# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2010 data_global _journal_name_full Chem.Commun. #TrackingRef 'CCDC773683.cif' _journal_coden_Cambridge 0182 _publ_section_title ; Formation of a cyclic tetrapeptide mimic by thermal azide-alkyne 1,3-dipolar cycloaddition ; loop_ _publ_author_name _publ_author_address 'Martin Krause' ; Fachbereich Chemie - Organische Chemie Technische Universit\"at Kaiserslautern 67663 Kaiserslautern Germany ; 'Richard Goddard' ; Max-Planck-Institut f\"ur Kohlenforschung Kaiser-Wilhelm-Platz 1 45470 M\"ulheim an der Ruhr Germany ; 'Stefan Kubik' ; Fachbereich Chemie - Organische Chemie Technische Universit\"at Kaiserslautern 67663 Kaiserslautern Germany ; _publ_contact_author_name 'Richard Goddard' _publ_contact_author_email goddard@mpi-muelheim.mpg.de data_9.2DMSO _database_code_depnum_ccdc_archive 'CCDC 773683' #TrackingRef 'CCDC773683.cif' _audit_creation_date 2010-02-18 _audit_block_code mk-369-Probe-1 _chemical_name_systematic ; cyclo-bis-((R)ethyl-1,5-triazol-2,6-pyridyl-amino-carbonyl) di(dimethylsulfoxide) solute ; _chemical_melting_point ? _chemical_compound_source dimethylsulfoxide/water _chemical_formula_moiety 'C20 H18 N10 O2, 2(C2 H6 O S)' _chemical_formula_sum 'C24 H30 N10 O4 S2' _chemical_formula_weight 586.70 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P 21 21 2' _symmetry_space_group_name_Hall 'p 2 2ab' _symmetry_Int_Tables_number 18 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-x+1/2, y+1/2, -z' 'x+1/2, -y+1/2, -z' _cell_length_a 12.2734(12) _cell_length_b 12.7812(13) _cell_length_c 8.6196(9) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1352.1(2) _cell_formula_units_Z 2 _cell_measurement_temperature 100 _cell_measurement_reflns_used 9387 _cell_measurement_theta_min 2.3006 _cell_measurement_theta_max 35.9860 loop_ _exptl_crystal_face_index_h _exptl_crystal_face_index_k _exptl_crystal_face_index_l _exptl_crystal_face_perp_dist -1.00 0.00 0.00 0.012 1.00 0.00 0.00 0.020 0.00 1.00 1.00 0.018 0.00 -1.00 -1.00 0.015 0.00 -1.00 1.00 0.010 0.00 1.00 -1.00 0.010 _exptl_crystal_description prism _exptl_crystal_colour colourless _exptl_crystal_size_max 0.045 _exptl_crystal_size_mid 0.040 _exptl_crystal_size_min 0.021 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.441 _exptl_crystal_density_method ? _exptl_crystal_F_000 616 _exptl_absorpt_coefficient_mu 0.249 _exptl_absorpt_correction_type gaussian _exptl_absorpt_correction_T_min 0.99192 _exptl_absorpt_correction_T_max 0.99527 _exptl_absorpt_process_details 'SADABS (Bruker AXS, 2008)' _exptl_special_details ; Crystal mounted on a MiTeGen loop using Perfluoropolyether PFO-XR75 ; _diffrn_ambient_temperature 100 _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type Mo-K\a _diffrn_radiation_source '0.2 x 2mm^2^ focus rotating anode' _diffrn_radiation_monochromator 'Incoatec Helios mirrors' _diffrn_measurement_device_type 'Bruker-AXS Kappa Mach3 APEX-II' _diffrn_measurement_method 'CCD \f- and \w-scans' _diffrn_detector_area_resol_mean 66.06 _diffrn_reflns_number 89526 _diffrn_reflns_av_R_equivalents 0.0388 _diffrn_reflns_av_sigmaI/netI 0.0179 _diffrn_reflns_limit_h_min -20 _diffrn_reflns_limit_h_max 20 _diffrn_reflns_limit_k_min -21 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 3.19 _diffrn_reflns_theta_max 36.50 _reflns_number_total 6518 _reflns_number_gt 6260 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'APEX2 (Bruker AXS, 2008)' _computing_cell_refinement 'SAINT software (Bruker AXS, 2004)' _computing_data_reduction 'SAINT software (Bruker AXS, 2004)' _computing_structure_solution 'SHELXS-97 (G. M. Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (G. M. Sheldrick, 2008)' _computing_molecular_graphics 'DIAMOND (Crystal Impact GbR, 2005)' _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. The minimum and maximum estimated transmissions from the multi-scan scaling are 0.9266 and 1.0000 (SADABS). There are two independent half dimethylsulfoxide solute molecules in the asymmetric unit which are disordered about two independent 2-fold axes. Since C11A and the symmetry related C11B of one of the disordered dimethylsulfoxide solute molecules are very close to one another the S1-C11A and S1-C11B distances were restrained to be equal with an effective standard deviation of 0.02. The Hooft factor y based on 2840 Bijvoet pairs is -0.064(14). (R. W. W. Hooft, L. H. Straver, A. L. Spek, J. Appl. Cryst. 2008, 41, 96-103.) Highest peak 0.55 at 0.5353 0.1949 0.2611 [ 0.67 A from N5 ] Deepest hole -0.52 at 0.0443 0.0889 0.2266 [ 0.92 A from H12C ] ; _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^)+(0.0054P)^2^+3.2988P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.06(15) _chemical_absolute_configuration rmad _refine_ls_number_reflns 6518 _refine_ls_number_parameters 217 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0776 _refine_ls_R_factor_gt 0.0751 _refine_ls_wR_factor_ref 0.1819 _refine_ls_wR_factor_gt 0.1809 _refine_ls_goodness_of_fit_ref 1.226 _refine_ls_restrained_S_all 1.226 _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 C1 C 0.68096(18) -0.08479(17) 0.1929(3) 0.0142(4) Uani 1 1 d . . . C2 C 0.6660(2) -0.16942(18) 0.0690(3) 0.0173(4) Uani 1 1 d . . . H2 H 0.5996 -0.1543 0.0100 0.021 Uiso 1 1 calc R . . C3 C 0.7627(3) -0.1702(2) -0.0421(5) 0.0373(9) Uani 1 1 d . . . H3A H 0.7521 -0.2234 -0.1192 0.056 Uiso 1 1 calc R . . H3B H 0.8283 -0.1845 0.0147 0.056 Uiso 1 1 calc R . . H3C H 0.7687 -0.1032 -0.0918 0.056 Uiso 1 1 calc R . . C4 C 0.6086(2) -0.39993(19) 0.2974(4) 0.0212(5) Uani 1 1 d . . . H4 H 0.5721 -0.4429 0.3673 0.025 Uiso 1 1 calc R . . C5 C 0.57409(17) -0.30267(16) 0.2486(3) 0.0135(3) Uani 1 1 d . . . C6 C 0.47575(18) -0.24328(16) 0.2914(3) 0.0123(3) Uani 1 1 d . . . C7 C 0.4080(2) -0.27700(19) 0.4122(3) 0.0168(4) Uani 1 1 d . . . H7 H 0.4220 -0.3389 0.4652 0.020 Uiso 1 1 calc R . . C8 C 0.3192(2) -0.2149(2) 0.4500(3) 0.0200(5) Uani 1 1 d . . . H8 H 0.2733 -0.2344 0.5307 0.024 Uiso 1 1 calc R . . C9 C 0.7013(2) 0.12352(19) 0.3677(3) 0.0190(4) Uani 1 1 d . . . H9 H 0.7601 0.0808 0.3925 0.023 Uiso 1 1 calc R . . C10 C 0.63064(17) 0.09802(16) 0.2463(3) 0.0130(3) Uani 1 1 d . . . C11A C 0.4294(14) 0.0891(16) 0.635(2) 0.077(6) Uani 0.50 1 d PD A -1 H11A H 0.4048 0.1507 0.6886 0.115 Uiso 0.50 1 calc PR A -1 H11B H 0.3730 0.0371 0.6373 0.115 Uiso 0.50 1 calc PR A -1 H11C H 0.4466 0.1063 0.5298 0.115 Uiso 0.50 1 calc PR A -1 C11B C 0.5786(11) -0.0668(11) 0.626(2) 0.041(3) Uani 0.50 1 d PD A -1 H11D H 0.6461 -0.0921 0.6678 0.061 Uiso 0.50 1 calc PR A -1 H11E H 0.5882 -0.0505 0.5178 0.061 Uiso 0.50 1 calc PR A -1 H11F H 0.5236 -0.1197 0.6366 0.061 Uiso 0.50 1 calc PR A -1 C12 C -0.0080(6) 0.1487(5) 0.1949(7) 0.0294(12) Uani 0.50 1 d P B -1 H12A H -0.0518 0.1951 0.2564 0.044 Uiso 0.50 1 calc PR B -1 H12B H -0.0174 0.1651 0.0870 0.044 Uiso 0.50 1 calc PR B -1 H12C H 0.0673 0.1570 0.2227 0.044 Uiso 0.50 1 calc PR B -1 C13 C 0.0457(5) -0.0454(6) 0.1009(9) 0.0333(14) Uani 0.50 1 d P B -1 H13A H 0.0357 -0.1198 0.1040 0.050 Uiso 0.50 1 calc PR B -1 H13B H 0.1186 -0.0286 0.1326 0.050 Uiso 0.50 1 calc PR B -1 H13C H 0.0338 -0.0206 -0.0028 0.050 Uiso 0.50 1 calc PR B -1 N1 N 0.64239(16) 0.01033(15) 0.1494(2) 0.0133(3) Uani 1 1 d . . . H1 H 0.6234 0.0176 0.0539 0.016 Uiso 1 1 calc R . . N2 N 0.65275(16) -0.27039(15) 0.1485(3) 0.0149(3) Uani 1 1 d . . . N3 N 0.73167(19) -0.34416(17) 0.1351(3) 0.0243(5) Uani 1 1 d . . . N4 N 0.7043(2) -0.42254(18) 0.2269(4) 0.0283(5) Uani 1 1 d . . . N5 N 0.45576(15) -0.15663(14) 0.2087(2) 0.0120(3) Uani 1 1 d . . . O1 O 0.72504(19) -0.10348(15) 0.3166(3) 0.0285(5) Uani 1 1 d . . . O2 O 0.5101(6) 0.0165(5) 0.8880(4) 0.0194(10) Uani 0.50 1 d P A -1 O3 O 0.0144(11) 0.0048(17) 0.3920(4) 0.029(2) Uani 0.50 1 d P B -1 S1 S 0.53968(12) 0.04261(14) 0.72272(16) 0.0273(3) Uani 0.50 1 d PD A -1 S2 S -0.04921(10) 0.01592(12) 0.22958(15) 0.0208(2) Uani 0.50 1 d P B -1 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 C1 0.0119(8) 0.0104(8) 0.0204(10) -0.0009(7) -0.0001(7) 0.0002(6) C2 0.0180(10) 0.0108(8) 0.0233(11) -0.0019(8) 0.0072(8) 0.0013(7) C3 0.0389(17) 0.0162(11) 0.057(2) 0.0004(12) 0.0360(17) 0.0041(11) C4 0.0178(10) 0.0118(8) 0.0341(13) 0.0039(9) -0.0042(10) 0.0017(7) C5 0.0126(8) 0.0104(8) 0.0175(9) -0.0012(7) -0.0019(7) 0.0008(6) C6 0.0147(8) 0.0105(7) 0.0116(8) -0.0005(6) -0.0019(7) -0.0013(6) C7 0.0243(11) 0.0132(8) 0.0127(9) 0.0018(7) 0.0022(8) -0.0011(8) C8 0.0260(11) 0.0141(9) 0.0200(11) 0.0016(8) 0.0079(9) -0.0028(9) C9 0.0198(10) 0.0134(9) 0.0238(11) 0.0001(8) -0.0110(9) -0.0005(8) C10 0.0132(8) 0.0097(7) 0.0161(9) 0.0003(7) -0.0017(7) -0.0009(6) C11A 0.112(15) 0.088(12) 0.030(6) 0.030(7) 0.009(8) -0.002(11) C11B 0.040(5) 0.053(5) 0.029(5) -0.027(4) 0.024(4) -0.024(4) C12 0.030(3) 0.035(3) 0.024(2) 0.010(2) -0.006(2) 0.008(2) C13 0.021(2) 0.039(3) 0.040(3) -0.008(3) 0.008(2) -0.003(2) N1 0.0146(7) 0.0101(7) 0.0151(7) 0.0001(6) 0.0007(6) 0.0011(6) N2 0.0138(7) 0.0104(7) 0.0205(9) -0.0015(6) 0.0014(7) 0.0025(6) N3 0.0181(9) 0.0128(8) 0.0422(14) -0.0005(9) 0.0042(10) 0.0041(7) N4 0.0208(10) 0.0141(8) 0.0499(17) 0.0032(10) 0.0002(11) 0.0039(7) N5 0.0124(7) 0.0098(6) 0.0138(7) -0.0001(6) -0.0014(6) -0.0002(5) O1 0.0326(11) 0.0134(7) 0.0396(12) -0.0004(8) -0.0233(10) 0.0017(7) O2 0.020(3) 0.028(4) 0.0103(11) 0.0010(13) -0.0003(13) -0.002(2) O3 0.038(7) 0.036(4) 0.0133(12) -0.007(2) 0.0011(18) -0.002(5) S1 0.0244(6) 0.0453(8) 0.0123(5) 0.0048(5) -0.0009(5) -0.0147(6) S2 0.0161(5) 0.0302(6) 0.0162(5) -0.0021(5) 0.0019(4) -0.0024(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 C1 O1 1.219(3) . y C1 N1 1.358(3) . y C1 C2 1.531(3) . y C2 N2 1.470(3) . y C2 C3 1.525(4) . y C4 N4 1.353(4) . y C4 C5 1.379(3) . y C5 N2 1.359(3) . y C5 C6 1.473(3) . y C6 N5 1.340(3) . y C6 C7 1.400(3) . y C7 C8 1.387(4) . y C8 C9 1.389(4) 2_655 y C9 C8 1.389(4) 2_655 y C9 C10 1.397(3) . y C10 N5 1.338(3) 2_655 y C10 N1 1.405(3) . y C11A S1 1.659(13) . y C11B S1 1.698(10) . y C12 S2 1.797(7) . y C13 S2 1.789(7) . y N2 N3 1.357(3) . y N3 N4 1.320(4) . y N5 C10 1.338(3) 2_655 y O2 S1 1.508(4) . y O3 S2 1.609(9) . y 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 O1 C1 N1 124.9(2) . . y O1 C1 C2 121.7(2) . . y N1 C1 C2 113.5(2) . . y N2 C2 C3 111.9(2) . . y N2 C2 C1 107.9(2) . . y C3 C2 C1 110.5(2) . . y N4 C4 C5 108.8(2) . . y N2 C5 C4 104.4(2) . . y N2 C5 C6 125.79(19) . . y C4 C5 C6 129.8(2) . . y N5 C6 C7 122.8(2) . . y N5 C6 C5 116.28(19) . . y C7 C6 C5 121.0(2) . . y C8 C7 C6 117.7(2) . . y C7 C8 C9 120.3(2) . 2_655 y C8 C9 C10 117.7(2) 2_655 . y N5 C10 C9 122.9(2) 2_655 . y N5 C10 N1 112.56(19) 2_655 . y C9 C10 N1 124.6(2) . . y C1 N1 C10 125.9(2) . . y N3 N2 C5 110.5(2) . . y N3 N2 C2 119.4(2) . . y C5 N2 C2 129.88(19) . . y N4 N3 N2 107.1(2) . . y N3 N4 C4 109.2(2) . . y C10 N5 C6 118.6(2) 2_655 . y O2 S1 C11A 108.1(8) . . y O2 S1 C11B 110.6(7) . . y C11A S1 C11B 107.5(7) . . y O3 S2 C13 100.7(7) . . y O3 S2 C12 95.3(7) . . y C13 S2 C12 97.3(3) . . y _diffrn_measured_fraction_theta_max 0.985 _diffrn_reflns_theta_full 35.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.553 _refine_diff_density_min -0.516 _refine_diff_density_rms 0.116 _chemical_name_common ; cyclo-bis-((R)ethyl-1,5-triazol-2,6-pyridyl-amino-carbonyl) di(dimethylsulfoxide) solute ; # Attachment 'CCDC773685.cif' data_10 _database_code_depnum_ccdc_archive 'CCDC 773685' #TrackingRef 'CCDC773685.cif' _audit_creation_date 2010-04-13 _audit_block_code KUB-POHL-Tetr-Pept _chemical_name_systematic ; cylo-bis[(L)-prolyl-alpha-6-amino-2-picolinyl] ; _chemical_melting_point none _chemical_compound_source 'sublimation at 260 degs C' _chemical_formula_moiety 'C22 H22 N6 O4' _chemical_formula_sum 'C22 H22 N6 O4' _chemical_formula_weight 434.46 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P 21 21 21' _symmetry_space_group_name_Hall 'P 2ac 2ab' _symmetry_Int_Tables_number 19 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' _cell_length_a 9.138(4) _cell_length_b 11.325(5) _cell_length_c 19.715(8) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2040.3(14) _cell_formula_units_Z 4 _cell_measurement_temperature 293 _cell_measurement_reflns_used 1005 _cell_measurement_theta_min 2.918 _cell_measurement_theta_max 32.156 _exptl_crystal_description needle _exptl_crystal_colour colourless _exptl_crystal_size_max 0.550 _exptl_crystal_size_mid 0.005 _exptl_crystal_size_min 0.005 _exptl_crystal_density_meas none _exptl_crystal_density_diffrn 1.414 _exptl_crystal_density_method none _exptl_crystal_F_000 912 _exptl_absorpt_coefficient_mu 0.832 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'SADABS, Bruker AXS (2004)' _exptl_absorpt_correction_T_min 0.632224 _exptl_absorpt_correction_T_max 1.0 _diffrn_ambient_temperature 294 _diffrn_radiation_wavelength 1.0 _diffrn_radiation_type synchrotron _diffrn_radiation_source 'SCD beamline, ANKA, Karlsruhe' _diffrn_radiation_monochromator Si-111 _diffrn_measurement_device_type 'Bruker AXS APEX1' _diffrn_measurement_method 'CCD \f- and \w-scans' _diffrn_standards_number 0 _diffrn_standards_decay_% 0.0 _diffrn_reflns_number 19076 _diffrn_reflns_av_R_equivalents 0.0867 _diffrn_reflns_av_sigmaI/netI 0.0731 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 2.91 _diffrn_reflns_theta_max 33.85 _reflns_number_total 2848 _reflns_number_gt 2661 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'SMART V5.631 (Bruker AXS, 2000)' _computing_cell_refinement 'SAINT V6.45a (Bruker AXS, 2000)' _computing_data_reduction 'SAINT V6.45a (Bruker AXS, 2000)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'DIAMOND (Crystal Impact GbR, 2005)' _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. The relatively low sine(theta_max)/wavelength of 0.557, instead of the preferred minimum of 0.575, and the percentage of diffraction data measured at maximum theta of 98% is due to the very small thickness (ca. 10 micron) of the needle causing difficulty in integrating intensities at high angles, in spite of using synchrotron radiation at the Karlsruhe ANKA synchrotron facility. The relatively high atomic displacement parameters of C4 and C15 relative to neighbours indicate conformational flexibility in the prolyl groups. The methylene group of one of the prolyl groups was refined using a disordered model (occupancy C4A:C4B 0.5:0.5). Highest peak 0.27 at 0.8574 0.4051 0.2322 [ 0.69 A from H15B ] Deepest hole -0.21 at 0.9208 0.4316 0.1865 [ 0.09 A from H15A ] ; _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^)+(0.0619P)^2^+0.7217P] 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_abs_structure_details 'Flack, H. D. (1983). Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.3(4) _chemical_absolute_configuration rm _refine_ls_number_reflns 2848 _refine_ls_number_parameters 298 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0535 _refine_ls_R_factor_gt 0.0496 _refine_ls_wR_factor_ref 0.1342 _refine_ls_wR_factor_gt 0.1297 _refine_ls_goodness_of_fit_ref 1.035 _refine_ls_restrained_S_all 1.035 _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 C1 C 0.7612(4) 0.2363(3) 0.79575(15) 0.0436(7) Uani 1 1 d . . . C2 C 0.8912(3) 0.1576(3) 0.78153(17) 0.0495(9) Uani 1 1 d . B . H2 H 0.9549 0.1529 0.8214 0.059 Uiso 1 1 calc R . . C3 C 0.9756(5) 0.2051(4) 0.72059(19) 0.0707(12) Uani 1 1 d . . . H3A H 0.9145 0.2590 0.6949 0.085 Uiso 1 1 calc R A 1 H3B H 1.0617 0.2476 0.7358 0.085 Uiso 1 1 calc R A 1 C4A C 1.0196(11) 0.1032(9) 0.6772(5) 0.069(2) Uani 0.50 1 d P B 1 H4A H 1.1135 0.0716 0.6911 0.083 Uiso 0.50 1 calc PR B 1 H4B H 1.0245 0.1257 0.6298 0.083 Uiso 0.50 1 calc PR B 1 C4B C 0.9274(13) 0.1380(9) 0.6647(4) 0.071(2) Uani 0.50 1 d P B 2 H4C H 1.0023 0.1363 0.6299 0.085 Uiso 0.50 1 calc PR B 2 H4D H 0.8395 0.1727 0.6456 0.085 Uiso 0.50 1 calc PR B 2 C5 C 0.8961(5) 0.0142(4) 0.68976(19) 0.0664(11) Uani 1 1 d . . . H5A H 0.8168 0.0257 0.6577 0.080 Uiso 1 1 calc R C 1 H5B H 0.9319 -0.0661 0.6857 0.080 Uiso 1 1 calc R C 1 C6 C 0.7640(4) -0.0435(3) 0.79093(17) 0.0504(8) Uani 1 1 d . . . C7 C 0.7145(4) -0.0298(3) 0.86311(17) 0.0460(8) Uani 1 1 d . B . C8 C 0.6201(5) -0.1125(3) 0.8898(2) 0.0648(11) Uani 1 1 d . . . H8 H 0.5916 -0.1773 0.8640 0.078 Uiso 1 1 calc R B . C9 C 0.5681(5) -0.0988(4) 0.9548(2) 0.0758(12) Uani 1 1 d . B . H9 H 0.5042 -0.1540 0.9732 0.091 Uiso 1 1 calc R . . C10 C 0.6117(4) -0.0025(3) 0.99202(19) 0.0599(10) Uani 1 1 d . . . H10 H 0.5769 0.0100 1.0358 0.072 Uiso 1 1 calc R B . C11 C 0.7094(3) 0.0752(3) 0.96213(16) 0.0424(7) Uani 1 1 d . B . C12 C 0.6897(3) 0.2514(3) 1.03645(14) 0.0398(7) Uani 1 1 d . B . C13 C 0.7858(3) 0.3466(3) 1.06618(15) 0.0410(7) Uani 1 1 d . . . H13 H 0.8688 0.3617 1.0359 0.049 Uiso 1 1 calc R . . C14 C 0.8414(6) 0.3054(4) 1.13486(19) 0.0783(13) Uani 1 1 d . . . H14A H 0.7824 0.2398 1.1508 0.094 Uiso 1 1 calc R . . H14B H 0.9419 0.2786 1.1308 0.094 Uiso 1 1 calc R . . C15 C 0.8336(7) 0.3985(5) 1.1809(2) 0.104(2) Uani 1 1 d . . . H15A H 0.9301 0.4321 1.1877 0.124 Uiso 1 1 calc R . . H15B H 0.7980 0.3700 1.2243 0.124 Uiso 1 1 calc R . . C16 C 0.7312(4) 0.4912(3) 1.15352(16) 0.0536(9) Uani 1 1 d . . . H16A H 0.6387 0.4903 1.1776 0.064 Uiso 1 1 calc R . . H16B H 0.7741 0.5693 1.1573 0.064 Uiso 1 1 calc R . . C17 C 0.6371(4) 0.5324(3) 1.04040(17) 0.0490(8) Uani 1 1 d . . . C18 C 0.6186(3) 0.5052(3) 0.96619(16) 0.0428(8) Uani 1 1 d . . . C19 C 0.5124(4) 0.5638(3) 0.92979(18) 0.0516(9) Uani 1 1 d . . . H19 H 0.4535 0.6199 0.9508 0.062 Uiso 1 1 calc R . . C20 C 0.4944(4) 0.5387(3) 0.86225(18) 0.0568(9) Uani 1 1 d . . . H20 H 0.4243 0.5787 0.8369 0.068 Uiso 1 1 calc R . . C21 C 0.5804(4) 0.4542(3) 0.83220(16) 0.0483(8) Uani 1 1 d . . . H21 H 0.5673 0.4332 0.7870 0.058 Uiso 1 1 calc R . . C22 C 0.6879(3) 0.4010(3) 0.87170(15) 0.0396(7) Uani 1 1 d . . . N1 N 0.7870(3) 0.3175(2) 0.84612(13) 0.0452(7) Uani 1 1 d . . . H1 H 0.8729 0.3171 0.8639 0.054 Uiso 1 1 calc R . . N2 N 0.8473(3) 0.0385(3) 0.75926(13) 0.0508(7) Uani 1 1 d . B . N3 N 0.7603(3) 0.0633(2) 0.89986(13) 0.0406(6) Uani 1 1 d . . . N4 N 0.7657(3) 0.1740(2) 0.99716(12) 0.0412(6) Uani 1 1 d . . . H4 H 0.8581 0.1867 0.9932 0.049 Uiso 1 1 calc R B . N5 N 0.7110(3) 0.4580(2) 1.08176(12) 0.0429(6) Uani 1 1 d . . . N6 N 0.7075(3) 0.4257(2) 0.93737(12) 0.0432(6) Uani 1 1 d . . . O1 O 0.6490(3) 0.2330(2) 0.76298(13) 0.0665(7) Uani 1 1 d . . . O2 O 0.7271(3) -0.1338(2) 0.76076(13) 0.0686(7) Uani 1 1 d . B . O3 O 0.5597(2) 0.2394(2) 1.04985(11) 0.0527(6) Uani 1 1 d . . . O4 O 0.5817(4) 0.6226(2) 1.06330(14) 0.0764(9) 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 C1 0.0478(18) 0.0461(19) 0.0369(16) -0.0040(14) 0.0018(15) -0.0110(16) C2 0.0455(18) 0.050(2) 0.0527(19) -0.0132(16) 0.0058(15) -0.0051(16) C3 0.065(2) 0.086(3) 0.061(2) -0.013(2) 0.0192(19) -0.015(2) C4A 0.057(5) 0.088(7) 0.063(5) -0.015(5) 0.009(4) 0.008(5) C4B 0.074(6) 0.085(7) 0.054(5) -0.017(5) 0.017(5) -0.010(6) C5 0.080(3) 0.067(3) 0.052(2) -0.0140(19) 0.0069(18) 0.004(2) C6 0.0470(18) 0.045(2) 0.0591(19) -0.0181(17) -0.0084(16) 0.0016(17) C7 0.0439(18) 0.0350(18) 0.0590(19) -0.0098(16) -0.0077(15) 0.0029(16) C8 0.083(3) 0.038(2) 0.073(3) -0.0122(19) 0.003(2) -0.014(2) C9 0.105(3) 0.049(2) 0.073(3) -0.005(2) 0.017(2) -0.032(2) C10 0.084(3) 0.040(2) 0.055(2) -0.0024(17) 0.0058(19) -0.012(2) C11 0.0485(17) 0.0339(16) 0.0448(17) -0.0022(14) -0.0053(14) 0.0057(15) C12 0.0441(18) 0.0370(17) 0.0382(15) 0.0026(14) -0.0012(13) 0.0071(15) C13 0.0398(16) 0.0411(18) 0.0422(16) -0.0054(14) -0.0048(13) 0.0035(15) C14 0.112(3) 0.065(3) 0.057(2) -0.013(2) -0.034(2) 0.029(3) C15 0.165(5) 0.099(4) 0.047(2) -0.012(2) -0.017(3) 0.052(4) C16 0.067(2) 0.051(2) 0.0420(17) -0.0082(15) 0.0008(16) 0.0032(18) C17 0.0585(19) 0.0339(18) 0.0546(19) -0.0057(16) 0.0064(16) 0.0105(17) C18 0.0529(18) 0.0252(15) 0.0504(18) -0.0014(14) 0.0059(15) 0.0012(15) C19 0.056(2) 0.0359(18) 0.063(2) 0.0028(16) 0.0006(17) 0.0106(17) C20 0.057(2) 0.048(2) 0.066(2) 0.0096(18) -0.0083(17) 0.0059(18) C21 0.0558(19) 0.0434(19) 0.0456(18) 0.0039(15) -0.0061(15) -0.0046(17) C22 0.0442(17) 0.0295(16) 0.0450(18) 0.0049(13) 0.0041(13) -0.0049(14) N1 0.0440(14) 0.0434(15) 0.0482(15) -0.0057(13) 0.0003(12) -0.0004(13) N2 0.0549(15) 0.0496(18) 0.0481(15) -0.0169(14) 0.0027(13) 0.0022(15) N3 0.0388(13) 0.0330(14) 0.0499(15) -0.0039(12) -0.0033(12) 0.0035(11) N4 0.0407(13) 0.0383(15) 0.0445(13) -0.0082(12) -0.0017(12) 0.0023(12) N5 0.0520(15) 0.0368(14) 0.0398(14) -0.0090(12) -0.0004(11) 0.0049(14) N6 0.0501(15) 0.0384(14) 0.0411(14) 0.0011(12) 0.0001(11) 0.0009(13) O1 0.0577(15) 0.0735(18) 0.0684(16) -0.0235(14) -0.0123(13) 0.0072(14) O2 0.0784(18) 0.0561(16) 0.0714(16) -0.0278(14) 0.0004(14) -0.0031(14) O3 0.0432(13) 0.0534(14) 0.0615(14) -0.0082(12) 0.0065(11) -0.0036(11) O4 0.110(2) 0.0525(16) 0.0668(16) -0.0132(13) -0.0066(15) 0.0304(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 C1 O1 1.213(4) . y C1 N1 1.374(4) . y C1 C2 1.511(5) . y C2 N2 1.475(4) . y C2 C3 1.526(5) . y C3 C4B 1.408(10) . y C3 C4A 1.491(10) . y C4A C5 1.533(10) . y C4B C5 1.514(10) . y C5 N2 1.467(5) . y C6 O2 1.230(4) . y C6 N2 1.353(4) . y C6 C7 1.501(5) . y C7 N3 1.346(4) . y C7 C8 1.379(5) . y C8 C9 1.374(6) . y C9 C10 1.374(5) . y C10 C11 1.385(5) . y C11 N3 1.319(4) . y C11 N4 1.413(4) . y C12 O3 1.225(4) . y C12 N4 1.360(4) . y C12 C13 1.509(4) . y C13 N5 1.467(4) . y C13 C14 1.520(5) . y C14 C15 1.393(6) . y C15 C16 1.507(6) . y C16 N5 1.476(4) . y C17 O4 1.227(4) . y C17 N5 1.353(4) . y C17 C18 1.505(5) . y C18 N6 1.339(4) . y C18 C19 1.378(5) . y C19 C20 1.371(5) . y C20 C21 1.373(5) . y C21 C22 1.390(5) . y C22 N6 1.337(4) . y C22 N1 1.403(4) . y 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 O1 C1 N1 123.4(3) . . y O1 C1 C2 123.2(3) . . y N1 C1 C2 113.2(3) . . y N2 C2 C1 112.4(3) . . y N2 C2 C3 103.0(3) . . y C1 C2 C3 109.6(3) . . y C4B C3 C2 105.5(5) . . y C4A C3 C2 108.4(5) . . y C3 C4A C5 102.6(6) . . y C3 C4B C5 107.7(7) . . y N2 C5 C4B 100.9(4) . . y N2 C5 C4A 104.6(4) . . y O2 C6 N2 120.1(3) . . y O2 C6 C7 117.5(3) . . y N2 C6 C7 122.4(3) . . y N3 C7 C8 121.4(3) . . y N3 C7 C6 119.9(3) . . y C8 C7 C6 118.7(3) . . y C9 C8 C7 119.7(3) . . y C10 C9 C8 119.2(4) . . y C9 C10 C11 117.6(3) . . y N3 C11 C10 123.9(3) . . y N3 C11 N4 114.0(3) . . y C10 C11 N4 122.0(3) . . y O3 C12 N4 123.2(3) . . y O3 C12 C13 124.0(3) . . y N4 C12 C13 112.6(3) . . y N5 C13 C12 115.1(2) . . y N5 C13 C14 103.5(3) . . y C12 C13 C14 108.7(3) . . y C15 C14 C13 109.3(3) . . y C14 C15 C16 109.0(3) . . y N5 C16 C15 104.1(3) . . y O4 C17 N5 120.2(3) . . y O4 C17 C18 118.8(3) . . y N5 C17 C18 121.0(3) . . y N6 C18 C19 122.0(3) . . y N6 C18 C17 118.8(3) . . y C19 C18 C17 119.1(3) . . y C20 C19 C18 119.3(3) . . y C19 C20 C21 119.7(3) . . y C20 C21 C22 117.7(3) . . y N6 C22 C21 123.1(3) . . y N6 C22 N1 113.7(3) . . y C21 C22 N1 123.1(3) . . y C1 N1 C22 126.9(3) . . y C6 N2 C5 118.3(3) . . y C6 N2 C2 130.0(3) . . y C5 N2 C2 111.5(3) . . y C11 N3 C7 118.1(3) . . y C12 N4 C11 127.1(3) . . y C17 N5 C13 129.9(2) . . y C17 N5 C16 118.8(3) . . y C13 N5 C16 111.2(3) . . y C22 N6 C18 118.1(3) . . y _diffrn_measured_fraction_theta_max 0.977 _diffrn_reflns_theta_full 33.85 _diffrn_measured_fraction_theta_full 0.977 _refine_diff_density_max 0.270 _refine_diff_density_min -0.209 _refine_diff_density_rms 0.047 _chemical_name_common cylo-bis((L)-prolyl-alpha-6-amino-2-picolinyl)