# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2009 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Ji-Chang Xiao' _publ_contact_author_email JCHXIAO@MAIL.SIOC.AC.CN _publ_section_title ; The Oxidation of Ni(II) N-Confused Porphyrins (NCPs) with Azo Radical Initiators and an Unexpected Intramolecular Nucleophilic Substitution Reaction via a Proposed Ni(III) NCP Intermediate ; loop_ _publ_author_name 'Ji-Chang Xiao' 'Hua Wei Jiang' 'Qing Yun Chen' 'Yu Cheng Gu' # Attachment 'cd28496.cif' data_cd28496 _database_code_depnum_ccdc_archive 'CCDC 715233' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C47 H34 Cl2 N4 O2' _chemical_formula_weight 757.68 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' Cl Cl 0.1484 0.1585 '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)/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 11.6814(10) _cell_length_b 17.6688(15) _cell_length_c 19.2955(17) _cell_angle_alpha 90.00 _cell_angle_beta 104.487(2) _cell_angle_gamma 90.00 _cell_volume 3855.9(6) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 3793 _cell_measurement_theta_min 4.371 _cell_measurement_theta_max 44.839 _exptl_crystal_description prismatic _exptl_crystal_colour black _exptl_crystal_size_max 0.462 _exptl_crystal_size_mid 0.347 _exptl_crystal_size_min 0.311 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.305 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1576 _exptl_absorpt_coefficient_mu 0.214 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.79115 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_process_details sadabs _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 20843 _diffrn_reflns_av_R_equivalents 0.0692 _diffrn_reflns_av_sigmaI/netI 0.0726 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -21 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 1.59 _diffrn_reflns_theta_max 26.00 _reflns_number_total 7564 _reflns_number_gt 4305 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _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^)+(0.1293P)^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 mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 7564 _refine_ls_number_parameters 505 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.1225 _refine_ls_R_factor_gt 0.0740 _refine_ls_wR_factor_ref 0.2336 _refine_ls_wR_factor_gt 0.2085 _refine_ls_goodness_of_fit_ref 0.996 _refine_ls_restrained_S_all 0.996 _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 Cl1 Cl 0.40724(18) 0.95365(15) 0.3128(2) 0.2053(17) Uani 1 1 d . . . Cl2 Cl 0.19145(16) 0.89207(10) 0.33192(9) 0.1311(6) Uani 1 1 d . . . N2 N 0.2015(3) 0.02702(16) 0.13423(15) 0.0622(8) Uani 1 1 d . . . N22 N 0.3196(2) 0.12652(15) -0.07432(14) 0.0435(7) Uani 1 1 d D . . N23 N 0.3069(2) 0.28520(13) -0.03341(13) 0.0418(6) Uani 1 1 d . . . N24 N 0.1897(3) 0.25659(15) 0.08560(14) 0.0446(7) Uani 1 1 d D . . O1 O 0.0172(2) 0.18947(14) -0.02196(12) 0.0630(7) Uani 1 1 d . . . O2 O 0.0688(2) 0.10513(12) -0.09397(12) 0.0591(7) Uani 1 1 d . . . C1 C 0.1512(3) 0.09403(17) 0.10056(17) 0.0463(8) Uani 1 1 d . . . C3 C 0.2419(3) -0.01120(18) 0.08804(17) 0.0519(9) Uani 1 1 d . . . H3 H 0.2801 -0.0576 0.0979 0.062 Uiso 1 1 calc R . . C4 C 0.2211(3) 0.02631(17) 0.01980(16) 0.0452(8) Uani 1 1 d . . . C5 C 0.2736(3) 0.00063(17) -0.03479(15) 0.0416(7) Uani 1 1 d . . . C6 C 0.3104(3) 0.04953(17) -0.08162(16) 0.0438(8) Uani 1 1 d . . . C7 C 0.3541(3) 0.03263(19) -0.14219(17) 0.0528(9) Uani 1 1 d . . . H7 H 0.3579 -0.0154 -0.1613 0.063 Uiso 1 1 calc R . . C8 C 0.3894(3) 0.09801(19) -0.16779(18) 0.0565(9) Uani 1 1 d . . . H8 H 0.4211 0.1023 -0.2073 0.068 Uiso 1 1 calc R . . C9 C 0.3697(3) 0.15820(17) -0.12407(15) 0.0440(8) Uani 1 1 d . . . C10 C 0.3994(3) 0.23497(17) -0.12687(15) 0.0430(8) Uani 1 1 d . . . C11 C 0.3742(3) 0.29219(17) -0.08240(16) 0.0425(8) Uani 1 1 d . . . C12 C 0.4161(3) 0.36847(18) -0.08336(18) 0.0510(9) Uani 1 1 d . . . H12 H 0.4644 0.3868 -0.1112 0.061 Uiso 1 1 calc R . . C13 C 0.3726(3) 0.40820(18) -0.03673(18) 0.0527(9) Uani 1 1 d . . . H13 H 0.3846 0.4594 -0.0261 0.063 Uiso 1 1 calc R . . C14 C 0.3030(3) 0.35593(17) -0.00585(16) 0.0428(8) Uani 1 1 d . . . C15 C 0.2417(3) 0.38012(17) 0.04463(16) 0.0426(8) Uani 1 1 d . . . C16 C 0.1854(3) 0.33278(16) 0.08410(16) 0.0420(7) Uani 1 1 d . . . C17 C 0.1120(3) 0.35373(19) 0.13010(18) 0.0522(9) Uani 1 1 d . . . H17 H 0.0926 0.4029 0.1399 0.063 Uiso 1 1 calc R . . C18 C 0.0757(3) 0.29057(18) 0.15676(17) 0.0510(9) Uani 1 1 d . . . H18 H 0.0270 0.2887 0.1882 0.061 Uiso 1 1 calc R . . C19 C 0.1240(3) 0.22669(17) 0.12892(16) 0.0434(8) Uani 1 1 d . . . C20 C 0.1131(3) 0.14972(17) 0.14183(16) 0.0431(8) Uani 1 1 d . . . C21 C 0.1591(3) 0.09394(17) 0.02793(16) 0.0436(8) Uani 1 1 d . . . C25 C 0.0758(3) 0.13580(17) -0.02992(17) 0.0426(8) Uani 1 1 d . . . C26 C -0.0107(4) 0.1417(2) -0.1534(2) 0.0844(14) Uani 1 1 d . . . H26A H -0.0887 0.1426 -0.1458 0.127 Uiso 1 1 calc R . . H26B H -0.0119 0.1143 -0.1966 0.127 Uiso 1 1 calc R . . H26C H 0.0156 0.1926 -0.1577 0.127 Uiso 1 1 calc R . . C27 C 0.0679(3) 0.12545(17) 0.20385(16) 0.0424(8) Uani 1 1 d . . . C28 C 0.1021(3) 0.16120(19) 0.27039(17) 0.0513(9) Uani 1 1 d . . . H28 H 0.1537 0.2021 0.2767 0.062 Uiso 1 1 calc R . . C29 C 0.0591(3) 0.1357(2) 0.32740(19) 0.0603(10) Uani 1 1 d . . . H29 H 0.0832 0.1594 0.3717 0.072 Uiso 1 1 calc R . . C30 C -0.0180(4) 0.0764(2) 0.3190(2) 0.0633(10) Uani 1 1 d . . . H30 H -0.0470 0.0601 0.3571 0.076 Uiso 1 1 calc R . . C31 C -0.0524(3) 0.0408(2) 0.2532(2) 0.0633(10) Uani 1 1 d . . . H31 H -0.1046 0.0002 0.2471 0.076 Uiso 1 1 calc R . . C32 C -0.0097(3) 0.06540(19) 0.19684(18) 0.0526(9) Uani 1 1 d . . . H32 H -0.0337 0.0409 0.1529 0.063 Uiso 1 1 calc R . . C33 C 0.2964(3) -0.08210(17) -0.03794(15) 0.0445(8) Uani 1 1 d . . . C34 C 0.2077(3) -0.13309(18) -0.03524(18) 0.0519(9) Uani 1 1 d . . . H34 H 0.1339 -0.1152 -0.0328 0.062 Uiso 1 1 calc R . . C35 C 0.2272(4) -0.2103(2) -0.03605(19) 0.0638(11) Uani 1 1 d . . . H35 H 0.1668 -0.2440 -0.0343 0.077 Uiso 1 1 calc R . . C36 C 0.3347(4) -0.2367(2) -0.03939(18) 0.0622(11) Uani 1 1 d . . . H36 H 0.3483 -0.2885 -0.0398 0.075 Uiso 1 1 calc R . . C37 C 0.4238(4) -0.1864(2) -0.04212(17) 0.0558(10) Uani 1 1 d . . . H37 H 0.4971 -0.2049 -0.0449 0.067 Uiso 1 1 calc R . . C38 C 0.4068(3) -0.11028(19) -0.04083(16) 0.0491(8) Uani 1 1 d . . . H38 H 0.4683 -0.0772 -0.0419 0.059 Uiso 1 1 calc R . . C39 C 0.4708(3) 0.25401(18) -0.17914(16) 0.0461(8) Uani 1 1 d . . . C40 C 0.5821(3) 0.2243(2) -0.17127(19) 0.0568(9) Uani 1 1 d . . . H40 H 0.6134 0.1925 -0.1328 0.068 Uiso 1 1 calc R . . C41 C 0.6475(4) 0.2405(2) -0.2188(2) 0.0682(11) Uani 1 1 d . . . H41 H 0.7229 0.2201 -0.2119 0.082 Uiso 1 1 calc R . . C42 C 0.6036(4) 0.2862(3) -0.2762(2) 0.0767(13) Uani 1 1 d . . . H42 H 0.6476 0.2956 -0.3094 0.092 Uiso 1 1 calc R . . C43 C 0.4947(5) 0.3179(3) -0.2846(2) 0.0795(13) Uani 1 1 d . . . H43 H 0.4657 0.3504 -0.3229 0.095 Uiso 1 1 calc R . . C44 C 0.4266(4) 0.3027(2) -0.23712(18) 0.0655(11) Uani 1 1 d . . . H44 H 0.3522 0.3246 -0.2435 0.079 Uiso 1 1 calc R . . C45 C 0.2346(3) 0.46299(18) 0.05712(17) 0.0458(8) Uani 1 1 d . . . C46 C 0.1687(4) 0.51060(19) 0.00631(19) 0.0654(11) Uani 1 1 d . . . H46 H 0.1257 0.4905 -0.0369 0.078 Uiso 1 1 calc R . . C47 C 0.1646(4) 0.5870(2) 0.0176(2) 0.0780(13) Uani 1 1 d . . . H47 H 0.1192 0.6177 -0.0180 0.094 Uiso 1 1 calc R . . C48 C 0.2255(4) 0.6181(2) 0.0797(2) 0.0703(12) Uani 1 1 d . . . H48 H 0.2227 0.6700 0.0869 0.084 Uiso 1 1 calc R . . C49 C 0.2905(4) 0.5731(2) 0.1314(2) 0.0709(12) Uani 1 1 d . . . H49 H 0.3330 0.5945 0.1741 0.085 Uiso 1 1 calc R . . C50 C 0.2951(3) 0.4951(2) 0.12162(19) 0.0605(10) Uani 1 1 d . . . H50 H 0.3384 0.4647 0.1582 0.073 Uiso 1 1 calc R . . C51 C 0.2638(5) 0.9669(3) 0.3043(3) 0.1171(19) Uani 1 1 d . . . H51A H 0.2265 0.9773 0.2544 0.140 Uiso 1 1 calc R . . H51B H 0.2538 1.0114 0.3316 0.140 Uiso 1 1 calc R . . H24 H 0.225(3) 0.2316(18) 0.0632(16) 0.059(11) Uiso 1 1 d D . . H22 H 0.299(3) 0.1521(16) -0.0439(14) 0.050(10) Uiso 1 1 d 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 Cl1 0.1048(15) 0.196(2) 0.331(5) -0.166(3) 0.079(2) -0.0234(14) Cl2 0.1546(16) 0.1349(13) 0.1070(11) 0.0253(9) 0.0390(10) -0.0042(11) N2 0.088(2) 0.0517(18) 0.0519(17) 0.0156(14) 0.0281(17) 0.0137(16) N22 0.0539(18) 0.0411(16) 0.0396(15) -0.0059(12) 0.0194(13) -0.0044(13) N23 0.0510(17) 0.0355(14) 0.0433(14) 0.0056(11) 0.0201(12) -0.0008(12) N24 0.0588(19) 0.0361(15) 0.0472(15) 0.0004(12) 0.0286(14) -0.0002(13) O1 0.0690(18) 0.0598(16) 0.0608(15) 0.0046(12) 0.0172(13) 0.0182(13) O2 0.0712(17) 0.0558(15) 0.0454(13) 0.0000(11) 0.0055(12) 0.0060(12) C1 0.060(2) 0.0381(17) 0.0458(18) 0.0104(14) 0.0225(16) -0.0003(15) C3 0.071(3) 0.0403(18) 0.0491(19) 0.0108(15) 0.0233(17) 0.0139(17) C4 0.054(2) 0.0380(17) 0.0462(18) 0.0029(14) 0.0175(15) -0.0005(15) C5 0.047(2) 0.0363(17) 0.0424(17) -0.0019(13) 0.0126(14) -0.0014(14) C6 0.050(2) 0.0385(18) 0.0449(17) -0.0054(14) 0.0157(15) -0.0043(15) C7 0.070(2) 0.0463(19) 0.0468(19) -0.0126(15) 0.0233(17) -0.0070(17) C8 0.072(3) 0.059(2) 0.0455(19) -0.0075(16) 0.0277(18) -0.0113(18) C9 0.051(2) 0.0478(19) 0.0360(16) -0.0011(14) 0.0153(14) -0.0062(15) C10 0.046(2) 0.0455(18) 0.0396(16) 0.0057(14) 0.0146(14) -0.0020(15) C11 0.046(2) 0.0422(18) 0.0426(17) 0.0102(14) 0.0175(14) 0.0018(14) C12 0.060(2) 0.0462(19) 0.055(2) 0.0056(16) 0.0284(17) -0.0067(16) C13 0.065(2) 0.0370(18) 0.063(2) 0.0038(16) 0.0287(18) -0.0058(16) C14 0.048(2) 0.0384(17) 0.0441(17) 0.0039(14) 0.0166(15) -0.0006(14) C15 0.048(2) 0.0375(17) 0.0443(17) 0.0019(14) 0.0150(15) -0.0015(14) C16 0.046(2) 0.0362(17) 0.0462(17) 0.0011(14) 0.0161(15) 0.0015(14) C17 0.067(2) 0.0413(18) 0.056(2) -0.0006(16) 0.0286(18) 0.0050(17) C18 0.063(2) 0.048(2) 0.0525(19) 0.0009(16) 0.0328(17) 0.0015(17) C19 0.047(2) 0.0450(18) 0.0433(17) 0.0013(14) 0.0211(15) -0.0026(15) C20 0.053(2) 0.0430(18) 0.0385(16) 0.0041(14) 0.0204(15) -0.0011(15) C21 0.054(2) 0.0367(17) 0.0453(18) 0.0052(13) 0.0220(15) -0.0010(15) C25 0.046(2) 0.0378(18) 0.0472(19) 0.0087(14) 0.0187(15) -0.0051(15) C26 0.106(4) 0.082(3) 0.052(2) 0.006(2) -0.005(2) 0.007(3) C27 0.051(2) 0.0406(17) 0.0402(17) 0.0070(14) 0.0194(15) 0.0007(15) C28 0.057(2) 0.055(2) 0.0435(18) 0.0006(15) 0.0160(16) -0.0035(17) C29 0.069(3) 0.074(3) 0.0426(19) 0.0025(18) 0.0222(18) 0.007(2) C30 0.068(3) 0.077(3) 0.054(2) 0.021(2) 0.0336(19) 0.004(2) C31 0.065(3) 0.064(2) 0.066(2) 0.0220(19) 0.026(2) -0.0067(19) C32 0.065(2) 0.049(2) 0.0452(18) 0.0083(15) 0.0165(16) -0.0066(17) C33 0.056(2) 0.0412(18) 0.0349(16) -0.0017(13) 0.0087(14) -0.0001(16) C34 0.056(2) 0.044(2) 0.055(2) 0.0074(15) 0.0138(17) 0.0013(16) C35 0.079(3) 0.043(2) 0.067(2) 0.0083(17) 0.012(2) -0.007(2) C36 0.092(3) 0.039(2) 0.050(2) 0.0020(16) 0.007(2) 0.009(2) C37 0.065(3) 0.057(2) 0.0430(19) -0.0058(16) 0.0088(17) 0.021(2) C38 0.052(2) 0.051(2) 0.0435(18) -0.0076(15) 0.0110(16) 0.0014(16) C39 0.055(2) 0.0466(19) 0.0412(17) 0.0001(14) 0.0204(15) -0.0086(16) C40 0.069(3) 0.053(2) 0.056(2) -0.0032(17) 0.0309(18) 0.0014(18) C41 0.071(3) 0.073(3) 0.072(3) -0.014(2) 0.040(2) -0.003(2) C42 0.084(3) 0.101(3) 0.060(3) -0.016(2) 0.045(2) -0.022(3) C43 0.088(4) 0.109(4) 0.043(2) 0.015(2) 0.020(2) -0.025(3) C44 0.060(3) 0.089(3) 0.049(2) 0.015(2) 0.0163(18) -0.009(2) C45 0.054(2) 0.0426(18) 0.0457(18) 0.0000(14) 0.0227(16) -0.0076(15) C46 0.098(3) 0.040(2) 0.052(2) 0.0026(17) 0.007(2) -0.0062(19) C47 0.118(4) 0.043(2) 0.071(3) 0.012(2) 0.019(3) 0.004(2) C48 0.099(3) 0.042(2) 0.080(3) -0.004(2) 0.041(3) -0.014(2) C49 0.077(3) 0.066(3) 0.073(3) -0.030(2) 0.024(2) -0.021(2) C50 0.065(3) 0.058(2) 0.057(2) -0.0086(18) 0.0113(19) -0.0031(19) C51 0.118(5) 0.113(4) 0.112(4) -0.014(3) 0.014(4) -0.013(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 Cl1 C51 1.658(6) . ? Cl2 C51 1.724(6) . ? N2 C3 1.298(4) . ? N2 C1 1.407(4) . ? N22 C9 1.363(4) . ? N22 C6 1.369(4) . ? N22 H22 0.823(18) . ? N23 C14 1.363(4) . ? N23 C11 1.378(4) . ? N24 C16 1.347(4) . ? N24 C19 1.374(4) . ? N24 H24 0.800(18) . ? O1 C25 1.201(4) . ? O2 C25 1.333(4) . ? O2 C26 1.436(4) . ? C1 C20 1.406(4) . ? C1 C21 1.427(4) . ? C3 C4 1.439(4) . ? C3 H3 0.9300 . ? C4 C5 1.419(4) . ? C4 C21 1.426(4) . ? C5 C6 1.394(4) . ? C5 C33 1.490(4) . ? C6 C7 1.419(4) . ? C7 C8 1.361(5) . ? C7 H7 0.9300 . ? C8 C9 1.412(4) . ? C8 H8 0.9300 . ? C9 C10 1.404(4) . ? C10 C11 1.404(4) . ? C10 C39 1.499(4) . ? C11 C12 1.435(4) . ? C12 C13 1.337(5) . ? C12 H12 0.9300 . ? C13 C14 1.453(4) . ? C13 H13 0.9300 . ? C14 C15 1.411(4) . ? C15 C16 1.401(4) . ? C15 C45 1.490(4) . ? C16 C17 1.428(4) . ? C17 C18 1.341(4) . ? C17 H17 0.9300 . ? C18 C19 1.426(4) . ? C18 H18 0.9300 . ? C19 C20 1.394(4) . ? C20 C27 1.487(4) . ? C21 C25 1.482(4) . ? C26 H26A 0.9600 . ? C26 H26B 0.9600 . ? C26 H26C 0.9600 . ? C27 C32 1.380(5) . ? C27 C28 1.397(4) . ? C28 C29 1.394(5) . ? C28 H28 0.9300 . ? C29 C30 1.364(5) . ? C29 H29 0.9300 . ? C30 C31 1.383(5) . ? C30 H30 0.9300 . ? C31 C32 1.376(5) . ? C31 H31 0.9300 . ? C32 H32 0.9300 . ? C33 C34 1.385(5) . ? C33 C38 1.396(5) . ? C34 C35 1.384(5) . ? C34 H34 0.9300 . ? C35 C36 1.356(6) . ? C35 H35 0.9300 . ? C36 C37 1.379(5) . ? C36 H36 0.9300 . ? C37 C38 1.361(5) . ? C37 H37 0.9300 . ? C38 H38 0.9300 . ? C39 C40 1.375(5) . ? C39 C44 1.404(5) . ? C40 C41 1.362(5) . ? C40 H40 0.9300 . ? C41 C42 1.364(6) . ? C41 H41 0.9300 . ? C42 C43 1.362(6) . ? C42 H42 0.9300 . ? C43 C44 1.381(5) . ? C43 H43 0.9300 . ? C44 H44 0.9300 . ? C45 C46 1.373(5) . ? C45 C50 1.390(5) . ? C46 C47 1.369(5) . ? C46 H46 0.9300 . ? C47 C48 1.348(6) . ? C47 H47 0.9300 . ? C48 C49 1.351(6) . ? C48 H48 0.9300 . ? C49 C50 1.394(5) . ? C49 H49 0.9300 . ? C50 H50 0.9300 . ? C51 H51A 0.9700 . ? C51 H51B 0.9700 . ? 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 C3 N2 C1 107.6(3) . . ? C9 N22 C6 111.8(3) . . ? C9 N22 H22 122(2) . . ? C6 N22 H22 126(2) . . ? C14 N23 C11 105.4(2) . . ? C16 N24 C19 111.9(3) . . ? C16 N24 H24 124(3) . . ? C19 N24 H24 124(3) . . ? C25 O2 C26 115.8(3) . . ? C20 C1 N2 118.8(3) . . ? C20 C1 C21 131.6(3) . . ? N2 C1 C21 109.3(3) . . ? N2 C3 C4 112.4(3) . . ? N2 C3 H3 123.8 . . ? C4 C3 H3 123.8 . . ? C5 C4 C21 132.5(3) . . ? C5 C4 C3 121.8(3) . . ? C21 C4 C3 105.0(3) . . ? C6 C5 C4 122.9(3) . . ? C6 C5 C33 119.6(3) . . ? C4 C5 C33 117.3(3) . . ? N22 C6 C5 125.3(3) . . ? N22 C6 C7 105.0(3) . . ? C5 C6 C7 129.5(3) . . ? C8 C7 C6 108.9(3) . . ? C8 C7 H7 125.5 . . ? C6 C7 H7 125.5 . . ? C7 C8 C9 108.2(3) . . ? C7 C8 H8 125.9 . . ? C9 C8 H8 125.9 . . ? N22 C9 C10 125.2(3) . . ? N22 C9 C8 105.9(3) . . ? C10 C9 C8 128.8(3) . . ? C11 C10 C9 125.5(3) . . ? C11 C10 C39 119.1(3) . . ? C9 C10 C39 115.3(3) . . ? N23 C11 C10 126.7(3) . . ? N23 C11 C12 110.4(3) . . ? C10 C11 C12 122.9(3) . . ? C13 C12 C11 107.2(3) . . ? C13 C12 H12 126.4 . . ? C11 C12 H12 126.4 . . ? C12 C13 C14 106.7(3) . . ? C12 C13 H13 126.6 . . ? C14 C13 H13 126.6 . . ? N23 C14 C15 128.2(3) . . ? N23 C14 C13 110.2(3) . . ? C15 C14 C13 121.5(3) . . ? C16 C15 C14 125.6(3) . . ? C16 C15 C45 116.5(3) . . ? C14 C15 C45 117.9(3) . . ? N24 C16 C15 126.0(3) . . ? N24 C16 C17 105.7(3) . . ? C15 C16 C17 128.3(3) . . ? C18 C17 C16 108.6(3) . . ? C18 C17 H17 125.7 . . ? C16 C17 H17 125.7 . . ? C17 C18 C19 108.7(3) . . ? C17 C18 H18 125.6 . . ? C19 C18 H18 125.6 . . ? N24 C19 C20 125.0(3) . . ? N24 C19 C18 105.0(3) . . ? C20 C19 C18 130.0(3) . . ? C19 C20 C1 121.7(3) . . ? C19 C20 C27 119.4(3) . . ? C1 C20 C27 118.7(3) . . ? C4 C21 C1 105.6(3) . . ? C4 C21 C25 126.2(3) . . ? C1 C21 C25 123.2(3) . . ? O1 C25 O2 122.3(3) . . ? O1 C25 C21 125.8(3) . . ? O2 C25 C21 111.8(3) . . ? O2 C26 H26A 109.5 . . ? O2 C26 H26B 109.5 . . ? H26A C26 H26B 109.5 . . ? O2 C26 H26C 109.5 . . ? H26A C26 H26C 109.5 . . ? H26B C26 H26C 109.5 . . ? C32 C27 C28 117.9(3) . . ? C32 C27 C20 120.0(3) . . ? C28 C27 C20 122.1(3) . . ? C29 C28 C27 120.2(3) . . ? C29 C28 H28 119.9 . . ? C27 C28 H28 119.9 . . ? C30 C29 C28 120.8(3) . . ? C30 C29 H29 119.6 . . ? C28 C29 H29 119.6 . . ? C29 C30 C31 119.4(3) . . ? C29 C30 H30 120.3 . . ? C31 C30 H30 120.3 . . ? C32 C31 C30 120.2(4) . . ? C32 C31 H31 119.9 . . ? C30 C31 H31 119.9 . . ? C31 C32 C27 121.6(3) . . ? C31 C32 H32 119.2 . . ? C27 C32 H32 119.2 . . ? C34 C33 C38 118.5(3) . . ? C34 C33 C5 119.6(3) . . ? C38 C33 C5 121.9(3) . . ? C35 C34 C33 120.9(4) . . ? C35 C34 H34 119.5 . . ? C33 C34 H34 119.5 . . ? C36 C35 C34 119.8(4) . . ? C36 C35 H35 120.1 . . ? C34 C35 H35 120.1 . . ? C35 C36 C37 119.8(3) . . ? C35 C36 H36 120.1 . . ? C37 C36 H36 120.1 . . ? C38 C37 C36 121.4(4) . . ? C38 C37 H37 119.3 . . ? C36 C37 H37 119.3 . . ? C37 C38 C33 119.6(3) . . ? C37 C38 H38 120.2 . . ? C33 C38 H38 120.2 . . ? C40 C39 C44 118.1(3) . . ? C40 C39 C10 120.6(3) . . ? C44 C39 C10 121.2(3) . . ? C41 C40 C39 121.3(4) . . ? C41 C40 H40 119.4 . . ? C39 C40 H40 119.4 . . ? C40 C41 C42 120.8(4) . . ? C40 C41 H41 119.6 . . ? C42 C41 H41 119.6 . . ? C43 C42 C41 119.3(4) . . ? C43 C42 H42 120.4 . . ? C41 C42 H42 120.4 . . ? C42 C43 C44 121.2(4) . . ? C42 C43 H43 119.4 . . ? C44 C43 H43 119.4 . . ? C43 C44 C39 119.3(4) . . ? C43 C44 H44 120.4 . . ? C39 C44 H44 120.4 . . ? C46 C45 C50 117.3(3) . . ? C46 C45 C15 122.1(3) . . ? C50 C45 C15 120.7(3) . . ? C47 C46 C45 121.7(3) . . ? C47 C46 H46 119.1 . . ? C45 C46 H46 119.1 . . ? C48 C47 C46 120.8(4) . . ? C48 C47 H47 119.6 . . ? C46 C47 H47 119.6 . . ? C47 C48 C49 119.4(4) . . ? C47 C48 H48 120.3 . . ? C49 C48 H48 120.3 . . ? C48 C49 C50 121.0(4) . . ? C48 C49 H49 119.5 . . ? C50 C49 H49 119.5 . . ? C45 C50 C49 119.8(4) . . ? C45 C50 H50 120.1 . . ? C49 C50 H50 120.1 . . ? Cl1 C51 Cl2 115.0(4) . . ? Cl1 C51 H51A 108.5 . . ? Cl2 C51 H51A 108.5 . . ? Cl1 C51 H51B 108.5 . . ? Cl2 C51 H51B 108.5 . . ? H51A C51 H51B 107.5 . . ? 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 N2 C1 C20 -172.7(3) . . . . ? C3 N2 C1 C21 2.1(4) . . . . ? C1 N2 C3 C4 -0.6(4) . . . . ? N2 C3 C4 C5 170.1(3) . . . . ? N2 C3 C4 C21 -1.1(4) . . . . ? C21 C4 C5 C6 23.6(6) . . . . ? C3 C4 C5 C6 -144.9(3) . . . . ? C21 C4 C5 C33 -160.5(3) . . . . ? C3 C4 C5 C33 31.1(4) . . . . ? C9 N22 C6 C5 173.5(3) . . . . ? C9 N22 C6 C7 -2.3(4) . . . . ? C4 C5 C6 N22 11.5(5) . . . . ? C33 C5 C6 N22 -164.4(3) . . . . ? C4 C5 C6 C7 -173.8(3) . . . . ? C33 C5 C6 C7 10.4(5) . . . . ? N22 C6 C7 C8 1.2(4) . . . . ? C5 C6 C7 C8 -174.4(3) . . . . ? C6 C7 C8 C9 0.2(4) . . . . ? C6 N22 C9 C10 -174.7(3) . . . . ? C6 N22 C9 C8 2.5(4) . . . . ? C7 C8 C9 N22 -1.6(4) . . . . ? C7 C8 C9 C10 175.4(3) . . . . ? N22 C9 C10 C11 -5.1(5) . . . . ? C8 C9 C10 C11 178.3(3) . . . . ? N22 C9 C10 C39 170.7(3) . . . . ? C8 C9 C10 C39 -5.8(5) . . . . ? C14 N23 C11 C10 -177.2(3) . . . . ? C14 N23 C11 C12 2.0(3) . . . . ? C9 C10 C11 N23 -6.7(5) . . . . ? C39 C10 C11 N23 177.6(3) . . . . ? C9 C10 C11 C12 174.2(3) . . . . ? C39 C10 C11 C12 -1.5(5) . . . . ? N23 C11 C12 C13 -1.4(4) . . . . ? C10 C11 C12 C13 177.8(3) . . . . ? C11 C12 C13 C14 0.3(4) . . . . ? C11 N23 C14 C15 177.5(3) . . . . ? C11 N23 C14 C13 -1.8(3) . . . . ? C12 C13 C14 N23 0.9(4) . . . . ? C12 C13 C14 C15 -178.4(3) . . . . ? N23 C14 C15 C16 9.6(5) . . . . ? C13 C14 C15 C16 -171.2(3) . . . . ? N23 C14 C15 C45 -169.8(3) . . . . ? C13 C14 C15 C45 9.4(5) . . . . ? C19 N24 C16 C15 -179.4(3) . . . . ? C19 N24 C16 C17 0.3(4) . . . . ? C14 C15 C16 N24 6.8(5) . . . . ? C45 C15 C16 N24 -173.9(3) . . . . ? C14 C15 C16 C17 -172.8(3) . . . . ? C45 C15 C16 C17 6.5(5) . . . . ? N24 C16 C17 C18 -0.1(4) . . . . ? C15 C16 C17 C18 179.5(3) . . . . ? C16 C17 C18 C19 -0.1(4) . . . . ? C16 N24 C19 C20 -179.0(3) . . . . ? C16 N24 C19 C18 -0.4(4) . . . . ? C17 C18 C19 N24 0.3(4) . . . . ? C17 C18 C19 C20 178.8(3) . . . . ? N24 C19 C20 C1 -12.4(5) . . . . ? C18 C19 C20 C1 169.4(3) . . . . ? N24 C19 C20 C27 163.3(3) . . . . ? C18 C19 C20 C27 -14.9(5) . . . . ? N2 C1 C20 C19 144.2(3) . . . . ? C21 C1 C20 C19 -29.3(6) . . . . ? N2 C1 C20 C27 -31.6(5) . . . . ? C21 C1 C20 C27 154.9(3) . . . . ? C5 C4 C21 C1 -167.5(3) . . . . ? C3 C4 C21 C1 2.3(4) . . . . ? C5 C4 C21 C25 37.1(6) . . . . ? C3 C4 C21 C25 -153.0(3) . . . . ? C20 C1 C21 C4 171.2(4) . . . . ? N2 C1 C21 C4 -2.8(4) . . . . ? C20 C1 C21 C25 -32.6(6) . . . . ? N2 C1 C21 C25 153.5(3) . . . . ? C26 O2 C25 O1 1.9(5) . . . . ? C26 O2 C25 C21 179.6(3) . . . . ? C4 C21 C25 O1 174.1(3) . . . . ? C1 C21 C25 O1 22.8(5) . . . . ? C4 C21 C25 O2 -3.6(4) . . . . ? C1 C21 C25 O2 -154.8(3) . . . . ? C19 C20 C27 C32 139.5(3) . . . . ? C1 C20 C27 C32 -44.6(5) . . . . ? C19 C20 C27 C28 -41.1(5) . . . . ? C1 C20 C27 C28 134.8(3) . . . . ? C32 C27 C28 C29 0.6(5) . . . . ? C20 C27 C28 C29 -178.9(3) . . . . ? C27 C28 C29 C30 -0.9(5) . . . . ? C28 C29 C30 C31 0.8(6) . . . . ? C29 C30 C31 C32 -0.3(6) . . . . ? C30 C31 C32 C27 0.0(6) . . . . ? C28 C27 C32 C31 -0.2(5) . . . . ? C20 C27 C32 C31 179.3(3) . . . . ? C6 C5 C33 C34 -135.5(3) . . . . ? C4 C5 C33 C34 48.4(4) . . . . ? C6 C5 C33 C38 47.0(4) . . . . ? C4 C5 C33 C38 -129.1(3) . . . . ? C38 C33 C34 C35 -0.6(5) . . . . ? C5 C33 C34 C35 -178.2(3) . . . . ? C33 C34 C35 C36 0.1(5) . . . . ? C34 C35 C36 C37 -0.2(5) . . . . ? C35 C36 C37 C38 0.6(5) . . . . ? C36 C37 C38 C33 -1.1(5) . . . . ? C34 C33 C38 C37 1.1(5) . . . . ? C5 C33 C38 C37 178.6(3) . . . . ? C11 C10 C39 C40 113.3(4) . . . . ? C9 C10 C39 C40 -62.9(4) . . . . ? C11 C10 C39 C44 -66.4(4) . . . . ? C9 C10 C39 C44 117.4(4) . . . . ? C44 C39 C40 C41 -1.0(5) . . . . ? C10 C39 C40 C41 179.3(3) . . . . ? C39 C40 C41 C42 -0.8(6) . . . . ? C40 C41 C42 C43 2.2(6) . . . . ? C41 C42 C43 C44 -2.0(7) . . . . ? C42 C43 C44 C39 0.3(6) . . . . ? C40 C39 C44 C43 1.2(5) . . . . ? C10 C39 C44 C43 -179.1(3) . . . . ? C16 C15 C45 C46 -110.1(4) . . . . ? C14 C15 C45 C46 69.3(4) . . . . ? C16 C15 C45 C50 69.7(4) . . . . ? C14 C15 C45 C50 -110.9(4) . . . . ? C50 C45 C46 C47 1.6(6) . . . . ? C15 C45 C46 C47 -178.6(4) . . . . ? C45 C46 C47 C48 -0.2(7) . . . . ? C46 C47 C48 C49 -0.4(7) . . . . ? C47 C48 C49 C50 -0.4(6) . . . . ? C46 C45 C50 C49 -2.4(5) . . . . ? C15 C45 C50 C49 177.8(3) . . . . ? C48 C49 C50 C45 1.8(6) . . . . ? 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 N24 H24 N23 0.800(18) 2.49(3) 2.996(4) 123(3) . N22 H22 N23 0.823(18) 2.36(3) 2.926(4) 127(3) . _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.344 _refine_diff_density_min -0.616 _refine_diff_density_rms 0.059