# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2003 data_global _journal_coden_Cambridge 182 loop_ _publ_author_name 'Philip Gale' 'Michael B. Hursthouse' 'Mark E. Light' 'Colin N. Warriner' _publ_contact_author_name 'Dr Philip Gale' _publ_contact_author_address ; School of Chemistry University of Southampton Southampton Hampshire SO17 1BJ UNITED KINGDOM ; _publ_contact_author_email PHILIP.GALE@SOTON.AC.UK _publ_requested_journal 'Chemical Communications' _publ_section_title ; Pentapyrrolic calix[4]pyrrole ; data_s92 _database_code_CSD 208974 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C14 H12 Br3 N3' _chemical_formula_weight 462.00 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 P21/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 17.13(4) _cell_length_b 10.965(8) _cell_length_c 17.450(15) _cell_angle_alpha 90.00 _cell_angle_beta 114.25(7) _cell_angle_gamma 90.00 _cell_volume 2989(7) _cell_formula_units_Z 8 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max 0.10 _exptl_crystal_size_mid 0.03 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.053 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1776 _exptl_absorpt_coefficient_mu 8.090 _exptl_absorpt_correction_type Multi-scans _exptl_absorpt_correction_T_min 0.4984 _exptl_absorpt_correction_T_max 0.7934 _exptl_absorpt_process_details 'SORTAV (Blessing, 1997)' _exptl_special_details ; This was a non-merohedral twin (180 degree roation around the direct lattice c vector) ; _diffrn_ambient_temperature 120(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Bruker Nonius FR591 Rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker Nonius Kappa CCD Area detector' _diffrn_measurement_method '\f and \w scans to fill the asymmetric unit' _diffrn_detector_area_resol_mean '9.091 pixels mm^1^' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 13791 _diffrn_reflns_av_R_equivalents 0.0742 _diffrn_reflns_av_sigmaI/netI 0.0810 _diffrn_reflns_limit_h_min -19 _diffrn_reflns_limit_h_max 20 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 4.90 _diffrn_reflns_theta_max 25.03 _reflns_number_total 3468 _reflns_number_gt 2351 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'COLLECT (Hooft, 1998)' _computing_cell_refinement 'EVALCCD ' _computing_data_reduction 'EVALCCD, COLLECT)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'CAMERON (Watkin, et al., 1993)' _computing_publication_material 'WINGX (Farrugia, 1998)' _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^)+(0.0488P)^2^+2.3714P] 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 0.00032(17) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 3468 _refine_ls_number_parameters 364 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0915 _refine_ls_R_factor_gt 0.0480 _refine_ls_wR_factor_ref 0.1081 _refine_ls_wR_factor_gt 0.0952 _refine_ls_goodness_of_fit_ref 1.043 _refine_ls_restrained_S_all 1.043 _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 0.09245(7) -0.09399(9) -0.03799(6) 0.0439(3) Uani 1 1 d . . . Br2 Br 0.09172(7) -0.38805(8) 0.06020(6) 0.0392(3) Uani 1 1 d . . . Br3 Br 0.13529(6) -0.32371(7) 0.27499(6) 0.0302(3) Uani 1 1 d . . . N1 N 0.1236(4) -0.0354(6) 0.1292(4) 0.0178(15) Uani 1 1 d . . . H1 H 0.1256 0.0428 0.1188 0.021 Uiso 1 1 calc R . . N2 N 0.2206(5) -0.0175(7) 0.4356(5) 0.044(2) Uani 1 1 d . . . H2 H 0.1827 0.0262 0.4456 0.053 Uiso 1 1 calc R . . N3 N 0.2358(4) 0.1743(5) 0.2742(4) 0.0208(17) Uani 1 1 d . . . H3 H 0.2836 0.1319 0.2944 0.025 Uiso 1 1 calc R . . C1 C 0.1090(5) -0.1256(8) 0.0712(5) 0.027(2) Uani 1 1 d . . . C2 C 0.1107(5) -0.2338(7) 0.1109(5) 0.021(2) Uani 1 1 d . . . C3 C 0.1272(5) -0.2060(6) 0.1943(5) 0.0169(18) Uani 1 1 d . . . C4 C 0.1348(5) -0.0818(7) 0.2051(5) 0.0199(19) Uani 1 1 d . . . C5 C 0.1436(5) -0.0010(7) 0.2781(5) 0.0201(19) Uani 1 1 d . . . C6 C 0.0584(5) -0.0138(7) 0.2881(5) 0.027(2) Uani 1 1 d . . . H6A H 0.0106 0.0091 0.2354 0.040 Uiso 1 1 calc R . . H6B H 0.0593 0.0399 0.3334 0.040 Uiso 1 1 calc R . . H6C H 0.0512 -0.0985 0.3020 0.040 Uiso 1 1 calc R . . C7 C 0.2169(5) -0.0438(7) 0.3573(5) 0.022(2) Uani 1 1 d . . . C8 C 0.2911(8) -0.0689(10) 0.4948(7) 0.059(3) Uani 1 1 d . . . H8 H 0.3087 -0.0623 0.5538 0.071 Uiso 1 1 calc R . . C9 C 0.3319(6) -0.1300(8) 0.4569(7) 0.051(3) Uani 1 1 d . . . H9 H 0.3824 -0.1770 0.4840 0.061 Uiso 1 1 calc R . . C10 C 0.2863(5) -0.1129(7) 0.3669(6) 0.030(2) Uani 1 1 d . . . H10 H 0.3016 -0.1434 0.3240 0.036 Uiso 1 1 calc R . . C11 C 0.1563(5) 0.1300(7) 0.2602(5) 0.0169(18) Uani 1 1 d . . . C12 C 0.0990(6) 0.2245(7) 0.2283(5) 0.024(2) Uani 1 1 d . . . H12 H 0.0389 0.2209 0.2118 0.028 Uiso 1 1 calc R . . C13 C 0.1467(6) 0.3274(7) 0.2250(5) 0.024(2) Uani 1 1 d . . . H13 H 0.1243 0.4066 0.2068 0.029 Uiso 1 1 calc R . . C14 C 0.2294(7) 0.2944(7) 0.2522(5) 0.025(2) Uani 1 1 d . . . H14 H 0.2754 0.3457 0.2555 0.029 Uiso 1 1 calc R . . Br4 Br 0.32169(7) -0.07851(10) 0.15017(7) 0.0480(3) Uani 1 1 d . . . Br5 Br 0.53109(6) -0.08626(8) 0.31463(5) 0.0325(3) Uani 1 1 d . . . Br6 Br 0.66315(6) 0.11606(8) 0.25310(6) 0.0320(3) Uani 1 1 d . . . N4 N 0.4986(4) 0.1328(5) 0.1199(4) 0.0201(16) Uani 1 1 d . . . H4 H 0.5175 0.1832 0.0922 0.024 Uiso 1 1 calc R . . N5 N 0.1970(4) 0.1852(6) -0.0695(4) 0.0222(18) Uani 1 1 d . . . H5 H 0.1912 0.1630 -0.1200 0.027 Uiso 1 1 calc R . . N6 N 0.3897(4) 0.3235(6) -0.0348(4) 0.0234(16) Uani 1 1 d . . . H6 H 0.3651 0.3636 -0.0070 0.028 Uiso 1 1 calc R . . C15 C 0.5454(5) 0.0865(7) 0.1968(5) 0.0199(19) Uani 1 1 d . . . C16 C 0.4955(5) 0.0109(7) 0.2190(5) 0.023(2) Uani 1 1 d . . . C17 C 0.4135(5) 0.0145(7) 0.1521(5) 0.0200(19) Uani 1 1 d . . . C18 C 0.4157(5) 0.0880(6) 0.0916(5) 0.0167(18) Uani 1 1 d . . . C19 C 0.3509(5) 0.1157(6) 0.0016(5) 0.0181(18) Uani 1 1 d . . . C20 C 0.3283(5) -0.0059(7) -0.0463(5) 0.026(2) Uani 1 1 d . . . H20A H 0.3070 -0.0633 -0.0163 0.039 Uiso 1 1 calc R . . H20B H 0.3795 -0.0398 -0.0502 0.039 Uiso 1 1 calc R . . H20C H 0.2840 0.0078 -0.1030 0.039 Uiso 1 1 calc R . . C21 C 0.2711(5) 0.1734(7) 0.0031(5) 0.0219(19) Uani 1 1 d . . . C22 C 0.2546(6) 0.2195(8) 0.0677(6) 0.032(2) Uani 1 1 d . . . H22 H 0.2939 0.2247 0.1250 0.038 Uiso 1 1 calc R . . C23 C 0.1673(6) 0.2586(8) 0.0332(5) 0.029(2) Uani 1 1 d . . . H23 H 0.1372 0.2938 0.0629 0.034 Uiso 1 1 calc R . . C24 C 0.1357(5) 0.2349(7) -0.0516(5) 0.025(2) Uani 1 1 d . . . H24 H 0.0791 0.2515 -0.0912 0.030 Uiso 1 1 calc R . . C25 C 0.3918(5) 0.2007(6) -0.0409(5) 0.0187(19) Uani 1 1 d . . . C26 C 0.4364(5) 0.1731(7) -0.0870(5) 0.0207(19) Uani 1 1 d . . . H26 H 0.4487 0.0935 -0.1005 0.025 Uiso 1 1 calc R . . C27 C 0.4616(5) 0.2847(7) -0.1118(5) 0.029(2) Uani 1 1 d . . . H27 H 0.4933 0.2937 -0.1452 0.034 Uiso 1 1 calc R . . C28 C 0.4315(5) 0.3761(7) -0.0785(5) 0.025(2) Uani 1 1 d . . . H28 H 0.4384 0.4611 -0.0844 0.031 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 0.0536(7) 0.0549(7) 0.0185(6) -0.0038(5) 0.0101(5) -0.0031(5) Br2 0.0461(7) 0.0296(5) 0.0452(6) -0.0210(5) 0.0221(5) -0.0084(5) Br3 0.0355(6) 0.0202(5) 0.0412(6) 0.0019(4) 0.0219(5) -0.0019(4) N1 0.018(4) 0.022(4) 0.014(4) 0.003(3) 0.007(3) 0.000(3) N2 0.039(5) 0.057(5) 0.034(5) 0.007(4) 0.014(4) -0.018(4) N3 0.029(4) 0.020(4) 0.013(4) 0.008(3) 0.008(3) 0.009(3) C1 0.024(5) 0.030(5) 0.026(5) -0.005(4) 0.009(4) -0.002(4) C2 0.020(5) 0.017(4) 0.022(5) -0.006(4) 0.002(4) 0.004(4) C3 0.012(4) 0.018(4) 0.016(5) -0.003(4) 0.002(4) -0.006(3) C4 0.015(5) 0.028(5) 0.013(5) -0.003(4) 0.003(4) 0.003(4) C5 0.018(5) 0.021(4) 0.021(5) -0.006(4) 0.009(4) -0.001(4) C6 0.026(5) 0.023(5) 0.028(6) -0.005(4) 0.008(4) 0.003(4) C7 0.033(5) 0.022(4) 0.010(5) -0.003(4) 0.009(4) -0.005(4) C8 0.062(9) 0.060(8) 0.034(7) 0.016(6) -0.002(7) -0.030(7) C9 0.027(6) 0.028(6) 0.062(8) 0.023(5) -0.019(6) -0.005(5) C10 0.020(5) 0.017(4) 0.045(7) -0.007(4) 0.005(5) 0.003(4) C11 0.020(5) 0.021(4) 0.009(4) -0.005(3) 0.005(4) 0.003(4) C12 0.035(6) 0.017(4) 0.022(5) -0.008(4) 0.014(5) -0.003(4) C13 0.046(6) 0.017(5) 0.009(5) -0.009(4) 0.012(5) 0.001(5) C14 0.042(7) 0.017(5) 0.011(5) -0.002(4) 0.008(5) 0.000(4) Br4 0.0331(6) 0.0679(7) 0.0434(7) 0.0230(6) 0.0163(5) -0.0068(6) Br5 0.0392(6) 0.0363(5) 0.0217(5) 0.0117(4) 0.0122(5) 0.0066(4) Br6 0.0269(5) 0.0353(5) 0.0276(6) 0.0014(4) 0.0049(4) -0.0031(4) N4 0.029(4) 0.018(3) 0.019(4) 0.000(3) 0.016(4) 0.003(3) N5 0.023(4) 0.036(4) 0.007(4) 0.015(3) 0.006(4) 0.005(4) N6 0.028(4) 0.029(4) 0.015(4) -0.004(3) 0.012(3) 0.006(3) C15 0.022(5) 0.020(4) 0.006(4) -0.001(4) -0.006(4) 0.001(4) C16 0.031(5) 0.024(5) 0.016(5) 0.006(4) 0.011(4) 0.007(4) C17 0.017(5) 0.023(4) 0.022(5) 0.004(4) 0.009(4) 0.000(4) C18 0.021(5) 0.015(4) 0.016(5) 0.004(4) 0.010(4) 0.003(4) C19 0.021(5) 0.015(4) 0.020(5) 0.004(4) 0.010(4) 0.003(4) C20 0.019(5) 0.036(5) 0.021(5) 0.006(4) 0.006(4) 0.003(4) C21 0.028(5) 0.024(4) 0.019(5) 0.011(4) 0.014(4) 0.006(4) C22 0.029(6) 0.040(6) 0.028(6) -0.003(5) 0.014(5) -0.001(5) C23 0.025(6) 0.043(6) 0.021(6) 0.007(5) 0.013(5) 0.013(5) C24 0.011(5) 0.040(5) 0.024(6) 0.009(4) 0.006(4) 0.008(4) C25 0.020(5) 0.016(4) 0.017(5) 0.002(4) 0.004(4) 0.001(4) C26 0.021(5) 0.020(4) 0.021(5) -0.007(4) 0.008(4) 0.003(4) C27 0.023(5) 0.040(5) 0.021(5) 0.000(4) 0.007(4) -0.002(4) C28 0.021(5) 0.022(5) 0.029(6) 0.006(4) 0.006(4) -0.001(4) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Br1 C1 1.840(9) . ? Br2 C2 1.874(7) . ? Br3 C3 1.873(7) . ? N1 C4 1.357(10) . ? N1 C1 1.363(10) . ? N2 C8 1.349(13) . ? N2 C7 1.372(10) . ? N3 C14 1.363(10) . ? N3 C11 1.369(10) . ? C1 C2 1.369(10) . ? C2 C3 1.397(10) . ? C3 C4 1.374(10) . ? C4 C5 1.506(11) . ? C5 C11 1.505(10) . ? C5 C7 1.511(10) . ? C5 C6 1.547(11) . ? C7 C10 1.360(11) . ? C8 C9 1.323(15) . ? C9 C10 1.450(13) . ? C11 C12 1.378(10) . ? C12 C13 1.408(11) . ? C13 C14 1.347(12) . ? Br4 C17 1.864(8) . ? Br5 C16 1.859(8) . ? Br6 C15 1.874(9) . ? N4 C15 1.347(9) . ? N4 C18 1.388(10) . ? N5 C24 1.328(10) . ? N5 C21 1.383(10) . ? N6 C25 1.352(9) . ? N6 C28 1.371(10) . ? C15 C16 1.357(10) . ? C16 C17 1.411(11) . ? C17 C18 1.340(10) . ? C18 C19 1.536(11) . ? C19 C21 1.517(11) . ? C19 C25 1.527(10) . ? C19 C20 1.537(10) . ? C21 C22 1.367(11) . ? C22 C23 1.429(12) . ? C23 C24 1.376(11) . ? C25 C26 1.353(10) . ? C26 C27 1.424(11) . ? C27 C28 1.362(11) . ? 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 C4 N1 C1 111.3(7) . . ? C8 N2 C7 109.6(9) . . ? C14 N3 C11 109.5(7) . . ? N1 C1 C2 107.0(7) . . ? N1 C1 Br1 122.4(6) . . ? C2 C1 Br1 130.6(6) . . ? C1 C2 C3 106.9(6) . . ? C1 C2 Br2 125.4(6) . . ? C3 C2 Br2 127.7(6) . . ? C4 C3 C2 109.1(7) . . ? C4 C3 Br3 127.3(6) . . ? C2 C3 Br3 123.6(5) . . ? N1 C4 C3 105.6(7) . . ? N1 C4 C5 122.0(7) . . ? C3 C4 C5 132.1(8) . . ? C11 C5 C4 111.0(7) . . ? C11 C5 C7 110.4(6) . . ? C4 C5 C7 110.3(6) . . ? C11 C5 C6 109.5(6) . . ? C4 C5 C6 105.8(6) . . ? C7 C5 C6 109.7(7) . . ? C10 C7 N2 108.3(8) . . ? C10 C7 C5 130.0(8) . . ? N2 C7 C5 121.8(8) . . ? C9 C8 N2 108.6(10) . . ? C8 C9 C10 108.4(9) . . ? C7 C10 C9 105.1(8) . . ? N3 C11 C12 107.2(7) . . ? N3 C11 C5 121.4(7) . . ? C12 C11 C5 131.4(7) . . ? C11 C12 C13 106.8(8) . . ? C14 C13 C12 108.3(8) . . ? C13 C14 N3 108.0(9) . . ? C15 N4 C18 109.0(6) . . ? C24 N5 C21 109.9(7) . . ? C25 N6 C28 109.8(7) . . ? N4 C15 C16 109.0(7) . . ? N4 C15 Br6 122.0(6) . . ? C16 C15 Br6 128.7(6) . . ? C15 C16 C17 106.1(7) . . ? C15 C16 Br5 126.4(6) . . ? C17 C16 Br5 127.3(6) . . ? C18 C17 C16 109.2(7) . . ? C18 C17 Br4 127.6(6) . . ? C16 C17 Br4 123.1(6) . . ? C17 C18 N4 106.7(7) . . ? C17 C18 C19 133.1(7) . . ? N4 C18 C19 119.8(6) . . ? C21 C19 C25 110.5(6) . . ? C21 C19 C18 110.0(6) . . ? C25 C19 C18 109.6(6) . . ? C21 C19 C20 110.1(6) . . ? C25 C19 C20 109.2(6) . . ? C18 C19 C20 107.4(6) . . ? C22 C21 N5 107.3(8) . . ? C22 C21 C19 131.4(8) . . ? N5 C21 C19 121.3(7) . . ? C21 C22 C23 107.4(8) . . ? C24 C23 C22 106.1(8) . . ? N5 C24 C23 109.3(7) . . ? N6 C25 C26 108.0(7) . . ? N6 C25 C19 122.5(7) . . ? C26 C25 C19 129.5(7) . . ? C25 C26 C27 107.8(7) . . ? C28 C27 C26 106.7(7) . . ? C27 C28 N6 107.7(7) . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N6 H6 Br5 0.88 3.13 3.646(7) 119.3 2_655 _diffrn_measured_fraction_theta_max 0.657 _diffrn_reflns_theta_full 25.03 _diffrn_measured_fraction_theta_full 0.657 _refine_diff_density_max 0.626 _refine_diff_density_min -0.835 _refine_diff_density_rms 0.120