# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2004 data_global _journal_coden_Cambridge 182 _journal_volume ? _journal_year ? _journal_page_first ? _publ_requested_journal 'Chemical Communications' loop_ _publ_author_name 'Jonathan Steed' 'Michael B. Hursthouse' 'Mark E. Light' 'David R. Turner' _publ_contact_author_name 'Dr Jonathan Steed' _publ_contact_author_address ; Department of Chemistry University of Durham South Road Durham DH1 3QY UNITED KINGDOM ; _publ_contact_author_email JON.STEED@DURHAM.AC.UK _publ_section_title ; Linear Distortion of Octahedral Metal Centres by Multiple Hydrogen Bonds in Modular ML4 Systems ; data_C:\Dave\Structs\TUPNiSO4\DTNi021\DTNI021.CIF _database_code_depnum_ccdc_archive 'CCDC 233240' _audit_creation_method SHELXL-97 _chemical_name_systematic ; [Ni(TUP)4(H2O)2]SO4.2H2O ; _chemical_name_common '[Ni(TUP)4(H2O)2]SO4.2H2O' _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C52 H58 N12 Ni O12 S' _chemical_formula_weight 1133.87 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' Ni Ni 0.3393 1.1124 '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/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y+1/2, x, z' '-x+1/2, -y+1/2, z' 'y, -x+1/2, z' '-x, -y, -z' 'y-1/2, -x, -z' 'x-1/2, y-1/2, -z' '-y, x-1/2, -z' _cell_length_a 18.028(3) _cell_length_b 18.028(3) _cell_length_c 8.1143(16) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2637.3(7) _cell_formula_units_Z 2 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description Block _exptl_crystal_colour Green/blue _exptl_crystal_size_max 0.3 _exptl_crystal_size_mid 0.3 _exptl_crystal_size_min 0.4 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.428 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1188 _exptl_absorpt_coefficient_mu 0.482 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; Data were corrected for decay and absorption using the program Scalepack Z. Otwinowski and W. Minor, in Methods in Enzymology, ed. C. W. Carter and R. M. Sweet, Academic Press: London, 1997, vol. 276, pp 307. ; _diffrn_ambient_temperature 120(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 'Nonius KappaCCD' _diffrn_measurement_method ? _diffrn_detector_area_resol_mean 0.71 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0.0 _diffrn_reflns_number 4131 _diffrn_reflns_av_R_equivalents 0.0564 _diffrn_reflns_av_sigmaI/netI 0.0888 _diffrn_reflns_limit_h_min -23 _diffrn_reflns_limit_h_max 23 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 7 _diffrn_reflns_theta_min 2.75 _diffrn_reflns_theta_max 27.45 _reflns_number_total 2540 _reflns_number_gt 1738 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Hooft, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'X-Seed (Barbour, 1999)' _computing_publication_material 'CIFTAB (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^)+(0.0396P)^2^+0.0000P] where P==(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0121(11) _refine_ls_extinction_expression Fc^*^==kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 2540 _refine_ls_number_parameters 210 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0822 _refine_ls_R_factor_gt 0.0406 _refine_ls_wR_factor_ref 0.0958 _refine_ls_wR_factor_gt 0.0847 _refine_ls_goodness_of_fit_ref 1.000 _refine_ls_restrained_S_all 1.000 _refine_ls_shift/su_max 1.898 _refine_ls_shift/su_mean 0.015 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 Ni1 Ni 0.7500 0.7500 0.24189(7) 0.0181(2) Uani 1 4 d S . . S1 S 0.7500 1.2500 0.5000 0.0214(3) Uani 1 4 d S . . N2 N 0.77587(10) 1.03467(9) 0.4842(2) 0.0261(5) Uani 1 1 d . A . H2N H 0.7753 1.0824 0.4613 0.031 Uiso 1 1 calc R . . C5 C 0.76169(12) 0.91041(11) 0.3565(3) 0.0222(5) Uani 1 1 d . . . H5 H 0.7920 0.8888 0.4394 0.027 Uiso 1 1 calc R . . C8 C 0.83779(12) 1.13245(11) 0.9943(3) 0.0264(6) Uani 1 1 d . . . H8 H 0.8090 1.1728 0.9547 0.032 Uiso 1 1 calc R . . N1 N 0.73260(9) 0.86649(9) 0.2403(2) 0.0199(4) Uani 1 1 d . . . C3 C 0.70980(13) 1.01794(12) 0.2326(3) 0.0285(6) Uani 1 1 d . . . H3 H 0.7027 1.0701 0.2282 0.034 Uiso 1 1 calc R . . N3 N 0.81998(10) 1.07297(10) 0.7330(2) 0.0258(5) Uani 1 1 d . A . H3N H 0.8133 1.1174 0.6907 0.031 Uiso 1 1 calc R . . C1 C 0.69168(12) 0.89783(12) 0.1219(3) 0.0279(6) Uani 1 1 d . . . H1 H 0.6692 0.8667 0.0416 0.033 Uiso 1 1 calc R . . C9 C 0.86886(13) 1.13626(13) 1.1492(3) 0.0293(6) Uani 1 1 d . . . H9 H 0.8613 1.1794 1.2141 0.035 Uiso 1 1 calc R . . C2 C 0.68068(13) 0.97309(12) 0.1114(3) 0.0324(6) Uani 1 1 d . . . H2 H 0.6535 0.9938 0.0222 0.039 Uiso 1 1 calc R . . C10 C 0.91105(13) 1.07815(13) 1.2126(3) 0.0298(6) Uani 1 1 d . . . O3A O 0.7938(3) 0.9513(5) 0.6875(14) 0.0309(16) Uani 0.50 1 d P A 1 C11 C 0.91804(14) 1.01574(13) 1.1155(3) 0.0358(7) Uani 1 1 d . . . H11 H 0.9446 0.9744 1.1578 0.043 Uiso 1 1 calc R . . C4 C 0.74927(11) 0.98659(11) 0.3606(3) 0.0220(5) Uani 1 1 d . . . C7 C 0.84789(12) 1.07052(12) 0.8953(3) 0.0247(6) Uani 1 1 d . . . C6 C 0.80226(14) 1.01512(13) 0.6349(3) 0.0324(6) Uani 1 1 d . . . C13 C 0.94877(15) 1.08358(16) 1.3767(3) 0.0460(7) Uani 1 1 d . . . H13A H 0.9483 1.0349 1.4305 0.069 Uiso 1 1 calc R . . H13C H 0.9225 1.1195 1.4460 0.069 Uiso 1 1 calc R . . H13B H 1.0002 1.0999 1.3611 0.069 Uiso 1 1 calc R . . C12 C 0.88804(13) 1.01083(13) 0.9588(3) 0.0347(7) Uani 1 1 d . . . H12 H 0.8947 0.9671 0.8951 0.042 Uiso 1 1 calc R . . O4 O 0.68993(8) 1.28093(8) 0.6018(2) 0.0377(5) Uani 1 1 d . . . O1 O 0.7500 0.7500 0.4979(5) 0.0260(9) Uani 1 4 d S . . O2 O 0.7500 0.7500 -0.0195(5) 0.0242(8) Uani 1 4 d S . . O5 O 0.8406(2) 0.8055(2) 0.7357(4) 0.0278(8) Uani 0.50 1 d PD . . H3O H 0.727(5) 0.777(5) -0.080(8) 0.00(2) Uiso 0.25 1 d P . . H2O H 0.723(5) 0.726(5) 0.529(10) 0.00(2) Uiso 0.25 1 d P . . O3B O 0.8250(4) 0.9497(5) 0.6671(14) 0.044(2) Uani 0.50 1 d P A 2 H4O H 0.879(3) 0.788(3) 0.719(6) 0.030(17) Uiso 0.50 1 d PD . . H5O H 0.853(2) 0.851(3) 0.724(6) 0.020(13) Uiso 0.50 1 d PD . . 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 Ni1 0.0179(2) 0.0179(2) 0.0185(4) 0.000 0.000 0.000 S1 0.0173(4) 0.0173(4) 0.0296(8) 0.000 0.000 0.000 N2 0.0380(11) 0.0132(9) 0.0271(13) -0.0004(9) -0.0050(10) -0.0009(8) C5 0.0229(11) 0.0204(12) 0.0233(14) 0.0001(11) -0.0023(11) 0.0026(9) C8 0.0251(12) 0.0195(12) 0.0346(16) -0.0022(12) 0.0033(12) -0.0003(9) N1 0.0172(9) 0.0212(10) 0.0214(12) 0.0005(9) -0.0015(9) 0.0001(8) C3 0.0323(13) 0.0181(12) 0.0351(17) 0.0021(12) -0.0023(12) 0.0032(10) N3 0.0361(12) 0.0155(10) 0.0259(13) -0.0007(9) -0.0032(9) -0.0009(8) C1 0.0297(13) 0.0250(13) 0.0291(16) -0.0007(11) -0.0098(12) 0.0016(10) C9 0.0321(14) 0.0277(13) 0.0280(16) -0.0086(12) 0.0065(12) -0.0053(10) C2 0.0369(14) 0.0283(13) 0.0320(17) 0.0024(12) -0.0123(13) 0.0070(10) C10 0.0269(13) 0.0366(15) 0.0258(16) 0.0009(12) 0.0026(11) -0.0058(11) O3A 0.041(4) 0.018(3) 0.033(3) 0.003(2) -0.011(4) -0.003(3) C11 0.0419(15) 0.0298(14) 0.0357(18) 0.0033(13) -0.0042(13) 0.0100(11) C4 0.0230(12) 0.0202(12) 0.0229(14) -0.0001(11) 0.0014(11) -0.0019(9) C7 0.0257(12) 0.0248(13) 0.0237(15) 0.0006(11) 0.0014(11) -0.0038(10) C6 0.0453(16) 0.0207(13) 0.0310(17) 0.0007(13) -0.0035(13) -0.0005(11) C13 0.0466(17) 0.0543(18) 0.0372(19) -0.0043(15) -0.0051(14) -0.0006(13) C12 0.0468(16) 0.0240(13) 0.0332(18) -0.0048(12) -0.0035(14) 0.0079(11) O4 0.0311(9) 0.0291(9) 0.0529(13) -0.0075(8) 0.0191(9) 0.0014(7) O1 0.0268(14) 0.0268(14) 0.024(2) 0.000 0.000 0.000 O2 0.0267(12) 0.0267(12) 0.019(2) 0.000 0.000 0.000 O5 0.024(2) 0.028(2) 0.032(2) 0.0032(17) -0.0014(16) 0.0000(17) O3B 0.073(6) 0.017(2) 0.042(4) -0.002(2) -0.029(5) 0.009(4) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ni1 O1 2.077(4) . ? Ni1 O2 2.121(4) . ? Ni1 N1 2.1234(17) 2_655 ? Ni1 N1 2.1234(17) . ? Ni1 N1 2.1234(17) 3_665 ? Ni1 N1 2.1234(17) 4_565 ? S1 O4 1.4720(15) 8_766 ? S1 O4 1.4720(15) 3_675 ? S1 O4 1.4720(15) . ? S1 O4 1.4720(15) 6_576 ? N2 C6 1.359(3) . ? N2 C4 1.410(3) . ? C5 N1 1.338(3) . ? C5 C4 1.392(3) . ? C8 C9 1.377(3) . ? C8 C7 1.388(3) . ? N1 C1 1.336(3) . ? C3 C2 1.377(3) . ? C3 C4 1.380(3) . ? N3 C6 1.350(3) . ? N3 C7 1.410(3) . ? C1 C2 1.374(3) . ? C9 C10 1.393(3) . ? C10 C11 1.379(3) . ? C10 C13 1.499(3) . ? O3A C6 1.237(10) . ? C11 C12 1.384(4) . ? C7 C12 1.396(3) . ? C6 O3B 1.277(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 O1 Ni1 O2 180.000(1) . . ? O1 Ni1 N1 90.35(5) . 2_655 ? O2 Ni1 N1 89.65(5) . 2_655 ? O1 Ni1 N1 90.35(5) . . ? O2 Ni1 N1 89.65(5) . . ? N1 Ni1 N1 89.998(1) 2_655 . ? O1 Ni1 N1 90.35(5) . 3_665 ? O2 Ni1 N1 89.65(5) . 3_665 ? N1 Ni1 N1 89.998(1) 2_655 3_665 ? N1 Ni1 N1 179.31(11) . 3_665 ? O1 Ni1 N1 90.35(5) . 4_565 ? O2 Ni1 N1 89.65(5) . 4_565 ? N1 Ni1 N1 179.31(11) 2_655 4_565 ? N1 Ni1 N1 89.998(1) . 4_565 ? N1 Ni1 N1 89.998(1) 3_665 4_565 ? O4 S1 O4 108.37(7) 8_766 3_675 ? O4 S1 O4 108.37(7) 8_766 . ? O4 S1 O4 111.69(14) 3_675 . ? O4 S1 O4 111.69(14) 8_766 6_576 ? O4 S1 O4 108.37(7) 3_675 6_576 ? O4 S1 O4 108.37(7) . 6_576 ? C6 N2 C4 126.87(18) . . ? N1 C5 C4 122.5(2) . . ? C9 C8 C7 121.0(2) . . ? C1 N1 C5 118.19(19) . . ? C1 N1 Ni1 120.27(15) . . ? C5 N1 Ni1 121.54(14) . . ? C2 C3 C4 119.6(2) . . ? C6 N3 C7 127.6(2) . . ? N1 C1 C2 122.8(2) . . ? C8 C9 C10 121.4(2) . . ? C1 C2 C3 118.7(2) . . ? C11 C10 C9 116.9(2) . . ? C11 C10 C13 121.3(2) . . ? C9 C10 C13 121.8(2) . . ? C10 C11 C12 122.8(2) . . ? C3 C4 C5 118.0(2) . . ? C3 C4 N2 117.32(19) . . ? C5 C4 N2 124.7(2) . . ? C8 C7 C12 118.3(2) . . ? C8 C7 N3 118.0(2) . . ? C12 C7 N3 123.7(2) . . ? O3A C6 O3B 27.0(4) . . ? O3A C6 N3 123.0(6) . . ? O3B C6 N3 121.1(5) . . ? O3A C6 N2 120.6(5) . . ? O3B C6 N2 122.5(6) . . ? N3 C6 N2 114.4(2) . . ? C11 C12 C7 119.5(2) . . ? 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 N2 H2N O4 0.88 2.25 3.061(2) 153.7 8_766 N3 H3N O4 0.88 1.97 2.846(2) 173.7 3_675 O2 H3O O5 0.80(6) 1.98(6) 2.759(5) 165(8) 2_654 O1 H2O O5 0.70(6) 2.11(7) 2.719(4) 147(9) 3_665 O5 H4O O3A 0.77(5) 1.99(5) 2.709(10) 156(5) 4_565 O5 H4O O3B 0.77(5) 2.45(5) 3.117(10) 147(5) 4_565 O5 H5O O3B 0.87(5) 1.90(5) 2.672(11) 148(4) . O5 H5O O3A 0.87(5) 2.12(5) 2.788(10) 134(4) . _diffrn_measured_fraction_theta_max 0.839 _diffrn_reflns_theta_full 27.45 _diffrn_measured_fraction_theta_full 0.839 _refine_diff_density_max 0.349 _refine_diff_density_min -0.500 _refine_diff_density_rms 0.076 data_c:\dave\structs\dtheat\dtco1\dtco1 _database_code_depnum_ccdc_archive 'CCDC 233241' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C52 H64 Co N12 O12 S' _chemical_formula_weight 1140.14 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' Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting ? _symmetry_space_group_name_H-M ? loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y+1/2, x, z' '-x+1/2, -y+1/2, z' 'y, -x+1/2, z' '-x, -y, -z' 'y-1/2, -x, -z' 'x-1/2, y-1/2, -z' '-y, x-1/2, -z' _cell_length_a 18.070(3) _cell_length_b 18.070(3) _cell_length_c 8.0756(16) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2636.9(7) _cell_formula_units_Z 2 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max ? _exptl_crystal_size_mid ? _exptl_crystal_size_min ? _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.436 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1198 _exptl_absorpt_coefficient_mu 0.440 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 173(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 ? _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 4642 _diffrn_reflns_av_R_equivalents 0.0345 _diffrn_reflns_av_sigmaI/netI 0.0345 _diffrn_reflns_limit_h_min -23 _diffrn_reflns_limit_h_max 23 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -6 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 2.52 _diffrn_reflns_theta_max 27.48 _reflns_number_total 3007 _reflns_number_gt 2864 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0000P)^2^+4.2991P] 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 0.018(2) _refine_ls_extinction_expression Fc^*^==kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 3007 _refine_ls_number_parameters 198 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0484 _refine_ls_R_factor_gt 0.0429 _refine_ls_wR_factor_ref 0.1018 _refine_ls_wR_factor_gt 0.1007 _refine_ls_goodness_of_fit_ref 1.177 _refine_ls_restrained_S_all 1.177 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Co1 Co 0.2500 0.2500 0.23627(6) 0.00996(16) Uani 1 4 d S . . S1 S 0.2500 0.7500 0.5000 0.0117(2) Uani 1 4 d S . . N2 N 0.22515(10) 0.53611(9) 0.4829(2) 0.0172(4) Uani 1 1 d . A . H2 H 0.2258 0.5838 0.4610 0.021 Uiso 1 1 calc R . . C8 C 0.16345(11) 0.63216(11) 0.9966(3) 0.0164(4) Uani 1 1 d . . . H8 H 0.1923 0.6724 0.9568 0.020 Uiso 1 1 calc R . . O2 O 0.2500 0.2500 -0.0272(4) 0.0153(5) Uani 1 4 d S . . N1 N 0.26772(9) 0.36859(8) 0.2353(2) 0.0135(3) Uani 1 1 d . . . O1 O 0.2500 0.2500 0.4935(3) 0.0166(6) Uani 1 4 d S . . C11 C 0.08213(14) 0.51518(13) 1.1171(3) 0.0274(5) Uani 1 1 d . . . H11 H 0.0551 0.4741 1.1587 0.033 Uiso 1 1 calc R . . C10 C 0.09022(12) 0.57733(12) 1.2161(3) 0.0211(4) Uani 1 1 d . . . C9 C 0.13253(11) 0.63561(11) 1.1537(3) 0.0187(4) Uani 1 1 d . . . H9 H 0.1403 0.6784 1.2199 0.022 Uiso 1 1 calc R . . C13 C 0.05267(14) 0.58227(15) 1.3829(3) 0.0310(5) Uani 1 1 d . . . H13A H 0.0006 0.5957 1.3675 0.047 Uiso 1 1 calc R . . H13B H 0.0773 0.6200 1.4503 0.047 Uiso 1 1 calc R . . H13C H 0.0558 0.5343 1.4389 0.047 Uiso 1 1 calc R . . C7 C 0.15259(11) 0.57032(11) 0.8968(3) 0.0168(4) Uani 1 1 d . . . C12 C 0.11219(14) 0.51083(12) 0.9592(3) 0.0270(5) Uani 1 1 d . . . H12 H 0.1053 0.4676 0.8942 0.032 Uiso 1 1 calc R . . O4 O 0.28082(8) 0.68991(8) 0.3966(2) 0.0221(3) Uani 1 1 d . . . C5 C 0.23867(10) 0.41226(10) 0.3539(2) 0.0149(4) Uani 1 1 d . . . H5 H 0.2086 0.3904 0.4371 0.018 Uiso 1 1 calc R . . C2 C 0.31997(13) 0.47570(12) 0.1071(3) 0.0238(5) Uani 1 1 d . . . H2A H 0.3474 0.4966 0.0183 0.029 Uiso 1 1 calc R . . C1 C 0.30854(12) 0.39981(11) 0.1153(3) 0.0197(4) Uani 1 1 d . . . H1 H 0.3303 0.3690 0.0333 0.024 Uiso 1 1 calc R . . N3 N 0.18073(10) 0.57378(9) 0.7333(2) 0.0174(4) Uani 1 1 d . A . H3 H 0.1871 0.6182 0.6912 0.021 Uiso 1 1 calc R . . C3 C 0.29109(12) 0.52031(11) 0.2295(3) 0.0207(4) Uani 1 1 d . . . H3A H 0.2984 0.5723 0.2257 0.025 Uiso 1 1 calc R . . C4 C 0.25114(11) 0.48866(10) 0.3587(2) 0.0152(4) Uani 1 1 d . . . C6 C 0.19884(14) 0.51567(11) 0.6350(3) 0.0248(5) Uani 1 1 d . . . O3A O 0.2079(2) 0.4513(3) 0.6895(6) 0.0190(9) Uani 0.50 1 d P A 1 O5 O 0.30608(15) 0.34063(15) 0.7292(3) 0.0158(5) Uani 0.50 1 d P . . O3B O 0.1748(3) 0.4508(3) 0.6627(6) 0.0305(11) Uani 0.50 1 d P A 2 H2O H 0.2811 0.2261 -0.0987 0.23(4) Uiso 1 1 d R . . H1O H 0.2632 0.2831 0.5689 0.43(6) Uiso 1 1 d R . . H4 H 0.3557 0.3475 0.7187 0.010(11) Uiso 0.50 1 d PR . . H6 H 0.2831 0.3769 0.7630 0.06(2) Uiso 0.50 1 d 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 Co1 0.00966(19) 0.00966(19) 0.0106(3) 0.000 0.000 0.000 S1 0.0089(3) 0.0089(3) 0.0172(5) 0.000 0.000 0.000 N2 0.0249(9) 0.0075(7) 0.0192(8) -0.0014(6) 0.0045(7) 0.0005(6) C8 0.0142(9) 0.0136(9) 0.0215(10) -0.0013(7) -0.0019(7) -0.0004(7) O2 0.0171(8) 0.0171(8) 0.0118(12) 0.000 0.000 0.000 N1 0.0138(7) 0.0099(7) 0.0168(8) -0.0003(6) 0.0014(6) -0.0007(6) O1 0.0190(8) 0.0190(8) 0.0119(13) 0.000 0.000 0.000 C11 0.0352(13) 0.0250(11) 0.0219(11) 0.0016(9) 0.0038(9) -0.0118(9) C10 0.0191(10) 0.0273(11) 0.0169(10) -0.0007(8) -0.0013(8) 0.0012(8) C9 0.0176(9) 0.0192(9) 0.0194(10) -0.0066(8) -0.0044(8) 0.0034(7) C13 0.0284(12) 0.0437(14) 0.0209(11) -0.0024(10) 0.0032(9) -0.0011(10) C7 0.0190(9) 0.0146(9) 0.0167(9) -0.0006(7) -0.0001(8) 0.0007(7) C12 0.0415(13) 0.0174(10) 0.0223(11) -0.0051(8) 0.0038(10) -0.0101(9) O4 0.0168(7) 0.0183(7) 0.0313(8) -0.0103(6) 0.0043(6) 0.0003(6) C5 0.0150(9) 0.0133(9) 0.0163(9) 0.0006(7) 0.0014(7) 0.0002(7) C2 0.0320(12) 0.0166(10) 0.0229(11) 0.0017(8) 0.0106(9) -0.0062(8) C1 0.0242(10) 0.0148(9) 0.0202(10) -0.0027(8) 0.0095(8) -0.0020(8) N3 0.0239(9) 0.0106(7) 0.0176(8) -0.0003(6) 0.0026(7) -0.0005(6) C3 0.0274(11) 0.0114(9) 0.0232(11) 0.0011(8) 0.0041(9) -0.0025(8) C4 0.0170(9) 0.0122(9) 0.0165(9) -0.0009(7) -0.0005(7) 0.0013(7) C6 0.0421(13) 0.0113(9) 0.0209(11) 0.0000(8) 0.0063(10) 0.0014(9) O3A 0.027(2) 0.0104(15) 0.0194(19) 0.0011(13) 0.0033(18) 0.0008(18) O5 0.0138(13) 0.0154(13) 0.0183(14) -0.0020(11) 0.0013(11) -0.0004(11) O3B 0.055(3) 0.0104(16) 0.026(2) -0.0019(15) 0.014(2) -0.008(2) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Co1 O1 2.077(3) . ? Co1 O2 2.127(3) . ? Co1 N1 2.1667(16) 3 ? Co1 N1 2.1667(16) . ? Co1 N1 2.1667(16) 2 ? Co1 N1 2.1667(16) 4 ? S1 O4 1.4786(14) 8_666 ? S1 O4 1.4786(14) . ? S1 O4 1.4786(14) 6_566 ? S1 O4 1.4786(14) 3_565 ? N2 C6 1.368(3) . ? N2 C4 1.401(2) . ? C8 C9 1.388(3) . ? C8 C7 1.392(3) . ? N1 C1 1.343(3) . ? N1 C5 1.347(2) . ? C11 C10 1.386(3) . ? C11 C12 1.388(3) . ? C10 C9 1.395(3) . ? C10 C13 1.511(3) . ? C7 C12 1.394(3) . ? C7 N3 1.416(3) . ? C5 C4 1.399(3) . ? C2 C3 1.378(3) . ? C2 C1 1.388(3) . ? N3 C6 1.357(3) . ? C3 C4 1.391(3) . ? C6 O3A 1.255(5) . ? C6 O3B 1.270(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 O1 Co1 O2 180.000(1) . . ? O1 Co1 N1 90.21(5) . 3 ? O2 Co1 N1 89.79(5) . 3 ? O1 Co1 N1 90.21(5) . . ? O2 Co1 N1 89.79(5) . . ? N1 Co1 N1 179.59(9) 3 . ? O1 Co1 N1 90.21(5) . 2 ? O2 Co1 N1 89.79(5) . 2 ? N1 Co1 N1 89.999(1) 3 2 ? N1 Co1 N1 89.999(1) . 2 ? O1 Co1 N1 90.21(5) . 4 ? O2 Co1 N1 89.79(5) . 4 ? N1 Co1 N1 89.999(1) 3 4 ? N1 Co1 N1 89.999(1) . 4 ? N1 Co1 N1 179.59(9) 2 4 ? O4 S1 O4 108.59(6) 8_666 . ? O4 S1 O4 111.25(13) 8_666 6_566 ? O4 S1 O4 108.59(6) . 6_566 ? O4 S1 O4 108.59(6) 8_666 3_565 ? O4 S1 O4 111.25(13) . 3_565 ? O4 S1 O4 108.59(6) 6_566 3_565 ? C6 N2 C4 126.47(17) . . ? C9 C8 C7 120.59(19) . . ? C1 N1 C5 118.76(16) . . ? C1 N1 Co1 119.96(13) . . ? C5 N1 Co1 121.28(13) . . ? C10 C11 C12 122.3(2) . . ? C11 C10 C9 117.5(2) . . ? C11 C10 C13 121.0(2) . . ? C9 C10 C13 121.5(2) . . ? C8 C9 C10 121.10(19) . . ? C8 C7 C12 118.91(19) . . ? C8 C7 N3 116.99(18) . . ? C12 C7 N3 124.03(18) . . ? C11 C12 C7 119.6(2) . . ? N1 C5 C4 122.33(18) . . ? C3 C2 C1 119.17(19) . . ? N1 C1 C2 122.07(19) . . ? C6 N3 C7 126.74(18) . . ? C2 C3 C4 119.59(18) . . ? C3 C4 C5 117.92(18) . . ? C3 C4 N2 117.34(17) . . ? C5 C4 N2 124.73(18) . . ? O3A C6 O3B 29.2(2) . . ? O3A C6 N3 123.0(3) . . ? O3B C6 N3 121.9(3) . . ? O3A C6 N2 121.3(3) . . ? O3B C6 N2 121.8(3) . . ? N3 C6 N2 113.60(18) . . ? 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 N2 H2 O4 0.88 2.22 3.037(2) 154.0 . N3 H3 O4 0.88 1.96 2.834(2) 173.7 6_566 O2 H2O O5 0.92 1.85 2.753(3) 168.4 4_554 O1 H1O O5 0.89 1.83 2.708(3) 169.3 . O5 H4 O3B 0.91 1.82 2.685(6) 157.4 4 O5 H4 O3A 0.91 2.01 2.785(5) 142.2 4 O5 H6 O3B 0.82 2.51 3.144(6) 135.4 . O5 H6 O3A 0.82 2.00 2.691(5) 141.2 . _diffrn_measured_fraction_theta_max 0.985 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 0.985 _refine_diff_density_max 0.372 _refine_diff_density_min -0.565 _refine_diff_density_rms 0.093 data_C:\Dave\Structs\DTZn032\DTZN032.CIF _database_code_depnum_ccdc_archive 'CCDC 233242' _audit_creation_method SHELXL-97 _chemical_name_systematic ; [Zn(TUP)4(H2O)2]SO4.2H2O ; _chemical_name_common '[Zn(TUP)4(H2O)2]SO4.2H2O' _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C52 H60 N12 O14 S Zn' _chemical_formula_weight 1174.55 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 tetragonal _symmetry_space_group_name_H-M P4/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y+1/2, x, z' '-x+1/2, -y+1/2, z' 'y, -x+1/2, z' '-x, -y, -z' 'y-1/2, -x, -z' 'x-1/2, y-1/2, -z' '-y, x-1/2, -z' _cell_length_a 18.0760(5) _cell_length_b 18.0760(5) _cell_length_c 8.1208(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2653.41(14) _cell_formula_units_Z 2 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description Block _exptl_crystal_colour Red _exptl_crystal_size_max 0.2 _exptl_crystal_size_mid 0.2 _exptl_crystal_size_min 0.3 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.470 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1228 _exptl_absorpt_coefficient_mu 0.582 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; Data were corrected for decay and absorption using the program Scalepack Z. Otwinowski and W. Minor, in Methods in Enzymology, ed. C. W. Carter and R. M. Sweet, Academic Press: London, 1997, vol. 276, pp 307. ; _diffrn_ambient_temperature 120(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 'Nonius KappaCCD' _diffrn_measurement_method ? _diffrn_detector_area_resol_mean 0.71 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0.0 _diffrn_reflns_number 4860 _diffrn_reflns_av_R_equivalents 0.0428 _diffrn_reflns_av_sigmaI/netI 0.0865 _diffrn_reflns_limit_h_min -23 _diffrn_reflns_limit_h_max 23 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 8 _diffrn_reflns_theta_min 2.51 _diffrn_reflns_theta_max 27.46 _reflns_number_total 3035 _reflns_number_gt 2061 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Hooft, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'X-Seed (Barbour, 1999)' _computing_publication_material 'CIFTAB (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^)+(0.0974P)^2^+0.0000P] where P==(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0066(15) _refine_ls_extinction_expression Fc^*^==kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 3035 _refine_ls_number_parameters 198 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0997 _refine_ls_R_factor_gt 0.0575 _refine_ls_wR_factor_ref 0.1639 _refine_ls_wR_factor_gt 0.1454 _refine_ls_goodness_of_fit_ref 1.036 _refine_ls_restrained_S_all 1.036 _refine_ls_shift/su_max 1.145 _refine_ls_shift/su_mean 0.006 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 Zn1 Zn 0.7500 0.7500 0.23992(8) 0.0130(2) Uani 1 4 d S . . S2 S 0.7500 1.2500 0.5000 0.0146(4) Uani 1 4 d S . . O2 O 0.7500 0.7500 -0.0295(5) 0.0181(9) Uani 1 4 d S . . N3 N 0.81921(14) 1.07391(14) 0.7328(3) 0.0183(6) Uani 1 1 d . A . H3 H 0.8125 1.1184 0.6913 0.022 Uiso 1 1 calc R . . N2 N 0.77473(14) 1.03628(13) 0.4837(3) 0.0191(6) Uani 1 1 d . A . H2 H 0.7738 1.0840 0.4619 0.023 Uiso 1 1 calc R . . C3 C 0.70956(18) 1.01995(17) 0.2308(4) 0.0198(7) Uani 1 1 d . A . H3A H 0.7024 1.0720 0.2262 0.024 Uiso 1 1 calc R . . C9 C 0.86765(17) 1.13526(17) 1.1514(4) 0.0205(7) Uani 1 1 d . . . H9 H 0.8599 1.1780 1.2173 0.025 Uiso 1 1 calc R . . C5 C 0.76105(16) 0.91244(16) 0.3560(4) 0.0160(6) Uani 1 1 d . A . H5 H 0.7903 0.8905 0.4401 0.019 Uiso 1 1 calc R . . N1 N 0.73286(13) 0.86897(14) 0.2371(3) 0.0158(6) Uani 1 1 d . . . C10 C 0.90971(18) 1.07740(18) 1.2139(4) 0.0225(7) Uani 1 1 d . . . C1 C 0.69223(17) 0.90034(17) 0.1180(4) 0.0210(7) Uani 1 1 d . . . H1 H 0.6703 0.8695 0.0367 0.025 Uiso 1 1 calc R . . C7 C 0.84744(17) 1.07047(16) 0.8958(4) 0.0176(7) Uani 1 1 d . . . C8 C 0.83663(16) 1.13220(16) 0.9955(4) 0.0189(7) Uani 1 1 d . . . H8 H 0.8078 1.1725 0.9563 0.023 Uiso 1 1 calc R . . C11 C 0.9173(2) 1.01504(19) 1.1147(4) 0.0271(8) Uani 1 1 d . . . H11 H 0.9439 0.9737 1.1560 0.032 Uiso 1 1 calc R . . O1 O 0.7500 0.7500 0.5026(5) 0.0173(9) Uani 1 4 d S . . C6 C 0.8016(2) 1.01633(18) 0.6348(4) 0.0258(8) Uani 1 1 d . . . C2 C 0.68104(19) 0.97545(18) 0.1091(4) 0.0247(8) Uani 1 1 d . . . H2A H 0.6540 0.9963 0.0201 0.030 Uiso 1 1 calc R . . C13 C 0.9467(2) 1.0822(2) 1.3785(4) 0.0322(9) Uani 1 1 d . . . H13A H 0.9988 1.0958 1.3636 0.048 Uiso 1 1 calc R . . H13B H 0.9437 1.0342 1.4339 0.048 Uiso 1 1 calc R . . H13C H 0.9219 1.1198 1.4457 0.048 Uiso 1 1 calc R . . C4 C 0.74866(16) 0.98909(16) 0.3600(4) 0.0161(7) Uani 1 1 d . . . O3B O 0.8249(4) 0.9514(5) 0.6619(12) 0.032(2) Uani 0.50 1 d P A 2 C12 C 0.88745(19) 1.01115(18) 0.9574(4) 0.0262(8) Uani 1 1 d . . . H12 H 0.8944 0.9681 0.8923 0.031 Uiso 1 1 calc R . . O4 O 0.71956(12) 1.18968(12) 0.3977(3) 0.0249(6) Uani 1 1 d . . . O5 O 0.8433(3) 0.8075(2) 0.7335(5) 0.0876(13) Uani 1 1 d . . . O3A O 0.7930(4) 0.9517(5) 0.6904(11) 0.0224(16) Uani 0.50 1 d P A 1 H2O H 0.7603 0.7090 -0.0971 0.24(10) Uiso 0.50 1 d PR . . H1O H 0.7592 0.7045 0.5867 2(2) Uiso 0.50 1 d PR . . H5A H 0.8495 0.8814 0.7285 0.20(8) Uiso 0.50 1 d PR . . H5B H 0.9161 0.7973 0.6896 0.06(2) Uiso 0.50 1 d 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 Zn1 0.0130(3) 0.0130(3) 0.0131(4) 0.000 0.000 0.000 S2 0.0120(5) 0.0120(5) 0.0199(8) 0.000 0.000 0.000 O2 0.0185(13) 0.0185(13) 0.017(2) 0.000 0.000 0.000 N3 0.0248(14) 0.0113(12) 0.0187(14) -0.0006(10) -0.0018(11) 0.0002(11) N2 0.0271(15) 0.0117(12) 0.0184(13) 0.0007(10) -0.0021(11) -0.0021(11) C3 0.0236(17) 0.0121(15) 0.0238(17) 0.0027(13) -0.0015(14) 0.0013(12) C9 0.0198(16) 0.0199(16) 0.0218(17) -0.0061(14) 0.0045(13) -0.0065(13) C5 0.0166(15) 0.0156(15) 0.0159(15) 0.0016(12) -0.0022(12) 0.0005(12) N1 0.0139(12) 0.0157(13) 0.0178(13) -0.0002(10) -0.0004(10) -0.0009(10) C10 0.0198(16) 0.0288(18) 0.0190(16) -0.0013(14) 0.0036(13) -0.0038(14) C1 0.0230(16) 0.0187(16) 0.0211(17) -0.0008(13) -0.0071(13) 0.0003(13) C7 0.0192(15) 0.0172(15) 0.0164(15) -0.0017(12) 0.0009(13) -0.0025(13) C8 0.0154(15) 0.0160(15) 0.0254(17) 0.0007(13) 0.0028(13) -0.0020(12) C11 0.0323(19) 0.0245(17) 0.0243(18) 0.0039(14) -0.0017(15) 0.0087(15) O1 0.0203(13) 0.0203(13) 0.011(2) 0.000 0.000 0.000 C6 0.039(2) 0.0167(16) 0.0218(17) -0.0002(14) -0.0083(15) -0.0009(15) C2 0.0281(18) 0.0233(17) 0.0228(17) 0.0049(14) -0.0092(14) 0.0055(14) C13 0.0303(19) 0.041(2) 0.0250(19) 0.0000(16) -0.0026(15) -0.0044(16) C4 0.0149(15) 0.0165(15) 0.0169(15) -0.0011(13) 0.0030(12) -0.0011(12) O3B 0.057(6) 0.014(3) 0.026(4) -0.001(3) -0.012(4) 0.001(4) C12 0.036(2) 0.0199(17) 0.0227(18) -0.0051(14) -0.0011(15) 0.0054(14) O4 0.0215(12) 0.0216(12) 0.0315(13) -0.0100(10) -0.0046(10) -0.0003(9) O5 0.095(3) 0.083(3) 0.085(3) -0.002(2) 0.000(2) -0.008(2) O3A 0.032(4) 0.017(3) 0.018(3) 0.004(2) -0.004(3) -0.003(4) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Zn1 O1 2.133(4) . ? Zn1 N1 2.173(2) 2_655 ? Zn1 N1 2.173(2) . ? Zn1 N1 2.173(2) 3_665 ? Zn1 N1 2.173(2) 4_565 ? Zn1 O2 2.188(4) . ? S2 O4 1.477(2) . ? S2 O4 1.477(2) 6_576 ? S2 O4 1.477(2) 8_766 ? S2 O4 1.477(2) 3_675 ? N3 C6 1.348(4) . ? N3 C7 1.420(4) . ? N2 C6 1.368(4) . ? N2 C4 1.400(4) . ? C3 C2 1.375(4) . ? C3 C4 1.382(4) . ? C9 C8 1.386(4) . ? C9 C10 1.389(5) . ? C5 N1 1.345(4) . ? C5 C4 1.404(4) . ? N1 C1 1.340(4) . ? C10 C11 1.392(4) . ? C10 C13 1.497(4) . ? C1 C2 1.374(4) . ? C7 C12 1.387(4) . ? C7 C8 1.392(4) . ? C11 C12 1.389(5) . ? C6 O3A 1.262(10) . ? C6 O3B 1.267(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 O1 Zn1 N1 90.61(7) . 2_655 ? O1 Zn1 N1 90.61(6) . . ? N1 Zn1 N1 89.994(2) 2_655 . ? O1 Zn1 N1 90.61(6) . 3_665 ? N1 Zn1 N1 89.994(2) 2_655 3_665 ? N1 Zn1 N1 178.79(13) . 3_665 ? O1 Zn1 N1 90.61(7) . 4_565 ? N1 Zn1 N1 178.79(13) 2_655 4_565 ? N1 Zn1 N1 89.994(2) . 4_565 ? N1 Zn1 N1 89.994(2) 3_665 4_565 ? O1 Zn1 O2 180.000(2) . . ? N1 Zn1 O2 89.39(6) 2_655 . ? N1 Zn1 O2 89.39(6) . . ? N1 Zn1 O2 89.39(6) 3_665 . ? N1 Zn1 O2 89.39(6) 4_565 . ? O4 S2 O4 108.44(9) . 6_576 ? O4 S2 O4 108.44(9) . 8_766 ? O4 S2 O4 111.54(18) 6_576 8_766 ? O4 S2 O4 111.54(18) . 3_675 ? O4 S2 O4 108.44(9) 6_576 3_675 ? O4 S2 O4 108.44(9) 8_766 3_675 ? C6 N3 C7 127.0(3) . . ? C6 N2 C4 127.1(3) . . ? C2 C3 C4 120.1(3) . . ? C8 C9 C10 121.7(3) . . ? N1 C5 C4 122.2(3) . . ? C1 N1 C5 118.6(3) . . ? C1 N1 Zn1 120.3(2) . . ? C5 N1 Zn1 121.10(19) . . ? C9 C10 C11 116.9(3) . . ? C9 C10 C13 121.8(3) . . ? C11 C10 C13 121.3(3) . . ? N1 C1 C2 122.4(3) . . ? C12 C7 C8 118.9(3) . . ? C12 C7 N3 123.9(3) . . ? C8 C7 N3 117.2(3) . . ? C9 C8 C7 120.4(3) . . ? C12 C11 C10 122.3(3) . . ? O3A C6 O3B 28.5(4) . . ? O3A C6 N3 122.2(5) . . ? O3B C6 N3 122.3(5) . . ? O3A C6 N2 121.4(5) . . ? O3B C6 N2 121.2(5) . . ? N3 C6 N2 114.2(3) . . ? C3 C2 C1 119.0(3) . . ? C3 C4 N2 118.1(3) . . ? C3 C4 C5 117.5(3) . . ? N2 C4 C5 124.4(3) . . ? C7 C12 C11 119.7(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 N3 H3 O4 0.88 1.97 2.842(3) 173.2 8_766 N2 H2 O4 0.88 2.21 3.028(3) 154.6 . O2 H2O O5 0.94 1.87 2.762(5) 156.3 4_564 O1 H1O O5 1.08 1.71 2.728(5) 154.4 4_565 O5 H5A O3B 1.34 1.45 2.686(11) 149.0 . O5 H5A O3A 1.34 1.66 2.782(11) 135.8 . O5 H5B O3A 1.38 1.75 2.694(9) 118.3 4_565 O5 H5B O3B 1.38 2.31 3.144(10) 114.7 4_565 _diffrn_measured_fraction_theta_max 0.989 _diffrn_reflns_theta_full 27.46 _diffrn_measured_fraction_theta_full 0.989 _refine_diff_density_max 0.665 _refine_diff_density_min -1.012 _refine_diff_density_rms 0.107 data_C:\Dave\Structs\DtCu067_P4n\S921.CIF _database_code_depnum_ccdc_archive 'CCDC 233243' _audit_creation_method SHELXL-97 _chemical_name_systematic ; [Cu(TUP)4(H2O)2]SO4.2H2O ; _chemical_name_common '[Cu(TUP)4(H2O)2]SO4.2H2O' _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C52 H56 Cu N12 O12 S' _chemical_formula_weight 1136.69 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' Cu Cu 0.3201 1.2651 '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/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y+1/2, x, z' '-x+1/2, -y+1/2, z' 'y, -x+1/2, z' '-x, -y, -z' 'y-1/2, -x, -z' 'x-1/2, y-1/2, -z' '-y, x-1/2, -z' _cell_length_a 17.846(3) _cell_length_b 17.846(3) _cell_length_c 8.3019(17) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2644.0(8) _cell_formula_units_Z 2 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description Plate _exptl_crystal_colour 'Pale blue' _exptl_crystal_size_max 0.05 _exptl_crystal_size_mid 0.2 _exptl_crystal_size_min 0.2 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.428 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1186 _exptl_absorpt_coefficient_mu 0.527 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; Data were corrected for decay and absorption using the program Scalepack Z. Otwinowski and W. Minor, in Methods in Enzymology, ed. C. W. Carter and R. M. Sweet, Academic Press: London, 1997, vol. 276, pp 307. ; _diffrn_ambient_temperature 120(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 'Nonius KappaCCD' _diffrn_measurement_method ? _diffrn_detector_area_resol_mean 0.71 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0.0 _diffrn_reflns_number 4682 _diffrn_reflns_av_R_equivalents 0.0326 _diffrn_reflns_av_sigmaI/netI 0.0469 _diffrn_reflns_limit_h_min -23 _diffrn_reflns_limit_h_max 23 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -6 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 3.61 _diffrn_reflns_theta_max 27.47 _reflns_number_total 3021 _reflns_number_gt 2499 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Hooft, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'X-Seed (Barbour, 1999)' _computing_publication_material 'CIFTAB (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^)+(0.0418P)^2^+3.6372P] 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 0.0014(7) _refine_ls_extinction_expression Fc^*^==kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 3021 _refine_ls_number_parameters 193 _refine_ls_number_restraints 144 _refine_ls_R_factor_all 0.0603 _refine_ls_R_factor_gt 0.0470 _refine_ls_wR_factor_ref 0.1196 _refine_ls_wR_factor_gt 0.1112 _refine_ls_goodness_of_fit_ref 1.055 _refine_ls_restrained_S_all 1.059 _refine_ls_shift/su_max 0.015 _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 Cu1 Cu 0.7500 0.7500 0.26396(6) 0.01421(17) Uani 1 4 d SU . . S1 S 0.2500 0.7500 0.5000 0.0155(2) Uani 1 4 d SU . . O1 O 0.7500 0.7500 0.5387(4) 0.0214(7) Uani 1 4 d SU . . N1 N 0.63646(10) 0.73351(10) 0.2565(2) 0.0161(4) Uani 1 1 d U . . C1 C 0.60578(13) 0.69515(13) 0.1345(3) 0.0225(5) Uani 1 1 d U . . H1 H 0.6376 0.6738 0.0551 0.027 Uiso 1 1 calc R . . O2 O 0.7500 0.7500 -0.0326(4) 0.0268(7) Uani 1 4 d SU . . N2 N 0.46474(10) 0.77833(11) 0.4882(2) 0.0201(4) Uani 1 1 d U A . H2N H 0.4166 0.7765 0.4655 0.024 Uiso 1 1 calc R . . C2 C 0.52913(14) 0.68574(14) 0.1208(3) 0.0250(5) Uani 1 1 d U . . H2 H 0.5086 0.6597 0.0313 0.030 Uiso 1 1 calc R . . N3 N 0.42493(11) 0.82364(11) 0.7307(2) 0.0190(4) Uani 1 1 d U A . H3N H 0.3801 0.8174 0.6886 0.023 Uiso 1 1 calc R . . C3 C 0.48274(13) 0.71456(13) 0.2385(3) 0.0211(5) Uani 1 1 d U . . H3 H 0.4299 0.7088 0.2307 0.025 Uiso 1 1 calc R . . O5 O 0.69184(15) 0.85248(15) 0.7476(3) 0.0253(7) Uani 0.50 1 d PU . . H2O H 0.7487 0.7883 -0.1285 0.39(12) Uiso 0.50 1 d PR . . H1O H 0.7121 0.7503 0.5950 0.05(2) Uiso 0.50 1 d PR . . O3B O 0.54772(15) 0.79835(15) 0.6981(3) 0.0213(9) Uani 0.50 1 d PRU A 2 C4 C 0.51421(12) 0.75222(12) 0.3691(3) 0.0173(5) Uani 1 1 d U . . O4 O 0.31199(9) 0.72194(9) 0.3994(2) 0.0238(4) Uani 1 1 d U . . C5 C 0.59178(12) 0.76233(12) 0.3713(3) 0.0174(4) Uani 1 1 d U . . H5 H 0.6136 0.7904 0.4564 0.021 Uiso 1 1 calc R . . C6 C 0.48404(13) 0.80638(15) 0.6361(3) 0.0259(5) Uani 1 1 d U . . C7 C 0.42781(12) 0.85066(12) 0.8907(3) 0.0187(5) Uani 1 1 d U . . C8 C 0.36449(13) 0.84053(12) 0.9861(3) 0.0196(5) Uani 1 1 d U A . H8 H 0.3232 0.8129 0.9449 0.024 Uiso 1 1 calc R . . C9 C 0.36076(13) 0.87021(13) 1.1402(3) 0.0229(5) Uani 1 1 d U . . H9 H 0.3169 0.8627 1.2029 0.027 Uiso 1 1 calc R A . C10 C 0.42011(14) 0.91074(13) 1.2046(3) 0.0234(5) Uani 1 1 d U A . C11 C 0.48395(14) 0.91787(15) 1.1103(3) 0.0273(5) Uani 1 1 d U . . H11 H 0.5261 0.9434 1.1535 0.033 Uiso 1 1 calc R A . C12 C 0.48862(14) 0.88916(15) 0.9553(3) 0.0266(5) Uani 1 1 d U A . H12 H 0.5330 0.8957 0.8937 0.032 Uiso 1 1 calc R . . C13 C 0.41528(16) 0.94769(15) 1.3681(3) 0.0313(6) Uani 1 1 d U . . H13A H 0.4640 0.9444 1.4220 0.047 Uiso 1 1 calc R A . H13B H 0.3773 0.9222 1.4333 0.047 Uiso 1 1 calc R . . H13C H 0.4014 1.0005 1.3549 0.047 Uiso 1 1 calc R . . O3A O 0.5497(2) 0.8285(2) 0.6614(5) 0.0256(9) Uani 0.50 1 d PU A 1 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 0.0126(2) 0.0126(2) 0.0174(3) 0.000 0.000 0.000 S1 0.0127(3) 0.0127(3) 0.0209(5) 0.000 0.000 0.000 O1 0.0228(9) 0.0228(9) 0.0186(13) 0.000 0.000 0.000 N1 0.0133(9) 0.0150(9) 0.0200(9) 0.0001(7) -0.0001(7) 0.0005(7) C1 0.0182(11) 0.0248(12) 0.0244(12) -0.0046(10) 0.0000(9) -0.0005(9) O2 0.0281(9) 0.0281(9) 0.0243(14) 0.000 0.000 0.000 N2 0.0109(9) 0.0269(10) 0.0224(10) -0.0028(8) 0.0015(7) 0.0006(7) C2 0.0219(12) 0.0273(13) 0.0260(12) -0.0084(10) -0.0025(10) -0.0035(10) N3 0.0125(9) 0.0232(10) 0.0211(10) -0.0026(8) 0.0012(7) 0.0007(7) C3 0.0133(11) 0.0239(12) 0.0261(12) -0.0035(10) -0.0019(9) -0.0009(9) O5 0.0242(14) 0.0254(14) 0.0262(14) 0.0002(12) -0.0022(12) 0.0007(12) O3B 0.0181(14) 0.0239(15) 0.0218(15) 0.0042(13) 0.0000(12) 0.0001(13) C4 0.0164(10) 0.0163(10) 0.0193(11) 0.0006(9) -0.0002(8) 0.0003(8) O4 0.0209(8) 0.0206(8) 0.0300(9) -0.0036(7) 0.0072(7) -0.0002(6) C5 0.0148(10) 0.0180(11) 0.0194(11) -0.0003(8) -0.0003(8) -0.0002(8) C6 0.0174(11) 0.0367(14) 0.0236(12) -0.0063(11) 0.0008(9) 0.0002(10) C7 0.0176(11) 0.0182(11) 0.0202(11) 0.0002(9) 0.0016(9) 0.0018(8) C8 0.0179(11) 0.0161(11) 0.0249(11) 0.0022(9) 0.0007(9) 0.0004(9) C9 0.0219(12) 0.0227(12) 0.0241(12) 0.0045(9) 0.0051(9) 0.0040(9) C10 0.0291(13) 0.0202(12) 0.0209(11) 0.0021(9) 0.0006(10) 0.0047(10) C11 0.0243(13) 0.0307(13) 0.0268(12) -0.0015(10) -0.0012(10) -0.0051(10) C12 0.0199(12) 0.0345(14) 0.0255(12) -0.0033(10) 0.0048(10) -0.0057(10) C13 0.0378(12) 0.0297(12) 0.0264(11) -0.0015(10) 0.0028(10) 0.0020(10) O3A 0.0158(14) 0.0407(17) 0.0203(14) -0.0039(14) 0.0043(12) -0.0077(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 Cu1 N1 2.0485(19) 3_665 ? Cu1 N1 2.0485(18) 4_565 ? Cu1 N1 2.0485(18) 2_655 ? Cu1 N1 2.0485(19) . ? Cu1 O1 2.281(3) . ? Cu1 O2 2.462(4) . ? S1 O4 1.4741(16) 8_666 ? S1 O4 1.4741(16) 3_565 ? S1 O4 1.4741(16) . ? S1 O4 1.4741(16) 6_566 ? N1 C1 1.339(3) . ? N1 C5 1.345(3) . ? C1 C2 1.383(3) . ? N2 C6 1.370(3) . ? N2 C4 1.405(3) . ? C2 C3 1.380(3) . ? N3 C6 1.351(3) . ? N3 C7 1.414(3) . ? C3 C4 1.393(3) . ? O3B C6 1.256(4) . ? C4 C5 1.396(3) . ? C6 O3A 1.254(4) . ? C7 C8 1.391(3) . ? C7 C12 1.392(3) . ? C8 C9 1.387(3) . ? C9 C10 1.390(4) . ? C10 C11 1.388(3) . ? C10 C13 1.511(3) . ? C11 C12 1.387(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 N1 Cu1 N1 89.947(4) 3_665 4_565 ? N1 Cu1 N1 89.947(4) 3_665 2_655 ? N1 Cu1 N1 176.53(11) 4_565 2_655 ? N1 Cu1 N1 176.53(11) 3_665 . ? N1 Cu1 N1 89.947(4) 4_565 . ? N1 Cu1 N1 89.947(4) 2_655 . ? N1 Cu1 O1 91.74(5) 3_665 . ? N1 Cu1 O1 91.74(5) 4_565 . ? N1 Cu1 O1 91.74(5) 2_655 . ? N1 Cu1 O1 91.74(5) . . ? N1 Cu1 O2 88.26(5) 3_665 . ? N1 Cu1 O2 88.26(5) 4_565 . ? N1 Cu1 O2 88.26(5) 2_655 . ? N1 Cu1 O2 88.26(5) . . ? O1 Cu1 O2 180.000(1) . . ? O4 S1 O4 108.74(7) 8_666 3_565 ? O4 S1 O4 108.74(7) 8_666 . ? O4 S1 O4 110.94(14) 3_565 . ? O4 S1 O4 110.94(14) 8_666 6_566 ? O4 S1 O4 108.74(7) 3_565 6_566 ? O4 S1 O4 108.74(7) . 6_566 ? C1 N1 C5 119.27(19) . . ? C1 N1 Cu1 120.04(15) . . ? C5 N1 Cu1 120.67(15) . . ? N1 C1 C2 121.9(2) . . ? C6 N2 C4 126.44(19) . . ? C3 C2 C1 119.3(2) . . ? C6 N3 C7 126.6(2) . . ? C2 C3 C4 119.3(2) . . ? C3 C4 C5 118.2(2) . . ? C3 C4 N2 117.0(2) . . ? C5 C4 N2 124.8(2) . . ? N1 C5 C4 121.9(2) . . ? O3A C6 O3B 28.6(2) . . ? O3A C6 N3 124.1(3) . . ? O3B C6 N3 119.6(2) . . ? O3A C6 N2 120.0(3) . . ? O3B C6 N2 123.6(2) . . ? N3 C6 N2 114.1(2) . . ? C8 C7 C12 118.6(2) . . ? C8 C7 N3 117.4(2) . . ? C12 C7 N3 124.0(2) . . ? C9 C8 C7 121.0(2) . . ? C8 C9 C10 121.2(2) . . ? C11 C10 C9 117.1(2) . . ? C11 C10 C13 120.9(2) . . ? C9 C10 C13 122.0(2) . . ? C12 C11 C10 122.6(2) . . ? C11 C12 C7 119.5(2) . . ? 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 N2 H2N O4 0.88 2.18 2.998(3) 155.3 . N2 H2N S1 0.88 3.02 3.8667(19) 161.0 . N3 H3N O4 0.88 1.96 2.842(3) 175.3 8_666 O2 H2O O5 1.05 1.84 2.784(4) 147.1 1_554 O2 H2O O5 1.05 2.15 2.784(4) 116.9 4_564 O1 H1O O5 0.82 2.01 2.726(3) 145.9 2_655 O1 H1O O5 0.82 2.25 2.726(3) 117.2 . _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 27.47 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.755 _refine_diff_density_min -0.755 _refine_diff_density_rms 0.069