# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2007 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 #============================================================================== _publ_contact_author_name 'Professor Guo-Yu Yang' _publ_contact_author_address ; State Key Laboratory of The Structural Chemistry Fujian Institute of Research on the structure of matter Chinese Academy of Sciences Fuzhou, Fujian 350002 P. R. China ; _publ_contact_author_email ygy@fjirsm.ac.cn _publ_contact_author_fax '86 591 83710051' _publ_contact_author_phone '86 591 83710051' _publ_requested_coeditor_name ? #============================================================================ #============================================================================ # TITLE AND AUTHOR LIST _publ_section_title ; First (3,6)-connected framework constructed from sandwich-type polyoxometalate building blocks containing novel octa-copper cluster ; _publ_section_title_footnote ; ? ; loop_ _publ_author_name _publ_author_address 'Jun-Wei Zhao' ; State Key Laboratory of The Structural Chemistry Fujian Institute of Research on the structure of matter Chinese Academy of Sciences Fuzhou, Fujian 350002 P. R. China ; 'Jie Zhang' ; State Key Laboratory of The Structural Chemistry Fujian Institute of Research on the structure of matter Chinese Academy of Sciences Fuzhou, Fujian 350002 P. R. China ; 'Shou-Tian Zheng' ; State Key Laboratory of The Structural Chemistry Fujian Institute of Research on the structure of matter Chinese Academy of Sciences Fuzhou, Fujian 350002 P. R. China ; 'Guo-Yu Yang' ; State Key Laboratory of The Structural Chemistry Fujian Institute of Research on the structure of matter Chinese Academy of Sciences Fuzhou, Fujian 350002 P. R. China ; #============================================================================ data_q _database_code_depnum_ccdc_archive 'CCDC 644937' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C12 H50 Cu9 Ge2 N8 O72 W18' _chemical_formula_weight 5484.94 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' Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ge Ge 0.1547 1.8001 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' W W -0.8490 6.8722 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting tetragonal _symmetry_space_group_name_H-M P4(2)/ncm loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y+1/2, z' '-y+1/2, x, z+1/2' 'y, -x+1/2, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y, -z+1/2' 'y+1/2, x+1/2, -z' '-y, -x, -z' '-x, -y, -z' 'x-1/2, y-1/2, -z' 'y-1/2, -x, -z-1/2' '-y, x-1/2, -z-1/2' 'x, -y-1/2, z-1/2' '-x-1/2, y, z-1/2' '-y-1/2, -x-1/2, z' 'y, x, z' _cell_length_a 21.6769(2) _cell_length_b 21.6769(2) _cell_length_c 18.8529(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 8858.75(18) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 273 _cell_measurement_theta_min 2.54 _cell_measurement_theta_max 25.63 _exptl_crystal_description ployhedron _exptl_crystal_colour 'dark green' _exptl_crystal_size_max 0.17 _exptl_crystal_size_mid 0.11 _exptl_crystal_size_min 0.07 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 4.113 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 9644 _exptl_absorpt_coefficient_mu 26.137 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.0555 _exptl_absorpt_correction_T_max 0.1751 _exptl_absorpt_process_details 'SADABS (Sheldrick, 1996)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Siemens Smart 1K' _diffrn_measurement_method CCD_Profile_fitting _diffrn_detector_area_resol_mean ? _diffrn_standards_number none _diffrn_standards_interval_count none _diffrn_standards_interval_time none _diffrn_standards_decay_% none _diffrn_reflns_number 44138 _diffrn_reflns_av_R_equivalents 0.0763 _diffrn_reflns_av_sigmaI/netI 0.0299 _diffrn_reflns_limit_h_min -26 _diffrn_reflns_limit_h_max 26 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 26 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 2.54 _diffrn_reflns_theta_max 25.63 _reflns_number_total 4235 _reflns_number_gt 3404 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Siemens SMART' _computing_cell_refinement 'Siemens SMART' _computing_data_reduction 'Siemens SMART' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'PLATON (Spek, 2003)' _computing_publication_material 'PLATON (Spek, 2003)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0182P)^2^+185.1553P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.000090(5) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 4235 _refine_ls_number_parameters 299 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0511 _refine_ls_R_factor_gt 0.0308 _refine_ls_wR_factor_ref 0.0681 _refine_ls_wR_factor_gt 0.0596 _refine_ls_goodness_of_fit_ref 1.121 _refine_ls_restrained_S_all 1.121 _refine_ls_shift/su_max 0.004 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group W1 W 0.21120(2) 0.41100(2) 0.18327(2) 0.02309(12) Uani 1 1 d . . . W2 W 0.184858(19) 0.43593(2) 0.00762(2) 0.01970(11) Uani 1 1 d . . . W3 W 0.174919(19) 0.55385(2) 0.12522(2) 0.02081(12) Uani 1 1 d . . . W4 W 0.04665(2) 0.56256(2) 0.25894(2) 0.02141(12) Uani 1 1 d . . . W5 W 0.08154(2) 0.41846(2) 0.31308(3) 0.02320(16) Uani 1 2 d S . . Ge Ge 0.05400(5) 0.44600(5) 0.12467(7) 0.0137(3) Uani 1 2 d S . . Cu1 Cu 0.05693(6) 0.64862(6) 0.11887(7) 0.0223(3) Uani 1 1 d . . . Cu2 Cu -0.06054(6) 0.56054(6) 0.11424(9) 0.0162(4) Uani 1 2 d S . . Cu3 Cu 0.04960(5) 0.54960(5) 0.0000 0.0144(3) Uani 1 2 d S . . Cu4 Cu 0.15937(19) 0.34063(19) 0.4550(3) 0.0641(16) Uani 0.50 2 d SP . . O1 O 0.2756(4) 0.3865(4) 0.2278(5) 0.042(2) Uani 1 1 d . . . O2 O 0.1565(3) 0.4284(3) 0.2615(4) 0.0247(17) Uani 1 1 d . . . O3 O 0.2280(3) 0.4981(3) 0.1785(4) 0.0247(17) Uani 1 1 d . . . O4 O 0.1334(3) 0.4578(3) 0.1125(3) 0.0163(15) Uani 1 1 d . . . O5 O 0.1638(3) 0.3362(3) 0.1737(5) 0.023(2) Uani 1 2 d S . . O6 O 0.2367(3) 0.4029(4) 0.0877(4) 0.0259(17) Uani 1 1 d . . . O7 O 0.2393(3) 0.4205(4) -0.0566(4) 0.0319(19) Uani 1 1 d . . . O8 O 0.1406(3) 0.3594(3) 0.0125(6) 0.023(2) Uani 1 2 d S . . O9 O 0.1217(3) 0.4711(3) -0.0429(4) 0.0205(16) Uani 1 1 d . . . O10 O 0.2117(3) 0.5170(3) 0.0402(4) 0.0230(16) Uani 1 1 d . . . O11 O 0.2181(4) 0.6200(4) 0.1287(4) 0.0311(19) Uani 1 1 d . . . O12 O 0.1058(3) 0.5806(3) 0.0725(4) 0.0193(15) Uani 1 1 d . . . O13 O 0.1249(3) 0.5623(3) 0.2097(4) 0.0232(17) Uani 1 1 d . . . O14 O -0.0330(3) 0.5330(3) 0.2917(5) 0.023(2) Uani 1 2 d S . . O15 O 0.0531(4) 0.6303(4) 0.3054(4) 0.035(2) Uani 1 1 d . . . O16 O 0.0091(3) 0.5872(3) 0.1748(4) 0.0204(16) Uani 1 1 d . . . O17 O 0.0365(3) 0.4635(3) 0.2126(5) 0.018(2) Uani 1 2 d S . . O18 O -0.0060(3) 0.4188(3) 0.3295(4) 0.0230(17) Uani 1 1 d . . . O19 O 0.1073(4) 0.3927(4) 0.3950(5) 0.030(3) Uani 1 2 d S . . O20 O 0.0111(3) 0.4889(3) 0.0637(5) 0.014(2) Uani 1 2 d S . . O1W O -0.1277(4) 0.6277(4) 0.1680(7) 0.039(3) Uani 1 2 d S . . O2W O 0.1986(13) 0.3014(13) 0.366(2) 0.034(11) Uiso 0.50 2 d SP . . O3W O 0.1339(10) 0.3661(10) 0.5439(16) 0.033(7) Uiso 0.50 2 d SP . . N1 N 0.0179(5) 0.7190(5) 0.1701(5) 0.037(3) Uani 1 1 d . . . H1A H -0.0231 0.7186 0.1623 0.044 Uiso 1 1 calc R . . H1B H 0.0243 0.7147 0.2170 0.044 Uiso 1 1 calc R . . N2 N 0.1123(5) 0.7120(4) 0.0788(6) 0.035(2) Uani 1 1 d . . . H2A H 0.1511 0.6974 0.0761 0.041 Uiso 1 1 calc R . . H2B H 0.0999 0.7225 0.0349 0.041 Uiso 1 1 calc R . . C1 C 0.0435(8) 0.7780(6) 0.1463(8) 0.049(4) Uani 1 1 d . . . H1C H 0.0401 0.8085 0.1837 0.058 Uiso 1 1 calc R . . H1D H 0.0209 0.7928 0.1052 0.058 Uiso 1 1 calc R . . C2 C 0.1101(8) 0.7677(6) 0.1274(9) 0.056(4) Uani 1 1 d D . . C3 C 0.142(6) 0.823(4) 0.101(7) 0.09(4) Uiso 0.15 1 d PD . . H3A H 0.1839 0.8125 0.0882 0.132 Uiso 0.15 1 calc PR . . H3B H 0.1434 0.8539 0.1380 0.132 Uiso 0.15 1 calc PR . . H3C H 0.1212 0.8393 0.0607 0.132 Uiso 0.15 1 calc PR . . C3' C 0.1487(9) 0.7564(11) 0.1923(11) 0.070(6) Uani 0.85 1 d P . . H3'A H 0.1908 0.7494 0.1785 0.105 Uiso 0.85 1 calc PR . . H3'B H 0.1335 0.7208 0.2170 0.105 Uiso 0.85 1 calc PR . . H3'C H 0.1467 0.7917 0.2230 0.105 Uiso 0.85 1 calc PR . . 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 W1 0.0190(2) 0.0299(3) 0.0203(2) 0.00297(19) -0.00573(18) 0.00498(18) W2 0.0164(2) 0.0254(2) 0.0172(2) 0.00051(17) 0.00078(17) 0.00567(17) W3 0.0170(2) 0.0229(2) 0.0225(2) -0.00086(18) -0.00432(17) -0.00076(17) W4 0.0276(2) 0.0229(2) 0.0138(2) -0.00289(17) -0.00315(17) 0.00035(18) W5 0.0284(2) 0.0284(2) 0.0129(3) 0.00359(18) -0.00359(18) 0.0023(3) Ge 0.0149(4) 0.0149(4) 0.0115(7) 0.0007(4) -0.0007(4) 0.0020(6) Cu1 0.0265(7) 0.0191(7) 0.0214(7) -0.0039(5) 0.0014(6) -0.0007(5) Cu2 0.0174(5) 0.0174(5) 0.0138(8) 0.0007(5) -0.0007(5) 0.0013(7) Cu3 0.0160(5) 0.0160(5) 0.0114(8) 0.0002(5) -0.0002(5) -0.0003(7) Cu4 0.075(3) 0.075(3) 0.043(3) 0.0016(18) -0.0016(18) 0.0023(3) O1 0.035(5) 0.049(6) 0.041(5) 0.007(4) -0.019(4) 0.009(4) O2 0.031(4) 0.030(4) 0.012(3) 0.000(3) -0.007(3) 0.005(3) O3 0.017(4) 0.028(4) 0.029(4) 0.001(3) -0.006(3) -0.001(3) O4 0.014(3) 0.017(4) 0.018(4) -0.005(3) -0.001(3) 0.004(3) O5 0.027(4) 0.027(4) 0.016(5) -0.001(3) 0.001(3) 0.008(5) O6 0.019(4) 0.029(4) 0.029(4) 0.001(3) 0.000(3) 0.005(3) O7 0.017(4) 0.039(5) 0.039(5) 0.003(4) 0.011(4) 0.008(3) O8 0.021(3) 0.021(3) 0.027(6) -0.003(3) 0.003(3) 0.003(4) O9 0.016(4) 0.023(4) 0.022(4) -0.002(3) 0.001(3) 0.000(3) O10 0.019(4) 0.024(4) 0.026(4) -0.007(3) -0.006(3) -0.004(3) O11 0.024(4) 0.033(5) 0.037(5) -0.005(4) -0.003(4) -0.007(4) O12 0.021(4) 0.019(4) 0.018(4) 0.000(3) 0.003(3) 0.004(3) O13 0.026(4) 0.029(4) 0.015(3) -0.003(3) -0.007(3) -0.001(3) O14 0.029(4) 0.029(4) 0.011(5) 0.000(3) 0.000(3) -0.002(5) O15 0.051(6) 0.028(5) 0.026(4) -0.013(4) -0.004(4) 0.002(4) O16 0.024(4) 0.019(4) 0.018(4) 0.000(3) -0.002(3) 0.001(3) O17 0.020(3) 0.020(3) 0.015(5) -0.001(3) 0.001(3) 0.004(4) O18 0.028(4) 0.029(4) 0.012(4) 0.003(3) 0.004(3) -0.002(3) O19 0.036(4) 0.036(4) 0.018(5) 0.009(3) -0.009(3) 0.004(5) O20 0.017(3) 0.017(3) 0.008(5) 0.005(3) -0.005(3) 0.006(4) O1W 0.036(4) 0.036(4) 0.044(8) -0.015(4) 0.015(4) 0.004(6) N1 0.047(7) 0.032(6) 0.031(6) -0.009(5) 0.002(5) 0.007(5) N2 0.038(6) 0.028(6) 0.038(6) -0.008(5) -0.002(5) -0.006(5) C1 0.081(11) 0.027(7) 0.037(7) -0.015(6) 0.004(7) -0.002(7) C2 0.060(10) 0.031(8) 0.077(11) -0.020(8) 0.003(9) -0.018(7) C3' 0.042(11) 0.094(16) 0.074(14) -0.021(12) -0.026(10) -0.013(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 W1 O1 1.714(8) . ? W1 O6 1.893(7) . ? W1 O3 1.925(7) . ? W1 O5 1.928(2) . ? W1 O2 1.930(7) . ? W1 O4 2.378(6) . ? W2 O7 1.724(7) . ? W2 O9 1.834(7) . ? W2 O8 1.918(3) . ? W2 O10 1.951(7) . ? W2 O6 2.014(7) . ? W2 O4 2.318(6) . ? W3 O11 1.714(8) . ? W3 O12 1.889(7) . ? W3 O13 1.936(7) . ? W3 O3 1.947(7) . ? W3 O10 1.961(7) . ? W3 O4 2.280(7) . ? W4 O15 1.716(7) . ? W4 O16 1.861(7) . ? W4 O13 1.933(7) . ? W4 O14 1.943(5) . ? W4 O18 1.958(7) 15_665 ? W4 O17 2.328(7) . ? W5 O19 1.735(10) . ? W5 O2 1.905(8) 15_665 ? W5 O2 1.905(8) . ? W5 O18 1.923(7) . ? W5 O18 1.923(7) 15_665 ? W5 O17 2.344(9) . ? Ge O17 1.744(9) . ? Ge O20 1.747(8) . ? Ge O4 1.756(7) 15_665 ? Ge O4 1.756(7) . ? Cu1 N2 1.975(10) . ? Cu1 O16 1.990(7) . ? Cu1 N1 1.993(10) . ? Cu1 O12 2.015(7) . ? Cu1 O9 2.418(7) 7_455 ? Cu2 O16 1.979(7) 15_665 ? Cu2 O16 1.979(7) . ? Cu2 O9 2.010(7) 9_565 ? Cu2 O9 2.010(7) 7_455 ? Cu2 O1W 2.296(11) . ? Cu2 O20 2.392(9) . ? Cu3 O12 1.951(7) . ? Cu3 O12 1.951(7) 7_455 ? Cu3 O20 1.967(6) 9_565 ? Cu3 O20 1.967(6) . ? Cu3 Cu3 3.041(3) 9_565 ? Cu4 O3W 1.85(3) . ? Cu4 O19 1.957(12) . ? Cu4 O2W 2.07(4) . ? O5 W1 1.928(2) 15_665 ? O8 W2 1.918(3) 15_665 ? O9 Cu2 2.010(7) 9_565 ? O9 Cu1 2.418(7) 7_455 ? O14 W4 1.943(5) 15_665 ? O17 W4 2.328(7) 15_665 ? O18 W4 1.958(7) 15_665 ? O20 Cu3 1.967(6) 9_565 ? N1 C1 1.464(17) . ? N1 H1A 0.9000 . ? N1 H1B 0.9000 . ? N2 C2 1.516(17) . ? N2 H2A 0.9000 . ? N2 H2B 0.9000 . ? C1 C2 1.50(2) . ? C1 H1C 0.9700 . ? C1 H1D 0.9700 . ? C2 C3 1.479(10) . ? C2 C3' 1.50(2) . ? C3 H3A 0.9600 . ? C3 H3B 0.9600 . ? C3 H3C 0.9600 . ? C3' H3'A 0.9600 . ? C3' H3'B 0.9600 . ? C3' H3'C 0.9600 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 W1 O6 101.5(4) . . ? O1 W1 O3 100.0(4) . . ? O6 W1 O3 89.5(3) . . ? O1 W1 O5 102.7(4) . . ? O6 W1 O5 89.3(4) . . ? O3 W1 O5 157.1(4) . . ? O1 W1 O2 100.8(4) . . ? O6 W1 O2 157.7(3) . . ? O3 W1 O2 87.7(3) . . ? O5 W1 O2 84.8(4) . . ? O1 W1 O4 170.1(4) . . ? O6 W1 O4 73.3(3) . . ? O3 W1 O4 71.9(3) . . ? O5 W1 O4 85.9(3) . . ? O2 W1 O4 84.8(3) . . ? O7 W2 O9 103.1(3) . . ? O7 W2 O8 102.0(4) . . ? O9 W2 O8 90.6(4) . . ? O7 W2 O10 101.0(4) . . ? O9 W2 O10 90.6(3) . . ? O8 W2 O10 156.0(4) . . ? O7 W2 O6 94.3(3) . . ? O9 W2 O6 162.6(3) . . ? O8 W2 O6 86.4(4) . . ? O10 W2 O6 85.3(3) . . ? O7 W2 O4 165.4(3) . . ? O9 W2 O4 90.0(3) . . ? O8 W2 O4 84.0(3) . . ? O10 W2 O4 72.0(3) . . ? O6 W2 O4 72.7(3) . . ? O11 W3 O12 101.3(3) . . ? O11 W3 O13 101.2(3) . . ? O12 W3 O13 87.6(3) . . ? O11 W3 O3 100.2(3) . . ? O12 W3 O3 158.5(3) . . ? O13 W3 O3 88.0(3) . . ? O11 W3 O10 98.6(3) . . ? O12 W3 O10 91.0(3) . . ? O13 W3 O10 160.0(3) . . ? O3 W3 O10 85.9(3) . . ? O11 W3 O4 169.6(3) . . ? O12 W3 O4 84.9(3) . . ? O13 W3 O4 87.3(3) . . ? O3 W3 O4 73.8(3) . . ? O10 W3 O4 72.7(3) . . ? O15 W4 O16 103.0(3) . . ? O15 W4 O13 100.1(4) . . ? O16 W4 O13 88.6(3) . . ? O15 W4 O14 101.1(4) . . ? O16 W4 O14 88.6(4) . . ? O13 W4 O14 158.7(3) . . ? O15 W4 O18 99.1(3) . 15_665 ? O16 W4 O18 157.9(3) . 15_665 ? O13 W4 O18 89.4(3) . 15_665 ? O14 W4 O18 85.3(4) . 15_665 ? O15 W4 O17 171.3(4) . . ? O16 W4 O17 84.5(3) . . ? O13 W4 O17 84.3(3) . . ? O14 W4 O17 74.4(3) . . ? O18 W4 O17 73.4(3) 15_665 . ? O19 W5 O2 102.5(3) . 15_665 ? O19 W5 O2 102.5(3) . . ? O2 W5 O2 86.1(4) 15_665 . ? O19 W5 O18 100.1(3) . . ? O2 W5 O18 88.5(3) 15_665 . ? O2 W5 O18 157.4(3) . . ? O19 W5 O18 100.1(3) . 15_665 ? O2 W5 O18 157.4(3) 15_665 15_665 ? O2 W5 O18 88.5(3) . 15_665 ? O18 W5 O18 88.1(4) . 15_665 ? O19 W5 O17 170.9(5) . . ? O2 W5 O17 84.0(3) 15_665 . ? O2 W5 O17 84.0(3) . . ? O18 W5 O17 73.6(3) . . ? O18 W5 O17 73.6(3) 15_665 . ? O17 Ge O20 113.1(4) . . ? O17 Ge O4 107.9(3) . 15_665 ? O20 Ge O4 111.0(3) . 15_665 ? O17 Ge O4 107.9(3) . . ? O20 Ge O4 111.0(3) . . ? O4 Ge O4 105.6(4) 15_665 . ? N2 Cu1 O16 170.1(4) . . ? N2 Cu1 N1 84.9(4) . . ? O16 Cu1 N1 91.9(4) . . ? N2 Cu1 O12 91.4(4) . . ? O16 Cu1 O12 90.8(3) . . ? N1 Cu1 O12 173.2(4) . . ? N2 Cu1 O9 114.1(4) . 7_455 ? O16 Cu1 O9 75.6(3) . 7_455 ? N1 Cu1 O9 98.3(4) . 7_455 ? O12 Cu1 O9 88.3(3) . 7_455 ? O16 Cu2 O16 96.5(4) 15_665 . ? O16 Cu2 O9 86.1(3) 15_665 9_565 ? O16 Cu2 O9 171.6(3) . 9_565 ? O16 Cu2 O9 171.6(3) 15_665 7_455 ? O16 Cu2 O9 86.1(3) . 7_455 ? O9 Cu2 O9 90.2(4) 9_565 7_455 ? O16 Cu2 O1W 92.5(3) 15_665 . ? O16 Cu2 O1W 92.5(3) . . ? O9 Cu2 O1W 95.4(3) 9_565 . ? O9 Cu2 O1W 95.4(3) 7_455 . ? O16 Cu2 O20 85.7(2) 15_665 . ? O16 Cu2 O20 85.7(2) . . ? O9 Cu2 O20 86.6(2) 9_565 . ? O9 Cu2 O20 86.6(2) 7_455 . ? O1W Cu2 O20 177.3(4) . . ? O12 Cu3 O12 93.5(4) . 7_455 ? O12 Cu3 O20 172.6(3) . 9_565 ? O12 Cu3 O20 93.8(3) 7_455 9_565 ? O12 Cu3 O20 93.8(3) . . ? O12 Cu3 O20 172.6(3) 7_455 . ? O20 Cu3 O20 78.8(4) 9_565 . ? O12 Cu3 Cu3 133.2(2) . 9_565 ? O12 Cu3 Cu3 133.2(2) 7_455 9_565 ? O20 Cu3 Cu3 39.39(19) 9_565 9_565 ? O20 Cu3 Cu3 39.39(19) . 9_565 ? O3W Cu4 O19 100.3(10) . . ? O3W Cu4 O2W 169.4(14) . . ? O19 Cu4 O2W 90.3(11) . . ? W5 O2 W1 153.1(4) . . ? W1 O3 W3 121.4(4) . . ? Ge O4 W3 120.4(3) . . ? Ge O4 W2 123.6(3) . . ? W3 O4 W2 95.0(2) . . ? Ge O4 W1 124.0(3) . . ? W3 O4 W1 92.9(2) . . ? W2 O4 W1 92.9(2) . . ? W1 O5 W1 152.5(6) . 15_665 ? W1 O6 W2 121.1(4) . . ? W2 O8 W2 149.6(6) . 15_665 ? W2 O9 Cu2 134.3(4) . 9_565 ? W2 O9 Cu1 116.6(3) . 7_455 ? Cu2 O9 Cu1 91.5(3) 9_565 7_455 ? W2 O10 W3 120.2(4) . . ? W3 O12 Cu3 139.3(4) . . ? W3 O12 Cu1 114.4(3) . . ? Cu3 O12 Cu1 103.2(3) . . ? W4 O13 W3 152.5(4) . . ? W4 O14 W4 119.0(5) 15_665 . ? W4 O16 Cu2 137.8(4) . . ? W4 O16 Cu1 114.6(4) . . ? Cu2 O16 Cu1 106.7(3) . . ? Ge O17 W4 122.5(3) . . ? Ge O17 W4 122.5(3) . 15_665 ? W4 O17 W4 92.0(3) . 15_665 ? Ge O17 W5 125.9(5) . . ? W4 O17 W5 92.4(3) . . ? W4 O17 W5 92.4(3) 15_665 . ? W5 O18 W4 120.7(3) . 15_665 ? W5 O19 Cu4 152.3(7) . . ? Ge O20 Cu3 122.1(3) . 9_565 ? Ge O20 Cu3 122.1(3) . . ? Cu3 O20 Cu3 101.2(4) 9_565 . ? Ge O20 Cu2 115.5(4) . . ? Cu3 O20 Cu2 94.9(3) 9_565 . ? Cu3 O20 Cu2 94.9(3) . . ? C1 N1 Cu1 111.0(8) . . ? C1 N1 H1A 109.4 . . ? Cu1 N1 H1A 109.4 . . ? C1 N1 H1B 109.4 . . ? Cu1 N1 H1B 109.4 . . ? H1A N1 H1B 108.0 . . ? C2 N2 Cu1 107.6(8) . . ? C2 N2 H2A 110.2 . . ? Cu1 N2 H2A 110.2 . . ? C2 N2 H2B 110.2 . . ? Cu1 N2 H2B 110.2 . . ? H2A N2 H2B 108.5 . . ? N1 C1 C2 107.8(11) . . ? N1 C1 H1C 110.1 . . ? C2 C1 H1C 110.1 . . ? N1 C1 H1D 110.1 . . ? C2 C1 H1D 110.1 . . ? H1C C1 H1D 108.5 . . ? C3 C2 C3' 98(6) . . ? C3 C2 C1 114(6) . . ? C3' C2 C1 111.6(15) . . ? C3 C2 N2 116(6) . . ? C3' C2 N2 110.1(14) . . ? C1 C2 N2 107.0(11) . . ? C2 C3 H3A 109.5 . . ? C2 C3 H3B 109.5 . . ? H3A C3 H3B 109.5 . . ? C2 C3 H3C 109.5 . . ? H3A C3 H3C 109.5 . . ? H3B C3 H3C 109.5 . . ? C2 C3' H3'A 109.5 . . ? C2 C3' H3'B 109.5 . . ? H3'A C3' H3'B 109.5 . . ? C2 C3' H3'C 109.5 . . ? H3'A C3' H3'C 109.5 . . ? H3'B C3' H3'C 109.5 . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N1 H1A O7 0.90 2.38 3.038(14) 129.8 7_455 N1 H1B O3 0.90 2.40 3.108(12) 136.0 11_566 N1 H1B O15 0.90 2.55 3.284(13) 138.8 . N2 H2A O11 0.90 2.43 3.180(13) 141.1 . N2 H2B O10 0.90 2.30 3.050(13) 140.8 7_455 _diffrn_measured_fraction_theta_max 0.973 _diffrn_reflns_theta_full 25.63 _diffrn_measured_fraction_theta_full 0.973 _refine_diff_density_max 2.984 _refine_diff_density_min -1.619 _refine_diff_density_rms 0.289 #============================================================================ data_q _database_code_depnum_ccdc_archive 'CCDC 663471' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C8 H42 Cu9 N8 O72 Si2 W18' _chemical_formula_weight 5339.84 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 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' Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Si Si 0.0817 0.0704 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' W W -0.8490 6.8722 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting tetragonal _symmetry_space_group_name_H-M P4(2)/ncm loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y+1/2, z' '-y+1/2, x, z+1/2' 'y, -x+1/2, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y, -z+1/2' 'y+1/2, x+1/2, -z' '-y, -x, -z' '-x, -y, -z' 'x-1/2, y-1/2, -z' 'y-1/2, -x, -z-1/2' '-y, x-1/2, -z-1/2' 'x, -y-1/2, z-1/2' '-x-1/2, y, z-1/2' '-y-1/2, -x-1/2, z' 'y, x, z' _cell_length_a 21.3874(13) _cell_length_b 21.3874(13) _cell_length_c 18.634(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 8523.4(12) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 21980 _cell_measurement_theta_min 2.1292 _cell_measurement_theta_max 27.4835 _exptl_crystal_description ployhedron _exptl_crystal_colour 'dark green' _exptl_crystal_size_max 0.35 _exptl_crystal_size_mid 0.34 _exptl_crystal_size_min 0.33 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 4.161 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 9372 _exptl_absorpt_coefficient_mu 26.499 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.0388 _exptl_absorpt_correction_T_max 0.0415 _exptl_absorpt_process_details 'SADABS (Sheldrick, 1996)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Saturn70 (4x4 bin mode)' _diffrn_measurement_method CCD_Profile_fitting _diffrn_detector_area_resol_mean ? _diffrn_standards_number none _diffrn_standards_interval_count none _diffrn_standards_interval_time none _diffrn_standards_decay_% none _diffrn_reflns_number 51668 _diffrn_reflns_av_R_equivalents 0.2017 _diffrn_reflns_av_sigmaI/netI 0.0670 _diffrn_reflns_limit_h_min -25 _diffrn_reflns_limit_h_max 25 _diffrn_reflns_limit_k_min -25 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 2.69 _diffrn_reflns_theta_max 25.00 _reflns_number_total 3859 _reflns_number_gt 3206 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_cell_refinement 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_data_reduction 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'PLATON (Spek, 2003)' _computing_publication_material 'PLATON (Spek, 2003)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.1155P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3859 _refine_ls_number_parameters 285 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0834 _refine_ls_R_factor_gt 0.0747 _refine_ls_wR_factor_ref 0.1966 _refine_ls_wR_factor_gt 0.1870 _refine_ls_goodness_of_fit_ref 1.077 _refine_ls_restrained_S_all 1.077 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group W1 W 0.21035(4) 0.41150(4) 0.18327(4) 0.0449(3) Uani 1 1 d . . . W2 W 0.18421(4) 0.43599(4) 0.00715(4) 0.0407(3) Uani 1 1 d . . . W3 W 0.17361(4) 0.55443(4) 0.12431(4) 0.0423(3) Uani 1 1 d . . . W4 W 0.04622(4) 0.56322(4) 0.25726(4) 0.0427(3) Uani 1 1 d . . . W5 W 0.08114(4) 0.41886(4) 0.31266(5) 0.0450(3) Uani 1 2 d S . . Si Si 0.0547(2) 0.4453(2) 0.1249(3) 0.0265(14) Uani 1 2 d S . . Cu1 Cu 0.05646(11) 0.64987(12) 0.11771(12) 0.0437(6) Uani 1 1 d . . . Cu2 Cu -0.06042(11) 0.56042(11) 0.11400(16) 0.0364(7) Uani 1 2 d S . . Cu3 Cu 0.04840(11) 0.54840(11) 0.0000 0.0353(7) Uani 1 2 d S . . Cu4 Cu 0.1600(4) 0.3400(4) 0.4546(6) 0.102(3) Uani 0.50 2 d SP . . O1 O 0.2766(7) 0.3870(8) 0.2250(8) 0.063(4) Uani 1 1 d . . . O2 O 0.1558(7) 0.4276(6) 0.2600(6) 0.043(3) Uani 1 1 d . . . O3 O 0.2266(6) 0.4995(7) 0.1791(6) 0.050(3) Uani 1 1 d . . . O4 O 0.1297(6) 0.4572(5) 0.1130(6) 0.039(3) Uani 1 1 d . . . O5 O 0.1642(6) 0.3358(6) 0.1760(10) 0.056(5) Uani 1 2 d S . . O6 O 0.2355(6) 0.4038(6) 0.0868(6) 0.045(3) Uani 1 1 d . . . O7 O 0.2386(6) 0.4213(6) -0.0557(7) 0.051(3) Uani 1 1 d . . . O8 O 0.1414(5) 0.3586(5) 0.0122(9) 0.044(4) Uani 1 2 d S . . O9 O 0.1213(5) 0.4709(6) -0.0430(6) 0.040(3) Uani 1 1 d . . . O10 O 0.2099(6) 0.5163(6) 0.0410(6) 0.043(3) Uani 1 1 d . . . O11 O 0.2170(6) 0.6205(7) 0.1269(7) 0.053(3) Uani 1 1 d . . . O12 O 0.1059(6) 0.5819(6) 0.0717(6) 0.038(3) Uani 1 1 d . . . O13 O 0.1223(7) 0.5640(6) 0.2099(7) 0.046(3) Uani 1 1 d . . . O14 O -0.0328(6) 0.5328(6) 0.2887(9) 0.047(4) Uani 1 2 d S . . O15 O 0.0521(7) 0.6327(7) 0.3045(7) 0.051(3) Uani 1 1 d . . . O16 O 0.0088(6) 0.5894(6) 0.1734(6) 0.040(3) Uani 1 1 d . . . O17 O 0.0359(6) 0.4641(6) 0.2064(8) 0.041(4) Uani 1 2 d S . . O18 O -0.0054(7) 0.4188(7) 0.3269(7) 0.050(3) Uani 1 1 d . . . O19 O 0.1057(6) 0.3943(6) 0.3961(9) 0.049(5) Uani 1 2 d S . . O20 O 0.0163(6) 0.4837(6) 0.0649(8) 0.038(4) Uani 1 2 d S . . O1W O -0.1276(8) 0.6276(8) 0.1704(12) 0.070(6) Uani 1 2 d S . . O2W O 0.198(3) 0.302(3) 0.376(5) 0.14(3) Uiso 0.50 2 d SP . . O3W O 0.129(2) 0.371(2) 0.555(3) 0.102(18) Uiso 0.50 2 d SP . . N1 N 0.0198(10) 0.7195(9) 0.1704(9) 0.062(5) Uani 1 1 d . . . H1A H -0.0219 0.7194 0.1639 0.074 Uiso 1 1 calc R . . H1B H 0.0274 0.7145 0.2176 0.074 Uiso 1 1 calc R . . N2 N 0.1135(10) 0.7133(9) 0.0765(11) 0.067(5) Uani 1 1 d . . . H2A H 0.1525 0.6979 0.0717 0.080 Uiso 1 1 calc R . . H2B H 0.0998 0.7263 0.0333 0.080 Uiso 1 1 calc R . . C1 C 0.1119(11) 0.7642(15) 0.129(2) 0.103(12) Uani 1 1 d D . . H1C H 0.1335 0.8004 0.1097 0.124 Uiso 1 1 calc R . . H1D H 0.1333 0.7513 0.1724 0.124 Uiso 1 1 calc R . . C2 C 0.0459(11) 0.7812(13) 0.1462(14) 0.075(7) Uani 1 1 d D . . H2C H 0.0241 0.7969 0.1043 0.090 Uiso 1 1 calc R . . H2D H 0.0440 0.8122 0.1842 0.090 Uiso 1 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 W1 0.0406(5) 0.0521(5) 0.0421(5) 0.0029(3) -0.0069(3) 0.0064(4) W2 0.0371(5) 0.0463(5) 0.0387(5) 0.0003(3) 0.0007(3) 0.0064(4) W3 0.0372(5) 0.0453(5) 0.0443(5) -0.0016(3) -0.0049(3) -0.0005(3) W4 0.0490(5) 0.0446(5) 0.0344(5) -0.0031(3) -0.0039(3) 0.0008(4) W5 0.0510(5) 0.0510(5) 0.0330(6) 0.0044(3) -0.0044(3) 0.0033(6) Si 0.029(2) 0.029(2) 0.022(3) -0.0015(17) 0.0015(17) 0.001(3) Cu1 0.0495(14) 0.0396(13) 0.0421(12) -0.0048(10) 0.0014(10) -0.0017(11) Cu2 0.0379(11) 0.0379(11) 0.0334(14) -0.0015(9) 0.0015(9) -0.0004(14) Cu3 0.0392(11) 0.0392(11) 0.0274(14) -0.0005(9) 0.0005(9) -0.0009(14) Cu4 0.114(5) 0.114(5) 0.079(6) 0.001(4) -0.001(4) 0.004(7) O1 0.049(8) 0.077(11) 0.065(9) -0.004(8) -0.025(7) -0.005(8) O2 0.055(8) 0.045(8) 0.029(6) 0.000(5) -0.010(6) 0.000(7) O3 0.041(7) 0.066(9) 0.041(7) -0.003(6) -0.014(6) 0.005(7) O4 0.045(7) 0.032(6) 0.039(6) -0.005(5) -0.004(6) 0.010(6) O5 0.054(8) 0.054(8) 0.059(11) -0.018(7) 0.018(7) 0.015(10) O6 0.051(8) 0.044(7) 0.040(6) -0.004(6) -0.009(6) 0.007(6) O7 0.042(7) 0.052(8) 0.058(8) 0.015(7) 0.000(7) 0.004(6) O8 0.046(7) 0.046(7) 0.040(8) 0.008(5) -0.008(5) 0.031(9) O9 0.028(6) 0.057(8) 0.034(6) -0.011(6) -0.009(5) -0.009(6) O10 0.042(7) 0.052(8) 0.035(6) -0.004(6) -0.012(6) 0.000(6) O11 0.040(7) 0.053(9) 0.066(9) -0.006(7) -0.013(6) -0.004(7) O12 0.034(6) 0.042(7) 0.038(6) -0.002(6) -0.004(5) -0.005(6) O13 0.056(8) 0.039(7) 0.042(7) 0.003(6) -0.003(6) 0.004(6) O14 0.052(7) 0.052(7) 0.035(9) -0.004(6) 0.004(6) 0.014(10) O15 0.059(8) 0.042(8) 0.051(7) -0.014(6) -0.010(6) 0.002(7) O16 0.040(7) 0.040(7) 0.040(6) -0.006(5) -0.006(6) -0.005(6) O17 0.051(7) 0.051(7) 0.021(7) -0.003(6) 0.003(6) -0.015(9) O18 0.061(9) 0.051(8) 0.039(7) -0.004(6) -0.007(6) 0.004(7) O19 0.058(7) 0.058(7) 0.031(8) -0.006(6) 0.006(6) 0.006(11) O20 0.040(6) 0.040(6) 0.033(8) 0.005(5) -0.005(5) 0.002(8) O1W 0.070(9) 0.070(9) 0.070(14) -0.022(9) 0.022(9) -0.012(13) N1 0.084(14) 0.061(11) 0.040(8) -0.017(8) -0.005(9) 0.006(11) N2 0.065(12) 0.065(12) 0.071(12) -0.004(10) 0.016(10) -0.007(10) C1 0.061(17) 0.074(19) 0.17(4) 0.00(2) -0.022(19) 0.004(16) C2 0.087(19) 0.069(17) 0.068(15) -0.006(13) 0.007(14) -0.022(15) _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 W1 O1 1.699(13) . ? W1 O2 1.877(13) . ? W1 O6 1.884(12) . ? W1 O5 1.901(5) . ? W1 O3 1.915(15) . ? W1 O4 2.376(12) . ? W2 O7 1.681(14) . ? W2 O9 1.800(12) . ? W2 O8 1.893(4) . ? W2 O10 1.911(13) . ? W2 O6 1.970(12) . ? W2 O4 2.336(12) . ? W3 O11 1.692(14) . ? W3 O12 1.844(12) . ? W3 O10 1.918(12) . ? W3 O3 1.926(13) . ? W3 O13 1.946(13) . ? W3 O4 2.291(12) . ? W4 O15 1.732(13) . ? W4 O16 1.843(12) . ? W4 O13 1.852(14) . ? W4 O14 1.904(9) . ? W4 O18 1.942(14) 15_665 ? W4 O17 2.333(12) . ? W5 O19 1.722(18) . ? W5 O18 1.871(16) 15_665 ? W5 O18 1.871(16) . ? W5 O2 1.883(14) . ? W5 O2 1.883(14) 15_665 ? W5 O17 2.406(17) . ? Si O20 1.613(17) . ? Si O17 1.622(16) . ? Si O4 1.638(14) 15_665 ? Si O4 1.638(14) . ? Cu1 O16 1.946(13) . ? Cu1 N1 1.948(17) . ? Cu1 N2 1.980(19) . ? Cu1 O12 1.992(13) . ? Cu1 O9 2.380(13) 7_455 ? Cu2 O16 1.950(12) . ? Cu2 O16 1.950(12) 15_665 ? Cu2 O9 1.973(11) 9_565 ? Cu2 O9 1.973(11) 7_455 ? Cu2 O1W 2.29(2) . ? Cu3 O12 1.953(12) . ? Cu3 O12 1.953(12) 7_455 ? Cu3 O20 1.962(10) 9_565 ? Cu3 O20 1.962(10) . ? Cu3 O9 2.412(12) . ? Cu3 O9 2.412(12) 7_455 ? Cu3 Cu3 2.928(7) 9_565 ? Cu4 O2W 1.86(9) . ? Cu4 O19 1.97(2) . ? Cu4 O3W 2.08(6) . ? O5 W1 1.901(5) 15_665 ? O8 W2 1.893(4) 15_665 ? O9 Cu2 1.973(11) 9_565 ? O9 Cu1 2.380(13) 7_455 ? O14 W4 1.904(9) 15_665 ? O17 W4 2.333(12) 15_665 ? O18 W4 1.942(14) 15_665 ? O20 Cu3 1.962(10) 9_565 ? N1 C2 1.50(3) . ? N1 H1A 0.9000 . ? N1 H1B 0.9000 . ? N2 C1 1.46(4) . ? N2 H2A 0.9000 . ? N2 H2B 0.9000 . ? C1 C2 1.492(10) . ? C1 H1C 0.9700 . ? C1 H1D 0.9700 . ? C2 H2C 0.9700 . ? C2 H2D 0.9700 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 W1 O2 103.1(7) . . ? O1 W1 O6 99.9(7) . . ? O2 W1 O6 157.0(5) . . ? O1 W1 O5 101.7(8) . . ? O2 W1 O5 83.6(6) . . ? O6 W1 O5 90.3(7) . . ? O1 W1 O3 99.8(7) . . ? O2 W1 O3 87.9(6) . . ? O6 W1 O3 89.7(5) . . ? O5 W1 O3 158.2(7) . . ? O1 W1 O4 169.9(6) . . ? O2 W1 O4 83.8(5) . . ? O6 W1 O4 73.6(5) . . ? O5 W1 O4 86.2(7) . . ? O3 W1 O4 72.9(5) . . ? O7 W2 O9 103.5(6) . . ? O7 W2 O8 101.9(7) . . ? O9 W2 O8 91.5(6) . . ? O7 W2 O10 101.5(6) . . ? O9 W2 O10 90.8(5) . . ? O8 W2 O10 155.3(6) . . ? O7 W2 O6 94.2(6) . . ? O9 W2 O6 162.2(5) . . ? O8 W2 O6 85.8(6) . . ? O10 W2 O6 84.6(5) . . ? O7 W2 O4 166.0(6) . . ? O9 W2 O4 89.1(5) . . ? O8 W2 O4 83.5(6) . . ? O10 W2 O4 72.0(5) . . ? O6 W2 O4 73.1(5) . . ? O11 W3 O12 100.4(6) . . ? O11 W3 O10 99.0(6) . . ? O12 W3 O10 91.3(5) . . ? O11 W3 O3 99.9(6) . . ? O12 W3 O3 159.7(6) . . ? O10 W3 O3 86.1(5) . . ? O11 W3 O13 101.4(6) . . ? O12 W3 O13 87.7(5) . . ? O10 W3 O13 159.4(5) . . ? O3 W3 O13 87.8(6) . . ? O11 W3 O4 170.3(6) . . ? O12 W3 O4 85.3(5) . . ? O10 W3 O4 72.9(5) . . ? O3 W3 O4 74.7(5) . . ? O13 W3 O4 86.5(5) . . ? O15 W4 O16 101.6(6) . . ? O15 W4 O13 99.9(6) . . ? O16 W4 O13 88.5(6) . . ? O15 W4 O14 101.6(7) . . ? O16 W4 O14 88.8(7) . . ? O13 W4 O14 158.5(6) . . ? O15 W4 O18 100.3(6) . 15_665 ? O16 W4 O18 158.0(6) . 15_665 ? O13 W4 O18 89.2(6) . 15_665 ? O14 W4 O18 85.4(7) . 15_665 ? O15 W4 O17 173.3(6) . . ? O16 W4 O17 83.7(6) . . ? O13 W4 O17 84.1(5) . . ? O14 W4 O17 74.4(5) . . ? O18 W4 O17 74.3(6) 15_665 . ? O19 W5 O18 100.0(6) . 15_665 ? O19 W5 O18 100.0(6) . . ? O18 W5 O18 88.9(9) 15_665 . ? O19 W5 O2 104.0(6) . . ? O18 W5 O2 88.6(6) 15_665 . ? O18 W5 O2 155.9(5) . . ? O19 W5 O2 104.0(6) . 15_665 ? O18 W5 O2 155.9(5) 15_665 15_665 ? O18 W5 O2 88.6(6) . 15_665 ? O2 W5 O2 84.1(8) . 15_665 ? O19 W5 O17 170.9(8) . . ? O18 W5 O17 73.7(5) 15_665 . ? O18 W5 O17 73.7(5) . . ? O2 W5 O17 82.6(5) . . ? O2 W5 O17 82.6(5) 15_665 . ? O20 Si O17 113.4(10) . . ? O20 Si O4 108.9(6) . 15_665 ? O17 Si O4 109.3(6) . 15_665 ? O20 Si O4 108.9(6) . . ? O17 Si O4 109.3(6) . . ? O4 Si O4 106.7(9) 15_665 . ? O16 Cu1 N1 91.7(7) . . ? O16 Cu1 N2 170.1(7) . . ? N1 Cu1 N2 85.4(9) . . ? O16 Cu1 O12 91.3(5) . . ? N1 Cu1 O12 171.3(7) . . ? N2 Cu1 O12 90.3(7) . . ? O16 Cu1 O9 74.8(4) . 7_455 ? N1 Cu1 O9 100.5(7) . 7_455 ? N2 Cu1 O9 115.0(7) . 7_455 ? O12 Cu1 O9 88.2(5) . 7_455 ? O16 Cu2 O16 99.3(7) . 15_665 ? O16 Cu2 O9 171.6(5) . 9_565 ? O16 Cu2 O9 85.0(5) 15_665 9_565 ? O16 Cu2 O9 85.0(5) . 7_455 ? O16 Cu2 O9 171.6(5) 15_665 7_455 ? O9 Cu2 O9 89.8(7) 9_565 7_455 ? O16 Cu2 O1W 90.9(6) . . ? O16 Cu2 O1W 90.9(6) 15_665 . ? O9 Cu2 O1W 96.2(6) 9_565 . ? O9 Cu2 O1W 96.2(6) 7_455 . ? O12 Cu3 O12 90.4(7) . 7_455 ? O12 Cu3 O20 174.1(6) . 9_565 ? O12 Cu3 O20 93.3(5) 7_455 9_565 ? O12 Cu3 O20 93.3(5) . . ? O12 Cu3 O20 174.1(6) 7_455 . ? O20 Cu3 O20 83.5(7) 9_565 . ? O12 Cu3 O9 94.1(4) . . ? O12 Cu3 O9 88.2(5) 7_455 . ? O20 Cu3 O9 90.6(6) 9_565 . ? O20 Cu3 O9 86.8(6) . . ? O12 Cu3 O9 88.2(5) . 7_455 ? O12 Cu3 O9 94.1(4) 7_455 7_455 ? O20 Cu3 O9 86.8(6) 9_565 7_455 ? O20 Cu3 O9 90.6(6) . 7_455 ? O9 Cu3 O9 176.6(6) . 7_455 ? O12 Cu3 Cu3 134.8(4) . 9_565 ? O12 Cu3 Cu3 134.8(4) 7_455 9_565 ? O20 Cu3 Cu3 41.7(3) 9_565 9_565 ? O20 Cu3 Cu3 41.7(3) . 9_565 ? O9 Cu3 Cu3 88.3(3) . 9_565 ? O9 Cu3 Cu3 88.3(3) 7_455 9_565 ? O2W Cu4 O19 94(3) . . ? O2W Cu4 O3W 169(3) . . ? O19 Cu4 O3W 97.0(19) . . ? W1 O2 W5 154.9(7) . . ? W1 O3 W3 120.9(7) . . ? Si O4 W3 122.0(6) . . ? Si O4 W2 124.9(6) . . ? W3 O4 W2 92.8(5) . . ? Si O4 W1 124.8(7) . . ? W3 O4 W1 91.4(4) . . ? W2 O4 W1 91.3(4) . . ? W1 O5 W1 151.5(11) . 15_665 ? W1 O6 W2 121.9(7) . . ? W2 O8 W2 147.5(9) . 15_665 ? W2 O9 Cu2 134.5(7) . 9_565 ? W2 O9 Cu1 115.5(6) . 7_455 ? Cu2 O9 Cu1 92.2(5) 9_565 7_455 ? W2 O9 Cu3 126.6(5) . . ? Cu2 O9 Cu3 91.7(5) 9_565 . ? Cu1 O9 Cu3 80.3(4) 7_455 . ? W2 O10 W3 122.2(7) . . ? W3 O12 Cu3 137.9(7) . . ? W3 O12 Cu1 114.9(6) . . ? Cu3 O12 Cu1 103.2(5) . . ? W4 O13 W3 152.3(8) . . ? W4 O14 W4 120.8(9) 15_665 . ? W4 O16 Cu1 115.3(6) . . ? W4 O16 Cu2 135.6(7) . . ? Cu1 O16 Cu2 107.9(6) . . ? Si O17 W4 125.6(5) . . ? Si O17 W4 125.6(5) . 15_665 ? W4 O17 W4 90.4(6) . 15_665 ? Si O17 W5 124.8(10) . . ? W4 O17 W5 89.6(4) . . ? W4 O17 W5 89.6(4) 15_665 . ? W5 O18 W4 122.4(7) . 15_665 ? W5 O19 Cu4 149.1(11) . . ? Si O20 Cu3 127.5(5) . 9_565 ? Si O20 Cu3 127.5(5) . . ? Cu3 O20 Cu3 96.5(7) 9_565 . ? C2 N1 Cu1 111.8(14) . . ? C2 N1 H1A 109.3 . . ? Cu1 N1 H1A 109.3 . . ? C2 N1 H1B 109.3 . . ? Cu1 N1 H1B 109.3 . . ? H1A N1 H1B 107.9 . . ? C1 N2 Cu1 103.6(16) . . ? C1 N2 H2A 111.0 . . ? Cu1 N2 H2A 111.0 . . ? C1 N2 H2B 111.0 . . ? Cu1 N2 H2B 111.0 . . ? H2A N2 H2B 109.0 . . ? N2 C1 C2 110(2) . . ? N2 C1 H1C 109.6 . . ? C2 C1 H1C 109.6 . . ? N2 C1 H1D 109.6 . . ? C2 C1 H1D 109.6 . . ? H1C C1 H1D 108.1 . . ? C1 C2 N1 102(2) . . ? C1 C2 H2C 111.4 . . ? N1 C2 H2C 111.4 . . ? C1 C2 H2D 111.4 . . ? N1 C2 H2D 111.4 . . ? H2C C2 H2D 109.3 . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N1 H1A O7 0.90 2.39 3.03(2) 128.0 7_455 N1 H1B O3 0.90 2.38 3.06(2) 133.1 11_566 N1 H1B O15 0.90 2.44 3.19(2) 140.5 . N2 H2A O11 0.90 2.39 3.12(3) 138.2 . N2 H2B O10 0.90 2.29 3.02(3) 138.4 7_455 _diffrn_measured_fraction_theta_max 0.986 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.986 _refine_diff_density_max 4.734 _refine_diff_density_min -3.302 _refine_diff_density_rms 0.565