# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2009 # Attachment 'TzC.cif' data_publication_text _publ_requested_journal 'Dalton Trans.' _publ_contact_author_name 'Enrique Colacio' _publ_contact_author_address ;Departamento de Qu\'imica Inorg\'anica Universidad de Granada 18071, Granada, Spain ; _publ_contact_author_email ecolacio@ugr.es _publ_contact_author_phone 0034958243236 loop_ _publ_author_name _publ_author_address A.Rodriguez-Dieguez ;Departamento de Qu\'imica Inorg\'anica Universidad de Granada 18071, Granada, Spain ; A.J.Mota ;Departamento de Qu\'imica Inorg\'anica Universidad de Granada 18071, Granada, Spain ; 'J.Cano ' ;Departament de Qu\'imica Inorg\`anica and Centre de Recerca en Qu\'imica Te\'orica Instituci\'o Catalana de Recerca i Estudis Avan\,cats (ICREA) Universitat de Barcelona, Av. Diagonal 647, 08027 Barcelona, (Spain) ; J.Ruiz ;Departamento de Qu\'imica Inorg\'anica Universidad de Granada 18071, Granada, Spain ; ; D.Choquesillo-Lazarte ; ;Laboratorio de Estudios Cristalogr\'aficos IACT-CSIC 18100, Granada (Spain) ; E.Colacio ;Departamento de Qu\'imica Inorg\'anica Universidad de Granada 18071, Granada, Spain ; data_compound1 _database_code_depnum_ccdc_archive 'CCDC 717035' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C2 H4 Mn N4 O4' _chemical_formula_weight 203.03 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' Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'P21/c ' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 6.352(5) _cell_length_b 6.435(5) _cell_length_c 15.131(5) _cell_angle_alpha 90.00 _cell_angle_beta 97.833(5) _cell_angle_gamma 90.00 _cell_volume 612.7(7) _cell_formula_units_Z 4 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 1453 _cell_measurement_theta_min 2.718 _cell_measurement_theta_max 25.655 _exptl_crystal_description prismatic _exptl_crystal_colour colourless _exptl_crystal_size_max 0.16 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.201 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 404 _exptl_absorpt_coefficient_mu 2.124 _exptl_absorpt_correction_type MULTI-SCAN _exptl_absorpt_correction_T_min 0.7274 _exptl_absorpt_correction_T_max 0.8157 _exptl_absorpt_process_details ; 'SADABS in APEX2, 2008' ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 298(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean ? _diffrn_reflns_number 3669 _diffrn_reflns_av_R_equivalents 0.0176 _diffrn_reflns_av_sigmaI/netI 0.0222 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 7 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 2.72 _diffrn_reflns_theta_max 28.36 _reflns_number_total 1385 _reflns_number_gt 1183 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker APEX2' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _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^)+(0.0221P)^2^+4.2882P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1385 _refine_ls_number_parameters 65 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0689 _refine_ls_R_factor_gt 0.0587 _refine_ls_wR_factor_ref 0.1206 _refine_ls_wR_factor_gt 0.1144 _refine_ls_goodness_of_fit_ref 0.994 _refine_ls_restrained_S_all 0.994 _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 Mn1 Mn 0.59431(11) 0.10948(11) 0.82938(5) 0.0340(2) Uani 1 1 d . . . N1 N 0.7320(10) 0.2647(10) 0.9467(4) 0.0322(4) Uani 0.609(3) 1 d P . 1 N2 N 0.7981(10) 0.2066(10) 1.0293(4) 0.0322(4) Uani 0.609(3) 1 d P . 1 N3 N 0.8286(11) 0.3730(10) 1.0830(4) 0.0322(4) Uani 0.609(3) 1 d P . 1 N4 N 0.7782(10) 0.5451(10) 1.0298(4) 0.0322(4) Uani 0.609(3) 1 d P . 1 C5 C 0.7109(12) 0.4744(12) 0.9435(5) 0.0322(4) Uani 0.609(3) 1 d P . 1 C6 C 0.6356(12) 0.5930(12) 0.8670(5) 0.0322(4) Uani 0.609(3) 1 d P . 1 O7 O 0.5709(8) 0.4805(8) 0.8033(3) 0.0322(4) Uani 0.609(3) 1 d P . 1 O8 O 0.6383(9) 0.7802(8) 0.8723(4) 0.0322(4) Uani 0.609(3) 1 d P . 1 N1A N 0.6276(8) 0.4376(7) 0.8558(3) 0.0322(4) Uani 0.391(3) 1 d PG . 2 N2A N 0.5643(10) 0.6109(9) 0.8004(3) 0.0322(4) Uani 0.391(3) 1 d PG . 2 N3A N 0.6072(11) 0.7941(7) 0.8520(4) 0.0322(4) Uani 0.391(3) 1 d PG . 2 N4A N 0.6970(10) 0.7341(6) 0.9394(3) 0.0322(4) Uani 0.391(3) 1 d PG . 2 C5A C 0.7096(6) 0.5138(6) 0.9417(3) 0.0322(4) Uani 0.391(3) 1 d PG . 2 C6A C 0.7512(7) 0.3748(6) 1.0002(3) 0.0322(4) Uani 0.391(3) 1 d PG . 2 O7A O 0.7412(10) 0.1731(6) 0.9775(4) 0.0322(4) Uani 0.391(3) 1 d PG . 2 O8A O 0.8018(11) 0.4435(8) 1.0741(3) 0.0322(4) Uani 0.391(3) 1 d PG . 2 O1W O 0.8792(5) 0.1095(6) 0.7676(2) 0.0462(9) Uani 1 1 d . . . H1A H 0.8656 0.1229 0.7097 0.055 Uiso 1 1 d R . . H1B H 1.0026 0.1120 0.7930 0.055 Uiso 1 1 d R . . O2W O 0.2782(5) 0.1218(6) 0.8745(2) 0.0429(9) Uani 1 1 d . . . H2A H 0.2517 0.2311 0.8976 0.051 Uiso 1 1 d R . . H2B H 0.2432 0.0379 0.9042 0.051 Uiso 1 1 d R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Mn1 0.0316(4) 0.0270(4) 0.0451(4) -0.0092(3) 0.0117(3) -0.0034(3) N1 0.0337(9) 0.0264(9) 0.0374(10) 0.0005(8) 0.0083(8) -0.0008(8) N2 0.0337(9) 0.0264(9) 0.0374(10) 0.0005(8) 0.0083(8) -0.0008(8) N3 0.0337(9) 0.0264(9) 0.0374(10) 0.0005(8) 0.0083(8) -0.0008(8) N4 0.0337(9) 0.0264(9) 0.0374(10) 0.0005(8) 0.0083(8) -0.0008(8) C5 0.0337(9) 0.0264(9) 0.0374(10) 0.0005(8) 0.0083(8) -0.0008(8) C6 0.0337(9) 0.0264(9) 0.0374(10) 0.0005(8) 0.0083(8) -0.0008(8) O7 0.0337(9) 0.0264(9) 0.0374(10) 0.0005(8) 0.0083(8) -0.0008(8) O8 0.0337(9) 0.0264(9) 0.0374(10) 0.0005(8) 0.0083(8) -0.0008(8) N1A 0.0337(9) 0.0264(9) 0.0374(10) 0.0005(8) 0.0083(8) -0.0008(8) N2A 0.0337(9) 0.0264(9) 0.0374(10) 0.0005(8) 0.0083(8) -0.0008(8) N3A 0.0337(9) 0.0264(9) 0.0374(10) 0.0005(8) 0.0083(8) -0.0008(8) N4A 0.0337(9) 0.0264(9) 0.0374(10) 0.0005(8) 0.0083(8) -0.0008(8) C5A 0.0337(9) 0.0264(9) 0.0374(10) 0.0005(8) 0.0083(8) -0.0008(8) C6A 0.0337(9) 0.0264(9) 0.0374(10) 0.0005(8) 0.0083(8) -0.0008(8) O7A 0.0337(9) 0.0264(9) 0.0374(10) 0.0005(8) 0.0083(8) -0.0008(8) O8A 0.0337(9) 0.0264(9) 0.0374(10) 0.0005(8) 0.0083(8) -0.0008(8) O1W 0.0299(17) 0.074(3) 0.0355(18) -0.0081(18) 0.0071(14) -0.0047(18) O2W 0.0338(17) 0.053(2) 0.0439(19) -0.0160(17) 0.0119(14) -0.0072(16) _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 Mn1 N3A 2.058(6) 1_545 ? Mn1 N2A 2.081(7) 2_646 ? Mn1 O1W 2.147(4) . ? Mn1 N1 2.119(6) . ? Mn1 N1A 2.154(5) . ? Mn1 O2W 2.209(4) . ? Mn1 O8 2.222(6) 1_545 ? Mn1 O7 2.290(5) 2_646 ? Mn1 O7A 2.344(6) . ? Mn1 O7 2.421(6) . ? N1 N2 1.317(9) . ? N1 C5 1.356(10) . ? N2 N3 1.342(9) . ? N3 N4 1.380(9) . ? N4 C5 1.395(10) . ? C5 C6 1.414(11) . ? C6 O8 1.207(9) . ? C6 O7 1.231(9) . ? O7 Mn1 2.290(5) 2_656 ? O8 Mn1 2.222(6) 1_565 ? N1A N2A 1.4200 . ? N1A C5A 1.4200 . ? N2A N3A 1.4200 . ? N2A Mn1 2.081(4) 2_656 ? N3A N4A 1.4200 . ? N3A Mn1 2.058(5) 1_565 ? N4A C5A 1.4200 . ? C5A C6A 1.2598 . ? C6A O8A 1.2054 . ? C6A O7A 1.3419 . ? O1W H1A 0.8717 . ? O1W H1B 0.8253 . ? O2W H2A 0.8130 . ? O2W H2B 0.7546 . ? 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 N3A Mn1 N2A 99.45(16) 1_545 2_646 ? N3A Mn1 O1W 93.2(5) 1_545 . ? N2A Mn1 O1W 85.3(5) 2_646 . ? N3A Mn1 N1 108.8(3) 1_545 . ? N2A Mn1 N1 151.6(3) 2_646 . ? O1W Mn1 N1 95.1(2) . . ? N3A Mn1 N1A 159.3(3) 1_545 . ? N2A Mn1 N1A 101.2(3) 2_646 . ? O1W Mn1 N1A 90.79(18) . . ? N1 Mn1 N1A 50.5(2) . . ? N3A Mn1 O2W 90.1(5) 1_545 . ? N2A Mn1 O2W 87.0(5) 2_646 . ? O1W Mn1 O2W 172.00(13) . . ? N1 Mn1 O2W 90.74(19) . . ? N1A Mn1 O2W 88.73(18) . . ? N3A Mn1 O8 8.4(3) 1_545 1_545 ? N2A Mn1 O8 107.8(3) 2_646 1_545 ? O1W Mn1 O8 92.71(19) . 1_545 ? N1 Mn1 O8 100.6(2) . 1_545 ? N1A Mn1 O8 151.05(18) . 1_545 ? O2W Mn1 O8 91.57(18) . 1_545 ? N3A Mn1 O7 78.0(3) 1_545 2_646 ? N2A Mn1 O7 21.5(3) 2_646 2_646 ? O1W Mn1 O7 86.04(16) . 2_646 ? N1 Mn1 O7 173.0(2) . 2_646 ? N1A Mn1 O7 122.66(18) . 2_646 ? O2W Mn1 O7 87.50(16) . 2_646 ? O8 Mn1 O7 86.26(19) 1_545 2_646 ? N3A Mn1 O7A 90.7(3) 1_545 . ? N2A Mn1 O7A 168.5(3) 2_646 . ? O1W Mn1 O7A 99.64(19) . . ? N1 Mn1 O7A 18.44(18) . . ? N1A Mn1 O7A 68.59(12) . . ? O2W Mn1 O7A 87.61(19) . . ? O8 Mn1 O7A 82.50(18) 1_545 . ? O7 Mn1 O7A 167.61(18) 2_646 . ? N3A Mn1 O7 178.7(5) 1_545 . ? N2A Mn1 O7 80.3(3) 2_646 . ? O1W Mn1 O7 88.03(17) . . ? N1 Mn1 O7 71.4(2) . . ? N1A Mn1 O7 20.93(16) . . ? O2W Mn1 O7 88.68(16) . . ? O8 Mn1 O7 171.98(19) 1_545 . ? O7 Mn1 O7 101.75(13) 2_646 . ? O7A Mn1 O7 89.51(16) . . ? N2 N1 C5 109.5(6) . . ? N2 N1 Mn1 134.7(5) . . ? C5 N1 Mn1 114.3(5) . . ? N1 N2 N3 110.4(6) . . ? N2 N3 N4 106.5(6) . . ? N3 N4 C5 107.5(6) . . ? N1 C5 C6 126.0(7) . . ? N1 C5 N4 105.9(7) . . ? C6 C5 N4 128.1(7) . . ? O8 C6 O7 129.7(8) . . ? O8 C6 C5 119.0(7) . . ? O7 C6 C5 111.3(7) . . ? C6 O7 Mn1 122.5(5) . 2_656 ? C6 O7 Mn1 116.5(5) . . ? Mn1 O7 Mn1 120.7(2) 2_656 . ? C6 O8 Mn1 158.7(6) . 1_565 ? N2A N1A C5A 108.0 . . ? N2A N1A Mn1 130.33(19) . . ? C5A N1A Mn1 121.51(18) . . ? N3A N2A N1A 108.0 . . ? N3A N2A Mn1 123.7(3) . 2_656 ? N1A N2A Mn1 128.0(3) . 2_656 ? N2A N3A N4A 108.0 . . ? N2A N3A Mn1 136.6(3) . 1_565 ? N4A N3A Mn1 115.1(3) . 1_565 ? C5A N4A N3A 108.0 . . ? C6A C5A N4A 137.0 . . ? C6A C5A N1A 114.4 . . ? N4A C5A N1A 108.0 . . ? O8A C6A C5A 113.3 . . ? O8A C6A O7A 126.1 . . ? C5A C6A O7A 120.6 . . ? C6A O7A Mn1 114.32(15) . . ? Mn1 O1W H1A 117.6 . . ? Mn1 O1W H1B 126.9 . . ? H1A O1W H1B 115.1 . . ? Mn1 O2W H2A 114.4 . . ? Mn1 O2W H2B 120.8 . . ? H2A O2W H2B 105.6 . . ? _diffrn_measured_fraction_theta_max 0.904 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 1.062 _refine_diff_density_min -1.008 _refine_diff_density_rms 0.110 data_compound2 _database_code_depnum_ccdc_archive 'CCDC 717036' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C4 H12 Mn2 N8 O10, 4(H2 O)' _chemical_formula_sum 'C4 H20 Mn2 N8 O14' _chemical_formula_weight 514.16 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' Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'C2/c ' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 7.3589(9) _cell_length_b 13.0212(16) _cell_length_c 19.866(3) _cell_angle_alpha 90.00 _cell_angle_beta 100.0030(10) _cell_angle_gamma 90.00 _cell_volume 1874.6(4) _cell_formula_units_Z 4 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 4533 _cell_measurement_theta_min 3.122 _cell_measurement_theta_max 27.895 _exptl_crystal_description prismatic _exptl_crystal_colour colourless _exptl_crystal_size_max 0.22 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_min 0.16 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.822 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1048 _exptl_absorpt_coefficient_mu 1.432 _exptl_absorpt_correction_type MULTI-SCAN _exptl_absorpt_correction_T_min 0.7435 _exptl_absorpt_correction_T_max 0.8033 _exptl_absorpt_process_details 'SADABS in APEX2, 2008' _exptl_special_details ; ? ; _diffrn_ambient_temperature 298(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_reflns_number 10648 _diffrn_reflns_av_R_equivalents 0.0291 _diffrn_reflns_av_sigmaI/netI 0.0242 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -25 _diffrn_reflns_limit_l_max 25 _diffrn_reflns_theta_min 2.08 _diffrn_reflns_theta_max 28.28 _reflns_number_total 2194 _reflns_number_gt 1995 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker APEX2' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _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^)+(0.0335P)^2^+1.0837P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2194 _refine_ls_number_parameters 128 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0297 _refine_ls_R_factor_gt 0.0265 _refine_ls_wR_factor_ref 0.0675 _refine_ls_wR_factor_gt 0.0658 _refine_ls_goodness_of_fit_ref 1.041 _refine_ls_restrained_S_all 1.041 _refine_ls_shift/su_max 0.002 _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 Mn1 Mn 0.28601(3) 0.180934(17) 0.604605(11) 0.02488(9) Uani 1 1 d . . . N1 N 0.05635(18) 0.31616(9) 0.48472(6) 0.0257(3) Uani 1 1 d . . . N2 N 0.06133(18) 0.28032(10) 0.54792(6) 0.0266(3) Uani 1 1 d . . . N3 N -0.07978(19) 0.31705(10) 0.57284(7) 0.0298(3) Uani 1 1 d . . . N4 N -0.17935(17) 0.37784(10) 0.52606(6) 0.0283(3) Uani 1 1 d . . . C5 C -0.09287(19) 0.37531(11) 0.47286(7) 0.0230(3) Uani 1 1 d . . . C6 C -0.1443(2) 0.42929(11) 0.40578(8) 0.0253(3) Uani 1 1 d . . . O7 O -0.03645(15) 0.41312(9) 0.36442(6) 0.0330(3) Uani 1 1 d . . . O8 O -0.28481(15) 0.48371(10) 0.39610(6) 0.0355(3) Uani 1 1 d . . . O1W O 0.1914(2) 0.16835(9) 0.69941(7) 0.0475(4) Uani 1 1 d . . . H1A H 0.1474 0.1199 0.7104 0.057 Uiso 1 1 d R . . H1B H 0.2072 0.2094 0.7270 0.057 Uiso 1 1 d R . . O2W O 0.41125(18) 0.32224(9) 0.64913(8) 0.0438(3) Uani 1 1 d . . . H2A H 0.5206 0.3222 0.6570 0.053 Uiso 1 1 d R . . H2B H 0.3796 0.3758 0.6288 0.053 Uiso 1 1 d R . . O3W O 0.13073(17) 0.04519(9) 0.57123(7) 0.0438(3) Uani 1 1 d . . . H3A H 0.0226 0.0414 0.5766 0.053 Uiso 1 1 d R . . H3B H 0.1687 -0.0057 0.5572 0.053 Uiso 1 1 d R . . O4W O 0.77545(17) 0.31532(9) 0.69735(6) 0.0349(3) Uani 1 1 d . . . H4A H 0.8328 0.3683 0.7166 0.042 Uiso 1 1 d R . . H4B H 0.8239 0.3013 0.6697 0.042 Uiso 1 1 d R . . O5W O 1.0000 0.01440(15) 0.7500 0.0591(6) Uani 1 2 d S . . H5A H 0.9366 -0.0140 0.7167 0.071 Uiso 1 1 d R . . O6W O 1.0000 0.52660(12) 0.2500 0.0378(4) Uani 1 2 d S . . H6 H 0.9907 0.4883 0.2859 0.045 Uiso 1 1 d R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Mn1 0.02193(14) 0.02898(15) 0.02505(14) 0.00458(8) 0.00775(10) 0.00589(9) N1 0.0226(6) 0.0309(7) 0.0247(7) 0.0048(5) 0.0068(5) 0.0068(5) N2 0.0246(6) 0.0328(7) 0.0234(6) 0.0040(5) 0.0074(5) 0.0070(5) N3 0.0290(7) 0.0363(7) 0.0254(7) 0.0030(5) 0.0089(5) 0.0084(6) N4 0.0261(7) 0.0331(7) 0.0270(7) 0.0023(5) 0.0077(5) 0.0097(5) C5 0.0200(7) 0.0235(7) 0.0262(7) 0.0001(5) 0.0057(6) 0.0025(5) C6 0.0214(7) 0.0246(7) 0.0296(8) 0.0028(6) 0.0034(6) 0.0010(6) O7 0.0286(6) 0.0425(6) 0.0297(6) 0.0114(5) 0.0101(5) 0.0111(5) O8 0.0265(6) 0.0382(7) 0.0423(7) 0.0121(5) 0.0075(5) 0.0128(5) O1W 0.0753(10) 0.0390(7) 0.0354(7) -0.0064(5) 0.0300(7) -0.0146(6) O2W 0.0316(7) 0.0326(7) 0.0622(9) 0.0100(6) -0.0053(6) 0.0002(5) O3W 0.0281(6) 0.0364(6) 0.0705(9) -0.0180(6) 0.0189(6) -0.0007(5) O4W 0.0328(6) 0.0432(7) 0.0302(6) -0.0015(5) 0.0093(5) -0.0031(5) O5W 0.0731(15) 0.0446(11) 0.0675(14) 0.000 0.0340(12) 0.000 O6W 0.0562(11) 0.0306(8) 0.0269(8) 0.000 0.0076(8) 0.000 _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Mn1 O1W 2.1246(13) . ? Mn1 O3W 2.1463(13) . ? Mn1 O2W 2.1757(13) . ? Mn1 O7 2.2093(11) 7_556 ? Mn1 N2 2.2428(13) . ? Mn1 N1 2.2829(13) 7_556 ? N1 C5 1.3284(18) . ? N1 N2 1.3338(17) . ? N1 Mn1 2.2829(13) 7_556 ? N2 N3 1.3156(18) . ? N3 N4 1.3381(18) . ? N4 C5 1.3253(19) . ? C5 C6 1.496(2) . ? C6 O8 1.2409(18) . ? C6 O7 1.2551(18) . ? O7 Mn1 2.2093(11) 7_556 ? O1W H1A 0.7589 . ? O1W H1B 0.7601 . ? O2W H2A 0.7926 . ? O2W H2B 0.8194 . ? O3W H3A 0.8222 . ? O3W H3B 0.7886 . ? O4W H4A 0.8629 . ? O4W H4B 0.7274 . ? O5W H5A 0.8283 . ? O6W H6 0.8829 . ? 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 O1W Mn1 O3W 88.37(5) . . ? O1W Mn1 O2W 83.44(5) . . ? O3W Mn1 O2W 170.83(5) . . ? O1W Mn1 O7 95.52(5) . 7_556 ? O3W Mn1 O7 90.18(5) . 7_556 ? O2W Mn1 O7 94.68(5) . 7_556 ? O1W Mn1 N2 99.39(5) . . ? O3W Mn1 N2 90.78(5) . . ? O2W Mn1 N2 86.53(5) . . ? O7 Mn1 N2 165.07(4) 7_556 . ? O1W Mn1 N1 168.33(6) . 7_556 ? O3W Mn1 N1 95.09(5) . 7_556 ? O2W Mn1 N1 93.75(5) . 7_556 ? O7 Mn1 N1 73.36(4) 7_556 7_556 ? N2 Mn1 N1 91.72(4) . 7_556 ? C5 N1 N2 104.86(12) . . ? C5 N1 Mn1 111.62(9) . 7_556 ? N2 N1 Mn1 143.40(10) . 7_556 ? N3 N2 N1 109.42(12) . . ? N3 N2 Mn1 125.59(10) . . ? N1 N2 Mn1 124.88(9) . . ? N2 N3 N4 109.05(12) . . ? C5 N4 N3 104.96(12) . . ? N4 C5 N1 111.69(13) . . ? N4 C5 C6 128.06(13) . . ? N1 C5 C6 120.24(13) . . ? O8 C6 O7 126.80(14) . . ? O8 C6 C5 118.77(13) . . ? O7 C6 C5 114.43(12) . . ? C6 O7 Mn1 120.15(9) . 7_556 ? Mn1 O1W H1A 122.8 . . ? Mn1 O1W H1B 123.5 . . ? H1A O1W H1B 113.4 . . ? Mn1 O2W H2A 115.1 . . ? Mn1 O2W H2B 117.1 . . ? H2A O2W H2B 106.8 . . ? Mn1 O3W H3A 119.0 . . ? Mn1 O3W H3B 126.8 . . ? H3A O3W H3B 113.9 . . ? H4A O4W H4B 105.6 . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O1W H1A O5W 0.76 1.99 2.739(2) 167.2 1_455 O1W H1B O4W 0.76 2.03 2.7847(17) 174.3 2_656 O2W H2A O4W 0.79 1.91 2.6865(18) 166.4 . O2W H2B O8 0.82 1.99 2.7870(17) 164.3 5_566 O3W H3A O8 0.82 1.95 2.7598(16) 169.2 7_456 O3W H3B N4 0.79 2.04 2.8182(17) 167.7 3_545 O4W H4A O6W 0.86 1.88 2.7315(17) 167.7 5_766 O4W H4B N3 0.73 2.17 2.8581(18) 157.2 1_655 O5W H5A O8 0.83 2.36 3.0554(12) 142.5 7_556 O5W H5A O2W 0.83 2.51 3.201(2) 141.9 3_545 O6W H6 O7 0.88 1.88 2.7630(14) 176.6 1_655 _diffrn_measured_fraction_theta_max 0.946 _diffrn_reflns_theta_full 28.28 _diffrn_measured_fraction_theta_full 0.946 _refine_diff_density_max 0.387 _refine_diff_density_min -0.229 _refine_diff_density_rms 0.056 data_compound3 _database_code_depnum_ccdc_archive 'CCDC 717037' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C4 H12 Cu2 N8 O10, 2(H2 O)' _chemical_formula_sum 'C4 H16 Cu2 N8 O12' _chemical_formula_weight 495.33 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cu Cu -1.9646 0.5888 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'C2/c ' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 15.5436(3) _cell_length_b 6.47630(10) _cell_length_c 17.8074(4) _cell_angle_alpha 90.00 _cell_angle_beta 114.3420(10) _cell_angle_gamma 90.00 _cell_volume 1633.22(5) _cell_formula_units_Z 4 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 4780 _cell_measurement_theta_min 6.38 _cell_measurement_theta_max 66.01 _exptl_crystal_description prsimatic _exptl_crystal_colour blue _exptl_crystal_size_max 0.14 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.06 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.014 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1000 _exptl_absorpt_coefficient_mu 4.002 _exptl_absorpt_correction_type MULTI-SCAN _exptl_absorpt_correction_T_min 0.6042 _exptl_absorpt_correction_T_max 0.7952 _exptl_absorpt_process_details ; 'SADABS in APEX2, 2008' ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 298(2) _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus rotating anode' _diffrn_radiation_monochromator 'Montel multilayer optics' _diffrn_measurement_device_type 'Bruker X8 Proteum' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean ? _diffrn_reflns_number 1390 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.0187 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 7 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 6.38 _diffrn_reflns_theta_max 66.47 _reflns_number_total 1390 _reflns_number_gt 1368 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker APEX2' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _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^)+(0.0595P)^2^+4.3306P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1390 _refine_ls_number_parameters 118 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0322 _refine_ls_R_factor_gt 0.0318 _refine_ls_wR_factor_ref 0.0911 _refine_ls_wR_factor_gt 0.0909 _refine_ls_goodness_of_fit_ref 0.998 _refine_ls_restrained_S_all 0.998 _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 Cu1 Cu 0.49805(2) 0.09095(6) 0.390417(19) 0.02454(19) Uani 1 1 d . . . N1 N 0.59524(14) -0.0101(3) 0.49674(12) 0.0237(4) Uani 1 1 d . . . N2 N 0.39285(15) 0.0654(3) 0.42702(13) 0.0244(5) Uani 1 1 d . . . N3 N 0.30201(15) 0.0968(3) 0.38197(13) 0.0286(5) Uani 1 1 d . . . N4 N 0.74665(15) -0.0622(3) 0.57225(13) 0.0288(5) Uani 1 1 d . . . C5 C 0.68126(16) -0.0098(4) 0.49829(14) 0.0224(5) Uani 1 1 d . . . C6 C 0.69137(18) 0.0572(4) 0.42217(15) 0.0243(5) Uani 1 1 d . . . O7 O 0.61241(13) 0.1061(3) 0.36397(11) 0.0291(4) Uani 1 1 d . . . O8 O 0.76953(13) 0.0650(3) 0.42048(11) 0.0318(4) Uani 1 1 d . . . O9 O 0.47832(14) -0.2286(3) 0.32233(12) 0.0367(4) Uani 1 1 d . . . H9A H 0.4248 -0.2748 0.3048 0.044 Uiso 1 1 d R . . H9B H 0.5201 -0.3024 0.3566 0.044 Uiso 1 1 d R . . O10 O 0.54488(14) 0.4536(3) 0.44883(12) 0.0374(5) Uani 1 1 d . . . H10A H 0.5423 0.5288 0.4088 0.045 Uiso 1 1 d R . . H10B H 0.6013 0.4645 0.4748 0.045 Uiso 1 1 d R . . O11 O 0.41594(14) 0.2243(3) 0.28832(10) 0.0370(5) Uani 1 1 d . . . H11A H 0.3849 0.3292 0.2867 0.044 Uiso 1 1 d R . . H11B H 0.4046 0.1678 0.2450 0.044 Uiso 1 1 d R . . O12 O 0.31407(13) 0.5625(3) 0.28729(11) 0.0328(4) Uani 1 1 d . . . H12A H 0.2956 0.5688 0.3284 0.039 Uiso 1 1 d R . . H12B H 0.2666 0.5902 0.2378 0.039 Uiso 1 1 d R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cu1 0.0202(3) 0.0385(3) 0.0165(3) 0.00534(13) 0.00917(18) 0.00291(13) N1 0.0238(10) 0.0314(11) 0.0176(9) 0.0026(8) 0.0102(8) 0.0005(8) N2 0.0227(11) 0.0340(11) 0.0171(10) 0.0029(8) 0.0089(8) 0.0019(8) N3 0.0221(11) 0.0433(13) 0.0201(11) 0.0044(8) 0.0084(9) 0.0028(8) N4 0.0227(11) 0.0391(12) 0.0245(11) 0.0033(9) 0.0095(9) 0.0017(9) C5 0.0216(11) 0.0261(12) 0.0217(11) -0.0001(9) 0.0111(9) -0.0007(9) C6 0.0271(13) 0.0262(11) 0.0217(12) -0.0027(9) 0.0121(10) -0.0034(10) O7 0.0248(9) 0.0429(11) 0.0214(9) 0.0056(7) 0.0113(8) -0.0007(7) O8 0.0253(10) 0.0455(11) 0.0311(10) 0.0022(8) 0.0180(8) -0.0011(8) O9 0.0337(10) 0.0376(10) 0.0376(10) -0.0034(8) 0.0136(8) -0.0041(8) O10 0.0305(10) 0.0450(11) 0.0340(11) 0.0008(9) 0.0107(8) 0.0014(9) O11 0.0464(11) 0.0475(11) 0.0174(8) 0.0035(8) 0.0136(8) 0.0192(9) O12 0.0269(9) 0.0483(11) 0.0230(9) 0.0018(8) 0.0100(8) 0.0046(8) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Cu1 O11 1.9410(17) . ? Cu1 N1 1.984(2) . ? Cu1 N2 2.001(2) . ? Cu1 O7 2.0203(18) . ? Cu1 O9 2.3539(19) . ? Cu1 O10 2.550(2) . ? N1 C5 1.326(3) . ? N1 N2 1.341(3) 5_656 ? N2 N3 1.321(3) . ? N3 N4 1.340(3) 5_656 ? N4 C5 1.334(3) . ? C5 C6 1.492(3) . ? C6 O8 1.229(3) . ? C6 O7 1.277(3) . ? O9 H9A 0.8156 . ? O9 H9B 0.8346 . ? O10 H10A 0.8509 . ? O10 H10B 0.8082 . ? O11 H11A 0.8267 . ? O11 H11B 0.8049 . ? O12 H12A 0.8906 . ? O12 H12B 0.9045 . ? 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 O11 Cu1 N1 171.33(9) . . ? O11 Cu1 N2 91.82(8) . . ? N1 Cu1 N2 93.72(8) . . ? O11 Cu1 O7 93.57(8) . . ? N1 Cu1 O7 80.88(8) . . ? N2 Cu1 O7 174.59(7) . . ? O11 Cu1 O9 90.75(8) . . ? N1 Cu1 O9 95.04(8) . . ? N2 Cu1 O9 98.31(8) . . ? O7 Cu1 O9 82.12(7) . . ? O11 Cu1 O10 86.51(8) . . ? N1 Cu1 O10 86.42(8) . . ? N2 Cu1 O10 94.45(8) . . ? O7 Cu1 O10 85.41(7) . . ? O9 Cu1 O10 167.03(7) . . ? C5 N1 N2 105.20(19) . 5_656 ? C5 N1 Cu1 112.58(15) . . ? N2 N1 Cu1 141.92(16) 5_656 . ? N3 N2 N1 108.8(2) . 5_656 ? N3 N2 Cu1 127.01(17) . . ? N1 N2 Cu1 124.16(16) 5_656 . ? N2 N3 N4 109.6(2) . 5_656 ? C5 N4 N3 104.6(2) . 5_656 ? N1 C5 N4 111.8(2) . . ? N1 C5 C6 117.7(2) . . ? N4 C5 C6 130.4(2) . . ? O8 C6 O7 126.8(2) . . ? O8 C6 C5 120.6(2) . . ? O7 C6 C5 112.6(2) . . ? C6 O7 Cu1 116.24(15) . . ? Cu1 O9 H9A 114.5 . . ? Cu1 O9 H9B 103.3 . . ? H9A O9 H9B 115.6 . . ? Cu1 O10 H10A 106.2 . . ? Cu1 O10 H10B 112.0 . . ? H10A O10 H10B 95.4 . . ? Cu1 O11 H11A 123.2 . . ? Cu1 O11 H11B 119.7 . . ? H11A O11 H11B 116.4 . . ? H12A O12 H12B 112.4 . . ? _diffrn_measured_fraction_theta_max 0.966 _diffrn_reflns_theta_full 66.47 _diffrn_measured_fraction_theta_full 0.966 _refine_diff_density_max 0.369 _refine_diff_density_min -0.313 _refine_diff_density_rms 0.071