Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2007 data_global _journal_name_full 'Dalton Trans.' #============================================================================== # 1. SUBMISSION DETAILS _journal_coden_Cambridge 0222 _publ_contact_author_name 'Franc Meyer' _publ_contact_author_address ; Institut fur Anorganische Chemie Georg August Universitat Gottingen Tammannstrase 4 D-37077 Gottingen Germany ; _publ_contact_author_email franc.meyer@chemie.uni-goettingen.de _publ_contact_author_fax 49(551)393063 _publ_contact_author_phone 49(551)393012 _publ_requested_coeditor_name ? #============================================================================== # 3. TITLE AND AUTHOR LIST _publ_section_title ; Pyrazolate-bridged copper(II) and nickel(II) [2 x 2] grid-type complexes: protonation-dependent self-assembly, structure and properties ; loop_ _publ_author_name _publ_author_address J.Klingele ; Institut fur Anorganische Chemie Georg August Universitat Gottingen Tammannstrase 4 D-37077 Gottingen Germany ; A.I.Prikhodko ; Institut fur Anorganische Chemie Georg August Universitat Gottingen Tammannstrase 4 D-37077 Gottingen Germany ; G.Leibeling ; Institut fur Anorganische Chemie Georg August Universitat Gottingen Tammannstrase 4 D-37077 Gottingen Germany ; S.Demeshko ; Institut fur Anorganische Chemie Georg August Universitat Gottingen Tammannstrase 4 D-37077 Gottingen Germany ; S.Dechert ; Institut fur Anorganische Chemie Georg August Universitat Gottingen Tammannstrase 4 D-37077 Gottingen Germany ; ; F.Meyer ; ; Institut fur Anorganische Chemie Georg August Universitat Gottingen Tammannstrase 4 D-37077 Gottingen Germany ; #============================================================================== data_H3L _database_code_depnum_ccdc_archive 'CCDC 636107' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C17 H16 N6 O2, 2(H2 O)' _chemical_formula_sum 'C17 H20 N6 O4' _chemical_formula_weight 372.39 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' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1' _symmetry_space_group_name_Hall '-P 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 11.9866(6) _cell_length_b 12.5344(6) _cell_length_c 13.7972(7) _cell_angle_alpha 66.677(4) _cell_angle_beta 78.628(4) _cell_angle_gamma 72.036(4) _cell_volume 1804.07(15) _cell_formula_units_Z 4 _cell_measurement_temperature 133(2) _cell_measurement_reflns_used 40196 _cell_measurement_theta_min 1.61 _cell_measurement_theta_max 24.80 _exptl_crystal_description block _exptl_crystal_colour colorless _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.31 _exptl_crystal_size_min 0.17 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.371 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 784 _exptl_absorpt_coefficient_mu 0.101 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 133(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 'Stoe IPDS II' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 40196 _diffrn_reflns_av_R_equivalents 0.0441 _diffrn_reflns_av_sigmaI/netI 0.0218 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 1.61 _diffrn_reflns_theta_max 24.80 _reflns_number_total 6177 _reflns_number_gt 5284 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'X-AREA (Stoe & Cie, 2002)' _computing_cell_refinement 'X-AREA (Stoe & Cie, 2002)' _computing_data_reduction 'X-AREA (Stoe & Cie, 2002)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'DIAMOND (Brandenburg, 2001)' _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^)+(0.0552P)^2^+0.3393P] 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 none _refine_ls_extinction_coef ? _refine_ls_number_reflns 6177 _refine_ls_number_parameters 543 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0397 _refine_ls_R_factor_gt 0.0338 _refine_ls_wR_factor_ref 0.0938 _refine_ls_wR_factor_gt 0.0914 _refine_ls_goodness_of_fit_ref 1.065 _refine_ls_restrained_S_all 1.065 _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 N1 N 0.87821(9) 0.70364(10) 0.44110(9) 0.0230(2) Uani 1 1 d . . . N2 N 0.94490(10) 0.62660(9) 0.52019(9) 0.0223(2) Uani 1 1 d . . . H2 H 1.0247(15) 0.6295(14) 0.5179(13) 0.036(4) Uiso 1 1 d . . . N3 N 0.87683(10) 0.39891(10) 0.76859(9) 0.0240(2) Uani 1 1 d . . . H3 H 0.8063(16) 0.4020(15) 0.7548(13) 0.038(5) Uiso 1 1 d . . . N4 N 0.95813(11) 0.33471(11) 1.03047(9) 0.0312(3) Uani 1 1 d . . . N5 N 0.68880(10) 0.83231(10) 0.31448(9) 0.0242(2) Uani 1 1 d . . . H5 H 0.7595(15) 0.8376(14) 0.2943(13) 0.029(4) Uiso 1 1 d . . . N6 N 0.41856(10) 1.06084(10) 0.21156(9) 0.0285(3) Uani 1 1 d . . . N11 N 0.34831(9) 0.38966(10) 0.75108(8) 0.0227(2) Uani 1 1 d . . . N12 N 0.28079(10) 0.46946(10) 0.67322(9) 0.0220(2) Uani 1 1 d . . . H12 H 0.1990(15) 0.4686(15) 0.6771(13) 0.036(4) Uiso 1 1 d . . . N13 N 0.33732(10) 0.72014(10) 0.43956(9) 0.0231(2) Uani 1 1 d . . . H13 H 0.4113(15) 0.7108(14) 0.4454(12) 0.029(4) Uiso 1 1 d . . . N14 N 0.11682(10) 0.99815(10) 0.33009(10) 0.0326(3) Uani 1 1 d . . . N15 N 0.53659(10) 0.25909(10) 0.87761(9) 0.0242(2) Uani 1 1 d . . . H15 H 0.4707(15) 0.2382(14) 0.8916(12) 0.028(4) Uiso 1 1 d . . . N16 N 0.72483(10) 0.17290(10) 1.09216(9) 0.0287(3) Uani 1 1 d . . . O1 O 1.04048(8) 0.46863(9) 0.71164(7) 0.0285(2) Uani 1 1 d . . . O2 O 0.57222(8) 0.72887(8) 0.44409(7) 0.0266(2) Uani 1 1 d . . . O3 O 1.13997(10) 0.13476(11) 1.01941(9) 0.0399(3) Uani 1 1 d . . . H3A H 1.074(2) 0.202(2) 1.027(2) 0.087(8) Uiso 1 1 d . . . H3B H 1.117(2) 0.065(3) 1.073(2) 0.099(9) Uiso 1 1 d . . . O4 O 0.37531(10) 1.12209(10) -0.00571(9) 0.0358(3) Uani 1 1 d . . . H4A H 0.3978(17) 1.0904(17) 0.0589(17) 0.052(5) Uiso 1 1 d . . . H4B H 0.291(2) 1.1333(19) 0.0036(16) 0.064(6) Uiso 1 1 d . . . O5 O 0.08720(10) 0.93307(10) 0.16504(9) 0.0382(3) Uani 1 1 d . . . H5A H 0.0893(19) 0.951(2) 0.2260(18) 0.067(6) Uiso 1 1 d . . . H5B H 0.004(2) 0.933(2) 0.1633(19) 0.085(7) Uiso 1 1 d . . . O6 O 0.86137(9) -0.06820(10) 1.14882(8) 0.0340(2) Uani 1 1 d . . . H6A H 0.8193(19) 0.009(2) 1.1253(17) 0.062(6) Uiso 1 1 d . . . H6B H 0.865(2) -0.101(2) 1.086(2) 0.097(8) Uiso 1 1 d . . . O11 O 0.16927(8) 0.66077(8) 0.50403(8) 0.0274(2) Uani 1 1 d . . . O12 O 0.64065(8) 0.39220(8) 0.76969(8) 0.0295(2) Uani 1 1 d . . . C1 C 0.77312(11) 0.58436(11) 0.56979(10) 0.0225(3) Uani 1 1 d . . . H1 H 0.7113 0.5504 0.6069 0.080 Uiso 1 1 calc R . . C2 C 0.77290(11) 0.67822(11) 0.47138(10) 0.0211(3) Uani 1 1 d . . . C3 C 0.88537(11) 0.55360(11) 0.59921(10) 0.0208(3) Uani 1 1 d . . . C4 C 0.94193(11) 0.46896(11) 0.69713(10) 0.0219(3) Uani 1 1 d . . . C5 C 0.91687(12) 0.32195(12) 0.87247(11) 0.0269(3) Uani 1 1 d . . . H5C H 1.0011 0.2880 0.8649 0.080 Uiso 1 1 calc R . . H5D H 0.8794 0.2561 0.9016 0.080 Uiso 1 1 calc R . . C6 C 0.89058(12) 0.38708(12) 0.94930(10) 0.0259(3) Uani 1 1 d . . . C7 C 0.80360(13) 0.49378(13) 0.93739(12) 0.0317(3) Uani 1 1 d . . . H7 H 0.7561 0.5274 0.8814 0.080 Uiso 1 1 calc R . . C8 C 0.78848(14) 0.54935(15) 1.00954(13) 0.0385(4) Uani 1 1 d . . . H8 H 0.7310 0.6209 1.0027 0.080 Uiso 1 1 calc R . . C9 C 0.85997(14) 0.49706(16) 1.09198(12) 0.0393(4) Uani 1 1 d . . . H9 H 0.8528 0.5333 1.1409 0.080 Uiso 1 1 calc R . . C10 C 0.94192(14) 0.39011(15) 1.10000(11) 0.0368(4) Uani 1 1 d . . . H10 H 0.9887 0.3540 1.1565 0.080 Uiso 1 1 calc R . . C11 C 0.67037(11) 0.74806(11) 0.40809(10) 0.0216(3) Uani 1 1 d . . . C12 C 0.59471(12) 0.90084(12) 0.24488(11) 0.0257(3) Uani 1 1 d . . . H12A H 0.5498 0.8471 0.2475 0.080 Uiso 1 1 calc R . . H12B H 0.6296 0.9307 0.1728 0.080 Uiso 1 1 calc R . . C13 C 0.51109(12) 1.00581(12) 0.27059(10) 0.0243(3) Uani 1 1 d . . . C14 C 0.52640(13) 1.04431(13) 0.34734(11) 0.0314(3) Uani 1 1 d . . . H14 H 0.5911 1.0049 0.3872 0.080 Uiso 1 1 calc R . . C15 C 0.44410(15) 1.14225(14) 0.36374(12) 0.0372(4) Uani 1 1 d . . . H15A H 0.4534 1.1702 0.4141 0.080 Uiso 1 1 calc R . . C16 C 0.34809(14) 1.19783(13) 0.30439(13) 0.0380(4) Uani 1 1 d . . . H16 H 0.2908 1.2630 0.3146 0.080 Uiso 1 1 calc R . . C17 C 0.33935(13) 1.15425(13) 0.22974(12) 0.0345(3) Uani 1 1 d . . . H17 H 0.2747 1.1919 0.1897 0.080 Uiso 1 1 calc R . . C101 C 0.44892(11) 0.51960(11) 0.63016(10) 0.0221(3) Uani 1 1 d . . . H101 H 0.5092 0.5571 0.5959 0.080 Uiso 1 1 calc R . . C102 C 0.45098(11) 0.42024(11) 0.72504(10) 0.0207(3) Uani 1 1 d . . . C103 C 0.33762(11) 0.54913(11) 0.59920(10) 0.0209(3) Uani 1 1 d . . . C104 C 0.27448(11) 0.64694(11) 0.51019(10) 0.0210(3) Uani 1 1 d . . . C105 C 0.28021(12) 0.82362(12) 0.35381(10) 0.0248(3) Uani 1 1 d . . . H10A H 0.2304 0.7991 0.3234 0.080 Uiso 1 1 calc R . . H10B H 0.3399 0.8518 0.2989 0.080 Uiso 1 1 calc R . . C106 C 0.20636(12) 0.92616(12) 0.38873(11) 0.0256(3) Uani 1 1 d . . . C107 C 0.23073(13) 0.94637(13) 0.47316(12) 0.0334(3) Uani 1 1 d . . . H107 H 0.2937 0.8951 0.5126 0.080 Uiso 1 1 calc R . . C108 C 0.15977(15) 1.04414(15) 0.49780(15) 0.0435(4) Uani 1 1 d . . . H108 H 0.1745 1.0594 0.5542 0.080 Uiso 1 1 calc R . . C109 C 0.06740(15) 1.11840(15) 0.43817(16) 0.0474(4) Uani 1 1 d . . . H109 H 0.0182 1.1844 0.4534 0.080 Uiso 1 1 calc R . . C110 C 0.04961(14) 1.09262(13) 0.35562(15) 0.0424(4) Uani 1 1 d . . . H110 H -0.0125 1.1434 0.3149 0.080 Uiso 1 1 calc R . . C111 C 0.55071(11) 0.35546(11) 0.79284(10) 0.0220(3) Uani 1 1 d . . . C112 C 0.62901(12) 0.18649(12) 0.94872(11) 0.0260(3) Uani 1 1 d . . . H11A H 0.7044 0.1816 0.9070 0.080 Uiso 1 1 calc R . . H11B H 0.6186 0.1056 0.9828 0.080 Uiso 1 1 calc R . . C113 C 0.63253(11) 0.23301(11) 1.03355(10) 0.0243(3) Uani 1 1 d . . . C114 C 0.54757(13) 0.32846(13) 1.05198(12) 0.0314(3) Uani 1 1 d . . . H114 H 0.4840 0.3686 1.0108 0.080 Uiso 1 1 calc R . . C115 C 0.55834(15) 0.36335(14) 1.13239(12) 0.0379(4) Uani 1 1 d . . . H115 H 0.5015 0.4264 1.1466 0.080 Uiso 1 1 calc R . . C116 C 0.65451(15) 0.30342(14) 1.19122(12) 0.0381(4) Uani 1 1 d . . . H116 H 0.6650 0.3262 1.2446 0.080 Uiso 1 1 calc R . . C117 C 0.73429(14) 0.20913(14) 1.16862(12) 0.0351(3) Uani 1 1 d . . . H117 H 0.7986 0.1681 1.2088 0.080 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 N1 0.0208(6) 0.0242(5) 0.0238(6) -0.0073(5) -0.0043(4) -0.0059(4) N2 0.0184(6) 0.0235(6) 0.0248(6) -0.0075(5) -0.0037(4) -0.0057(4) N3 0.0200(6) 0.0271(6) 0.0239(6) -0.0051(5) -0.0051(5) -0.0077(5) N4 0.0325(6) 0.0344(7) 0.0246(6) -0.0018(5) -0.0050(5) -0.0160(5) N5 0.0200(6) 0.0279(6) 0.0218(6) -0.0047(5) -0.0026(5) -0.0074(5) N6 0.0283(6) 0.0269(6) 0.0257(6) -0.0050(5) -0.0037(5) -0.0059(5) N11 0.0202(5) 0.0234(5) 0.0227(6) -0.0058(5) -0.0040(4) -0.0050(4) N12 0.0176(5) 0.0233(5) 0.0234(6) -0.0055(5) -0.0039(4) -0.0052(4) N13 0.0175(6) 0.0237(6) 0.0248(6) -0.0041(5) -0.0041(4) -0.0053(4) N14 0.0280(6) 0.0246(6) 0.0395(7) -0.0062(5) -0.0056(5) -0.0044(5) N15 0.0209(6) 0.0238(6) 0.0249(6) -0.0030(5) -0.0053(5) -0.0074(5) N16 0.0278(6) 0.0296(6) 0.0266(6) -0.0060(5) -0.0064(5) -0.0075(5) O1 0.0205(5) 0.0357(5) 0.0282(5) -0.0070(4) -0.0048(4) -0.0099(4) O2 0.0203(5) 0.0322(5) 0.0255(5) -0.0062(4) -0.0029(4) -0.0092(4) O3 0.0306(6) 0.0430(6) 0.0382(6) -0.0059(5) -0.0076(5) -0.0072(5) O4 0.0336(6) 0.0455(6) 0.0250(6) -0.0028(5) -0.0052(4) -0.0172(5) O5 0.0313(6) 0.0398(6) 0.0427(7) -0.0133(5) -0.0080(5) -0.0070(5) O6 0.0289(5) 0.0310(6) 0.0334(6) -0.0042(5) -0.0049(4) -0.0043(4) O11 0.0185(5) 0.0282(5) 0.0323(5) -0.0054(4) -0.0053(4) -0.0070(4) O12 0.0209(5) 0.0299(5) 0.0337(5) -0.0028(4) -0.0064(4) -0.0099(4) C1 0.0201(6) 0.0245(6) 0.0230(7) -0.0077(5) -0.0018(5) -0.0071(5) C2 0.0200(6) 0.0230(6) 0.0220(7) -0.0097(5) -0.0013(5) -0.0060(5) C3 0.0199(6) 0.0222(6) 0.0218(6) -0.0095(5) -0.0013(5) -0.0057(5) C4 0.0184(6) 0.0234(6) 0.0253(7) -0.0107(5) -0.0030(5) -0.0039(5) C5 0.0279(7) 0.0250(7) 0.0245(7) -0.0033(6) -0.0055(6) -0.0078(6) C6 0.0241(7) 0.0295(7) 0.0229(7) -0.0037(6) -0.0010(5) -0.0133(6) C7 0.0267(7) 0.0351(8) 0.0322(8) -0.0107(6) -0.0016(6) -0.0090(6) C8 0.0330(8) 0.0430(9) 0.0427(9) -0.0204(7) 0.0055(7) -0.0128(7) C9 0.0388(9) 0.0560(10) 0.0336(8) -0.0223(8) 0.0101(7) -0.0262(8) C10 0.0393(9) 0.0523(10) 0.0227(7) -0.0073(7) -0.0021(6) -0.0255(8) C11 0.0213(7) 0.0238(6) 0.0214(6) -0.0090(5) -0.0023(5) -0.0067(5) C12 0.0260(7) 0.0283(7) 0.0214(7) -0.0070(6) -0.0056(5) -0.0053(6) C13 0.0262(7) 0.0236(6) 0.0199(6) -0.0026(5) -0.0008(5) -0.0099(5) C14 0.0355(8) 0.0323(8) 0.0271(7) -0.0094(6) -0.0019(6) -0.0118(6) C15 0.0491(9) 0.0333(8) 0.0321(8) -0.0145(7) 0.0037(7) -0.0152(7) C16 0.0423(9) 0.0273(7) 0.0371(9) -0.0106(7) 0.0063(7) -0.0061(7) C17 0.0317(8) 0.0270(7) 0.0338(8) -0.0037(6) -0.0025(6) -0.0025(6) C101 0.0191(6) 0.0217(6) 0.0241(7) -0.0066(5) -0.0019(5) -0.0056(5) C102 0.0193(6) 0.0204(6) 0.0226(6) -0.0084(5) -0.0021(5) -0.0042(5) C103 0.0191(6) 0.0215(6) 0.0221(6) -0.0081(5) -0.0007(5) -0.0054(5) C104 0.0190(6) 0.0217(6) 0.0235(7) -0.0098(5) -0.0023(5) -0.0046(5) C105 0.0247(7) 0.0228(6) 0.0223(7) -0.0040(5) -0.0031(5) -0.0047(5) C106 0.0233(7) 0.0218(6) 0.0285(7) -0.0046(6) -0.0006(5) -0.0084(5) C107 0.0338(8) 0.0329(8) 0.0370(8) -0.0137(7) -0.0014(6) -0.0126(6) C108 0.0449(10) 0.0427(9) 0.0545(10) -0.0282(8) 0.0082(8) -0.0206(8) C109 0.0379(9) 0.0330(8) 0.0773(13) -0.0301(9) 0.0098(9) -0.0129(7) C110 0.0285(8) 0.0256(8) 0.0642(11) -0.0103(7) -0.0038(7) -0.0027(6) C111 0.0200(6) 0.0217(6) 0.0242(7) -0.0084(5) -0.0023(5) -0.0046(5) C112 0.0255(7) 0.0223(6) 0.0271(7) -0.0050(6) -0.0068(6) -0.0041(5) C113 0.0232(7) 0.0218(6) 0.0241(7) -0.0016(5) -0.0023(5) -0.0093(5) C114 0.0310(8) 0.0267(7) 0.0331(8) -0.0076(6) -0.0036(6) -0.0064(6) C115 0.0447(9) 0.0312(8) 0.0376(9) -0.0141(7) 0.0026(7) -0.0110(7) C116 0.0501(10) 0.0405(9) 0.0302(8) -0.0142(7) 0.0006(7) -0.0208(7) C117 0.0369(8) 0.0414(8) 0.0278(8) -0.0080(7) -0.0076(6) -0.0142(7) _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 N1 N2 1.3401(15) . ? N1 C2 1.3432(17) . ? N2 C3 1.3569(17) . ? N3 C4 1.3363(17) . ? N3 C5 1.4512(17) . ? N4 C6 1.3374(18) . ? N4 C10 1.346(2) . ? N5 C11 1.3355(17) . ? N5 C12 1.4521(17) . ? N6 C17 1.3372(19) . ? N6 C13 1.3449(17) . ? N11 C102 1.3410(16) . ? N11 N12 1.3424(15) . ? N12 C103 1.3572(17) . ? N13 C104 1.3370(17) . ? N13 C105 1.4517(16) . ? N14 C106 1.3371(18) . ? N14 C110 1.344(2) . ? N15 C111 1.3360(17) . ? N15 C112 1.4554(17) . ? N16 C117 1.3380(19) . ? N16 C113 1.3423(17) . ? O1 C4 1.2350(16) . ? O2 C11 1.2403(16) . ? O11 C104 1.2342(15) . ? O12 C111 1.2370(16) . ? C1 C3 1.3767(18) . ? C1 C2 1.4008(18) . ? C2 C11 1.4811(18) . ? C3 C4 1.4809(18) . ? C5 C6 1.511(2) . ? C6 C7 1.392(2) . ? C7 C8 1.382(2) . ? C8 C9 1.380(2) . ? C9 C10 1.374(2) . ? C12 C13 1.5092(19) . ? C13 C14 1.387(2) . ? C14 C15 1.384(2) . ? C15 C16 1.380(2) . ? C16 C17 1.376(2) . ? C101 C103 1.3764(18) . ? C101 C102 1.4029(18) . ? C102 C111 1.4847(17) . ? C103 C104 1.4785(17) . ? C105 C106 1.5125(19) . ? C106 C107 1.386(2) . ? C107 C108 1.383(2) . ? C108 C109 1.373(3) . ? C109 C110 1.370(3) . ? C112 C113 1.5122(19) . ? C113 C114 1.386(2) . ? C114 C115 1.384(2) . ? C115 C116 1.380(2) . ? C116 C117 1.373(2) . ? 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 N2 N1 C2 104.52(10) . . ? N1 N2 C3 112.50(10) . . ? C4 N3 C5 120.55(11) . . ? C6 N4 C10 117.93(13) . . ? C11 N5 C12 120.84(11) . . ? C17 N6 C13 117.93(13) . . ? C102 N11 N12 104.52(10) . . ? N11 N12 C103 112.43(10) . . ? C104 N13 C105 119.66(11) . . ? C106 N14 C110 117.61(14) . . ? C111 N15 C112 121.85(11) . . ? C117 N16 C113 118.02(13) . . ? C3 C1 C2 104.53(11) . . ? N1 C2 C1 111.61(11) . . ? N1 C2 C11 122.15(11) . . ? C1 C2 C11 126.16(11) . . ? N2 C3 C1 106.84(11) . . ? N2 C3 C4 120.18(11) . . ? C1 C3 C4 132.79(12) . . ? O1 C4 N3 123.55(12) . . ? O1 C4 C3 121.06(12) . . ? N3 C4 C3 115.32(11) . . ? N3 C5 C6 113.22(11) . . ? N4 C6 C7 121.84(14) . . ? N4 C6 C5 114.87(12) . . ? C7 C6 C5 123.29(12) . . ? C8 C7 C6 119.32(14) . . ? C9 C8 C7 118.98(15) . . ? C10 C9 C8 118.34(15) . . ? N4 C10 C9 123.56(14) . . ? O2 C11 N5 123.04(12) . . ? O2 C11 C2 119.79(11) . . ? N5 C11 C2 117.14(11) . . ? N5 C12 C13 115.06(11) . . ? N6 C13 C14 121.94(13) . . ? N6 C13 C12 113.91(12) . . ? C14 C13 C12 124.15(12) . . ? C15 C14 C13 119.10(14) . . ? C16 C15 C14 119.11(14) . . ? C17 C16 C15 118.23(14) . . ? N6 C17 C16 123.68(14) . . ? C103 C101 C102 104.45(11) . . ? N11 C102 C101 111.69(11) . . ? N11 C102 C111 122.06(11) . . ? C101 C102 C111 126.23(11) . . ? N12 C103 C101 106.90(11) . . ? N12 C103 C104 119.69(11) . . ? C101 C103 C104 133.34(12) . . ? O11 C104 N13 122.75(12) . . ? O11 C104 C103 121.24(11) . . ? N13 C104 C103 115.99(11) . . ? N13 C105 C106 113.19(11) . . ? N14 C106 C107 122.23(13) . . ? N14 C106 C105 114.79(12) . . ? C107 C106 C105 122.97(12) . . ? C108 C107 C106 118.87(15) . . ? C109 C108 C107 119.31(16) . . ? C110 C109 C108 118.23(15) . . ? N14 C110 C109 123.75(15) . . ? O12 C111 N15 123.52(12) . . ? O12 C111 C102 119.80(11) . . ? N15 C111 C102 116.68(11) . . ? N15 C112 C113 114.73(11) . . ? N16 C113 C114 121.70(13) . . ? N16 C113 C112 114.52(12) . . ? C114 C113 C112 123.77(12) . . ? C115 C114 C113 119.27(14) . . ? C116 C115 C114 119.14(14) . . ? C117 C116 C115 118.03(14) . . ? N16 C117 C116 123.81(14) . . ? 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 O11 0.962(17) 1.850(18) 2.8044(14) 171.0(15) 1_655 N3 H3 O12 0.889(18) 1.992(18) 2.8550(14) 163.2(15) . N5 H5 O6 0.852(17) 2.227(17) 2.9203(16) 138.4(14) 1_564 N12 H12 O1 0.974(17) 1.866(18) 2.8267(14) 168.4(15) 1_455 N13 H13 O2 0.874(17) 2.006(17) 2.8650(14) 167.4(14) . N15 H15 O4 0.870(17) 2.047(17) 2.8124(16) 146.3(14) 1_546 O3 H3A N4 0.99(3) 1.82(3) 2.8032(18) 175(2) . O3 H3B O5 0.97(3) 1.73(3) 2.7003(16) 175(3) 1_646 O4 H4A N6 0.88(2) 2.04(2) 2.8965(16) 163.8(18) . O4 H4B O3 0.97(2) 1.78(2) 2.7357(15) 172.3(19) 1_464 O5 H5A N14 0.96(2) 1.87(2) 2.8188(18) 169(2) . O5 H5B O6 1.00(3) 1.76(3) 2.7651(15) 175(2) 1_464 O6 H6A N16 0.90(2) 1.93(2) 2.8294(16) 173(2) . O6 H6B O3 1.08(3) 1.69(3) 2.7640(17) 173(2) 2_757 _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 24.80 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.298 _refine_diff_density_min -0.204 _refine_diff_density_rms 0.038 data_Cu4L4 _database_code_depnum_ccdc_archive 'CCDC 636108' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C68 H56 Cu4 N24 O8, 8(H2 O)' _chemical_formula_sum 'C68 H72 Cu4 N24 O16' _chemical_formula_weight 1735.66 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' _symmetry_cell_setting tetragonal _symmetry_space_group_name_H-M 'I 41/a' _symmetry_space_group_name_Hall '-I 4ad' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-y+3/4, x+1/4, z+1/4' 'y+3/4, -x+3/4, z+3/4' 'x+1/2, y+1/2, z+1/2' '-x+1, -y+1/2, z+1' '-y+5/4, x+3/4, z+3/4' 'y+5/4, -x+5/4, z+5/4' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'y-3/4, -x-1/4, -z-1/4' '-y-3/4, x-3/4, -z-3/4' '-x+1/2, -y+1/2, -z+1/2' 'x, y+1/2, -z' 'y-1/4, -x+1/4, -z+1/4' '-y-1/4, x-1/4, -z-1/4' _cell_length_a 22.8617(11) _cell_length_b 22.8617(11) _cell_length_c 13.8078(6) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 7216.7(6) _cell_formula_units_Z 4 _cell_measurement_temperature 133(2) _cell_measurement_reflns_used 21906 _cell_measurement_theta_min 1.72 _cell_measurement_theta_max 24.79 _exptl_crystal_description plate _exptl_crystal_colour blue _exptl_crystal_size_max 0.34 _exptl_crystal_size_mid 0.28 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.597 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3568 _exptl_absorpt_coefficient_mu 1.249 _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_T_min 0.6626 _exptl_absorpt_correction_T_max 0.7812 _exptl_absorpt_process_details 'X-RED (STOE & CIE, 2002)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 133(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 'STOE IPDS II' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 21906 _diffrn_reflns_av_R_equivalents 0.0447 _diffrn_reflns_av_sigmaI/netI 0.0226 _diffrn_reflns_limit_h_min -25 _diffrn_reflns_limit_h_max 26 _diffrn_reflns_limit_k_min -26 _diffrn_reflns_limit_k_max 23 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 1.72 _diffrn_reflns_theta_max 24.79 _reflns_number_total 3101 _reflns_number_gt 2620 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'X-AREA (Stoe & Cie, 2002)' _computing_cell_refinement 'X-AREA (Stoe & Cie, 2002)' _computing_data_reduction 'X-AREA (Stoe & Cie, 2002)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'DIAMOND (Brandenburg, 2001)' _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^)+(0.0377P)^2^+11.4388P] 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 none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3101 _refine_ls_number_parameters 273 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0421 _refine_ls_R_factor_gt 0.0319 _refine_ls_wR_factor_ref 0.0772 _refine_ls_wR_factor_gt 0.0731 _refine_ls_goodness_of_fit_ref 1.025 _refine_ls_restrained_S_all 1.025 _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 Cu1 Cu 0.587283(13) 0.695328(13) 0.53983(2) 0.02476(11) Uani 1 1 d . . . N1 N 0.50414(9) 0.67651(9) 0.51662(14) 0.0251(4) Uani 1 1 d . . . N2 N 0.45576(9) 0.66595(9) 0.56883(15) 0.0258(5) Uani 1 1 d . . . N3 N 0.58937(9) 0.69121(9) 0.40023(15) 0.0281(5) Uani 1 1 d . . . N4 N 0.67072(9) 0.72046(9) 0.51971(15) 0.0297(5) Uani 1 1 d . . . N5 N 0.31211(10) 0.62272(11) 0.48855(18) 0.0338(5) Uani 1 1 d . . . H5 H 0.3178(13) 0.6257(13) 0.435(2) 0.027(8) Uiso 1 1 d . . . N6 N 0.20106(11) 0.51081(11) 0.53318(19) 0.0456(6) Uani 1 1 d . . . O1 O 0.53257(8) 0.67798(9) 0.26288(12) 0.0353(4) Uani 1 1 d . . . O2 O 0.35006(8) 0.63487(8) 0.63896(13) 0.0323(4) Uani 1 1 d . . . C1 C 0.43309(11) 0.65453(11) 0.41106(18) 0.0280(6) Uani 1 1 d . . . H1 H 0.4128 0.6472 0.3540 0.034 Uiso 1 1 calc R . . C2 C 0.49123(11) 0.66988(10) 0.42175(17) 0.0254(5) Uani 1 1 d . . . C3 C 0.41197(11) 0.65257(11) 0.50571(18) 0.0264(5) Uani 1 1 d . . . C4 C 0.54044(11) 0.68005(11) 0.35270(18) 0.0278(5) Uani 1 1 d . . . C5 C 0.64257(12) 0.70834(12) 0.35110(19) 0.0313(6) Uani 1 1 d . . . H5A H 0.6351 0.7418 0.3098 0.038 Uiso 1 1 calc R . . H5B H 0.6566 0.6765 0.3110 0.038 Uiso 1 1 calc R . . C6 C 0.68768(12) 0.72367(11) 0.42639(19) 0.0311(6) Uani 1 1 d . . . C7 C 0.74467(12) 0.73926(13) 0.4021(2) 0.0384(7) Uani 1 1 d . . . H7 H 0.7558 0.7418 0.3375 0.046 Uiso 1 1 calc R . . C8 C 0.78444(13) 0.75099(14) 0.4744(2) 0.0439(7) Uani 1 1 d . . . H8 H 0.8226 0.7615 0.4591 0.053 Uiso 1 1 calc R . . C9 C 0.76692(13) 0.74698(14) 0.5705(2) 0.0434(7) Uani 1 1 d . . . H9 H 0.7932 0.7542 0.6204 0.052 Uiso 1 1 calc R . . C10 C 0.70985(12) 0.73217(13) 0.5903(2) 0.0378(6) Uani 1 1 d . . . H10 H 0.6978 0.7302 0.6545 0.045 Uiso 1 1 calc R . . C11 C 0.35543(11) 0.63655(11) 0.54948(18) 0.0297(6) Uani 1 1 d . . . C12 C 0.25653(12) 0.59995(13) 0.5223(2) 0.0376(6) Uani 1 1 d . . . H12A H 0.2260 0.6125 0.4782 0.045 Uiso 1 1 calc R . . H12B H 0.2481 0.6165 0.5854 0.045 Uiso 1 1 calc R . . C13 C 0.25498(13) 0.53354(13) 0.5299(2) 0.0389(7) Uani 1 1 d . . . C14 C 0.30416(15) 0.49887(14) 0.5358(2) 0.0468(7) Uani 1 1 d . . . H14 H 0.3411 0.5157 0.5332 0.056 Uiso 1 1 calc R . . C15 C 0.29840(17) 0.43924(15) 0.5455(2) 0.0544(9) Uani 1 1 d . . . H15 H 0.3312 0.4154 0.5509 0.065 Uiso 1 1 calc R . . C16 C 0.24371(18) 0.41579(16) 0.5471(2) 0.0570(9) Uani 1 1 d . . . H16 H 0.2386 0.3755 0.5516 0.068 Uiso 1 1 calc R . . C17 C 0.19658(17) 0.45199(15) 0.5418(2) 0.0529(9) Uani 1 1 d . . . H17 H 0.1594 0.4355 0.5442 0.063 Uiso 1 1 calc R . . O3 O 0.09394(11) 0.56739(11) 0.51851(18) 0.0488(6) Uani 1 1 d . . . H3B H 0.091(2) 0.596(2) 0.476(3) 0.084(15) Uiso 1 1 d . . . H3A H 0.1311(19) 0.5544(17) 0.515(3) 0.062(11) Uiso 1 1 d . . . O4 O 0.58879(12) 0.67308(12) 0.0864(2) 0.0517(6) Uani 1 1 d . . . H4A H 0.5786(16) 0.6782(16) 0.138(3) 0.055(12) Uiso 1 1 d . . . H4B H 0.5803(17) 0.6996(17) 0.065(3) 0.052(13) Uiso 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cu1 0.02709(18) 0.02683(18) 0.02037(16) -0.00141(12) 0.00046(12) -0.00119(12) N1 0.0278(11) 0.0270(11) 0.0205(10) -0.0006(8) 0.0014(9) -0.0012(9) N2 0.0258(11) 0.0270(11) 0.0248(10) -0.0008(9) 0.0014(9) 0.0005(8) N3 0.0299(11) 0.0290(11) 0.0253(11) 0.0004(9) 0.0039(9) -0.0030(9) N4 0.0301(11) 0.0297(11) 0.0293(11) -0.0004(9) 0.0010(9) -0.0003(9) N5 0.0291(12) 0.0435(14) 0.0288(13) -0.0012(11) -0.0024(10) -0.0065(10) N6 0.0444(15) 0.0456(15) 0.0467(15) 0.0050(12) -0.0096(12) -0.0085(12) O1 0.0404(11) 0.0458(11) 0.0196(9) -0.0014(8) 0.0010(8) -0.0041(9) O2 0.0315(10) 0.0387(11) 0.0267(10) 0.0012(8) 0.0021(8) -0.0020(8) C1 0.0332(14) 0.0293(13) 0.0216(12) -0.0012(10) -0.0026(10) 0.0004(10) C2 0.0325(14) 0.0223(12) 0.0214(12) 0.0005(10) 0.0010(10) 0.0007(10) C3 0.0272(13) 0.0263(13) 0.0257(12) -0.0004(10) -0.0024(10) -0.0002(10) C4 0.0340(14) 0.0235(13) 0.0258(13) 0.0001(10) 0.0007(11) -0.0008(10) C5 0.0338(14) 0.0329(14) 0.0271(13) 0.0006(11) 0.0035(11) -0.0016(11) C6 0.0339(15) 0.0255(13) 0.0341(14) -0.0002(11) 0.0026(11) 0.0007(11) C7 0.0348(15) 0.0403(16) 0.0400(16) 0.0025(13) 0.0077(13) -0.0015(12) C8 0.0296(15) 0.0457(17) 0.0563(19) 0.0022(15) 0.0047(14) -0.0037(13) C9 0.0344(16) 0.0497(18) 0.0462(17) -0.0001(15) -0.0076(13) -0.0061(13) C10 0.0338(15) 0.0429(16) 0.0367(15) -0.0024(13) -0.0035(13) -0.0032(12) C11 0.0314(14) 0.0273(13) 0.0304(14) 0.0014(11) -0.0018(11) 0.0001(11) C12 0.0284(14) 0.0416(16) 0.0427(16) -0.0022(13) 0.0009(12) -0.0034(12) C13 0.0421(16) 0.0456(17) 0.0290(14) -0.0007(12) -0.0037(12) -0.0073(13) C14 0.0512(19) 0.0467(18) 0.0423(17) 0.0001(14) 0.0068(15) 0.0046(15) C15 0.070(2) 0.049(2) 0.0439(18) 0.0024(15) 0.0102(17) 0.0123(17) C16 0.085(3) 0.0419(18) 0.0439(18) -0.0030(15) -0.0014(18) 0.0024(18) C17 0.063(2) 0.051(2) 0.0443(18) 0.0028(16) -0.0075(16) -0.0181(17) O3 0.0471(14) 0.0471(14) 0.0521(14) -0.0073(12) 0.0100(11) 0.0011(11) O4 0.0698(17) 0.0480(15) 0.0374(13) 0.0075(12) 0.0206(12) 0.0101(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 N3 1.930(2) . ? Cu1 N2 1.967(2) 12_767 ? Cu1 N1 1.975(2) . ? Cu1 N4 2.012(2) . ? Cu1 O2 2.4730(18) 12_767 ? Cu1 Cu1 4.0768(4) 12_767 ? Cu1 Cu1 4.0768(4) 15_566 ? Cu1 Cu1 4.7091(5) 6_564 ? N1 N2 1.342(3) . ? N1 C2 1.351(3) . ? N2 C3 1.362(3) . ? N2 Cu1 1.967(2) 15_566 ? N3 C4 1.322(3) . ? N3 C5 1.447(3) . ? N4 C6 1.348(3) . ? N4 C10 1.349(4) . ? N5 C11 1.338(3) . ? N5 C12 1.450(4) . ? N6 C13 1.338(4) . ? N6 C17 1.354(4) . ? O1 C4 1.254(3) . ? O2 C11 1.242(3) . ? C1 C2 1.383(4) . ? C1 C3 1.394(4) . ? C2 C4 1.493(4) . ? C3 C11 1.473(4) . ? C5 C6 1.506(4) . ? C6 C7 1.392(4) . ? C7 C8 1.377(4) . ? C8 C9 1.388(4) . ? C9 C10 1.375(4) . ? C12 C13 1.522(4) . ? C13 C14 1.378(4) . ? C14 C15 1.376(5) . ? C15 C16 1.361(5) . ? C16 C17 1.361(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 N3 Cu1 N2 175.77(9) . 12_767 ? N3 Cu1 N1 81.44(9) . . ? N2 Cu1 N1 98.70(8) 12_767 . ? N3 Cu1 N4 81.53(9) . . ? N2 Cu1 N4 97.93(9) 12_767 . ? N1 Cu1 N4 162.27(8) . . ? N3 Cu1 O2 110.35(8) . 12_767 ? N2 Cu1 O2 73.86(7) 12_767 12_767 ? N1 Cu1 O2 96.92(7) . 12_767 ? N4 Cu1 O2 93.57(8) . 12_767 ? N2 N1 C2 108.7(2) . . ? N2 N1 Cu1 138.18(16) . . ? C2 N1 Cu1 113.07(16) . . ? N1 N2 C3 107.6(2) . . ? N1 N2 Cu1 129.74(16) . 15_566 ? C3 N2 Cu1 122.50(17) . 15_566 ? C4 N3 C5 122.1(2) . . ? C4 N3 Cu1 118.97(17) . . ? C5 N3 Cu1 118.41(16) . . ? C6 N4 C10 119.3(2) . . ? C6 N4 Cu1 114.86(17) . . ? C10 N4 Cu1 125.85(18) . . ? C11 N5 C12 122.1(2) . . ? C13 N6 C17 117.3(3) . . ? C2 C1 C3 103.9(2) . . ? N1 C2 C1 110.0(2) . . ? N1 C2 C4 115.9(2) . . ? C1 C2 C4 134.1(2) . . ? N2 C3 C1 109.8(2) . . ? N2 C3 C11 116.0(2) . . ? C1 C3 C11 134.2(2) . . ? O1 C4 N3 128.3(2) . . ? O1 C4 C2 121.2(2) . . ? N3 C4 C2 110.5(2) . . ? N3 C5 C6 108.4(2) . . ? N4 C6 C7 120.9(3) . . ? N4 C6 C5 116.8(2) . . ? C7 C6 C5 122.3(2) . . ? C8 C7 C6 119.6(3) . . ? C7 C8 C9 119.3(3) . . ? C10 C9 C8 118.7(3) . . ? N4 C10 C9 122.3(3) . . ? O2 C11 N5 123.0(2) . . ? O2 C11 C3 120.2(2) . . ? N5 C11 C3 116.8(2) . . ? N5 C12 C13 113.6(2) . . ? N6 C13 C14 121.7(3) . . ? N6 C13 C12 114.3(3) . . ? C14 C13 C12 124.0(3) . . ? C15 C14 C13 119.8(3) . . ? C16 C15 C14 118.7(3) . . ? C17 C16 C15 119.2(3) . . ? N6 C17 C16 123.3(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 N5 H5 O3 0.76(3) 2.40(3) 3.135(4) 165(3) 4_454 O3 H3B O4 0.88(5) 1.97(5) 2.819(4) 163(4) 10_556 O3 H3A N6 0.90(4) 1.90(4) 2.777(4) 163(3) . O4 H4A O1 0.76(4) 2.02(4) 2.758(3) 164(4) . O4 H4B O1 0.70(4) 2.19(4) 2.879(3) 168(4) 12_766 _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 24.79 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.314 _refine_diff_density_min -0.219 _refine_diff_density_rms 0.051 data_Ni4L4 _database_code_depnum_ccdc_archive 'CCDC 636109' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C68 H56 N24 Ni4 O8, 8(H2 O)' _chemical_formula_sum 'C68 H72 N24 Ni4 O16' _chemical_formula_weight 1716.34 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' 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 'I 41/a' _symmetry_space_group_name_Hall '-I 4ad' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-y+3/4, x+1/4, z+1/4' 'y+3/4, -x+3/4, z+3/4' 'x+1/2, y+1/2, z+1/2' '-x+1, -y+1/2, z+1' '-y+5/4, x+3/4, z+3/4' 'y+5/4, -x+5/4, z+5/4' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'y-3/4, -x-1/4, -z-1/4' '-y-3/4, x-3/4, -z-3/4' '-x+1/2, -y+1/2, -z+1/2' 'x, y+1/2, -z' 'y-1/4, -x+1/4, -z+1/4' '-y-1/4, x-1/4, -z-1/4' _cell_length_a 22.7567(9) _cell_length_b 22.7567(9) _cell_length_c 13.7394(7) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 7115.2(5) _cell_formula_units_Z 4 _cell_measurement_temperature 133(2) _cell_measurement_reflns_used 53638 _cell_measurement_theta_min 1.73 _cell_measurement_theta_max 24.90 _exptl_crystal_description block _exptl_crystal_colour orange _exptl_crystal_size_max 0.22 _exptl_crystal_size_mid 0.19 _exptl_crystal_size_min 0.14 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.602 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3552 _exptl_absorpt_coefficient_mu 1.130 _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_T_min 0.7263 _exptl_absorpt_correction_T_max 0.8819 _exptl_absorpt_process_details 'X-RED (Stoe & Cie, 2002)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 133(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 'Stoe IPDS II' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 53638 _diffrn_reflns_av_R_equivalents 0.0752 _diffrn_reflns_av_sigmaI/netI 0.0302 _diffrn_reflns_limit_h_min -26 _diffrn_reflns_limit_h_max 26 _diffrn_reflns_limit_k_min -26 _diffrn_reflns_limit_k_max 26 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 1.73 _diffrn_reflns_theta_max 24.90 _reflns_number_total 3081 _reflns_number_gt 2415 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'X-AREA (Stoe & Cie, 2002)' _computing_cell_refinement 'X-AREA (Stoe & Cie, 2002)' _computing_data_reduction 'X-AREA (Stoe & Cie, 2002)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'DIAMOND (Brandenburg, 2001)' _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^)+(0.0395P)^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 none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3081 _refine_ls_number_parameters 273 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0422 _refine_ls_R_factor_gt 0.0288 _refine_ls_wR_factor_ref 0.0673 _refine_ls_wR_factor_gt 0.0647 _refine_ls_goodness_of_fit_ref 1.006 _refine_ls_restrained_S_all 1.006 _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 Ni1 Ni 0.581870(12) 0.700012(13) 0.537474(19) 0.02043(10) Uani 1 1 d . . . N1 N 0.50219(8) 0.67911(8) 0.51915(12) 0.0216(4) Uani 1 1 d . . . N2 N 0.45425(8) 0.66882(8) 0.57489(13) 0.0217(4) Uani 1 1 d . . . N3 N 0.58401(8) 0.69517(8) 0.40348(13) 0.0244(4) Uani 1 1 d . . . N4 N 0.66261(8) 0.72118(8) 0.52373(13) 0.0243(4) Uani 1 1 d . . . N5 N 0.31023(9) 0.62075(10) 0.49448(16) 0.0318(5) Uani 1 1 d . . . N6 N 0.19530(11) 0.51170(10) 0.53912(17) 0.0453(6) Uani 1 1 d . . . O1 O 0.53010(7) 0.67407(7) 0.26481(10) 0.0293(4) Uani 1 1 d . . . O2 O 0.34539(7) 0.63642(8) 0.64632(11) 0.0316(4) Uani 1 1 d . . . C1 C 0.43003(10) 0.65197(10) 0.41799(16) 0.0240(5) Uani 1 1 d . . . H1 H 0.4091 0.6422 0.3621 0.080 Uiso 1 1 calc R . . C2 C 0.48761(10) 0.66931(10) 0.42491(15) 0.0215(5) Uani 1 1 d . . . C3 C 0.40993(10) 0.65238(10) 0.51417(16) 0.0225(5) Uani 1 1 d . . . C4 C 0.53623(11) 0.67965(9) 0.35543(15) 0.0242(5) Uani 1 1 d . . . C5 C 0.63818(10) 0.71051(11) 0.35359(16) 0.0279(5) Uani 1 1 d . . . H5A H 0.6320 0.7442 0.3116 0.080 Uiso 1 1 calc R . . H5B H 0.6517 0.6778 0.3142 0.080 Uiso 1 1 calc R . . C6 C 0.68233(10) 0.72471(10) 0.43091(16) 0.0258(5) Uani 1 1 d . . . C7 C 0.74007(11) 0.73949(11) 0.40994(18) 0.0320(6) Uani 1 1 d . . . H7 H 0.7525 0.7422 0.3456 0.080 Uiso 1 1 calc R . . C8 C 0.77910(11) 0.75010(12) 0.48512(19) 0.0359(6) Uani 1 1 d . . . H8 H 0.8180 0.7598 0.4722 0.080 Uiso 1 1 calc R . . C9 C 0.75895(11) 0.74595(12) 0.58013(19) 0.0338(6) Uani 1 1 d . . . H9 H 0.7843 0.7527 0.6320 0.080 Uiso 1 1 calc R . . C10 C 0.70117(11) 0.73183(11) 0.59680(18) 0.0298(5) Uani 1 1 d . . . H10 H 0.6880 0.7295 0.6607 0.080 Uiso 1 1 calc R . . C11 C 0.35285(10) 0.63632(10) 0.55751(16) 0.0246(5) Uani 1 1 d . . . C12 C 0.25386(11) 0.59911(11) 0.52773(19) 0.0345(6) Uani 1 1 d . . . H12A H 0.2236 0.6130 0.4837 0.080 Uiso 1 1 calc R . . H12B H 0.2458 0.6156 0.5915 0.080 Uiso 1 1 calc R . . C13 C 0.24997(12) 0.53286(11) 0.53415(17) 0.0334(6) Uani 1 1 d . . . C14 C 0.29896(15) 0.49642(13) 0.5368(2) 0.0464(7) Uani 1 1 d . . . H14 H 0.3365 0.5124 0.5329 0.080 Uiso 1 1 calc R . . C15 C 0.29164(19) 0.43693(15) 0.5452(2) 0.0617(10) Uani 1 1 d . . . H15 H 0.3240 0.4121 0.5480 0.080 Uiso 1 1 calc R . . C16 C 0.2358(2) 0.41462(15) 0.5492(2) 0.0664(11) Uani 1 1 d . . . H16 H 0.2295 0.3743 0.5537 0.080 Uiso 1 1 calc R . . C17 C 0.18933(18) 0.45291(15) 0.5465(2) 0.0613(10) Uani 1 1 d . . . H17 H 0.1515 0.4375 0.5498 0.080 Uiso 1 1 calc R . . O3 O 0.08811(11) 0.56883(11) 0.51134(19) 0.0530(6) Uani 1 1 d . . . O4 O 0.59434(10) 0.67467(10) 0.09294(16) 0.0447(5) Uani 1 1 d . . . H3A H 0.1262(18) 0.5514(16) 0.510(3) 0.068(11) Uiso 1 1 d . . . H3B H 0.0853(15) 0.5945(15) 0.471(2) 0.050(11) Uiso 1 1 d . . . H4A H 0.5789(17) 0.6809(16) 0.148(3) 0.074(12) Uiso 1 1 d . . . H4B H 0.5831(14) 0.7031(15) 0.064(3) 0.053(11) Uiso 1 1 d . . . H5 H 0.3165(13) 0.6233(13) 0.433(2) 0.049(9) Uiso 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Ni1 0.02226(17) 0.02251(17) 0.01652(14) -0.00070(11) 0.00056(12) -0.00086(12) N1 0.0265(10) 0.0204(10) 0.0178(9) -0.0010(7) 0.0029(8) 0.0003(8) N2 0.0189(10) 0.0227(10) 0.0235(9) 0.0003(8) -0.0001(8) 0.0000(8) N3 0.0242(10) 0.0259(11) 0.0231(9) -0.0011(8) 0.0019(8) -0.0037(8) N4 0.0282(11) 0.0215(10) 0.0232(10) -0.0009(8) 0.0001(8) 0.0024(8) N5 0.0251(11) 0.0418(13) 0.0286(11) -0.0046(10) -0.0032(9) -0.0042(10) N6 0.0503(15) 0.0413(14) 0.0443(13) 0.0108(11) -0.0222(12) -0.0172(11) O1 0.0360(10) 0.0359(10) 0.0161(8) -0.0011(7) 0.0007(7) -0.0044(8) O2 0.0284(9) 0.0424(10) 0.0242(9) 0.0041(7) 0.0016(7) -0.0035(8) C1 0.0284(13) 0.0244(12) 0.0192(11) -0.0008(9) -0.0026(9) 0.0000(10) C2 0.0275(13) 0.0216(12) 0.0153(10) 0.0006(9) 0.0004(9) 0.0012(10) C3 0.0229(12) 0.0213(11) 0.0234(11) -0.0014(9) -0.0022(9) -0.0002(9) C4 0.0317(13) 0.0199(12) 0.0209(11) 0.0013(9) 0.0022(10) 0.0003(10) C5 0.0291(13) 0.0316(13) 0.0231(11) -0.0006(10) 0.0050(10) -0.0032(10) C6 0.0290(13) 0.0220(12) 0.0264(11) -0.0002(10) 0.0033(10) -0.0002(10) C7 0.0300(14) 0.0315(14) 0.0344(13) 0.0019(11) 0.0073(11) -0.0002(11) C8 0.0243(13) 0.0366(15) 0.0467(15) 0.0009(12) 0.0042(11) -0.0020(11) C9 0.0262(13) 0.0366(15) 0.0386(14) -0.0014(12) -0.0043(11) -0.0042(11) C10 0.0286(13) 0.0306(14) 0.0302(12) -0.0015(10) -0.0032(10) -0.0017(11) C11 0.0259(12) 0.0221(12) 0.0258(13) -0.0010(9) -0.0027(10) 0.0001(10) C12 0.0233(13) 0.0343(14) 0.0460(15) -0.0049(12) -0.0027(11) -0.0025(11) C13 0.0430(15) 0.0353(14) 0.0219(11) -0.0023(10) -0.0052(11) -0.0044(12) C14 0.062(2) 0.0416(17) 0.0357(14) 0.0049(13) 0.0131(14) 0.0147(14) C15 0.100(3) 0.0453(19) 0.0392(17) 0.0092(14) 0.0282(18) 0.0195(19) C16 0.132(4) 0.0319(17) 0.0354(17) 0.0031(13) 0.001(2) 0.004(2) C17 0.090(3) 0.058(2) 0.0364(16) 0.0128(15) -0.0234(17) -0.036(2) O3 0.0525(15) 0.0432(13) 0.0632(15) -0.0120(12) 0.0261(12) -0.0050(11) O4 0.0532(13) 0.0432(13) 0.0377(12) 0.0094(10) 0.0186(10) 0.0118(10) _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 N3 1.8450(18) . ? Ni1 N1 1.8914(19) . ? Ni1 N2 1.8935(18) 12_767 ? Ni1 N4 1.909(2) . ? Ni1 O2 2.6489(16) 12_767 ? Ni1 Ni1 3.9134(5) 15_566 ? Ni1 Ni1 4.3658(6) 6_564 ? Ni1 Ni1 9.0835(5) 7_544 ? N1 N2 1.353(3) . ? N1 C2 1.355(3) . ? N2 C3 1.361(3) . ? N2 Ni1 1.8935(18) 15_566 ? N3 C4 1.320(3) . ? N3 C5 1.453(3) . ? N4 C6 1.354(3) . ? N4 C10 1.355(3) . ? N5 C11 1.348(3) . ? N5 C12 1.448(3) . ? N6 C13 1.336(3) . ? N6 C17 1.348(4) . ? O1 C4 1.259(3) . ? O2 C11 1.232(3) . ? C1 C2 1.372(3) . ? C1 C3 1.398(3) . ? C2 C4 1.480(3) . ? C3 C11 1.475(3) . ? C5 C6 1.497(3) . ? C6 C7 1.387(3) . ? C7 C8 1.384(4) . ? C8 C9 1.387(4) . ? C9 C10 1.373(3) . ? C12 C13 1.513(4) . ? C13 C14 1.390(4) . ? C14 C15 1.369(4) . ? C15 C16 1.370(5) . ? C16 C17 1.370(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 N3 Ni1 N1 82.96(8) . . ? N3 Ni1 N2 178.85(9) . 12_767 ? N1 Ni1 N2 97.92(8) . 12_767 ? N3 Ni1 N4 83.74(8) . . ? N1 Ni1 N4 166.67(7) . . ? N2 Ni1 N4 95.39(8) 12_767 . ? N3 Ni1 O2 106.37(7) . 12_767 ? N1 Ni1 O2 94.64(7) . 12_767 ? N2 Ni1 O2 72.85(7) 12_767 12_767 ? N4 Ni1 O2 89.92(7) . 12_767 ? N3 Ni1 Ni1 128.49(6) . 15_566 ? N1 Ni1 Ni1 45.58(5) . 15_566 ? N2 Ni1 Ni1 52.36(6) 12_767 15_566 ? N4 Ni1 Ni1 147.74(6) . 15_566 ? O2 Ni1 Ni1 80.28(4) 12_767 15_566 ? N3 Ni1 Ni1 93.08(6) . 6_564 ? N1 Ni1 Ni1 46.59(5) . 6_564 ? N2 Ni1 Ni1 88.07(6) 12_767 6_564 ? N4 Ni1 Ni1 133.63(6) . 6_564 ? O2 Ni1 Ni1 134.50(4) 12_767 6_564 ? Ni1 Ni1 Ni1 56.096(4) 15_566 6_564 ? N3 Ni1 Ni1 64.51(6) . 7_544 ? N1 Ni1 Ni1 68.97(5) . 7_544 ? N2 Ni1 Ni1 115.08(6) 12_767 7_544 ? N4 Ni1 Ni1 105.80(6) . 7_544 ? O2 Ni1 Ni1 47.36(4) 12_767 7_544 ? Ni1 Ni1 Ni1 90.009(8) 15_566 7_544 ? Ni1 Ni1 Ni1 114.359(9) 6_564 7_544 ? N2 N1 C2 108.36(18) . . ? N2 N1 Ni1 137.81(14) . . ? C2 N1 Ni1 113.78(15) . . ? N1 N2 C3 107.33(17) . . ? N1 N2 Ni1 127.42(14) . 15_566 ? C3 N2 Ni1 124.89(15) . 15_566 ? C4 N3 C5 121.81(18) . . ? C4 N3 Ni1 119.56(15) . . ? C5 N3 Ni1 118.61(15) . . ? C6 N4 C10 118.2(2) . . ? C6 N4 Ni1 115.27(15) . . ? C10 N4 Ni1 126.52(16) . . ? C11 N5 C12 121.6(2) . . ? C13 N6 C17 117.1(3) . . ? C2 C1 C3 104.19(19) . . ? N1 C2 C1 110.33(19) . . ? N1 C2 C4 114.0(2) . . ? C1 C2 C4 135.6(2) . . ? N2 C3 C1 109.8(2) . . ? N2 C3 C11 118.24(19) . . ? C1 C3 C11 131.9(2) . . ? O1 C4 N3 127.8(2) . . ? O1 C4 C2 122.6(2) . . ? N3 C4 C2 109.61(18) . . ? N3 C5 C6 106.64(18) . . ? N4 C6 C7 121.6(2) . . ? N4 C6 C5 115.7(2) . . ? C7 C6 C5 122.7(2) . . ? C8 C7 C6 119.7(2) . . ? C7 C8 C9 118.6(2) . . ? C10 C9 C8 119.3(2) . . ? N4 C10 C9 122.6(2) . . ? O2 C11 N5 122.5(2) . . ? O2 C11 C3 121.4(2) . . ? N5 C11 C3 116.1(2) . . ? N5 C12 C13 114.2(2) . . ? N6 C13 C14 122.0(3) . . ? N6 C13 C12 114.6(2) . . ? C14 C13 C12 123.3(2) . . ? C15 C14 C13 119.6(3) . . ? C14 C15 C16 118.9(3) . . ? C17 C16 C15 118.6(3) . . ? N6 C17 C16 123.7(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 N5 H5 O3 0.86(3) 2.52(3) 3.343(4) 162(3) 4_454 O3 H3B O4 0.81(3) 2.03(4) 2.806(4) 159(3) 10_556 O3 H3A N6 0.95(4) 1.86(4) 2.790(4) 166(3) . O4 H4A O1 0.85(4) 1.95(4) 2.777(3) 163(4) . O4 H4B O1 0.80(4) 2.07(4) 2.850(3) 166(3) 12_766 _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 24.90 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.229 _refine_diff_density_min -0.304 _refine_diff_density_rms 0.048 data_Cu2Ni2L4 _database_code_depnum_ccdc_archive 'CCDC 636110' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C68 H56 Cu2 N24 Ni2 O8, 8 (H2 O)' _chemical_formula_sum 'C68 H72 Cu2 N24 Ni2 O16' _chemical_formula_weight 1726.00 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' Ni Ni 0.3393 1.1124 '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 'I 41/a' _symmetry_space_group_name_Hall '-I 4ad' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-y+3/4, x+1/4, z+1/4' 'y+3/4, -x+3/4, z+3/4' 'x+1/2, y+1/2, z+1/2' '-x+1, -y+1/2, z+1' '-y+5/4, x+3/4, z+3/4' 'y+5/4, -x+5/4, z+5/4' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'y-3/4, -x-1/4, -z-1/4' '-y-3/4, x-3/4, -z-3/4' '-x+1/2, -y+1/2, -z+1/2' 'x, y+1/2, -z' 'y-1/4, -x+1/4, -z+1/4' '-y-1/4, x-1/4, -z-1/4' _cell_length_a 22.8396(10) _cell_length_b 22.8396(10) _cell_length_c 13.7885(7) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 7192.7(6) _cell_formula_units_Z 4 _cell_measurement_temperature 133(2) _cell_measurement_reflns_used 33886 _cell_measurement_theta_min 1.73 _cell_measurement_theta_max 24.81 _exptl_crystal_description block _exptl_crystal_colour 'dark grey' _exptl_crystal_size_max 0.39 _exptl_crystal_size_mid 0.29 _exptl_crystal_size_min 0.16 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.594 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3560 _exptl_absorpt_coefficient_mu 1.185 _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_T_min 0.6201 _exptl_absorpt_correction_T_max 0.8472 _exptl_absorpt_process_details 'X-RED (Stoe & Cie, 2002)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 133(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 'Stoe IPDS II' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 33886 _diffrn_reflns_av_R_equivalents 0.0666 _diffrn_reflns_av_sigmaI/netI 0.0342 _diffrn_reflns_limit_h_min -26 _diffrn_reflns_limit_h_max 26 _diffrn_reflns_limit_k_min -26 _diffrn_reflns_limit_k_max 26 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 1.73 _diffrn_reflns_theta_max 24.81 _reflns_number_total 3095 _reflns_number_gt 2373 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'X-AREA (Stoe & Cie, 2002)' _computing_cell_refinement 'X-AREA (Stoe & Cie, 2002)' _computing_data_reduction 'X-AREA (Stoe & Cie, 2002)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'DIAMOND (Brandenburg, 2001)' _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^)+(0.0315P)^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 none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3095 _refine_ls_number_parameters 273 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0450 _refine_ls_R_factor_gt 0.0281 _refine_ls_wR_factor_ref 0.0602 _refine_ls_wR_factor_gt 0.0574 _refine_ls_goodness_of_fit_ref 1.003 _refine_ls_restrained_S_all 1.003 _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 Ni1 Ni 0.585083(12) 0.697605(12) 0.538983(19) 0.02240(9) Uani 0.50 1 d P . . Cu1 Cu 0.585083(12) 0.697605(12) 0.538983(19) 0.02240(9) Uani 0.50 1 d P . . N1 N 0.50353(8) 0.67763(8) 0.51789(13) 0.0235(4) Uani 1 1 d . . . N2 N 0.45541(8) 0.66723(8) 0.57126(13) 0.0246(4) Uani 1 1 d . . . N3 N 0.58713(8) 0.69320(8) 0.40178(12) 0.0261(4) Uani 1 1 d . . . N4 N 0.66718(8) 0.72110(8) 0.52137(13) 0.0268(4) Uani 1 1 d . . . N5 N 0.31192(9) 0.62141(10) 0.49090(16) 0.0315(5) Uani 1 1 d . . . N6 N 0.19933(10) 0.51098(10) 0.53568(16) 0.0418(5) Uani 1 1 d . . . O1 O 0.53163(7) 0.67637(7) 0.26404(11) 0.0319(4) Uani 1 1 d . . . O2 O 0.34865(7) 0.63555(7) 0.64193(12) 0.0332(4) Uani 1 1 d . . . C1 C 0.43217(10) 0.65335(10) 0.41414(16) 0.0258(5) Uani 1 1 d . . . H1 H 0.4116 0.6449 0.3576 0.080 Uiso 1 1 calc R . . C2 C 0.48991(10) 0.66972(9) 0.42314(16) 0.0236(5) Uani 1 1 d . . . C3 C 0.41162(10) 0.65229(10) 0.50919(16) 0.0247(5) Uani 1 1 d . . . C4 C 0.53891(10) 0.68011(9) 0.35412(16) 0.0248(5) Uani 1 1 d . . . C5 C 0.64075(10) 0.70956(11) 0.35247(17) 0.0298(5) Uani 1 1 d . . . H5A H 0.6339 0.7430 0.3107 0.080 Uiso 1 1 calc R . . H5B H 0.6546 0.6773 0.3128 0.080 Uiso 1 1 calc R . . C6 C 0.68535(10) 0.72451(10) 0.42833(17) 0.0274(5) Uani 1 1 d . . . C7 C 0.74248(11) 0.73983(11) 0.4056(2) 0.0372(6) Uani 1 1 d . . . H7 H 0.7542 0.7424 0.3412 0.080 Uiso 1 1 calc R . . C8 C 0.78193(11) 0.75125(12) 0.4792(2) 0.0446(7) Uani 1 1 d . . . H8 H 0.8204 0.7615 0.4649 0.080 Uiso 1 1 calc R . . C9 C 0.76331(12) 0.74717(12) 0.5742(2) 0.0437(7) Uani 1 1 d . . . H9 H 0.7892 0.7543 0.6250 0.080 Uiso 1 1 calc R . . C10 C 0.70601(11) 0.73248(11) 0.5930(2) 0.0360(6) Uani 1 1 d . . . H10 H 0.6935 0.7303 0.6571 0.080 Uiso 1 1 calc R . . C11 C 0.35488(10) 0.63635(10) 0.55300(16) 0.0266(5) Uani 1 1 d . . . C12 C 0.25607(11) 0.59922(11) 0.52456(19) 0.0356(6) Uani 1 1 d . . . H12A H 0.2257 0.6123 0.4805 0.080 Uiso 1 1 calc R . . H12B H 0.2478 0.6159 0.5878 0.080 Uiso 1 1 calc R . . C13 C 0.25349(11) 0.53297(11) 0.53207(17) 0.0334(6) Uani 1 1 d . . . C14 C 0.30284(13) 0.49777(12) 0.5366(2) 0.0435(7) Uani 1 1 d . . . H14 H 0.3399 0.5144 0.5336 0.080 Uiso 1 1 calc R . . C15 C 0.29679(16) 0.43820(13) 0.5456(2) 0.0537(8) Uani 1 1 d . . . H15 H 0.3295 0.4140 0.5494 0.080 Uiso 1 1 calc R . . C16 C 0.24120(17) 0.41513(13) 0.5488(2) 0.0562(9) Uani 1 1 d . . . H16 H 0.2356 0.3749 0.5541 0.080 Uiso 1 1 calc R . . C17 C 0.19437(15) 0.45216(13) 0.5440(2) 0.0534(8) Uani 1 1 d . . . H17 H 0.1570 0.4361 0.5467 0.080 Uiso 1 1 calc R . . O3 O 0.09193(11) 0.56792(10) 0.51632(18) 0.0497(5) Uani 1 1 d . . . O4 O 0.59088(10) 0.67377(10) 0.08848(17) 0.0459(5) Uani 1 1 d . . . H5 H 0.3176(12) 0.6257(12) 0.431(2) 0.043(8) Uiso 1 1 d . . . H3A H 0.131(2) 0.5549(19) 0.509(3) 0.108(15) Uiso 1 1 d . . . H3B H 0.0842(14) 0.5905(14) 0.474(2) 0.044(10) Uiso 1 1 d . . . H4A H 0.5772(16) 0.6787(16) 0.141(3) 0.079(13) Uiso 1 1 d . . . H4B H 0.5814(15) 0.7019(15) 0.061(3) 0.061(12) Uiso 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Ni1 0.02497(16) 0.02606(16) 0.01618(14) -0.00175(12) 0.00071(12) -0.00222(12) Cu1 0.02497(16) 0.02606(16) 0.01618(14) -0.00175(12) 0.00071(12) -0.00222(12) N1 0.0275(10) 0.0245(10) 0.0184(10) 0.0005(8) 0.0004(8) 0.0007(8) N2 0.0257(10) 0.0253(10) 0.0229(9) 0.0016(8) -0.0010(8) 0.0008(8) N3 0.0262(10) 0.0313(11) 0.0208(9) 0.0005(8) 0.0021(9) -0.0021(8) N4 0.0315(11) 0.0256(10) 0.0232(10) -0.0004(8) -0.0028(8) 0.0012(8) N5 0.0276(11) 0.0414(13) 0.0254(11) -0.0024(10) -0.0013(9) -0.0039(9) N6 0.0466(14) 0.0403(13) 0.0385(12) 0.0067(11) -0.0144(11) -0.0099(10) O1 0.0394(10) 0.0400(10) 0.0163(8) -0.0005(7) -0.0004(7) -0.0026(8) O2 0.0380(10) 0.0396(10) 0.0220(9) 0.0021(7) 0.0005(7) -0.0031(8) C1 0.0301(13) 0.0274(13) 0.0199(11) -0.0005(10) -0.0036(10) -0.0001(9) C2 0.0297(13) 0.0232(12) 0.0180(11) 0.0002(9) -0.0010(10) 0.0016(10) C3 0.0258(12) 0.0243(12) 0.0239(12) 0.0011(9) -0.0041(10) 0.0006(9) C4 0.0337(13) 0.0214(12) 0.0194(11) 0.0004(9) -0.0004(10) 0.0008(10) C5 0.0325(13) 0.0337(13) 0.0233(12) 0.0023(10) 0.0044(10) -0.0031(11) C6 0.0304(13) 0.0213(12) 0.0304(13) 0.0024(10) 0.0026(10) 0.0010(10) C7 0.0324(14) 0.0323(14) 0.0469(16) 0.0054(12) 0.0075(13) -0.0004(11) C8 0.0270(14) 0.0401(16) 0.067(2) 0.0026(15) 0.0011(14) -0.0041(12) C9 0.0351(15) 0.0404(16) 0.0556(18) -0.0010(14) -0.0127(13) -0.0051(12) C10 0.0365(15) 0.0339(14) 0.0377(14) -0.0010(11) -0.0067(12) -0.0018(11) C11 0.0314(13) 0.0228(12) 0.0256(13) 0.0004(10) -0.0031(10) 0.0012(10) C12 0.0295(13) 0.0349(14) 0.0425(15) -0.0009(12) -0.0001(11) -0.0027(11) C13 0.0416(15) 0.0352(14) 0.0235(12) -0.0010(11) -0.0036(11) -0.0026(11) C14 0.0529(17) 0.0421(16) 0.0354(14) 0.0057(13) 0.0112(13) 0.0097(13) C15 0.078(2) 0.0477(18) 0.0353(16) 0.0071(14) 0.0186(16) 0.0172(16) C16 0.101(3) 0.0348(16) 0.0324(16) 0.0002(13) -0.0004(17) 0.0085(17) C17 0.072(2) 0.0517(18) 0.0369(16) 0.0084(15) -0.0171(15) -0.0233(16) O3 0.0504(14) 0.0450(13) 0.0536(14) -0.0071(11) 0.0180(11) -0.0014(10) O4 0.0568(13) 0.0444(13) 0.0367(12) 0.0078(10) 0.0175(11) 0.0084(10) _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 N3 1.8951(17) . ? Ni1 N2 1.9360(18) 12_767 ? Ni1 N1 1.9396(19) . ? Ni1 N4 1.965(2) . ? Ni1 O2 2.5426(16) 12_767 ? Ni1 Ni1 4.0054(5) 12_767 ? Ni1 Ni1 4.0054(5) 15_566 ? Ni1 Ni1 4.5643(6) 6_564 ? Cu1 N3 1.8951(17) . ? Cu1 N2 1.9360(18) 12_767 ? Cu1 N1 1.9396(19) . ? Cu1 N4 1.965(2) . ? Cu1 O2 2.5426(16) 12_767 ? Cu1 Cu1 4.0054(5) 12_767 ? Cu1 Cu1 4.0054(5) 15_566 ? Cu1 Cu1 4.5643(6) 6_564 ? N1 N2 1.344(3) . ? N1 C2 1.355(3) . ? N2 C3 1.360(3) . ? N2 Ni1 1.9360(18) 15_566 ? N2 Cu1 1.9360(18) 15_566 ? N3 C4 1.317(3) . ? N3 C5 1.450(3) . ? N4 C6 1.351(3) . ? N4 C10 1.353(3) . ? N5 C11 1.346(3) . ? N5 C12 1.449(3) . ? N6 C13 1.336(3) . ? N6 C17 1.353(4) . ? O1 C4 1.256(3) . ? O2 C11 1.235(3) . ? C1 C2 1.376(3) . ? C1 C3 1.392(3) . ? C2 C4 1.488(3) . ? C3 C11 1.475(3) . ? C5 C6 1.500(3) . ? C6 C7 1.387(3) . ? C7 C8 1.382(4) . ? C8 C9 1.381(4) . ? C9 C10 1.376(4) . ? C12 C13 1.518(3) . ? C13 C14 1.386(4) . ? C14 C15 1.373(4) . ? C15 C16 1.375(5) . ? C16 C17 1.365(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 N3 Ni1 N2 177.75(8) . 12_767 ? N3 Ni1 N1 82.05(8) . . ? N2 Ni1 N1 98.32(8) 12_767 . ? N3 Ni1 N4 82.39(8) . . ? N2 Ni1 N4 97.11(8) 12_767 . ? N1 Ni1 N4 164.13(7) . . ? N3 Ni1 O2 108.68(7) . 12_767 ? N2 Ni1 O2 73.51(7) 12_767 12_767 ? N1 Ni1 O2 95.76(7) . 12_767 ? N4 Ni1 O2 92.14(7) . 12_767 ? N3 Cu1 N2 177.75(8) . 12_767 ? N3 Cu1 N1 82.05(8) . . ? N2 Cu1 N1 98.32(8) 12_767 . ? N3 Cu1 N4 82.39(8) . . ? N2 Cu1 N4 97.11(8) 12_767 . ? N1 Cu1 N4 164.13(7) . . ? N3 Cu1 O2 108.68(7) . 12_767 ? N2 Cu1 O2 73.51(7) 12_767 12_767 ? N1 Cu1 O2 95.76(7) . 12_767 ? N4 Cu1 O2 92.14(7) . 12_767 ? N2 N1 C2 108.46(18) . . ? N2 N1 Ni1 138.15(14) . . ? C2 N1 Ni1 113.35(15) . . ? N2 N1 Cu1 138.15(14) . . ? C2 N1 Cu1 113.35(15) . . ? N1 N2 C3 107.53(18) . . ? N1 N2 Ni1 128.70(14) . 15_566 ? C3 N2 Ni1 123.49(15) . 15_566 ? N1 N2 Cu1 128.70(14) . 15_566 ? C3 N2 Cu1 123.49(15) . 15_566 ? C4 N3 C5 122.07(18) . . ? C4 N3 Ni1 119.31(15) . . ? C5 N3 Ni1 118.39(15) . . ? C4 N3 Cu1 119.31(15) . . ? C5 N3 Cu1 118.39(15) . . ? C6 N4 C10 118.8(2) . . ? C6 N4 Ni1 115.23(15) . . ? C10 N4 Ni1 125.99(17) . . ? C6 N4 Cu1 115.23(15) . . ? C10 N4 Cu1 125.99(17) . . ? C11 N5 C12 121.8(2) . . ? C13 N6 C17 117.0(2) . . ? C2 C1 C3 104.05(19) . . ? N1 C2 C1 110.1(2) . . ? N1 C2 C4 115.00(19) . . ? C1 C2 C4 134.9(2) . . ? N2 C3 C1 109.9(2) . . ? N2 C3 C11 116.76(19) . . ? C1 C3 C11 133.3(2) . . ? O1 C4 N3 128.3(2) . . ? O1 C4 C2 121.5(2) . . ? N3 C4 C2 110.24(19) . . ? N3 C5 C6 107.78(18) . . ? N4 C6 C7 121.2(2) . . ? N4 C6 C5 116.1(2) . . ? C7 C6 C5 122.6(2) . . ? C8 C7 C6 119.7(2) . . ? C9 C8 C7 118.9(2) . . ? C10 C9 C8 119.2(3) . . ? N4 C10 C9 122.2(3) . . ? O2 C11 N5 123.0(2) . . ? O2 C11 C3 120.8(2) . . ? N5 C11 C3 116.2(2) . . ? N5 C12 C13 113.9(2) . . ? N6 C13 C14 122.2(2) . . ? N6 C13 C12 114.4(2) . . ? C14 C13 C12 123.4(2) . . ? C15 C14 C13 119.8(3) . . ? C14 C15 C16 118.4(3) . . ? C17 C16 C15 119.0(3) . . ? N6 C17 C16 123.6(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 N5 H5 O3 0.84(3) 2.39(3) 3.211(3) 166(3) 4_454 O3 H3B O4 0.79(3) 2.10(3) 2.817(3) 151(3) 10_556 O3 H3A N6 0.95(5) 1.89(5) 2.789(3) 157(4) . O4 H4A O1 0.80(4) 1.99(4) 2.774(3) 167(4) . O4 H4B O1 0.77(4) 2.10(4) 2.867(3) 169(4) 12_766 _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 24.81 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.252 _refine_diff_density_min -0.229 _refine_diff_density_rms 0.044