Electronic Supplementary Material for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2006 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_cambridge 0177 _journal_year ? _journal_volume ? _journal_page_first ? _publ_contact_author 'Jonathan Clayden' _publ_contact_author_email j.p.clayden@manchester.ac.uk _publ_contact_letter ; ENTER TEXT OF LETTER ; _publ_requested_coeditor_name ? _publ_section_title ; Conformational arm-wrestling: battles for stereochemical control in benzamides bearing matched and mismatched chiral 2- and 6- substituents ; loop_ _publ_author_name J.Clayden 'Yann J.Y.Foricher' 'Madeleine Helliwell' 'Paul Johnson' 'David Mitjans' ; V.Vinander ; _publ_contact_author_name 'Jonathan Clayden' data_S830 _database_code_depnum_ccdc_archive 'CCDC 286090' #------------------------------------------------------------------------------ _audit_creation_date 19100-04-26 _audit_creation_method 'by teXsan v1.7' _audit_update_record ; ? ; _publ_section_abstract ; ENTER ABSTRACT ; _publ_section_exptl_prep ; ENTER EXPERIMENTAL SECTION ; _publ_section_exptl_refinement ; The structure was solved by direct methods. Non-H atoms were refined anisotropically, and H atoms were included in calculated positions. ; _publ_section_comment ; ENTER TEXT ; _publ_section_references ; ENTER OTHER REFERENCES Molecular Structure Corporation. (1995). teXsan. Single Crystal Structure Analysis Software. Version 1.7. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA. Altomare, A., Cascarano, M., Giacovazzo, C., Guagliardi, A. (1993). J. Appl. Cryst., 26, 343. ; _publ_section_acknowledgements ; ENTER ACKNOWLEDGEMENTS ; _publ_section_table_legends ; ENTER TABLE LEGENDS ; _publ_section_figure_captions ; ENTER FIGURE CAPTIONS ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C35 H45 N3 O3' _chemical_formula_weight 555.74 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 monoclinic _symmetry_space_group_name_H-M 'P 21/n ' _symmetry_Int_Tables_number 14 _symmetry_space_group_name_Hall ? 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 14.361(3) _cell_length_b 7.2093(13) _cell_length_c 31.922(5) _cell_angle_alpha 90.00 _cell_angle_beta 92.459(14) _cell_angle_gamma 90.00 _cell_volume 3301.9(10) _cell_formula_units_Z 4 _cell_measurement_temperature 296.2 _cell_measurement_reflns_used 24 _cell_measurement_theta_min 14.4 _cell_measurement_theta_max 15.7 _exptl_crystal_description tabular _exptl_crystal_colour colourless _exptl_crystal_size_max 0.65 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.118 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1200 _exptl_absorpt_coefficient_mu 0.558 _exptl_absorpt_correction_type ; \y scans (North,Phillips & Matthews, 1968) ; _exptl_absorpt_correction_T_max 1.000 _exptl_absorpt_correction_T_min 0.945 _exptl_special_details ; The scan width was (1.00+0.30tan\q)\% with an \w scan speed of 16\% per minute (up to 4 scans to achieve I/\s(I) > 10). Stationary background counts were recorded at each end of the scan, and the scan time:background time ratio was 2:1. ; #------------------------------------------------------------------------------ _diffrn_special_details ; ? ; _diffrn_ambient_temperature 296.2 _diffrn_radiation_wavelength 1.5418 _diffrn_radiation_type 'Cu K\a' _diffrn_radiation_source 'Rigaku rotating anode' _diffrn_radiation_monochromator graphite _diffrn_radiation_detector 'scintillation counter' _diffrn_measurement_device 'Rigaku AFC5R' _diffrn_measurement_method \w-2\q _diffrn_standards_number 3 _diffrn_standards_interval_count 150 _diffrn_standards_decay_% -0.76 loop_ _diffrn_standard_refln_index_h _diffrn_standard_refln_index_k _diffrn_standard_refln_index_l -4 0 -6 -1 2 -5 -2 2 4 _diffrn_reflns_number 6543 _diffrn_reflns_av_R_equivalents 0.0213 _diffrn_reflns_av_sigmaI/netI 0.0340 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -40 _diffrn_reflns_limit_l_max 40 _diffrn_reflns_theta_min 2.77 _diffrn_reflns_theta_max 78.20 _diffrn_reflns_reduction_process 'Lp corrections applied' _diffrn_orient_matrix_UB_11 -0.05401 _diffrn_orient_matrix_UB_12 0.00376 _diffrn_orient_matrix_UB_13 -0.02082 _diffrn_orient_matrix_UB_21 -0.04399 _diffrn_orient_matrix_UB_22 0.00300 _diffrn_orient_matrix_UB_23 0.02344 _diffrn_orient_matrix_UB_31 0.00239 _diffrn_orient_matrix_UB_32 0.13863 _diffrn_orient_matrix_UB_33 0.00005 _reflns_number_total 6276 _reflns_number_gt 4187 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'MSC/AFC Diffractometer Control' _computing_cell_refinement 'MSC/AFC Diffractometer Control' _computing_data_reduction 'teXsan (MSC, 1995)' _computing_structure_solution ; SIR92 (Altomare, et. al. 1993) ; _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_publication_material 'teXsan (MSC, 1995)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme 'calc w=1/[\s^2^(Fo^2^)+(0.0590P)^2^+0.5858P] 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 0.00118(12) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 6276 _refine_ls_number_parameters 379 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0858 _refine_ls_R_factor_gt 0.0486 _refine_ls_wR_factor_ref 0.1425 _refine_ls_wR_factor_gt 0.1245 _refine_ls_goodness_of_fit_ref 1.028 _refine_ls_restrained_S_all 1.028 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group O1 O 0.89201(11) 0.1387(2) 0.58378(4) 0.0686(4) Uani 1 d . . . O2 O 1.06579(10) 0.55281(19) 0.67033(4) 0.0574(4) Uani 1 d . . . O3 O 1.01311(11) 0.2175(2) 0.78965(4) 0.0627(4) Uani 1 d . . . N1 N 0.85230(13) 0.4408(3) 0.58432(6) 0.0661(5) Uani 1 d . . . N2 N 1.11533(10) 0.2566(2) 0.66464(4) 0.0419(3) Uani 1 d . . . N3 N 0.96898(12) 0.5161(2) 0.78587(5) 0.0538(4) Uani 1 d . . . C1 C 0.88836(14) 0.2803(3) 0.65197(6) 0.0566(5) Uani 1 d . . . C2 C 0.95538(13) 0.3203(3) 0.68370(6) 0.0476(4) Uani 1 d . . . C3 C 0.93236(13) 0.3088(3) 0.72576(6) 0.0533(5) Uani 1 d . . . C4 C 0.84412(16) 0.2503(4) 0.73530(7) 0.0766(7) Uani 1 d . . . H4 H 0.8285 0.2417 0.7632 0.092 Uiso 1 calc R . . C5 C 0.77903(16) 0.2045(5) 0.70408(8) 0.0912(10) Uani 1 d . . . H5 H 0.7206 0.1612 0.7109 0.109 Uiso 1 calc R . . C6 C 0.80071(15) 0.2231(4) 0.66278(7) 0.0786(8) Uani 1 d . . . H6 H 0.7557 0.1969 0.6418 0.094 Uiso 1 calc R . . C7 C 0.91025(15) 0.3039(3) 0.60646(6) 0.0595(5) Uani 1 d . . . H7 H 0.9760 0.3376 0.6044 0.071 Uiso 1 calc R . . C8 C 0.87533(17) 0.1884(4) 0.54050(6) 0.0688(6) Uani 1 d . . . H8 H 0.9288 0.1486 0.5247 0.083 Uiso 1 calc R . . C9 C 0.87191(18) 0.4020(4) 0.54071(7) 0.0767(7) Uani 1 d . . . H9 H 0.9344 0.4486 0.5355 0.092 Uiso 1 calc R . . C10 C 0.78966(16) 0.0911(3) 0.52309(6) 0.0630(6) Uani 1 d . . . C11 C 0.78419(19) 0.0368(4) 0.48154(7) 0.0820(8) Uani 1 d . . . H11 H 0.8348 0.0566 0.4649 0.098 Uiso 1 calc R . . C12 C 0.7052(2) -0.0461(4) 0.46443(9) 0.0910(9) Uani 1 d . . . H12 H 0.7026 -0.0805 0.4363 0.109 Uiso 1 calc R . . C13 C 0.6307(2) -0.0782(4) 0.48831(10) 0.0894(8) Uani 1 d . . . H13 H 0.5774 -0.1345 0.4767 0.107 Uiso 1 calc R . . C14 C 0.6350(2) -0.0271(4) 0.52952(9) 0.0916(9) Uani 1 d . . . H14 H 0.5844 -0.0491 0.5461 0.110 Uiso 1 calc R . . C15 C 0.71377(18) 0.0567(4) 0.54671(7) 0.0769(7) Uani 1 d . . . H15 H 0.7157 0.0908 0.5748 0.092 Uiso 1 calc R . . C16 C 0.8036(2) 0.4923(5) 0.50963(9) 0.1098(11) Uani 1 d . . . H16A H 0.7413 0.4574 0.5160 0.165 Uiso 1 calc R . . H16B H 0.8164 0.4522 0.4818 0.165 Uiso 1 calc R . . H16C H 0.8098 0.6247 0.5114 0.165 Uiso 1 calc R . . C17 C 0.8742(2) 0.6310(4) 0.59707(10) 0.1046(10) Uani 1 d . . . H17A H 0.8672 0.6436 0.6267 0.157 Uiso 1 calc R . . H17B H 0.8325 0.7150 0.5823 0.157 Uiso 1 calc R . . H17C H 0.9372 0.6594 0.5905 0.157 Uiso 1 calc R . . C18 C 1.05082(13) 0.3858(3) 0.67233(5) 0.0436(4) Uani 1 d . . . C19 C 1.09901(14) 0.0549(3) 0.66841(6) 0.0471(4) Uani 1 d . . . H19 H 1.0342 0.0390 0.6762 0.057 Uiso 1 calc R . . C20 C 1.10876(18) -0.0436(3) 0.62688(7) 0.0674(6) Uani 1 d . . . H20A H 1.0712 0.0180 0.6055 0.101 Uiso 1 calc R . . H20B H 1.0885 -0.1699 0.6293 0.101 Uiso 1 calc R . . H20C H 1.1728 -0.0414 0.6195 0.101 Uiso 1 calc R . . C21 C 1.15953(17) -0.0278(3) 0.70332(7) 0.0662(6) Uani 1 d . . . H21A H 1.2239 -0.0148 0.6969 0.099 Uiso 1 calc R . . H21B H 1.1448 -0.1569 0.7063 0.099 Uiso 1 calc R . . H21C H 1.1484 0.0357 0.7291 0.099 Uiso 1 calc R . . C22 C 1.20850(13) 0.3148(3) 0.65161(6) 0.0502(5) Uani 1 d . . . H22 H 1.2436 0.2003 0.6472 0.060 Uiso 1 calc R . . C23 C 1.20342(18) 0.4148(4) 0.60958(7) 0.0722(7) Uani 1 d . . . H23A H 1.1653 0.3447 0.5899 0.108 Uiso 1 calc R . . H23B H 1.2650 0.4271 0.5994 0.108 Uiso 1 calc R . . H23C H 1.1767 0.5356 0.6130 0.108 Uiso 1 calc R . . C24 C 1.26220(16) 0.4208(4) 0.68564(8) 0.0759(7) Uani 1 d . . . H24A H 1.2347 0.5411 0.6888 0.114 Uiso 1 calc R . . H24B H 1.3258 0.4346 0.6781 0.114 Uiso 1 calc R . . H24C H 1.2602 0.3541 0.7116 0.114 Uiso 1 calc R . . C25 C 1.00098(14) 0.3635(3) 0.76046(6) 0.0522(5) Uani 1 d . . . H25 H 1.0609 0.3952 0.7488 0.063 Uiso 1 calc R . . C26 C 1.05105(14) 0.2985(3) 0.82755(6) 0.0555(5) Uani 1 d . . . H26 H 1.1188 0.2815 0.8282 0.067 Uiso 1 calc R . . C27 C 1.03051(16) 0.5089(3) 0.82338(6) 0.0600(5) Uani 1 d . . . H27 H 1.0887 0.5725 0.8173 0.072 Uiso 1 calc R . . C28 C 1.01388(15) 0.1994(3) 0.86470(6) 0.0558(5) Uani 1 d . . . C29 C 1.07059(18) 0.1753(4) 0.90014(7) 0.0738(7) Uani 1 d . . . H29 H 1.1313 0.2205 0.9006 0.089 Uiso 1 calc R . . C30 C 1.0392(2) 0.0855(5) 0.93503(8) 0.0985(10) Uani 1 d . . . H30 H 1.0787 0.0707 0.9586 0.118 Uiso 1 calc R . . C31 C 0.9513(3) 0.0193(5) 0.93497(9) 0.0960(9) Uani 1 d . . . H31 H 0.9307 -0.0424 0.9584 0.115 Uiso 1 calc R . . C32 C 0.8926(2) 0.0427(4) 0.90044(9) 0.0880(8) Uani 1 d . . . H32 H 0.8317 -0.0011 0.9006 0.106 Uiso 1 calc R . . C33 C 0.92432(17) 0.1320(4) 0.86527(7) 0.0712(6) Uani 1 d . . . H33 H 0.8845 0.1465 0.8418 0.085 Uiso 1 calc R . . C34 C 0.9893(3) 0.6021(4) 0.86053(8) 0.1010(10) Uani 1 d . . . H34A H 0.9810 0.7318 0.8548 0.152 Uiso 1 calc R . . H34B H 1.0305 0.5868 0.8848 0.152 Uiso 1 calc R . . H34C H 0.9300 0.5469 0.8657 0.152 Uiso 1 calc R . . C35 C 0.9720(2) 0.6943(4) 0.76456(8) 0.0802(7) Uani 1 d . . . H35A H 1.0343 0.7180 0.7563 0.120 Uiso 1 calc R . . H35B H 0.9531 0.7905 0.7832 0.120 Uiso 1 calc R . . H35C H 0.9305 0.6918 0.7402 0.120 Uiso 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 O1 0.0810(11) 0.0764(11) 0.0473(8) 0.0054(8) -0.0097(7) 0.0079(9) O2 0.0652(9) 0.0401(8) 0.0674(9) 0.0017(7) 0.0085(7) -0.0008(7) O3 0.0849(10) 0.0577(9) 0.0447(7) -0.0076(7) -0.0053(7) 0.0086(8) N1 0.0753(12) 0.0653(12) 0.0560(10) 0.0098(9) -0.0152(9) -0.0065(10) N2 0.0432(8) 0.0405(8) 0.0421(7) 0.0022(6) 0.0026(6) -0.0039(7) N3 0.0562(10) 0.0555(11) 0.0500(9) -0.0001(8) 0.0076(7) 0.0039(8) C1 0.0499(11) 0.0724(14) 0.0470(10) 0.0047(10) -0.0015(8) -0.0021(10) C2 0.0447(10) 0.0525(12) 0.0456(9) 0.0024(8) 0.0017(8) 0.0015(9) C3 0.0479(11) 0.0660(13) 0.0464(10) 0.0006(9) 0.0057(8) -0.0013(10) C4 0.0579(13) 0.122(2) 0.0501(11) 0.0026(13) 0.0111(10) -0.0125(14) C5 0.0492(13) 0.160(3) 0.0646(14) 0.0030(17) 0.0057(11) -0.0271(16) C6 0.0508(12) 0.127(2) 0.0571(12) 0.0034(14) -0.0040(10) -0.0154(14) C7 0.0516(11) 0.0773(15) 0.0491(11) 0.0086(11) -0.0052(9) -0.0043(11) C8 0.0669(14) 0.0961(19) 0.0432(10) 0.0038(11) -0.0001(10) 0.0048(13) C9 0.0796(16) 0.095(2) 0.0549(13) 0.0224(13) -0.0104(11) -0.0175(14) C10 0.0712(14) 0.0703(15) 0.0468(10) 0.0004(10) -0.0035(10) 0.0082(12) C11 0.0869(18) 0.111(2) 0.0482(12) -0.0063(13) -0.0004(12) 0.0079(16) C12 0.107(2) 0.101(2) 0.0635(15) -0.0203(15) -0.0182(15) 0.0129(19) C13 0.091(2) 0.087(2) 0.0877(19) -0.0117(16) -0.0211(16) -0.0051(16) C14 0.0858(18) 0.106(2) 0.0832(18) -0.0056(17) -0.0001(15) -0.0203(17) C15 0.0826(17) 0.0925(19) 0.0557(13) -0.0077(13) 0.0033(12) -0.0095(15) C16 0.153(3) 0.098(2) 0.0748(17) 0.0325(17) -0.0401(19) -0.008(2) C17 0.139(3) 0.076(2) 0.095(2) 0.0087(16) -0.0370(19) -0.0106(19) C18 0.0498(11) 0.0447(11) 0.0363(8) 0.0016(8) 0.0007(7) -0.0002(9) C19 0.0529(11) 0.0392(10) 0.0492(10) 0.0046(8) 0.0034(8) -0.0045(9) C20 0.0963(17) 0.0461(12) 0.0596(13) -0.0059(10) 0.0002(12) -0.0062(12) C21 0.0831(16) 0.0534(13) 0.0616(13) 0.0142(11) -0.0025(11) 0.0055(12) C22 0.0465(10) 0.0455(11) 0.0590(11) -0.0006(9) 0.0082(9) -0.0035(9) C23 0.0796(16) 0.0691(15) 0.0702(14) 0.0135(12) 0.0287(12) -0.0058(13) C24 0.0571(13) 0.0750(17) 0.0949(18) -0.0116(14) -0.0071(12) -0.0127(12) C25 0.0495(11) 0.0646(13) 0.0430(9) -0.0020(9) 0.0067(8) 0.0005(10) C26 0.0539(12) 0.0645(14) 0.0479(10) -0.0100(10) -0.0014(9) 0.0064(10) C27 0.0656(13) 0.0613(14) 0.0528(11) -0.0066(10) -0.0008(10) -0.0016(11) C28 0.0612(13) 0.0575(13) 0.0486(10) -0.0062(9) 0.0018(9) 0.0113(10) C29 0.0716(15) 0.0940(19) 0.0554(13) -0.0011(13) -0.0019(11) 0.0189(14) C30 0.109(2) 0.129(3) 0.0568(14) 0.0117(16) 0.0007(15) 0.031(2) C31 0.130(3) 0.095(2) 0.0645(16) 0.0083(15) 0.0225(17) 0.016(2) C32 0.091(2) 0.087(2) 0.0877(19) -0.0096(16) 0.0270(16) -0.0124(16) C33 0.0729(16) 0.0801(17) 0.0605(13) -0.0064(12) 0.0026(11) -0.0010(13) C34 0.171(3) 0.0709(18) 0.0611(15) -0.0158(13) 0.0021(17) 0.034(2) C35 0.0988(19) 0.0676(16) 0.0747(16) 0.0100(13) 0.0098(14) 0.0056(14) _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 O1 C7 1.413(3) . ? O1 C8 1.437(2) . ? O2 C18 1.225(2) . ? O3 C25 1.411(2) . ? O3 C26 1.430(2) . ? N1 C7 1.455(3) . ? N1 C9 1.459(3) . ? N1 C17 1.461(3) . ? N2 C18 1.344(2) . ? N2 C22 1.479(2) . ? N2 C19 1.479(2) . ? N3 C25 1.454(3) . ? N3 C35 1.455(3) . ? N3 C27 1.458(3) . ? C1 C6 1.382(3) . ? C1 C2 1.397(3) . ? C1 C7 1.509(3) . ? C2 C3 1.399(2) . ? C2 C18 1.509(3) . ? C3 C4 1.382(3) . ? C3 C25 1.503(3) . ? C4 C5 1.377(3) . ? C4 H4 0.9300 . ? C5 C6 1.374(3) . ? C5 H5 0.9300 . ? C6 H6 0.9300 . ? C7 H7 0.9800 . ? C8 C10 1.502(3) . ? C8 C9 1.541(4) . ? C8 H8 0.9800 . ? C9 C16 1.512(3) . ? C9 H9 0.9800 . ? C10 C15 1.374(3) . ? C10 C11 1.382(3) . ? C11 C12 1.375(4) . ? C11 H11 0.9300 . ? C12 C13 1.359(4) . ? C12 H12 0.9300 . ? C13 C14 1.365(4) . ? C13 H13 0.9300 . ? C14 C15 1.376(4) . ? C14 H14 0.9300 . ? C15 H15 0.9300 . ? C16 H16A 0.9600 . ? C16 H16B 0.9600 . ? C16 H16C 0.9600 . ? C17 H17A 0.9600 . ? C17 H17B 0.9600 . ? C17 H17C 0.9600 . ? C19 C21 1.506(3) . ? C19 C20 1.516(3) . ? C19 H19 0.9800 . ? C20 H20A 0.9600 . ? C20 H20B 0.9600 . ? C20 H20C 0.9600 . ? C21 H21A 0.9600 . ? C21 H21B 0.9600 . ? C21 H21C 0.9600 . ? C22 C24 1.512(3) . ? C22 C23 1.522(3) . ? C22 H22 0.9800 . ? C23 H23A 0.9600 . ? C23 H23B 0.9600 . ? C23 H23C 0.9600 . ? C24 H24A 0.9600 . ? C24 H24B 0.9600 . ? C24 H24C 0.9600 . ? C25 H25 0.9800 . ? C26 C28 1.502(3) . ? C26 C27 1.550(3) . ? C26 H26 0.9800 . ? C27 C34 1.506(3) . ? C27 H27 0.9800 . ? C28 C33 1.376(3) . ? C28 C29 1.376(3) . ? C29 C30 1.381(4) . ? C29 H29 0.9300 . ? C30 C31 1.349(4) . ? C30 H30 0.9300 . ? C31 C32 1.369(4) . ? C31 H31 0.9300 . ? C32 C33 1.388(4) . ? C32 H32 0.9300 . ? C33 H33 0.9300 . ? C34 H34A 0.9600 . ? C34 H34B 0.9600 . ? C34 H34C 0.9600 . ? C35 H35A 0.9600 . ? C35 H35B 0.9600 . ? C35 H35C 0.9600 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C7 O1 C8 107.59(17) . . ? C25 O3 C26 106.62(16) . . ? C7 N1 C9 101.75(19) . . ? C7 N1 C17 112.93(19) . . ? C9 N1 C17 113.5(2) . . ? C18 N2 C22 119.64(16) . . ? C18 N2 C19 123.62(15) . . ? C22 N2 C19 116.75(15) . . ? C25 N3 C35 113.01(17) . . ? C25 N3 C27 103.67(16) . . ? C35 N3 C27 112.73(19) . . ? C6 C1 C2 119.14(18) . . ? C6 C1 C7 120.23(19) . . ? C2 C1 C7 120.61(18) . . ? C1 C2 C3 119.99(18) . . ? C1 C2 C18 119.66(16) . . ? C3 C2 C18 120.27(16) . . ? C4 C3 C2 119.10(19) . . ? C4 C3 C25 119.73(18) . . ? C2 C3 C25 121.15(17) . . ? C5 C4 C3 120.9(2) . . ? C5 C4 H4 119.5 . . ? C3 C4 H4 119.5 . . ? C6 C5 C4 119.8(2) . . ? C6 C5 H5 120.1 . . ? C4 C5 H5 120.1 . . ? C5 C6 C1 121.0(2) . . ? C5 C6 H6 119.5 . . ? C1 C6 H6 119.5 . . ? O1 C7 N1 103.49(16) . . ? O1 C7 C1 110.88(18) . . ? N1 C7 C1 113.97(19) . . ? O1 C7 H7 109.4 . . ? N1 C7 H7 109.4 . . ? C1 C7 H7 109.4 . . ? O1 C8 C10 109.85(19) . . ? O1 C8 C9 104.41(19) . . ? C10 C8 C9 116.3(2) . . ? O1 C8 H8 108.7 . . ? C10 C8 H8 108.7 . . ? C9 C8 H8 108.7 . . ? N1 C9 C16 113.4(2) . . ? N1 C9 C8 101.74(18) . . ? C16 C9 C8 116.6(2) . . ? N1 C9 H9 108.2 . . ? C16 C9 H9 108.2 . . ? C8 C9 H9 108.2 . . ? C15 C10 C11 117.5(2) . . ? C15 C10 C8 122.5(2) . . ? C11 C10 C8 120.0(2) . . ? C12 C11 C10 121.1(3) . . ? C12 C11 H11 119.5 . . ? C10 C11 H11 119.5 . . ? C13 C12 C11 120.5(3) . . ? C13 C12 H12 119.8 . . ? C11 C12 H12 119.8 . . ? C12 C13 C14 119.4(3) . . ? C12 C13 H13 120.3 . . ? C14 C13 H13 120.3 . . ? C13 C14 C15 120.3(3) . . ? C13 C14 H14 119.8 . . ? C15 C14 H14 119.8 . . ? C10 C15 C14 121.2(2) . . ? C10 C15 H15 119.4 . . ? C14 C15 H15 119.4 . . ? C9 C16 H16A 109.5 . . ? C9 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? C9 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? N1 C17 H17A 109.5 . . ? N1 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? N1 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 109.5 . . ? O2 C18 N2 123.19(18) . . ? O2 C18 C2 118.91(17) . . ? N2 C18 C2 117.89(17) . . ? N2 C19 C21 111.14(16) . . ? N2 C19 C20 111.64(15) . . ? C21 C19 C20 112.94(18) . . ? N2 C19 H19 106.9 . . ? C21 C19 H19 106.9 . . ? C20 C19 H19 106.9 . . ? C19 C20 H20A 109.5 . . ? C19 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? C19 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? C19 C21 H21A 109.5 . . ? C19 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? C19 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? N2 C22 C24 112.39(17) . . ? N2 C22 C23 111.86(17) . . ? C24 C22 C23 113.4(2) . . ? N2 C22 H22 106.2 . . ? C24 C22 H22 106.2 . . ? C23 C22 H22 106.2 . . ? 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 . . ? C22 C24 H24A 109.5 . . ? C22 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? C22 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? O3 C25 N3 103.24(14) . . ? O3 C25 C3 110.46(17) . . ? N3 C25 C3 113.38(17) . . ? O3 C25 H25 109.9 . . ? N3 C25 H25 109.9 . . ? C3 C25 H25 109.9 . . ? O3 C26 C28 109.78(18) . . ? O3 C26 C27 105.24(16) . . ? C28 C26 C27 117.41(17) . . ? O3 C26 H26 108.0 . . ? C28 C26 H26 108.0 . . ? C27 C26 H26 108.0 . . ? N3 C27 C34 112.7(2) . . ? N3 C27 C26 102.22(16) . . ? C34 C27 C26 116.7(2) . . ? N3 C27 H27 108.3 . . ? C34 C27 H27 108.3 . . ? C26 C27 H27 108.3 . . ? C33 C28 C29 117.7(2) . . ? C33 C28 C26 122.86(19) . . ? C29 C28 C26 119.4(2) . . ? C28 C29 C30 121.3(3) . . ? C28 C29 H29 119.3 . . ? C30 C29 H29 119.3 . . ? C31 C30 C29 120.2(3) . . ? C31 C30 H30 119.9 . . ? C29 C30 H30 119.9 . . ? C30 C31 C32 120.1(3) . . ? C30 C31 H31 120.0 . . ? C32 C31 H31 120.0 . . ? C31 C32 C33 119.7(3) . . ? C31 C32 H32 120.1 . . ? C33 C32 H32 120.1 . . ? C28 C33 C32 120.9(2) . . ? C28 C33 H33 119.5 . . ? C32 C33 H33 119.5 . . ? C27 C34 H34A 109.5 . . ? C27 C34 H34B 109.5 . . ? H34A C34 H34B 109.5 . . ? C27 C34 H34C 109.5 . . ? H34A C34 H34C 109.5 . . ? H34B C34 H34C 109.5 . . ? N3 C35 H35A 109.5 . . ? N3 C35 H35B 109.5 . . ? H35A C35 H35B 109.5 . . ? N3 C35 H35C 109.5 . . ? H35A C35 H35C 109.5 . . ? H35B C35 H35C 109.5 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C6 C1 C2 C3 -2.3(3) . . . . ? C7 C1 C2 C3 176.0(2) . . . . ? C6 C1 C2 C18 -179.0(2) . . . . ? C7 C1 C2 C18 -0.7(3) . . . . ? C1 C2 C3 C4 2.6(3) . . . . ? C18 C2 C3 C4 179.3(2) . . . . ? C1 C2 C3 C25 -175.8(2) . . . . ? C18 C2 C3 C25 0.9(3) . . . . ? C2 C3 C4 C5 -0.4(4) . . . . ? C25 C3 C4 C5 178.1(3) . . . . ? C3 C4 C5 C6 -2.2(5) . . . . ? C4 C5 C6 C1 2.6(5) . . . . ? C2 C1 C6 C5 -0.3(4) . . . . ? C7 C1 C6 C5 -178.7(3) . . . . ? C8 O1 C7 N1 33.3(2) . . . . ? C8 O1 C7 C1 155.85(17) . . . . ? C9 N1 C7 O1 -46.2(2) . . . . ? C17 N1 C7 O1 -168.1(2) . . . . ? C9 N1 C7 C1 -166.68(19) . . . . ? C17 N1 C7 C1 71.3(3) . . . . ? C6 C1 C7 O1 -55.8(3) . . . . ? C2 C1 C7 O1 125.9(2) . . . . ? C6 C1 C7 N1 60.5(3) . . . . ? C2 C1 C7 N1 -117.8(2) . . . . ? C7 O1 C8 C10 -133.0(2) . . . . ? C7 O1 C8 C9 -7.7(2) . . . . ? C7 N1 C9 C16 165.9(2) . . . . ? C17 N1 C9 C16 -72.5(3) . . . . ? C7 N1 C9 C8 39.9(2) . . . . ? C17 N1 C9 C8 161.5(2) . . . . ? O1 C8 C9 N1 -20.4(2) . . . . ? C10 C8 C9 N1 100.8(2) . . . . ? O1 C8 C9 C16 -144.3(2) . . . . ? C10 C8 C9 C16 -23.1(3) . . . . ? O1 C8 C10 C15 34.8(3) . . . . ? C9 C8 C10 C15 -83.5(3) . . . . ? O1 C8 C10 C11 -146.9(2) . . . . ? C9 C8 C10 C11 94.9(3) . . . . ? C15 C10 C11 C12 0.9(4) . . . . ? C8 C10 C11 C12 -177.5(3) . . . . ? C10 C11 C12 C13 -0.7(5) . . . . ? C11 C12 C13 C14 0.1(5) . . . . ? C12 C13 C14 C15 0.2(5) . . . . ? C11 C10 C15 C14 -0.6(4) . . . . ? C8 C10 C15 C14 177.8(3) . . . . ? C13 C14 C15 C10 0.0(5) . . . . ? C22 N2 C18 O2 -2.2(3) . . . . ? C19 N2 C18 O2 177.78(17) . . . . ? C22 N2 C18 C2 177.39(15) . . . . ? C19 N2 C18 C2 -2.6(2) . . . . ? C1 C2 C18 O2 93.2(2) . . . . ? C3 C2 C18 O2 -83.5(2) . . . . ? C1 C2 C18 N2 -86.4(2) . . . . ? C3 C2 C18 N2 96.9(2) . . . . ? C18 N2 C19 C21 -114.3(2) . . . . ? C22 N2 C19 C21 65.7(2) . . . . ? C18 N2 C19 C20 118.6(2) . . . . ? C22 N2 C19 C20 -61.4(2) . . . . ? C18 N2 C22 C24 65.3(2) . . . . ? C19 N2 C22 C24 -114.7(2) . . . . ? C18 N2 C22 C23 -63.6(2) . . . . ? C19 N2 C22 C23 116.38(19) . . . . ? C26 O3 C25 N3 -38.62(19) . . . . ? C26 O3 C25 C3 -160.15(16) . . . . ? C35 N3 C25 O3 166.73(18) . . . . ? C27 N3 C25 O3 44.37(19) . . . . ? C35 N3 C25 C3 -73.7(2) . . . . ? C27 N3 C25 C3 163.91(17) . . . . ? C4 C3 C25 O3 55.7(3) . . . . ? C2 C3 C25 O3 -125.8(2) . . . . ? C4 C3 C25 N3 -59.6(3) . . . . ? C2 C3 C25 N3 118.8(2) . . . . ? C25 O3 C26 C28 145.28(16) . . . . ? C25 O3 C26 C27 18.0(2) . . . . ? C25 N3 C27 C34 -157.9(2) . . . . ? C35 N3 C27 C34 79.6(3) . . . . ? C25 N3 C27 C26 -31.8(2) . . . . ? C35 N3 C27 C26 -154.39(18) . . . . ? O3 C26 C27 N3 9.0(2) . . . . ? C28 C26 C27 N3 -113.39(19) . . . . ? O3 C26 C27 C34 132.4(2) . . . . ? C28 C26 C27 C34 10.0(3) . . . . ? O3 C26 C28 C33 -36.1(3) . . . . ? C27 C26 C28 C33 84.0(3) . . . . ? O3 C26 C28 C29 144.6(2) . . . . ? C27 C26 C28 C29 -95.3(2) . . . . ? C33 C28 C29 C30 0.5(4) . . . . ? C26 C28 C29 C30 179.8(2) . . . . ? C28 C29 C30 C31 -0.1(5) . . . . ? C29 C30 C31 C32 -0.7(5) . . . . ? C30 C31 C32 C33 1.1(5) . . . . ? C29 C28 C33 C32 -0.1(4) . . . . ? C26 C28 C33 C32 -179.4(2) . . . . ? C31 C32 C33 C28 -0.7(4) . . . . ? _diffrn_measured_fraction_theta_max 0.819 _diffrn_reflns_theta_full 78.20 _diffrn_measured_fraction_theta_full 0.819 _refine_diff_density_max 0.174 _refine_diff_density_min -0.143 _refine_diff_density_rms 0.031