# Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2001 # CCDC Number: 186/2326 #============================================================================== data_global #============================================================================== _publ_contact_author ; Dr David L. Hughes, Biological Chemistry Department, John Innes Centre, Norwich Research Park, Colney, Norwich, NR4 7UH, UK. ; _publ_contact_author_phone '01 603 450 709' _publ_contact_author_fax '01 603 450 018' _publ_contact_author_email hughes@bbsrc.ac.uk _publ_requested_journal 'J. Chem. Soc., Dalton Trans.' _publ_requested_coeditor_name ? _publ_contact_letter ; Please find, following, the .CIF for seven complexes for the MS submitted to Dalton Transactions, paper no. B008476J. Thank you. ; #============================================================================== _publ_section_title ; Copper complexes of the functionalised tripodal ligand 1,1,1-tris(2-pyridyl)- methylamine and its derivatives. ; loop_ _publ_author_name _publ_author_address 'Arnold, Phillip J.' ; Department of Chemistry, Queen Mary and Westfield College, Mile End Road, London, E1 4NS, UK. ; 'Davies, Sian C.' ; Biological Chemistry Department, John Innes Centre, Norwich Research Park, Colney, Norwich, NR4 7UH, UK. ; 'Dilworth, Jonathan R.' ; Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, UK. ; 'Durrant, Marcus C.' ; Biological Chemistry Department, John Innes Centre, Norwich Research Park, Colney, Norwich, NR4 7UH, UK. ; 'Griffiths, D. Vaughan' ; Department of Chemistry, Queen Mary and Westfield College, Mile End Road, London, E1 4NS, UK. ; 'Hughes, David L.' ; Biological Chemistry Department, John Innes Centre, Norwich Research Park, Colney, Norwich, NR4 7UH, UK. ; 'Richards, Raymond L.' ; School of Chemistry, Physics and Environmental Science, University of Sussex, Falmer, Brighton, BN1 9QJ, UK. ; 'Sharpe, Philip C.' ; Department of Chemistry, Queen Mary and Westfield College, Mile End Road, London, E1 4NS, UK. ; #============================================================================== data_marcus11 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common 'Complex 1' _chemical_formula_moiety 'C16 H16 Cu N4 O5 S, 3(H2 O)' _chemical_formula_structural '[Cu(SO4)(tpm)(H2O)].3H2O' _chemical_formula_analytical ? _chemical_formula_sum 'C16 H22 Cu N4 O8 S' _chemical_formula_weight 493.98 _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' 0.0033 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' 'Cu' 'Cu' 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'S' 'S' 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P n a 21 (no. 33)' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z+1/2' '-x+1/2, y+1/2, z+1/2' 'x+1/2, -y+1/2, z' _cell_length_a 13.729(3) _cell_length_b 8.0736(9) _cell_length_c 17.869(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1980.7(5) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 10 _cell_measurement_theta_max 11 _exptl_crystal_description 'thick plates' _exptl_crystal_colour turquoise _exptl_crystal_size_max 0.48 _exptl_crystal_size_mid 0.21 _exptl_crystal_size_min 0.14 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.657 _exptl_crystal_density_method ? _exptl_crystal_F_000 1020 _exptl_absorpt_coefficient_mu 1.262 _exptl_absorpt_correction_type 'semi-empirical psi-scans' _exptl_absorpt_correction_T_min 0.125 _exptl_absorpt_correction_T_max 0.235 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type Mo-K\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Enraf-Nonius CAD4 diffractometer' _diffrn_measurement_method 'scintillation counter; \w/\q scans' _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time '10000 s' _diffrn_standards_decay_% 0 _diffrn_reflns_number 2858 _diffrn_reflns_av_R_equivalents 0.019 _diffrn_reflns_av_sigmaI/netI 0.0436 _diffrn_reflns_limit_h_min -1 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -1 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -1 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 2.28 _diffrn_reflns_theta_max 27.97 _reflns_number_total 2457 _reflns_number_observed 1963 _reflns_observed_criterion I>2sigma(I) _computing_data_collection 'CAD4/EXPRESS (Enraf-Nonius, 1992)' _computing_cell_refinement 'CAD4/EXPRESS (Enraf-Nonius, 1992)' _computing_data_reduction 'CAD4 (Hursthouse, 1976)' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'ORTEP (Johnson, 1971)' _computing_publication_material 'SHELXL-93 (Sheldrick, 1993)' _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^)+(0.0909P)^2^] 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 ; Hydrogen atoms on the pyridyl rings were included in idealised positions; the two amino hydrogens were located in a difference map and refined with geometrical constraints. The isotropic factors of all hydrogen atoms were allowed to refine freely. ; _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 0.04(3) _refine_ls_number_reflns 2457 _refine_ls_number_parameters 336 _refine_ls_number_restraints 6 _refine_ls_R_factor_all 0.0648 _refine_ls_R_factor_obs 0.0537 _refine_ls_wR_factor_all 0.1389 _refine_ls_wR_factor_obs 0.1279 _refine_ls_goodness_of_fit_all 1.077 _refine_ls_goodness_of_fit_obs 1.128 _refine_ls_restrained_S_all 1.075 _refine_ls_restrained_S_obs 1.126 _refine_ls_shift/esd_max 0.000 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Cu Cu 0.24595(5) 0.26588(7) 0.23351(9) 0.0331(2) Uani 1 d . . N11 N 0.1459(4) 0.3625(6) 0.3185(3) 0.0378(11) Uani 1 d . . C12 C 0.1706(4) 0.3525(6) 0.3896(3) 0.0304(10) Uani 1 d . . C13 C 0.1166(5) 0.4261(8) 0.4458(3) 0.0413(13) Uani 1 d . . H13 H 0.1344(5) 0.4156(8) 0.4957(3) 0.052(20) Uiso 1 calc R . C14 C 0.0341(5) 0.5169(9) 0.4248(4) 0.049(2) Uani 1 d . . H14 H -0.0031(5) 0.5701(9) 0.4611(4) 0.043(18) Uiso 1 calc R . C15 C 0.0083(4) 0.5274(9) 0.3518(5) 0.048(2) Uani 1 d . . H15 H -0.0461(4) 0.5875(9) 0.3370(5) 0.078(28) Uiso 1 calc R . C16 C 0.0660(4) 0.4454(8) 0.3001(4) 0.0430(14) Uani 1 d . . H16 H 0.0478(4) 0.4487(8) 0.2500(4) 0.058(22) Uiso 1 calc R . N21 N 0.3559(3) 0.3579(5) 0.2958(3) 0.0302(9) Uani 1 d . . C22 C 0.3533(4) 0.3483(7) 0.3707(3) 0.0316(11) Uani 1 d . . C23 C 0.4245(4) 0.4214(8) 0.4132(4) 0.0396(13) Uani 1 d . . H23 H 0.4232(4) 0.4116(8) 0.4650(4) 0.116(41) Uiso 1 calc R . C24 C 0.4976(4) 0.5092(10) 0.3790(5) 0.050(2) Uani 1 d . . H24 H 0.5442(4) 0.5634(10) 0.4077(5) 0.107(36) Uiso 1 calc R . C25 C 0.5020(4) 0.5169(10) 0.3023(5) 0.049(2) Uani 1 d . . H25 H 0.5519(4) 0.5732(10) 0.2779(5) 0.092(33) Uiso 1 calc R . C26 C 0.4297(4) 0.4379(8) 0.2632(4) 0.0411(14) Uani 1 d . . H26 H 0.4322(4) 0.4401(8) 0.2112(4) 0.027(15) Uiso 1 calc R . N31 N 0.2561(3) 0.0636(6) 0.2995(3) 0.0334(10) Uani 1 d . . C32 C 0.2607(4) 0.0796(7) 0.3744(3) 0.0294(10) Uani 1 d . . C33 C 0.2636(4) -0.0601(8) 0.4206(4) 0.0446(15) Uani 1 d . . H33 H 0.2663(4) -0.0482(8) 0.4723(4) 0.070(27) Uiso 1 calc R . C34 C 0.2623(5) -0.2149(8) 0.3890(6) 0.053(2) Uani 1 d . . H34 H 0.2652(5) -0.3088(8) 0.4190(6) 0.055(22) Uiso 1 calc R . C35 C 0.2568(5) -0.2300(8) 0.3121(6) 0.051(2) Uani 1 d . . H35 H 0.2550(5) -0.3339(8) 0.2897(6) 0.074(31) Uiso 1 calc R . C36 C 0.2539(4) -0.0887(8) 0.2694(5) 0.0443(15) Uani 1 d . . H36 H 0.2504(4) -0.0989(8) 0.2177(5) 0.106(49) Uiso 1 calc R . C1 C 0.2675(4) 0.2566(7) 0.4067(3) 0.0311(11) Uani 1 d D . N1 N 0.2787(4) 0.2435(7) 0.4878(3) 0.0402(11) Uani 1 d D . H1A H 0.2703(40) 0.3466(26) 0.5080(10) 0.080(31) Uiso 1 d D . H1B H 0.3419(15) 0.2143(62) 0.4976(10) 0.033(16) Uiso 1 d D . O41 O 0.1403(4) 0.1684(7) 0.1763(3) 0.0564(13) Uani 1 d . . S4A S 0.1193(3) 0.1082(6) 0.1000(2) 0.0423(9) Uani 0.648(12) d P 1 O42A O 0.0716(11) -0.0515(14) 0.1038(7) 0.108(5) Uani 0.648(12) d P 1 O43A O 0.0510(14) 0.2258(21) 0.0660(8) 0.111(6) Uani 0.648(12) d P 1 O44A O 0.2011(23) 0.0922(32) 0.0511(16) 0.069(5) Uani 0.648(12) d P 1 S4B S 0.1203(6) 0.1881(20) 0.0931(5) 0.057(3) Uani 0.352(12) d P 2 O42B O 0.0258(13) 0.1245(28) 0.0762(10) 0.065(6) Uani 0.352(12) d P 2 O43B O 0.1148(13) 0.3707(24) 0.0755(9) 0.070(6) Uani 0.352(12) d P 2 O44B O 0.2088(41) 0.1367(68) 0.0581(30) 0.084(15) Uani 0.352(12) d P 2 O5 O 0.2408(3) 0.4743(8) 0.1713(3) 0.0590(14) Uani 1 d . . O6 O 0.3745(7) 0.1511(12) 0.1351(5) 0.122(3) Uani 1 d . . O7A O 0.3758(14) 0.5765(36) 0.0782(13) 0.150(13) Uani 0.648(12) d P . O7B O 0.3716(38) 0.6200(61) 0.0845(27) 0.115(13) Uiso 0.352(12) d P . O8A O 0.4286(11) 0.0983(17) 0.6079(10) 0.137(7) Uani 0.648(12) d P . O8B O 0.5402(26) 0.1542(41) 0.6529(18) 0.146(12) Uiso 0.352(12) d P . 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 0.0434(4) 0.0289(3) 0.0269(3) -0.0015(5) -0.0033(3) 0.0009(3) N11 0.043(3) 0.038(3) 0.033(2) 0.000(2) 0.000(2) 0.003(2) C12 0.038(3) 0.018(2) 0.035(3) -0.003(2) 0.001(2) -0.005(2) C13 0.042(3) 0.042(3) 0.040(3) 0.001(2) 0.004(2) -0.003(3) C14 0.037(3) 0.044(4) 0.066(4) -0.014(3) 0.013(3) 0.009(3) C15 0.037(3) 0.043(4) 0.064(4) 0.008(3) 0.004(3) 0.004(3) C16 0.039(3) 0.044(3) 0.047(3) 0.004(3) -0.009(3) 0.006(3) N21 0.039(2) 0.025(2) 0.026(2) -0.001(2) 0.001(2) 0.004(2) C22 0.034(3) 0.028(2) 0.033(3) -0.004(2) 0.000(2) 0.009(2) C23 0.039(3) 0.039(3) 0.041(3) -0.010(2) 0.000(2) 0.000(2) C24 0.035(3) 0.052(4) 0.065(4) -0.012(3) 0.004(3) -0.010(3) C25 0.042(3) 0.050(4) 0.056(4) 0.003(3) 0.007(3) -0.005(3) C26 0.039(3) 0.042(3) 0.042(3) 0.002(2) 0.007(2) 0.000(3) N31 0.038(2) 0.023(2) 0.040(3) -0.008(2) -0.004(2) 0.000(2) C32 0.029(2) 0.023(2) 0.036(3) 0.001(2) 0.000(2) 0.001(2) C33 0.048(3) 0.032(3) 0.054(4) 0.013(3) 0.006(3) 0.003(2) C34 0.045(4) 0.022(3) 0.091(6) 0.016(3) 0.004(3) 0.002(2) C35 0.048(4) 0.022(3) 0.082(6) -0.006(3) 0.001(3) -0.003(3) C36 0.046(4) 0.025(3) 0.062(4) -0.014(3) 0.003(3) 0.001(2) C1 0.040(3) 0.026(3) 0.028(3) -0.001(2) -0.003(2) -0.001(2) N1 0.048(3) 0.044(3) 0.029(2) 0.004(2) -0.004(2) 0.003(2) O41 0.059(3) 0.073(3) 0.038(2) -0.013(2) -0.002(2) -0.023(3) S4A 0.052(2) 0.042(2) 0.0325(13) -0.009(2) -0.0033(11) -0.004(2) O42A 0.165(12) 0.074(7) 0.085(7) -0.034(6) 0.032(7) -0.071(7) O43A 0.129(14) 0.119(14) 0.085(9) 0.026(9) -0.031(10) 0.035(11) O44A 0.078(12) 0.073(9) 0.056(10) -0.046(7) 0.012(7) -0.032(8) S4B 0.050(3) 0.087(7) 0.033(3) -0.022(4) 0.000(2) -0.013(5) O42B 0.062(9) 0.085(15) 0.048(9) -0.011(9) -0.005(7) -0.044(10) O43B 0.080(11) 0.081(12) 0.050(9) 0.005(8) -0.018(8) 0.017(10) O44B 0.065(13) 0.139(41) 0.050(12) -0.070(21) 0.024(9) -0.063(22) O5 0.066(3) 0.064(4) 0.047(3) 0.018(3) -0.006(2) 0.000(2) O6 0.152(8) 0.136(7) 0.078(5) 0.001(5) -0.014(5) -0.087(6) O7A 0.060(7) 0.247(28) 0.145(16) 0.164(20) 0.003(7) 0.018(11) O8A 0.123(11) 0.114(11) 0.175(15) 0.075(10) 0.051(10) 0.048(9) _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 O41 1.941(5) . ? Cu N21 2.017(5) . ? Cu O5 2.018(6) . ? Cu N31 2.019(5) . ? Cu N11 2.192(5) . ? N11 C12 1.317(7) . ? N11 C16 1.327(8) . ? C12 C13 1.382(8) . ? C12 C1 1.569(8) . ? C13 C14 1.400(9) . ? C13 H13 0.93 . ? C14 C15 1.354(11) . ? C14 H14 0.93 . ? C15 C16 1.385(10) . ? C15 H15 0.93 . ? C16 H16 0.93 . ? N21 C26 1.336(8) . ? N21 C22 1.340(7) . ? C22 C23 1.371(8) . ? C22 C1 1.533(8) . ? C23 C24 1.372(9) . ? C23 H23 0.93 . ? C24 C25 1.373(12) . ? C24 H24 0.93 . ? C25 C26 1.370(10) . ? C25 H25 0.93 . ? C26 H26 0.93 . ? N31 C36 1.342(8) . ? N31 C32 1.347(8) . ? C32 C33 1.397(8) . ? C32 C1 1.544(7) . ? C33 C34 1.372(11) . ? C33 H33 0.93 . ? C34 C35 1.381(15) . ? C34 H34 0.93 . ? C35 C36 1.372(11) . ? C35 H35 0.93 . ? C36 H36 0.93 . ? C1 N1 1.462(8) . ? N1 H1A 0.914(11) . ? N1 H1B 0.916(10) . ? O41 S4A 1.477(6) . ? O41 S4B 1.521(10) . ? S4A O44A 1.43(3) . ? S4A O42A 1.448(10) . ? S4A O43A 1.467(14) . ? S4B O42B 1.43(2) . ? S4B O44B 1.43(5) . ? S4B O43B 1.51(2) . ? O8A O8B 1.79(4) . ? 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 O41 Cu N21 177.4(2) . . ? O41 Cu O5 91.3(2) . . ? N21 Cu O5 91.3(2) . . ? O41 Cu N31 91.8(2) . . ? N21 Cu N31 85.6(2) . . ? O5 Cu N31 176.9(2) . . ? O41 Cu N11 92.3(2) . . ? N21 Cu N11 87.4(2) . . ? O5 Cu N11 93.6(2) . . ? N31 Cu N11 85.8(2) . . ? C12 N11 C16 118.9(5) . . ? C12 N11 Cu 119.0(4) . . ? C16 N11 Cu 121.7(4) . . ? N11 C12 C13 122.3(5) . . ? N11 C12 C1 115.9(5) . . ? C13 C12 C1 121.8(5) . . ? C12 C13 C14 117.8(6) . . ? C12 C13 H13 121.1(3) . . ? C14 C13 H13 121.1(4) . . ? C15 C14 C13 120.1(6) . . ? C15 C14 H14 120.0(4) . . ? C13 C14 H14 120.0(4) . . ? C14 C15 C16 117.6(6) . . ? C14 C15 H15 121.2(4) . . ? C16 C15 H15 121.2(4) . . ? N11 C16 C15 123.2(6) . . ? N11 C16 H16 118.4(3) . . ? C15 C16 H16 118.4(4) . . ? C26 N21 C22 118.9(5) . . ? C26 N21 Cu 120.4(4) . . ? C22 N21 Cu 120.7(4) . . ? N21 C22 C23 120.6(5) . . ? N21 C22 C1 117.8(5) . . ? C23 C22 C1 121.5(5) . . ? C22 C23 C24 119.8(6) . . ? C22 C23 H23 120.1(4) . . ? C24 C23 H23 120.1(4) . . ? C23 C24 C25 120.0(6) . . ? C23 C24 H24 120.0(4) . . ? C25 C24 H24 120.0(4) . . ? C26 C25 C24 117.1(6) . . ? C26 C25 H25 121.5(4) . . ? C24 C25 H25 121.5(4) . . ? N21 C26 C25 123.5(6) . . ? N21 C26 H26 118.2(3) . . ? C25 C26 H26 118.2(4) . . ? C36 N31 C32 119.1(6) . . ? C36 N31 Cu 120.4(5) . . ? C32 N31 Cu 120.4(4) . . ? N31 C32 C33 120.7(6) . . ? N31 C32 C1 117.5(5) . . ? C33 C32 C1 121.7(6) . . ? C34 C33 C32 119.5(7) . . ? C34 C33 H33 120.3(5) . . ? C32 C33 H33 120.3(4) . . ? C33 C34 C35 119.4(7) . . ? C33 C34 H34 120.3(5) . . ? C35 C34 H34 120.3(4) . . ? C36 C35 C34 118.7(7) . . ? C36 C35 H35 120.6(5) . . ? C34 C35 H35 120.6(4) . . ? N31 C36 C35 122.6(7) . . ? N31 C36 H36 118.7(4) . . ? C35 C36 H36 118.7(5) . . ? N1 C1 C22 111.7(5) . . ? N1 C1 C32 108.0(5) . . ? C22 C1 C32 109.7(5) . . ? N1 C1 C12 108.5(5) . . ? C22 C1 C12 109.4(4) . . ? C32 C1 C12 109.5(4) . . ? C1 N1 H1A 108.1(13) . . ? C1 N1 H1B 107.9(12) . . ? H1A N1 H1B 106.2(16) . . ? S4A O41 Cu 139.9(4) . . ? S4B O41 Cu 127.4(5) . . ? O44A S4A O42A 107.7(10) . . ? O44A S4A O43A 107.9(17) . . ? O42A S4A O43A 107.8(11) . . ? O44A S4A O41 116.2(10) . . ? O42A S4A O41 109.8(6) . . ? O43A S4A O41 107.1(8) . . ? O42B S4B O44B 125.2(17) . . ? O42B S4B O43B 105.2(16) . . ? O44B S4B O43B 103.6(25) . . ? O42B S4B O41 109.4(11) . . ? O44B S4B O41 104.1(27) . . ? O43B S4B O41 108.3(9) . . ? _refine_diff_density_max 0.850 _refine_diff_density_min -1.000 _refine_diff_density_rms 0.112 #===END data_marcus10b _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common 'Complex 5' _chemical_formula_moiety 'C32 H28 Br3 Cu2 N8, Br, 3(C H4 O)' _chemical_formula_structural [{Cu(tpm)}2Br3]Br.3MeOH _chemical_formula_analytical ? _chemical_formula_sum 'C35 H40 Br4 Cu2 N8 O3' _chemical_formula_weight 1067.5 _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' 0.0033 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' 'Br' 'Br' -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Cu' 'Cu' 0.3201 1.2651 '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 orthorhombic _symmetry_space_group_name_H-M 'Pnmm (equiv. to no. 59)' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x, y, -z+1/2' 'x, -y+1/2, z' 'x, -y+1/2, -z+1/2' '-x, -y, -z' '-x, -y, z-1/2' '-x, y-1/2, -z' '-x, y-1/2, z-1/2' _cell_length_a 8.1466(14) _cell_length_b 14.188(2) _cell_length_c 31.992(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3697.8(10) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 10 _cell_measurement_theta_max 12 _exptl_crystal_description 'rectangular prisms' _exptl_crystal_colour brown _exptl_crystal_size_max 0.57 _exptl_crystal_size_mid 0.17 _exptl_crystal_size_min 0.07 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.917 _exptl_crystal_density_method ? _exptl_crystal_F_000 2112 _exptl_absorpt_coefficient_mu 5.52 _exptl_absorpt_correction_type 'semi-empirical psi-scans' _exptl_absorpt_correction_T_min 0.075 _exptl_absorpt_correction_T_max 0.112 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type Mo-K\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Enraf-Nonius CAD4 diffractometer' _diffrn_measurement_method 'scintillation counter; \w/\q scans' _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time '10000 s' _diffrn_standards_decay_% 0 _diffrn_reflns_number 6014 _diffrn_reflns_av_R_equivalents 0.100 _diffrn_reflns_av_sigmaI/netI 0.0879 _diffrn_reflns_limit_h_min -1 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -1 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -38 _diffrn_reflns_limit_l_max 38 _diffrn_reflns_theta_min 2.39 _diffrn_reflns_theta_max 25.0 _reflns_number_total 3461 _reflns_number_observed 1490 _reflns_observed_criterion I>2sigma(I) _computing_data_collection 'CAD4/EXPRESS (Enraf-Nonius, 1992)' _computing_cell_refinement 'CAD4/EXPRESS (Enraf-Nonius, 1992)' _computing_data_reduction 'CAD4 (Hursthouse, 1976)' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'ORTEP (Johnson, 1971)' _computing_publication_material 'SHELXL-93 (Sheldrick, 1993)' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 1065 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^)+(0.1260P)^2^] 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 none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2396 _refine_ls_number_parameters 179 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1436 _refine_ls_R_factor_obs 0.0729 _refine_ls_wR_factor_all 0.2561 _refine_ls_wR_factor_obs 0.1850 _refine_ls_goodness_of_fit_all 1.027 _refine_ls_goodness_of_fit_obs 1.121 _refine_ls_restrained_S_all 1.005 _refine_ls_restrained_S_obs 1.121 _refine_ls_shift/esd_max 0.678 _refine_ls_shift/esd_mean 0.032 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 0.4869(3) 0.2500 0.55013(7) 0.0347(6) Uani 1 d S . Cu2 Cu 0.5348(3) 0.2500 0.44705(7) 0.0372(6) Uani 1 d S . Br1 Br 0.7789(3) 0.2500 0.49400(7) 0.0603(7) Uani 1 d S . Br2 Br 0.3821(2) 0.12729(10) 0.50043(4) 0.0583(5) Uani 1 d . . N11A N 0.2804(16) 0.2500 0.5912(4) 0.036(3) Uiso 1 d S . C12A C 0.3090(20) 0.2500 0.6317(5) 0.034(4) Uiso 1 d S . C13A C 0.1745(20) 0.2500 0.6614(6) 0.042(5) Uiso 1 d S . H13A H 0.1918(20) 0.2500 0.6901(6) 0.050 Uiso 1 calc SR . C14A C 0.0216(23) 0.2500 0.6445(6) 0.046(5) Uiso 1 d S . H14A H -0.0696(23) 0.2500 0.6620(6) 0.055 Uiso 1 calc SR . C15A C 0.0003(23) 0.2500 0.6034(6) 0.053(5) Uiso 1 d S . H15A H -0.1054(23) 0.2500 0.5924(6) 0.063 Uiso 1 calc SR . C16A C 0.1261(19) 0.2500 0.5783(5) 0.034(4) Uiso 1 d S . H16A H 0.1064(19) 0.2500 0.5497(5) 0.041 Uiso 1 calc SR . N21A N 0.5919(11) 0.1516(7) 0.5892(3) 0.035(2) Uiso 1 d . . C22A C 0.5803(13) 0.1605(8) 0.6299(3) 0.030(3) Uiso 1 d . . C23A C 0.6460(14) 0.0959(9) 0.6582(4) 0.046(3) Uiso 1 d . . H23A H 0.6353(14) 0.1031(9) 0.6870(4) 0.055 Uiso 1 calc R . C24A C 0.7284(16) 0.0203(10) 0.6406(4) 0.051(3) Uiso 1 d . . H24A H 0.7762(16) -0.0247(10) 0.6579(4) 0.061 Uiso 1 calc R . C25A C 0.7404(16) 0.0109(10) 0.5984(4) 0.052(3) Uiso 1 d . . H25A H 0.7955(16) -0.0401(10) 0.5867(4) 0.062 Uiso 1 calc R . C26A C 0.6692(14) 0.0787(9) 0.5731(4) 0.040(3) Uiso 1 d . . H26A H 0.6760(14) 0.0726(9) 0.5442(4) 0.048 Uiso 1 calc R . C1A C 0.4882(21) 0.2500 0.6471(5) 0.037(4) Uiso 1 d S . N1A N 0.4897(22) 0.2500 0.6936(5) 0.030(5) Uiso 1 d S . N11B N 0.3415(15) 0.2500 0.4068(4) 0.032(3) Uiso 1 d S . C12B C 0.3627(19) 0.2500 0.3663(5) 0.029(4) Uiso 1 d S . C13B C 0.2380(22) 0.2500 0.3380(6) 0.045(5) Uiso 1 d S . H13B H 0.2596(22) 0.2500 0.3095(6) 0.054 Uiso 1 calc SR . C14B C 0.0775(23) 0.2500 0.3528(6) 0.049(5) Uiso 1 d S . H14B H -0.0112(23) 0.2500 0.3345(6) 0.059 Uiso 1 calc SR . C15B C 0.0546(21) 0.2500 0.3950(5) 0.041(4) Uiso 1 d S . H15B H -0.0509(21) 0.2500 0.4061(5) 0.049 Uiso 1 calc SR . C16B C 0.1876(19) 0.2500 0.4208(5) 0.035(4) Uiso 1 d S . H16B H 0.1701(19) 0.2500 0.4495(5) 0.042 Uiso 1 calc SR . N21B N 0.6322(11) 0.1470(7) 0.4070(3) 0.037(2) Uiso 1 d . . C22B C 0.6333(13) 0.1608(8) 0.3669(3) 0.030(3) Uiso 1 d . . C23B C 0.7077(15) 0.0981(9) 0.3389(4) 0.049(3) Uiso 1 d . . H23B H 0.7071(15) 0.1096(9) 0.3103(4) 0.059 Uiso 1 calc R . C24B C 0.7834(17) 0.0172(10) 0.3555(4) 0.054(4) Uiso 1 d . . H24B H 0.8336(17) -0.0269(10) 0.3382(4) 0.065 Uiso 1 calc R . C25B C 0.7803(16) 0.0057(11) 0.3990(4) 0.056(4) Uiso 1 d . . H25B H 0.8337(16) -0.0451(11) 0.4114(4) 0.067 Uiso 1 calc R . C26B C 0.6989(15) 0.0692(10) 0.4227(4) 0.049(3) Uiso 1 d . . H26B H 0.6892(15) 0.0580(10) 0.4512(4) 0.058 Uiso 1 calc R . C1B C 0.5442(22) 0.2500 0.3499(6) 0.041(4) Uiso 1 d S . N1B N 0.5556(24) 0.2500 0.3035(6) 0.030(5) Uiso 1 d S . Br11 Br 0.6567(16) 0.5785(9) 0.2500 0.106(3) Uani 0.371(6) d SP . Br21 Br 0.3826(14) 0.0665(6) 0.2500 0.085(3) Uani 0.371(6) d SP . Br12 Br 0.1599(26) 0.7500 0.2500 0.087(6) Uani 0.371(6) d SP . Br22 Br 0.8939(23) 0.2500 0.2500 0.130(7) Uani 0.371(6) d SP . O1X O 0.6800 0.2500 0.5050 0.156(49) Uiso 0.25 d SP . C1X C 0.8661(52) 0.2227(27) 0.5078(11) 0.023(10) Uiso 0.25 d P . O11 O 0.6090 0.6087 0.2500 0.287(54) Uiso 0.50 d SP . O21 O 0.4237(38) 0.1007(23) 0.2500 0.042(10) Uiso 0.50 d SP . O12 O 0.2063(95) 0.7500 0.2500 0.063(28) Uiso 0.50 d SP . O22 O 0.8140(87) 0.2500 0.2500 0.113(33) Uiso 0.50 d SP . C81 C 0.0757(26) 0.0920(18) 0.2500 0.065(6) Uiso 1 d S . C82 C 0.0283(30) -0.0042(22) 0.2500 0.086(8) Uiso 1 d S . C83 C -0.0152(29) -0.0927(21) 0.2500 0.081(8) Uiso 1 d S . C91 C 0.5363(64) 0.2500 0.6985(16) 0.051(17) Uiso 0.50 d SP . C92 C 0.5754(69) 0.2500 0.5535(18) 0.080(20) Uiso 0.50 d SP . C93 C 0.4395(64) 0.2500 0.4476(16) 0.069(16) Uiso 0.50 d SP . C94 C 0.5120(69) 0.2500 0.3028(20) 0.056(20) Uiso 0.50 d SP . 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 0.0406(15) 0.0325(15) 0.0310(12) 0.000 -0.0018(11) 0.000 Cu2 0.0384(14) 0.040(2) 0.0333(13) 0.000 -0.0026(11) 0.000 Br1 0.060(2) 0.0589(14) 0.0619(15) 0.000 -0.0119(13) 0.000 Br2 0.0724(11) 0.0450(8) 0.0576(9) -0.0100(8) -0.0119(8) 0.0052(8) Br11 0.160(8) 0.106(7) 0.052(4) 0.000 0.000 -0.017(7) Br21 0.155(9) 0.047(5) 0.052(4) 0.000 0.000 -0.020(6) Br12 0.072(11) 0.154(16) 0.036(6) 0.000 0.000 0.000 Br22 0.106(13) 0.209(20) 0.076(9) 0.000 0.000 0.000 _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 C92 0.73(6) . ? Cu1 N21A 2.060(10) . ? Cu1 N21A 2.060(10) 3 ? Cu1 N11A 2.134(13) . ? Cu1 O1X 2.135(2) . ? Cu1 Br2 2.508(2) 3 ? Cu1 Br2 2.508(2) . ? Cu2 C93 0.78(5) . ? Cu2 N11B 2.034(13) . ? Cu2 N21B 2.099(10) . ? Cu2 N21B 2.099(10) 3 ? Cu2 O1X 2.199(2) . ? Cu2 Br1 2.492(3) . ? Cu2 Br2 2.737(2) 3 ? Cu2 Br2 2.737(2) . ? Br1 O1X 0.879(3) . ? Br1 C1X 0.92(4) 3 ? Br1 C1X 0.92(4) . ? N11A C16A 1.32(2) . ? N11A C12A 1.32(2) . ? C12A C13A 1.45(2) . ? C12A C1A 1.54(2) . ? C13A C14A 1.36(2) . ? C13A H13A 0.93 . ? C14A C15A 1.33(2) . ? C14A H14A 0.93 . ? C15A C16A 1.30(2) . ? C15A H15A 0.93 . ? C16A H16A 0.93 . ? N21A C22A 1.313(12) . ? N21A C26A 1.316(14) . ? N21A C92 1.81(4) . ? C22A C23A 1.39(2) . ? C22A C1A 1.574(14) . ? C23A C24A 1.38(2) . ? C23A H23A 0.93 . ? C24A C25A 1.36(2) . ? C24A H24A 0.93 . ? C25A C26A 1.38(2) . ? C25A H25A 0.93 . ? C26A H26A 0.93 . ? C1A N1A 1.49(2) . ? C1A C22A 1.574(14) 3 ? C1A C91 1.69(5) . ? N11B C12B 1.31(2) . ? N11B C16B 1.33(2) . ? N11B C93 1.53(5) . ? C12B C13B 1.36(2) . ? C12B C1B 1.57(2) . ? C13B C14B 1.39(2) . ? C13B H13B 0.93 . ? C14B C15B 1.36(2) . ? C14B H14B 0.93 . ? C15B C16B 1.36(2) . ? C15B H15B 0.93 . ? C16B H16B 0.93 . ? N21B C22B 1.298(13) . ? N21B C26B 1.33(2) . ? C22B C23B 1.40(2) . ? C22B C1B 1.557(15) . ? C23B C24B 1.41(2) . ? C23B H23B 0.93 . ? C24B C25B 1.40(2) . ? C24B H24B 0.93 . ? C25B C26B 1.35(2) . ? C25B H25B 0.93 . ? C26B H26B 0.93 . ? C1B N1B 1.49(3) . ? C1B C94 1.53(7) . ? C1B C22B 1.557(15) 3 ? Br11 O11 0.579(15) . ? Br21 O21 0.59(3) . ? Br22 O22 0.65(7) . ? O1X C1X 1.57(4) . ? O1X C1X 1.57(4) 3 ? O1X C92 1.77(6) . ? C1X C1X 0.78(8) 3 ? C81 C82 1.42(3) . ? C82 C83 1.30(3) . ? C92 N21A 1.81(4) 3 ? 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 C92 Cu1 N21A 60.0(29) . . ? C92 Cu1 N21A 60.0(29) . 3 ? N21A Cu1 N21A 85.3(5) . 3 ? C92 Cu1 N11A 133.5(47) . . ? N21A Cu1 N11A 87.4(4) . . ? N21A Cu1 N11A 87.4(4) 3 . ? C92 Cu1 O1X 51.0(46) . . ? N21A Cu1 O1X 96.0(3) . . ? N21A Cu1 O1X 96.0(3) 3 . ? N11A Cu1 O1X 175.4(4) . . ? C92 Cu1 Br2 115.5(30) . 3 ? N21A Cu1 Br2 175.3(3) . 3 ? N21A Cu1 Br2 93.2(3) 3 3 ? N11A Cu1 Br2 97.0(3) . 3 ? O1X Cu1 Br2 79.74(7) . 3 ? C92 Cu1 Br2 115.5(30) . . ? N21A Cu1 Br2 93.2(3) . . ? N21A Cu1 Br2 175.3(3) 3 . ? N11A Cu1 Br2 97.0(3) . . ? O1X Cu1 Br2 79.74(7) . . ? Br2 Cu1 Br2 87.94(10) 3 . ? C93 Cu2 N11B 40.6(39) . . ? C93 Cu2 N21B 113.1(26) . . ? N11B Cu2 N21B 84.7(4) . . ? C93 Cu2 N21B 113.1(26) . 3 ? N11B Cu2 N21B 84.6(4) . 3 ? N21B Cu2 N21B 88.2(5) . 3 ? C93 Cu2 O1X 121.2(39) . . ? N11B Cu2 O1X 161.8(4) . . ? N21B Cu2 O1X 108.1(3) . . ? N21B Cu2 O1X 108.1(3) 3 . ? C93 Cu2 Br1 141.6(39) . . ? N11B Cu2 Br1 177.8(4) . . ? N21B Cu2 Br1 93.8(3) . . ? N21B Cu2 Br1 93.8(3) 3 . ? O1X Cu2 Br1 20.39(6) . . ? C93 Cu2 Br2 62.1(27) . 3 ? N11B Cu2 Br2 92.5(3) . 3 ? N21B Cu2 Br2 174.4(3) . 3 ? N21B Cu2 Br2 96.3(3) 3 3 ? O1X Cu2 Br2 73.65(6) . 3 ? Br1 Cu2 Br2 89.23(8) . 3 ? C93 Cu2 Br2 62.1(27) . . ? N11B Cu2 Br2 92.5(3) . . ? N21B Cu2 Br2 96.3(3) . . ? N21B Cu2 Br2 174.4(3) 3 . ? O1X Cu2 Br2 73.65(6) . . ? Br1 Cu2 Br2 89.23(8) . . ? Br2 Cu2 Br2 78.99(9) 3 . ? O1X Br1 C1X 120.9(23) . 3 ? O1X Br1 C1X 120.9(23) . . ? C1X Br1 C1X 49.7(44) 3 . ? O1X Br1 Cu2 60.67(14) . . ? C1X Br1 Cu2 154.7(22) 3 . ? C1X Br1 Cu2 154.7(22) . . ? Cu1 Br2 Cu2 78.43(7) . . ? C16A N11A C12A 118.4(14) . . ? C16A N11A Cu1 123.8(11) . . ? C12A N11A Cu1 117.8(11) . . ? N11A C12A C13A 120.8(15) . . ? N11A C12A C1A 118.8(15) . . ? C13A C12A C1A 120.4(14) . . ? C14A C13A C12A 115.5(16) . . ? C14A C13A H13A 122.2(11) . . ? C12A C13A H13A 122.2(9) . . ? C15A C14A C13A 121.0(19) . . ? C15A C14A H14A 119.4(12) . . ? C13A C14A H14A 119.5(12) . . ? C16A C15A C14A 120.5(19) . . ? C16A C15A H15A 119.7(11) . . ? C14A C15A H15A 119.8(12) . . ? C15A C16A N11A 123.8(17) . . ? C15A C16A H16A 118.1(11) . . ? N11A C16A H16A 118.1(9) . . ? C22A N21A C26A 119.8(10) . . ? C22A N21A C92 123.2(17) . . ? C26A N21A C92 113.3(17) . . ? C22A N21A Cu1 120.5(8) . . ? C26A N21A Cu1 119.7(8) . . ? C92 N21A Cu1 20.4(18) . . ? N21A C22A C23A 123.6(11) . . ? N21A C22A C1A 117.2(11) . . ? C23A C22A C1A 119.2(11) . . ? C24A C23A C22A 115.5(12) . . ? C24A C23A H23A 122.2(8) . . ? C22A C23A H23A 122.2(7) . . ? C25A C24A C23A 121.0(13) . . ? C25A C24A H24A 119.5(9) . . ? C23A C24A H24A 119.5(8) . . ? C24A C25A C26A 118.8(14) . . ? C24A C25A H25A 120.6(9) . . ? C26A C25A H25A 120.6(8) . . ? N21A C26A C25A 121.3(12) . . ? N21A C26A H26A 119.3(7) . . ? C25A C26A H26A 119.4(8) . . ? N1A C1A C12A 109.1(15) . . ? N1A C1A C22A 110.2(9) . 3 ? C12A C1A C22A 109.9(9) . 3 ? N1A C1A C22A 110.2(9) . . ? C12A C1A C22A 109.9(9) . . ? C22A C1A C22A 107.6(13) 3 . ? N1A C1A C91 12.9(21) . . ? C12A C1A C91 122.0(22) . . ? C22A C1A C91 103.2(13) 3 . ? C22A C1A C91 103.2(13) . . ? C12B N11B C16B 117.3(14) . . ? C12B N11B C93 140.9(23) . . ? C16B N11B C93 101.8(22) . . ? C12B N11B Cu2 121.7(11) . . ? C16B N11B Cu2 121.1(11) . . ? C93 N11B Cu2 19.3(19) . . ? N11B C12B C13B 124.1(16) . . ? N11B C12B C1B 117.1(14) . . ? C13B C12B C1B 118.9(14) . . ? C12B C13B C14B 118.4(17) . . ? C12B C13B H13B 120.8(10) . . ? C14B C13B H13B 120.8(11) . . ? C15B C14B C13B 117.8(18) . . ? C15B C14B H14B 121.1(11) . . ? C13B C14B H14B 121.1(11) . . ? C14B C15B C16B 119.5(17) . . ? C14B C15B H15B 120.3(11) . . ? C16B C15B H15B 120.3(10) . . ? N11B C16B C15B 123.0(16) . . ? N11B C16B H16B 118.5(9) . . ? C15B C16B H16B 118.5(10) . . ? C22B N21B C26B 119.7(11) . . ? C22B N21B Cu2 120.0(8) . . ? C26B N21B Cu2 120.2(8) . . ? N21B C22B C23B 122.7(11) . . ? N21B C22B C1B 117.7(11) . . ? C23B C22B C1B 119.6(11) . . ? C22B C23B C24B 117.7(12) . . ? C22B C23B H23B 121.1(7) . . ? C24B C23B H23B 121.1(8) . . ? C25B C24B C23B 117.5(13) . . ? C25B C24B H24B 121.2(9) . . ? C23B C24B H24B 121.2(8) . . ? C26B C25B C24B 119.2(14) . . ? C26B C25B H25B 120.4(9) . . ? C24B C25B H25B 120.4(9) . . ? N21B C26B C25B 122.9(13) . . ? N21B C26B H26B 118.5(7) . . ? C25B C26B H26B 118.5(9) . . ? N1B C1B C94 13.4(24) . . ? N1B C1B C22B 108.6(10) . 3 ? C94 C1B C22B 115.1(13) . 3 ? N1B C1B C22B 108.6(10) . . ? C94 C1B C22B 115.1(13) . . ? C22B C1B C22B 108.8(14) 3 . ? N1B C1B C12B 113.0(15) . . ? C94 C1B C12B 99.6(25) . . ? C22B C1B C12B 108.8(9) 3 . ? C22B C1B C12B 108.8(9) . . ? Br1 O1X C1X 30.3(13) . . ? Br1 O1X C1X 30.3(13) . 3 ? C1X O1X C1X 28.6(27) . 3 ? Br1 O1X C92 142.4(19) . . ? C1X O1X C92 114.5(22) . . ? C1X O1X C92 114.5(22) 3 . ? Br1 O1X Cu1 161.1(2) . . ? C1X O1X Cu1 132.3(13) . . ? C1X O1X Cu1 132.3(13) 3 . ? C92 O1X Cu1 18.7(19) . . ? Br1 O1X Cu2 98.9(2) . . ? C1X O1X Cu2 124.7(12) . . ? C1X O1X Cu2 124.7(12) 3 . ? C92 O1X Cu2 118.7(19) . . ? Cu1 O1X Cu2 100.00(9) . . ? C1X C1X Br1 65.1(22) 3 . ? C1X C1X O1X 75.7(13) 3 . ? Br1 C1X O1X 28.8(14) . . ? C83 C82 C81 180.0(25) . . ? Cu1 C92 O1X 110.3(56) . . ? Cu1 C92 N21A 99.6(35) . . ? O1X C92 N21A 121.2(20) . . ? Cu1 C92 N21A 99.6(35) . 3 ? O1X C92 N21A 121.2(20) . 3 ? N21A C92 N21A 101.0(29) . 3 ? Cu2 C93 N11B 120.2(51) . . ? _refine_diff_density_max 1.212 _refine_diff_density_min -0.905 _refine_diff_density_rms 0.231 #===END data_marcus15 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common 'Complex 6' _chemical_formula_moiety 'C32 H28 Cu N8, 2(B F4), C3 H6 O' _chemical_formula_structural '[Cu(tpm)2](BF4)2.Me2CO' _chemical_formula_analytical ? _chemical_formula_sum 'C35 H34 B2 Cu F8 N8 O' _chemical_formula_weight 819.9 _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' 0.0033 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' 'B' 'B' 0.0013 0.0007 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Cu' 'Cu' 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'F' 'F' 0.0171 0.0103 '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 'A 2/a (equiv. to no. 15)' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x+1/2, -y, z' 'x, y+1/2, z+1/2' 'x+1/2, -y+1/2, z+1/2' '-x, -y, -z' '-x-1/2, y, -z' '-x, -y+1/2, -z+1/2' '-x-1/2, y+1/2, -z+1/2' _cell_length_a 15.8308(14) _cell_length_b 10.8103(12) _cell_length_c 22.990(2) _cell_angle_alpha 90.00 _cell_angle_beta 111.259(8) _cell_angle_gamma 90.00 _cell_volume 3666.6(6) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 24 _cell_measurement_theta_min 10 _cell_measurement_theta_max 11 _exptl_crystal_description plates _exptl_crystal_colour 'pale blue' _exptl_crystal_size_max 0.60 _exptl_crystal_size_mid 0.21 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.485 _exptl_crystal_density_method ? _exptl_crystal_F_000 1676 _exptl_absorpt_coefficient_mu 0.678 _exptl_absorpt_correction_type 'semi-empirical psi-scans' _exptl_absorpt_correction_T_min 0.917 _exptl_absorpt_correction_T_max 0.995 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type Mo-K\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Enraf-Nonius CAD4 diffractometer' _diffrn_measurement_method 'scintillation counter; \w/\q scans' _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time '10000 s' _diffrn_standards_decay_% 2.7 _diffrn_reflns_number 3588 _diffrn_reflns_av_R_equivalents 0.016 _diffrn_reflns_av_sigmaI/netI 0.0507 _diffrn_reflns_limit_h_min -1 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -1 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -27 _diffrn_reflns_limit_l_max 27 _diffrn_reflns_theta_min 1.90 _diffrn_reflns_theta_max 24.98 _reflns_number_total 3211 _reflns_number_observed 2284 _reflns_observed_criterion I>2sigma(I) _computing_data_collection 'CAD4/EXPRESS (Enraf-Nonius, 1992)' _computing_cell_refinement 'CAD4/EXPRESS (Enraf-Nonius, 1992)' _computing_data_reduction 'CAD4 (Hursthouse, 1976)' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'ORTEP (Johnson, 1971)' _computing_publication_material 'SHELXL-93 (Sheldrick, 1993)' _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^)+(0.0163P)^2^+3.9788P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary 'automated Patterson' _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment ; The cation hydrogen atoms were included in idealised positions and then allowed to refine freely. The solvent H atoms were input in idealised positions and set to ride on the parent carbon atoms. Isotropic thermal parameters of all H atoms were refined freely. ; _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3211 _refine_ls_number_parameters 347 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0579 _refine_ls_R_factor_obs 0.0357 _refine_ls_wR_factor_all 0.0857 _refine_ls_wR_factor_obs 0.0745 _refine_ls_goodness_of_fit_all 1.033 _refine_ls_goodness_of_fit_obs 1.089 _refine_ls_restrained_S_all 1.033 _refine_ls_restrained_S_obs 1.089 _refine_ls_shift/esd_max 0.046 _refine_ls_shift/esd_mean 0.005 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 Cu Cu 0.0000 0.2500 0.2500 0.03295(14) Uani 1 d S . N11 N -0.0210(2) 0.0376(3) 0.26437(11) 0.0520(7) Uani 1 d . . C12 C 0.0511(2) 0.0006(3) 0.31213(12) 0.0367(6) Uani 1 d . . C13 C 0.0507(2) -0.1054(3) 0.3449(2) 0.0610(9) Uani 1 d . . H13 H 0.1019(22) -0.1201(29) 0.3809(14) 0.066(10) Uiso 1 d . . C14 C -0.0266(3) -0.1770(4) 0.3269(2) 0.0808(12) Uani 1 d . . H14 H -0.0272(30) -0.2507(43) 0.3481(21) 0.124(17) Uiso 1 d . . C15 C -0.0988(3) -0.1427(4) 0.2762(2) 0.0776(12) Uani 1 d . . H15 H -0.1524(27) -0.1851(38) 0.2616(18) 0.098(13) Uiso 1 d . . C16 C -0.0949(2) -0.0357(5) 0.2468(2) 0.0743(12) Uani 1 d . . H16 H -0.1437(25) -0.0019(35) 0.2153(17) 0.089(13) Uiso 1 d . . N21 N 0.05215(13) 0.2709(2) 0.34465(9) 0.0354(5) Uani 1 d . . C22 C 0.1116(2) 0.1825(2) 0.37512(11) 0.0318(6) Uani 1 d . . C23 C 0.1447(2) 0.1757(3) 0.43916(12) 0.0386(7) Uani 1 d . . H23 H 0.1840(18) 0.1121(26) 0.4565(12) 0.044(8) Uiso 1 d . . C24 C 0.1218(2) 0.2651(3) 0.47293(13) 0.0455(7) Uani 1 d . . H24 H 0.1421(19) 0.2612(28) 0.5143(14) 0.054(8) Uiso 1 d . . C25 C 0.0637(2) 0.3584(3) 0.44197(14) 0.0482(8) Uani 1 d . . H25 H 0.0457(17) 0.4221(25) 0.4613(12) 0.038(7) Uiso 1 d . . C26 C 0.0295(2) 0.3579(3) 0.37790(13) 0.0438(7) Uani 1 d . . H26 H -0.0078(18) 0.4181(26) 0.3531(12) 0.045(8) Uiso 1 d . . C1 C 0.1309(2) 0.0905(2) 0.33113(11) 0.0322(6) Uani 1 d . . N1 N 0.1245(2) 0.1641(2) 0.27472(11) 0.0367(5) Uani 1 d . . H1A H 0.1329(18) 0.1189(26) 0.2447(13) 0.047(9) Uiso 1 d . . H1B H 0.1672(17) 0.2125(24) 0.2847(11) 0.028(8) Uiso 1 d . . N31 N 0.2903(2) 0.0835(2) 0.40035(12) 0.0537(7) Uani 1 d . . C32 C 0.2232(2) 0.0255(2) 0.35685(11) 0.0354(6) Uani 1 d . . C33 C 0.2359(2) -0.0848(3) 0.3318(2) 0.0582(9) Uani 1 d . . H33 H 0.1885(23) -0.1196(31) 0.3031(15) 0.074(11) Uiso 1 d . . C34 C 0.3196(3) -0.1394(4) 0.3533(2) 0.0702(11) Uani 1 d . . H34 H 0.3289(27) -0.2114(39) 0.3359(19) 0.105(15) Uiso 1 d . . C35 C 0.3888(2) -0.0820(4) 0.3987(2) 0.0676(10) Uani 1 d . . H35 H 0.4470(23) -0.1163(30) 0.4148(14) 0.069(10) Uiso 1 d . . C36 C 0.3721(2) 0.0287(4) 0.4203(2) 0.0695(11) Uani 1 d . . H36 H 0.4197(26) 0.0767(37) 0.4569(17) 0.099(13) Uiso 1 d . . B B 0.1759(3) -0.0601(4) 0.1416(2) 0.0572(10) Uani 1 d . . F1A F 0.0904(8) -0.0935(8) 0.1016(5) 0.079(3) Uani 0.610(9) d P 1 F2A F 0.2221(6) -0.1535(8) 0.1847(3) 0.082(2) Uani 0.610(9) d P 1 F3A F 0.2324(3) -0.0379(7) 0.1076(2) 0.106(2) Uani 0.610(9) d P 1 F4A F 0.1782(3) 0.0397(5) 0.1766(2) 0.071(2) Uani 0.610(9) d P 1 F1B F 0.1069(12) -0.0847(17) 0.0926(7) 0.104(6) Uani 0.390(9) d P 2 F2B F 0.2298(8) -0.1476(12) 0.1556(5) 0.098(5) Uani 0.390(9) d P 2 F3B F 0.2001(7) 0.0560(8) 0.1388(6) 0.156(8) Uani 0.390(9) d P 2 F4B F 0.1330(6) -0.0504(9) 0.1901(3) 0.106(4) Uani 0.390(9) d P 2 O41 O 0.2500 0.3609(5) 0.0000 0.117(2) Uani 1 d S . C42 C 0.2500 0.2510(8) 0.0000 0.111(2) Uani 1 d S . C43 C 0.3331(6) 0.1784(8) 0.0162(4) 0.210(4) Uani 1 d . . H43A H 0.3842(6) 0.2331(8) 0.0261(4) 0.136(23) Uiso 1 calc R . H43B H 0.3303(6) 0.1272(8) -0.0186(4) 0.342(61) Uiso 1 calc R . H43C H 0.3394(6) 0.1272(8) 0.0516(4) 0.177(29) 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 Cu 0.0319(2) 0.0360(3) 0.0252(2) 0.0019(2) 0.0035(2) 0.0056(2) N11 0.0358(14) 0.065(2) 0.0467(14) 0.0058(12) 0.0043(11) -0.0037(12) C12 0.0341(14) 0.036(2) 0.0364(14) -0.0023(12) 0.0088(12) 0.0018(12) C13 0.056(2) 0.044(2) 0.076(2) 0.012(2) 0.016(2) -0.003(2) C14 0.071(3) 0.051(2) 0.120(4) 0.003(2) 0.035(3) -0.014(2) C15 0.058(2) 0.072(3) 0.104(3) -0.032(3) 0.029(2) -0.029(2) C16 0.041(2) 0.100(3) 0.067(2) -0.012(2) 0.002(2) -0.009(2) N21 0.0344(11) 0.0368(14) 0.0322(11) 0.0012(10) 0.0085(9) 0.0052(10) C22 0.0264(13) 0.0337(14) 0.0304(13) 0.0032(11) 0.0045(11) 0.0023(11) C23 0.0322(14) 0.045(2) 0.0333(14) 0.0012(13) 0.0052(12) 0.0066(13) C24 0.041(2) 0.062(2) 0.0290(13) -0.004(2) 0.0076(12) 0.002(2) C25 0.049(2) 0.049(2) 0.047(2) -0.012(2) 0.0165(14) 0.004(2) C26 0.041(2) 0.044(2) 0.042(2) 0.0036(14) 0.0109(13) 0.0083(14) C1 0.0311(13) 0.0318(14) 0.0294(13) 0.0047(11) 0.0058(11) 0.0022(11) N1 0.0405(14) 0.0385(14) 0.0297(12) 0.0005(11) 0.0109(11) 0.0007(12) N31 0.0353(13) 0.054(2) 0.061(2) -0.0130(13) 0.0056(12) 0.0070(12) C32 0.0338(14) 0.039(2) 0.0317(13) 0.0014(12) 0.0097(11) 0.0035(12) C33 0.045(2) 0.059(2) 0.059(2) -0.019(2) 0.005(2) 0.011(2) C34 0.066(2) 0.060(2) 0.080(3) -0.014(2) 0.021(2) 0.022(2) C35 0.047(2) 0.083(3) 0.067(2) 0.003(2) 0.013(2) 0.030(2) C36 0.041(2) 0.086(3) 0.066(2) -0.018(2) 0.002(2) 0.013(2) B 0.055(2) 0.049(2) 0.057(2) -0.006(2) 0.008(2) 0.006(2) F1A 0.049(3) 0.070(4) 0.106(7) -0.011(3) 0.015(3) -0.008(2) F2A 0.096(3) 0.058(3) 0.076(4) 0.002(3) 0.011(3) 0.019(2) F3A 0.103(3) 0.154(6) 0.081(3) -0.008(3) 0.059(3) -0.017(3) F4A 0.074(3) 0.059(4) 0.066(3) -0.017(2) 0.008(2) 0.023(3) F1B 0.071(9) 0.179(13) 0.045(4) -0.045(6) 0.002(5) 0.009(7) F2B 0.079(5) 0.081(6) 0.102(9) -0.023(7) -0.006(6) 0.050(5) F3B 0.123(8) 0.057(6) 0.215(16) 0.044(9) -0.026(9) -0.021(5) F4B 0.138(7) 0.112(7) 0.062(4) -0.006(4) 0.030(4) 0.050(6) O41 0.158(5) 0.074(3) 0.128(4) 0.000 0.062(3) 0.000 C42 0.179(8) 0.073(4) 0.060(3) 0.000 0.020(4) 0.000 C43 0.268(11) 0.146(7) 0.141(7) -0.032(6) -0.017(6) 0.085(8) _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 N21 2.041(2) . ? Cu N21 2.041(2) 7 ? Cu N1 2.063(2) . ? Cu N1 2.063(2) 7 ? Cu N11 2.360(3) 7 ? Cu N11 2.360(3) . ? N11 C12 1.326(3) . ? N11 C16 1.349(4) . ? C12 C13 1.372(4) . ? C12 C1 1.527(3) . ? C13 C14 1.378(5) . ? C13 H13 0.94(3) . ? C14 C15 1.355(6) . ? C14 H14 0.94(5) . ? C15 C16 1.352(6) . ? C15 H15 0.91(4) . ? C16 H16 0.92(4) . ? N21 C26 1.341(3) . ? N21 C22 1.346(3) . ? C22 C23 1.374(3) . ? C22 C1 1.527(3) . ? C23 C24 1.368(4) . ? C23 H23 0.92(3) . ? C24 C25 1.376(4) . ? C24 H24 0.89(3) . ? C25 C26 1.373(4) . ? C25 H25 0.92(3) . ? C26 H26 0.92(3) . ? C1 N1 1.493(3) . ? C1 C32 1.533(3) . ? N1 H1A 0.89(3) . ? N1 H1B 0.82(3) . ? N31 C32 1.323(3) . ? N31 C36 1.345(4) . ? C32 C33 1.370(4) . ? C33 C34 1.369(5) . ? C33 H33 0.88(3) . ? C34 C35 1.359(5) . ? C34 H34 0.91(4) . ? C35 C36 1.358(5) . ? C35 H35 0.94(3) . ? C36 H36 1.04(4) . ? B F2B 1.236(11) . ? B F1B 1.28(2) . ? B F3B 1.321(9) . ? B F4A 1.339(6) . ? B F1A 1.380(11) . ? B F3A 1.404(6) . ? B F2A 1.418(8) . ? B F4B 1.506(9) . ? O41 C42 1.188(8) . ? C42 C43 1.459(7) . ? C42 C43 1.460(7) 6_655 ? C43 H43A 0.96 . ? C43 H43B 0.96 . ? C43 H43C 0.96 . ? 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 N21 Cu N21 180.0 . 7 ? N21 Cu N1 77.26(9) . . ? N21 Cu N1 102.74(9) 7 . ? N21 Cu N1 102.74(9) . 7 ? N21 Cu N1 77.26(9) 7 7 ? N1 Cu N1 180.0 . 7 ? N21 Cu N11 91.05(8) . 7 ? N21 Cu N11 88.95(8) 7 7 ? N1 Cu N11 107.90(9) . 7 ? N1 Cu N11 72.10(9) 7 7 ? N21 Cu N11 88.95(8) . . ? N21 Cu N11 91.05(8) 7 . ? N1 Cu N11 72.10(9) . . ? N1 Cu N11 107.90(9) 7 . ? N11 Cu N11 180.0 7 . ? C12 N11 C16 117.6(3) . . ? C12 N11 Cu 106.7(2) . . ? C16 N11 Cu 132.9(3) . . ? N11 C12 C13 122.2(3) . . ? N11 C12 C1 114.8(2) . . ? C13 C12 C1 122.8(2) . . ? C12 C13 C14 119.0(4) . . ? C12 C13 H13 116.8(20) . . ? C14 C13 H13 123.9(20) . . ? C15 C14 C13 118.9(4) . . ? C15 C14 H14 121.1(29) . . ? C13 C14 H14 119.9(29) . . ? C16 C15 C14 119.2(4) . . ? C16 C15 H15 116.7(26) . . ? C14 C15 H15 124.0(26) . . ? N11 C16 C15 123.0(4) . . ? N11 C16 H16 113.0(25) . . ? C15 C16 H16 123.8(25) . . ? C26 N21 C22 118.9(2) . . ? C26 N21 Cu 126.7(2) . . ? C22 N21 Cu 114.4(2) . . ? N21 C22 C23 121.3(2) . . ? N21 C22 C1 112.9(2) . . ? C23 C22 C1 125.8(2) . . ? C24 C23 C22 119.6(3) . . ? C24 C23 H23 124.1(17) . . ? C22 C23 H23 116.3(17) . . ? C23 C24 C25 119.3(3) . . ? C23 C24 H24 120.4(20) . . ? C25 C24 H24 120.2(20) . . ? C26 C25 C24 118.8(3) . . ? C26 C25 H25 116.8(16) . . ? C24 C25 H25 124.4(16) . . ? N21 C26 C25 122.1(3) . . ? N21 C26 H26 112.7(17) . . ? C25 C26 H26 125.1(17) . . ? N1 C1 C22 105.1(2) . . ? N1 C1 C12 107.6(2) . . ? C22 C1 C12 105.1(2) . . ? N1 C1 C32 109.6(2) . . ? C22 C1 C32 115.8(2) . . ? C12 C1 C32 113.2(2) . . ? C1 N1 Cu 103.7(2) . . ? C1 N1 H1A 113.4(18) . . ? Cu N1 H1A 115.4(17) . . ? C1 N1 H1B 108.0(17) . . ? Cu N1 H1B 113.5(17) . . ? H1A N1 H1B 103.0(25) . . ? C32 N31 C36 117.3(3) . . ? N31 C32 C33 122.1(3) . . ? N31 C32 C1 117.7(2) . . ? C33 C32 C1 120.0(2) . . ? C34 C33 C32 119.6(3) . . ? C34 C33 H33 122.3(22) . . ? C32 C33 H33 118.1(22) . . ? C35 C34 C33 119.1(3) . . ? C35 C34 H34 120.9(26) . . ? C33 C34 H34 120.0(26) . . ? C36 C35 C34 118.3(3) . . ? C36 C35 H35 119.9(20) . . ? C34 C35 H35 121.8(20) . . ? N31 C36 C35 123.6(3) . . ? N31 C36 H36 112.4(22) . . ? C35 C36 H36 123.7(22) . . ? F2B B F1B 111.0(11) . . ? F2B B F3B 123.7(9) . . ? F1B B F3B 108.9(10) . . ? F4A B F1A 114.7(6) . . ? F4A B F3A 108.2(4) . . ? F1A B F3A 110.0(6) . . ? F4A B F2A 105.0(4) . . ? F1A B F2A 114.4(6) . . ? F3A B F2A 103.8(5) . . ? F2B B F4B 108.3(7) . . ? F1B B F4B 101.4(9) . . ? F3B B F4B 100.8(8) . . ? O41 C42 C43 122.5(5) . . ? O41 C42 C43 122.5(5) . 6_655 ? C43 C42 C43 114.9(10) . 6_655 ? C42 C43 H43A 109.5(5) . . ? C42 C43 H43B 109.5(4) . . ? H43A C43 H43B 109.5 . . ? C42 C43 H43C 109.5(4) . . ? H43A C43 H43C 109.5 . . ? H43B C43 H43C 109.5 . . ? _refine_diff_density_max 0.216 _refine_diff_density_min -0.198 _refine_diff_density_rms 0.045 #===END data_marcus19 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common 'Complex 9' _chemical_formula_moiety 'C36 H32 Cu N8 O2, 2(B F4)' _chemical_formula_structural '[Cu(tpma)2](BF4)2' _chemical_formula_analytical ? _chemical_formula_sum 'C36 H32 B2 Cu F8 N8 O2' _chemical_formula_weight 845.9 _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' 0.0033 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' 'B' 'B' 0.0013 0.0007 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Cu' 'Cu' 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'F' 'F' 0.0171 0.0103 '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 Orthorhombic _symmetry_space_group_name_H-M 'P b c a (no. 61)' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' '-x+1/2, -y, z+1/2' '-x, -y, -z' '-x-1/2, y-1/2, z' 'x, -y-1/2, z-1/2' 'x-1/2, y, -z-1/2' _cell_length_a 11.714(2) _cell_length_b 13.828(2) _cell_length_c 23.072(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3737.0(9) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 24 _cell_measurement_theta_min 10 _cell_measurement_theta_max 11 _exptl_crystal_description 'square blocks' _exptl_crystal_colour 'transparent lilac' _exptl_crystal_size_max 0.26 _exptl_crystal_size_mid 0.19 _exptl_crystal_size_min 0.14 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.503 _exptl_crystal_density_method ? _exptl_crystal_F_000 1724 _exptl_absorpt_coefficient_mu 0.670 _exptl_absorpt_correction_type 'semi-empirical psi-scans' _exptl_absorpt_correction_T_min 0.16 _exptl_absorpt_correction_T_max 0.21 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type Mo-K\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Enraf-Nonius CAD4 diffractometer' _diffrn_measurement_method 'scintillation counter; \w/\q scans' _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time '10000 s' _diffrn_standards_decay_% 0 _diffrn_reflns_number 3657 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.1026 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 28 _diffrn_reflns_theta_min 1.77 _diffrn_reflns_theta_max 25.96 _reflns_number_total 3657 _reflns_number_observed 1450 _reflns_observed_criterion I>2sigma(I) _computing_data_collection 'CAD4/EXPRESS (Enraf-Nonius, 1992)' _computing_cell_refinement 'CAD4/EXPRESS (Enraf-Nonius, 1992)' _computing_data_reduction 'CAD4 (Hursthouse, 1976)' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'ORTEP (Johnson, 1971)' _computing_publication_material 'SHELXL-93 (Sheldrick, 1993)' _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^)+(0.0573P)^2^+] 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 ; Hydrogen atoms were included in idealised positions and all parameters were refined freely. ; _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3657 _refine_ls_number_parameters 347 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1437 _refine_ls_R_factor_obs 0.0536 _refine_ls_wR_factor_all 0.1592 _refine_ls_wR_factor_obs 0.1104 _refine_ls_goodness_of_fit_all 0.962 _refine_ls_goodness_of_fit_obs 1.143 _refine_ls_restrained_S_all 0.962 _refine_ls_restrained_S_obs 1.143 _refine_ls_shift/esd_max -0.001 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Cu Cu 0.0000 0.0000 0.5000 0.0355(2) Uani 1 d S . N11 N 0.0172(3) -0.1382(3) 0.4721(2) 0.0383(10) Uani 1 d . . C12 C -0.0175(4) -0.1620(4) 0.4183(2) 0.0348(12) Uani 1 d . . C13 C 0.0248(4) -0.2435(4) 0.3912(2) 0.0425(14) Uani 1 d . . H13 H 0.0091(41) -0.2530(34) 0.3533(21) 0.042(14) Uiso 1 d . . C14 C 0.0988(5) -0.3030(4) 0.4204(3) 0.056(2) Uani 1 d . . H14 H 0.1187(37) -0.3586(34) 0.4012(19) 0.031(13) Uiso 1 d . . C15 C 0.1276(5) -0.2817(4) 0.4766(3) 0.051(2) Uani 1 d . . H15 H 0.1718(53) -0.3195(45) 0.4958(25) 0.078(22) Uiso 1 d . . C16 C 0.0862(4) -0.2000(4) 0.5006(3) 0.0447(13) Uani 1 d . . H16 H 0.1123(41) -0.1780(35) 0.5346(21) 0.038(15) Uiso 1 d . . N21 N 0.0240(4) 0.0465(3) 0.4025(2) 0.0448(12) Uani 1 d . . C22 C -0.0196(4) -0.0104(4) 0.3620(2) 0.0412(13) Uani 1 d . . C23 C 0.0068(7) 0.0026(6) 0.3040(2) 0.071(2) Uani 1 d . . H23 H -0.0259(47) -0.0469(41) 0.2793(22) 0.060(18) Uiso 1 d . . C24 C 0.0765(7) 0.0770(6) 0.2884(3) 0.096(3) Uani 1 d . . H24 H 0.0933(54) 0.0843(46) 0.2441(29) 0.098(23) Uiso 1 d . . C25 C 0.1190(6) 0.1357(6) 0.3293(3) 0.066(2) Uani 1 d . . H25 H 0.1605(50) 0.1900(44) 0.3246(25) 0.070(21) Uiso 1 d . . C26 C 0.0915(5) 0.1181(5) 0.3856(3) 0.055(2) Uani 1 d . . H26 H 0.1283(37) 0.1537(32) 0.4183(18) 0.030(13) Uiso 1 d . . N31 N -0.1643(3) -0.0121(3) 0.4770(2) 0.0367(10) Uani 1 d . . C32 C -0.1907(4) -0.0428(4) 0.4237(2) 0.0360(12) Uani 1 d . . C33 C -0.2981(5) -0.0250(4) 0.4017(3) 0.049(2) Uani 1 d . . H33 H -0.3120(39) -0.0461(32) 0.3678(20) 0.028(14) Uiso 1 d . . C34 C -0.3809(5) 0.0210(4) 0.4348(3) 0.052(2) Uani 1 d . . H34 H -0.4577(56) 0.0302(43) 0.4205(26) 0.080(21) Uiso 1 d . . C35 C -0.3536(5) 0.0475(4) 0.4906(3) 0.0505(15) Uani 1 d . . H35 H -0.4130(46) 0.0795(38) 0.5201(22) 0.064(18) Uiso 1 d . . C36 C -0.2450(5) 0.0295(4) 0.5103(2) 0.0438(14) Uani 1 d . . H36 H -0.2296(48) 0.0516(40) 0.5483(23) 0.066(19) Uiso 1 d . . C1 C -0.0970(4) -0.0913(4) 0.3865(2) 0.0348(12) Uani 1 d . . N1 N -0.1540(4) -0.1446(3) 0.3394(2) 0.0394(11) Uani 1 d . . H1 H -0.1519(41) -0.1177(34) 0.3049(20) 0.036(15) Uiso 1 d . . C41 C -0.2270(4) -0.2190(4) 0.3523(2) 0.0452(14) Uani 1 d . . O41 O -0.2389(3) -0.2481(3) 0.4014(2) 0.0554(10) Uani 1 d . . C42 C -0.2900(8) -0.2610(8) 0.3016(4) 0.074(2) Uani 1 d . . H42A H -0.2729(59) -0.2242(47) 0.2660(29) 0.093(27) Uiso 1 d . . H42B H -0.3614(77) -0.2406(63) 0.3079(37) 0.136(40) Uiso 1 d . . H42C H -0.3015(60) -0.3174(49) 0.3042(28) 0.074(28) Uiso 1 d . . B5 B 0.1288(12) 0.4151(11) 0.3342(6) 0.110(4) Uani 1 d . . F51 F 0.1249(10) 0.5020(7) 0.3465(5) 0.125(4) Uani 0.63 d P . F52 F 0.1768(10) 0.3893(10) 0.2837(3) 0.123(4) Uani 0.63 d P . F53 F 0.0191(9) 0.3875(10) 0.3241(5) 0.156(4) Uani 0.63 d P . F54 F 0.1763(14) 0.3628(8) 0.3770(4) 0.168(5) Uani 0.63 d P . F61 F 0.0850(18) 0.3570(11) 0.2929(7) 0.094(5) Uiso 0.35 d P . F62 F 0.1948(23) 0.4633(20) 0.2714(11) 0.128(10) Uiso 0.25 d P . F63 F 0.0525(17) 0.3571(13) 0.3765(9) 0.089(5) Uiso 0.25 d P . F64 F 0.0629(20) 0.5054(22) 0.3316(10) 0.094(8) Uiso 0.25 d P . F65 F 0.2069(34) 0.4680(31) 0.3562(16) 0.103(12) Uiso 0.15 d P . F66 F 0.2363(24) 0.3833(22) 0.3496(11) 0.113(9) Uiso 0.25 d P . 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 0.0324(4) 0.0366(4) 0.0376(4) -0.0032(4) -0.0024(4) 0.0001(4) N11 0.039(3) 0.039(2) 0.037(2) -0.002(2) -0.003(2) 0.003(2) C12 0.032(3) 0.040(3) 0.032(3) -0.003(2) 0.003(2) -0.008(2) C13 0.040(3) 0.047(3) 0.041(3) -0.011(3) 0.002(3) -0.001(3) C14 0.057(4) 0.033(3) 0.079(5) -0.020(3) 0.001(3) 0.008(3) C15 0.047(4) 0.034(3) 0.073(4) 0.000(3) -0.003(3) 0.008(3) C16 0.042(3) 0.040(3) 0.052(3) -0.003(3) -0.006(3) 0.004(3) N21 0.050(3) 0.047(3) 0.037(2) 0.000(2) 0.004(2) -0.015(2) C22 0.037(3) 0.047(3) 0.039(3) 0.004(3) 0.006(2) 0.000(3) C23 0.090(5) 0.087(5) 0.036(3) -0.010(4) 0.014(4) -0.042(5) C24 0.124(7) 0.116(7) 0.048(4) 0.012(4) 0.021(4) -0.071(6) C25 0.067(5) 0.068(5) 0.064(5) 0.007(4) 0.013(4) -0.024(4) C26 0.049(4) 0.059(4) 0.056(4) -0.003(3) 0.002(3) -0.021(3) N31 0.032(2) 0.042(3) 0.037(2) -0.004(2) 0.003(2) -0.001(2) C32 0.033(3) 0.036(3) 0.039(3) 0.000(2) 0.001(2) -0.006(2) C33 0.040(3) 0.058(4) 0.049(4) -0.006(3) -0.007(3) -0.003(3) C34 0.032(3) 0.059(4) 0.064(4) 0.002(3) 0.000(3) 0.007(3) C35 0.037(3) 0.049(3) 0.066(4) -0.011(3) 0.008(3) -0.004(3) C36 0.037(3) 0.055(4) 0.039(3) -0.007(3) 0.005(3) -0.003(3) C1 0.035(3) 0.043(3) 0.027(3) -0.006(2) 0.004(2) -0.006(3) N1 0.036(3) 0.050(3) 0.032(2) -0.002(2) 0.004(2) -0.003(2) C41 0.033(3) 0.051(4) 0.051(3) -0.009(3) 0.003(3) -0.005(3) O41 0.054(3) 0.065(3) 0.047(2) 0.001(2) 0.007(2) -0.014(2) C42 0.062(6) 0.085(7) 0.073(6) -0.024(5) 0.001(4) -0.027(5) B5 0.103(11) 0.122(11) 0.104(10) -0.034(9) -0.020(8) -0.006(9) F51 0.112(9) 0.089(7) 0.174(10) -0.084(6) 0.032(7) -0.007(7) F52 0.151(9) 0.167(10) 0.053(5) -0.034(5) -0.005(5) 0.082(8) F53 0.103(8) 0.235(13) 0.131(8) 0.010(8) -0.007(7) -0.013(9) F54 0.250(16) 0.176(11) 0.079(6) 0.007(7) -0.084(9) 0.017(11) _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 N31 2.003(4) . ? Cu N31 2.003(4) 5_556 ? Cu N11 2.027(4) 5_556 ? Cu N11 2.027(4) . ? Cu N21 2.357(4) . ? Cu N21 2.357(4) 5_556 ? N11 C12 1.347(6) . ? N11 C16 1.348(6) . ? C12 C13 1.380(7) . ? C12 C1 1.536(7) . ? C13 C14 1.371(8) . ? C13 H13 0.90(5) . ? C14 C15 1.373(8) . ? C14 H14 0.92(5) . ? C15 C16 1.348(8) . ? C15 H15 0.86(6) . ? C16 H16 0.90(5) . ? N21 C22 1.323(6) . ? N21 C26 1.325(7) . ? C22 C23 1.386(7) . ? C22 C1 1.546(6) . ? C23 C24 1.361(9) . ? C23 H23 0.97(5) . ? C24 C25 1.341(9) . ? C24 H24 1.05(6) . ? C25 C26 1.360(8) . ? C25 H25 0.90(6) . ? C26 H26 1.00(4) . ? N31 C32 1.337(6) . ? N31 C36 1.348(6) . ? C32 C33 1.379(7) . ? C32 C1 1.546(7) . ? C33 C34 1.388(8) . ? C33 H33 0.85(4) . ? C34 C35 1.377(8) . ? C34 H34 0.97(6) . ? C35 C36 1.373(8) . ? C35 H35 1.07(5) . ? C36 H36 0.95(5) . ? C1 N1 1.473(6) . ? N1 C41 1.371(6) . ? N1 H1 0.88(5) . ? C41 O41 1.210(6) . ? C41 C42 1.501(9) . ? C42 H42A 0.99(7) . ? C42 H42B 0.89(9) . ? C42 H42C 0.79(6) . ? B5 F51 1.235(15) . ? B5 F65 1.28(4) . ? B5 F52 1.343(14) . ? B5 F54 1.344(15) . ? B5 F61 1.35(2) . ? B5 F53 1.360(15) . ? B5 F66 1.38(3) . ? B5 F64 1.47(3) . ? B5 F63 1.55(2) . ? B5 F62 1.77(3) . ? F51 F64 0.80(2) . ? F51 F65 1.09(4) . ? F52 F62 1.08(2) . ? F52 F61 1.18(2) . ? F52 F66 1.68(3) . ? F53 F61 1.14(2) . ? F53 F63 1.34(2) . ? F53 F64 1.72(3) . ? F54 F66 0.99(2) . ? F54 F63 1.45(2) . ? F54 F65 1.57(4) . ? F65 F66 1.23(4) . ? 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 N31 Cu N31 180.0 . 5_556 ? N31 Cu N11 93.9(2) . 5_556 ? N31 Cu N11 86.1(2) 5_556 5_556 ? N31 Cu N11 86.1(2) . . ? N31 Cu N11 93.9(2) 5_556 . ? N11 Cu N11 180.0 5_556 . ? N31 Cu N21 83.3(2) . . ? N31 Cu N21 96.7(2) 5_556 . ? N11 Cu N21 93.3(2) 5_556 . ? N11 Cu N21 86.7(2) . . ? N31 Cu N21 96.7(2) . 5_556 ? N31 Cu N21 83.3(2) 5_556 5_556 ? N11 Cu N21 86.7(2) 5_556 5_556 ? N11 Cu N21 93.3(2) . 5_556 ? N21 Cu N21 180.0 . 5_556 ? C12 N11 C16 118.4(5) . . ? C12 N11 Cu 119.6(3) . . ? C16 N11 Cu 120.1(4) . . ? N11 C12 C13 120.5(5) . . ? N11 C12 C1 117.9(4) . . ? C13 C12 C1 121.4(4) . . ? C14 C13 C12 119.7(5) . . ? C14 C13 H13 121.1(31) . . ? C12 C13 H13 118.9(31) . . ? C13 C14 C15 119.4(6) . . ? C13 C14 H14 115.3(29) . . ? C15 C14 H14 125.0(29) . . ? C16 C15 C14 118.6(6) . . ? C16 C15 H15 121.1(43) . . ? C14 C15 H15 120.3(42) . . ? C15 C16 N11 123.2(6) . . ? C15 C16 H16 121.4(32) . . ? N11 C16 H16 114.7(32) . . ? C22 N21 C26 117.8(5) . . ? C22 N21 Cu 117.7(3) . . ? C26 N21 Cu 123.8(4) . . ? N21 C22 C23 121.2(5) . . ? N21 C22 C1 113.6(4) . . ? C23 C22 C1 125.2(5) . . ? C24 C23 C22 119.2(6) . . ? C24 C23 H23 127.9(33) . . ? C22 C23 H23 112.8(33) . . ? C25 C24 C23 119.6(7) . . ? C25 C24 H24 124.0(37) . . ? C23 C24 H24 116.4(37) . . ? C24 C25 C26 118.4(7) . . ? C24 C25 H25 128.3(39) . . ? C26 C25 H25 113.1(39) . . ? N21 C26 C25 123.8(6) . . ? N21 C26 H26 113.7(25) . . ? C25 C26 H26 122.1(25) . . ? C32 N31 C36 119.9(4) . . ? C32 N31 Cu 119.5(3) . . ? C36 N31 Cu 119.2(3) . . ? N31 C32 C33 119.5(5) . . ? N31 C32 C1 118.9(4) . . ? C33 C32 C1 121.4(5) . . ? C32 C33 C34 121.2(6) . . ? C32 C33 H33 116.8(32) . . ? C34 C33 H33 122.0(32) . . ? C35 C34 C33 118.3(6) . . ? C35 C34 H34 120.0(37) . . ? C33 C34 H34 121.5(37) . . ? C36 C35 C34 118.4(5) . . ? C36 C35 H35 117.8(29) . . ? C34 C35 H35 123.7(29) . . ? N31 C36 C35 122.6(5) . . ? N31 C36 H36 122.2(36) . . ? C35 C36 H36 115.1(35) . . ? N1 C1 C12 108.0(4) . . ? N1 C1 C22 111.0(4) . . ? C12 C1 C22 106.2(4) . . ? N1 C1 C32 107.7(4) . . ? C12 C1 C32 116.2(4) . . ? C22 C1 C32 107.7(4) . . ? C41 N1 C1 119.8(4) . . ? C41 N1 H1 122.2(32) . . ? C1 N1 H1 116.3(32) . . ? O41 C41 N1 121.7(5) . . ? O41 C41 C42 123.0(6) . . ? N1 C41 C42 115.3(6) . . ? C41 C42 H42A 110.4(39) . . ? C41 C42 H42B 102.2(57) . . ? H42A C42 H42B 99.4(71) . . ? C41 C42 H42C 113.8(53) . . ? H42A C42 H42C 127.3(64) . . ? H42B C42 H42C 98.0(70) . . ? F51 B5 F65 51.5(20) . . ? F51 B5 F52 118.1(15) . . ? F65 B5 F52 101.4(22) . . ? F51 B5 F54 111.7(13) . . ? F65 B5 F54 73.7(20) . . ? F52 B5 F54 108.8(13) . . ? F51 B5 F61 136.6(16) . . ? F65 B5 F61 153.5(25) . . ? F52 B5 F61 52.2(9) . . ? F54 B5 F61 110.9(14) . . ? F51 B5 F53 106.1(14) . . ? F65 B5 F53 154.9(26) . . ? F52 B5 F53 99.9(10) . . ? F54 B5 F53 111.5(15) . . ? F61 B5 F53 49.6(9) . . ? F51 B5 F66 106.5(16) . . ? F65 B5 F66 55.0(21) . . ? F52 B5 F66 75.9(14) . . ? F54 B5 F66 42.5(11) . . ? F61 B5 F66 109.9(19) . . ? F53 B5 F66 144.8(19) . . ? F51 B5 F64 33.2(10) . . ? F65 B5 F64 84.6(24) . . ? F52 B5 F64 114.2(14) . . ? F54 B5 F64 134.8(15) . . ? F61 B5 F64 106.1(16) . . ? F53 B5 F64 74.6(13) . . ? F66 B5 F64 139.5(19) . . ? F51 B5 F63 109.9(13) . . ? F65 B5 F63 117.5(21) . . ? F52 B5 F63 130.7(14) . . ? F54 B5 F63 59.8(12) . . ? F61 B5 F63 85.3(14) . . ? F53 B5 F63 54.4(10) . . ? F66 B5 F63 101.6(17) . . ? F64 B5 F63 99.4(15) . . ? F51 B5 F62 80.6(13) . . ? F65 B5 F62 78.3(20) . . ? F52 B5 F62 37.5(9) . . ? F54 B5 F62 128.5(16) . . ? F61 B5 F62 79.1(13) . . ? F53 B5 F62 112.1(13) . . ? F66 B5 F62 86.1(16) . . ? F64 B5 F62 82.9(15) . . ? F63 B5 F62 164.2(15) . . ? F64 F51 F65 155.1(34) . . ? F64 F51 B5 89.6(25) . . ? F65 F51 B5 66.2(22) . . ? F62 F52 F61 125.5(21) . . ? F62 F52 B5 93.4(17) . . ? F61 F52 B5 64.1(10) . . ? F62 F52 F66 101.7(20) . . ? F61 F52 F66 101.3(13) . . ? B5 F52 F66 53.0(11) . . ? F61 F53 F63 104.8(15) . . ? F61 F53 B5 64.6(11) . . ? F63 F53 B5 69.9(11) . . ? F61 F53 F64 102.3(14) . . ? F63 F53 F64 96.9(13) . . ? B5 F53 F64 55.6(11) . . ? F66 F54 B5 70.7(20) . . ? F66 F54 F63 136.1(25) . . ? B5 F54 F63 67.0(12) . . ? F66 F54 F65 51.4(21) . . ? B5 F54 F65 51.2(14) . . ? F63 F54 F65 106.0(19) . . ? F53 F61 F52 126.2(17) . . ? F53 F61 B5 65.7(12) . . ? F52 F61 B5 63.7(11) . . ? F52 F62 B5 49.1(12) . . ? F53 F63 F54 106.4(14) . . ? F53 F63 B5 55.7(9) . . ? F54 F63 B5 53.2(9) . . ? F51 F64 B5 57.2(20) . . ? F51 F64 F53 104.9(28) . . ? B5 F64 F53 49.8(11) . . ? F51 F65 F66 129.0(37) . . ? F51 F65 B5 62.3(20) . . ? F66 F65 B5 66.8(26) . . ? F51 F65 F54 105.1(28) . . ? F66 F65 F54 38.9(16) . . ? B5 F65 F54 55.1(17) . . ? F54 F66 F65 89.7(28) . . ? F54 F66 B5 66.8(19) . . ? F65 F66 B5 58.2(21) . . ? F54 F66 F52 107.4(26) . . ? F65 F66 F52 87.1(26) . . ? B5 F66 F52 51.0(13) . . ? _refine_diff_density_max 0.412 _refine_diff_density_min -0.712 _refine_diff_density_rms 0.075 #===END data_marcus22 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common 'Complex 10' _chemical_formula_moiety 'C40 H34 Cu N8 O6, 8(H2 O)' _chemical_formula_structural [Cu(tpms)2].8H2O _chemical_formula_analytical ? _chemical_formula_sum 'C40 H50 Cu N8 O14' _chemical_formula_weight 930.4 _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' 0.0033 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' 'Cu' 'Cu' 0.3201 1.2651 '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 'P 21/n (equiv. to no. 14) 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 14.7630(12) _cell_length_b 11.1802(15) _cell_length_c 14.511(2) _cell_angle_alpha 90.00 _cell_angle_beta 117.133(8) _cell_angle_gamma 90.00 _cell_volume 2131.5(4) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 24 _cell_measurement_theta_min 10 _cell_measurement_theta_max 11 _exptl_crystal_description rhombs _exptl_crystal_colour lilac _exptl_crystal_size_max 0.52 _exptl_crystal_size_mid 0.38 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.450 _exptl_crystal_density_method ? _exptl_crystal_F_000 974 _exptl_absorpt_coefficient_mu 0.590 _exptl_absorpt_correction_type 'semi-empirical psi-scans' _exptl_absorpt_correction_T_min 0.956 _exptl_absorpt_correction_T_max 0.993 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type Mo-K\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Enraf-Nonius CAD4 diffractometer' _diffrn_measurement_method 'scintillation counter; \w/\q scans' _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time '10000 s' _diffrn_standards_decay_% 4.0 _diffrn_reflns_number 4876 _diffrn_reflns_av_R_equivalents 0.025 _diffrn_reflns_av_sigmaI/netI 0.0482 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -1 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -1 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 1.63 _diffrn_reflns_theta_max 25.97 _reflns_number_total 4176 _reflns_number_observed 3111 _reflns_observed_criterion I>2sigma(I) _computing_data_collection 'CAD4/EXPRESS (Enraf-Nonius, 1992)' _computing_cell_refinement 'CAD4/EXPRESS (Enraf-Nonius, 1992)' _computing_data_reduction 'CAD4 (Hursthouse, 1976)' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'ORTEP (Johnson, 1971)' _computing_publication_material 'SHELXL-93 (Sheldrick, 1993)' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 1 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^)+(0.0682P)^2^] 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 ; Hydrogen atoms of the complex were included in idealised positions; those of the solvent molecules were located in difference maps. All hydrogen atom parameters were refined freely. ; _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4175 _refine_ls_number_parameters 386 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0572 _refine_ls_R_factor_obs 0.0405 _refine_ls_wR_factor_all 0.1223 _refine_ls_wR_factor_obs 0.1034 _refine_ls_goodness_of_fit_all 1.056 _refine_ls_goodness_of_fit_obs 1.108 _refine_ls_restrained_S_all 1.115 _refine_ls_restrained_S_obs 1.108 _refine_ls_shift/esd_max -0.001 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Cu Cu 0.0000 0.0000 0.0000 0.02951(14) Uani 1 d S . N11 N 0.08349(14) 0.1466(2) 0.06392(15) 0.0305(4) Uani 1 d . . C12 C 0.1663(2) 0.1676(2) 0.0501(2) 0.0279(5) Uani 1 d . . C13 C 0.2060(2) 0.2818(2) 0.0622(2) 0.0381(6) Uani 1 d . . H13 H 0.2630(22) 0.2963(26) 0.0529(23) 0.054(8) Uiso 1 d . . C14 C 0.1645(2) 0.3732(3) 0.0935(2) 0.0476(7) Uani 1 d . . H14 H 0.1934(21) 0.4497(28) 0.1026(22) 0.051(8) Uiso 1 d . . C15 C 0.0831(2) 0.3500(2) 0.1139(2) 0.0440(6) Uani 1 d . . H15 H 0.0573(21) 0.4082(26) 0.1368(22) 0.047(8) Uiso 1 d . . C16 C 0.0449(2) 0.2365(2) 0.0978(2) 0.0384(6) Uani 1 d . . H16 H -0.0131(20) 0.2171(24) 0.1067(20) 0.040(7) Uiso 1 d . . N21 N 0.13266(14) -0.0920(2) 0.07517(15) 0.0322(4) Uani 1 d . . C22 C 0.2139(2) -0.0594(2) 0.0634(2) 0.0282(5) Uani 1 d . . C23 C 0.2946(2) -0.1375(2) 0.0879(2) 0.0368(5) Uani 1 d . . H23 H 0.3480(21) -0.1132(24) 0.0760(21) 0.045(7) Uiso 1 d . . C24 C 0.2947(2) -0.2460(2) 0.1329(2) 0.0420(6) Uani 1 d . . H24 H 0.3528(24) -0.2948(28) 0.1517(25) 0.060(9) Uiso 1 d . . C25 C 0.2151(2) -0.2754(2) 0.1532(2) 0.0409(6) Uani 1 d . . H25 H 0.2119(20) -0.3462(24) 0.1850(20) 0.038(7) Uiso 1 d . . C26 C 0.1353(2) -0.1971(2) 0.1216(2) 0.0378(6) Uani 1 d . . H26 H 0.0794(19) -0.2149(22) 0.1286(19) 0.032(6) Uiso 1 d . . N31 N 0.04617(14) 0.0346(2) -0.13217(15) 0.0353(5) Uani 1 d . . C32 C 0.1455(2) 0.0460(2) -0.1040(2) 0.0276(5) Uani 1 d . . C33 C 0.1835(2) 0.0375(2) -0.1749(2) 0.0384(6) Uani 1 d . . H33 H 0.2485(23) 0.0377(26) -0.1562(23) 0.049(8) Uiso 1 d . . C34 C 0.1157(2) 0.0204(3) -0.2782(2) 0.0448(6) Uani 1 d . . H34 H 0.1403(23) 0.0084(24) -0.3281(25) 0.055(9) Uiso 1 d . . C35 C 0.0136(2) 0.0125(2) -0.3076(2) 0.0452(6) Uani 1 d . . H35 H -0.0361(24) -0.0012(24) -0.3753(25) 0.052(8) Uiso 1 d . . C36 C -0.0182(2) 0.0190(3) -0.2323(2) 0.0433(6) Uani 1 d . . H36 H -0.0862(23) 0.0131(24) -0.2478(21) 0.043(8) Uiso 1 d . . C1 C 0.2116(2) 0.0638(2) 0.0132(2) 0.0279(5) Uani 1 d . . N1 N 0.31552(14) 0.0950(2) 0.0358(2) 0.0312(4) Uani 1 d . . H1 H 0.3245(22) 0.1147(26) -0.0100(23) 0.049(9) Uiso 1 d . . C41 C 0.3895(2) 0.1075(2) 0.1349(2) 0.0324(5) Uani 1 d . . O41 O 0.37281(12) 0.0914(2) 0.20883(13) 0.0414(4) Uani 1 d . . C42 C 0.4928(2) 0.1412(3) 0.1448(2) 0.0451(7) Uani 1 d . . H42A H 0.5041(22) 0.0938(28) 0.0992(24) 0.056(9) Uiso 1 d . . H42B H 0.4826(28) 0.2232(37) 0.1151(31) 0.090(13) Uiso 1 d . . C43 C 0.5759(2) 0.1350(4) 0.2534(2) 0.0499(7) Uani 1 d . . H43A H 0.5798(25) 0.0622(36) 0.2786(28) 0.073(11) Uiso 1 d . . H43B H 0.5608(33) 0.1936(39) 0.2986(34) 0.108(15) Uiso 1 d . . C44 C 0.6810(2) 0.1683(2) 0.2673(2) 0.0390(6) Uani 1 d . . O441 O 0.69239(13) 0.1984(2) 0.19070(14) 0.0477(5) Uani 1 d . . O442 O 0.75224(13) 0.1631(2) 0.35883(14) 0.0532(5) Uani 1 d . . O5 O 0.5846(2) 0.3216(2) 0.0104(2) 0.0588(6) Uani 1 d . . H5A H 0.5308(27) 0.2910(31) -0.0299(28) 0.063(10) Uiso 1 d . . H5B H 0.6141(30) 0.2693(37) 0.0658(34) 0.089(13) Uiso 1 d . . O6 O 0.9076(2) 0.3062(3) 0.3875(2) 0.0620(6) Uani 1 d . . H6A H 0.8675(32) 0.2588(36) 0.3808(32) 0.076(14) Uiso 1 d . . H6B H 0.9168(25) 0.3119(30) 0.3406(28) 0.051(12) Uiso 1 d . . O7 O 0.7585(2) -0.0343(2) 0.4757(2) 0.0612(6) Uani 1 d . . H7A H 0.8075(30) -0.0631(35) 0.4826(30) 0.079(14) Uiso 1 d . . H7B H 0.7660(28) 0.0269(34) 0.4456(30) 0.073(13) Uiso 1 d . . O8 O 0.8648(2) 0.2868(3) 0.1721(2) 0.0698(7) Uani 1 d . . H8A H 0.8369(34) 0.3432(41) 0.1297(36) 0.098(16) Uiso 1 d . . H8B H 0.8215(41) 0.2473(47) 0.1744(43) 0.126(20) Uiso 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 Cu 0.0228(2) 0.0324(2) 0.0354(2) -0.0014(2) 0.0151(2) -0.0057(2) N11 0.0261(9) 0.0350(10) 0.0343(10) -0.0034(8) 0.0173(8) -0.0047(8) C12 0.0239(10) 0.0343(12) 0.0254(11) -0.0013(9) 0.0113(9) -0.0051(9) C13 0.0369(13) 0.0357(13) 0.0480(15) -0.0013(11) 0.0247(12) -0.0062(11) C14 0.050(2) 0.0348(14) 0.063(2) -0.0073(13) 0.0301(14) -0.0100(12) C15 0.048(2) 0.0385(14) 0.052(2) -0.0082(12) 0.0287(13) 0.0014(12) C16 0.0352(13) 0.0455(14) 0.0394(14) -0.0073(11) 0.0213(11) -0.0012(11) N21 0.0303(10) 0.0352(10) 0.0355(11) 0.0006(8) 0.0187(9) -0.0049(8) C22 0.0281(11) 0.0327(12) 0.0261(11) -0.0022(9) 0.0143(9) -0.0033(9) C23 0.0334(12) 0.0419(14) 0.0413(14) 0.0003(11) 0.0225(11) 0.0016(11) C24 0.0449(15) 0.0400(14) 0.0427(14) 0.0011(12) 0.0214(12) 0.0084(12) C25 0.055(2) 0.0334(13) 0.0398(14) 0.0051(11) 0.0268(13) -0.0002(12) C26 0.0394(13) 0.0382(13) 0.0423(14) 0.0018(11) 0.0243(12) -0.0061(11) N31 0.0267(10) 0.0504(12) 0.0296(10) -0.0049(9) 0.0138(8) -0.0087(9) C32 0.0286(11) 0.0283(10) 0.0283(11) 0.0016(9) 0.0150(9) -0.0029(9) C33 0.0355(13) 0.0473(14) 0.0387(14) -0.0062(11) 0.0223(12) -0.0034(11) C34 0.053(2) 0.052(2) 0.0364(14) -0.0089(12) 0.0273(13) -0.0059(12) C35 0.050(2) 0.051(2) 0.0285(13) -0.0070(12) 0.0118(12) -0.0051(12) C36 0.0310(13) 0.059(2) 0.0350(14) -0.0071(12) 0.0105(11) -0.0062(12) C1 0.0226(10) 0.0346(12) 0.0298(11) -0.0006(9) 0.0149(9) -0.0055(9) N1 0.0248(9) 0.0428(11) 0.0311(10) 0.0016(9) 0.0171(8) -0.0060(8) C41 0.0259(11) 0.0399(13) 0.0334(12) -0.0015(10) 0.0151(10) -0.0027(10) O41 0.0337(9) 0.0626(12) 0.0327(9) -0.0028(8) 0.0194(7) -0.0066(8) C42 0.0250(12) 0.073(2) 0.0388(15) -0.0028(14) 0.0157(11) -0.0099(12) C43 0.0289(13) 0.077(2) 0.041(2) 0.010(2) 0.0139(12) -0.0054(14) C44 0.0277(12) 0.0446(14) 0.0416(14) 0.0068(11) 0.0131(11) 0.0033(10) O441 0.0292(9) 0.0686(13) 0.0447(11) 0.0113(9) 0.0163(8) -0.0015(8) O442 0.0292(9) 0.0789(15) 0.0433(11) 0.0136(10) 0.0095(8) 0.0023(9) O5 0.0454(12) 0.078(2) 0.0457(12) 0.0123(11) 0.0141(10) -0.0176(12) O6 0.0466(13) 0.069(2) 0.055(2) -0.0082(13) 0.0097(12) -0.0039(12) O7 0.067(2) 0.0580(15) 0.071(2) 0.0095(12) 0.0419(13) 0.0190(12) O8 0.0420(12) 0.087(2) 0.083(2) 0.0159(15) 0.0309(12) 0.0002(13) _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 N11 2.006(2) 3 ? Cu N11 2.006(2) . ? Cu N21 2.033(2) . ? Cu N21 2.033(2) 3 ? Cu N31 2.342(2) . ? Cu N31 2.342(2) 3 ? N11 C12 1.346(3) . ? N11 C16 1.353(3) . ? C12 C13 1.383(3) . ? C12 C1 1.552(3) . ? C13 C14 1.370(4) . ? C13 H13 0.92(3) . ? C14 C15 1.387(4) . ? C14 H14 0.94(3) . ? C15 C16 1.365(4) . ? C15 H15 0.89(3) . ? C16 H16 0.95(3) . ? N21 C22 1.337(3) . ? N21 C26 1.346(3) . ? C22 C23 1.387(3) . ? C22 C1 1.551(3) . ? C23 C24 1.377(4) . ? C23 H23 0.92(3) . ? C24 C25 1.376(4) . ? C24 H24 0.95(3) . ? C25 C26 1.369(4) . ? C25 H25 0.93(3) . ? C26 H26 0.90(2) . ? N31 C36 1.336(3) . ? N31 C32 1.337(3) . ? C32 C33 1.381(3) . ? C32 C1 1.540(3) . ? C33 C34 1.385(4) . ? C33 H33 0.87(3) . ? C34 C35 1.370(4) . ? C34 H34 0.96(3) . ? C35 C36 1.374(4) . ? C35 H35 0.93(3) . ? C36 H36 0.93(3) . ? C1 N1 1.458(3) . ? N1 C41 1.359(3) . ? N1 H1 0.77(3) . ? C41 O41 1.218(3) . ? C41 C42 1.514(3) . ? C42 C43 1.494(4) . ? C42 H42A 0.92(3) . ? C42 H42B 1.00(4) . ? C43 C44 1.516(3) . ? C43 H43A 0.88(4) . ? C43 H43B 1.02(4) . ? C44 O441 1.244(3) . ? C44 O442 1.265(3) . ? O5 H5A 0.82(4) . ? O5 H5B 0.93(4) . ? O6 H6A 0.77(4) . ? O6 H6B 0.75(3) . ? O7 H7A 0.76(4) . ? O7 H7B 0.85(4) . ? O8 H8A 0.85(5) . ? O8 H8B 0.79(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 N11 Cu N11 180.0 3 . ? N11 Cu N21 94.19(7) 3 . ? N11 Cu N21 85.81(7) . . ? N11 Cu N21 85.81(7) 3 3 ? N11 Cu N21 94.19(7) . 3 ? N21 Cu N21 180.0 . 3 ? N11 Cu N31 95.93(7) 3 . ? N11 Cu N31 84.07(7) . . ? N21 Cu N31 87.37(7) . . ? N21 Cu N31 92.63(7) 3 . ? N11 Cu N31 84.07(7) 3 3 ? N11 Cu N31 95.93(7) . 3 ? N21 Cu N31 92.64(7) . 3 ? N21 Cu N31 87.37(7) 3 3 ? N31 Cu N31 180.0 . 3 ? C12 N11 C16 119.1(2) . . ? C12 N11 Cu 118.79(15) . . ? C16 N11 Cu 120.22(15) . . ? N11 C12 C13 120.2(2) . . ? N11 C12 C1 119.0(2) . . ? C13 C12 C1 120.7(2) . . ? C14 C13 C12 120.1(2) . . ? C14 C13 H13 119.4(18) . . ? C12 C13 H13 120.3(18) . . ? C13 C14 C15 119.6(3) . . ? C13 C14 H14 118.9(17) . . ? C15 C14 H14 121.5(17) . . ? C16 C15 C14 117.9(2) . . ? C16 C15 H15 121.9(18) . . ? C14 C15 H15 120.3(18) . . ? N11 C16 C15 122.9(2) . . ? N11 C16 H16 115.9(16) . . ? C15 C16 H16 121.2(16) . . ? C22 N21 C26 118.7(2) . . ? C22 N21 Cu 119.6(2) . . ? C26 N21 Cu 120.7(2) . . ? N21 C22 C23 120.8(2) . . ? N21 C22 C1 118.2(2) . . ? C23 C22 C1 120.8(2) . . ? C24 C23 C22 119.4(2) . . ? C24 C23 H23 122.2(17) . . ? C22 C23 H23 118.3(17) . . ? C25 C24 C23 119.7(3) . . ? C25 C24 H24 123.4(19) . . ? C23 C24 H24 116.7(19) . . ? C26 C25 C24 117.7(2) . . ? C26 C25 H25 118.8(16) . . ? C24 C25 H25 123.5(16) . . ? N21 C26 C25 123.3(2) . . ? N21 C26 H26 115.6(16) . . ? C25 C26 H26 121.0(16) . . ? C36 N31 C32 118.8(2) . . ? C36 N31 Cu 122.7(2) . . ? C32 N31 Cu 117.01(15) . . ? N31 C32 C33 121.8(2) . . ? N31 C32 C1 113.8(2) . . ? C33 C32 C1 124.3(2) . . ? C32 C33 C34 118.5(2) . . ? C32 C33 H33 122.1(20) . . ? C34 C33 H33 119.2(20) . . ? C35 C34 C33 119.7(2) . . ? C35 C34 H34 120.0(19) . . ? C33 C34 H34 120.2(19) . . ? C34 C35 C36 118.4(2) . . ? C34 C35 H35 124.4(20) . . ? C36 C35 H35 117.1(20) . . ? N31 C36 C35 122.7(2) . . ? N31 C36 H36 115.4(17) . . ? C35 C36 H36 121.9(17) . . ? N1 C1 C32 110.5(2) . . ? N1 C1 C22 108.1(2) . . ? C32 C1 C22 105.7(2) . . ? N1 C1 C12 108.5(2) . . ? C32 C1 C12 108.8(2) . . ? C22 C1 C12 115.0(2) . . ? C41 N1 C1 121.2(2) . . ? C41 N1 H1 121.0(22) . . ? C1 N1 H1 116.9(23) . . ? O41 C41 N1 121.9(2) . . ? O41 C41 C42 123.6(2) . . ? N1 C41 C42 114.5(2) . . ? C43 C42 C41 113.3(2) . . ? C43 C42 H42A 113.7(19) . . ? C41 C42 H42A 107.1(19) . . ? C43 C42 H42B 112.9(22) . . ? C41 C42 H42B 103.9(22) . . ? H42A C42 H42B 105.2(30) . . ? C42 C43 C44 115.2(2) . . ? C42 C43 H43A 110.3(23) . . ? C44 C43 H43A 107.6(22) . . ? C42 C43 H43B 109.5(24) . . ? C44 C43 H43B 105.5(25) . . ? H43A C43 H43B 108.5(33) . . ? O441 C44 O442 124.3(2) . . ? O441 C44 C43 119.7(2) . . ? O442 C44 C43 116.0(2) . . ? H5A O5 H5B 106.0(34) . . ? H6A O6 H6B 112.9(42) . . ? H7A O7 H7B 94.0(38) . . ? H8A O8 H8B 108.3(47) . . ? _refine_diff_density_max 0.327 _refine_diff_density_min -1.042 _refine_diff_density_rms 0.063 #===END data_marcus23 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common 'Complex 18' _chemical_formula_moiety 'C26 H30 CU2 N6 O8 S4, 3(O H2)' _chemical_formula_structural [{Cu(mde)(SO4)-O,O'}2].3(H2O) _chemical_formula_analytical ? _chemical_formula_sum 'C26 H36 Cu2 N6 O11 S4' _chemical_formula_weight 863.9 _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' 0.0033 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' 'Cu' 'Cu' 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'S' 'S' 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'P 21 / n (equiv. to no. 14)' 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 9.1541(14) _cell_length_b 13.264(2) _cell_length_c 14.255(4) _cell_angle_alpha 90.00 _cell_angle_beta 95.24(2) _cell_angle_gamma 90.00 _cell_volume 1723.7(6) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 24 _cell_measurement_theta_min 10 _cell_measurement_theta_max 11 _exptl_crystal_description 'irregular octahedra' _exptl_crystal_colour 'Bright blue' _exptl_crystal_size_max 0.19 _exptl_crystal_size_mid 0.17 _exptl_crystal_size_min 0.14 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.67 _exptl_crystal_density_method ? _exptl_crystal_F_000 892 _exptl_absorpt_coefficient_mu 1.54 _exptl_absorpt_correction_type 'semi-empirical psi-scans' _exptl_absorpt_correction_T_min 0.723 _exptl_absorpt_correction_T_max 0.961 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type Mo-K\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Enraf-Nonius CAD4 diffractometer' _diffrn_measurement_method 'scintillation counter; \w/\q scans' _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time '10000 s' _diffrn_standards_decay_% 4.93 _diffrn_reflns_number '4859 (to theta of 26.0)' _diffrn_reflns_av_R_equivalents 0.0813 _diffrn_reflns_av_sigmaI/netI 0.0984 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 1.50 _diffrn_reflns_theta_max '24.00 (collected to theta of 26.0)' _reflns_number_total '2712 (3374 to theta of 26.0)' _reflns_number_observed '1798 (2015 to theta of 26.0)' _reflns_observed_criterion I>2sigma(I) _computing_data_collection 'CAD4/EXPRESS (Enraf-Nonius, 1992)' _computing_cell_refinement 'CAD4/EXPRESS (Enraf-Nonius, 1992)' _computing_data_reduction 'CAD4 (Hursthouse, 1976)' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'ORTEP (Johnson, 1971)' _computing_publication_material 'SHELXL-93 (Sheldrick, 1993)' _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^)+(0.0467P)^2^] 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 ; Coordinates of the complex hydrogens were located in idealised postions and set to ride on the parent atoms. Those of one of the two solvent water hydrogens were geometrically constrained. Hydrogens were not included in the second water molecule. All isotropic thermal displacement parameters were set to be 1.2 x Ueq of the parent atoms. ; _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2712 _refine_ls_number_parameters 232 _refine_ls_number_restraints 3 _refine_ls_R_factor_all 0.0787 _refine_ls_R_factor_obs 0.0489 _refine_ls_wR_factor_all 0.1176 _refine_ls_wR_factor_obs 0.0976 _refine_ls_goodness_of_fit_all 1.048 _refine_ls_goodness_of_fit_obs 1.091 _refine_ls_restrained_S_all 1.048 _refine_ls_restrained_S_obs 1.091 _refine_ls_shift/esd_max 0.001 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Cu Cu 0.00929(6) 0.35246(4) 0.04551(4) 0.0312(2) Uani 1 d . . N11 N 0.2456(4) 0.3880(3) 0.1134(3) 0.0320(10) Uani 1 d . . C12 C 0.2826(5) 0.3123(4) 0.1729(3) 0.0316(12) Uani 1 d . . C13 C 0.4243(6) 0.2948(4) 0.2089(4) 0.0438(14) Uani 1 d . . H13 H 0.4476(6) 0.2400(4) 0.2481(4) 0.053 Uiso 1 calc R . C14 C 0.5311(6) 0.3609(5) 0.1851(4) 0.051(2) Uani 1 d . . H14 H 0.6284(6) 0.3507(5) 0.2079(4) 0.062 Uiso 1 calc R . C15 C 0.4940(6) 0.4413(5) 0.1282(4) 0.051(2) Uani 1 d . . H15 H 0.5645(6) 0.4877(5) 0.1135(4) 0.061 Uiso 1 calc R . C16 C 0.3502(6) 0.4521(4) 0.0932(4) 0.0394(13) Uani 1 d . . H16 H 0.3248(6) 0.5064(4) 0.0538(4) 0.047 Uiso 1 calc R . N21 N 0.0853(5) 0.2113(3) 0.0256(3) 0.0399(11) Uani 1 d . . C22 C 0.1474(6) 0.1694(4) 0.1049(4) 0.0397(13) Uani 1 d . . C23 C 0.2057(8) 0.0741(4) 0.1051(5) 0.065(2) Uani 1 d . . H23 H 0.2482(8) 0.0458(4) 0.1607(5) 0.077 Uiso 1 calc R . C24 C 0.2003(10) 0.0210(5) 0.0220(5) 0.092(3) Uani 1 d . . H24 H 0.2374(10) -0.0442(5) 0.0211(5) 0.111 Uiso 1 calc R . C25 C 0.1395(10) 0.0652(5) -0.0601(5) 0.084(3) Uani 1 d . . H25 H 0.1373(10) 0.0314(5) -0.1174(5) 0.101 Uiso 1 calc R . C26 C 0.0824(7) 0.1605(4) -0.0549(4) 0.059(2) Uani 1 d . . H26 H 0.0401(7) 0.1906(4) -0.1097(4) 0.071 Uiso 1 calc R . N3 N 0.0189(4) 0.3013(3) 0.1764(3) 0.0318(10) Uani 1 d . . H3A H 0.0221(4) 0.3528(3) 0.2177(3) 0.038 Uiso 1 calc R . H3B H -0.0601(4) 0.2630(3) 0.1848(3) 0.038 Uiso 1 calc R . C1 C 0.1539(5) 0.2410(4) 0.1897(4) 0.0326(12) Uani 1 d . . C41 C 0.1708(6) 0.1863(4) 0.2841(4) 0.0421(14) Uani 1 d . . H41A H 0.2606(6) 0.1472(4) 0.2878(4) 0.051 Uiso 1 calc R . H41B H 0.0898(6) 0.1395(4) 0.2865(4) 0.051 Uiso 1 calc R . S42 S 0.1756(2) 0.26720(14) 0.38513(11) 0.0575(5) Uani 1 d . . C43 C -0.0089(9) 0.2659(8) 0.4138(6) 0.108(3) Uani 1 d . . H43A H -0.0180(9) 0.3077(8) 0.4679(6) 0.162 Uiso 1 calc R . H43B H -0.0368(9) 0.1981(8) 0.4275(6) 0.162 Uiso 1 calc R . H43C H -0.0718(9) 0.2911(8) 0.3615(6) 0.162 Uiso 1 calc R . S5 S -0.08313(14) 0.55079(9) 0.13720(9) 0.0334(3) Uani 1 d . . O51 O -0.1215(4) 0.4623(2) 0.0757(2) 0.0367(8) Uani 1 d . . O52 O 0.0172(4) 0.6163(3) 0.0879(2) 0.0395(9) Uani 1 d . . O53 O -0.0043(4) 0.5195(3) 0.2255(2) 0.0455(10) Uani 1 d . . O54 O -0.2163(4) 0.6062(3) 0.1491(3) 0.0590(12) Uani 1 d . . O6 O -0.2920(6) 0.6551(4) 0.3217(4) 0.085(2) Uani 1 d D . H6A H -0.2045(62) 0.6543(62) 0.3583(50) 0.102 Uiso 1 d D . H6B H -0.2784(83) 0.6291(61) 0.2658(36) 0.102 Uiso 1 d D . O7 O -0.0491(9) 0.5577(9) 0.4086(6) 0.073(3) Uani 0.50 d P . 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 0.0363(4) 0.0237(3) 0.0320(4) 0.0051(3) -0.0047(2) -0.0030(3) N11 0.036(2) 0.028(2) 0.031(2) 0.005(2) -0.002(2) -0.007(2) C12 0.041(3) 0.028(3) 0.025(3) 0.001(2) -0.001(2) 0.000(2) C13 0.044(3) 0.048(3) 0.038(3) 0.005(3) -0.005(3) 0.003(3) C14 0.033(3) 0.073(4) 0.047(3) 0.005(3) -0.004(3) 0.004(3) C15 0.039(3) 0.062(4) 0.051(4) 0.004(3) 0.002(3) -0.008(3) C16 0.045(3) 0.039(3) 0.034(3) 0.010(3) 0.003(2) -0.003(3) N21 0.052(3) 0.027(2) 0.038(3) 0.001(2) -0.013(2) 0.000(2) C22 0.053(3) 0.027(3) 0.038(3) 0.005(2) -0.006(3) -0.005(2) C23 0.105(5) 0.032(3) 0.053(4) 0.009(3) -0.013(4) 0.026(3) C24 0.166(8) 0.034(4) 0.069(5) -0.012(4) -0.030(5) 0.029(5) C25 0.146(7) 0.047(4) 0.053(4) -0.020(4) -0.023(5) 0.027(4) C26 0.091(5) 0.038(3) 0.044(4) -0.002(3) -0.024(3) 0.008(3) N3 0.034(2) 0.023(2) 0.037(2) 0.001(2) -0.002(2) -0.006(2) C1 0.041(3) 0.021(2) 0.035(3) 0.003(2) -0.006(2) -0.004(2) C41 0.057(4) 0.035(3) 0.032(3) 0.009(3) -0.009(3) 0.000(3) S42 0.0653(10) 0.0679(11) 0.0384(8) -0.0067(8) 0.0002(7) -0.0150(9) C43 0.097(6) 0.129(8) 0.106(7) -0.028(7) 0.052(5) -0.030(6) S5 0.0381(7) 0.0299(7) 0.0314(7) 0.0018(6) -0.0007(6) 0.0029(6) O51 0.037(2) 0.029(2) 0.042(2) 0.002(2) -0.008(2) -0.001(2) O52 0.048(2) 0.038(2) 0.031(2) 0.008(2) -0.006(2) -0.009(2) O53 0.060(2) 0.044(2) 0.031(2) 0.006(2) -0.005(2) 0.002(2) O54 0.052(2) 0.056(3) 0.071(3) -0.013(2) 0.012(2) 0.020(2) O6 0.098(4) 0.085(4) 0.078(4) 0.004(3) 0.036(3) 0.045(3) O7 0.054(5) 0.125(9) 0.040(5) -0.003(5) 0.001(4) 0.031(5) _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 O52 1.940(3) 3_565 ? Cu O51 1.959(3) . ? Cu N3 1.980(4) . ? Cu N21 2.027(4) . ? Cu N11 2.336(4) . ? N11 C16 1.331(6) . ? N11 C12 1.338(6) . ? C12 C13 1.370(7) . ? C12 C1 1.547(7) . ? C13 C14 1.379(8) . ? C13 H13 0.93 . ? C14 C15 1.364(8) . ? C14 H14 0.93 . ? C15 C16 1.372(7) . ? C15 H15 0.93 . ? C16 H16 0.93 . ? N21 C26 1.329(7) . ? N21 C22 1.339(6) . ? C22 C23 1.371(8) . ? C22 C1 1.535(7) . ? C23 C24 1.375(9) . ? C23 H23 0.93 . ? C24 C25 1.380(9) . ? C24 H24 0.93 . ? C25 C26 1.372(9) . ? C25 H25 0.93 . ? C26 H26 0.93 . ? N3 C1 1.469(6) . ? N3 H3A 0.90 . ? N3 H3B 0.90 . ? C1 C41 1.524(7) . ? C41 S42 1.793(6) . ? C41 H41A 0.97 . ? C41 H41B 0.97 . ? S42 C43 1.774(8) . ? C43 H43A 0.96 . ? C43 H43B 0.96 . ? C43 H43C 0.96 . ? S5 O54 1.447(4) . ? S5 O53 1.453(3) . ? S5 O52 1.487(4) . ? S5 O51 1.488(3) . ? O52 Cu 1.940(3) 3_565 ? O6 H6A 0.92(4) . ? O6 H6B 0.89(4) . ? 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 O52 Cu O51 91.83(15) 3_565 . ? O52 Cu N3 171.08(15) 3_565 . ? O51 Cu N3 91.4(2) . . ? O52 Cu N21 94.2(2) 3_565 . ? O51 Cu N21 160.5(2) . . ? N3 Cu N21 80.2(2) . . ? O52 Cu N11 113.04(14) 3_565 . ? O51 Cu N11 108.68(14) . . ? N3 Cu N11 73.69(15) . . ? N21 Cu N11 85.9(2) . . ? C16 N11 C12 118.0(4) . . ? C16 N11 Cu 134.2(3) . . ? C12 N11 Cu 106.4(3) . . ? N11 C12 C13 122.8(5) . . ? N11 C12 C1 113.9(4) . . ? C13 C12 C1 123.1(4) . . ? C12 C13 C14 117.9(5) . . ? C12 C13 H13 121.0(3) . . ? C14 C13 H13 121.0(3) . . ? C15 C14 C13 120.0(5) . . ? C15 C14 H14 120.0(3) . . ? C13 C14 H14 120.0(3) . . ? C14 C15 C16 118.5(5) . . ? C14 C15 H15 120.8(3) . . ? C16 C15 H15 120.8(3) . . ? N11 C16 C15 122.7(5) . . ? N11 C16 H16 118.6(3) . . ? C15 C16 H16 118.6(3) . . ? C26 N21 C22 119.5(5) . . ? C26 N21 Cu 127.5(4) . . ? C22 N21 Cu 113.0(3) . . ? N21 C22 C23 121.3(5) . . ? N21 C22 C1 113.0(4) . . ? C23 C22 C1 125.6(5) . . ? C22 C23 C24 119.1(6) . . ? C22 C23 H23 120.4(4) . . ? C24 C23 H23 120.4(4) . . ? C23 C24 C25 119.5(6) . . ? C23 C24 H24 120.2(4) . . ? C25 C24 H24 120.2(4) . . ? C26 C25 C24 118.1(6) . . ? C26 C25 H25 120.9(4) . . ? C24 C25 H25 120.9(4) . . ? N21 C26 C25 122.4(6) . . ? N21 C26 H26 118.8(3) . . ? C25 C26 H26 118.8(4) . . ? C1 N3 Cu 105.8(3) . . ? C1 N3 H3A 110.6(2) . . ? Cu N3 H3A 110.58(12) . . ? C1 N3 H3B 110.6(2) . . ? Cu N3 H3B 110.58(11) . . ? H3A N3 H3B 108.7 . . ? N3 C1 C41 112.9(4) . . ? N3 C1 C22 105.3(4) . . ? C41 C1 C22 113.2(4) . . ? N3 C1 C12 106.9(4) . . ? C41 C1 C12 114.2(4) . . ? C22 C1 C12 103.4(4) . . ? C1 C41 S42 114.7(4) . . ? C1 C41 H41A 108.6(3) . . ? S42 C41 H41A 108.6(2) . . ? C1 C41 H41B 108.6(3) . . ? S42 C41 H41B 108.6(2) . . ? H41A C41 H41B 107.6 . . ? C43 S42 C41 103.0(4) . . ? S42 C43 H43A 109.5(3) . . ? S42 C43 H43B 109.5(4) . . ? H43A C43 H43B 109.5 . . ? S42 C43 H43C 109.5(3) . . ? H43A C43 H43C 109.5 . . ? H43B C43 H43C 109.5 . . ? O54 S5 O53 113.6(2) . . ? O54 S5 O52 108.8(2) . . ? O53 S5 O52 107.3(2) . . ? O54 S5 O51 108.3(2) . . ? O53 S5 O51 110.9(2) . . ? O52 S5 O51 107.8(2) . . ? S5 O51 Cu 126.9(2) . . ? S5 O52 Cu 124.1(2) . 3_565 ? H6A O6 H6B 108.6(62) . . ? _refine_diff_density_max 0.636 _refine_diff_density_min -0.767 _refine_diff_density_rms 0.103 #===END data_philip1 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common 'Complex 20' _chemical_formula_moiety '2(C16 H20 N4 O3 Zn), H12 O6 Zn, 3(S O4), 3(H2 O)' _chemical_formula_structural '[Zn(tpm)(H2O)3]2 [Zn(H2O)6] (SO4)3 .3H2O' _chemical_formula_analytical ? _chemical_formula_sum 'C32 H58 N8 O27 S3 Zn3' _chemical_formula_weight 1279.15 _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' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'S' 'S' 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Zn' 'Zn' 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting 'Monoclinic, twinned' _symmetry_space_group_name_H-M 'P 21/a (equiv. to no. 14)' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z' '-x, -y, -z' 'x-1/2, -y-1/2, z' _cell_length_a 16.5362(15) _cell_length_b 13.789(2) _cell_length_c 22.407(2) _cell_angle_alpha 90.00 _cell_angle_beta 111.652(8) _cell_angle_gamma 90.00 _cell_volume 4748.6(9) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 24 _cell_measurement_theta_min 10 _cell_measurement_theta_max 11 _exptl_crystal_description prisms _exptl_crystal_colour colourless _exptl_crystal_size_max 0.90 _exptl_crystal_size_mid 0.29 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.789 _exptl_crystal_density_method ? _exptl_crystal_F_000 2640 _exptl_absorpt_coefficient_mu 1.736 _exptl_absorpt_correction_type 'semi-empirical psi-scans' _exptl_absorpt_correction_T_min 0.16 _exptl_absorpt_correction_T_max 0.19 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type Mo-K\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Enraf-Nonius CAD4 diffractometer' _diffrn_measurement_method 'scintillation counter; \w/\q scans' _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time '10000 s' _diffrn_standards_decay_% 0 _diffrn_reflns_number 11830 _diffrn_reflns_av_R_equivalents 0.0123 _diffrn_reflns_av_sigmaI/netI 0.0486 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 21 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -29 _diffrn_reflns_limit_l_max 29 _diffrn_reflns_theta_min 1.77 _diffrn_reflns_theta_max 27.97 _reflns_number_total 11434 _reflns_number_observed 9411 _reflns_observed_criterion I>2sigma(I) _computing_data_collection 'CAD4/EXPRESS (Enraf-Nonius, 1992)' _computing_cell_refinement 'CAD4/EXPRESS (Enraf-Nonius, 1992)' _computing_data_reduction 'CAD4 (Hursthouse, 1976)' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'ORTEP (Johnson, 1971)' _computing_publication_material 'SHELXL-93 (Sheldrick, 1993)' _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^)+(0.0677P)^2^] 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 ; Hydrogen atoms on the pyridyl rings were included in idealised positions and, in the refinement, all parameters were set to ride on those of the parent C atoms. Some of the H atoms of the amine groups and the water molecules were located from difference maps and were refined with constrained O-H or N-H distances. ; _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 11434 _refine_ls_number_parameters 752 _refine_ls_number_restraints 20 _refine_ls_R_factor_all 0.0544 _refine_ls_R_factor_obs 0.0436 _refine_ls_wR_factor_all 0.1154 _refine_ls_wR_factor_obs 0.1045 _refine_ls_goodness_of_fit_all 1.079 _refine_ls_goodness_of_fit_obs 1.083 _refine_ls_restrained_S_all 1.078 _refine_ls_restrained_S_obs 1.082 _refine_ls_shift/esd_max -0.003 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Zn1 Zn 0.02940(3) 0.73016(3) 0.10253(2) 0.02762(11) Uani 1 d . . N11 N -0.0510(2) 0.6328(2) 0.0333(2) 0.0282(7) Uani 1 d . . C12 C -0.0727(2) 0.6493(3) -0.0290(2) 0.0249(8) Uani 1 d . . C13 C -0.1292(3) 0.5876(3) -0.0745(2) 0.0325(9) Uani 1 d . . H13 H -0.1431(3) 0.5988(3) -0.1181(2) 0.039 Uiso 1 calc R . C14 C -0.1643(3) 0.5090(3) -0.0539(2) 0.0401(11) Uani 1 d . . H14 H -0.2027(3) 0.4676(3) -0.0838(2) 0.048 Uiso 1 calc R . C15 C -0.1430(3) 0.4928(3) 0.0090(2) 0.0407(11) Uani 1 d . . H15 H -0.1669(3) 0.4410(3) 0.0233(2) 0.049 Uiso 1 calc R . C16 C -0.0845(3) 0.5550(3) 0.0523(2) 0.0345(9) Uani 1 d . . H16 H -0.0678(3) 0.5426(3) 0.0960(2) 0.041 Uiso 1 calc R . N21 N 0.1036(2) 0.7402(2) 0.0426(2) 0.0268(7) Uani 1 d . . C22 C 0.0637(3) 0.7448(3) -0.0218(2) 0.0231(7) Uani 1 d . . C23 C 0.1114(3) 0.7551(3) -0.0605(2) 0.0320(9) Uani 1 d . . H23 H 0.0837(3) 0.7566(3) -0.1049(2) 0.038 Uiso 1 calc R . C24 C 0.2016(3) 0.7632(3) -0.0324(2) 0.0379(10) Uani 1 d . . H24 H 0.2343(3) 0.7717(3) -0.0580(2) 0.046 Uiso 1 calc R . C25 C 0.2417(3) 0.7586(3) 0.0324(2) 0.0366(10) Uani 1 d . . H25 H 0.3019(3) 0.7639(3) 0.0519(2) 0.044 Uiso 1 calc R . C26 C 0.1905(3) 0.7456(3) 0.0683(2) 0.0338(9) Uani 1 d . . H26 H 0.2177(3) 0.7404(3) 0.1126(2) 0.041 Uiso 1 calc R . N31 N -0.0497(2) 0.8384(2) 0.0395(2) 0.0278(7) Uani 1 d . . C32 C -0.0698(2) 0.8331(3) -0.0245(2) 0.0236(7) Uani 1 d . . C33 C -0.1139(3) 0.9078(3) -0.0643(2) 0.0353(9) Uani 1 d . . H33 H -0.1253(3) 0.9054(3) -0.1082(2) 0.042 Uiso 1 calc R . C34 C -0.1410(3) 0.9867(3) -0.0378(3) 0.0416(11) Uani 1 d . . H34 H -0.1714(3) 1.0373(3) -0.0639(3) 0.050 Uiso 1 calc R . C35 C -0.1229(3) 0.9896(3) 0.0263(2) 0.0409(11) Uani 1 d . . H35 H -0.1419(3) 1.0411(3) 0.0446(2) 0.049 Uiso 1 calc R . C36 C -0.0763(3) 0.9157(3) 0.0635(2) 0.0369(10) Uani 1 d . . H36 H -0.0622(3) 0.9191(3) 0.1076(2) 0.044 Uiso 1 calc R . C17 C -0.0375(2) 0.7424(3) -0.0497(2) 0.0232(7) Uani 1 d . . N18 N -0.0733(2) 0.7464(3) -0.1199(2) 0.0295(7) Uani 1 d D . H18A H -0.0547(37) 0.6959(26) -0.1332(25) 0.054(17) Uiso 1 d D . O41 O 0.1044(3) 0.8345(3) 0.1673(2) 0.0578(11) Uani 1 d D . H41A H 0.0917(55) 0.8366(62) 0.1994(25) 0.107(32) Uiso 1 d D . O42 O 0.1075(2) 0.6181(3) 0.1566(2) 0.0456(8) Uani 1 d D . H42A H 0.1459(24) 0.6373(36) 0.1892(14) 0.036(14) Uiso 1 d D . O43 O -0.0478(3) 0.7152(3) 0.1589(2) 0.0463(8) Uani 1 d D . H43A H -0.0800(37) 0.7591(35) 0.1608(31) 0.067(21) Uiso 1 d D . H43B H -0.0251(32) 0.6823(32) 0.1914(15) 0.039(15) Uiso 1 d D . Zn2 Zn 0.20039(3) 0.75351(4) 0.40027(2) 0.02961(11) Uani 1 d . . N51 N 0.3294(2) 0.7542(2) 0.4686(2) 0.0260(7) Uani 1 d . . C52 C 0.3451(3) 0.7634(3) 0.5316(2) 0.0252(8) Uani 1 d . . C53 C 0.4288(3) 0.7686(3) 0.5764(2) 0.0334(9) Uani 1 d . . H53 H 0.4385(3) 0.7771(3) 0.6197(2) 0.040 Uiso 1 calc R . C54 C 0.4989(3) 0.7608(3) 0.5558(2) 0.0399(10) Uani 1 d . . H54 H 0.5558(3) 0.7624(3) 0.5854(2) 0.048 Uiso 1 calc R . C55 C 0.4824(3) 0.7508(4) 0.4912(2) 0.0409(11) Uani 1 d . . H55 H 0.5277(3) 0.7457(4) 0.4763(2) 0.049 Uiso 1 calc R . C56 C 0.3969(3) 0.7486(3) 0.4493(2) 0.0338(9) Uani 1 d . . H56 H 0.3856(3) 0.7430(3) 0.4056(2) 0.041 Uiso 1 calc R . N61 N 0.1728(2) 0.6588(2) 0.4657(2) 0.0295(7) Uani 1 d . . C62 C 0.2110(2) 0.6712(3) 0.5296(2) 0.0237(7) Uani 1 d . . C63 C 0.2001(3) 0.6048(3) 0.5730(2) 0.0368(10) Uani 1 d . . H63 H 0.2286(3) 0.6132(3) 0.6170(2) 0.044 Uiso 1 calc R . C64 C 0.1458(4) 0.5261(4) 0.5490(3) 0.0487(13) Uani 1 d . . H64 H 0.1372(4) 0.4810(4) 0.5769(3) 0.058 Uiso 1 calc R . C65 C 0.1045(4) 0.5150(4) 0.4833(3) 0.0493(13) Uani 1 d . . H65 H 0.0664(4) 0.4636(4) 0.4665(3) 0.059 Uiso 1 calc R . C66 C 0.1210(3) 0.5815(4) 0.4434(3) 0.0425(11) Uani 1 d . . H66 H 0.0952(3) 0.5726(4) 0.3992(3) 0.051 Uiso 1 calc R . N71 N 0.1774(2) 0.8644(3) 0.4588(2) 0.0300(7) Uani 1 d . . C72 C 0.2059(2) 0.8528(3) 0.5226(2) 0.0246(7) Uani 1 d . . C73 C 0.1813(3) 0.9172(3) 0.5608(2) 0.0334(9) Uani 1 d . . H73 H 0.2013(3) 0.9088(3) 0.6051(2) 0.040 Uiso 1 calc R . C74 C 0.1267(3) 0.9936(3) 0.5321(3) 0.0441(12) Uani 1 d . . H74 H 0.1103(3) 1.0375(3) 0.5571(3) 0.053 Uiso 1 calc R . C75 C 0.0968(3) 1.0045(3) 0.4663(3) 0.0443(12) Uani 1 d . . H75 H 0.0592(3) 1.0548(3) 0.4461(3) 0.053 Uiso 1 calc R . C76 C 0.1240(3) 0.9391(3) 0.4316(2) 0.0382(10) Uani 1 d . . H76 H 0.1047(3) 0.9466(3) 0.3873(2) 0.046 Uiso 1 calc R . C57 C 0.2653(3) 0.7660(3) 0.5526(2) 0.0248(8) Uani 1 d . . N58 N 0.2916(2) 0.7719(2) 0.6223(2) 0.0296(7) Uani 1 d D . H58A H 0.3315(23) 0.7300(27) 0.6410(20) 0.034(13) Uiso 1 d D . H58B H 0.3279(26) 0.8191(26) 0.6339(23) 0.043(15) Uiso 1 d D . O44 O 0.2250(2) 0.6325(3) 0.3527(2) 0.0439(8) Uani 1 d D . H44A H 0.2415(36) 0.6517(40) 0.3246(20) 0.052(18) Uiso 1 d D . O45 O 0.2314(3) 0.8491(3) 0.3392(2) 0.0483(9) Uani 1 d D . H45A H 0.1917(31) 0.8531(50) 0.3041(16) 0.075(23) Uiso 1 d D . H45B H 0.2800(28) 0.8572(81) 0.3383(49) 0.146(42) Uiso 1 d D . O46 O 0.0713(3) 0.7505(3) 0.3352(2) 0.0628(12) Uani 1 d D . H46A H 0.0278(23) 0.7807(37) 0.3325(28) 0.047(16) Uiso 1 d D . Zn3 Zn 0.34048(3) 0.33778(3) 0.24175(2) 0.03018(11) Uani 1 d . . O81 O 0.3096(2) 0.2408(3) 0.3028(2) 0.0427(8) Uani 1 d D . H81A H 0.2854(28) 0.2603(34) 0.3261(19) 0.029(13) Uiso 1 d D . O82 O 0.3690(2) 0.4343(2) 0.17737(15) 0.0342(6) Uani 1 d D . H82A H 0.4210(10) 0.4384(38) 0.1839(23) 0.037(14) Uiso 1 d D . O83 O 0.4314(2) 0.4190(3) 0.3201(2) 0.0405(7) Uani 1 d D . H83A H 0.4743(43) 0.4175(87) 0.3538(28) 0.172(48) Uiso 1 d D . H83B H 0.4280(41) 0.4781(10) 0.3235(29) 0.055(18) Uiso 1 d D . O84 O 0.4445(2) 0.2550(2) 0.2421(2) 0.0402(8) Uani 1 d D . H84A H 0.4939(12) 0.2741(28) 0.2620(16) 0.013(10) Uiso 1 d D . O85 O 0.2613(2) 0.2517(2) 0.1670(2) 0.0350(7) Uani 1 d D . H85A H 0.2083(8) 0.2562(52) 0.1505(29) 0.074(22) Uiso 1 d D . O86 O 0.2430(2) 0.4329(2) 0.2389(2) 0.0432(8) Uani 1 d D . H86A H 0.2047(30) 0.4210(51) 0.2526(29) 0.073(22) Uiso 1 d D . S9 S 0.10474(6) 0.06119(7) 0.25183(5) 0.0283(2) Uani 1 d . . O91 O 0.0877(2) 0.1175(3) 0.3022(2) 0.0460(8) Uani 1 d . . O92 O 0.1907(2) 0.0838(3) 0.2518(2) 0.0475(8) Uani 1 d . . O93 O 0.0375(2) 0.0853(3) 0.1890(2) 0.0462(8) Uani 1 d . . O94 O 0.0977(2) -0.0427(2) 0.2634(2) 0.0420(8) Uani 1 d . . S10 S 0.54369(7) 0.02264(8) 0.26237(5) 0.0325(2) Uani 1 d . . O101 O 0.4821(3) 0.0723(3) 0.2843(2) 0.0562(10) Uani 1 d . . O102 O 0.6325(3) 0.0385(3) 0.3075(2) 0.0628(11) Uani 1 d . . O103 O 0.5279(3) -0.0824(3) 0.2597(2) 0.0649(12) Uani 1 d . . O104 O 0.5318(4) 0.0528(4) 0.1985(2) 0.0799(14) Uani 1 d . . S11 S 0.35215(7) 0.66632(7) 0.25238(6) 0.0348(2) Uani 1 d . . O111 O 0.3660(3) 0.6356(3) 0.1945(2) 0.0610(11) Uani 1 d . . O112 O 0.3569(4) 0.7723(3) 0.2539(3) 0.060(2) Uani 0.729(7) d P . O113 O 0.2679(3) 0.6314(3) 0.2472(2) 0.0444(13) Uani 0.729(7) d P . O114 O 0.4205(3) 0.6284(4) 0.3085(2) 0.0493(14) Uani 0.729(7) d P . O115 O 0.3497(10) 0.5904(11) 0.3026(7) 0.059(4) Uiso 0.271(7) d P . O116 O 0.2701(14) 0.7217(15) 0.2423(9) 0.084(6) Uiso 0.271(7) d P . O117 O 0.4190(14) 0.7305(15) 0.3000(9) 0.083(6) Uiso 0.271(7) d P . O121 O 0.2536(3) 0.9356(3) 0.1929(2) 0.0663(11) Uani 1 d . . O122 O 0.3333(3) 1.0837(3) 0.1459(2) 0.0532(9) Uani 1 d D . H22A H 0.3179(38) 1.0693(44) 0.1766(19) 0.055(19) Uiso 1 d D . O123 O 0.3937(4) 0.9245(4) 0.3347(3) 0.0810(14) Uani 1 d D . H23A H 0.4376(29) 0.9041(55) 0.3301(35) 0.084(26) Uiso 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 Zn1 0.0307(2) 0.0261(2) 0.0264(2) 0.0021(2) 0.0110(2) 0.0036(2) N11 0.032(2) 0.019(2) 0.035(2) 0.0052(13) 0.0144(15) 0.0018(13) C12 0.023(2) 0.020(2) 0.033(2) 0.0025(15) 0.012(2) 0.0031(14) C13 0.035(2) 0.024(2) 0.034(2) 0.000(2) 0.007(2) 0.001(2) C14 0.045(3) 0.013(2) 0.059(3) -0.002(2) 0.014(2) -0.004(2) C15 0.044(3) 0.024(2) 0.057(3) 0.005(2) 0.022(2) -0.007(2) C16 0.048(3) 0.022(2) 0.037(2) 0.006(2) 0.020(2) -0.002(2) N21 0.028(2) 0.023(2) 0.031(2) -0.0005(13) 0.0122(14) 0.0006(13) C22 0.026(2) 0.015(2) 0.028(2) 0.0004(13) 0.0101(15) 0.0011(13) C23 0.037(2) 0.025(2) 0.041(2) 0.002(2) 0.022(2) 0.002(2) C24 0.031(2) 0.033(2) 0.056(3) 0.000(2) 0.023(2) -0.004(2) C25 0.030(2) 0.029(2) 0.053(3) -0.002(2) 0.017(2) 0.000(2) C26 0.026(2) 0.034(2) 0.035(2) -0.003(2) 0.004(2) 0.000(2) N31 0.036(2) 0.019(2) 0.032(2) 0.0027(13) 0.0171(15) 0.0057(13) C32 0.023(2) 0.013(2) 0.034(2) 0.0026(14) 0.010(2) 0.0011(13) C33 0.037(2) 0.028(2) 0.035(2) 0.005(2) 0.007(2) 0.002(2) C34 0.043(3) 0.021(2) 0.056(3) 0.008(2) 0.013(2) 0.014(2) C35 0.045(3) 0.023(2) 0.055(3) -0.004(2) 0.019(2) 0.011(2) C36 0.049(3) 0.024(2) 0.042(2) -0.003(2) 0.022(2) 0.006(2) C17 0.025(2) 0.020(2) 0.025(2) 0.0013(13) 0.0094(15) 0.0000(14) N18 0.031(2) 0.031(2) 0.0237(15) 0.0010(13) 0.0068(13) 0.0023(15) O41 0.063(3) 0.066(3) 0.037(2) -0.021(2) 0.011(2) -0.012(2) O42 0.037(2) 0.047(2) 0.050(2) 0.020(2) 0.013(2) 0.011(2) O43 0.052(2) 0.052(2) 0.042(2) 0.007(2) 0.026(2) 0.014(2) Zn2 0.0270(2) 0.0329(2) 0.0271(2) -0.0002(2) 0.0078(2) 0.0016(2) N51 0.026(2) 0.019(2) 0.033(2) 0.0002(13) 0.0116(14) -0.0005(12) C52 0.027(2) 0.012(2) 0.036(2) 0.0032(14) 0.012(2) 0.0002(14) C53 0.031(2) 0.032(2) 0.034(2) 0.002(2) 0.008(2) -0.006(2) C54 0.021(2) 0.036(2) 0.057(3) 0.006(2) 0.007(2) 0.000(2) C55 0.034(2) 0.033(2) 0.061(3) 0.008(2) 0.024(2) 0.001(2) C56 0.037(2) 0.027(2) 0.041(2) 0.003(2) 0.019(2) 0.001(2) N61 0.030(2) 0.025(2) 0.037(2) -0.0053(13) 0.0154(15) -0.0051(14) C62 0.026(2) 0.016(2) 0.033(2) 0.0012(14) 0.015(2) 0.0030(14) C63 0.045(3) 0.025(2) 0.044(2) 0.005(2) 0.021(2) 0.004(2) C64 0.059(3) 0.028(2) 0.070(4) 0.005(2) 0.038(3) -0.010(2) C65 0.051(3) 0.029(3) 0.074(4) -0.012(2) 0.031(3) -0.014(2) C66 0.039(2) 0.037(3) 0.055(3) -0.017(2) 0.022(2) -0.012(2) N71 0.031(2) 0.025(2) 0.032(2) 0.0040(13) 0.0084(14) 0.0070(14) C72 0.025(2) 0.016(2) 0.034(2) 0.0006(14) 0.013(2) -0.0001(14) C73 0.039(2) 0.025(2) 0.033(2) -0.001(2) 0.009(2) 0.006(2) C74 0.050(3) 0.024(2) 0.055(3) -0.004(2) 0.015(2) 0.011(2) C75 0.038(3) 0.029(2) 0.058(3) 0.012(2) 0.009(2) 0.013(2) C76 0.038(2) 0.030(2) 0.042(2) 0.011(2) 0.009(2) 0.010(2) C57 0.026(2) 0.018(2) 0.030(2) -0.0004(14) 0.010(2) 0.0026(14) N58 0.033(2) 0.026(2) 0.028(2) 0.0005(13) 0.0094(15) 0.0042(15) O44 0.046(2) 0.044(2) 0.046(2) -0.014(2) 0.023(2) -0.005(2) O45 0.041(2) 0.061(2) 0.041(2) 0.021(2) 0.013(2) 0.004(2) O46 0.039(2) 0.064(3) 0.060(2) -0.008(2) -0.012(2) 0.006(2) Zn3 0.0276(2) 0.0287(2) 0.0343(2) 0.0009(2) 0.0115(2) 0.0020(2) O81 0.048(2) 0.047(2) 0.039(2) 0.004(2) 0.023(2) -0.005(2) O82 0.035(2) 0.0301(15) 0.039(2) 0.0048(13) 0.0153(14) 0.0010(13) O83 0.043(2) 0.037(2) 0.037(2) -0.0044(14) 0.0094(15) -0.0006(15) O84 0.025(2) 0.029(2) 0.064(2) -0.002(2) 0.014(2) 0.0010(12) O85 0.029(2) 0.032(2) 0.040(2) -0.0035(13) 0.0080(14) -0.0009(13) O86 0.036(2) 0.036(2) 0.067(2) -0.002(2) 0.029(2) 0.0051(14) S9 0.0267(5) 0.0208(4) 0.0362(5) 0.0000(4) 0.0104(4) -0.0013(3) O91 0.040(2) 0.045(2) 0.055(2) -0.021(2) 0.020(2) -0.005(2) O92 0.036(2) 0.048(2) 0.066(2) -0.009(2) 0.027(2) -0.0106(15) O93 0.038(2) 0.049(2) 0.048(2) 0.018(2) 0.0118(15) 0.000(2) O94 0.050(2) 0.0199(14) 0.058(2) 0.0052(13) 0.021(2) 0.0027(13) S10 0.0317(5) 0.0281(5) 0.0365(6) -0.0032(4) 0.0112(4) 0.0040(4) O101 0.055(2) 0.035(2) 0.092(3) -0.003(2) 0.043(2) 0.011(2) O102 0.042(2) 0.051(2) 0.080(3) -0.020(2) 0.004(2) -0.002(2) O103 0.064(3) 0.025(2) 0.091(3) -0.018(2) 0.012(2) 0.003(2) O104 0.104(4) 0.083(3) 0.058(3) 0.013(2) 0.036(3) 0.009(3) S11 0.0312(5) 0.0226(5) 0.0491(6) 0.0000(4) 0.0129(5) 0.0005(4) O111 0.078(3) 0.043(2) 0.071(3) 0.004(2) 0.039(2) 0.000(2) O112 0.078(4) 0.016(2) 0.077(4) -0.006(2) 0.018(3) 0.003(2) O113 0.033(2) 0.043(3) 0.057(3) -0.003(2) 0.016(2) -0.006(2) O114 0.042(3) 0.046(3) 0.048(3) 0.001(2) 0.003(2) -0.002(2) O121 0.060(3) 0.066(3) 0.075(3) 0.012(2) 0.027(2) 0.003(2) O122 0.055(2) 0.041(2) 0.063(2) 0.003(2) 0.021(2) 0.006(2) O123 0.083(4) 0.074(3) 0.102(4) -0.005(3) 0.053(3) 0.000(3) _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 Zn1 O42 2.090(3) . ? Zn1 O41 2.094(4) . ? Zn1 N11 2.111(3) . ? Zn1 O43 2.112(4) . ? Zn1 N21 2.131(3) . ? Zn1 N31 2.137(3) . ? N11 C12 1.325(5) . ? N11 C16 1.347(5) . ? C12 C13 1.391(6) . ? C12 C17 1.551(5) . ? C13 C14 1.386(6) . ? C13 H13 0.93 . ? C14 C15 1.339(7) . ? C14 H14 0.93 . ? C15 C16 1.385(7) . ? C15 H15 0.93 . ? C16 H16 0.93 . ? N21 C26 1.338(5) . ? N21 C22 1.348(5) . ? C22 C23 1.379(6) . ? C22 C17 1.555(5) . ? C23 C24 1.393(7) . ? C23 H23 0.93 . ? C24 C25 1.357(7) . ? C24 H24 0.93 . ? C25 C26 1.379(7) . ? C25 H25 0.93 . ? C26 H26 0.93 . ? N31 C36 1.338(5) . ? N31 C32 1.350(5) . ? C32 C33 1.382(5) . ? C32 C17 1.546(5) . ? C33 C34 1.391(6) . ? C33 H33 0.93 . ? C34 C35 1.355(7) . ? C34 H34 0.93 . ? C35 C36 1.361(6) . ? C35 H35 0.93 . ? C36 H36 0.93 . ? C17 N18 1.462(5) . ? N18 H18A 0.858(10) . ? O41 H41A 0.821(10) . ? O42 H42A 0.814(10) . ? O43 H43A 0.817(10) . ? O43 H43B 0.822(10) . ? Zn2 O46 2.094(4) . ? Zn2 O45 2.095(4) . ? Zn2 O44 2.099(3) . ? Zn2 N51 2.118(3) . ? Zn2 N61 2.135(3) . ? Zn2 N71 2.139(4) . ? N51 C56 1.338(6) . ? N51 C52 1.346(5) . ? C52 C53 1.379(6) . ? C52 C57 1.555(6) . ? C53 C54 1.401(7) . ? C53 H53 0.93 . ? C54 C55 1.378(7) . ? C54 H54 0.93 . ? C55 C56 1.380(6) . ? C55 H55 0.93 . ? C56 H56 0.93 . ? N61 C66 1.343(6) . ? N61 C62 1.346(5) . ? C62 C63 1.395(6) . ? C62 C57 1.561(5) . ? C63 C64 1.384(7) . ? C63 H63 0.93 . ? C64 C65 1.383(8) . ? C64 H64 0.93 . ? C65 C66 1.377(7) . ? C65 H65 0.93 . ? C66 H66 0.93 . ? N71 C72 1.338(5) . ? N71 C76 1.347(5) . ? C72 C73 1.394(6) . ? C72 C57 1.538(5) . ? C73 C74 1.382(6) . ? C73 H73 0.93 . ? C74 C75 1.379(7) . ? C74 H74 0.93 . ? C75 C76 1.371(7) . ? C75 H75 0.93 . ? C76 H76 0.93 . ? C57 N58 1.461(5) . ? N58 H58A 0.861(10) . ? N58 H58B 0.858(10) . ? O44 H44A 0.817(10) . ? O45 H45A 0.819(10) . ? O45 H45B 0.819(10) . ? O46 H46A 0.815(10) . ? Zn3 O86 2.060(3) . ? Zn3 O84 2.063(3) . ? Zn3 O85 2.076(3) . ? Zn3 O81 2.106(3) . ? Zn3 O82 2.140(3) . ? Zn3 O83 2.156(3) . ? O81 H81A 0.813(10) . ? O82 H82A 0.818(10) . ? O83 H83A 0.824(10) . ? O83 H83B 0.821(10) . ? O84 H84A 0.816(10) . ? O85 H85A 0.819(10) . ? O86 H86A 0.817(10) . ? S9 O92 1.454(3) . ? S9 O94 1.469(3) . ? S9 O93 1.475(3) . ? S9 O91 1.479(3) . ? S10 O104 1.432(4) . ? S10 O101 1.455(4) . ? S10 O102 1.459(4) . ? S10 O103 1.470(4) . ? S11 O113 1.437(5) . ? S11 O114 1.442(5) . ? S11 O111 1.461(4) . ? S11 O112 1.464(4) . ? S11 O116 1.50(2) . ? S11 O117 1.51(2) . ? S11 O115 1.55(2) . ? O112 O117 1.29(2) . ? O112 O116 1.53(2) . ? O113 O116 1.25(2) . ? O113 O115 1.57(2) . ? O114 O115 1.24(2) . ? O114 O117 1.42(2) . ? O122 H22A 0.840(10) . ? O123 H23A 0.820(10) . ? 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 O42 Zn1 O41 91.4(2) . . ? O42 Zn1 N11 92.46(14) . . ? O41 Zn1 N11 176.10(15) . . ? O42 Zn1 O43 87.79(14) . . ? O41 Zn1 O43 89.2(2) . . ? N11 Zn1 O43 91.27(15) . . ? O42 Zn1 N21 92.15(13) . . ? O41 Zn1 N21 93.5(2) . . ? N11 Zn1 N21 86.02(13) . . ? O43 Zn1 N21 177.28(14) . . ? O42 Zn1 N31 174.72(14) . . ? O41 Zn1 N31 92.3(2) . . ? N11 Zn1 N31 83.83(13) . . ? O43 Zn1 N31 96.03(14) . . ? N21 Zn1 N31 83.86(13) . . ? C12 N11 C16 119.1(4) . . ? C12 N11 Zn1 121.1(3) . . ? C16 N11 Zn1 119.7(3) . . ? N11 C12 C13 120.9(4) . . ? N11 C12 C17 118.2(3) . . ? C13 C12 C17 120.8(3) . . ? C14 C13 C12 119.0(4) . . ? C14 C13 H13 120.5(3) . . ? C12 C13 H13 120.5(2) . . ? C15 C14 C13 120.0(4) . . ? C15 C14 H14 120.0(3) . . ? C13 C14 H14 120.0(3) . . ? C14 C15 C16 118.6(4) . . ? C14 C15 H15 120.7(3) . . ? C16 C15 H15 120.7(3) . . ? N11 C16 C15 122.3(4) . . ? N11 C16 H16 118.9(2) . . ? C15 C16 H16 118.9(3) . . ? C26 N21 C22 118.7(4) . . ? C26 N21 Zn1 120.6(3) . . ? C22 N21 Zn1 120.6(3) . . ? N21 C22 C23 120.7(4) . . ? N21 C22 C17 117.3(3) . . ? C23 C22 C17 121.9(3) . . ? C22 C23 C24 119.3(4) . . ? C22 C23 H23 120.4(3) . . ? C24 C23 H23 120.4(3) . . ? C25 C24 C23 120.0(4) . . ? C25 C24 H24 120.0(3) . . ? C23 C24 H24 120.0(3) . . ? C24 C25 C26 117.8(4) . . ? C24 C25 H25 121.1(3) . . ? C26 C25 H25 121.1(3) . . ? N21 C26 C25 123.4(4) . . ? N21 C26 H26 118.3(2) . . ? C25 C26 H26 118.3(3) . . ? C36 N31 C32 118.7(3) . . ? C36 N31 Zn1 120.2(3) . . ? C32 N31 Zn1 121.0(2) . . ? N31 C32 C33 120.7(4) . . ? N31 C32 C17 116.7(3) . . ? C33 C32 C17 122.5(4) . . ? C32 C33 C34 118.9(4) . . ? C32 C33 H33 120.5(3) . . ? C34 C33 H33 120.5(3) . . ? C35 C34 C33 119.8(4) . . ? C35 C34 H34 120.1(3) . . ? C33 C34 H34 120.1(3) . . ? C34 C35 C36 118.7(4) . . ? C34 C35 H35 120.7(3) . . ? C36 C35 H35 120.7(3) . . ? N31 C36 C35 123.2(4) . . ? N31 C36 H36 118.4(2) . . ? C35 C36 H36 118.4(3) . . ? N18 C17 C32 107.8(3) . . ? N18 C17 C12 107.8(3) . . ? C32 C17 C12 109.9(3) . . ? N18 C17 C22 112.4(3) . . ? C32 C17 C22 107.6(3) . . ? C12 C17 C22 111.3(3) . . ? C17 N18 H18A 106.8(37) . . ? Zn1 O41 H41A 110.7(62) . . ? Zn1 O42 H42A 113.0(37) . . ? Zn1 O43 H43A 120.5(49) . . ? Zn1 O43 H43B 113.8(38) . . ? H43A O43 H43B 117.2(59) . . ? O46 Zn2 O45 89.4(2) . . ? O46 Zn2 O44 88.3(2) . . ? O45 Zn2 O44 91.6(2) . . ? O46 Zn2 N51 177.9(2) . . ? O45 Zn2 N51 92.59(14) . . ? O44 Zn2 N51 92.17(13) . . ? O46 Zn2 N61 92.5(2) . . ? O45 Zn2 N61 177.70(15) . . ? O44 Zn2 N61 89.59(14) . . ? N51 Zn2 N61 85.43(13) . . ? O46 Zn2 N71 94.3(2) . . ? O45 Zn2 N71 95.3(2) . . ? O44 Zn2 N71 172.61(14) . . ? N51 Zn2 N71 85.05(13) . . ? N61 Zn2 N71 83.37(13) . . ? C56 N51 C52 118.9(4) . . ? C56 N51 Zn2 120.3(3) . . ? C52 N51 Zn2 120.8(3) . . ? N51 C52 C53 121.4(4) . . ? N51 C52 C57 117.5(3) . . ? C53 C52 C57 121.0(4) . . ? C52 C53 C54 119.2(4) . . ? C52 C53 H53 120.4(3) . . ? C54 C53 H53 120.4(3) . . ? C55 C54 C53 119.1(4) . . ? C55 C54 H54 120.5(3) . . ? C53 C54 H54 120.5(3) . . ? C54 C55 C56 118.3(4) . . ? C54 C55 H55 120.9(3) . . ? C56 C55 H55 120.9(3) . . ? N51 C56 C55 123.1(4) . . ? N51 C56 H56 118.4(2) . . ? C55 C56 H56 118.4(3) . . ? C66 N61 C62 118.8(4) . . ? C66 N61 Zn2 119.9(3) . . ? C62 N61 Zn2 121.1(3) . . ? N61 C62 C63 121.8(4) . . ? N61 C62 C57 116.4(3) . . ? C63 C62 C57 121.8(4) . . ? C64 C63 C62 118.4(4) . . ? C64 C63 H63 120.8(3) . . ? C62 C63 H63 120.8(3) . . ? C65 C64 C63 119.7(4) . . ? C65 C64 H64 120.2(3) . . ? C63 C64 H64 120.2(3) . . ? C66 C65 C64 118.6(5) . . ? C66 C65 H65 120.7(3) . . ? C64 C65 H65 120.7(3) . . ? N61 C66 C65 122.6(5) . . ? N61 C66 H66 118.7(3) . . ? C65 C66 H66 118.7(3) . . ? C72 N71 C76 119.2(4) . . ? C72 N71 Zn2 119.8(3) . . ? C76 N71 Zn2 120.3(3) . . ? N71 C72 C73 120.8(4) . . ? N71 C72 C57 118.4(3) . . ? C73 C72 C57 120.8(4) . . ? C74 C73 C72 119.3(4) . . ? C74 C73 H73 120.4(3) . . ? C72 C73 H73 120.4(2) . . ? C75 C74 C73 119.7(4) . . ? C75 C74 H74 120.2(3) . . ? C73 C74 H74 120.2(3) . . ? C76 C75 C74 118.1(4) . . ? C76 C75 H75 120.9(3) . . ? C74 C75 H75 120.9(3) . . ? N71 C76 C75 122.9(4) . . ? N71 C76 H76 118.6(3) . . ? C75 C76 H76 118.6(3) . . ? N58 C57 C72 108.3(3) . . ? N58 C57 C52 111.9(3) . . ? C72 C57 C52 111.3(3) . . ? N58 C57 C62 107.9(3) . . ? C72 C57 C62 108.1(3) . . ? C52 C57 C62 109.3(3) . . ? C57 N58 H58A 110.9(31) . . ? C57 N58 H58B 105.5(33) . . ? H58A N58 H58B 92.1(46) . . ? Zn2 O44 H44A 108.4(42) . . ? Zn2 O45 H45A 111.5(50) . . ? Zn2 O45 H45B 125.5(76) . . ? H45A O45 H45B 114.4(83) . . ? Zn2 O46 H46A 133.5(43) . . ? O86 Zn3 O84 173.86(14) . . ? O86 Zn3 O85 94.91(14) . . ? O84 Zn3 O85 87.90(13) . . ? O86 Zn3 O81 92.87(15) . . ? O84 Zn3 O81 92.77(14) . . ? O85 Zn3 O81 85.91(14) . . ? O86 Zn3 O82 86.99(13) . . ? O84 Zn3 O82 87.44(13) . . ? O85 Zn3 O82 92.44(12) . . ? O81 Zn3 O82 178.32(13) . . ? O86 Zn3 O83 89.82(14) . . ? O84 Zn3 O83 87.41(14) . . ? O85 Zn3 O83 175.27(13) . . ? O81 Zn3 O83 93.70(14) . . ? O82 Zn3 O83 87.97(13) . . ? Zn3 O81 H81A 120.2(36) . . ? Zn3 O82 H82A 113.6(37) . . ? Zn3 O83 H83A 147.0(84) . . ? Zn3 O83 H83B 122.7(44) . . ? H83A O83 H83B 90.3(84) . . ? Zn3 O84 H84A 119.2(29) . . ? Zn3 O85 H85A 124.9(49) . . ? Zn3 O86 H86A 124.5(51) . . ? O92 S9 O94 110.5(2) . . ? O92 S9 O93 110.2(2) . . ? O94 S9 O93 107.9(2) . . ? O92 S9 O91 110.4(2) . . ? O94 S9 O91 109.1(2) . . ? O93 S9 O91 108.7(2) . . ? O104 S10 O101 110.2(3) . . ? O104 S10 O102 112.4(3) . . ? O101 S10 O102 110.3(3) . . ? O104 S10 O103 106.8(3) . . ? O101 S10 O103 110.0(2) . . ? O102 S10 O103 107.1(2) . . ? O113 S11 O114 111.9(3) . . ? O113 S11 O111 107.2(3) . . ? O114 S11 O111 109.9(3) . . ? O113 S11 O112 112.2(3) . . ? O114 S11 O112 108.9(3) . . ? O111 S11 O112 106.6(3) . . ? O113 S11 O116 50.4(8) . . ? O114 S11 O116 133.6(8) . . ? O111 S11 O116 116.3(8) . . ? O112 S11 O116 62.2(8) . . ? O113 S11 O117 133.6(8) . . ? O114 S11 O117 57.5(8) . . ? O111 S11 O117 119.0(8) . . ? O112 S11 O117 51.6(8) . . ? O116 S11 O117 101.2(11) . . ? O113 S11 O115 63.1(6) . . ? O114 S11 O115 49.0(6) . . ? O111 S11 O115 120.3(6) . . ? O112 S11 O115 132.4(6) . . ? O116 S11 O115 100.8(10) . . ? O117 S11 O115 95.2(9) . . ? O117 O112 S11 66.0(9) . . ? O117 O112 O116 110.5(13) . . ? S11 O112 O116 60.1(8) . . ? O116 O113 S11 67.5(10) . . ? O116 O113 O115 112.6(12) . . ? S11 O113 O115 61.9(6) . . ? O115 O114 O117 115.7(12) . . ? O115 O114 S11 69.9(7) . . ? O117 O114 S11 63.6(8) . . ? O114 O115 S11 61.0(7) . . ? O114 O115 O113 115.7(11) . . ? S11 O115 O113 54.9(5) . . ? O113 O116 S11 62.2(9) . . ? O113 O116 O112 119.6(15) . . ? S11 O116 O112 57.7(8) . . ? O112 O117 O114 121.2(15) . . ? O112 O117 S11 62.5(9) . . ? O114 O117 S11 59.0(8) . . ? _refine_diff_density_max 1.021 _refine_diff_density_min -0.734 _refine_diff_density_rms 0.108 #===END