Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2003 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 loop_ _publ_author_name 'Lin Bi-Zhou' 'Yan-Min Chen' 'Pei-De Liu' _publ_contact_author_name 'Prof Bi-Zhou Lin' _publ_contact_author_address ; Institute of Materials Physical Chemistry Huaqiao University Quanzhou 362011 CHINA ; _publ_contact_author_email BZLIN@HQU.EDU.CN _publ_section_title ; A new polymeric chain formed by paradodecatungstate clusters and {Cu(en)2}2+ complexes: hydrothermal synthesis and characterization of [Cu(en)2]3[{Cu(en)2}2(H2W12O42)]-12H2O ; data_(I) _database_code_CSD 185816 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'Cu5 C20 H80 N20 W12 H2 O42 O12 H24' _chemical_formula_sum 'C20 H106 Cu5 N20 O54 W12' _chemical_formula_weight 4015.15 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' W W -0.8490 6.8722 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M 'P -1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 12.1989(7) _cell_length_b 14.0042(8) _cell_length_c 14.7254(9) _cell_angle_alpha 62.1440(10) _cell_angle_beta 67.294(3) _cell_angle_gamma 77.875(2) _cell_volume 2050.4(2) _cell_formula_units_Z 1 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 520 _cell_measurement_theta_min 10 _cell_measurement_theta_max 20 _exptl_crystal_description needle _exptl_crystal_colour purple _exptl_crystal_size_max 0.616 _exptl_crystal_size_mid 0.042 _exptl_crystal_size_min 0.024 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 3.252 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1831 _exptl_absorpt_coefficient_mu 18.121 _exptl_absorpt_correction_type psi-scan _exptl_absorpt_correction_T_min 0.0320 _exptl_absorpt_correction_T_max 0.6807 _exptl_absorpt_process_details ; Higashi, T. (1995). Program for Absorption Correction. Rigaku Corporation, Tokyo, Japan. ; _exptl_special_details ; crystal coated in epoxy glue ; _diffrn_ambient_temperature 295(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Rigaku R-AXIS-Parid IP' _diffrn_measurement_method 'Oscillation scans' _diffrn_detector_area_resol_mean 10.0 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 18810 _diffrn_reflns_av_R_equivalents 0.0283 _diffrn_reflns_av_sigmaI/netI 0.0256 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 0 _diffrn_reflns_theta_min 1.65 _diffrn_reflns_theta_max 27.48 _reflns_number_total 9153 _reflns_number_gt 7882 _reflns_threshold_expression >2sigma(I) _computing_data_collection ; Rigaku R-AXIS RAPID diffractometer Control Software (RAPID AUTO) ; _computing_cell_refinement 'RAPID AUTO' _computing_data_reduction ; TEXRAY (Molecuar Structure Corporation, 1987) ; _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL/PC (Sheldrick, 1990)' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0502P)^2^+2.6375P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.00066(4) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 9153 _refine_ls_number_parameters 491 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0345 _refine_ls_R_factor_gt 0.0275 _refine_ls_wR_factor_ref 0.0767 _refine_ls_wR_factor_gt 0.0738 _refine_ls_goodness_of_fit_ref 1.049 _refine_ls_restrained_S_all 1.049 _refine_ls_shift/su_max 0.007 _refine_ls_shift/su_mean 0.001 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_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 0.27565(2) 0.66109(2) 0.118024(19) 0.02139(7) Uani 1 1 d . . . W2 W 0.44243(2) 0.447380(19) 0.224155(18) 0.01815(7) Uani 1 1 d . . . W3 W 0.16834(2) 0.40296(2) 0.178914(19) 0.02035(7) Uani 1 1 d . . . W4 W 0.32547(2) 0.18786(2) 0.292783(19) 0.02260(7) Uani 1 1 d . . . W5 W 0.61778(2) 0.20801(2) 0.181038(19) 0.02033(7) Uani 1 1 d . . . W6 W 0.43083(2) 0.32474(2) -0.010651(19) 0.01947(7) Uani 1 1 d . . . Cu1 Cu -0.10274(8) 0.31109(7) 0.17537(7) 0.03177(19) Uani 1 1 d . . . Cu2 Cu 0.0000 0.5000 0.5000 0.0400(3) Uani 1 2 d S . . Cu3 Cu 0.5000 0.0000 0.5000 0.0386(3) Uani 1 2 d S . . Cu4 Cu 0.5000 0.0000 0.0000 0.0797(6) Uani 1 2 d S . . O1 O 0.1571(5) 0.7390(5) 0.1650(4) 0.0403(13) Uani 1 1 d . . . O2 O 0.4052(4) 0.7421(4) 0.0718(4) 0.0269(10) Uani 1 1 d . . . O3 O 0.3033(4) 0.5606(4) 0.2449(3) 0.0250(9) Uani 1 1 d . . . O4 O 0.4294(4) 0.5602(3) 0.0589(3) 0.0190(8) Uani 1 1 d . . . H4 H 0.4477 0.5626 -0.0024 0.080 Uiso 1 1 d R . . O5 O 0.1882(4) 0.5489(4) 0.1324(4) 0.0251(9) Uani 1 1 d . . . O6 O 0.4393(4) 0.3970(4) 0.3563(4) 0.0316(11) Uani 1 1 d . . . O7 O 0.5374(4) 0.5731(3) 0.1625(3) 0.0201(8) Uani 1 1 d . . . O8 O 0.5644(4) 0.3731(4) 0.1658(4) 0.0251(9) Uani 1 1 d . . . O9 O 0.3232(4) 0.3704(3) 0.2368(3) 0.0212(9) Uani 1 1 d . . . O10 O 0.0756(4) 0.4168(4) 0.1074(4) 0.0289(10) Uani 1 1 d . . . O11 O 0.0647(4) 0.3781(4) 0.3091(4) 0.0317(11) Uani 1 1 d . . . O12 O 0.3203(4) 0.4134(4) 0.0364(3) 0.0254(10) Uani 1 1 d . . . O13 O 0.2136(4) 0.2501(4) 0.2182(3) 0.0246(9) Uani 1 1 d . . . O14 O 0.2371(5) 0.1726(4) 0.4232(4) 0.0341(11) Uani 1 1 d . . . O15 O 0.3267(5) 0.0582(4) 0.3045(4) 0.0365(12) Uani 1 1 d . . . O16 O 0.4748(4) 0.1796(4) 0.3096(3) 0.0239(9) Uani 1 1 d . . . O17 O 0.4644(4) 0.2464(4) 0.1236(3) 0.0215(9) Uani 1 1 d . . . O18 O 0.7174(4) 0.2025(4) 0.2417(4) 0.0311(11) Uani 1 1 d . . . O19 O 0.6340(5) 0.0781(4) 0.1881(4) 0.0348(11) Uani 1 1 d . . . O20 O 0.7130(4) 0.2792(4) 0.0350(3) 0.0247(9) Uani 1 1 d . . . O21 O 0.3516(5) 0.2335(4) -0.0058(4) 0.0373(12) Uani 1 1 d . . . O22 O 0.1489(19) 0.6565(13) 0.4262(13) 0.235(10) Uani 1 1 d . . . H22A H 0.1870 0.6230 0.3730 0.080 Uiso 1 1 d R . . H22B H 0.1198 0.6233 0.4974 0.080 Uiso 1 1 d R . . O23 O 0.1963(9) 0.0602(10) -0.1270(11) 0.135(5) Uani 1 1 d . . . H23A H 0.2385 0.1172 -0.1488 0.080 Uiso 1 1 d R . . H23B H 0.2490 0.0169 -0.1468 0.080 Uiso 1 1 d R . . O24 O 0.3348(13) 0.2325(10) -0.1905(11) 0.156(6) Uani 1 1 d . . . H24A H 0.3167 0.2990 -0.2461 0.080 Uiso 1 1 d R . . H24B H 0.3343 0.2219 -0.1241 0.080 Uiso 1 1 d R . . O25 O 0.002(2) 0.096(2) -0.1750(19) 0.327(15) Uiso 1 1 d . . . H25A H 0.0568 0.0854 -0.1451 0.080 Uiso 1 1 d R . . H25B H -0.0447 0.1470 -0.1740 0.080 Uiso 1 1 d R . . O26 O -0.1283(19) 0.0778(18) 0.5183(19) 0.279(12) Uiso 1 1 d . . . H26A H -0.1871 0.0399 0.5680 0.080 Uiso 1 1 d R . . H26B H -0.0775 0.0704 0.5479 0.080 Uiso 1 1 d R . . O27 O -0.071(3) -0.051(3) 0.364(3) 0.52(3) Uiso 1 1 d . . . H27A H -0.0398 -0.0720 0.3130 0.080 Uiso 1 1 d R . . H27B H -0.1088 -0.0913 0.4296 0.080 Uiso 1 1 d R . . N1 N -0.1983(5) 0.4503(5) 0.1373(5) 0.0332(13) Uani 1 1 d . . . H1A H -0.1600 0.4990 0.0700 0.080 Uiso 1 1 d R . . H1B H -0.2695 0.4397 0.1391 0.080 Uiso 1 1 d R . . N2 N -0.1514(5) 0.3078(6) 0.3238(5) 0.0385(15) Uani 1 1 d . . . H2A H -0.1797 0.2427 0.3754 0.080 Uiso 1 1 d R . . H2B H -0.0887 0.3194 0.3347 0.080 Uiso 1 1 d R . . N3 N 0.0014(6) 0.1739(6) 0.2071(7) 0.0482(18) Uani 1 1 d . . . H3A H 0.0622 0.1812 0.2233 0.080 Uiso 1 1 d R . . H3B H -0.0420 0.1181 0.2620 0.080 Uiso 1 1 d R . . N4 N -0.0551(6) 0.3222(6) 0.0257(6) 0.0451(17) Uani 1 1 d . . . H4A H -0.1194 0.3176 0.0124 0.080 Uiso 1 1 d R . . H4B H -0.0223 0.3863 -0.0235 0.080 Uiso 1 1 d R . . N5 N 0.1404(7) 0.4080(7) 0.4628(6) 0.0511(19) Uani 1 1 d . . . H5A H 0.1253 0.3711 0.4329 0.080 Uiso 1 1 d R . . H5B H 0.2022 0.4503 0.4133 0.080 Uiso 1 1 d R . . N6 N 0.0210(7) 0.4338(6) 0.6444(5) 0.0469(17) Uani 1 1 d . . . H6A H 0.0136 0.4850 0.6673 0.080 Uiso 1 1 d R . . H6B H -0.0348 0.3847 0.6936 0.080 Uiso 1 1 d R . . N7 N 0.3804(7) 0.0835(7) 0.5776(6) 0.055(2) Uani 1 1 d . . . H7A H 0.3375 0.1302 0.5358 0.080 Uiso 1 1 d R . . H7B H 0.3306 0.0380 0.6406 0.080 Uiso 1 1 d R . . N8 N 0.3795(7) -0.0884(6) 0.5177(6) 0.0477(18) Uani 1 1 d . . . H8A H 0.3302 -0.1150 0.5871 0.080 Uiso 1 1 d R . . H8B H 0.3361 -0.0475 0.4742 0.080 Uiso 1 1 d R . . N9 N 0.4783(10) -0.0489(13) 0.1521(10) 0.107(5) Uani 1 1 d . . . H9A H 0.5439 -0.0853 0.1672 0.080 Uiso 1 1 d R . . H9B H 0.4656 0.0093 0.1662 0.080 Uiso 1 1 d R . . N10 N 0.3327(11) -0.0368(9) 0.0481(10) 0.092(4) Uani 1 1 d . . . H10A H 0.2939 0.0184 0.0077 0.080 Uiso 1 1 d R . . H10D H 0.3294 -0.0959 0.0400 0.080 Uiso 1 1 d R . . C1 C -0.2142(7) 0.4899(7) 0.2217(7) 0.0399(17) Uani 1 1 d . . . H1C H -0.2773 0.5454 0.2206 0.080 Uiso 1 1 d R . . H1D H -0.1412 0.5199 0.2072 0.080 Uiso 1 1 d R . . C2 C -0.2452(8) 0.3916(8) 0.3302(7) 0.047(2) Uani 1 1 d . . . H2C H -0.2499 0.4105 0.3871 0.080 Uiso 1 1 d R . . H2D H -0.3218 0.3660 0.3471 0.080 Uiso 1 1 d R . . C3 C 0.0457(14) 0.1569(11) 0.1082(12) 0.097(5) Uani 1 1 d . . . H3C H 0.1306 0.1413 0.0919 0.080 Uiso 1 1 d R . . H3D H 0.0099 0.0927 0.1244 0.080 Uiso 1 1 d R . . C4 C 0.0291(17) 0.2374(16) 0.0165(13) 0.141(9) Uani 1 1 d . . . H4C H 0.0044 0.2044 -0.0173 0.080 Uiso 1 1 d R . . H4D H 0.1052 0.2692 -0.0333 0.080 Uiso 1 1 d R . . C5 C 0.1707(9) 0.3333(9) 0.5583(8) 0.066(3) Uani 1 1 d . . . H5C H 0.2556 0.3162 0.5376 0.080 Uiso 1 1 d R . . H5D H 0.1292 0.2667 0.5926 0.080 Uiso 1 1 d R . . C6 C 0.1364(10) 0.3810(10) 0.6353(9) 0.065(3) Uani 1 1 d . . . H6C H 0.1376 0.3254 0.7061 0.080 Uiso 1 1 d R . . H6D H 0.1940 0.4340 0.6099 0.080 Uiso 1 1 d R . . C7 C 0.4482(11) 0.1420(9) 0.5971(9) 0.069(3) Uani 1 1 d . . . H7C H 0.4006 0.2039 0.6057 0.080 Uiso 1 1 d R . . H7D H 0.4641 0.0950 0.6646 0.080 Uiso 1 1 d R . . C8 C 0.4423(11) -0.1780(10) 0.4873(11) 0.080(4) Uani 1 1 d . . . H8C H 0.3925 -0.2023 0.4647 0.080 Uiso 1 1 d R . . H8D H 0.4573 -0.2384 0.5502 0.080 Uiso 1 1 d R . . C9 C 0.3725(17) -0.1180(13) 0.2211(14) 0.114(6) Uani 1 1 d . . . H9C H 0.3913 -0.1887 0.2208 0.080 Uiso 1 1 d R . . H9D H 0.3451 -0.1266 0.2957 0.080 Uiso 1 1 d R . . C10 C 0.2740(13) -0.0579(14) 0.1693(15) 0.104(5) Uani 1 1 d . . . H10B H 0.2036 -0.0999 0.2025 0.080 Uiso 1 1 d R . . H10C H 0.2509 0.0098 0.1759 0.080 Uiso 1 1 d 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 0.01843(12) 0.02352(13) 0.02052(12) -0.01107(10) -0.00446(9) 0.00260(10) W2 0.01641(11) 0.02209(12) 0.01595(11) -0.00763(9) -0.00550(9) -0.00173(9) W3 0.01342(11) 0.02564(13) 0.01867(12) -0.00646(9) -0.00427(9) -0.00385(9) W4 0.02023(12) 0.02277(13) 0.01915(12) -0.00194(10) -0.00713(10) -0.00605(10) W5 0.01824(12) 0.02067(12) 0.01990(12) -0.00600(9) -0.00764(9) -0.00060(9) W6 0.01849(12) 0.02308(12) 0.01791(12) -0.00785(9) -0.00664(9) -0.00398(9) Cu1 0.0305(4) 0.0318(4) 0.0351(4) -0.0122(4) -0.0174(4) 0.0023(4) Cu2 0.0367(7) 0.0528(8) 0.0224(6) -0.0183(6) -0.0030(5) 0.0068(6) Cu3 0.0344(7) 0.0444(8) 0.0367(7) -0.0151(6) -0.0116(6) -0.0070(6) Cu4 0.1022(16) 0.0759(14) 0.1004(16) -0.0538(13) -0.0672(14) 0.0249(12) O1 0.031(3) 0.047(3) 0.042(3) -0.023(3) -0.016(2) 0.018(2) O2 0.029(2) 0.028(2) 0.027(2) -0.0143(19) -0.0054(19) -0.0072(19) O3 0.028(2) 0.026(2) 0.018(2) -0.0120(18) -0.0039(18) 0.0025(19) O4 0.0177(19) 0.019(2) 0.0193(19) -0.0097(16) -0.0049(16) 0.0021(16) O5 0.0124(18) 0.026(2) 0.033(2) -0.0101(19) -0.0060(17) -0.0014(17) O6 0.033(3) 0.041(3) 0.020(2) -0.012(2) -0.0075(19) -0.004(2) O7 0.0187(19) 0.025(2) 0.0163(19) -0.0072(17) -0.0055(16) -0.0046(17) O8 0.022(2) 0.020(2) 0.029(2) -0.0076(18) -0.0092(18) -0.0011(18) O9 0.0171(19) 0.022(2) 0.021(2) -0.0048(17) -0.0060(17) -0.0034(17) O10 0.021(2) 0.034(3) 0.026(2) -0.008(2) -0.0061(18) -0.0069(19) O11 0.025(2) 0.046(3) 0.023(2) -0.014(2) -0.0051(19) -0.008(2) O12 0.0158(19) 0.034(2) 0.020(2) -0.0071(19) -0.0064(17) 0.0016(18) O13 0.017(2) 0.027(2) 0.024(2) -0.0065(18) -0.0054(17) -0.0032(18) O14 0.036(3) 0.042(3) 0.022(2) -0.009(2) -0.009(2) -0.010(2) O15 0.036(3) 0.026(2) 0.045(3) -0.005(2) -0.019(2) -0.009(2) O16 0.021(2) 0.028(2) 0.022(2) -0.0083(18) -0.0075(17) -0.0054(18) O17 0.019(2) 0.025(2) 0.0166(19) -0.0036(17) -0.0069(16) -0.0031(17) O18 0.022(2) 0.034(3) 0.029(2) -0.004(2) -0.0117(19) -0.003(2) O19 0.035(3) 0.029(3) 0.038(3) -0.014(2) -0.010(2) -0.002(2) O20 0.023(2) 0.023(2) 0.021(2) -0.0063(18) -0.0062(17) 0.0020(18) O21 0.039(3) 0.038(3) 0.043(3) -0.017(2) -0.019(2) -0.008(2) O22 0.41(3) 0.177(16) 0.107(11) -0.009(10) -0.078(15) -0.129(18) O23 0.090(7) 0.137(10) 0.205(13) -0.120(10) -0.046(8) 0.052(7) O24 0.274(17) 0.124(9) 0.187(12) -0.119(9) -0.183(13) 0.099(10) N1 0.025(3) 0.041(3) 0.037(3) -0.014(3) -0.016(3) -0.003(3) N2 0.030(3) 0.051(4) 0.031(3) -0.010(3) -0.014(3) -0.008(3) N3 0.041(4) 0.035(4) 0.068(5) -0.012(3) -0.030(4) 0.002(3) N4 0.036(3) 0.063(5) 0.042(4) -0.025(3) -0.016(3) 0.000(3) N5 0.044(4) 0.071(5) 0.041(4) -0.032(4) -0.014(3) 0.012(4) N6 0.055(4) 0.054(4) 0.031(3) -0.023(3) -0.005(3) -0.006(4) N7 0.053(4) 0.072(6) 0.043(4) -0.027(4) -0.027(4) 0.019(4) N8 0.055(4) 0.047(4) 0.037(4) -0.005(3) -0.020(3) -0.018(4) N9 0.071(7) 0.179(14) 0.112(10) -0.086(10) -0.035(7) -0.016(8) N10 0.148(11) 0.061(6) 0.112(9) -0.037(6) -0.093(9) 0.010(7) C1 0.040(4) 0.041(4) 0.050(5) -0.024(4) -0.018(4) -0.006(3) C2 0.040(4) 0.066(6) 0.037(4) -0.027(4) -0.002(3) -0.015(4) C3 0.102(10) 0.060(7) 0.119(12) -0.049(8) -0.030(9) 0.030(7) C4 0.174(17) 0.180(18) 0.105(11) -0.111(13) -0.090(12) 0.129(15) C5 0.061(6) 0.082(7) 0.068(6) -0.049(6) -0.041(5) 0.052(6) C6 0.071(7) 0.080(7) 0.055(6) -0.045(6) -0.025(5) 0.022(6) C7 0.096(9) 0.060(6) 0.064(6) -0.038(5) -0.023(6) -0.009(6) C8 0.087(9) 0.060(7) 0.092(9) -0.005(6) -0.051(7) -0.028(6) C9 0.176(18) 0.084(10) 0.132(14) -0.065(10) -0.107(14) 0.052(11) C10 0.080(9) 0.107(12) 0.153(15) -0.089(12) -0.027(10) 0.000(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 W1 O1 1.741(5) . ? W1 O3 1.848(4) . ? W1 O2 1.856(5) . ? W1 O20 1.961(4) 2_665 ? W1 O5 1.967(5) . ? W1 O4 2.247(4) . ? W2 O6 1.719(5) . ? W2 O8 1.798(4) . ? W2 O9 1.890(4) . ? W2 O7 1.953(4) . ? W2 O3 2.100(4) . ? W2 O4 2.246(4) . ? W3 O10 1.749(5) . ? W3 O11 1.757(4) . ? W3 O5 1.865(5) . ? W3 O13 1.954(5) . ? W3 O12 2.164(4) . ? W3 O9 2.242(4) . ? W4 O14 1.735(5) . ? W4 O15 1.739(5) . ? W4 O13 1.896(4) . ? W4 O16 1.904(4) . ? W4 O17 2.273(4) . ? W4 O9 2.288(4) . ? W5 O18 1.736(5) . ? W5 O19 1.745(5) . ? W5 O20 1.876(4) . ? W5 O16 1.956(4) . ? W5 O8 2.194(4) . ? W5 O17 2.209(4) . ? W6 O21 1.719(5) . ? W6 O12 1.795(4) . ? W6 O17 1.921(4) . ? W6 O7 1.942(4) 2_665 ? W6 O2 2.073(5) 2_665 ? W6 O4 2.271(4) 2_665 ? Cu1 N4 1.987(7) . ? Cu1 N1 2.001(6) . ? Cu1 N2 2.012(6) . ? Cu1 N3 2.029(7) . ? Cu1 O10 2.493(5) . ? Cu1 O18 2.538(5) 1_455 ? Cu2 N5 1.975(7) . ? Cu2 N5 1.975(7) 2_566 ? Cu2 N6 1.982(7) . ? Cu2 N6 1.982(7) 2_566 ? Cu3 N8 1.982(7) 2_656 ? Cu3 N8 1.982(7) . ? Cu3 N7 2.012(7) . ? Cu3 N7 2.012(7) 2_656 ? Cu4 N9 1.935(12) . ? Cu4 N9 1.935(12) 2_655 ? Cu4 N10 1.979(12) 2_655 ? Cu4 N10 1.979(12) . ? O2 W6 2.073(5) 2_665 ? O4 W6 2.271(4) 2_665 ? O4 H4 0.8272 . ? O7 W6 1.942(4) 2_665 ? O20 W1 1.961(4) 2_665 ? O22 H22A 1.0111 . ? O22 H22B 0.8756 . ? O23 H23A 0.8992 . ? O23 H23B 0.8507 . ? O24 H24A 0.9621 . ? O24 H24B 0.9165 . ? O25 H25A 0.8828 . ? O25 H25B 0.8142 . ? O26 H26A 0.8498 . ? O26 H26B 0.8501 . ? O27 H27A 0.8502 . ? O27 H27B 0.8499 . ? N1 C1 1.518(10) . ? N1 H1A 0.9002 . ? N1 H1B 0.9000 . ? N2 C2 1.466(11) . ? N2 H2A 0.9003 . ? N2 H2B 0.8999 . ? N3 C3 1.459(16) . ? N3 H3A 0.9000 . ? N3 H3B 0.8928 . ? N4 C4 1.419(14) . ? N4 H4A 0.8999 . ? N4 H4B 0.9002 . ? N5 C5 1.440(11) . ? N5 H5A 0.9002 . ? N5 H5B 0.9001 . ? N6 C6 1.434(12) . ? N6 H6A 0.8999 . ? N6 H6B 0.9000 . ? N7 C7 1.457(13) . ? N7 H7A 0.9003 . ? N7 H7B 0.9002 . ? N8 C8 1.490(15) . ? N8 H8A 0.9000 . ? N8 H8B 0.8999 . ? N9 C9 1.49(2) . ? N9 H9A 0.9002 . ? N9 H9B 0.8999 . ? N10 C10 1.547(18) . ? N10 H10A 0.9003 . ? N10 H10D 0.9002 . ? C1 C2 1.513(12) . ? C1 H1C 0.9703 . ? C1 H1D 0.9698 . ? C2 H2C 0.9698 . ? C2 H2D 0.9700 . ? C3 C4 1.352(19) . ? C3 H3C 0.9700 . ? C3 H3D 0.9702 . ? C4 H4C 0.9700 . ? C4 H4D 0.9699 . ? C5 C6 1.460(13) . ? C5 H5C 0.9701 . ? C5 H5D 0.9702 . ? C6 H6C 0.9702 . ? C6 H6D 0.9701 . ? C7 C8 1.413(16) 2_656 ? C7 H7C 0.9700 . ? C7 H7D 0.9701 . ? C8 C7 1.413(16) 2_656 ? C8 H8C 0.9703 . ? C8 H8D 0.9702 . ? C9 C10 1.55(2) . ? C9 H9C 0.9703 . ? C9 H9D 0.9699 . ? C10 H10B 0.9700 . ? C10 H10C 0.9706 . ? 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 O3 102.2(2) . . ? O1 W1 O2 102.1(3) . . ? O3 W1 O2 93.9(2) . . ? O1 W1 O20 101.0(2) . 2_665 ? O3 W1 O20 155.78(19) . 2_665 ? O2 W1 O20 87.8(2) . 2_665 ? O1 W1 O5 100.0(2) . . ? O3 W1 O5 86.9(2) . . ? O2 W1 O5 157.14(19) . . ? O20 W1 O5 82.51(19) 2_665 . ? O1 W1 O4 179.3(2) . . ? O3 W1 O4 77.21(17) . . ? O2 W1 O4 77.59(18) . . ? O20 W1 O4 79.58(16) 2_665 . ? O5 W1 O4 80.32(17) . . ? O6 W2 O8 103.9(2) . . ? O6 W2 O9 103.0(2) . . ? O8 W2 O9 94.9(2) . . ? O6 W2 O7 97.8(2) . . ? O8 W2 O7 93.30(19) . . ? O9 W2 O7 155.05(17) . . ? O6 W2 O3 92.5(2) . . ? O8 W2 O3 163.36(18) . . ? O9 W2 O3 84.13(19) . . ? O7 W2 O3 81.37(18) . . ? O6 W2 O4 162.3(2) . . ? O8 W2 O4 90.79(17) . . ? O9 W2 O4 85.34(17) . . ? O7 W2 O4 71.00(16) . . ? O3 W2 O4 72.57(15) . . ? O10 W3 O11 101.3(2) . . ? O10 W3 O5 98.8(2) . . ? O11 W3 O5 97.7(2) . . ? O10 W3 O13 98.2(2) . . ? O11 W3 O13 93.3(2) . . ? O5 W3 O13 157.48(18) . . ? O10 W3 O12 88.78(19) . . ? O11 W3 O12 168.4(2) . . ? O5 W3 O12 86.43(19) . . ? O13 W3 O12 79.30(18) . . ? O10 W3 O9 164.37(19) . . ? O11 W3 O9 92.59(19) . . ? O5 W3 O9 86.28(18) . . ? O13 W3 O9 73.60(17) . . ? O12 W3 O9 76.73(16) . . ? O14 W4 O15 101.3(3) . . ? O14 W4 O13 100.9(2) . . ? O15 W4 O13 96.3(2) . . ? O14 W4 O16 96.9(2) . . ? O15 W4 O16 98.9(2) . . ? O13 W4 O16 153.71(18) . . ? O14 W4 O17 162.9(2) . . ? O15 W4 O17 93.8(2) . . ? O13 W4 O17 85.07(16) . . ? O16 W4 O17 72.70(16) . . ? O14 W4 O9 89.7(2) . . ? O15 W4 O9 166.4(2) . . ? O13 W4 O9 73.53(18) . . ? O16 W4 O9 87.52(17) . . ? O17 W4 O9 76.61(15) . . ? O18 W5 O19 102.2(2) . . ? O18 W5 O20 98.2(2) . . ? O19 W5 O20 97.9(2) . . ? O18 W5 O16 97.1(2) . . ? O19 W5 O16 95.5(2) . . ? O20 W5 O16 157.01(18) . . ? O18 W5 O8 88.9(2) . . ? O19 W5 O8 168.5(2) . . ? O20 W5 O8 83.45(18) . . ? O16 W5 O8 79.77(18) . . ? O18 W5 O17 164.2(2) . . ? O19 W5 O17 91.4(2) . . ? O20 W5 O17 87.79(17) . . ? O16 W5 O17 73.28(16) . . ? O8 W5 O17 77.17(17) . . ? O21 W6 O12 104.9(2) . . ? O21 W6 O17 102.0(2) . . ? O12 W6 O17 94.21(19) . . ? O21 W6 O7 99.1(2) . 2_665 ? O12 W6 O7 92.73(18) . 2_665 ? O17 W6 O7 155.24(17) . 2_665 ? O21 W6 O2 94.1(2) . 2_665 ? O12 W6 O2 161.0(2) . 2_665 ? O17 W6 O2 82.70(18) . 2_665 ? O7 W6 O2 83.04(18) 2_665 2_665 ? O21 W6 O4 164.1(2) . 2_665 ? O12 W6 O4 88.11(18) . 2_665 ? O17 W6 O4 85.87(17) . 2_665 ? O7 W6 O4 70.62(16) 2_665 2_665 ? O2 W6 O4 73.00(16) 2_665 2_665 ? N4 Cu1 N1 91.7(3) . . ? N4 Cu1 N2 177.2(3) . . ? N1 Cu1 N2 85.8(3) . . ? N4 Cu1 N3 86.4(3) . . ? N1 Cu1 N3 177.0(3) . . ? N2 Cu1 N3 96.0(3) . . ? N4 Cu1 O10 86.8(2) . . ? N1 Cu1 O10 88.6(2) . . ? N2 Cu1 O10 91.8(2) . . ? N3 Cu1 O10 89.0(2) . . ? N4 Cu1 O18 92.3(2) . 1_455 ? N1 Cu1 O18 91.8(2) . 1_455 ? N2 Cu1 O18 89.2(2) . 1_455 ? N3 Cu1 O18 90.6(2) . 1_455 ? O10 Cu1 O18 178.98(17) . 1_455 ? N5 Cu2 N5 180.000(1) . 2_566 ? N5 Cu2 N6 84.5(3) . . ? N5 Cu2 N6 95.5(3) 2_566 . ? N5 Cu2 N6 95.5(3) . 2_566 ? N5 Cu2 N6 84.5(3) 2_566 2_566 ? N6 Cu2 N6 180.00(19) . 2_566 ? N8 Cu3 N8 180.0(3) 2_656 . ? N8 Cu3 N7 85.6(4) 2_656 . ? N8 Cu3 N7 94.4(4) . . ? N8 Cu3 N7 94.4(4) 2_656 2_656 ? N8 Cu3 N7 85.6(4) . 2_656 ? N7 Cu3 N7 180.0(4) . 2_656 ? N9 Cu4 N9 180.0(11) . 2_655 ? N9 Cu4 N10 93.0(5) . 2_655 ? N9 Cu4 N10 87.0(5) 2_655 2_655 ? N9 Cu4 N10 87.0(5) . . ? N9 Cu4 N10 93.0(5) 2_655 . ? N10 Cu4 N10 180.0(7) 2_655 . ? W1 O2 W6 115.0(2) . 2_665 ? W1 O3 W2 114.7(2) . . ? W2 O4 W1 95.53(15) . . ? W2 O4 W6 96.77(16) . 2_665 ? W1 O4 W6 94.42(16) . 2_665 ? W2 O4 H4 140.2 . . ? W1 O4 H4 121.0 . . ? W6 O4 H4 95.6 2_665 . ? W3 O5 W1 149.1(2) . . ? W6 O7 W2 120.2(2) 2_665 . ? W2 O8 W5 140.6(2) . . ? W2 O9 W3 139.0(2) . . ? W2 O9 W4 126.1(2) . . ? W3 O9 W4 93.56(16) . . ? W3 O10 Cu1 127.4(2) . . ? W6 O12 W3 138.6(2) . . ? W4 O13 W3 118.1(2) . . ? W4 O16 W5 118.1(2) . . ? W6 O17 W5 138.6(2) . . ? W6 O17 W4 125.2(2) . . ? W5 O17 W4 95.25(15) . . ? W5 O20 W1 146.2(3) . 2_665 ? H22A O22 H22B 127.7 . . ? H23A O23 H23B 103.0 . . ? H24A O24 H24B 127.0 . . ? H25A O25 H25B 116.1 . . ? H26A O26 H26B 107.2 . . ? H27A O27 H27B 125.1 . . ? C1 N1 Cu1 106.6(5) . . ? C1 N1 H1A 110.5 . . ? Cu1 N1 H1A 110.4 . . ? C1 N1 H1B 110.3 . . ? Cu1 N1 H1B 110.4 . . ? H1A N1 H1B 108.6 . . ? C2 N2 Cu1 107.9(5) . . ? C2 N2 H2A 109.6 . . ? Cu1 N2 H2A 109.7 . . ? C2 N2 H2B 110.8 . . ? Cu1 N2 H2B 110.5 . . ? H2A N2 H2B 108.4 . . ? C3 N3 Cu1 106.1(6) . . ? C3 N3 H3A 110.5 . . ? Cu1 N3 H3A 110.7 . . ? C3 N3 H3B 109.5 . . ? Cu1 N3 H3B 109.9 . . ? H3A N3 H3B 110.2 . . ? C4 N4 Cu1 108.8(7) . . ? C4 N4 H4A 110.4 . . ? Cu1 N4 H4A 109.8 . . ? C4 N4 H4B 109.5 . . ? Cu1 N4 H4B 110.0 . . ? H4A N4 H4B 108.3 . . ? C5 N5 Cu2 110.8(5) . . ? C5 N5 H5A 109.5 . . ? Cu2 N5 H5A 109.7 . . ? C5 N5 H5B 109.6 . . ? Cu2 N5 H5B 109.1 . . ? H5A N5 H5B 108.0 . . ? C6 N6 Cu2 108.7(5) . . ? C6 N6 H6A 110.5 . . ? Cu2 N6 H6A 109.9 . . ? C6 N6 H6B 109.2 . . ? Cu2 N6 H6B 110.1 . . ? H6A N6 H6B 108.4 . . ? C7 N7 Cu3 106.4(6) . . ? C7 N7 H7A 110.2 . . ? Cu3 N7 H7A 110.2 . . ? C7 N7 H7B 111.3 . . ? Cu3 N7 H7B 110.1 . . ? H7A N7 H7B 108.6 . . ? C8 N8 Cu3 108.5(6) . . ? C8 N8 H8A 110.5 . . ? Cu3 N8 H8A 109.8 . . ? C8 N8 H8B 109.6 . . ? Cu3 N8 H8B 110.1 . . ? H8A N8 H8B 108.3 . . ? C9 N9 Cu4 109.5(9) . . ? C9 N9 H9A 110.8 . . ? Cu4 N9 H9A 110.5 . . ? C9 N9 H9B 109.0 . . ? Cu4 N9 H9B 108.6 . . ? H9A N9 H9B 108.3 . . ? C10 N10 Cu4 108.1(8) . . ? C10 N10 H10A 109.9 . . ? Cu4 N10 H10A 109.8 . . ? C10 N10 H10D 110.2 . . ? Cu4 N10 H10D 110.4 . . ? H10A N10 H10D 108.4 . . ? C2 C1 N1 105.7(6) . . ? C2 C1 H1C 111.0 . . ? N1 C1 H1C 110.6 . . ? C2 C1 H1D 110.6 . . ? N1 C1 H1D 110.4 . . ? H1C C1 H1D 108.7 . . ? N2 C2 C1 108.4(6) . . ? N2 C2 H2C 109.6 . . ? C1 C2 H2C 109.6 . . ? N2 C2 H2D 110.8 . . ? C1 C2 H2D 110.1 . . ? H2C C2 H2D 108.4 . . ? C4 C3 N3 118.5(10) . . ? C4 C3 H3C 107.1 . . ? N3 C3 H3C 107.7 . . ? C4 C3 H3D 108.2 . . ? N3 C3 H3D 107.7 . . ? H3C C3 H3D 107.0 . . ? C3 C4 N4 118.5(12) . . ? C3 C4 H4C 107.1 . . ? N4 C4 H4C 107.2 . . ? C3 C4 H4D 108.3 . . ? N4 C4 H4D 108.1 . . ? H4C C4 H4D 107.1 . . ? N5 C5 C6 109.5(8) . . ? N5 C5 H5C 109.6 . . ? C6 C5 H5C 110.3 . . ? N5 C5 H5D 109.9 . . ? C6 C5 H5D 109.2 . . ? H5C C5 H5D 108.3 . . ? N6 C6 C5 111.6(9) . . ? N6 C6 H6C 110.1 . . ? C5 C6 H6C 109.7 . . ? N6 C6 H6D 108.6 . . ? C5 C6 H6D 108.7 . . ? H6C C6 H6D 108.0 . . ? C8 C7 N7 113.5(9) 2_656 . ? C8 C7 H7C 108.8 2_656 . ? N7 C7 H7C 108.9 . . ? C8 C7 H7D 108.6 2_656 . ? N7 C7 H7D 108.8 . . ? H7C C7 H7D 108.0 . . ? C7 C8 N8 109.4(9) 2_656 . ? C7 C8 H8C 111.0 2_656 . ? N8 C8 H8C 109.7 . . ? C7 C8 H8D 109.3 2_656 . ? N8 C8 H8D 109.2 . . ? H8C C8 H8D 108.2 . . ? N9 C9 C10 105.8(13) . . ? N9 C9 H9C 110.3 . . ? C10 C9 H9C 110.5 . . ? N9 C9 H9D 111.6 . . ? C10 C9 H9D 109.5 . . ? H9C C9 H9D 109.2 . . ? N10 C10 C9 104.8(12) . . ? N10 C10 H10B 110.3 . . ? C9 C10 H10B 112.9 . . ? N10 C10 H10C 110.5 . . ? C9 C10 H10C 109.7 . . ? H10B C10 H10C 108.6 . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O4 H4 O8 0.83 2.19 2.962(6) 154.3 2_665 O4 H4 O4 0.83 2.28 2.832(8) 124.8 2_665 O23 H23A O24 0.90 1.92 2.816(19) 176.4 . O23 H23B O19 0.85 1.86 2.712(10) 178.7 2_655 O24 H24B O21 0.92 1.91 2.811(11) 165.9 . O26 H26A O15 0.85 2.10 2.95(2) 177.1 2_556 O27 H27A O25 0.85 2.08 2.91(5) 163.9 2 O27 H27B O14 0.85 2.07 2.90(4) 165.5 2_556 N1 H1A O10 0.90 2.20 3.071(8) 163.1 2_565 N1 H1B O8 0.90 2.23 3.111(7) 166.6 1_455 N1 H1B O12 0.90 2.65 3.096(7) 111.4 2_565 N2 H2A O26 0.90 2.45 3.21(2) 141.2 . N2 H2B O11 0.90 2.03 2.901(8) 161.9 . N3 H3A O13 0.90 2.22 3.085(9) 161.6 . N3 H3B O27 0.89 2.15 2.97(4) 153.3 . N4 H4A O20 0.90 2.09 2.954(8) 161.8 1_455 N4 H4A O5 0.90 2.40 3.013(8) 125.8 2_565 N4 H4B O10 0.90 2.50 3.250(9) 141.5 2_565 N5 H5A O11 0.90 2.17 2.969(9) 147.0 . N5 H5B O3 0.90 2.22 3.044(9) 152.4 . N6 H6A O11 0.90 2.08 2.912(9) 154.1 2_566 N6 H6B O1 0.90 2.21 3.099(9) 169.9 2_566 N7 H7A O14 0.90 2.22 3.047(9) 151.9 . N7 H7B O19 0.90 2.43 3.075(9) 128.7 2_656 N8 H8A O18 0.90 2.12 2.962(8) 156.4 2_656 N8 H8B O15 0.90 2.27 3.077(9) 149.4 . N9 H9A O24 0.90 2.24 3.051(18) 150.1 2_655 N9 H9B O15 0.90 2.37 3.078(14) 135.1 . N9 H9B O19 0.90 2.63 3.183(13) 120.9 . N10 H10A O23 0.90 2.48 3.217(16) 139.8 . N10 H10D O2 0.90 2.16 2.928(12) 142.1 1_545 _diffrn_measured_fraction_theta_max 0.974 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 0.974 _refine_diff_density_max 0.782 _refine_diff_density_min -0.835 _refine_diff_density_rms 0.324