Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2007 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 # 1. SUBMISSION DETAILS _publ_contact_author_name 'Nikolai Korotkikh' _publ_contact_author_address ; Institute of Physical Organic and Coal Chemistry Ukrainian Academy of Sciences 70 R. Luxemburg, Donetsk, 83114 Ukraine ; _publ_contact_author_email nkorotkikh@ua.fm _publ_contact_letter ; Organic and Biomolecular Chemistry ; # 2. TITLE AND AUTHOR LIST _publ_section_title ; Reaction of 1-tert-Butyl-3,4-Diphenyl-1,2,4-Triazol-5-ylidenes with a Malonic Ester ; loop_ _publ_author_name _publ_author_address 'Alan H. Cowley' ; Department of Chemistry and Biochemistry University of Texas-Austin 1 University Station, A5300 Austin, TX 78701 USA ; 'Nataliya V. Glinyanaya' ; Institute of Physical Organic and Coal Chemistry Ukrainian Academy of Sciences 70 R. Luxemburg, Donetsk, 83114 Ukraine ; 'Ilia S. Panov' ; Institute of Physical Organic and Coal Chemistry Ukrainian Academy of Sciences 70 R. Luxemburg, Donetsk, 83114 Ukraine ; 'Gennady F. Rayenko' ; Institute of Physical Organic and Coal Chemistry Ukrainian Academy of Sciences 70 R. Luxemburg, Donetsk, 83114 Ukraine ; ; T.M.Pekhtereva ; ; Institute of Physical Organic and Coal Chemistry Ukrainian Academy of Sciences 70 R. Luxemburg, Donetsk, 83114 Ukraine ; 'Nikolai Korotkikh' . 'Jennifer Moore' . 'Oles P. Shvaika' . _publ_section_synopsis ; ; _publ_section_abstract ; The stable carbenes 1-tert-butyl-3,4-diaryl-1,2,4-triazol-5-ylidenes (1?-d), including new fluorine-containing compounds (1c,d) react with a malonic ester to afford heterocyclic zwitterionic compounds 6a-d. The reactions with more acidic compounds (acetoacetic ester, malononitrile and 1,3-dimethylbarbituric acid) proceed with substrate deprotonation to form the respective azlium salts 7a-c. The X-ray crystal structure of 6a was determined. ; _publ_section_comment ; ; _publ_section_references ; Allen, F.H. (2002). Acta Cryst. B58, 380-388. Cremer D. & Pople J.A. (1975). J. Am. Chem. Soc. 97, 1358-1367. Altomare A., Burla M.C., Camalli M., Cascarano G.L., Giacovazzo C., Guagliardi A., Moliterni A.G.G., Polidori G.,Spagna R. Sir97. (1999) J. Appl. Cryst. 32, 115-119. Otwinowski, Z. and Minor, W. (1997). Methods in Enzymology, 276, Macromolecular Crystallography, part A, 307-326, C. W. Carter, Jr. and R. M. Sweets, Eds., Academic Press. Sheldrick, G. M. (1998). SHELXTL/PC. Release 5.10. Siemens Analytical X-ray Instruments, Inc., Madison, WI, USA. Sluis, P. v.d. & Spek, A. L. (1990). SQUEEZE. Acta Cryst. A46, 194-201. Spek, A. L. (1998) PLATON, A Multipurpose Crystallographic Tool, Utrecht University, Utrecht, The Netherlands. ; _publ_section_figure_captions ; ; _publ_section_exptl_prep ; ; data_i.p.1.7 _database_code_depnum_ccdc_archive 'CCDC 607811' _audit_creation_method ; manual editing of the .cif file created by SHELXTL Ver. 6.10 ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C23 H25 N3 O3' _chemical_formula_sum 'C23 H25 N3 O3' _chemical_formula_weight 391.46 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 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' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M cc _symmetry_space_group_name_Hall C-2yc loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x, -y, z+1/2' 'x+1/2, y+1/2, z' 'x+1/2, -y+1/2, z+1/2' _cell_length_a 11.961(5) _cell_length_b 19.647(5) _cell_length_c 9.048(5) _cell_angle_alpha 90 _cell_angle_beta 94.251(5) _cell_angle_gamma 90 _cell_volume 2120.4(16) _cell_formula_units_Z 4 _cell_measurement_temperature 153(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description block _exptl_crystal_colour colorless _exptl_crystal_size_max 0.14 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.226 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 832.5 _exptl_absorpt_coefficient_mu 0.082 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9890 _exptl_absorpt_correction_T_max 0.9906 _exptl_absorpt_process_details 'DENZO and Scalepack (Otwinoski and Minor, 1997' _exptl_special_details ; ? ; _diffrn_ambient_temperature 153(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 'Nonius Kappa CCD' _diffrn_measurement_method \w-scan _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 4386 _diffrn_reflns_av_R_equivalents 0.0455 _diffrn_reflns_av_sigmaI/netI 0.2667 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -25 _diffrn_reflns_limit_k_max 24 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 2.00 _diffrn_reflns_theta_max 27.49 _reflns_number_total 4375 _reflns_number_gt 4308 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect software, Nonius B.V. 1998' _computing_cell_refinement 'Collect software, Nonius B.V. 1998' _computing_data_reduction ; DENZO and Scalepack (Otwinoski and Minor, 1997) ; _computing_structure_solution ; SIR97 - Altomare A., Burla M.C., Camalli M., Cascarano G.L., Giacovazzo C., Guagliardi A., Moliterni A.G.G., Polidori G.,Spagna R. ; _computing_structure_refinement 'XL SHELXTL/PC, Siemens Analytical' _computing_molecular_graphics 'XP SHELXTL/PC, Siemens Analytical' _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0673P)^2^+0.7529P] 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 0.00(3) _refine_ls_number_reflns 4375 _refine_ls_number_parameters 266 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.2404 _refine_ls_R_factor_gt 0.0646 _refine_ls_wR_factor_ref 0.1718 _refine_ls_wR_factor_gt 0.1139 _refine_ls_goodness_of_fit_ref 0.967 _refine_ls_restrained_S_all 0.966 _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 C1 C 0.0971(4) 0.3019(3) 0.0398(6) 0.0358(15) Uani 1 1 d . . . C2 C 0.0311(4) 0.2033(3) 0.1031(6) 0.0341(14) Uani 1 1 d . . . C3 C -0.0096(4) 0.1331(3) 0.1004(6) 0.0300(13) Uani 1 1 d . . . C4 C 0.0320(5) 0.0821(3) 0.0110(6) 0.0355(16) Uani 1 1 d . . . H4 H 0.0899 0.0928 -0.0516 0.043 Uiso 1 1 calc R . . C5 C -0.0091(5) 0.0171(3) 0.0124(6) 0.0437(17) Uani 1 1 d . . . H5 H 0.0194 -0.0168 -0.0495 0.052 Uiso 1 1 calc R . . C6 C -0.0925(5) 0.0012(3) 0.1047(7) 0.0431(16) Uani 1 1 d . . . H6 H -0.1216 -0.0437 0.1061 0.052 Uiso 1 1 calc R . . C7 C -0.1334(5) 0.0504(3) 0.1943(6) 0.0438(16) Uani 1 1 d . . . H7 H -0.1903 0.0389 0.2578 0.053 Uiso 1 1 calc R . . C8 C -0.0928(5) 0.1162(3) 0.1935(6) 0.0348(15) Uani 1 1 d . . . H8 H -0.1216 0.1497 0.2561 0.042 Uiso 1 1 calc R . . C9 C 0.0912(5) 0.2152(3) -0.1600(6) 0.0334(14) Uani 1 1 d . . . C10 C 0.1995(5) 0.2080(3) -0.2005(6) 0.0392(15) Uani 1 1 d . . . H10 H 0.2614 0.2186 -0.1324 0.047 Uiso 1 1 calc R . . C11 C 0.2169(5) 0.1849(3) -0.3435(7) 0.0468(17) Uani 1 1 d . . . H11 H 0.2909 0.1793 -0.3734 0.056 Uiso 1 1 calc R . . C12 C 0.1266(6) 0.1704(3) -0.4393(7) 0.0478(17) Uani 1 1 d . . . H12 H 0.1379 0.1546 -0.5363 0.057 Uiso 1 1 calc R . . C13 C 0.0181(5) 0.1785(3) -0.3964(7) 0.0444(17) Uani 1 1 d . . . H13 H -0.0442 0.1680 -0.4638 0.053 Uiso 1 1 calc R . . C14 C 0.0009(5) 0.2019(3) -0.2561(6) 0.0381(15) Uani 1 1 d . . . H14 H -0.0729 0.2085 -0.2270 0.046 Uiso 1 1 calc R . . C15 C 0.0865(5) 0.3600(3) 0.2927(7) 0.0401(15) Uani 1 1 d . . . C16 C 0.2055(5) 0.3521(4) 0.3623(8) 0.070(2) Uani 1 1 d . . . H16A H 0.2126 0.3085 0.4145 0.105 Uiso 1 1 calc R . . H16B H 0.2223 0.3893 0.4327 0.105 Uiso 1 1 calc R . . H16C H 0.2584 0.3536 0.2846 0.105 Uiso 1 1 calc R . . C17 C 0.0698(6) 0.4285(3) 0.2140(8) 0.065(2) Uani 1 1 d . . . H17A H 0.1344 0.4380 0.1567 0.098 Uiso 1 1 calc R . . H17B H 0.0627 0.4645 0.2877 0.098 Uiso 1 1 calc R . . H17C H 0.0015 0.4269 0.1471 0.098 Uiso 1 1 calc R . . C18 C -0.0011(6) 0.3515(3) 0.4033(7) 0.061(2) Uani 1 1 d . . . H18A H -0.0760 0.3537 0.3516 0.091 Uiso 1 1 calc R . . H18B H 0.0070 0.3879 0.4772 0.091 Uiso 1 1 calc R . . H18C H 0.0089 0.3073 0.4527 0.091 Uiso 1 1 calc R . . C19 C 0.1538(5) 0.3544(3) -0.0542(6) 0.0366(15) Uani 1 1 d . . . C20 C 0.0855(5) 0.3871(3) -0.1602(7) 0.0355(14) Uani 1 1 d . . . H20 H 0.1194 0.4150 -0.2301 0.043 Uiso 1 1 calc R . . C21 C -0.0332(5) 0.3816(3) -0.1708(7) 0.0408(16) Uani 1 1 d . . . C22 C -0.2014(5) 0.4217(3) -0.3024(7) 0.0526(18) Uani 1 1 d . . . H23A H -0.2312 0.3766 -0.2767 0.063 Uiso 1 1 calc R . . H23B H -0.2253 0.4312 -0.4075 0.063 Uiso 1 1 calc R . . C23 C -0.2485(5) 0.4755(3) -0.2054(8) 0.068(2) Uani 1 1 d . . . H24A H -0.2274 0.4651 -0.1011 0.103 Uiso 1 1 calc R . . H24B H -0.3303 0.4763 -0.2220 0.103 Uiso 1 1 calc R . . H24C H -0.2182 0.5201 -0.2300 0.103 Uiso 1 1 calc R . . N1 N 0.0705(4) 0.3045(2) 0.1793(5) 0.0316(11) Uani 1 1 d . . . N2 N 0.0278(4) 0.2424(2) 0.2212(5) 0.0359(12) Uani 1 1 d . . . N3 N 0.0756(4) 0.2375(2) -0.0112(5) 0.0334(12) Uani 1 1 d . . . O1 O 0.2587(3) 0.35722(18) -0.0240(4) 0.0428(10) Uani 1 1 d . . . O2 O -0.0914(3) 0.3468(2) -0.0926(4) 0.0472(12) Uani 1 1 d . . . O3 O -0.0803(3) 0.42055(19) -0.2834(4) 0.0435(11) 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 0.030(4) 0.036(4) 0.042(4) -0.001(3) 0.004(3) -0.007(3) C2 0.035(4) 0.039(4) 0.028(3) 0.002(3) 0.006(3) 0.004(3) C3 0.030(3) 0.025(3) 0.035(3) 0.001(3) 0.001(3) -0.007(3) C4 0.042(4) 0.024(4) 0.041(4) 0.002(3) 0.009(3) -0.001(3) C5 0.050(4) 0.032(4) 0.049(4) -0.007(3) 0.011(4) -0.005(3) C6 0.047(4) 0.028(4) 0.054(4) -0.002(3) -0.004(4) -0.002(3) C7 0.036(4) 0.054(5) 0.042(4) 0.006(3) 0.009(3) -0.002(3) C8 0.044(4) 0.027(4) 0.033(4) 0.001(3) 0.001(3) 0.001(3) C9 0.040(4) 0.032(4) 0.028(4) -0.002(3) 0.004(3) -0.005(3) C10 0.042(4) 0.035(4) 0.042(4) -0.006(3) 0.006(3) 0.003(3) C11 0.052(4) 0.041(4) 0.049(5) -0.008(3) 0.015(4) -0.003(3) C12 0.075(5) 0.032(4) 0.038(4) -0.002(3) 0.015(4) 0.002(4) C13 0.060(5) 0.034(4) 0.040(4) 0.002(3) 0.004(4) -0.007(3) C14 0.039(4) 0.036(4) 0.039(4) 0.009(3) 0.003(3) -0.011(3) C15 0.045(4) 0.026(4) 0.048(4) -0.009(3) -0.004(3) -0.004(3) C16 0.052(4) 0.076(5) 0.080(6) -0.038(4) -0.015(4) 0.009(4) C17 0.089(5) 0.039(4) 0.067(5) -0.016(4) 0.009(4) -0.006(4) C18 0.080(5) 0.056(5) 0.050(4) -0.017(3) 0.034(4) -0.022(4) C19 0.043(4) 0.030(4) 0.039(4) -0.009(3) 0.013(3) -0.006(3) C20 0.035(4) 0.033(4) 0.039(3) 0.002(3) 0.009(3) -0.006(3) C21 0.039(4) 0.038(4) 0.047(4) -0.007(3) 0.010(3) 0.004(3) C22 0.039(4) 0.066(5) 0.052(4) 0.005(4) -0.002(3) 0.007(4) C23 0.052(4) 0.075(5) 0.080(6) -0.013(5) 0.015(4) 0.011(4) N1 0.035(3) 0.025(3) 0.035(3) -0.004(2) 0.003(2) -0.005(2) N2 0.040(3) 0.030(3) 0.038(3) 0.001(2) 0.007(2) -0.004(2) N3 0.037(3) 0.032(3) 0.031(3) -0.002(2) 0.001(2) -0.003(2) O1 0.037(3) 0.047(3) 0.046(3) 0.001(2) 0.009(2) -0.005(2) O2 0.040(3) 0.050(3) 0.053(3) 0.012(2) 0.011(2) -0.004(2) O3 0.036(3) 0.049(3) 0.047(3) 0.012(2) 0.007(2) 0.004(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 C1 N1 1.326(6) . ? C1 N3 1.365(6) . ? C1 C19 1.526(8) . ? C2 N2 1.318(7) . ? C2 N3 1.373(7) . ? C2 C3 1.462(7) . ? C3 C8 1.391(7) . ? C3 C4 1.402(7) . ? C4 C5 1.369(7) . ? C4 H4 0.9500 . ? C5 C6 1.383(7) . ? C5 H5 0.9500 . ? C6 C7 1.373(8) . ? C6 H6 0.9500 . ? C7 C8 1.382(8) . ? C7 H7 0.9500 . ? C8 H8 0.9500 . ? C9 C14 1.360(7) . ? C9 C10 1.380(7) . ? C9 N3 1.442(7) . ? C10 C11 1.402(8) . ? C10 H10 0.9500 . ? C11 C12 1.364(8) . ? C11 H11 0.9500 . ? C12 C13 1.391(8) . ? C12 H12 0.9500 . ? C13 C14 1.379(8) . ? C13 H13 0.9500 . ? C14 H14 0.9500 . ? C15 N1 1.500(7) . ? C15 C18 1.511(8) . ? C15 C16 1.521(8) . ? C15 C17 1.528(8) . ? C16 H16A 0.9800 . ? C16 H16B 0.9800 . ? C16 H16C 0.9800 . ? C17 H17A 0.9800 . ? C17 H17B 0.9800 . ? C17 H17C 0.9800 . ? C18 H18A 0.9800 . ? C18 H18B 0.9800 . ? C18 H18C 0.9800 . ? C19 O1 1.266(7) . ? C19 C20 1.373(8) . ? C20 C21 1.419(8) . ? C20 H20 0.9500 . ? C21 O2 1.236(6) . ? C21 O3 1.362(7) . ? C22 O3 1.446(7) . ? C22 C23 1.509(8) . ? C22 H23A 0.9900 . ? C22 H23B 0.9900 . ? C23 H24A 0.9800 . ? C23 H24B 0.9800 . ? C23 H24C 0.9800 . ? N1 N2 1.388(5) . ? 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 N3 107.7(5) . . ? N1 C1 C19 130.7(5) . . ? N3 C1 C19 121.2(5) . . ? N2 C2 N3 111.3(5) . . ? N2 C2 C3 122.2(5) . . ? N3 C2 C3 126.5(5) . . ? C8 C3 C4 118.6(5) . . ? C8 C3 C2 117.9(5) . . ? C4 C3 C2 123.5(5) . . ? C5 C4 C3 121.2(5) . . ? C5 C4 H4 119.4 . . ? C3 C4 H4 119.4 . . ? C4 C5 C6 119.5(6) . . ? C4 C5 H5 120.3 . . ? C6 C5 H5 120.3 . . ? C7 C6 C5 120.1(5) . . ? C7 C6 H6 119.9 . . ? C5 C6 H6 119.9 . . ? C6 C7 C8 120.9(5) . . ? C6 C7 H7 119.5 . . ? C8 C7 H7 119.5 . . ? C7 C8 C3 119.6(5) . . ? C7 C8 H8 120.2 . . ? C3 C8 H8 120.2 . . ? C14 C9 C10 121.8(5) . . ? C14 C9 N3 120.3(5) . . ? C10 C9 N3 117.9(5) . . ? C9 C10 C11 119.0(5) . . ? C9 C10 H10 120.5 . . ? C11 C10 H10 120.5 . . ? C12 C11 C10 119.3(6) . . ? C12 C11 H11 120.3 . . ? C10 C11 H11 120.3 . . ? C11 C12 C13 120.7(6) . . ? C11 C12 H12 119.7 . . ? C13 C12 H12 119.7 . . ? C14 C13 C12 120.0(6) . . ? C14 C13 H13 120.0 . . ? C12 C13 H13 120.0 . . ? C9 C14 C13 119.2(6) . . ? C9 C14 H14 120.4 . . ? C13 C14 H14 120.4 . . ? N1 C15 C18 108.2(4) . . ? N1 C15 C16 106.1(5) . . ? C18 C15 C16 112.8(5) . . ? N1 C15 C17 108.4(5) . . ? C18 C15 C17 109.4(5) . . ? C16 C15 C17 111.7(5) . . ? 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 . . ? C15 C17 H17A 109.5 . . ? C15 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? C15 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 109.5 . . ? C15 C18 H18A 109.5 . . ? C15 C18 H18B 109.5 . . ? H18A C18 H18B 109.5 . . ? C15 C18 H18C 109.5 . . ? H18A C18 H18C 109.5 . . ? H18B C18 H18C 109.5 . . ? O1 C19 C20 131.2(5) . . ? O1 C19 C1 112.6(5) . . ? C20 C19 C1 116.1(5) . . ? C19 C20 C21 123.5(5) . . ? C19 C20 H20 118.2 . . ? C21 C20 H20 118.2 . . ? O2 C21 O3 121.3(5) . . ? O2 C21 C20 127.3(6) . . ? O3 C21 C20 111.4(5) . . ? O3 C22 C23 110.8(5) . . ? O3 C22 H23A 109.5 . . ? C23 C22 H23A 109.5 . . ? O3 C22 H23B 109.5 . . ? C23 C22 H23B 109.5 . . ? H23A C22 H23B 108.1 . . ? C22 C23 H24A 109.5 . . ? C22 C23 H24B 109.5 . . ? H24A C23 H24B 109.5 . . ? C22 C23 H24C 109.5 . . ? H24A C23 H24C 109.5 . . ? H24B C23 H24C 109.5 . . ? C1 N1 N2 110.2(4) . . ? C1 N1 C15 130.7(5) . . ? N2 N1 C15 118.9(4) . . ? C2 N2 N1 104.9(4) . . ? C1 N3 C2 105.8(4) . . ? C1 N3 C9 124.3(4) . . ? C2 N3 C9 129.7(5) . . ? C21 O3 C22 117.0(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 N2 C2 C3 C8 26.9(8) . . . . ? N3 C2 C3 C8 -152.4(5) . . . . ? N2 C2 C3 C4 -151.9(5) . . . . ? N3 C2 C3 C4 28.8(8) . . . . ? C8 C3 C4 C5 1.2(8) . . . . ? C2 C3 C4 C5 -179.9(5) . . . . ? C3 C4 C5 C6 -0.7(8) . . . . ? C4 C5 C6 C7 -0.1(8) . . . . ? C5 C6 C7 C8 0.4(9) . . . . ? C6 C7 C8 C3 0.1(8) . . . . ? C4 C3 C8 C7 -0.9(8) . . . . ? C2 C3 C8 C7 -179.8(5) . . . . ? C14 C9 C10 C11 -1.4(8) . . . . ? N3 C9 C10 C11 178.5(5) . . . . ? C9 C10 C11 C12 0.3(8) . . . . ? C10 C11 C12 C13 0.1(8) . . . . ? C11 C12 C13 C14 0.4(8) . . . . ? C10 C9 C14 C13 2.0(8) . . . . ? N3 C9 C14 C13 -178.0(5) . . . . ? C12 C13 C14 C9 -1.5(8) . . . . ? N1 C1 C19 O1 77.3(8) . . . . ? N3 C1 C19 O1 -95.4(6) . . . . ? N1 C1 C19 C20 -106.0(7) . . . . ? N3 C1 C19 C20 81.3(7) . . . . ? O1 C19 C20 C21 -174.9(5) . . . . ? C1 C19 C20 C21 9.1(8) . . . . ? C19 C20 C21 O2 -1.9(9) . . . . ? C19 C20 C21 O3 178.5(5) . . . . ? N3 C1 N1 N2 -1.8(6) . . . . ? C19 C1 N1 N2 -175.3(5) . . . . ? N3 C1 N1 C15 173.7(5) . . . . ? C19 C1 N1 C15 0.3(10) . . . . ? C18 C15 N1 C1 154.4(6) . . . . ? C16 C15 N1 C1 -84.2(7) . . . . ? C17 C15 N1 C1 35.9(8) . . . . ? C18 C15 N1 N2 -30.3(7) . . . . ? C16 C15 N1 N2 91.0(6) . . . . ? C17 C15 N1 N2 -148.9(5) . . . . ? N3 C2 N2 N1 0.9(6) . . . . ? C3 C2 N2 N1 -178.5(5) . . . . ? C1 N1 N2 C2 0.6(6) . . . . ? C15 N1 N2 C2 -175.6(5) . . . . ? N1 C1 N3 C2 2.3(6) . . . . ? C19 C1 N3 C2 176.5(5) . . . . ? N1 C1 N3 C9 178.3(5) . . . . ? C19 C1 N3 C9 -7.5(8) . . . . ? N2 C2 N3 C1 -2.0(6) . . . . ? C3 C2 N3 C1 177.4(5) . . . . ? N2 C2 N3 C9 -177.8(5) . . . . ? C3 C2 N3 C9 1.6(9) . . . . ? C14 C9 N3 C1 -108.9(6) . . . . ? C10 C9 N3 C1 71.1(7) . . . . ? C14 C9 N3 C2 66.2(8) . . . . ? C10 C9 N3 C2 -113.8(6) . . . . ? O2 C21 O3 C22 2.8(8) . . . . ? C20 C21 O3 C22 -177.5(5) . . . . ? C23 C22 O3 C21 86.5(6) . . . . ? _diffrn_measured_fraction_theta_max 0.976 _diffrn_reflns_theta_full 27.49 _diffrn_measured_fraction_theta_full 0.99 _refine_diff_density_max 0.239 _refine_diff_density_min -0.298 _refine_diff_density_rms 0.060