# Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 1999 # CCDC Number: 186/1640 #SUBMISSION DETAILS data_global _pulic_contact_author ;Dr G\'abor Speier Department of Organic Chemistry University of Veszpr\'em Wartha V. u. 1 H-8201 Veszpr\'em Hungary ; _publ_contact_author_email speier@almos.vein.hu _publ_contact_author_fax '36(88)427492' _publ_contact_author_phone '36(88)422022' _publ_requested_journal 'J Chem. Soc. Dalton Trans.' #======================================================== #TITLE AND AUTHOR LIST _public_section_title ;Kinetic Studies on the Copper(II)-mediated Oxygenolysis of the Flavonolate Ligand. The Crystal Structures of Cu(fla)~2~ (fla = flavonolate) and Cu(O-bs)~2~(py)~3~) (O-bs = O-benzoylsalicylate) ; loop_ _publ_author_name _publ_author_address 'Speier, Gabor' ;Department of Organic Chemistry University of Veszpr\'em 8201 Veszpr\'em Hungary ; 'Balogh-Hergovich, Eva' ;Research Group for Petrochemistry of the Hungarian Academy of Sciences 8201 Veszpr\'em Hungary ; 'Kaizer, Jozsef' ;Department of Organic Chemistry University of Veszpr\'em 8201 Veszpr\'em Hungary ; 'Argay, Gyula' ;Central Research Institute for Chemistry of the Hungarian academy of Sciences 1525 Budapest Hungary ; 'Parkanyi, Laszlo' ;Central Research Institute for Chemistry of the Hungarian academy of Sciences 1525 Budapest Hungary ; #===================================================== data_g129 #(Supplementary material to the article cited above) _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C32 H20 Cl6 Cu O6' _chemical_formula_weight 776.72 _chemical_melting_point ? _chemical_compound_source ? 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' 'Cu' 'Cu' -1.9646 0.5888 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Cl' 'Cl' 0.3639 0.7018 '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 Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 7.273(1) _cell_length_b 10.691(1) _cell_length_c 11.229(1) _cell_angle_alpha 103.77(2) _cell_angle_beta 105.76(2) _cell_angle_gamma 99.61(2) _cell_volume 790.70(15) _cell_formula_units_Z 1 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 24.17 _cell_measurement_theta_max 29.64 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.631 _exptl_crystal_density_method ? _exptl_crystal_F_000 391 _exptl_absorpt_coefficient_mu 6.023 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 1.54180 _diffrn_radiation_type CuKa _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Enraf-Nonius CAD4' _diffrn_measurement_method omega/theta _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 1hr _diffrn_standards_decay_% 0 _diffrn_reflns_number 3250 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.1402 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 0 _diffrn_reflns_theta_min 4.29 _diffrn_reflns_theta_max 74.98 _reflns_number_total 3250 _reflns_number_observed 2295 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Enraf-Nonius CAD4 Program' _computing_cell_refinement 'Enraf-Nonius CAD4 Program' _computing_data_reduction 'Enraf-Nonius MoLen: Process' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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^)+( 0.1414P)^2^+3.5674P] 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 riding _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0025(6) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^l^3^/sin(2q)]^-1/4^' _refine_ls_number_reflns 3250 _refine_ls_number_parameters 207 _refine_ls_number_restraints 3 _refine_ls_R_factor_all 0.0714 _refine_ls_R_factor_obs 0.0529 _refine_ls_wR_factor_all 0.1717 _refine_ls_wR_factor_obs 0.1472 _refine_ls_goodness_of_fit_all 0.488 _refine_ls_goodness_of_fit_obs 0.501 _refine_ls_restrained_S_all 0.488 _refine_ls_restrained_S_obs 0.501 _refine_ls_shift/esd_max -0.005 _refine_ls_shift/esd_mean 0.001 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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Cu1 Cu 1.0000 0.0000 1.0000 0.0439(2) Uani 1 d S . Cl1 Cl 0.5767(2) 0.1525(2) 0.2164(2) 0.1144(6) Uani 1 d D . Cl2 Cl 0.7439(3) 0.37949(14) 0.1537(2) 0.1060(5) Uani 1 d D . Cl3 Cl 0.3854(2) 0.1975(2) -0.02031(15) 0.1094(6) Uani 1 d D . O1 O 0.7542(3) 0.0487(2) 0.5566(2) 0.0478(5) Uani 1 d . . O2 O 0.8927(3) 0.1104(2) 0.9043(2) 0.0462(5) Uani 1 d . . O3 O 0.9682(4) -0.1213(2) 0.8326(2) 0.0485(5) Uani 1 d . . C1 C 0.7917(4) 0.1155(3) 0.6840(3) 0.0420(7) Uani 1 d . . C2 C 0.8572(4) 0.0564(3) 0.7790(3) 0.0400(6) Uani 1 d . . C3 C 0.8988(4) -0.0722(3) 0.7429(3) 0.0409(6) Uani 1 d . . C4 C 0.8591(5) -0.1384(3) 0.6085(3) 0.0434(7) Uani 1 d . . C5 C 0.8897(5) -0.2648(3) 0.5634(3) 0.0496(7) Uani 1 d . . H5 H 0.9397(5) -0.3090(3) 0.6220(3) 0.064 Uiso 1 calc R . C6 C 0.8461(6) -0.3231(4) 0.4331(4) 0.0582(9) Uani 1 d . . H6 H 0.8663(6) -0.4069(4) 0.4032(4) 0.076 Uiso 1 calc R . C7 C 0.7712(6) -0.2566(4) 0.3451(4) 0.0585(9) Uani 1 d . . H7 H 0.7414(6) -0.2970(4) 0.2568(4) 0.076 Uiso 1 calc R . C8 C 0.7408(5) -0.1327(4) 0.3866(3) 0.0548(8) Uani 1 d . . H8 H 0.6915(5) -0.0888(4) 0.3274(3) 0.071 Uiso 1 calc R . C9 C 0.7851(5) -0.0742(3) 0.5188(3) 0.0447(7) Uani 1 d . . C11 C 0.7592(5) 0.2484(3) 0.7003(4) 0.0465(7) Uani 1 d . . C12 C 0.6998(6) 0.2938(4) 0.5929(4) 0.0564(9) Uani 1 d . . H12 H 0.6781(6) 0.2383(4) 0.5103(4) 0.073 Uiso 1 calc R . C13 C 0.6728(6) 0.4217(5) 0.6084(5) 0.0691(12) Uani 1 d . . H13 H 0.6333(6) 0.4509(5) 0.5360(5) 0.090 Uiso 1 calc R . C14 C 0.7034(7) 0.5049(5) 0.7283(5) 0.0716(12) Uani 1 d . . H14 H 0.6843(7) 0.5901(5) 0.7377(5) 0.093 Uiso 1 calc R . C15 C 0.7628(7) 0.4617(4) 0.8350(5) 0.0722(11) Uani 1 d . . H15 H 0.7839(7) 0.5184(4) 0.9170(5) 0.094 Uiso 1 calc R . C16 C 0.7915(6) 0.3355(4) 0.8224(4) 0.0570(9) Uani 1 d . . H16 H 0.8327(6) 0.3083(4) 0.8959(4) 0.074 Uiso 1 calc R . C17 C 0.6134(6) 0.2157(4) 0.0928(4) 0.0615(9) Uani 1 d D . H17 H 0.6890(6) 0.1640(4) 0.0497(4) 0.080 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 Cu1 0.0493(4) 0.0471(4) 0.0427(4) 0.0163(3) 0.0185(3) 0.0215(3) Cl1 0.0845(9) 0.169(2) 0.1146(12) 0.0877(12) 0.0351(8) 0.0262(10) Cl2 0.1205(12) 0.0683(8) 0.1031(10) -0.0012(7) 0.0351(9) -0.0049(7) Cl3 0.0757(8) 0.1453(14) 0.0848(9) 0.0411(9) 0.0011(7) 0.0003(8) O1 0.0474(12) 0.0553(13) 0.0440(11) 0.0201(10) 0.0154(9) 0.0128(10) O2 0.0555(13) 0.0469(12) 0.0421(11) 0.0136(9) 0.0187(10) 0.0229(10) O3 0.0600(14) 0.0466(12) 0.0474(12) 0.0178(10) 0.0212(10) 0.0238(10) C1 0.0349(14) 0.047(2) 0.048(2) 0.0170(13) 0.0163(12) 0.0108(12) C2 0.0393(15) 0.0409(15) 0.046(2) 0.0160(12) 0.0180(12) 0.0135(12) C3 0.0362(14) 0.042(2) 0.048(2) 0.0148(13) 0.0172(12) 0.0089(12) C4 0.038(2) 0.046(2) 0.045(2) 0.0119(13) 0.0164(12) 0.0041(12) C5 0.050(2) 0.047(2) 0.050(2) 0.0103(14) 0.0190(14) 0.0083(14) C6 0.056(2) 0.054(2) 0.058(2) 0.002(2) 0.023(2) 0.008(2) C7 0.054(2) 0.065(2) 0.046(2) 0.004(2) 0.018(2) 0.003(2) C8 0.048(2) 0.068(2) 0.045(2) 0.016(2) 0.0158(15) 0.006(2) C9 0.039(2) 0.048(2) 0.047(2) 0.0141(14) 0.0164(13) 0.0048(13) C11 0.038(2) 0.049(2) 0.062(2) 0.025(2) 0.0210(14) 0.0152(13) C12 0.054(2) 0.064(2) 0.068(2) 0.035(2) 0.025(2) 0.027(2) C13 0.060(2) 0.075(3) 0.101(3) 0.057(3) 0.035(2) 0.034(2) C14 0.069(3) 0.061(2) 0.111(4) 0.044(3) 0.044(3) 0.032(2) C15 0.082(3) 0.052(2) 0.091(3) 0.023(2) 0.036(2) 0.025(2) C16 0.059(2) 0.051(2) 0.065(2) 0.022(2) 0.020(2) 0.017(2) C17 0.054(2) 0.062(2) 0.069(2) 0.012(2) 0.025(2) 0.017(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 Cu1 O2 1.900(2) . ? Cu1 O2 1.900(2) 2_757 ? Cu1 O3 1.942(2) 2_757 ? Cu1 O3 1.942(2) . ? Cl1 C17 1.744(5) . ? Cl2 C17 1.719(4) . ? Cl3 C17 1.741(4) . ? O1 C1 1.366(4) . ? O1 C9 1.357(4) . ? O2 C2 1.321(4) . ? O3 C3 1.268(4) . ? C1 C2 1.383(4) . ? C1 C11 1.456(4) . ? C2 C3 1.445(4) . ? C3 C4 1.431(4) . ? C4 C9 1.391(5) . ? C4 C5 1.403(5) . ? C5 C6 1.371(5) . ? C6 C7 1.396(6) . ? C7 C8 1.371(6) . ? C8 C9 1.389(5) . ? C11 C12 1.394(5) . ? C11 C16 1.395(5) . ? C12 C13 1.390(6) . ? C13 C14 1.361(7) . ? C14 C15 1.373(7) . ? C15 C16 1.380(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 O2 Cu1 O2 179.999(1) . 2_757 ? O2 Cu1 O3 94.31(9) . 2_757 ? O2 Cu1 O3 85.69(9) 2_757 2_757 ? O2 Cu1 O3 85.69(9) . . ? O2 Cu1 O3 94.31(9) 2_757 . ? O3 Cu1 O3 180.0 2_757 . ? C1 O1 C9 122.2(3) . . ? C2 O2 Cu1 110.6(2) . . ? C3 O3 Cu1 110.0(2) . . ? O1 C1 C2 120.1(3) . . ? O1 C1 C11 111.8(3) . . ? C2 C1 C11 128.1(3) . . ? O2 C2 C1 125.1(3) . . ? O2 C2 C3 115.7(3) . . ? C1 C2 C3 119.2(3) . . ? O3 C3 C4 123.2(3) . . ? O3 C3 C2 118.0(3) . . ? C4 C3 C2 118.8(3) . . ? C9 C4 C5 118.7(3) . . ? C9 C4 C3 118.1(3) . . ? C5 C4 C3 123.1(3) . . ? C6 C5 C4 120.1(4) . . ? C5 C6 C7 119.9(4) . . ? C6 C7 C8 121.2(3) . . ? C9 C8 C7 118.6(4) . . ? O1 C9 C4 121.4(3) . . ? O1 C9 C8 117.1(3) . . ? C4 C9 C8 121.5(3) . . ? C12 C11 C16 117.8(3) . . ? C12 C11 C1 120.3(3) . . ? C16 C11 C1 121.9(3) . . ? C11 C12 C13 120.4(4) . . ? C14 C13 C12 120.9(4) . . ? C13 C14 C15 119.3(4) . . ? C14 C15 C16 121.0(5) . . ? C15 C16 C11 120.5(4) . . ? Cl2 C17 Cl3 111.0(3) . . ? Cl2 C17 Cl1 111.1(2) . . ? Cl3 C17 Cl1 109.0(2) . . ? _refine_diff_density_max 0.856 _refine_diff_density_min -0.779 _refine_diff_density_rms 0.072 #======END data_cupyr _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety '(C43 H33 Cu N3 O8) . 0.91(C5 H5 N)' _chemical_formula_sum 'C47.59 H37.59 Cu N3.92 O8' _chemical_formula_weight 855.84 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' 'Cu' 'Cu' -1.9646 0.5888 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M C2/c 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' '-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 30.948(3) _cell_length_b 9.641(1) _cell_length_c 16.159(1) _cell_angle_alpha 90.00 _cell_angle_beta 115.53(1) _cell_angle_gamma 90.00 _cell_volume 4350.6(7) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 43.9 _cell_measurement_theta_max 45.8 _exptl_crystal_description block _exptl_crystal_colour blue _exptl_crystal_size_max 0.60 _exptl_crystal_size_mid 0.45 _exptl_crystal_size_min 0.25 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.307 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1774 _exptl_absorpt_coefficient_mu 1.184 _exptl_absorpt_correction_type 'empirical (Psi scan)' _exptl_absorpt_correction_T_min 0.8775 _exptl_absorpt_correction_T_max 0.9987 _exptl_absorpt_process_details ; North A.C., Philips, D.C. and Mathews, F. (1968) Acta Cryst. A24 350-359. ; _exptl_special_details ; The crystal was mounted in a sealed capillary. ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 1.54180 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Enraf-Nonius CAD4' _diffrn_measurement_method '/w-2/q scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 1hr _diffrn_standards_decay_% 0 _diffrn_reflns_number 4650 _diffrn_reflns_av_R_equivalents 0.0117 _diffrn_reflns_av_sigmaI/netI 0.0099 _diffrn_reflns_limit_h_min -38 _diffrn_reflns_limit_h_max 34 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 3.16 _diffrn_reflns_theta_max 75.75 _reflns_number_total 4478 _reflns_number_gt 4153 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Enraf-Nonius Express' _computing_cell_refinement 'Enraf-Nonius Express' _computing_data_reduction 'XCAD4 (Harms. 1996)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP-III (Burnett, Johnson, 1996)' _computing_publication_material 'PCIFTAB (Parkanyi, 1999)' _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^)+(0.0924P)^2^+1.5986P] 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 0.00114(11) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 4478 _refine_ls_number_parameters 310 _refine_ls_number_restraints 55 _refine_ls_R_factor_all 0.0486 _refine_ls_R_factor_gt 0.0463 _refine_ls_wR_factor_ref 0.1404 _refine_ls_wR_factor_gt 0.1376 _refine_ls_goodness_of_fit_ref 1.057 _refine_ls_restrained_S_all 1.101 _refine_ls_shift/su_max 0.002 _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 Cu Cu 0.0000 0.27125(4) 0.2500 0.04934(16) Uani 1 2 d S . . O1 O 0.06920(5) 0.26928(13) 0.28263(10) 0.0573(3) Uani 1 1 d . . . C2 C 0.08975(6) 0.3821(2) 0.27951(12) 0.0553(4) Uani 1 1 d . . . O3 O 0.07073(6) 0.49632(15) 0.26453(13) 0.0763(4) Uani 1 1 d . . . C4 C 0.14074(7) 0.3689(2) 0.29192(13) 0.0599(4) Uani 1 1 d . . . C5 C 0.15621(9) 0.4585(3) 0.24267(17) 0.0803(6) Uani 1 1 d . . . H5 H 0.1358 0.5281 0.2073 0.104 Uiso 1 1 calc R . . C6 C 0.20105(12) 0.4464(5) 0.2451(2) 0.1084(11) Uani 1 1 d . . . H6 H 0.2102 0.5059 0.2102 0.141 Uiso 1 1 calc R . . C7 C 0.23186(11) 0.3483(5) 0.2980(3) 0.1237(14) Uani 1 1 d . . . H7 H 0.2621 0.3401 0.2992 0.161 Uiso 1 1 calc R . . C8 C 0.21856(10) 0.2607(4) 0.3501(3) 0.1032(10) Uani 1 1 d . . . H8 H 0.2399 0.1944 0.3874 0.134 Uiso 1 1 calc R . . C9 C 0.17327(8) 0.2717(3) 0.34682(18) 0.0712(6) Uani 1 1 d . . . O10 O 0.16167(6) 0.1743(2) 0.39808(13) 0.0826(5) Uani 1 1 d . A . C11 C 0.15621(8) 0.2233(3) 0.47223(19) 0.0810(7) Uani 1 1 d D . . O12 O 0.15963(9) 0.3420(3) 0.49227(15) 0.1007(6) Uani 1 1 d . A . C13' C 0.1486(7) 0.1231(16) 0.5348(10) 0.077(4) Uani 0.36(4) 1 d PGD A 1 C14' C 0.1434(8) -0.0173(17) 0.5131(11) 0.106(4) Uani 0.36(4) 1 d PG A 1 H14' H 0.1476 -0.0495 0.4629 0.138 Uiso 0.36(4) 1 calc PR A 1 C15' C 0.1319(8) -0.1096(19) 0.5667(14) 0.122(6) Uani 0.36(4) 1 d PG A 1 H15' H 0.1284 -0.2036 0.5522 0.159 Uiso 0.36(4) 1 calc PR A 1 C16' C 0.1256(7) -0.062(3) 0.6418(14) 0.120(7) Uani 0.36(4) 1 d PG A 1 H16' H 0.1179 -0.1233 0.6777 0.156 Uiso 0.36(4) 1 calc PR A 1 C17' C 0.1308(7) 0.079(3) 0.6635(13) 0.135(7) Uani 0.36(4) 1 d PG A 1 H17' H 0.1266 0.1110 0.7138 0.175 Uiso 0.36(4) 1 calc PR A 1 C18' C 0.1423(7) 0.171(2) 0.6100(12) 0.091(4) Uani 0.36(4) 1 d PG A 1 H18' H 0.1457 0.2651 0.6244 0.119 Uiso 0.36(4) 1 calc PR A 1 C13 C 0.1448(4) 0.0990(12) 0.5144(11) 0.092(3) Uani 0.64(4) 1 d PGD A 2 C14 C 0.1484(4) -0.0379(12) 0.4912(12) 0.122(3) Uani 0.64(4) 1 d PG A 2 H14 H 0.1559 -0.0576 0.4426 0.159 Uiso 0.64(4) 1 calc PR A 2 C15 C 0.1407(5) -0.1455(14) 0.5406(14) 0.159(5) Uani 0.64(4) 1 d PG A 2 H15 H 0.1432 -0.2371 0.5251 0.206 Uiso 0.64(4) 1 calc PR A 2 C16 C 0.1295(5) -0.116(2) 0.6133(15) 0.155(6) Uani 0.64(4) 1 d PG A 2 H16 H 0.1244 -0.1880 0.6463 0.202 Uiso 0.64(4) 1 calc PR A 2 C17 C 0.1259(5) 0.021(2) 0.6365(14) 0.153(6) Uani 0.64(4) 1 d PG A 2 H17 H 0.1184 0.0405 0.6851 0.199 Uiso 0.64(4) 1 calc PR A 2 C18 C 0.1335(5) 0.1284(18) 0.5871(13) 0.117(3) Uani 0.64(4) 1 d PG A 2 H18 H 0.1311 0.2200 0.6026 0.152 Uiso 0.64(4) 1 calc PR A 2 N19 N 0.01469(6) 0.29699(19) 0.38420(11) 0.0598(4) Uani 1 1 d . . . C20 C 0.04285(8) 0.4015(2) 0.43284(14) 0.0674(5) Uani 1 1 d . . . H20 H 0.0558 0.4610 0.4042 0.088 Uiso 1 1 calc R . . C21 C 0.05321(10) 0.4237(3) 0.52366(17) 0.0835(7) Uani 1 1 d . . . H21 H 0.0726 0.4975 0.5554 0.109 Uiso 1 1 calc R . . C22 C 0.03470(11) 0.3364(4) 0.56661(17) 0.0920(8) Uani 1 1 d . . . H22 H 0.0414 0.3497 0.6280 0.120 Uiso 1 1 calc R . . C23 C 0.00631(13) 0.2298(3) 0.5184(2) 0.0918(8) Uani 1 1 d . . . H23 H -0.0064 0.1687 0.5467 0.119 Uiso 1 1 calc R . . C24 C -0.00363(10) 0.2127(3) 0.42621(17) 0.0756(6) Uani 1 1 d . . . H24 H -0.0236 0.1406 0.3932 0.098 Uiso 1 1 calc R . . N25 N 0.0000 0.0348(2) 0.2500 0.0590(5) Uani 1 2 d S . . C26 C -0.04063(8) -0.0371(2) 0.21558(17) 0.0683(5) Uani 1 1 d . . . H26 H -0.0695 0.0112 0.1912 0.089 Uiso 1 1 calc R . . C27 C -0.04184(9) -0.1805(3) 0.21450(18) 0.0752(6) Uani 1 1 d . . . H27 H -0.0710 -0.2273 0.1898 0.098 Uiso 1 1 calc R . . C28 C 0.0000 -0.2523(3) 0.2500 0.0719(8) Uani 1 2 d S . . H28 H 0.0000 -0.3488 0.2500 0.093 Uiso 1 2 calc SR . . N1S N 0.2476(3) -0.3536(8) 0.5549(6) 0.205(3) Uani 0.458(5) 1 d PDU . . H1S H 0.2430 -0.4231 0.5835 0.266 Uiso 0.458(5) 1 d PR . . C2S C 0.2162(3) -0.3441(8) 0.4629(6) 0.210(3) Uani 0.917(9) 1 d PDU . . H2S H 0.1932 -0.4134 0.4390 0.272 Uiso 0.917(9) 1 d PR . . C3S C 0.2155(4) -0.2437(10) 0.4008(7) 0.227(4) Uani 0.917(9) 1 d PDU . . H3S H 0.1949 -0.2391 0.3387 0.295 Uiso 0.917(9) 1 d PR . . C1S' C 0.2476(3) -0.3536(8) 0.5549(6) 0.205(3) Uani 0.458(5) 1 d PU . . 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 Cu 0.0440(2) 0.0523(2) 0.0517(2) 0.000 0.02061(16) 0.000 O1 0.0459(6) 0.0568(7) 0.0678(8) 0.0027(5) 0.0233(6) -0.0018(5) C2 0.0511(9) 0.0592(10) 0.0546(9) 0.0033(7) 0.0220(7) -0.0012(7) O3 0.0806(10) 0.0580(8) 0.0975(11) 0.0133(7) 0.0453(9) 0.0096(7) C4 0.0498(9) 0.0701(11) 0.0583(9) -0.0024(8) 0.0219(8) -0.0105(8) C5 0.0701(13) 0.0976(17) 0.0739(13) 0.0034(12) 0.0315(11) -0.0241(12) C6 0.0829(18) 0.152(3) 0.104(2) 0.001(2) 0.0537(17) -0.033(2) C7 0.0618(15) 0.193(4) 0.129(3) -0.003(3) 0.0525(18) -0.015(2) C8 0.0556(14) 0.135(3) 0.113(2) 0.0069(19) 0.0302(15) 0.0100(14) C9 0.0513(10) 0.0845(15) 0.0740(13) 0.0011(10) 0.0233(10) -0.0013(9) O10 0.0675(9) 0.0844(11) 0.0874(11) 0.0185(9) 0.0254(8) 0.0102(8) C11 0.0506(11) 0.104(2) 0.0785(15) 0.0181(13) 0.0188(10) 0.0041(11) O12 0.1098(15) 0.1046(16) 0.0965(14) -0.0011(11) 0.0527(12) -0.0092(12) C13' 0.058(6) 0.089(6) 0.063(6) 0.018(5) 0.005(5) 0.001(4) C14' 0.125(10) 0.108(9) 0.078(6) 0.003(7) 0.036(6) -0.033(8) C15' 0.138(12) 0.102(9) 0.127(11) 0.042(8) 0.057(9) -0.020(8) C16' 0.098(9) 0.125(14) 0.125(11) 0.063(11) 0.036(7) 0.010(8) C17' 0.106(9) 0.199(16) 0.116(10) 0.058(11) 0.062(8) 0.043(11) C18' 0.066(6) 0.112(8) 0.100(8) 0.023(7) 0.039(6) 0.010(6) C13 0.054(3) 0.126(7) 0.076(5) 0.035(5) 0.011(3) 0.001(3) C14 0.113(5) 0.131(7) 0.106(6) 0.049(5) 0.032(4) 0.002(5) C15 0.161(8) 0.159(9) 0.153(10) 0.073(7) 0.066(7) 0.035(7) C16 0.121(6) 0.184(10) 0.168(11) 0.103(10) 0.069(7) 0.023(8) C17 0.134(8) 0.212(13) 0.151(10) 0.083(10) 0.097(7) 0.046(8) C18 0.090(6) 0.151(7) 0.115(7) 0.037(6) 0.049(5) 0.011(5) N19 0.0559(8) 0.0692(9) 0.0556(8) 0.0015(7) 0.0252(7) 0.0041(7) C20 0.0656(11) 0.0751(12) 0.0560(10) -0.0030(9) 0.0211(9) 0.0010(9) C21 0.0869(15) 0.0926(17) 0.0627(12) -0.0102(11) 0.0245(11) 0.0022(13) C22 0.1024(19) 0.119(2) 0.0561(12) -0.0014(13) 0.0353(13) 0.0117(17) C23 0.106(2) 0.109(2) 0.0772(16) 0.0145(14) 0.0555(17) 0.0043(16) C24 0.0808(15) 0.0862(15) 0.0682(13) 0.0003(11) 0.0400(12) -0.0073(12) N25 0.0589(12) 0.0483(10) 0.0703(13) 0.000 0.0282(10) 0.000 C26 0.0613(11) 0.0557(11) 0.0850(13) -0.0012(9) 0.0288(10) -0.0013(8) C27 0.0793(14) 0.0583(11) 0.0907(15) -0.0059(10) 0.0392(12) -0.0143(10) C28 0.098(2) 0.0484(13) 0.082(2) 0.000 0.0507(19) 0.000 N1S 0.256(5) 0.171(4) 0.225(4) -0.015(4) 0.139(4) -0.044(4) C2S 0.265(6) 0.161(5) 0.223(5) -0.041(4) 0.124(4) -0.055(4) C3S 0.287(7) 0.206(6) 0.208(6) -0.049(5) 0.127(5) -0.048(5) C1S' 0.256(5) 0.171(4) 0.225(4) -0.015(4) 0.139(4) -0.044(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 Cu O1 1.9727(13) . ? Cu O1 1.9727(13) 2 ? Cu N19 2.0301(16) . ? Cu N19 2.0301(16) 2 ? Cu N25 2.280(2) . ? O1 C2 1.272(2) . ? C2 O3 1.222(2) . ? C2 C4 1.508(3) . ? C4 C9 1.382(3) . ? C4 C5 1.392(3) . ? C5 C6 1.376(4) . ? C6 C7 1.354(6) . ? C7 C8 1.374(5) . ? C8 C9 1.383(4) . ? C9 O10 1.398(3) . ? O10 C11 1.364(4) . ? C11 O12 1.181(4) . ? C11 C13' 1.489(3) . ? C11 C13 1.494(3) . ? C13' C14' 1.3900 . ? C13' C18' 1.3900 . ? C14' C15' 1.3900 . ? C15' C16' 1.3900 . ? C16' C17' 1.3900 . ? C17' C18' 1.3900 . ? C13 C14 1.3900 . ? C13 C18 1.3900 . ? C14 C15 1.3900 . ? C15 C16 1.3900 . ? C16 C17 1.3900 . ? C17 C18 1.3900 . ? N19 C24 1.332(3) . ? N19 C20 1.342(3) . ? C20 C21 1.377(3) . ? C21 C22 1.364(4) . ? C22 C23 1.358(5) . ? C23 C24 1.395(4) . ? N25 C26 1.329(2) 2 ? N25 C26 1.329(2) . ? C26 C27 1.384(3) . ? C27 C28 1.358(3) . ? C28 C27 1.358(3) 2 ? N1S C2S 1.384(3) . ? N1S C3S 1.412(11) 7_546 ? C2S C3S 1.388(3) . ? C3S N1S 1.412(11) 7_546 ? C3S C1S' 1.412(11) 7_546 ? 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 Cu O1 178.90(7) . 2 ? O1 Cu N19 89.89(6) . . ? O1 Cu N19 90.24(6) 2 . ? O1 Cu N19 90.24(6) . 2 ? O1 Cu N19 89.89(6) 2 2 ? N19 Cu N19 165.95(11) . 2 ? O1 Cu N25 89.45(4) . . ? O1 Cu N25 89.45(4) 2 . ? N19 Cu N25 97.02(5) . . ? N19 Cu N25 97.02(5) 2 . ? C2 O1 Cu 119.00(11) . . ? O3 C2 O1 124.87(17) . . ? O3 C2 C4 119.30(18) . . ? O1 C2 C4 115.79(16) . . ? C9 C4 C5 116.9(2) . . ? C9 C4 C2 125.01(18) . . ? C5 C4 C2 118.0(2) . . ? C6 C5 C4 121.5(3) . . ? C7 C6 C5 120.3(3) . . ? C6 C7 C8 120.1(3) . . ? C7 C8 C9 119.7(3) . . ? C4 C9 C8 121.5(3) . . ? C4 C9 O10 122.3(2) . . ? C8 C9 O10 116.1(2) . . ? C11 O10 C9 116.6(2) . . ? O12 C11 O10 123.1(2) . . ? O12 C11 C13' 117.6(8) . . ? O10 C11 C13' 119.2(8) . . ? O12 C11 C13 131.5(8) . . ? O10 C11 C13 105.4(7) . . ? C13' C11 C13 14.6(9) . . ? C14' C13' C18' 120.0 . . ? C14' C13' C11 119.7(10) . . ? C18' C13' C11 120.0(10) . . ? C15' C14' C13' 120.0 . . ? C16' C15' C14' 120.0 . . ? C15' C16' C17' 120.0 . . ? C16' C17' C18' 120.0 . . ? C17' C18' C13' 120.0 . . ? C14 C13 C18 120.0 . . ? C14 C13 C11 125.2(7) . . ? C18 C13 C11 114.6(7) . . ? C15 C14 C13 120.0 . . ? C16 C15 C14 120.0 . . ? C17 C16 C15 120.0 . . ? C16 C17 C18 120.0 . . ? C17 C18 C13 120.0 . . ? C24 N19 C20 118.11(19) . . ? C24 N19 Cu 121.41(16) . . ? C20 N19 Cu 120.48(14) . . ? N19 C20 C21 122.3(2) . . ? C22 C21 C20 119.4(3) . . ? C23 C22 C21 119.0(2) . . ? C22 C23 C24 119.5(3) . . ? N19 C24 C23 121.7(3) . . ? C26 N25 C26 117.2(2) 2 . ? C26 N25 Cu 121.39(12) 2 . ? C26 N25 Cu 121.39(12) . . ? N25 C26 C27 122.8(2) . . ? C28 C27 C26 119.2(2) . . ? C27 C28 C27 118.7(3) 2 . ? C2S N1S C3S 122.7(7) . 7_546 ? N1S C2S C3S 127.4(9) . . ? C2S C3S N1S 109.9(8) . 7_546 ? C2S C3S C1S' 109.9(8) . 7_546 ? N1S C3S C1S' 0.002(2) 7_546 7_546 ? _diffrn_measured_fraction_theta_max 0.989 _diffrn_reflns_theta_full 75.75 _diffrn_measured_fraction_theta_full 0.989 _refine_diff_density_max 0.436 _refine_diff_density_min -0.631 _refine_diff_density_rms 0.050