Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2003 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 loop_ _publ_author_name 'Christoph Janiak' 'Khalid Abu-Shandi' 'Heiner Winkler' 'Biao Wu' _publ_contact_author_name 'Prof Christoph Janiak' _publ_contact_author_address ; Institut fur Anorganische und Analyt. Chemie Universitaet Freiburg Albertstr. 21 Freiburg 79104 GERMANY ; _publ_contact_author_email UNI-FREIBURG.DE _publ_section_title ; Mixed phosphato-hydrogenphosphato-iron network compounds 1 8 {[C4N2H11.2]1.5[FeIII2(PO4)(H0.6PO4)2]·H2O} and mixed-valence 3 8 [FeII5FeIII2(PO4)2(H0.5PO4)4]: Structure elucidation with the help of Mossbauer spectroscopy and a caveat on X-ray diffraction ; data_k4 #No 1 in manuscript _database_code_CSD 203657 _audit_creation_method SHELXL-97 _chemical_name_systematic ; piperazinedium-[bis(mu-hydrogenphosphato) (mu4-phosphato)diferrate(II,III)]-hydrate ; _chemical_name_common ; piperazinedium-(bis(mu-hydrogenphosphato) (mu4- phosphato)diferrate(II,III))-hydrate ; _chemical_melting_point ? _chemical_formula_moiety '2Fe, 1.5(C4N2H11.6), H2O, 2(H0.8PO4), PO4' _chemical_formula_sum 'C6 H21 Fe2 N3 O13 P3' _chemical_formula_weight 547.87 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P2(1)/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 8.3704(15) _cell_length_b 8.5616(15) _cell_length_c 23.865(4) _cell_angle_alpha 90.00 _cell_angle_beta 93.950(3) _cell_angle_gamma 90.00 _cell_volume 1706.2(5) _cell_formula_units_Z 4 _cell_measurement_temperature 213(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description plates _exptl_crystal_colour 'deep blue' _exptl_crystal_size_max 0.29 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.133 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1116 _exptl_absorpt_coefficient_mu 2.057 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.5869 _exptl_absorpt_correction_T_max 0.7904 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 213(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 'Bruker AXS CCD' _diffrn_measurement_method '\w scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 14884 _diffrn_reflns_av_R_equivalents 0.0186 _diffrn_reflns_av_sigmaI/netI 0.0206 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -30 _diffrn_reflns_limit_l_max 31 _diffrn_reflns_theta_min 2.44 _diffrn_reflns_theta_max 28.89 _reflns_number_total 4137 _reflns_number_gt 3487 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker 1997)' _computing_cell_refinement SMART _computing_data_reduction 'SAINT (Bruker 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. The hydrogen atoms of the water molecule, the hydrogenphosphato ligands and on nitrogen of the piperazinedium cation were found and refined with Ueq(H) = 1.2 Ueq(O,N). Hydrogen atoms on carbon of piperazinedium were calculated with appropriate riding models (AFIX 23) and Ueq(H) = 1.2 Ueq(C). The H atom positions on HPO4 and for the additional protons on piperazine (C4N2H10) are not fully occupied. Most likely is an occupation of 0.8 based on Moessbauer spectroscopy which suggested a mixed-valence oxidation state of +2 and +3 for the 2Fe. ; _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^)+(0.0405P)^2^+0.2957P] 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 4137 _refine_ls_number_parameters 274 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0295 _refine_ls_R_factor_gt 0.0240 _refine_ls_wR_factor_ref 0.0659 _refine_ls_wR_factor_gt 0.0637 _refine_ls_goodness_of_fit_ref 1.036 _refine_ls_restrained_S_all 1.036 _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 Fe1 Fe -0.39794(3) 0.78250(3) -0.185517(10) 0.01087(7) Uani 1 1 d . . . Fe2 Fe -0.43395(3) 0.27418(3) -0.178077(10) 0.01127(7) Uani 1 1 d . . . P1 P -0.50484(6) 0.55392(5) -0.088288(19) 0.01421(10) Uani 1 1 d . . . P2 P -0.32838(5) 0.50048(5) -0.272009(19) 0.01258(10) Uani 1 1 d . . . P3 P -0.16051(6) 0.04562(5) -0.13095(2) 0.01440(10) Uani 1 1 d . . . O1 O -0.53589(17) 0.41235(16) -0.12633(6) 0.0221(3) Uani 1 1 d . . . O2 O -0.50067(19) 0.70468(16) -0.12152(6) 0.0244(3) Uani 1 1 d . . . O3 O -0.33715(17) 0.5342(2) -0.05523(6) 0.0274(4) Uani 1 1 d . . . H31 H -0.346(4) 0.514(4) -0.0252(15) 0.033 Uiso 0.80 1 d P . . O4 O -0.63601(16) 0.56313(16) -0.04723(5) 0.0185(3) Uani 1 1 d . . . O5 O -0.29215(16) 0.59893(16) -0.21861(6) 0.0187(3) Uani 1 1 d . . . O6 O -0.17174(16) 0.43569(16) -0.29148(6) 0.0193(3) Uani 1 1 d . . . O7 O -0.43953(16) 0.36078(15) -0.25599(5) 0.0166(3) Uani 1 1 d . . . O8 O -0.41932(17) 0.59356(16) -0.31851(6) 0.0204(3) Uani 1 1 d . . . O9 O -0.22164(17) 0.20209(16) -0.15459(7) 0.0258(3) Uani 1 1 d . . . O10 O -0.20044(18) 0.01919(18) -0.07093(6) 0.0257(3) Uani 1 1 d . . . O11 O 0.02963(16) 0.05682(16) -0.12892(6) 0.0181(3) Uani 1 1 d . . . H11 H 0.073(4) 0.017(3) -0.1581(14) 0.022 Uiso 0.80 1 d P . . O12 O -0.20881(16) -0.08940(16) -0.17028(6) 0.0191(3) Uani 1 1 d . . . O13 O 0.0313(3) 0.2067(2) -0.00477(9) 0.0499(5) Uani 1 1 d . . . H13A H -0.055(4) 0.130(4) -0.0236(13) 0.060 Uiso 1 1 d . . . H13B H 0.103(4) 0.134(4) 0.0216(13) 0.060 Uiso 1 1 d . . . N1 N -0.3991(2) 0.1358(2) 0.00094(7) 0.0205(3) Uani 1 1 d . . . H11A H -0.372(3) 0.235(3) 0.0158(11) 0.025 Uiso 0.90 1 d P . . H12B H -0.330(3) 0.112(3) -0.0272(11) 0.025 Uiso 0.90 1 d P . . C1 C -0.3768(3) 0.0142(2) 0.04540(8) 0.0232(4) Uani 1 1 d . . . H1A H -0.4394 0.0417 0.0772 0.028 Uiso 1 1 calc R . . H1B H -0.2637 0.0090 0.0589 0.028 Uiso 1 1 calc R . . C2 C -0.5694(2) 0.1428(2) -0.02213(9) 0.0230(4) Uani 1 1 d . . . H2A H -0.5803 0.2215 -0.0520 0.028 Uiso 1 1 calc R . . H2B H -0.6378 0.1739 0.0077 0.028 Uiso 1 1 calc R . . N2 N -0.0290(2) 0.1583(2) -0.31828(7) 0.0193(3) Uani 1 1 d . . . H21A H -0.062(3) 0.256(3) -0.3059(11) 0.023 Uiso 0.90 1 d P . . H22B H 0.074(3) 0.131(3) -0.3019(11) 0.023 Uiso 0.90 1 d P . . N3 N -0.1194(2) -0.1238(2) -0.37737(9) 0.0283(4) Uani 1 1 d . . . H31A H -0.223(4) -0.099(3) -0.3901(12) 0.034 Uiso 0.90 1 d P . . H31B H -0.093(4) -0.223(4) -0.3857(12) 0.034 Uiso 0.90 1 d P . . C3 C -0.1446(2) 0.0477(2) -0.29552(9) 0.0239(4) Uani 1 1 d . . . H3A H -0.2540 0.0774 -0.3086 0.029 Uiso 1 1 calc R . . H3B H -0.1360 0.0523 -0.2544 0.029 Uiso 1 1 calc R . . C4 C -0.1107(3) -0.1162(3) -0.31455(10) 0.0292(5) Uani 1 1 d . . . H4A H -0.0038 -0.1482 -0.2995 0.035 Uiso 1 1 calc R . . H4B H -0.1891 -0.1882 -0.3002 0.035 Uiso 1 1 calc R . . C5 C -0.0339(3) 0.1512(2) -0.38094(8) 0.0241(4) Uani 1 1 d . . . H5A H 0.0477 0.2213 -0.3944 0.029 Uiso 1 1 calc R . . H5B H -0.1388 0.1870 -0.3967 0.029 Uiso 1 1 calc R . . C6 C -0.0044(3) -0.0125(2) -0.40083(9) 0.0258(4) Uani 1 1 d . . . H6A H -0.0163 -0.0157 -0.4420 0.031 Uiso 1 1 calc R . . H6B H 0.1054 -0.0438 -0.3890 0.031 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 Fe1 0.01108(13) 0.01097(13) 0.01046(13) -0.00029(9) 0.00012(9) -0.00083(9) Fe2 0.01191(13) 0.01089(13) 0.01090(13) -0.00078(9) 0.00003(9) -0.00003(9) P1 0.0162(2) 0.0144(2) 0.0121(2) 0.00001(16) 0.00160(17) -0.00078(17) P2 0.0123(2) 0.0114(2) 0.0142(2) -0.00006(16) 0.00158(17) 0.00014(16) P3 0.0129(2) 0.0140(2) 0.0163(2) -0.00111(17) 0.00076(17) -0.00034(16) O1 0.0251(7) 0.0184(7) 0.0233(7) -0.0066(6) 0.0049(6) -0.0018(6) O2 0.0363(8) 0.0174(7) 0.0209(7) 0.0038(5) 0.0111(6) 0.0016(6) O3 0.0162(7) 0.0495(10) 0.0166(7) 0.0035(7) 0.0012(6) 0.0002(6) O4 0.0185(7) 0.0212(7) 0.0162(7) 0.0010(5) 0.0031(5) 0.0006(5) O5 0.0175(7) 0.0179(7) 0.0205(7) -0.0054(5) -0.0006(5) 0.0004(5) O6 0.0178(7) 0.0177(7) 0.0231(7) 0.0022(5) 0.0059(5) 0.0037(5) O7 0.0184(6) 0.0175(7) 0.0140(6) 0.0008(5) 0.0005(5) -0.0049(5) O8 0.0235(7) 0.0195(7) 0.0181(7) 0.0020(5) 0.0013(5) 0.0066(5) O9 0.0182(7) 0.0156(7) 0.0424(9) 0.0028(6) -0.0057(6) 0.0008(5) O10 0.0245(8) 0.0335(8) 0.0198(7) -0.0014(6) 0.0061(6) -0.0013(6) O11 0.0135(6) 0.0196(7) 0.0213(7) -0.0039(5) 0.0013(5) -0.0009(5) O12 0.0177(7) 0.0171(7) 0.0223(7) -0.0033(5) 0.0006(5) -0.0029(5) O13 0.0599(14) 0.0440(11) 0.0439(12) -0.0029(9) -0.0105(10) -0.0012(10) N1 0.0248(9) 0.0162(8) 0.0211(9) -0.0016(7) 0.0059(7) -0.0007(7) C1 0.0271(11) 0.0223(10) 0.0198(10) -0.0011(8) -0.0010(8) 0.0019(8) C2 0.0261(10) 0.0175(10) 0.0255(10) 0.0033(8) 0.0022(8) 0.0028(8) N2 0.0209(8) 0.0156(8) 0.0210(8) -0.0021(6) -0.0018(6) -0.0005(6) N3 0.0177(9) 0.0168(9) 0.0496(12) -0.0098(8) -0.0033(8) 0.0024(7) C3 0.0195(10) 0.0255(11) 0.0273(11) 0.0017(8) 0.0055(8) -0.0004(8) C4 0.0239(11) 0.0183(10) 0.0461(14) 0.0069(9) 0.0073(10) -0.0015(8) C5 0.0310(11) 0.0198(10) 0.0207(10) 0.0029(8) -0.0029(8) -0.0029(8) C6 0.0270(11) 0.0271(11) 0.0233(10) -0.0039(8) 0.0016(8) 0.0021(9) _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 Fe1 O2 1.9227(14) . ? Fe1 O12 1.9396(14) 1_565 ? Fe1 O5 1.9936(13) . ? Fe1 O7 1.9967(13) 2_454 ? Fe2 O9 1.9277(14) . ? Fe2 O1 1.9488(14) . ? Fe2 O8 1.9729(14) 2_444 ? Fe2 O7 1.9993(13) . ? P1 O2 1.5166(14) . ? P1 O4 1.5230(14) . ? P1 O1 1.5260(14) . ? P1 O3 1.5711(15) . ? P2 O6 1.5253(14) . ? P2 O8 1.5263(14) . ? P2 O5 1.5404(14) . ? P2 O7 1.5784(13) . ? P3 O10 1.5101(15) . ? P3 O12 1.5259(14) . ? P3 O9 1.5281(15) . ? P3 O11 1.5919(14) . ? O3 H31 0.74(4) . ? O7 Fe1 1.9967(13) 2_444 ? O8 Fe2 1.9729(14) 2_454 ? O11 H11 0.88(3) . ? O12 Fe1 1.9396(14) 1_545 ? O13 H13A 1.05(3) . ? O13 H13B 1.05(3) . ? N1 C1 1.489(3) . ? N1 C2 1.494(3) . ? N1 H11A 0.94(3) . ? N1 H12B 0.94(3) . ? C1 C2 1.511(3) 3_455 ? C1 H1A 0.9800 . ? C1 H1B 0.9800 . ? C2 C1 1.511(3) 3_455 ? C2 H2A 0.9800 . ? C2 H2B 0.9800 . ? N2 C3 1.483(3) . ? N2 C5 1.494(3) . ? N2 H21A 0.93(3) . ? N2 H22B 0.95(3) . ? N3 C6 1.491(3) . ? N3 C4 1.497(3) . ? N3 H31A 0.92(3) . ? N3 H31B 0.91(3) . ? C3 C4 1.508(3) . ? C3 H3A 0.9800 . ? C3 H3B 0.9800 . ? C4 H4A 0.9800 . ? C4 H4B 0.9800 . ? C5 C6 1.506(3) . ? C5 H5A 0.9800 . ? C5 H5B 0.9800 . ? C6 H6A 0.9800 . ? C6 H6B 0.9800 . ? 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 O2 Fe1 O12 116.81(6) . 1_565 ? O2 Fe1 O5 106.06(6) . . ? O12 Fe1 O5 98.10(6) 1_565 . ? O2 Fe1 O7 110.56(6) . 2_454 ? O12 Fe1 O7 116.70(6) 1_565 2_454 ? O5 Fe1 O7 106.70(5) . 2_454 ? O9 Fe2 O1 116.44(7) . . ? O9 Fe2 O8 108.65(6) . 2_444 ? O1 Fe2 O8 101.74(6) . 2_444 ? O9 Fe2 O7 110.56(6) . . ? O1 Fe2 O7 112.40(6) . . ? O8 Fe2 O7 106.12(5) 2_444 . ? O2 P1 O4 109.63(8) . . ? O2 P1 O1 111.96(8) . . ? O4 P1 O1 108.85(8) . . ? O2 P1 O3 107.58(9) . . ? O4 P1 O3 109.95(8) . . ? O1 P1 O3 108.85(9) . . ? O6 P2 O8 111.38(8) . . ? O6 P2 O5 109.06(8) . . ? O8 P2 O5 112.06(8) . . ? O6 P2 O7 109.36(8) . . ? O8 P2 O7 107.40(8) . . ? O5 P2 O7 107.46(7) . . ? O10 P3 O12 113.79(8) . . ? O10 P3 O9 113.03(9) . . ? O12 P3 O9 111.67(8) . . ? O10 P3 O11 105.44(8) . . ? O12 P3 O11 106.64(8) . . ? O9 P3 O11 105.49(8) . . ? P1 O1 Fe2 142.67(9) . . ? P1 O2 Fe1 137.56(9) . . ? P1 O3 H31 111(3) . . ? P2 O5 Fe1 133.76(8) . . ? P2 O7 Fe1 118.01(7) . 2_444 ? P2 O7 Fe2 122.00(7) . . ? Fe1 O7 Fe2 119.79(6) 2_444 . ? P2 O8 Fe2 135.82(8) . 2_454 ? P3 O9 Fe2 131.80(9) . . ? P3 O11 H11 115(2) . . ? P3 O12 Fe1 136.21(9) . 1_545 ? H13A O13 H13B 104(2) . . ? C1 N1 C2 111.12(16) . . ? C1 N1 H11A 110.4(16) . . ? C2 N1 H11A 107.7(16) . . ? C1 N1 H12B 108.0(16) . . ? C2 N1 H12B 111.3(16) . . ? H11A N1 H12B 108(2) . . ? N1 C1 C2 109.91(16) . 3_455 ? N1 C1 H1A 109.7 . . ? C2 C1 H1A 109.7 3_455 . ? N1 C1 H1B 109.7 . . ? C2 C1 H1B 109.7 3_455 . ? H1A C1 H1B 108.2 . . ? N1 C2 C1 110.62(16) . 3_455 ? N1 C2 H2A 109.5 . . ? C1 C2 H2A 109.5 3_455 . ? N1 C2 H2B 109.5 . . ? C1 C2 H2B 109.5 3_455 . ? H2A C2 H2B 108.1 . . ? C3 N2 C5 111.54(16) . . ? C3 N2 H21A 104.1(16) . . ? C5 N2 H21A 111.4(16) . . ? C3 N2 H22B 106.9(16) . . ? C5 N2 H22B 111.2(15) . . ? H21A N2 H22B 111(2) . . ? C6 N3 C4 111.07(17) . . ? C6 N3 H31A 110.1(18) . . ? C4 N3 H31A 107.5(18) . . ? C6 N3 H31B 110.1(19) . . ? C4 N3 H31B 105.4(19) . . ? H31A N3 H31B 113(3) . . ? N2 C3 C4 110.03(17) . . ? N2 C3 H3A 109.7 . . ? C4 C3 H3A 109.7 . . ? N2 C3 H3B 109.7 . . ? C4 C3 H3B 109.7 . . ? H3A C3 H3B 108.2 . . ? N3 C4 C3 110.20(18) . . ? N3 C4 H4A 109.6 . . ? C3 C4 H4A 109.6 . . ? N3 C4 H4B 109.6 . . ? C3 C4 H4B 109.6 . . ? H4A C4 H4B 108.1 . . ? N2 C5 C6 111.04(17) . . ? N2 C5 H5A 109.4 . . ? C6 C5 H5A 109.4 . . ? N2 C5 H5B 109.4 . . ? C6 C5 H5B 109.4 . . ? H5A C5 H5B 108.0 . . ? N3 C6 C5 110.63(17) . . ? N3 C6 H6A 109.5 . . ? C5 C6 H6A 109.5 . . ? N3 C6 H6B 109.5 . . ? C5 C6 H6B 109.5 . . ? H6A C6 H6B 108.1 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag O2 P1 O1 Fe2 75.69(17) . . . . ? O4 P1 O1 Fe2 -162.95(13) . . . . ? O3 P1 O1 Fe2 -43.12(17) . . . . ? O9 Fe2 O1 P1 44.32(17) . . . . ? O8 Fe2 O1 P1 162.23(15) 2_444 . . . ? O7 Fe2 O1 P1 -84.67(16) . . . . ? O4 P1 O2 Fe1 -170.44(12) . . . . ? O1 P1 O2 Fe1 -49.53(17) . . . . ? O3 P1 O2 Fe1 70.01(16) . . . . ? O12 Fe1 O2 P1 -99.39(15) 1_565 . . . ? O5 Fe1 O2 P1 8.66(16) . . . . ? O7 Fe1 O2 P1 123.97(14) 2_454 . . . ? O6 P2 O5 Fe1 150.83(10) . . . . ? O8 P2 O5 Fe1 27.04(14) . . . . ? O7 P2 O5 Fe1 -90.72(12) . . . . ? O2 Fe1 O5 P2 106.98(12) . . . . ? O12 Fe1 O5 P2 -132.02(12) 1_565 . . . ? O7 Fe1 O5 P2 -10.92(13) 2_454 . . . ? O6 P2 O7 Fe1 -94.67(9) . . . 2_444 ? O8 P2 O7 Fe1 26.33(10) . . . 2_444 ? O5 P2 O7 Fe1 147.07(8) . . . 2_444 ? O6 P2 O7 Fe2 90.52(10) . . . . ? O8 P2 O7 Fe2 -148.48(9) . . . . ? O5 P2 O7 Fe2 -27.74(11) . . . . ? O9 Fe2 O7 P2 -58.07(10) . . . . ? O1 Fe2 O7 P2 73.91(10) . . . . ? O8 Fe2 O7 P2 -175.71(9) 2_444 . . . ? O9 Fe2 O7 Fe1 127.21(8) . . . 2_444 ? O1 Fe2 O7 Fe1 -100.81(8) . . . 2_444 ? O8 Fe2 O7 Fe1 9.57(9) 2_444 . . 2_444 ? O6 P2 O8 Fe2 -149.08(11) . . . 2_454 ? O5 P2 O8 Fe2 -26.60(15) . . . 2_454 ? O7 P2 O8 Fe2 91.20(13) . . . 2_454 ? O10 P3 O9 Fe2 -73.33(15) . . . . ? O12 P3 O9 Fe2 56.50(15) . . . . ? O11 P3 O9 Fe2 171.96(12) . . . . ? O1 Fe2 O9 P3 103.12(13) . . . . ? O8 Fe2 O9 P3 -10.93(15) 2_444 . . . ? O7 Fe2 O9 P3 -127.01(13) . . . . ? O10 P3 O12 Fe1 47.33(15) . . . 1_545 ? O9 P3 O12 Fe1 -82.11(14) . . . 1_545 ? O11 P3 O12 Fe1 163.14(11) . . . 1_545 ? C2 N1 C1 C2 57.2(2) . . . 3_455 ? C1 N1 C2 C1 -57.6(2) . . . 3_455 ? C5 N2 C3 C4 57.3(2) . . . . ? C6 N3 C4 C3 57.9(2) . . . . ? N2 C3 C4 N3 -57.9(2) . . . . ? C3 N2 C5 C6 -56.0(2) . . . . ? C4 N3 C6 C5 -56.2(2) . . . . ? N2 C5 C6 N3 54.9(2) . . . . ? _diffrn_measured_fraction_theta_max 0.922 _diffrn_reflns_theta_full 28.89 _diffrn_measured_fraction_theta_full 0.922 _refine_diff_density_max 0.451 _refine_diff_density_min -0.577 _refine_diff_density_rms 0.079 data_k9 _database_code_CSD 203658 _audit_creation_method SHELXL-97 _chemical_name_systematic ; Bis(mu6,7-hydrogenphosphato)-tetrakis(mu7-phosphato)- di-iron(III)-penta-iron(II) ; _chemical_name_common ; Bis(mu6,7-hydrogenphosphato)-tetrakis(mu7-phosphato)-di- iron(iii)-penta-iron(ii) ; _chemical_melting_point ? _chemical_formula_moiety 'Fe7, (H0.5PO4)4, (PO4)2' _chemical_formula_sum 'H Fe3.50 O12 P3' _chemical_formula_weight 481.39 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe 0.3463 0.8444 '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' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 6.562(3) _cell_length_b 7.980(4) _cell_length_c 9.536(4) _cell_angle_alpha 103.874(6) _cell_angle_beta 109.286(6) _cell_angle_gamma 101.577(6) _cell_volume 435.7(3) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description isometric _exptl_crystal_colour black-green _exptl_crystal_size_max 0.51 _exptl_crystal_size_mid 0.11 _exptl_crystal_size_min 0.11 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 3.669 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 466 _exptl_absorpt_coefficient_mu 6.351 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.1401 _exptl_absorpt_correction_T_max 0.5418 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker AXS CCD' _diffrn_measurement_method '\w scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 3935 _diffrn_reflns_av_R_equivalents 0.0185 _diffrn_reflns_av_sigmaI/netI 0.0311 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.40 _diffrn_reflns_theta_max 28.64 _reflns_number_total 2030 _reflns_number_gt 1773 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. The hydrogen atom on O11 of the hydrogenphosphato ligand around P1 could be found and refined with Ueq(H) = 10.08. The hydrogen atom on O22 on P2 could initially also be found but had subsequently to be refined with an appropriate riding model (AFIX 84) and Ueq(H) = 10.08. The H atom positions are not fully occupied. Most likely is an occupation of 0.5 based on Moessbauer and IR spectroscopy quantifications. ; _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^)+(0.0410P)^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 2030 _refine_ls_number_parameters 173 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0329 _refine_ls_R_factor_gt 0.0283 _refine_ls_wR_factor_ref 0.0712 _refine_ls_wR_factor_gt 0.0699 _refine_ls_goodness_of_fit_ref 1.027 _refine_ls_restrained_S_all 1.027 _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 Fe1 Fe -0.44925(8) -0.28543(6) 0.51477(5) 0.01180(12) Uani 1 1 d . . . Fe2 Fe 0.22380(8) 0.18710(6) 0.71978(5) 0.01160(12) Uani 1 1 d . . . Fe3 Fe 0.11128(7) 0.54437(6) 0.88762(5) 0.00940(12) Uani 1 1 d . . . Fe4 Fe 0.5000 1.0000 1.0000 0.01045(15) Uani 1 2 d S . . P1 P -0.27189(13) 0.14341(10) 0.77825(9) 0.00805(16) Uani 1 1 d . . . P2 P 0.08549(13) -0.23006(11) 0.62689(9) 0.00942(17) Uani 1 1 d . . . P3 P 0.58392(13) 0.57957(10) 0.82730(9) 0.00814(16) Uani 1 1 d . . . O11 O -0.2916(4) -0.0636(3) 0.7270(3) 0.0127(4) Uani 1 1 d . . . H11 H -0.331(18) -0.106(16) 0.804(13) 0.080 Uiso 0.50 1 d P . . O12 O -0.4803(3) 0.1693(3) 0.6631(2) 0.0117(4) Uani 1 1 d . . . O13 O -0.2741(4) 0.1860(3) 0.9440(2) 0.0107(4) Uani 1 1 d . . . O14 O -0.0542(3) 0.2451(3) 0.7710(3) 0.0122(4) Uani 1 1 d . . . O21 O -0.1204(4) -0.2050(3) 0.5091(2) 0.0130(5) Uani 1 1 d . . . O22 O 0.2276(4) -0.2900(4) 0.5293(3) 0.0212(5) Uani 1 1 d D . . H22 H 0.142(2) -0.375(2) 0.446(2) 0.080 Uiso 0.50 1 calc PRD . . O23 O 0.0193(4) -0.3802(3) 0.6890(3) 0.0191(5) Uani 1 1 d . . . O24 O 0.2315(4) -0.0510(3) 0.7606(3) 0.0123(4) Uani 1 1 d . . . O31 O 0.3731(3) 0.4591(3) 0.8326(2) 0.0107(4) Uani 1 1 d . . . O32 O 0.5533(4) 0.5452(3) 0.6543(2) 0.0123(4) Uani 1 1 d . . . O33 O 0.7988(3) 0.5375(3) 0.9143(2) 0.0104(4) Uani 1 1 d . . . O34 O 0.6072(4) 0.7812(3) 0.9026(3) 0.0141(5) Uani 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 Fe1 0.0141(2) 0.0109(2) 0.0100(2) 0.00351(18) 0.00473(18) 0.00306(18) Fe2 0.0142(2) 0.0090(2) 0.0132(2) 0.00419(18) 0.00652(18) 0.00446(17) Fe3 0.0104(2) 0.0100(2) 0.0085(2) 0.00338(17) 0.00400(17) 0.00397(17) Fe4 0.0122(3) 0.0098(3) 0.0103(3) 0.0035(2) 0.0052(2) 0.0038(2) P1 0.0088(4) 0.0078(4) 0.0076(4) 0.0023(3) 0.0034(3) 0.0027(3) P2 0.0090(4) 0.0095(4) 0.0086(4) 0.0028(3) 0.0022(3) 0.0030(3) P3 0.0084(4) 0.0081(4) 0.0079(4) 0.0030(3) 0.0029(3) 0.0028(3) O11 0.0176(11) 0.0077(11) 0.0123(11) 0.0012(9) 0.0070(9) 0.0035(9) O12 0.0089(10) 0.0155(11) 0.0120(11) 0.0071(9) 0.0028(8) 0.0056(9) O13 0.0136(10) 0.0091(10) 0.0085(10) 0.0020(8) 0.0046(8) 0.0023(8) O14 0.0101(10) 0.0118(11) 0.0151(11) 0.0041(9) 0.0062(9) 0.0022(9) O21 0.0135(11) 0.0194(12) 0.0087(11) 0.0058(9) 0.0040(9) 0.0095(9) O22 0.0144(11) 0.0345(15) 0.0127(12) 0.0014(11) 0.0059(10) 0.0102(11) O23 0.0207(12) 0.0140(12) 0.0168(12) 0.0085(10) 0.0013(10) 0.0000(10) O24 0.0113(10) 0.0093(11) 0.0117(11) 0.0020(9) 0.0010(9) 0.0012(8) O31 0.0099(10) 0.0093(10) 0.0114(11) 0.0022(9) 0.0040(8) 0.0016(8) O32 0.0176(11) 0.0107(11) 0.0083(10) 0.0035(9) 0.0044(9) 0.0048(9) O33 0.0100(10) 0.0130(11) 0.0093(10) 0.0051(9) 0.0032(8) 0.0051(8) O34 0.0170(11) 0.0082(11) 0.0160(11) 0.0015(9) 0.0071(9) 0.0036(9) _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 Fe1 O12 2.087(2) 2_456 ? Fe1 O32 2.111(2) 1_445 ? Fe1 O32 2.113(2) 2_556 ? Fe1 O11 2.113(2) . ? Fe1 O21 2.147(2) . ? Fe1 O22 2.164(2) 1_455 ? Fe2 O24 2.036(2) . ? Fe2 O31 2.039(2) . ? Fe2 O21 2.110(2) 2_556 ? Fe2 O14 2.145(2) . ? Fe2 O12 2.203(2) 1_655 ? Fe3 O23 2.062(2) 1_565 ? Fe3 O33 2.087(2) 2_667 ? Fe3 O33 2.139(2) 1_455 ? Fe3 O31 2.141(2) . ? Fe3 O13 2.153(2) 2_567 ? Fe3 O14 2.238(2) . ? Fe4 O34 2.134(2) . ? Fe4 O34 2.134(2) 2_677 ? Fe4 O13 2.169(2) 2_567 ? Fe4 O13 2.169(2) 1_665 ? Fe4 O24 2.257(2) 1_565 ? Fe4 O24 2.257(2) 2_667 ? P1 O14 1.527(2) . ? P1 O12 1.533(2) . ? P1 O13 1.540(2) . ? P1 O11 1.571(2) . ? P2 O23 1.509(2) . ? P2 O21 1.530(2) . ? P2 O24 1.535(2) . ? P2 O22 1.583(2) . ? P3 O33 1.530(2) . ? P3 O31 1.541(2) . ? P3 O32 1.542(2) . ? P3 O34 1.550(2) . ? O11 H11 0.97(12) . ? O12 Fe1 2.087(2) 2_456 ? O12 Fe2 2.203(2) 1_455 ? O13 Fe3 2.153(2) 2_567 ? O13 Fe4 2.169(2) 1_445 ? O21 Fe2 2.110(2) 2_556 ? O22 Fe1 2.164(2) 1_655 ? O22 H22 0.8388 . ? O23 Fe3 2.062(2) 1_545 ? O24 Fe4 2.257(2) 1_545 ? O32 Fe1 2.111(2) 1_665 ? O32 Fe1 2.113(2) 2_556 ? O33 Fe3 2.087(2) 2_667 ? O33 Fe3 2.139(2) 1_655 ? 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 O12 Fe1 O32 166.20(9) 2_456 1_445 ? O12 Fe1 O32 90.65(9) 2_456 2_556 ? O32 Fe1 O32 78.16(10) 1_445 2_556 ? O12 Fe1 O11 104.96(9) 2_456 . ? O32 Fe1 O11 87.22(9) 1_445 . ? O32 Fe1 O11 162.98(9) 2_556 . ? O12 Fe1 O21 79.45(8) 2_456 . ? O32 Fe1 O21 109.21(8) 1_445 . ? O32 Fe1 O21 94.71(9) 2_556 . ? O11 Fe1 O21 81.80(9) . . ? O12 Fe1 O22 91.38(9) 2_456 1_455 ? O32 Fe1 O22 82.31(9) 1_445 1_455 ? O32 Fe1 O22 97.92(9) 2_556 1_455 ? O11 Fe1 O22 88.60(9) . 1_455 ? O21 Fe1 O22 164.48(10) . 1_455 ? O24 Fe2 O31 139.59(9) . . ? O24 Fe2 O21 122.35(9) . 2_556 ? O31 Fe2 O21 95.17(9) . 2_556 ? O24 Fe2 O14 104.28(8) . . ? O31 Fe2 O14 82.61(9) . . ? O21 Fe2 O14 97.95(8) 2_556 . ? O24 Fe2 O12 84.54(8) . 1_655 ? O31 Fe2 O12 90.03(8) . 1_655 ? O21 Fe2 O12 77.71(8) 2_556 1_655 ? O14 Fe2 O12 171.13(8) . 1_655 ? O23 Fe3 O33 178.83(9) 1_565 2_667 ? O23 Fe3 O33 94.27(9) 1_565 1_455 ? O33 Fe3 O33 85.66(8) 2_667 1_455 ? O23 Fe3 O31 90.06(9) 1_565 . ? O33 Fe3 O31 89.64(8) 2_667 . ? O33 Fe3 O31 161.55(9) 1_455 . ? O23 Fe3 O13 96.80(9) 1_565 2_567 ? O33 Fe3 O13 84.37(9) 2_667 2_567 ? O33 Fe3 O13 91.44(8) 1_455 2_567 ? O31 Fe3 O13 105.86(9) . 2_567 ? O23 Fe3 O14 98.21(9) 1_565 . ? O33 Fe3 O14 80.62(9) 2_667 . ? O33 Fe3 O14 83.42(8) 1_455 . ? O31 Fe3 O14 78.21(8) . . ? O13 Fe3 O14 164.45(8) 2_567 . ? O34 Fe4 O34 180.000(1) . 2_677 ? O34 Fe4 O13 89.29(9) . 2_567 ? O34 Fe4 O13 90.71(9) 2_677 2_567 ? O34 Fe4 O13 90.71(9) . 1_665 ? O34 Fe4 O13 89.29(9) 2_677 1_665 ? O13 Fe4 O13 180.00(9) 2_567 1_665 ? O34 Fe4 O24 90.29(8) . 1_565 ? O34 Fe4 O24 89.71(8) 2_677 1_565 ? O13 Fe4 O24 92.56(8) 2_567 1_565 ? O13 Fe4 O24 87.44(8) 1_665 1_565 ? O34 Fe4 O24 89.71(8) . 2_667 ? O34 Fe4 O24 90.29(8) 2_677 2_667 ? O13 Fe4 O24 87.44(8) 2_567 2_667 ? O13 Fe4 O24 92.56(8) 1_665 2_667 ? O24 Fe4 O24 180.000(1) 1_565 2_667 ? O14 P1 O12 111.09(12) . . ? O14 P1 O13 115.10(12) . . ? O12 P1 O13 110.64(12) . . ? O14 P1 O11 107.00(12) . . ? O12 P1 O11 108.24(13) . . ? O13 P1 O11 104.28(12) . . ? O23 P2 O21 112.23(13) . . ? O23 P2 O24 111.81(13) . . ? O21 P2 O24 111.06(13) . . ? O23 P2 O22 107.45(14) . . ? O21 P2 O22 105.10(13) . . ? O24 P2 O22 108.85(13) . . ? O33 P3 O31 111.33(12) . . ? O33 P3 O32 108.53(12) . . ? O31 P3 O32 109.23(12) . . ? O33 P3 O34 110.04(13) . . ? O31 P3 O34 108.91(12) . . ? O32 P3 O34 108.77(13) . . ? P1 O11 Fe1 136.19(14) . . ? P1 O11 H11 105(7) . . ? Fe1 O11 H11 106(7) . . ? P1 O12 Fe1 137.39(13) . 2_456 ? P1 O12 Fe2 121.44(12) . 1_455 ? Fe1 O12 Fe2 97.25(8) 2_456 1_455 ? P1 O13 Fe3 120.64(12) . 2_567 ? P1 O13 Fe4 121.66(12) . 1_445 ? Fe3 O13 Fe4 116.27(10) 2_567 1_445 ? P1 O14 Fe2 138.68(14) . . ? P1 O14 Fe3 123.26(12) . . ? Fe2 O14 Fe3 96.38(8) . . ? P2 O21 Fe2 137.50(13) . 2_556 ? P2 O21 Fe1 120.90(13) . . ? Fe2 O21 Fe1 98.27(9) 2_556 . ? P2 O22 Fe1 150.24(15) . 1_655 ? P2 O22 H22 109.5 . . ? Fe1 O22 H22 99.5 1_655 . ? P2 O23 Fe3 142.15(15) . 1_545 ? P2 O24 Fe2 119.05(13) . . ? P2 O24 Fe4 129.99(13) . 1_545 ? Fe2 O24 Fe4 110.51(9) . 1_545 ? P3 O31 Fe2 127.18(13) . . ? P3 O31 Fe3 127.04(13) . . ? Fe2 O31 Fe3 102.76(9) . . ? P3 O32 Fe1 133.24(13) . 1_665 ? P3 O32 Fe1 124.37(13) . 2_556 ? Fe1 O32 Fe1 101.84(10) 1_665 2_556 ? P3 O33 Fe3 130.72(13) . 2_667 ? P3 O33 Fe3 134.92(13) . 1_655 ? Fe3 O33 Fe3 94.34(8) 2_667 1_655 ? P3 O34 Fe4 155.25(14) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag O14 P1 O11 Fe1 -93.3(2) . . . . ? O12 P1 O11 Fe1 26.5(2) . . . . ? O13 P1 O11 Fe1 144.34(17) . . . . ? O12 Fe1 O11 P1 17.4(2) 2_456 . . . ? O32 Fe1 O11 P1 -156.01(19) 1_445 . . . ? O32 Fe1 O11 P1 173.3(2) 2_556 . . . ? O21 Fe1 O11 P1 94.13(19) . . . . ? O22 Fe1 O11 P1 -73.6(2) 1_455 . . . ? O14 P1 O12 Fe1 7.1(2) . . . 2_456 ? O13 P1 O12 Fe1 136.18(18) . . . 2_456 ? O11 P1 O12 Fe1 -110.1(2) . . . 2_456 ? O14 P1 O12 Fe2 -144.97(13) . . . 1_455 ? O13 P1 O12 Fe2 -15.84(18) . . . 1_455 ? O11 P1 O12 Fe2 97.84(15) . . . 1_455 ? O14 P1 O13 Fe3 36.04(18) . . . 2_567 ? O12 P1 O13 Fe3 -90.90(15) . . . 2_567 ? O11 P1 O13 Fe3 152.93(13) . . . 2_567 ? O14 P1 O13 Fe4 -158.12(12) . . . 1_445 ? O12 P1 O13 Fe4 74.93(16) . . . 1_445 ? O11 P1 O13 Fe4 -41.23(16) . . . 1_445 ? O12 P1 O14 Fe2 -120.40(19) . . . . ? O13 P1 O14 Fe2 112.89(19) . . . . ? O11 P1 O14 Fe2 -2.4(2) . . . . ? O12 P1 O14 Fe3 78.27(17) . . . . ? O13 P1 O14 Fe3 -48.45(18) . . . . ? O11 P1 O14 Fe3 -163.78(13) . . . . ? O24 Fe2 O14 P1 -23.4(2) . . . . ? O31 Fe2 O14 P1 -162.8(2) . . . . ? O21 Fe2 O14 P1 103.0(2) 2_556 . . . ? O12 Fe2 O14 P1 163.1(4) 1_655 . . . ? O24 Fe2 O14 Fe3 141.00(9) . . . . ? O31 Fe2 O14 Fe3 1.60(8) . . . . ? O21 Fe2 O14 Fe3 -92.63(9) 2_556 . . . ? O12 Fe2 O14 Fe3 -32.6(6) 1_655 . . . ? O23 Fe3 O14 P1 -105.48(15) 1_565 . . . ? O33 Fe3 O14 P1 74.58(15) 2_667 . . . ? O33 Fe3 O14 P1 -12.09(14) 1_455 . . . ? O31 Fe3 O14 P1 166.18(16) . . . . ? O13 Fe3 O14 P1 59.2(4) 2_567 . . . ? O23 Fe3 O14 Fe2 86.80(10) 1_565 . . . ? O33 Fe3 O14 Fe2 -93.15(9) 2_667 . . . ? O33 Fe3 O14 Fe2 -179.81(9) 1_455 . . . ? O31 Fe3 O14 Fe2 -1.54(7) . . . . ? O13 Fe3 O14 Fe2 -108.5(3) 2_567 . . . ? O23 P2 O21 Fe2 -129.2(2) . . . 2_556 ? O24 P2 O21 Fe2 104.8(2) . . . 2_556 ? O22 P2 O21 Fe2 -12.7(2) . . . 2_556 ? O23 P2 O21 Fe1 25.12(19) . . . . ? O24 P2 O21 Fe1 -100.86(16) . . . . ? O22 P2 O21 Fe1 141.59(14) . . . . ? O12 Fe1 O21 P2 176.19(16) 2_456 . . . ? O32 Fe1 O21 P2 -14.94(17) 1_445 . . . ? O32 Fe1 O21 P2 -94.03(15) 2_556 . . . ? O11 Fe1 O21 P2 69.20(15) . . . . ? O22 Fe1 O21 P2 121.5(3) 1_455 . . . ? O12 Fe1 O21 Fe2 -21.02(9) 2_456 . . 2_556 ? O32 Fe1 O21 Fe2 147.85(8) 1_445 . . 2_556 ? O32 Fe1 O21 Fe2 68.77(10) 2_556 . . 2_556 ? O11 Fe1 O21 Fe2 -128.01(10) . . . 2_556 ? O22 Fe1 O21 Fe2 -75.7(3) 1_455 . . 2_556 ? O23 P2 O22 Fe1 -96.1(3) . . . 1_655 ? O21 P2 O22 Fe1 144.2(3) . . . 1_655 ? O24 P2 O22 Fe1 25.2(4) . . . 1_655 ? O21 P2 O23 Fe3 -146.4(2) . . . 1_545 ? O24 P2 O23 Fe3 -20.8(3) . . . 1_545 ? O22 P2 O23 Fe3 98.5(3) . . . 1_545 ? O23 P2 O24 Fe2 -152.18(14) . . . . ? O21 P2 O24 Fe2 -25.97(18) . . . . ? O22 P2 O24 Fe2 89.27(16) . . . . ? O23 P2 O24 Fe4 36.3(2) . . . 1_545 ? O21 P2 O24 Fe4 162.49(14) . . . 1_545 ? O22 P2 O24 Fe4 -82.27(18) . . . 1_545 ? O31 Fe2 O24 P2 -177.06(11) . . . . ? O21 Fe2 O24 P2 -21.75(18) 2_556 . . . ? O14 Fe2 O24 P2 87.53(15) . . . . ? O12 Fe2 O24 P2 -93.47(15) 1_655 . . . ? O31 Fe2 O24 Fe4 -3.97(18) . . . 1_545 ? O21 Fe2 O24 Fe4 151.34(9) 2_556 . . 1_545 ? O14 Fe2 O24 Fe4 -99.38(10) . . . 1_545 ? O12 Fe2 O24 Fe4 79.62(10) 1_655 . . 1_545 ? O33 P3 O31 Fe2 -69.70(18) . . . . ? O32 P3 O31 Fe2 50.13(19) . . . . ? O34 P3 O31 Fe2 168.79(14) . . . . ? O33 P3 O31 Fe3 133.42(15) . . . . ? O32 P3 O31 Fe3 -106.75(15) . . . . ? O34 P3 O31 Fe3 11.91(19) . . . . ? O24 Fe2 O31 P3 93.66(19) . . . . ? O21 Fe2 O31 P3 -65.58(16) 2_556 . . . ? O14 Fe2 O31 P3 -162.96(17) . . . . ? O12 Fe2 O31 P3 12.07(16) 1_655 . . . ? O24 Fe2 O31 Fe3 -105.09(13) . . . . ? O21 Fe2 O31 Fe3 95.67(9) 2_556 . . . ? O14 Fe2 O31 Fe3 -1.70(8) . . . . ? O12 Fe2 O31 Fe3 173.33(9) 1_655 . . . ? O23 Fe3 O31 P3 64.57(16) 1_565 . . . ? O33 Fe3 O31 P3 -116.56(15) 2_667 . . . ? O33 Fe3 O31 P3 168.38(19) 1_455 . . . ? O13 Fe3 O31 P3 -32.52(17) 2_567 . . . ? O14 Fe3 O31 P3 162.94(17) . . . . ? O23 Fe3 O31 Fe2 -96.72(10) 1_565 . . . ? O33 Fe3 O31 Fe2 82.14(10) 2_667 . . . ? O33 Fe3 O31 Fe2 7.1(3) 1_455 . . . ? O13 Fe3 O31 Fe2 166.19(8) 2_567 . . . ? O14 Fe3 O31 Fe2 1.65(8) . . . . ? O33 P3 O32 Fe1 -117.00(17) . . . 1_665 ? O31 P3 O32 Fe1 121.46(17) . . . 1_665 ? O34 P3 O32 Fe1 2.7(2) . . . 1_665 ? O33 P3 O32 Fe1 73.07(17) . . . 2_556 ? O31 P3 O32 Fe1 -48.48(18) . . . 2_556 ? O34 P3 O32 Fe1 -167.22(13) . . . 2_556 ? O31 P3 O33 Fe3 -33.2(2) . . . 2_667 ? O32 P3 O33 Fe3 -153.48(15) . . . 2_667 ? O34 P3 O33 Fe3 87.60(18) . . . 2_667 ? O31 P3 O33 Fe3 148.44(16) . . . 1_655 ? O32 P3 O33 Fe3 28.2(2) . . . 1_655 ? O34 P3 O33 Fe3 -90.72(19) . . . 1_655 ? O33 P3 O34 Fe4 -131.2(3) . . . . ? O31 P3 O34 Fe4 -8.9(4) . . . . ? O32 P3 O34 Fe4 110.0(3) . . . . ? O34 Fe4 O34 P3 31(100) 2_677 . . . ? O13 Fe4 O34 P3 23.1(3) 2_567 . . . ? O13 Fe4 O34 P3 -156.9(3) 1_665 . . . ? O24 Fe4 O34 P3 -69.5(3) 1_565 . . . ? O24 Fe4 O34 P3 110.5(3) 2_667 . . . ? _diffrn_measured_fraction_theta_max 0.909 _diffrn_reflns_theta_full 28.64 _diffrn_measured_fraction_theta_full 0.909 _refine_diff_density_max 0.620 _refine_diff_density_min -0.729 _refine_diff_density_rms 0.189