 5125 _diffrn_reflns_av_R_equivalents 0.0190 _diffrn_reflns_av_sigmaI/netI 0.0385 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 6 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 1.64 _diffrn_reflns_theta_max 28.28 _reflns_number_total 3345 _reflns_number_gt 3027 _reflns_threshold_expression >2\s(I) _computing_data_collection 'SMART (Bruker, 2001)' _computing_cell_refinement SMART _computing_data_reduction 'SAINT (Bruker, 2001)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL (Bruker, 2001)' _computing_publication_material SHELXTL _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^)+(0.0393P)^2^+0.0736P] 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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3345 _refine_ls_number_parameters 174 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0333 _refine_ls_R_factor_gt 0.0298 _refine_ls_wR_factor_ref 0.0747 _refine_ls_wR_factor_gt 0.0734 _refine_ls_goodness_of_fit_ref 1.075 _refine_ls_restrained_S_all 1.075 _refine_ls_shift/su_max 0.002 _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 Br1 Br 0.70029(4) 0.591968(19) 0.879633(14) 0.01805(8) Uani 1 1 d . . . C1 C 1.0997(4) 0.28261(19) 0.62926(15) 0.0148(4) Uani 1 1 d . . . H1 H 1.2403 0.2438 0.6733 0.018 Uiso 1 1 calc R . . C2 C 0.9303(4) 0.37911(18) 0.66501(15) 0.0143(4) Uani 1 1 d . . . C3 C 0.9612(4) 0.41185(19) 0.76351(15) 0.0144(4) Uani 1 1 d . . . C4 C 0.7658(4) 0.51043(18) 0.76839(14) 0.0134(4) Uani 1 1 d . . . C5 C 0.6162(4) 0.53740(18) 0.67490(15) 0.0138(4) Uani 1 1 d . . . C6 C 0.3973(4) 0.63095(18) 0.64393(15) 0.0135(4) Uani 1 1 d . . . C7 C 0.2543(4) 0.72850(18) 0.69082(15) 0.0142(4) Uani 1 1 d . . . H7 H 0.2921 0.7458 0.7546 0.017 Uiso 1 1 calc R . . C8 C 0.0546(4) 0.79241(18) 0.62857(15) 0.0129(3) Uani 1 1 d . . . C9 C 0.0692(4) 0.73457(18) 0.54112(15) 0.0142(4) Uani 1 1 d . . . C10 C -0.1007(4) 0.76703(19) 0.45847(15) 0.0152(4) Uani 1 1 d . . . H10 H -0.2399 0.8342 0.4631 0.018 Uiso 1 1 calc R . . C11 C 1.1604(4) 0.34500(19) 0.84345(15) 0.0163(4) Uani 1 1 d . . . H11A H 1.1742 0.4039 0.8885 0.020 Uiso 1 1 calc R . . H11B H 1.3296 0.3329 0.8042 0.020 Uiso 1 1 calc R . . C12 C 1.0986(4) 0.20800(19) 0.91713(15) 0.0185(4) Uani 1 1 d . . . H12A H 1.0922 0.1479 0.8723 0.022 Uiso 1 1 calc R . . H12B H 1.2396 0.1685 0.9661 0.022 Uiso 1 1 calc R . . C13 C 0.8446(4) 0.2161(2) 0.98383(16) 0.0232(4) Uani 1 1 d . . . H13A H 0.8521 0.2724 1.0308 0.035 Uiso 1 1 calc R . . H13B H 0.8144 0.1264 1.0277 0.035 Uiso 1 1 calc R . . H13C H 0.7039 0.2547 0.9359 0.035 Uiso 1 1 calc R . . C14 C -0.1528(4) 0.90013(19) 0.64677(16) 0.0158(4) Uani 1 1 d . . . H14A H -0.3221 0.8673 0.6546 0.019 Uiso 1 1 calc R . . H14B H -0.1528 0.9785 0.5825 0.019 Uiso 1 1 calc R . . C15 C -0.1217(4) 0.9442(2) 0.74533(16) 0.0180(4) Uani 1 1 d . . . H15A H -0.1123 0.8655 0.8094 0.022 Uiso 1 1 calc R . . H15B H 0.0420 0.9828 0.7359 0.022 Uiso 1 1 calc R . . C16 C -0.3435(4) 1.0468(2) 0.76385(19) 0.0241(5) Uani 1 1 d . . . H16A H -0.3490 1.1263 0.7018 0.036 Uiso 1 1 calc R . . H16B H -0.3186 1.0711 0.8286 0.036 Uiso 1 1 calc R . . H16C H -0.5060 1.0090 0.7731 0.036 Uiso 1 1 calc R . . N1 N 0.7201(3) 0.45524(16) 0.61493(13) 0.0142(3) Uani 1 1 d . . . N2 N 0.2792(3) 0.63931(16) 0.55315(13) 0.0142(3) Uani 1 1 d . . . H2 H 0.3309 0.5905 0.5090 0.017 Uiso 1 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 0.02115(12) 0.02039(12) 0.01368(11) -0.00738(8) -0.00256(7) 0.00014(7) C1 0.0113(8) 0.0159(9) 0.0158(9) -0.0027(7) -0.0031(7) 0.0007(7) C2 0.0136(9) 0.0145(9) 0.0139(9) -0.0019(7) -0.0015(7) -0.0024(7) C3 0.0151(9) 0.0150(9) 0.0127(9) -0.0022(7) -0.0011(7) -0.0042(7) C4 0.0164(9) 0.0137(9) 0.0101(8) -0.0029(7) -0.0009(7) -0.0034(7) C5 0.0150(9) 0.0143(9) 0.0121(9) -0.0030(7) -0.0008(7) -0.0032(7) C6 0.0139(9) 0.0138(9) 0.0124(8) -0.0025(7) -0.0002(7) -0.0038(7) C7 0.0158(9) 0.0131(9) 0.0136(9) -0.0041(7) 0.0009(7) -0.0022(7) C8 0.0146(9) 0.0111(8) 0.0125(8) -0.0025(7) 0.0009(7) -0.0033(7) C9 0.0143(9) 0.0129(9) 0.0146(9) -0.0033(7) 0.0004(7) -0.0016(7) C10 0.0140(9) 0.0128(9) 0.0169(9) -0.0029(7) -0.0014(7) 0.0018(7) C11 0.0146(9) 0.0187(10) 0.0153(9) -0.0042(7) -0.0033(7) -0.0005(7) C12 0.0177(10) 0.0192(10) 0.0151(9) 0.0000(7) -0.0048(7) 0.0011(7) C13 0.0218(11) 0.0268(11) 0.0173(10) 0.0000(8) -0.0014(8) -0.0047(9) C14 0.0138(9) 0.0158(9) 0.0178(9) -0.0061(7) -0.0010(7) 0.0006(7) C15 0.0174(9) 0.0173(9) 0.0205(10) -0.0086(8) -0.0016(8) 0.0007(7) C16 0.0175(10) 0.0253(11) 0.0338(12) -0.0178(9) -0.0002(9) 0.0018(8) N1 0.0139(8) 0.0135(8) 0.0143(8) -0.0035(6) -0.0019(6) 0.0006(6) N2 0.0143(8) 0.0144(8) 0.0136(7) -0.0047(6) -0.0016(6) 0.0007(6) _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 C4 1.8754(19) . ? C1 C10 1.393(3) 2_666 ? C1 C2 1.404(3) . ? C1 H1 0.9500 . ? C2 N1 1.367(2) . ? C2 C3 1.457(3) . ? C3 C4 1.360(3) . ? C3 C11 1.502(2) . ? C4 C5 1.455(2) . ? C5 N1 1.355(2) . ? C5 C6 1.409(3) . ? C6 N2 1.369(2) . ? C6 C7 1.431(3) . ? C7 C8 1.363(3) . ? C7 H7 0.9500 . ? C8 C9 1.437(3) . ? C8 C14 1.508(3) . ? C9 N2 1.366(2) . ? C9 C10 1.404(3) . ? C10 C1 1.393(3) 2_666 ? C10 H10 0.9500 . ? C11 C12 1.545(3) . ? C11 H11A 0.9900 . ? C11 H11B 0.9900 . ? C12 C13 1.523(3) . ? C12 H12A 0.9900 . ? C12 H12B 0.9900 . ? C13 H13A 0.9800 . ? C13 H13B 0.9800 . ? C13 H13C 0.9800 . ? C14 C15 1.524(3) . ? C14 H14A 0.9900 . ? C14 H14B 0.9900 . ? C15 C16 1.519(3) . ? C15 H15A 0.9900 . ? C15 H15B 0.9900 . ? C16 H16A 0.9800 . ? C16 H16B 0.9800 . ? C16 H16C 0.9800 . ? N2 H2 0.8800 . ? 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 C10 C1 C2 132.21(18) 2_666 . ? C10 C1 H1 113.9 2_666 . ? C2 C1 H1 113.9 . . ? N1 C2 C1 126.54(17) . . ? N1 C2 C3 110.57(17) . . ? C1 C2 C3 122.89(17) . . ? C4 C3 C2 105.03(16) . . ? C4 C3 C11 128.43(18) . . ? C2 C3 C11 126.48(18) . . ? C3 C4 C5 108.10(17) . . ? C3 C4 Br1 125.01(14) . . ? C5 C4 Br1 126.87(15) . . ? N1 C5 C6 121.36(17) . . ? N1 C5 C4 109.16(17) . . ? C6 C5 C4 129.48(18) . . ? N2 C6 C5 120.72(18) . . ? N2 C6 C7 106.81(17) . . ? C5 C6 C7 132.46(18) . . ? C8 C7 C6 108.53(17) . . ? C8 C7 H7 125.7 . . ? C6 C7 H7 125.7 . . ? C7 C8 C9 107.13(17) . . ? C7 C8 C14 128.16(17) . . ? C9 C8 C14 124.68(16) . . ? N2 C9 C10 125.39(18) . . ? N2 C9 C8 107.46(16) . . ? C10 C9 C8 127.15(18) . . ? C1 C10 C9 130.88(18) 2_666 . ? C1 C10 H10 114.6 2_666 . ? C9 C10 H10 114.6 . . ? C3 C11 C12 113.17(15) . . ? C3 C11 H11A 108.9 . . ? C12 C11 H11A 108.9 . . ? C3 C11 H11B 108.9 . . ? C12 C11 H11B 108.9 . . ? H11A C11 H11B 107.8 . . ? C13 C12 C11 113.19(17) . . ? C13 C12 H12A 108.9 . . ? C11 C12 H12A 108.9 . . ? C13 C12 H12B 108.9 . . ? C11 C12 H12B 108.9 . . ? H12A C12 H12B 107.8 . . ? 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 . . ? C8 C14 C15 113.95(16) . . ? C8 C14 H14A 108.8 . . ? C15 C14 H14A 108.8 . . ? C8 C14 H14B 108.8 . . ? C15 C14 H14B 108.8 . . ? H14A C14 H14B 107.7 . . ? C16 C15 C14 111.89(17) . . ? C16 C15 H15A 109.2 . . ? C14 C15 H15A 109.2 . . ? C16 C15 H15B 109.2 . . ? C14 C15 H15B 109.2 . . ? H15A C15 H15B 107.9 . . ? C15 C16 H16A 109.5 . . ? C15 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? C15 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? C5 N1 C2 107.12(15) . . ? C9 N2 C6 110.07(17) . . ? C9 N2 H2 125.0 . . ? C6 N2 H2 125.0 . . ? _diffrn_measured_fraction_theta_max 0.988 _diffrn_reflns_theta_full 28.28 _diffrn_measured_fraction_theta_full 0.988 _refine_diff_density_max 0.731 _refine_diff_density_min -0.330 _refine_diff_density_rms 0.085 # Attachment 'Tribromoporphycene_4_.cif' data_Tribromoporphycene _database_code_depnum_ccdc_archive 'CCDC 677020' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C32 H35 Br3 N4' _chemical_formula_weight 715.37 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' 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' _symmetry_space_group_name_Hall '-P 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 5.3757(5) _cell_length_b 10.3624(9) _cell_length_c 13.4652(12) _cell_angle_alpha 96.076(2) _cell_angle_beta 91.373(2) _cell_angle_gamma 94.714(2) _cell_volume 742.94(12) _cell_formula_units_Z 1 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 3053 _cell_measurement_theta_min 2.625 _cell_measurement_theta_max 27.40 _exptl_crystal_description needle _exptl_crystal_colour violet _exptl_crystal_size_max 0.42 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 1.599 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 360 _exptl_absorpt_coefficient_mu 4.101 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.2777 _exptl_absorpt_correction_T_max 0.6845 _exptl_absorpt_process_details 'SADABS; Sheldrick 1996' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(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 area detector' _diffrn_measurement_method '\p and \w scans' _diffrn_detector_area_resol_mean 8.366 _diffrn_standards_number 76 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 1110 _diffrn_standards_decay_% 0 _diffrn_reflns_number 6513 _diffrn_reflns_av_R_equivalents 0.0296 _diffrn_reflns_av_sigmaI/netI 0.0423 _diffrn_reflns_limit_h_min -6 _diffrn_reflns_limit_h_max 6 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 1.52 _diffrn_reflns_theta_max 25.68 _reflns_number_total 2837 _reflns_number_gt 2515 _reflns_threshold_expression >2\s(I) _computing_data_collection 'SMART (Bruker, 2001)' _computing_cell_refinement SMART _computing_data_reduction 'SAINT (Bruker, 2001)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL (Bruker, 2001)' _computing_publication_material SHELXTL _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^)+(0.0404P)^2^+7.6683P] 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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2837 _refine_ls_number_parameters 183 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1176 _refine_ls_R_factor_gt 0.1091 _refine_ls_wR_factor_ref 0.2459 _refine_ls_wR_factor_gt 0.2413 _refine_ls_goodness_of_fit_ref 1.162 _refine_ls_restrained_S_all 1.162 _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 Br1 Br -0.1627(4) 0.0182(2) 0.58912(14) 0.0957(7) Uani 0.75 1 d P . . Br2 Br 0.2688(3) 0.22626(17) 0.65207(10) 0.0702(5) Uani 0.75 1 d P . . C1 C -0.4072(15) -0.1200(7) 0.8326(7) 0.046(2) Uani 1 1 d . . . C2 C -0.4144(16) -0.1021(7) 0.7309(7) 0.047(2) Uani 1 1 d . . . C3 C -0.2153(17) -0.0194(8) 0.7150(7) 0.048(2) Uani 1 1 d . . . H3 H -0.1722 0.0096 0.6525 0.058 Uiso 0.25 1 calc PR . . C4 C -0.0807(15) 0.0172(8) 0.8074(7) 0.0426(19) Uani 1 1 d . . . C5 C 0.1380(15) 0.1004(7) 0.8359(6) 0.0402(18) Uani 1 1 d . . . C6 C 0.2966(15) 0.1844(8) 0.7826(7) 0.0447(19) Uani 1 1 d . . . H6 H 0.2725 0.1988 0.7147 0.054 Uiso 0.25 1 calc PR . . C7 C 0.4875(15) 0.2403(7) 0.8447(7) 0.044(2) Uani 1 1 d . . . C8 C 0.4411(14) 0.1939(7) 0.9378(7) 0.043(2) Uani 1 1 d . . . C9 C 0.5984(15) 0.2278(7) 1.0241(7) 0.048(2) Uani 1 1 d . . . H9 H 0.7435 0.2827 1.0135 0.057 Uiso 1 1 calc R . . C10 C 0.5802(15) 0.1963(8) 1.1189(7) 0.048(2) Uani 1 1 d . . . H10 H 0.7154 0.2348 1.1616 0.058 Uiso 1 1 calc R . . C11 C -0.6061(18) -0.1684(9) 0.6528(8) 0.059(3) Uani 1 1 d . . . H11A H -0.7722 -0.1740 0.6831 0.070 Uiso 1 1 calc R . . H11B H -0.6154 -0.1138 0.5970 0.070 Uiso 1 1 calc R . . C12 C -0.5484(16) -0.3015(8) 0.6122(7) 0.047(2) Uani 1 1 d . . . H12A H -0.5359 -0.3562 0.6679 0.057 Uiso 1 1 calc R . . H12B H -0.3849 -0.2962 0.5800 0.057 Uiso 1 1 calc R . . C13 C -0.7486(18) -0.3653(10) 0.5362(7) 0.061(3) Uani 1 1 d . . . H13A H -0.9109 -0.3702 0.5678 0.091 Uiso 1 1 calc R . . H13B H -0.7070 -0.4533 0.5123 0.091 Uiso 1 1 calc R . . H13C H -0.7564 -0.3133 0.4797 0.091 Uiso 1 1 calc R . . C14 C 0.7016(16) 0.3327(8) 0.8208(8) 0.051(2) Uani 1 1 d . . . H14A H 0.7331 0.3174 0.7485 0.062 Uiso 1 1 calc R . . H14B H 0.8533 0.3139 0.8579 0.062 Uiso 1 1 calc R . . C15 C 0.6573(15) 0.4740(8) 0.8465(8) 0.049(2) Uani 1 1 d . . . H15A H 0.6236 0.4899 0.9185 0.059 Uiso 1 1 calc R . . H15B H 0.5084 0.4942 0.8082 0.059 Uiso 1 1 calc R . . C16 C 0.8821(17) 0.5636(10) 0.8225(9) 0.062(3) Uani 1 1 d . . . H16A H 1.0330 0.5375 0.8545 0.093 Uiso 1 1 calc R . . H16B H 0.8569 0.6537 0.8477 0.093 Uiso 1 1 calc R . . H16C H 0.9010 0.5573 0.7500 0.093 Uiso 1 1 calc R . . N1 N -0.2003(12) -0.0469(6) 0.8777(5) 0.0396(15) Uani 1 1 d . . . H1 H -0.1540 -0.0426 0.9411 0.047 Uiso 0.50 1 calc PR . . N2 N 0.2294(12) 0.1092(6) 0.9312(5) 0.0389(15) Uani 1 1 d . . . H2 H 0.1651 0.0683 0.9798 0.047 Uiso 0.50 1 calc PR . . 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 0.1048(14) 0.1057(14) 0.0774(12) 0.0347(10) -0.0389(10) -0.0055(11) Br2 0.0573(8) 0.1008(12) 0.0520(8) 0.0222(7) 0.0131(6) -0.0173(7) C1 0.039(4) 0.025(4) 0.072(6) -0.003(4) -0.013(4) 0.006(3) C2 0.049(5) 0.025(4) 0.065(6) -0.010(4) -0.025(4) 0.011(3) C3 0.051(5) 0.038(4) 0.053(5) -0.007(4) -0.021(4) 0.011(4) C4 0.044(4) 0.031(4) 0.052(5) -0.004(3) -0.007(4) 0.006(3) C5 0.037(4) 0.029(4) 0.053(5) -0.003(3) -0.005(3) 0.007(3) C6 0.041(4) 0.033(4) 0.059(5) -0.002(4) 0.007(4) 0.005(3) C7 0.035(4) 0.025(4) 0.071(6) -0.004(4) 0.005(4) 0.004(3) C8 0.033(4) 0.029(4) 0.064(5) -0.011(4) -0.007(4) 0.002(3) C9 0.038(4) 0.026(4) 0.074(6) -0.009(4) -0.015(4) -0.003(3) C10 0.037(4) 0.031(4) 0.071(6) -0.011(4) -0.020(4) 0.005(3) C11 0.050(5) 0.049(5) 0.074(7) -0.004(5) -0.031(5) 0.008(4) C12 0.044(5) 0.048(5) 0.047(5) -0.006(4) -0.015(4) 0.002(4) C13 0.046(5) 0.070(7) 0.059(6) -0.015(5) -0.011(4) -0.004(5) C14 0.039(4) 0.037(4) 0.074(6) -0.010(4) 0.006(4) -0.001(4) C15 0.036(4) 0.033(4) 0.079(6) 0.003(4) 0.004(4) 0.006(3) C16 0.037(5) 0.050(5) 0.099(8) 0.012(5) 0.003(5) 0.001(4) N1 0.037(3) 0.020(3) 0.059(4) -0.008(3) -0.004(3) 0.003(3) N2 0.037(3) 0.021(3) 0.054(4) -0.010(3) -0.006(3) -0.002(2) _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 C3 1.802(10) . ? Br2 C6 1.860(9) . ? C1 N1 1.382(10) . ? C1 C10 1.391(13) 2_557 ? C1 C2 1.401(13) . ? C2 C3 1.351(13) . ? C2 C11 1.523(11) . ? C3 C4 1.424(11) . ? C4 N1 1.357(11) . ? C4 C5 1.419(11) . ? C5 N2 1.354(11) . ? C5 C6 1.428(12) . ? C6 C7 1.359(12) . ? C7 C8 1.410(13) . ? C7 C14 1.499(11) . ? C8 N2 1.374(10) . ? C8 C9 1.416(12) . ? C9 C10 1.354(13) . ? C10 C1 1.391(13) 2_557 ? C11 C12 1.489(12) . ? C12 C13 1.526(11) . ? C14 C15 1.509(11) . ? C15 C16 1.525(12) . ? 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 N1 C1 C10 125.4(9) . 2_557 ? N1 C1 C2 108.4(8) . . ? C10 C1 C2 126.2(8) 2_557 . ? C3 C2 C1 107.2(7) . . ? C3 C2 C11 126.8(9) . . ? C1 C2 C11 125.9(9) . . ? C2 C3 C4 108.7(9) . . ? C2 C3 Br1 118.3(7) . . ? C4 C3 Br1 133.0(7) . . ? N1 C4 C5 119.1(8) . . ? N1 C4 C3 107.2(7) . . ? C5 C4 C3 133.7(9) . . ? N2 C5 C4 119.4(8) . . ? N2 C5 C6 107.8(7) . . ? C4 C5 C6 132.7(8) . . ? C7 C6 C5 109.1(8) . . ? C7 C6 Br2 120.5(7) . . ? C5 C6 Br2 130.4(6) . . ? C6 C7 C8 105.3(7) . . ? C6 C7 C14 127.9(9) . . ? C8 C7 C14 126.8(8) . . ? N2 C8 C7 110.4(7) . . ? N2 C8 C9 125.7(9) . . ? C7 C8 C9 123.9(8) . . ? C10 C9 C8 131.9(8) . . ? C9 C10 C1 134.1(8) . 2_557 ? C12 C11 C2 113.5(7) . . ? C11 C12 C13 111.6(8) . . ? C7 C14 C15 113.4(7) . . ? C14 C15 C16 111.3(7) . . ? C4 N1 C1 108.4(7) . . ? C5 N2 C8 107.3(7) . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 25.68 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 1.574 _refine_diff_density_min -1.553 _refine_diff_density_rms 0.130 # Attachment 'Tetrabromoporphycene_5_.cif' data_Terabromoporphycene _database_code_depnum_ccdc_archive 'CCDC 677022' _audit_creation_method SHELXL-97 _chemical_name_systematic ; 3,6,13,16-tetrabromo-2,7,12,17-tetrapropylporphycene ; _chemical_name_common 3,6,13,16-tetrabromo-2,7,12,17-tetrapropylporphycene _chemical_melting_point ? _chemical_formula_moiety 'C32 H34 Br4 N4' _chemical_formula_sum 'C32 H34 Br4 N4' _chemical_formula_weight 794.27 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' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1)/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 17.0117(10) _cell_length_b 8.0919(4) _cell_length_c 22.1183(12) _cell_angle_alpha 90.00 _cell_angle_beta 92.2720(10) _cell_angle_gamma 90.00 _cell_volume 3042.3(3) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 5998 _cell_measurement_theta_min 2.40 _cell_measurement_theta_max 29.74 _exptl_crystal_description prism _exptl_crystal_colour purple _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.13 _exptl_crystal_density_meas 0 _exptl_crystal_density_diffrn 1.734 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1576 _exptl_absorpt_coefficient_mu 5.321 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.4159 _exptl_absorpt_correction_T_max 0.5446 _exptl_absorpt_process_details '(SADABS; Sheldrick, 1996)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(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 area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean 8.366 _diffrn_standards_number 202 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 356 _diffrn_standards_decay_% 0 _diffrn_reflns_number 20578 _diffrn_reflns_av_R_equivalents 0.0388 _diffrn_reflns_av_sigmaI/netI 0.0514 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 22 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -25 _diffrn_reflns_limit_l_max 28 _diffrn_reflns_theta_min 1.48 _diffrn_reflns_theta_max 27.48 _reflns_number_total 6996 _reflns_number_gt 5430 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0508P)^2^+1.6460P] 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 6996 _refine_ls_number_parameters 365 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0562 _refine_ls_R_factor_gt 0.0380 _refine_ls_wR_factor_ref 0.1030 _refine_ls_wR_factor_gt 0.0944 _refine_ls_goodness_of_fit_ref 1.053 _refine_ls_restrained_S_all 1.053 _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_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Br1 Br 0.01674(2) 0.71065(4) 0.142058(15) 0.02376(10) Uani 1 1 d . . . Br2 Br -0.07913(2) 1.03038(5) 0.201109(15) 0.02767(10) Uani 1 1 d . . . Br3 Br 0.17591(3) 0.50479(5) 0.612897(17) 0.03232(11) Uani 1 1 d . . . Br4 Br 0.33853(2) 0.70267(5) 0.570636(16) 0.03484(12) Uani 1 1 d . . . C1 C 0.2019(2) 0.6848(4) 0.26144(15) 0.0196(7) Uani 1 1 d . . . C2 C 0.1669(2) 0.6699(4) 0.20137(14) 0.0180(7) Uani 1 1 d . . . C3 C 0.09262(19) 0.7335(4) 0.20538(14) 0.0161(6) Uani 1 1 d . . . C4 C 0.0818(2) 0.7859(4) 0.26654(14) 0.0171(7) Uani 1 1 d . . . C5 C 0.0148(2) 0.8475(4) 0.29610(14) 0.0175(7) Uani 1 1 d . . . C6 C -0.0568(2) 0.9271(4) 0.27568(14) 0.0185(7) Uani 1 1 d . . . C7 C -0.1042(2) 0.9493(4) 0.32400(15) 0.0185(7) Uani 1 1 d . . . C8 C -0.0604(2) 0.8868(4) 0.37529(15) 0.0191(7) Uani 1 1 d . . . C9 C -0.0883(2) 0.8740(4) 0.43420(15) 0.0216(7) Uani 1 1 d . . . H9 H -0.1385 0.9226 0.4391 0.026 Uiso 1 1 calc R . . C10 C -0.0554(2) 0.8030(4) 0.48598(15) 0.0245(8) Uani 1 1 d . . . H10 H -0.0904 0.7959 0.5183 0.029 Uiso 1 1 calc R . . C11 C 0.0199(2) 0.7393(4) 0.49983(15) 0.0219(7) Uani 1 1 d . . . C12 C 0.0416(2) 0.6580(4) 0.55626(15) 0.0221(7) Uani 1 1 d . . . C13 C 0.1204(2) 0.6319(4) 0.55425(14) 0.0226(8) Uani 1 1 d . . . C14 C 0.1471(2) 0.6898(4) 0.49646(14) 0.0194(7) Uani 1 1 d . . . C15 C 0.2199(2) 0.6796(4) 0.46886(15) 0.0199(7) Uani 1 1 d . . . C16 C 0.3000(2) 0.6663(4) 0.49154(14) 0.0209(7) Uani 1 1 d . . . C17 C 0.3486(2) 0.6518(4) 0.44369(16) 0.0215(7) Uani 1 1 d . . . C18 C 0.2982(2) 0.6600(4) 0.39092(15) 0.0204(7) Uani 1 1 d . . . C19 C 0.3222(2) 0.6367(4) 0.33136(15) 0.0223(7) Uani 1 1 d . . . H19 H 0.3769 0.6162 0.3281 0.027 Uiso 1 1 calc R . . C20 C 0.2798(2) 0.6387(4) 0.27690(15) 0.0221(7) Uani 1 1 d . . . H20 H 0.3087 0.6019 0.2436 0.027 Uiso 1 1 calc R . . C21 C 0.2009(2) 0.5924(4) 0.14719(14) 0.0201(7) Uani 1 1 d . . . H21A H 0.1617 0.5155 0.1286 0.024 Uiso 1 1 calc R . . H21B H 0.2476 0.5266 0.1603 0.024 Uiso 1 1 calc R . . C22 C 0.2250(2) 0.7171(4) 0.09954(15) 0.0255(8) Uani 1 1 d . . . H22A H 0.2689 0.7856 0.1162 0.031 Uiso 1 1 calc R . . H22B H 0.1801 0.7913 0.0893 0.031 Uiso 1 1 calc R . . C23 C 0.2505(2) 0.6300(5) 0.04222(16) 0.0301(9) Uani 1 1 d . . . H23A H 0.2972 0.5625 0.0517 0.045 Uiso 1 1 calc R . . H23B H 0.2629 0.7127 0.0117 0.045 Uiso 1 1 calc R . . H23C H 0.2077 0.5590 0.0265 0.045 Uiso 1 1 calc R . . C24 C -0.1845(2) 1.0267(4) 0.32282(16) 0.0224(7) Uani 1 1 d . . . H24A H -0.1838 1.1289 0.2982 0.027 Uiso 1 1 calc R . . H24B H -0.1975 1.0581 0.3645 0.027 Uiso 1 1 calc R . . C25 C -0.2486(2) 0.9108(5) 0.29664(18) 0.0295(8) Uani 1 1 d . . . H25A H -0.2348 0.8769 0.2554 0.035 Uiso 1 1 calc R . . H25B H -0.2503 0.8100 0.3219 0.035 Uiso 1 1 calc R . . C26 C -0.3296(2) 0.9908(5) 0.29378(19) 0.0295(8) Uani 1 1 d . . . H26A H -0.3440 1.0227 0.3346 0.044 Uiso 1 1 calc R . . H26B H -0.3683 0.9120 0.2769 0.044 Uiso 1 1 calc R . . H26C H -0.3286 1.0891 0.2680 0.044 Uiso 1 1 calc R . . C27 C -0.0119(2) 0.6020(4) 0.60424(15) 0.0255(8) Uani 1 1 d . . . H27A H 0.0047 0.4906 0.6182 0.031 Uiso 1 1 calc R . . H27B H -0.0660 0.5927 0.5864 0.031 Uiso 1 1 calc R . . C28 C -0.0128(2) 0.7175(4) 0.65880(16) 0.0275(8) Uani 1 1 d . . . H28A H 0.0421 0.7418 0.6726 0.033 Uiso 1 1 calc R . . H28B H -0.0380 0.8231 0.6464 0.033 Uiso 1 1 calc R . . C29 C -0.0566(3) 0.6442(5) 0.71098(17) 0.0368(10) Uani 1 1 d . . . H29A H -0.1114 0.6233 0.6979 0.055 Uiso 1 1 calc R . . H29B H -0.0550 0.7220 0.7450 0.055 Uiso 1 1 calc R . . H29C H -0.0316 0.5401 0.7237 0.055 Uiso 1 1 calc R . . C30 C 0.4364(2) 0.6392(4) 0.44690(16) 0.0253(8) Uani 1 1 d . . . H30A H 0.4529 0.5560 0.4171 0.030 Uiso 1 1 calc R . . H30B H 0.4536 0.5996 0.4877 0.030 Uiso 1 1 calc R . . C31 C 0.4777(2) 0.8022(5) 0.43441(19) 0.0317(9) Uani 1 1 d . . . H31A H 0.4668 0.8343 0.3917 0.038 Uiso 1 1 calc R . . H31B H 0.4562 0.8896 0.4604 0.038 Uiso 1 1 calc R . . C32 C 0.5663(2) 0.7903(5) 0.44639(19) 0.0362(10) Uani 1 1 d . . . H32A H 0.5774 0.7629 0.4890 0.054 Uiso 1 1 calc R . . H32B H 0.5907 0.8965 0.4371 0.054 Uiso 1 1 calc R . . H32C H 0.5878 0.7039 0.4207 0.054 Uiso 1 1 calc R . . N1 N 0.14873(17) 0.7519(3) 0.29955(12) 0.0184(6) Uani 1 1 d . . . H1 H 0.1567 0.7698 0.3386 0.022 Uiso 0.50 1 calc PR . . N2 N 0.01125(16) 0.8311(3) 0.35760(12) 0.0176(6) Uani 1 1 d . . . H2 H 0.0489 0.7911 0.3818 0.021 Uiso 0.50 1 calc PR . . N3 N 0.08365(17) 0.7505(3) 0.46498(12) 0.0190(6) Uani 1 1 d . . . H3 H 0.0837 0.7906 0.4280 0.023 Uiso 0.50 1 calc PR . . N4 N 0.22219(17) 0.6815(3) 0.40719(12) 0.0185(6) Uani 1 1 d . . . H4 H 0.1813 0.6945 0.3820 0.022 Uiso 0.50 1 calc PR . . 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 0.02247(19) 0.0305(2) 0.01790(17) -0.00563(13) -0.00473(13) 0.00251(14) Br2 0.0333(2) 0.0320(2) 0.01738(18) 0.00179(14) -0.00340(14) 0.01089(16) Br3 0.0409(2) 0.0308(2) 0.0245(2) 0.00992(15) -0.00893(17) -0.00361(16) Br4 0.0317(2) 0.0521(3) 0.01981(19) -0.00177(16) -0.01092(15) -0.00353(18) C1 0.0198(18) 0.0203(16) 0.0189(16) 0.0018(13) 0.0022(13) -0.0001(13) C2 0.0206(17) 0.0176(16) 0.0157(15) 0.0003(12) 0.0002(13) -0.0008(13) C3 0.0186(17) 0.0167(15) 0.0129(15) 0.0030(12) -0.0028(12) -0.0017(13) C4 0.0206(17) 0.0158(15) 0.0150(15) 0.0016(12) 0.0005(13) -0.0016(13) C5 0.0217(18) 0.0155(15) 0.0152(15) -0.0020(12) 0.0010(13) -0.0026(13) C6 0.0235(18) 0.0175(16) 0.0142(15) -0.0016(12) -0.0042(13) -0.0001(13) C7 0.0163(17) 0.0163(15) 0.0229(17) -0.0029(13) 0.0011(13) -0.0009(13) C8 0.0187(17) 0.0194(16) 0.0192(16) -0.0023(13) 0.0009(13) -0.0025(13) C9 0.0208(18) 0.0246(18) 0.0196(16) -0.0011(14) 0.0031(14) 0.0005(14) C10 0.029(2) 0.0275(19) 0.0173(17) 0.0009(14) 0.0070(14) 0.0012(15) C11 0.030(2) 0.0209(16) 0.0147(16) -0.0011(13) 0.0011(14) -0.0015(15) C12 0.030(2) 0.0206(17) 0.0159(16) -0.0007(13) -0.0003(14) -0.0062(14) C13 0.035(2) 0.0197(17) 0.0125(15) 0.0029(13) -0.0057(14) -0.0047(15) C14 0.0247(19) 0.0185(16) 0.0149(15) -0.0027(12) -0.0026(13) -0.0009(14) C15 0.0276(19) 0.0154(15) 0.0163(16) -0.0004(12) -0.0038(14) -0.0003(13) C16 0.0269(19) 0.0202(16) 0.0148(16) 0.0012(13) -0.0093(13) 0.0000(14) C17 0.0222(19) 0.0170(16) 0.0248(18) -0.0020(13) -0.0049(14) 0.0036(14) C18 0.0205(18) 0.0173(16) 0.0230(17) -0.0002(13) -0.0034(14) 0.0026(13) C19 0.0164(17) 0.0263(18) 0.0240(17) -0.0025(14) -0.0032(14) 0.0033(14) C20 0.0207(19) 0.0253(18) 0.0206(17) -0.0028(14) 0.0026(14) 0.0008(14) C21 0.0190(18) 0.0226(17) 0.0186(16) -0.0039(13) 0.0006(13) 0.0017(14) C22 0.030(2) 0.0279(19) 0.0186(17) -0.0017(14) 0.0047(15) 0.0005(16) C23 0.028(2) 0.041(2) 0.0226(18) 0.0006(16) 0.0075(15) 0.0030(17) C24 0.0197(18) 0.0214(17) 0.0260(18) -0.0036(14) -0.0003(14) 0.0044(14) C25 0.022(2) 0.0251(19) 0.041(2) -0.0050(17) -0.0022(16) 0.0022(15) C26 0.0156(19) 0.033(2) 0.040(2) -0.0021(17) -0.0029(16) -0.0006(15) C27 0.034(2) 0.0227(17) 0.0199(17) 0.0008(14) 0.0006(15) -0.0101(15) C28 0.038(2) 0.0237(18) 0.0209(18) -0.0004(14) 0.0048(16) -0.0085(16) C29 0.049(3) 0.036(2) 0.027(2) -0.0023(17) 0.0140(19) -0.0088(19) C30 0.025(2) 0.0236(18) 0.0266(18) 0.0001(15) -0.0073(15) 0.0052(15) C31 0.025(2) 0.030(2) 0.040(2) 0.0042(17) -0.0063(17) -0.0003(16) C32 0.027(2) 0.045(2) 0.037(2) -0.0001(19) -0.0049(17) -0.0035(18) N1 0.0184(15) 0.0214(14) 0.0152(13) -0.0001(11) -0.0004(11) 0.0011(11) N2 0.0174(14) 0.0207(14) 0.0148(13) 0.0008(11) 0.0002(11) 0.0018(11) N3 0.0211(15) 0.0216(14) 0.0142(13) -0.0017(11) -0.0016(11) -0.0001(12) N4 0.0210(15) 0.0200(14) 0.0140(13) -0.0001(11) -0.0033(11) 0.0021(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 C3 1.876(3) . ? Br2 C6 1.875(3) . ? Br3 C13 1.880(3) . ? Br4 C16 1.867(3) . ? C1 N1 1.373(4) . ? C1 C20 1.406(5) . ? C1 C2 1.440(5) . ? C2 C3 1.370(5) . ? C2 C21 1.490(4) . ? C3 C4 1.437(4) . ? C4 N1 1.357(4) . ? C4 C5 1.426(5) . ? C5 N2 1.370(4) . ? C5 C6 1.434(5) . ? C6 C7 1.376(4) . ? C7 C8 1.425(5) . ? C7 C24 1.503(5) . ? C8 N2 1.370(4) . ? C8 C9 1.409(4) . ? C9 C10 1.380(5) . ? C9 H9 0.9500 . ? C10 C11 1.404(5) . ? C10 H10 0.9500 . ? C11 N3 1.359(4) . ? C11 C12 1.446(5) . ? C12 C13 1.360(5) . ? C12 C27 1.495(5) . ? C13 C14 1.451(4) . ? C14 N3 1.354(4) . ? C14 C15 1.403(5) . ? C15 N4 1.366(4) . ? C15 C16 1.438(5) . ? C16 C17 1.374(5) . ? C17 C18 1.423(5) . ? C17 C30 1.495(5) . ? C18 N4 1.366(4) . ? C18 C19 1.407(5) . ? C19 C20 1.379(5) . ? C19 H19 0.9500 . ? C20 H20 0.9500 . ? C21 C22 1.527(5) . ? C21 H21A 0.9900 . ? C21 H21B 0.9900 . ? C22 C23 1.528(5) . ? C22 H22A 0.9900 . ? C22 H22B 0.9900 . ? C23 H23A 0.9800 . ? C23 H23B 0.9800 . ? C23 H23C 0.9800 . ? C24 C25 1.534(5) . ? C24 H24A 0.9900 . ? C24 H24B 0.9900 . ? C25 C26 1.522(5) . ? C25 H25A 0.9900 . ? C25 H25B 0.9900 . ? C26 H26A 0.9800 . ? C26 H26B 0.9800 . ? C26 H26C 0.9800 . ? C27 C28 1.527(5) . ? C27 H27A 0.9900 . ? C27 H27B 0.9900 . ? C28 C29 1.519(5) . ? C28 H28A 0.9900 . ? C28 H28B 0.9900 . ? C29 H29A 0.9800 . ? C29 H29B 0.9800 . ? C29 H29C 0.9800 . ? C30 C31 1.525(5) . ? C30 H30A 0.9900 . ? C30 H30B 0.9900 . ? C31 C32 1.523(5) . ? C31 H31A 0.9900 . ? C31 H31B 0.9900 . ? C32 H32A 0.9800 . ? C32 H32B 0.9800 . ? C32 H32C 0.9800 . ? N1 H1 0.8800 . ? N2 H2 0.8800 . ? N3 H3 0.8800 . ? N4 H4 0.8800 . ? 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 N1 C1 C20 126.4(3) . . ? N1 C1 C2 109.9(3) . . ? C20 C1 C2 123.6(3) . . ? C3 C2 C1 104.9(3) . . ? C3 C2 C21 126.8(3) . . ? C1 C2 C21 128.2(3) . . ? C2 C3 C4 109.0(3) . . ? C2 C3 Br1 121.6(2) . . ? C4 C3 Br1 128.4(3) . . ? N1 C4 C5 119.6(3) . . ? N1 C4 C3 108.1(3) . . ? C5 C4 C3 132.1(3) . . ? N2 C5 C4 119.3(3) . . ? N2 C5 C6 106.6(3) . . ? C4 C5 C6 134.1(3) . . ? C7 C6 C5 109.3(3) . . ? C7 C6 Br2 121.4(3) . . ? C5 C6 Br2 128.1(2) . . ? C6 C7 C8 105.6(3) . . ? C6 C7 C24 127.0(3) . . ? C8 C7 C24 127.5(3) . . ? N2 C8 C9 125.2(3) . . ? N2 C8 C7 109.4(3) . . ? C9 C8 C7 125.3(3) . . ? C10 C9 C8 131.1(3) . . ? C10 C9 H9 114.4 . . ? C8 C9 H9 114.4 . . ? C9 C10 C11 132.1(3) . . ? C9 C10 H10 113.9 . . ? C11 C10 H10 113.9 . . ? N3 C11 C10 126.5(3) . . ? N3 C11 C12 109.8(3) . . ? C10 C11 C12 123.7(3) . . ? C13 C12 C11 105.1(3) . . ? C13 C12 C27 127.2(3) . . ? C11 C12 C27 127.5(3) . . ? C12 C13 C14 108.8(3) . . ? C12 C13 Br3 122.1(3) . . ? C14 C13 Br3 128.1(3) . . ? N3 C14 C15 119.8(3) . . ? N3 C14 C13 107.4(3) . . ? C15 C14 C13 132.6(3) . . ? N4 C15 C14 119.6(3) . . ? N4 C15 C16 106.5(3) . . ? C14 C15 C16 133.8(3) . . ? C17 C16 C15 109.2(3) . . ? C17 C16 Br4 122.4(3) . . ? C15 C16 Br4 127.5(3) . . ? C16 C17 C18 105.4(3) . . ? C16 C17 C30 126.9(3) . . ? C18 C17 C30 127.7(3) . . ? N4 C18 C19 125.2(3) . . ? N4 C18 C17 109.7(3) . . ? C19 C18 C17 125.0(3) . . ? C20 C19 C18 130.9(3) . . ? C20 C19 H19 114.6 . . ? C18 C19 H19 114.6 . . ? C19 C20 C1 132.1(3) . . ? C19 C20 H20 113.9 . . ? C1 C20 H20 113.9 . . ? C2 C21 C22 113.6(3) . . ? C2 C21 H21A 108.9 . . ? C22 C21 H21A 108.9 . . ? C2 C21 H21B 108.9 . . ? C22 C21 H21B 108.9 . . ? H21A C21 H21B 107.7 . . ? C21 C22 C23 111.1(3) . . ? C21 C22 H22A 109.4 . . ? C23 C22 H22A 109.4 . . ? C21 C22 H22B 109.4 . . ? C23 C22 H22B 109.4 . . ? H22A C22 H22B 108.0 . . ? C22 C23 H23A 109.5 . . ? C22 C23 H23B 109.5 . . ? H23A C23 H23B 109.5 . . ? C22 C23 H23C 109.5 . . ? H23A C23 H23C 109.5 . . ? H23B C23 H23C 109.5 . . ? C7 C24 C25 112.6(3) . . ? C7 C24 H24A 109.1 . . ? C25 C24 H24A 109.1 . . ? C7 C24 H24B 109.1 . . ? C25 C24 H24B 109.1 . . ? H24A C24 H24B 107.8 . . ? C26 C25 C24 112.6(3) . . ? C26 C25 H25A 109.1 . . ? C24 C25 H25A 109.1 . . ? C26 C25 H25B 109.1 . . ? C24 C25 H25B 109.1 . . ? H25A C25 H25B 107.8 . . ? C25 C26 H26A 109.5 . . ? C25 C26 H26B 109.5 . . ? H26A C26 H26B 109.5 . . ? C25 C26 H26C 109.5 . . ? H26A C26 H26C 109.5 . . ? H26B C26 H26C 109.5 . . ? C12 C27 C28 113.6(3) . . ? C12 C27 H27A 108.8 . . ? C28 C27 H27A 108.8 . . ? C12 C27 H27B 108.8 . . ? C28 C27 H27B 108.8 . . ? H27A C27 H27B 107.7 . . ? C29 C28 C27 112.5(3) . . ? C29 C28 H28A 109.1 . . ? C27 C28 H28A 109.1 . . ? C29 C28 H28B 109.1 . . ? C27 C28 H28B 109.1 . . ? H28A C28 H28B 107.8 . . ? C28 C29 H29A 109.5 . . ? C28 C29 H29B 109.5 . . ? H29A C29 H29B 109.5 . . ? C28 C29 H29C 109.5 . . ? H29A C29 H29C 109.5 . . ? H29B C29 H29C 109.5 . . ? C17 C30 C31 113.5(3) . . ? C17 C30 H30A 108.9 . . ? C31 C30 H30A 108.9 . . ? C17 C30 H30B 108.9 . . ? C31 C30 H30B 108.9 . . ? H30A C30 H30B 107.7 . . ? C32 C31 C30 111.9(3) . . ? C32 C31 H31A 109.2 . . ? C30 C31 H31A 109.2 . . ? C32 C31 H31B 109.2 . . ? C30 C31 H31B 109.2 . . ? H31A C31 H31B 107.9 . . ? C31 C32 H32A 109.5 . . ? C31 C32 H32B 109.5 . . ? H32A C32 H32B 109.5 . . ? C31 C32 H32C 109.5 . . ? H32A C32 H32C 109.5 . . ? H32B C32 H32C 109.5 . . ? C4 N1 C1 108.0(3) . . ? C4 N1 H1 126.0 . . ? C1 N1 H1 126.0 . . ? C5 N2 C8 109.0(3) . . ? C5 N2 H2 125.5 . . ? C8 N2 H2 125.5 . . ? C14 N3 C11 108.8(3) . . ? C14 N3 H3 125.6 . . ? C11 N3 H3 125.6 . . ? C18 N4 C15 109.1(3) . . ? C18 N4 H4 125.5 . . ? C15 N4 H4 125.5 . . ? 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 C3 C4 C5 C6 -22.8(6) . . . . ? C7 C8 C9 C10 173.2(4) . . . . ? C8 C9 C10 C11 9.5(7) . . . . ? C9 C10 C11 C12 -175.3(4) . . . . ? C13 C14 C15 C16 -26.8(6) . . . . ? C17 C18 C19 C20 178.9(4) . . . . ? C18 C19 C20 C1 9.6(7) . . . . ? C19 C20 C1 C2 -176.8(4) . . . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 1.733 _refine_diff_density_min -0.449 _refine_diff_density_rms 0.117