# Supplementary Material (ESI) for Journal of Materials Chemistry # This journal is (C) The Royal Society of Chemistry 2006 data_global _journal_name_full J.Mater.Chem. _journal_coden_Cambridge 1145 _publ_contact_author_name 'Keith Murray' _publ_contact_author_address ; Monash University School of Chemistry Wellington Road Clayton Victoria 3800 AUSTRALIA ; _publ_contact_author_email KEITH.MURRAY@SCI.MONASH.EDU.AU _publ_section_title ; Heptanuclear iron(III) clusters exhibiting unprecedented 'millennium dome'-like topologies and ground spin states of S = 5/2 ; loop_ _publ_author_name 'Keith Murray' 'Kevin J. Berry' 'John F. Boas' 'Paul Jensen' 'Leigh F. Jones' 'Boujemaa Moubaraki' ; J.Pilbrow ; # Attachment 'Fe7Revised cifs28Mar.cif' data_1 _database_code_depnum_ccdc_archive 'CCDC 299512' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety '[Fe8O3(piv)6(tea)(teaH)3F3].0.5MeOH.0.5H2O' _chemical_formula_sum 'C42.50 H84 F3 Fe8 N4 O28' _chemical_formula_weight 1602.94 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' F F 0.0171 0.0103 '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 Cubic _symmetry_space_group_name_H-M Pa-3 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'z, x, y' 'y, z, x' '-y+1/2, -z, x+1/2' 'z+1/2, -x+1/2, -y' '-y, z+1/2, -x+1/2' '-z+1/2, -x, y+1/2' '-z, x+1/2, -y+1/2' 'y+1/2, -z+1/2, -x' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' '-x, -y, -z' '-z, -x, -y' '-y, -z, -x' 'y-1/2, z, -x-1/2' '-z-1/2, x-1/2, y' 'y, -z-1/2, x-1/2' 'z-1/2, x, -y-1/2' 'z, -x-1/2, y-1/2' '-y-1/2, z-1/2, x' 'x-1/2, y, -z-1/2' '-x-1/2, y-1/2, z' 'x, -y-1/2, z-1/2' _cell_length_a 22.8942(1) _cell_length_b 22.8942(1) _cell_length_c 22.8942(1) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 11999.87(9) _cell_formula_units_Z 8 _cell_measurement_temperature 123(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description prism _exptl_crystal_colour red _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.40 _exptl_crystal_size_min 0.40 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.775 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 6608 _exptl_absorpt_coefficient_mu 1.974 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.85 _exptl_absorpt_correction_T_max 1.00 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 123(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'NOnius KappaCCD' _diffrn_measurement_method 'Phi scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 109464 _diffrn_reflns_av_R_equivalents 0.0426 _diffrn_reflns_av_sigmaI/netI 0.0162 _diffrn_reflns_limit_h_min -30 _diffrn_reflns_limit_h_max 30 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min -30 _diffrn_reflns_limit_l_max 30 _diffrn_reflns_theta_min 3.56 _diffrn_reflns_theta_max 28.29 _reflns_number_total 4973 _reflns_number_gt 4412 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'collect (nonius BV, 1997-2000)' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'HKL Denzo and Scalepack (Otwinowski & Minor' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0240P)^2^+18.4362P] 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 4973 _refine_ls_number_parameters 267 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0362 _refine_ls_R_factor_gt 0.0285 _refine_ls_wR_factor_ref 0.0674 _refine_ls_wR_factor_gt 0.0642 _refine_ls_goodness_of_fit_ref 1.118 _refine_ls_restrained_S_all 1.118 _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 Fe1 Fe 0.153605(12) 0.274309(12) 0.537237(12) 0.00846(7) Uani 1 1 d . . . Fe2 Fe 0.121596(12) 0.378404(12) 0.621596(12) 0.00896(10) Uani 1 3 d S . . Fe3 Fe 0.275879(12) 0.326431(12) 0.595104(12) 0.00892(7) Uani 1 1 d . . . Fe4 Fe 0.194527(12) 0.305473(12) 0.694527(12) 0.00832(10) Uani 1 3 d S . . F1 F 0.11081(5) 0.24480(5) 0.47246(5) 0.0139(2) Uani 1 1 d . . . O1 O 0.19235(6) 0.31622(6) 0.60409(6) 0.0089(3) Uani 1 1 d . . . O2 O 0.28261(6) 0.41044(6) 0.61401(6) 0.0118(3) Uani 1 1 d . . . O3 O 0.27760(6) 0.29919(6) 0.67778(6) 0.0118(3) Uani 1 1 d . . . O4 O 0.49493(8) 0.28456(9) 0.52085(8) 0.0292(4) Uani 1 1 d . . . O5 O 0.29740(6) 0.24272(6) 0.57275(7) 0.0158(3) Uani 1 1 d . . . O6 O 0.21832(6) 0.21380(6) 0.52345(6) 0.0148(3) Uani 1 1 d . . . O7 O 0.09330(6) 0.33355(6) 0.55527(6) 0.0120(3) Uani 1 1 d . . . O8 O 0.19299(6) 0.32960(7) 0.47640(6) 0.0165(3) Uani 1 1 d . . . O9 O 0.28315(6) 0.34516(7) 0.51043(6) 0.0179(3) Uani 1 1 d . . . O10' O 0.4410(4) 0.4410(4) 0.4410(4) 0.095(4) Uani 0.50 3 d SP A 2 O11 O 0.5000 0.5000 0.5000 0.277(12) Uani 1 6 d S . . N1 N 0.05491(7) 0.44509(7) 0.55491(7) 0.0123(6) Uani 1 3 d S . . N2 N 0.37271(7) 0.33330(7) 0.61450(7) 0.0116(3) Uani 1 1 d . . . C1 C 0.04064(9) 0.40739(9) 0.50553(9) 0.0158(4) Uani 1 1 d . . . H1A H 0.0701 0.4123 0.4743 0.019 Uiso 1 1 calc R . . H1B H 0.0019 0.4181 0.4895 0.019 Uiso 1 1 calc R . . C2 C 0.03991(9) 0.34467(9) 0.52605(9) 0.0141(4) Uani 1 1 d . . . H2A H 0.0066 0.3382 0.5529 0.017 Uiso 1 1 calc R . . H2B H 0.0356 0.3180 0.4923 0.017 Uiso 1 1 calc R . . C3 C 0.38392(9) 0.39579(9) 0.62904(9) 0.0149(4) Uani 1 1 d . . . H3A H 0.4236 0.4071 0.6161 0.018 Uiso 1 1 calc R . . H3B H 0.3813 0.4017 0.6718 0.018 Uiso 1 1 calc R . . C4 C 0.33877(8) 0.43265(9) 0.59835(9) 0.0139(4) Uani 1 1 d . . . H4A H 0.3424 0.4740 0.6105 0.017 Uiso 1 1 calc R . . H4B H 0.3443 0.4304 0.5555 0.017 Uiso 1 1 calc R . . C5 C 0.38124(9) 0.29478(9) 0.66624(9) 0.0145(4) Uani 1 1 d . . . H5A H 0.4186 0.3046 0.6857 0.017 Uiso 1 1 calc R . . H5B H 0.3831 0.2535 0.6535 0.017 Uiso 1 1 calc R . . C6 C 0.33082(9) 0.30283(10) 0.70888(9) 0.0153(4) Uani 1 1 d . . . H6A H 0.3322 0.2721 0.7393 0.018 Uiso 1 1 calc R . . H6B H 0.3339 0.3413 0.7283 0.018 Uiso 1 1 calc R . . C7 C 0.40680(9) 0.31416(9) 0.56271(9) 0.0164(4) Uani 1 1 d . . . H7A H 0.3938 0.3375 0.5287 0.020 Uiso 1 1 calc R . . H7B H 0.3968 0.2729 0.5546 0.020 Uiso 1 1 calc R . . C8 C 0.47264(9) 0.31894(10) 0.56690(10) 0.0187(4) Uani 1 1 d . . . H8A H 0.4852 0.3601 0.5626 0.022 Uiso 1 1 calc R . . H8B H 0.4866 0.3041 0.6051 0.022 Uiso 1 1 calc R . . C9 C 0.26971(9) 0.20671(8) 0.54207(8) 0.0117(4) Uani 1 1 d . . . C10 C 0.29993(9) 0.14973(9) 0.52714(10) 0.0185(4) Uani 1 1 d . . . H10A H 0.2916 0.1400 0.4858 0.022 Uiso 1 1 calc R . . H10B H 0.2831 0.1183 0.5516 0.022 Uiso 1 1 calc R . . C11 C 0.36601(10) 0.15065(11) 0.53599(12) 0.0271(5) Uani 1 1 d . . . H11A H 0.3829 0.1830 0.5136 0.041 Uiso 1 1 calc R . . H11B H 0.3827 0.1136 0.5225 0.041 Uiso 1 1 calc R . . H11C H 0.3748 0.1560 0.5776 0.041 Uiso 1 1 calc R . . C12 C 0.24327(9) 0.35017(9) 0.47215(9) 0.0136(4) Uani 1 1 d . . . C13 C 0.26008(11) 0.38479(11) 0.41827(10) 0.0249(5) Uani 1 1 d . . . H13A H 0.2673 0.4258 0.4300 0.030 Uiso 1 1 calc R . . H13B H 0.2973 0.3690 0.4029 0.030 Uiso 1 1 calc R . . C14 C 0.21555(13) 0.38445(12) 0.36976(11) 0.0319(6) Uani 1 1 d . . . H14A H 0.2091 0.3442 0.3566 0.048 Uiso 1 1 calc R . . H14B H 0.2299 0.4080 0.3371 0.048 Uiso 1 1 calc R . . H14C H 0.1787 0.4009 0.3841 0.048 Uiso 1 1 calc R . . C15 C 0.4670(9) 0.4670(9) 0.4670(9) 0.180(19) Uani 0.50 3 d SP B 1 H4 H 0.5326(16) 0.2830(15) 0.5234(14) 0.046(10) 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 Fe1 0.00808(13) 0.00929(13) 0.00800(13) -0.00131(10) -0.00088(10) -0.00025(10) Fe2 0.00896(10) 0.00896(10) 0.00896(10) -0.00045(10) 0.00045(10) -0.00045(10) Fe3 0.00742(13) 0.01099(13) 0.00836(13) -0.00136(10) 0.00013(10) -0.00038(10) Fe4 0.00832(10) 0.00832(10) 0.00832(10) -0.00009(10) 0.00009(10) -0.00009(10) F1 0.0140(6) 0.0159(6) 0.0118(6) -0.0029(4) -0.0033(4) -0.0012(5) O1 0.0082(6) 0.0102(6) 0.0082(6) -0.0008(5) -0.0002(5) -0.0008(5) O2 0.0090(6) 0.0101(6) 0.0165(7) -0.0006(5) 0.0021(5) -0.0010(5) O3 0.0082(6) 0.0169(7) 0.0103(6) 0.0007(5) -0.0013(5) 0.0005(5) O4 0.0151(8) 0.0447(11) 0.0277(9) -0.0128(8) 0.0033(7) 0.0046(8) O5 0.0135(7) 0.0142(7) 0.0196(7) -0.0065(6) -0.0027(6) 0.0017(5) O6 0.0104(7) 0.0150(7) 0.0190(7) -0.0063(6) -0.0025(5) 0.0022(5) O7 0.0104(6) 0.0133(7) 0.0122(7) -0.0022(5) -0.0037(5) 0.0031(5) O8 0.0162(7) 0.0210(8) 0.0124(7) 0.0028(6) -0.0012(6) -0.0048(6) O9 0.0139(7) 0.0282(8) 0.0115(7) 0.0008(6) 0.0001(5) -0.0026(6) O10' 0.095(4) 0.095(4) 0.095(4) 0.015(5) 0.015(5) 0.015(5) O11 0.277(12) 0.277(12) 0.277(12) 0.032(16) 0.032(16) 0.032(16) N1 0.0123(6) 0.0123(6) 0.0123(6) -0.0014(6) 0.0014(6) -0.0014(6) N2 0.0094(8) 0.0125(8) 0.0130(8) -0.0017(6) 0.0009(6) -0.0004(6) C1 0.0162(10) 0.0164(10) 0.0149(10) -0.0007(8) -0.0030(8) 0.0014(8) C2 0.0105(9) 0.0143(9) 0.0175(10) -0.0016(8) -0.0053(7) 0.0012(7) C3 0.0113(9) 0.0139(9) 0.0194(10) -0.0046(8) -0.0001(8) -0.0020(7) C4 0.0088(9) 0.0146(9) 0.0184(10) -0.0001(8) 0.0036(7) -0.0033(7) C5 0.0099(9) 0.0164(10) 0.0171(10) 0.0005(8) -0.0024(7) 0.0019(7) C6 0.0115(9) 0.0216(11) 0.0126(9) 0.0000(8) -0.0036(7) -0.0001(8) C7 0.0133(10) 0.0186(10) 0.0172(10) -0.0043(8) 0.0028(8) -0.0003(8) C8 0.0135(10) 0.0220(11) 0.0206(11) -0.0034(9) 0.0016(8) 0.0000(8) C9 0.0127(9) 0.0117(9) 0.0106(9) -0.0003(7) 0.0028(7) 0.0008(7) C10 0.0164(10) 0.0133(10) 0.0257(11) -0.0047(8) -0.0005(8) 0.0024(8) C11 0.0198(11) 0.0217(12) 0.0399(14) -0.0055(10) -0.0036(10) 0.0095(9) C12 0.0163(10) 0.0142(9) 0.0105(9) -0.0016(7) 0.0012(7) 0.0002(8) C13 0.0267(12) 0.0318(13) 0.0162(11) 0.0091(9) 0.0000(9) -0.0070(10) C14 0.0456(16) 0.0334(14) 0.0167(11) 0.0078(10) -0.0071(11) -0.0057(12) C15 0.180(19) 0.180(19) 0.180(19) -0.034(15) -0.034(15) -0.034(15) _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 F1 1.9014(11) . ? Fe1 O7 1.9789(14) . ? Fe1 O2 1.9885(14) 5_456 ? Fe1 O1 2.0125(13) . ? Fe1 O6 2.0527(14) . ? Fe1 O8 2.0869(15) . ? Fe2 O7 1.9443(14) . ? Fe2 O7 1.9443(14) 5_456 ? Fe2 O7 1.9443(14) 4_565 ? Fe2 O1 2.1934(13) . ? Fe2 O1 2.1934(13) 4_565 ? Fe2 O1 2.1934(13) 5_456 ? Fe2 Fe4 2.8920(7) . ? Fe3 O1 1.9376(13) . ? Fe3 O2 1.9775(14) . ? Fe3 O9 1.9924(15) . ? Fe3 O3 1.9934(14) . ? Fe3 O5 2.0438(14) . ? Fe3 N2 2.2664(16) . ? Fe4 O3 1.9454(14) 4_565 ? Fe4 O3 1.9454(14) 5_456 ? Fe4 O3 1.9454(14) . ? Fe4 O1 2.0856(13) 4_565 ? Fe4 O1 2.0856(13) 5_456 ? Fe4 O1 2.0856(13) . ? O2 C4 1.428(2) . ? O2 Fe1 1.9885(14) 4_565 ? O3 C6 1.414(2) . ? O4 C8 1.411(3) . ? O5 C9 1.255(2) . ? O6 C9 1.262(2) . ? O7 C2 1.416(2) . ? O8 C12 1.248(3) . ? O9 C12 1.271(2) . ? O11 C15 1.31(3) . ? O11 C15 1.31(3) 13_666 ? N1 C1 1.459(2) 5_456 ? N1 C1 1.459(2) . ? N1 C1 1.459(2) 4_565 ? N2 C7 1.486(3) . ? N2 C5 1.490(3) . ? N2 C3 1.491(3) . ? C1 C2 1.511(3) . ? C3 C4 1.508(3) . ? C5 C6 1.523(3) . ? C7 C8 1.514(3) . ? C9 C10 1.516(3) . ? C10 C11 1.526(3) . ? C12 C13 1.516(3) . ? C13 C14 1.507(3) . ? 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 F1 Fe1 O7 92.68(5) . . ? F1 Fe1 O2 90.12(5) . 5_456 ? O7 Fe1 O2 90.31(6) . 5_456 ? F1 Fe1 O1 171.75(5) . . ? O7 Fe1 O1 79.75(5) . . ? O2 Fe1 O1 93.17(5) 5_456 . ? F1 Fe1 O6 90.70(5) . . ? O7 Fe1 O6 176.52(6) . . ? O2 Fe1 O6 88.82(6) 5_456 . ? O1 Fe1 O6 96.93(6) . . ? F1 Fe1 O8 85.27(5) . . ? O7 Fe1 O8 91.43(6) . . ? O2 Fe1 O8 175.15(6) 5_456 . ? O1 Fe1 O8 91.60(6) . . ? O6 Fe1 O8 89.71(6) . . ? O7 Fe2 O7 109.16(4) . 5_456 ? O7 Fe2 O7 109.16(4) . 4_565 ? O7 Fe2 O7 109.16(4) 5_456 4_565 ? O7 Fe2 O1 76.15(5) . . ? O7 Fe2 O1 152.81(6) 5_456 . ? O7 Fe2 O1 93.21(5) 4_565 . ? O7 Fe2 O1 152.81(6) . 4_565 ? O7 Fe2 O1 93.21(5) 5_456 4_565 ? O7 Fe2 O1 76.15(5) 4_565 4_565 ? O1 Fe2 O1 76.95(5) . 4_565 ? O7 Fe2 O1 93.21(5) . 5_456 ? O7 Fe2 O1 76.15(5) 5_456 5_456 ? O7 Fe2 O1 152.81(6) 4_565 5_456 ? O1 Fe2 O1 76.95(5) . 5_456 ? O1 Fe2 O1 76.95(5) 4_565 5_456 ? O7 Fe2 Fe4 109.78(4) . . ? O7 Fe2 Fe4 109.78(4) 5_456 . ? O7 Fe2 Fe4 109.78(4) 4_565 . ? O1 Fe2 Fe4 45.92(4) . . ? O1 Fe2 Fe4 45.92(4) 4_565 . ? O1 Fe2 Fe4 45.92(4) 5_456 . ? O1 Fe3 O2 99.84(6) . . ? O1 Fe3 O9 102.23(6) . . ? O2 Fe3 O9 89.84(6) . . ? O1 Fe3 O3 83.16(6) . . ? O2 Fe3 O3 95.45(6) . . ? O9 Fe3 O3 171.73(6) . . ? O1 Fe3 O5 98.71(6) . . ? O2 Fe3 O5 161.45(6) . . ? O9 Fe3 O5 86.45(6) . . ? O3 Fe3 O5 86.54(6) . . ? O1 Fe3 N2 162.36(6) . . ? O2 Fe3 N2 79.25(6) . . ? O9 Fe3 N2 95.39(6) . . ? O3 Fe3 N2 79.42(6) . . ? O5 Fe3 N2 83.01(6) . . ? O3 Fe4 O3 97.75(5) 4_565 5_456 ? O3 Fe4 O3 97.75(5) 4_565 . ? O3 Fe4 O3 97.75(5) 5_456 . ? O3 Fe4 O1 80.59(5) 4_565 4_565 ? O3 Fe4 O1 161.62(6) 5_456 4_565 ? O3 Fe4 O1 100.61(6) . 4_565 ? O3 Fe4 O1 100.61(6) 4_565 5_456 ? O3 Fe4 O1 80.59(5) 5_456 5_456 ? O3 Fe4 O1 161.62(6) . 5_456 ? O1 Fe4 O1 81.74(6) 4_565 5_456 ? O3 Fe4 O1 161.62(6) 4_565 . ? O3 Fe4 O1 100.61(6) 5_456 . ? O3 Fe4 O1 80.59(5) . . ? O1 Fe4 O1 81.74(6) 4_565 . ? O1 Fe4 O1 81.74(6) 5_456 . ? O3 Fe4 Fe2 119.56(4) 4_565 . ? O3 Fe4 Fe2 119.56(4) 5_456 . ? O3 Fe4 Fe2 119.56(4) . . ? O1 Fe4 Fe2 49.07(4) 4_565 . ? O1 Fe4 Fe2 49.07(4) 5_456 . ? O1 Fe4 Fe2 49.07(4) . . ? Fe3 O1 Fe1 114.31(6) . . ? Fe3 O1 Fe4 95.51(6) . . ? Fe1 O1 Fe4 135.18(7) . . ? Fe3 O1 Fe2 132.07(7) . . ? Fe1 O1 Fe2 97.06(5) . . ? Fe4 O1 Fe2 85.00(5) . . ? C4 O2 Fe3 111.18(11) . . ? C4 O2 Fe1 119.33(12) . 4_565 ? Fe3 O2 Fe1 129.39(7) . 4_565 ? C6 O3 Fe4 137.65(12) . . ? C6 O3 Fe3 118.47(12) . . ? Fe4 O3 Fe3 98.32(6) . . ? C9 O5 Fe3 129.38(13) . . ? C9 O6 Fe1 135.06(13) . . ? C2 O7 Fe2 124.16(12) . . ? C2 O7 Fe1 128.81(12) . . ? Fe2 O7 Fe1 107.00(6) . . ? C12 O8 Fe1 132.82(14) . . ? C12 O9 Fe3 129.08(13) . . ? C15 O11 C15 180.0(14) . 13_666 ? C1 N1 C1 114.65(11) 5_456 . ? C1 N1 C1 114.65(11) 5_456 4_565 ? C1 N1 C1 114.65(11) . 4_565 ? C7 N2 C5 113.03(16) . . ? C7 N2 C3 111.77(16) . . ? C5 N2 C3 111.59(16) . . ? C7 N2 Fe3 109.69(12) . . ? C5 N2 Fe3 104.06(11) . . ? C3 N2 Fe3 106.18(11) . . ? N1 C1 C2 108.88(18) . . ? O7 C2 C1 107.93(16) . . ? N2 C3 C4 108.36(16) . . ? O2 C4 C3 107.51(16) . . ? N2 C5 C6 109.81(16) . . ? O3 C6 C5 108.86(16) . . ? N2 C7 C8 116.81(17) . . ? O4 C8 C7 105.81(17) . . ? O5 C9 O6 125.13(18) . . ? O5 C9 C10 117.46(18) . . ? O6 C9 C10 117.40(18) . . ? C9 C10 C11 114.24(18) . . ? O8 C12 O9 125.11(19) . . ? O8 C12 C13 119.67(19) . . ? O9 C12 C13 115.22(19) . . ? C14 C13 C12 115.2(2) . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 28.29 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.536 _refine_diff_density_min -0.304 _refine_diff_density_rms 0.074 data_2 _database_code_depnum_ccdc_archive 'CCDC 299513' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety '[Fe7O3(piv)9(bheapH)3(H2O)3]' _chemical_formula_sum 'C66 H132 Fe7 N3 O33' _chemical_formula_weight 1886.70 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' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Trigonal _symmetry_space_group_name_H-M P31c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'y, x, z+1/2' 'x-y, -y, z+1/2' '-x, -x+y, z+1/2' _cell_length_a 15.7648(2) _cell_length_b 15.7648(2) _cell_length_c 21.1873(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 4560.19(14) _cell_formula_units_Z 2 _cell_measurement_temperature 123(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description plate _exptl_crystal_colour red _exptl_crystal_size_max 0.28 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.374 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1990 _exptl_absorpt_coefficient_mu 1.158 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.920 _exptl_absorpt_correction_T_max 1.000 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 123(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius KappaCCD' _diffrn_measurement_method 'Phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 38197 _diffrn_reflns_av_R_equivalents 0.1059 _diffrn_reflns_av_sigmaI/netI 0.0661 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 3.95 _diffrn_reflns_theta_max 22.72 _reflns_number_total 4082 _reflns_number_gt 2923 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'collect (nonius BV, 1997-2000)' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'HKL Denzo and Scalepack (Otwinowski & Minor' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0667P)^2^+3.2911P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.01(3) _refine_ls_number_reflns 4082 _refine_ls_number_parameters 337 _refine_ls_number_restraints 27 _refine_ls_R_factor_all 0.0930 _refine_ls_R_factor_gt 0.0568 _refine_ls_wR_factor_ref 0.1319 _refine_ls_wR_factor_gt 0.1179 _refine_ls_goodness_of_fit_ref 1.026 _refine_ls_restrained_S_all 1.034 _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 -0.3333 0.3333 -0.05299(9) 0.0498(6) Uani 1 3 d S . . Fe2 Fe -0.22730(8) 0.54316(7) 0.04637(6) 0.0491(3) Uani 1 1 d . . . Fe3 Fe -0.11724(9) 0.45602(8) -0.03748(6) 0.0537(4) Uani 1 1 d . . . O1 O -0.2325(3) 0.4407(3) 0.0005(3) 0.0450(13) Uani 1 1 d . . . O2 O -0.2127(4) 0.3781(4) -0.1053(2) 0.0558(15) Uani 1 1 d . . . O3 O -0.1190(4) 0.3400(4) 0.0028(3) 0.0515(14) Uani 1 1 d . . . O4 O 0.1539(10) 0.4521(10) -0.1773(6) 0.192(5) Uani 1 1 d . . . O5 O -0.0153(4) 0.5408(4) 0.0266(3) 0.0591(15) Uani 1 1 d . . . O6 O -0.1079(4) 0.5576(4) 0.0992(3) 0.0596(15) Uani 1 1 d . . . O7 O -0.0773(4) 0.5858(4) -0.0827(3) 0.0664(16) Uani 1 1 d . . . O8 O -0.1313(4) 0.6525(4) -0.0106(3) 0.0614(16) Uani 1 1 d . . . O9 O -0.2160(4) 0.6523(4) 0.1035(3) 0.0613(15) Uani 1 1 d . . . O10 O -0.2770(5) 0.5887(6) 0.1961(3) 0.086(2) Uani 1 1 d . . . O11 O -0.3095(4) 0.4494(3) 0.1198(2) 0.0475(14) Uani 1 1 d . . . N1 N -0.0180(6) 0.4346(5) -0.1038(4) 0.068(2) Uani 1 1 d . . . C1 C -0.2361(15) 0.308(2) -0.2107(9) 0.172(16) Uani 0.50 1 d PDU A 1 H1A H -0.3054 0.2616 -0.2024 0.257 Uiso 0.25 1 calc PR A 1 H1B H -0.2095 0.2769 -0.2384 0.257 Uiso 0.25 1 calc PR A 1 H1C H -0.2294 0.3665 -0.2312 0.257 Uiso 0.25 1 calc PR A 1 H1D H -0.1908 0.3417 -0.2456 0.257 Uiso 0.25 1 calc PR A 1 H1E H -0.2867 0.3264 -0.2097 0.257 Uiso 0.25 1 calc PR A 1 H1F H -0.2668 0.2368 -0.2168 0.257 Uiso 0.25 1 calc PR A 1 C2 C -0.1809(8) 0.3358(8) -0.1498(5) 0.092(3) Uani 0.50 1 d PDU A 1 H2 H -0.1855 0.2755 -0.1308 0.110 Uiso 0.50 1 calc PR A 1 C1' C 0.202(2) 0.628(2) -0.202(2) 0.217(19) Uani 0.50 1 d PDU A 2 H1'A H 0.2282 0.6219 -0.2429 0.325 Uiso 0.25 1 calc PR A 2 H1'B H 0.2554 0.6619 -0.1721 0.325 Uiso 0.25 1 calc PR A 2 H1'C H 0.1678 0.6651 -0.2082 0.325 Uiso 0.25 1 calc PR A 2 H1'D H 0.2061 0.6773 -0.1726 0.325 Uiso 0.25 1 calc PR A 2 H1'E H 0.1789 0.6374 -0.2434 0.325 Uiso 0.25 1 calc PR A 2 H1'F H 0.2665 0.6342 -0.2073 0.325 Uiso 0.25 1 calc PR A 2 C2' C -0.1809(8) 0.3358(8) -0.1498(5) 0.092(3) Uani 0.50 1 d P A 2 H2'A H -0.2208 0.3207 -0.1886 0.110 Uiso 0.50 1 calc PR A 2 H2'B H -0.1882 0.2738 -0.1331 0.110 Uiso 0.50 1 calc PR A 2 C3 C -0.0752(7) 0.4061(8) -0.1646(5) 0.083(3) Uani 1 1 d D A . H3A H -0.0689 0.4650 -0.1857 0.100 Uiso 1 1 calc R B 1 H3B H -0.0494 0.3748 -0.1933 0.100 Uiso 1 1 calc R B 1 C4 C -0.0087(8) 0.3523(8) -0.0772(6) 0.094(3) Uani 1 1 d . A . H4A H 0.0582 0.3641 -0.0853 0.112 Uiso 1 1 calc R . . H4B H -0.0557 0.2907 -0.0988 0.112 Uiso 1 1 calc R . . C5 C -0.0283(6) 0.3414(7) -0.0077(4) 0.062(2) Uani 1 1 d . A . H5A H -0.0332 0.2798 0.0076 0.074 Uiso 1 1 calc R . . H5B H 0.0256 0.3968 0.0152 0.074 Uiso 1 1 calc R . . C6 C 0.0773(8) 0.5248(8) -0.1157(6) 0.092(3) Uani 1 1 d D A . H6A H 0.1216 0.5340 -0.0799 0.111 Uiso 1 1 calc R C 1 H6B H 0.0661 0.5812 -0.1158 0.111 Uiso 1 1 calc R C 1 C7 C 0.1312(10) 0.5279(10) -0.1778(8) 0.165(8) Uani 0.50 1 d PD A 1 H7A H 0.0888 0.5199 -0.2145 0.199 Uiso 0.50 1 calc PR A 1 H7B H 0.1921 0.5920 -0.1817 0.199 Uiso 0.50 1 calc PR A 1 C7' C 0.1312(10) 0.5279(10) -0.1778(8) 0.165(8) Uani 0.50 1 d PDU A 2 H7' H 0.0771 0.5037 -0.2096 0.199 Uiso 0.50 1 calc PR A 2 C8 C -0.0818(6) 0.6562(7) -0.0604(5) 0.060(2) Uani 1 1 d . A . C9 C -0.0262(7) 0.7547(7) -0.0925(5) 0.079(3) Uani 1 1 d D . . C10 C -0.0355(12) 0.7394(9) -0.1637(6) 0.168(7) Uani 1 1 d D A . H10A H -0.1044 0.7104 -0.1760 0.253 Uiso 1 1 calc R . . H10B H -0.0113 0.6952 -0.1759 0.253 Uiso 1 1 calc R . . H10C H 0.0033 0.8025 -0.1850 0.253 Uiso 1 1 calc R . . C11 C 0.0772(7) 0.7987(9) -0.0719(8) 0.185(10) Uani 1 1 d D A . H11A H 0.1022 0.7551 -0.0833 0.278 Uiso 1 1 calc R . . H11B H 0.0810 0.8080 -0.0260 0.278 Uiso 1 1 calc R . . H11C H 0.1166 0.8622 -0.0927 0.278 Uiso 1 1 calc R . . C12 C -0.0675(8) 0.8204(7) -0.0783(7) 0.137(6) Uani 1 1 d D A . H12A H -0.1356 0.7890 -0.0927 0.205 Uiso 1 1 calc R . . H12B H -0.0288 0.8830 -0.1003 0.205 Uiso 1 1 calc R . . H12C H -0.0649 0.8320 -0.0327 0.205 Uiso 1 1 calc R . . C13 C -0.0286(7) 0.5657(5) 0.0803(5) 0.054(2) Uani 1 1 d . A . C14 C 0.0566(6) 0.6049(6) 0.1269(4) 0.071(3) Uani 1 1 d D . . C15 C 0.0770(10) 0.5222(8) 0.1433(6) 0.135(6) Uani 1 1 d D A . H15A H 0.1314 0.5463 0.1734 0.203 Uiso 1 1 calc R . . H15B H 0.0943 0.4998 0.1048 0.203 Uiso 1 1 calc R . . H15C H 0.0183 0.4676 0.1622 0.203 Uiso 1 1 calc R . . C16 C 0.1479(8) 0.6891(9) 0.0945(7) 0.157(6) Uani 1 1 d D A . H16A H 0.1352 0.7423 0.0842 0.235 Uiso 1 1 calc R . . H16B H 0.1621 0.6648 0.0557 0.235 Uiso 1 1 calc R . . H16C H 0.2041 0.7136 0.1231 0.235 Uiso 1 1 calc R . . C17 C 0.0352(8) 0.6439(9) 0.1868(5) 0.111(4) Uani 1 1 d D A . H17A H 0.0232 0.6974 0.1760 0.166 Uiso 1 1 calc R . . H17B H 0.0914 0.6682 0.2154 0.166 Uiso 1 1 calc R . . H17C H -0.0229 0.5912 0.2075 0.166 Uiso 1 1 calc R . . C18 C -0.2328(7) 0.6606(8) 0.1598(6) 0.063(2) Uani 1 1 d . A . C19 C -0.1968(6) 0.7648(7) 0.1845(5) 0.085(4) Uani 1 1 d D . . C20 C -0.0932(8) 0.8238(8) 0.1686(8) 0.168(8) Uani 1 1 d D A . H20A H -0.0569 0.7955 0.1885 0.252 Uiso 1 1 calc R . . H20B H -0.0679 0.8908 0.1838 0.252 Uiso 1 1 calc R . . H20C H -0.0853 0.8246 0.1227 0.252 Uiso 1 1 calc R . . C21 C -0.2578(11) 0.7988(9) 0.1577(10) 0.277(17) Uani 1 1 d D A . H21A H -0.3259 0.7554 0.1706 0.415 Uiso 1 1 calc R . . H21B H -0.2533 0.7989 0.1116 0.415 Uiso 1 1 calc R . . H21C H -0.2360 0.8655 0.1726 0.415 Uiso 1 1 calc R . . C22 C -0.2027(13) 0.7642(11) 0.2558(7) 0.219(11) Uani 1 1 d D A . H22A H -0.1596 0.7422 0.2735 0.328 Uiso 1 1 calc R . . H22B H -0.2703 0.7196 0.2691 0.328 Uiso 1 1 calc R . . H22C H -0.1821 0.8305 0.2709 0.328 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 0.0504(8) 0.0504(8) 0.0486(13) 0.000 0.000 0.0252(4) Fe2 0.0426(7) 0.0423(6) 0.0606(7) -0.0019(7) 0.0012(6) 0.0199(6) Fe3 0.0485(7) 0.0493(7) 0.0648(8) 0.0052(6) 0.0092(6) 0.0256(6) O1 0.040(3) 0.043(3) 0.051(3) 0.003(3) 0.005(2) 0.020(2) O2 0.065(4) 0.068(4) 0.044(3) -0.004(3) 0.007(3) 0.040(3) O3 0.043(3) 0.047(3) 0.066(4) 0.002(3) 0.005(3) 0.023(3) O4 0.207(12) 0.240(13) 0.181(11) 0.069(10) 0.069(9) 0.152(11) O5 0.047(3) 0.051(3) 0.075(4) -0.003(3) -0.002(3) 0.021(3) O6 0.043(3) 0.067(4) 0.066(4) -0.014(3) -0.009(3) 0.026(3) O7 0.070(4) 0.052(4) 0.080(4) 0.012(3) 0.024(3) 0.034(3) O8 0.052(4) 0.042(3) 0.081(5) 0.005(3) 0.005(3) 0.017(3) O9 0.063(4) 0.055(4) 0.069(4) -0.011(3) 0.001(3) 0.032(3) O10 0.092(5) 0.079(5) 0.084(5) -0.016(4) 0.017(5) 0.041(4) O11 0.051(3) 0.040(3) 0.048(3) -0.002(2) 0.000(3) 0.020(3) N1 0.074(6) 0.063(5) 0.081(6) 0.012(4) 0.024(5) 0.045(5) C1 0.057(14) 0.23(3) 0.103(15) -0.11(2) 0.003(11) -0.017(17) C2 0.094(9) 0.102(8) 0.070(7) -0.007(6) 0.016(6) 0.042(7) C1' 0.14(3) 0.22(3) 0.23(3) 0.08(3) 0.14(3) 0.05(3) C2' 0.094(9) 0.102(8) 0.070(7) -0.007(6) 0.016(6) 0.042(7) C3 0.092(8) 0.090(8) 0.081(8) 0.000(6) 0.019(7) 0.055(7) C4 0.081(7) 0.080(8) 0.131(11) 0.009(7) 0.027(7) 0.049(6) C5 0.054(6) 0.051(5) 0.086(8) 0.012(5) 0.004(5) 0.031(5) C6 0.073(7) 0.078(7) 0.140(10) 0.012(7) 0.033(7) 0.048(6) C7 0.086(9) 0.095(9) 0.32(2) -0.005(11) 0.076(12) 0.052(8) C7' 0.086(9) 0.095(9) 0.32(2) -0.005(11) 0.076(12) 0.052(8) C8 0.049(6) 0.050(6) 0.073(7) 0.021(6) 0.008(5) 0.018(5) C9 0.087(8) 0.052(6) 0.092(8) 0.016(6) 0.019(6) 0.030(6) C10 0.238(19) 0.106(10) 0.124(13) 0.072(10) 0.032(13) 0.058(12) C11 0.054(8) 0.099(10) 0.37(3) 0.138(14) 0.017(10) 0.014(7) C12 0.105(9) 0.043(6) 0.251(17) 0.050(8) 0.075(11) 0.029(6) C13 0.063(7) 0.031(5) 0.062(6) 0.002(4) 0.004(5) 0.019(4) C14 0.056(6) 0.062(6) 0.093(8) -0.019(5) -0.026(5) 0.028(5) C15 0.175(13) 0.117(10) 0.155(12) -0.055(9) -0.097(11) 0.105(10) C16 0.075(9) 0.138(13) 0.158(13) -0.009(10) -0.010(9) -0.021(9) C17 0.100(9) 0.127(10) 0.110(9) -0.038(8) -0.052(8) 0.060(8) C18 0.047(6) 0.059(7) 0.082(8) -0.023(6) -0.006(6) 0.025(5) C19 0.060(7) 0.063(7) 0.126(10) -0.052(7) -0.001(6) 0.025(6) C20 0.084(9) 0.051(7) 0.31(2) -0.068(10) 0.021(11) -0.007(7) C21 0.208(18) 0.101(11) 0.59(5) -0.175(19) -0.24(2) 0.128(13) C22 0.24(2) 0.137(14) 0.185(18) -0.113(13) 0.004(16) 0.019(14) _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 O1 1.996(5) 3_455 ? Fe1 O1 1.996(5) . ? Fe1 O1 1.996(5) 2_565 ? Fe1 O2 2.000(5) . ? Fe1 O2 2.000(5) 3_455 ? Fe1 O2 2.000(5) 2_565 ? Fe1 Fe3 2.9775(12) 3_455 ? Fe1 Fe3 2.9775(12) . ? Fe1 Fe3 2.9775(12) 2_565 ? Fe2 O1 1.852(5) . ? Fe2 O3 1.988(5) 2_565 ? Fe2 O8 2.026(6) . ? Fe2 O9 2.038(6) . ? Fe2 O11 2.091(5) . ? Fe2 O6 2.102(5) . ? Fe3 O1 1.888(5) . ? Fe3 O2 1.997(5) . ? Fe3 O3 2.006(5) . ? Fe3 O5 2.017(6) . ? Fe3 O7 2.052(6) . ? Fe3 N1 2.250(7) . ? O2 C2 1.386(11) . ? O3 C5 1.436(9) . ? O3 Fe2 1.988(5) 3_455 ? O4 C7 1.409(15) . ? O5 C13 1.254(10) . ? O6 C13 1.258(10) . ? O7 C8 1.241(11) . ? O8 C8 1.297(10) . ? O9 C18 1.244(11) . ? O10 C18 1.253(11) . ? N1 C6 1.486(12) . ? N1 C4 1.486(12) . ? N1 C3 1.507(12) . ? C1 C2 1.495(16) . ? C2 C3 1.502(12) . ? C4 C5 1.497(13) . ? C6 C7 1.553(14) . ? C8 C9 1.510(12) . ? C9 C11 1.482(11) . ? C9 C12 1.503(11) . ? C9 C10 1.523(12) . ? C13 C14 1.527(12) . ? C14 C17 1.519(11) . ? C14 C15 1.530(11) . ? C14 C16 1.548(11) . ? C18 C19 1.536(13) . ? C19 C21 1.432(12) . ? C19 C20 1.459(11) . ? C19 C22 1.513(13) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Fe1 O1 91.0(2) 3_455 . ? O1 Fe1 O1 91.0(2) 3_455 2_565 ? O1 Fe1 O1 91.0(2) . 2_565 ? O1 Fe1 O2 100.2(2) 3_455 . ? O1 Fe1 O2 78.5(2) . . ? O1 Fe1 O2 164.7(2) 2_565 . ? O1 Fe1 O2 78.5(2) 3_455 3_455 ? O1 Fe1 O2 164.7(2) . 3_455 ? O1 Fe1 O2 100.2(2) 2_565 3_455 ? O2 Fe1 O2 92.3(2) . 3_455 ? O1 Fe1 O2 164.7(2) 3_455 2_565 ? O1 Fe1 O2 100.2(2) . 2_565 ? O1 Fe1 O2 78.5(2) 2_565 2_565 ? O2 Fe1 O2 92.3(2) . 2_565 ? O2 Fe1 O2 92.3(2) 3_455 2_565 ? O1 Fe1 Fe3 38.64(14) 3_455 3_455 ? O1 Fe1 Fe3 129.49(16) . 3_455 ? O1 Fe1 Fe3 87.55(14) 2_565 3_455 ? O2 Fe1 Fe3 107.71(16) . 3_455 ? O2 Fe1 Fe3 41.82(15) 3_455 3_455 ? O2 Fe1 Fe3 128.65(17) 2_565 3_455 ? O1 Fe1 Fe3 87.55(14) 3_455 . ? O1 Fe1 Fe3 38.64(14) . . ? O1 Fe1 Fe3 129.49(16) 2_565 . ? O2 Fe1 Fe3 41.82(15) . . ? O2 Fe1 Fe3 128.65(17) 3_455 . ? O2 Fe1 Fe3 107.71(16) 2_565 . ? Fe3 Fe1 Fe3 118.798(16) 3_455 . ? O1 Fe1 Fe3 129.49(16) 3_455 2_565 ? O1 Fe1 Fe3 87.55(14) . 2_565 ? O1 Fe1 Fe3 38.64(14) 2_565 2_565 ? O2 Fe1 Fe3 128.65(16) . 2_565 ? O2 Fe1 Fe3 107.71(16) 3_455 2_565 ? O2 Fe1 Fe3 41.82(15) 2_565 2_565 ? Fe3 Fe1 Fe3 118.798(16) 3_455 2_565 ? Fe3 Fe1 Fe3 118.798(16) . 2_565 ? O1 Fe2 O3 95.3(2) . 2_565 ? O1 Fe2 O8 96.8(2) . . ? O3 Fe2 O8 91.1(2) 2_565 . ? O1 Fe2 O9 174.7(2) . . ? O3 Fe2 O9 89.5(2) 2_565 . ? O8 Fe2 O9 85.6(2) . . ? O1 Fe2 O11 91.9(2) . . ? O3 Fe2 O11 95.8(2) 2_565 . ? O8 Fe2 O11 168.4(2) . . ? O9 Fe2 O11 85.2(2) . . ? O1 Fe2 O6 91.2(2) . . ? O3 Fe2 O6 173.5(2) 2_565 . ? O8 Fe2 O6 88.7(2) . . ? O9 Fe2 O6 84.0(2) . . ? O11 Fe2 O6 83.4(2) . . ? O1 Fe3 O2 81.2(2) . . ? O1 Fe3 O3 97.4(2) . . ? O2 Fe3 O3 94.8(2) . . ? O1 Fe3 O5 101.2(2) . . ? O2 Fe3 O5 176.3(2) . . ? O3 Fe3 O5 87.7(2) . . ? O1 Fe3 O7 97.1(2) . . ? O2 Fe3 O7 92.2(2) . . ? O3 Fe3 O7 164.8(2) . . ? O5 Fe3 O7 84.7(2) . . ? O1 Fe3 N1 160.6(3) . . ? O2 Fe3 N1 80.0(3) . . ? O3 Fe3 N1 79.8(2) . . ? O5 Fe3 N1 97.8(3) . . ? O7 Fe3 N1 88.2(3) . . ? O1 Fe3 Fe1 41.31(16) . . ? O2 Fe3 Fe1 41.89(15) . . ? O3 Fe3 Fe1 88.00(15) . . ? O5 Fe3 Fe1 141.15(18) . . ? O7 Fe3 Fe1 106.09(18) . . ? N1 Fe3 Fe1 119.3(2) . . ? Fe2 O1 Fe3 119.5(2) . . ? Fe2 O1 Fe1 134.9(3) . . ? Fe3 O1 Fe1 100.1(2) . . ? C2 O2 Fe3 116.3(5) . . ? C2 O2 Fe1 135.7(6) . . ? Fe3 O2 Fe1 96.3(2) . . ? C5 O3 Fe2 120.4(5) . 3_455 ? C5 O3 Fe3 111.1(5) . . ? Fe2 O3 Fe3 128.2(2) 3_455 . ? C13 O5 Fe3 128.0(6) . . ? C13 O6 Fe2 129.2(6) . . ? C8 O7 Fe3 126.0(6) . . ? C8 O8 Fe2 134.4(6) . . ? C18 O9 Fe2 136.5(6) . . ? C6 N1 C4 114.0(8) . . ? C6 N1 C3 107.9(8) . . ? C4 N1 C3 111.6(8) . . ? C6 N1 Fe3 114.1(6) . . ? C4 N1 Fe3 105.9(6) . . ? C3 N1 Fe3 102.7(5) . . ? O2 C2 C1 115.6(14) . . ? O2 C2 C3 108.7(8) . . ? C1 C2 C3 107.7(11) . . ? C2 C3 N1 108.7(8) . . ? N1 C4 C5 111.6(8) . . ? O3 C5 C4 107.5(7) . . ? N1 C6 C7 116.7(9) . . ? O4 C7 C6 109.5(12) . . ? O7 C8 O8 124.9(8) . . ? O7 C8 C9 119.0(9) . . ? O8 C8 C9 116.1(9) . . ? C11 C9 C12 111.8(8) . . ? C11 C9 C8 106.6(8) . . ? C12 C9 C8 113.0(9) . . ? C11 C9 C10 111.2(9) . . ? C12 C9 C10 105.5(8) . . ? C8 C9 C10 108.8(9) . . ? O5 C13 O6 124.8(8) . . ? O5 C13 C14 117.5(8) . . ? O6 C13 C14 117.6(8) . . ? C17 C14 C13 112.0(7) . . ? C17 C14 C15 109.9(8) . . ? C13 C14 C15 108.6(8) . . ? C17 C14 C16 108.8(7) . . ? C13 C14 C16 108.2(8) . . ? C15 C14 C16 109.3(8) . . ? O9 C18 O10 123.0(9) . . ? O9 C18 C19 117.0(10) . . ? O10 C18 C19 120.0(9) . . ? C21 C19 C20 114.6(10) . . ? C21 C19 C22 110.3(10) . . ? C20 C19 C22 106.3(9) . . ? C21 C19 C18 107.9(8) . . ? C20 C19 C18 107.5(8) . . ? C22 C19 C18 110.2(10) . . ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 22.72 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.370 _refine_diff_density_min -0.280 _refine_diff_density_rms 0.062 data_3 _database_code_depnum_ccdc_archive 'CCDC 299514' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety '[Fe7O3(piv)9(teaH)3(H2O)3]' _chemical_formula_sum 'C63 H126 Fe7 N3 O33' _chemical_formula_weight 1844.62 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' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Trigonal _symmetry_space_group_name_H-M P31c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'y, x, z+1/2' 'x-y, -y, z+1/2' '-x, -x+y, z+1/2' _cell_length_a 15.5829(8) _cell_length_b 15.5829(8) _cell_length_c 20.8930(10) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 4393.7(4) _cell_formula_units_Z 2 _cell_measurement_temperature 123(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description block _exptl_crystal_colour red _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.394 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1942 _exptl_absorpt_coefficient_mu 1.200 _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 123(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius KappaCCD' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 39976 _diffrn_reflns_av_R_equivalents 0.2060 _diffrn_reflns_av_sigmaI/netI 0.1214 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 3.59 _diffrn_reflns_theta_max 25.05 _reflns_number_total 5148 _reflns_number_gt 3937 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'collect (nonius BV, 1997-2000)' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'HKL Denzo and Scalepack (Otwinowski & Minor' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0551P)^2^+15.5883P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.41(4) _refine_ls_number_reflns 5148 _refine_ls_number_parameters 330 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.1324 _refine_ls_R_factor_gt 0.0979 _refine_ls_wR_factor_ref 0.1751 _refine_ls_wR_factor_gt 0.1623 _refine_ls_goodness_of_fit_ref 1.124 _refine_ls_restrained_S_all 1.124 _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 0.3333 0.6667 0.83803(10) 0.0216(6) Uani 1 3 d S . . Fe2 Fe 0.22641(11) 0.77207(11) 0.93910(6) 0.0248(3) Uani 1 1 d . . . Fe3 Fe 0.11430(11) 0.57300(10) 0.85430(6) 0.0236(3) Uani 1 1 d . . . O1 O 0.2315(5) 0.6729(5) 0.8934(3) 0.0229(15) Uani 1 1 d . . . O2 O 0.2106(4) 0.5946(5) 0.7846(3) 0.0261(16) Uani 1 1 d . . . O3 O 0.1169(5) 0.4565(5) 0.8941(3) 0.0244(15) Uani 1 1 d . . . O4 O -0.1744(7) 0.2908(7) 0.7225(4) 0.056(2) Uani 1 1 d . . . H4 H -0.2141 0.2627 0.6921 0.067 Uiso 1 1 calc R . . O5 O 0.0112(4) 0.5542(5) 0.9196(3) 0.0299(16) Uani 1 1 d . . . O6 O 0.1047(5) 0.6667(5) 0.9931(3) 0.0315(16) Uani 1 1 d . . . O7 O 0.0734(5) 0.6639(5) 0.8098(3) 0.0320(17) Uani 1 1 d . . . O8 O 0.1290(5) 0.7859(5) 0.8822(3) 0.0320(18) Uani 1 1 d . . . O9 O 0.2184(5) 0.8724(5) 0.9966(3) 0.0281(16) Uani 1 1 d . . . O10 O 0.2795(6) 0.8706(6) 1.0920(3) 0.043(2) Uani 1 1 d . . . O11 O 0.3104(5) 0.7602(5) 1.0141(3) 0.0279(16) Uani 1 1 d . . . N1 N 0.0144(6) 0.4536(6) 0.7855(4) 0.0257(19) Uani 1 1 d . . . C1 C 0.1763(8) 0.5279(8) 0.7334(5) 0.037(3) Uani 1 1 d . . . H1A H 0.1876 0.4720 0.7425 0.045 Uiso 1 1 calc R . . H1B H 0.2131 0.5614 0.6940 0.045 Uiso 1 1 calc R . . C2 C 0.0682(8) 0.4898(7) 0.7236(4) 0.032(3) Uani 1 1 d . . . H2A H 0.0581 0.5434 0.7065 0.038 Uiso 1 1 calc R . . H2B H 0.0416 0.4350 0.6921 0.038 Uiso 1 1 calc R . . C3 C 0.0118(8) 0.3624(7) 0.8077(4) 0.030(2) Uani 1 1 d . . . H3A H 0.0643 0.3553 0.7859 0.036 Uiso 1 1 calc R . . H3B H -0.0530 0.3040 0.7968 0.036 Uiso 1 1 calc R . . C4 C 0.0276(8) 0.3670(7) 0.8796(4) 0.031(3) Uani 1 1 d . . . H4A H -0.0290 0.3659 0.9019 0.037 Uiso 1 1 calc R . . H4B H 0.0326 0.3091 0.8941 0.037 Uiso 1 1 calc R . . C5 C -0.0873(8) 0.4426(8) 0.7832(5) 0.035(3) Uani 1 1 d . . . H5A H -0.0794 0.5097 0.7850 0.043 Uiso 1 1 calc R . . H5B H -0.1237 0.4068 0.8221 0.043 Uiso 1 1 calc R . . C6 C -0.1509(9) 0.3895(9) 0.7258(5) 0.047(3) Uani 1 1 d . . . H6A H -0.2129 0.3924 0.7279 0.057 Uiso 1 1 calc R . . H6B H -0.1153 0.4241 0.6863 0.057 Uiso 1 1 calc R . . C7 C 0.0763(7) 0.7388(8) 0.8324(5) 0.028(2) Uani 1 1 d . . . C8 C 0.0136(9) 0.7780(8) 0.8050(5) 0.037(3) Uani 1 1 d . . . C9 C -0.0098(17) 0.7466(13) 0.7364(7) 0.108(7) Uani 1 1 d . . . H9A H 0.0511 0.7794 0.7110 0.161 Uiso 1 1 calc R . . H9B H -0.0572 0.7653 0.7200 0.161 Uiso 1 1 calc R . . H9C H -0.0388 0.6746 0.7333 0.161 Uiso 1 1 calc R . . C10 C 0.0624(10) 0.8911(9) 0.8089(6) 0.052(3) Uani 1 1 d . . . H10A H 0.0773 0.9122 0.8536 0.079 Uiso 1 1 calc R . . H10B H 0.0171 0.9117 0.7915 0.079 Uiso 1 1 calc R . . H10C H 0.1239 0.9217 0.7840 0.079 Uiso 1 1 calc R . . C11 C -0.0822(9) 0.7324(11) 0.8464(8) 0.071(5) Uani 1 1 d . . . H11A H -0.1179 0.6601 0.8417 0.107 Uiso 1 1 calc R . . H11B H -0.1246 0.7585 0.8321 0.107 Uiso 1 1 calc R . . H11C H -0.0645 0.7498 0.8914 0.107 Uiso 1 1 calc R . . C12 C 0.0245(8) 0.5918(7) 0.9758(5) 0.027(2) Uani 1 1 d . . . C13 C -0.0619(8) 0.5435(8) 1.0224(5) 0.034(3) Uani 1 1 d . . . C14 C -0.0711(9) 0.4445(8) 1.0406(6) 0.051(3) Uani 1 1 d . . . H14A H -0.0106 0.4563 1.0627 0.076 Uiso 1 1 calc R . . H14B H -0.0803 0.4054 1.0018 0.076 Uiso 1 1 calc R . . H14C H -0.1282 0.4083 1.0690 0.076 Uiso 1 1 calc R . . C15 C -0.0426(9) 0.6058(8) 1.0810(5) 0.044(3) Uani 1 1 d . . . H15A H 0.0170 0.6142 1.1025 0.066 Uiso 1 1 calc R . . H15B H -0.0993 0.5731 1.1101 0.066 Uiso 1 1 calc R . . H15C H -0.0328 0.6708 1.0687 0.066 Uiso 1 1 calc R . . C16 C -0.1554(9) 0.5264(12) 0.9893(6) 0.066(4) Uani 1 1 d . . . H16A H -0.2108 0.4968 1.0196 0.099 Uiso 1 1 calc R . . H16B H -0.1696 0.4814 0.9530 0.099 Uiso 1 1 calc R . . H16C H -0.1465 0.5897 0.9739 0.099 Uiso 1 1 calc R . . C17 C 0.2352(7) 0.8986(8) 1.0533(5) 0.030(2) Uani 1 1 d . . . C18 C 0.2034(8) 0.9728(9) 1.0750(5) 0.037(3) Uani 1 1 d . . . C19 C 0.2436(11) 1.0578(9) 1.0291(8) 0.073(5) Uani 1 1 d . . . H19A H 0.2243 1.1058 1.0430 0.109 Uiso 1 1 calc R . . H19B H 0.2169 1.0334 0.9863 0.109 Uiso 1 1 calc R . . H19C H 0.3160 1.0899 1.0280 0.109 Uiso 1 1 calc R . . C20 C 0.0930(9) 0.9179(10) 1.0730(7) 0.058(4) Uani 1 1 d . . . H20A H 0.0676 0.8558 1.0969 0.087 Uiso 1 1 calc R . . H20B H 0.0707 0.9032 1.0284 0.087 Uiso 1 1 calc R . . H20C H 0.0681 0.9585 1.0923 0.087 Uiso 1 1 calc R . . C21 C 0.2376(12) 1.0099(14) 1.1428(7) 0.093(6) Uani 1 1 d . . . H21A H 0.2135 1.0548 1.1554 0.139 Uiso 1 1 calc R . . H21B H 0.3102 1.0454 1.1445 0.139 Uiso 1 1 calc R . . H21C H 0.2112 0.9534 1.1723 0.139 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 0.0241(9) 0.0241(9) 0.0165(13) 0.000 0.000 0.0121(4) Fe2 0.0278(9) 0.0267(8) 0.0209(7) -0.0023(6) -0.0006(6) 0.0145(7) Fe3 0.0242(8) 0.0254(8) 0.0216(7) -0.0031(6) -0.0003(6) 0.0126(7) O1 0.022(4) 0.035(4) 0.019(3) -0.001(3) 0.000(3) 0.020(3) O2 0.016(4) 0.027(4) 0.024(4) -0.006(3) 0.000(3) 0.003(3) O3 0.027(4) 0.025(4) 0.022(3) 0.005(3) -0.002(3) 0.014(3) O4 0.061(6) 0.059(6) 0.040(5) -0.005(4) -0.018(4) 0.025(5) O5 0.015(4) 0.039(4) 0.033(4) -0.004(3) 0.004(3) 0.012(3) O6 0.022(4) 0.035(4) 0.029(4) 0.003(3) 0.008(3) 0.009(4) O7 0.036(4) 0.033(4) 0.031(4) 0.001(3) -0.008(3) 0.019(4) O8 0.037(5) 0.031(4) 0.033(4) 0.002(3) 0.001(4) 0.022(4) O9 0.044(4) 0.038(4) 0.015(4) -0.010(3) -0.005(3) 0.030(4) O10 0.046(5) 0.061(6) 0.035(4) -0.010(4) -0.006(4) 0.036(5) O11 0.037(4) 0.032(4) 0.024(4) -0.009(3) -0.006(3) 0.025(4) N1 0.023(5) 0.026(5) 0.022(4) -0.008(4) -0.005(4) 0.008(4) C1 0.043(7) 0.037(7) 0.028(5) 0.004(5) 0.009(5) 0.017(6) C2 0.037(7) 0.021(6) 0.019(5) -0.003(4) -0.003(5) 0.001(5) C3 0.041(7) 0.018(6) 0.029(5) -0.008(4) -0.008(5) 0.013(5) C4 0.045(7) 0.019(6) 0.028(6) 0.000(4) 0.002(5) 0.015(5) C5 0.036(7) 0.029(6) 0.035(6) -0.002(5) -0.008(5) 0.011(5) C6 0.050(8) 0.054(9) 0.047(7) -0.006(6) -0.013(6) 0.032(7) C7 0.028(6) 0.037(7) 0.034(6) 0.009(5) 0.004(5) 0.027(5) C8 0.070(9) 0.041(7) 0.020(6) -0.007(5) -0.009(6) 0.042(7) C9 0.20(2) 0.115(15) 0.059(10) -0.029(10) -0.069(12) 0.121(16) C10 0.049(8) 0.050(8) 0.058(8) 0.005(6) -0.010(6) 0.025(7) C11 0.027(7) 0.061(10) 0.136(14) 0.020(9) -0.002(8) 0.029(7) C12 0.034(7) 0.031(6) 0.028(6) 0.016(5) 0.015(5) 0.026(6) C13 0.037(7) 0.030(6) 0.028(6) 0.005(5) 0.004(5) 0.012(5) C14 0.051(8) 0.040(8) 0.054(8) 0.004(6) 0.020(6) 0.017(6) C15 0.049(8) 0.039(7) 0.036(6) 0.010(5) 0.019(6) 0.017(6) C16 0.037(8) 0.102(12) 0.059(8) -0.003(8) 0.003(7) 0.034(8) C17 0.005(5) 0.044(7) 0.037(7) -0.001(5) 0.002(5) 0.010(5) C18 0.027(6) 0.043(7) 0.041(7) -0.011(6) 0.001(5) 0.019(6) C19 0.069(11) 0.035(8) 0.116(13) 0.008(8) 0.037(9) 0.027(8) C20 0.042(8) 0.059(9) 0.099(11) -0.002(8) 0.010(7) 0.044(7) C21 0.106(13) 0.171(18) 0.067(10) -0.067(11) -0.032(9) 0.118(14) _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 O1 2.004(6) . ? Fe1 O1 2.004(6) 3_565 ? Fe1 O1 2.004(6) 2_665 ? Fe1 O2 2.005(6) 3_565 ? Fe1 O2 2.005(6) . ? Fe1 O2 2.005(6) 2_665 ? Fe2 O1 1.852(6) . ? Fe2 O3 1.984(6) 3_565 ? Fe2 O8 2.022(7) . ? Fe2 O9 2.025(6) . ? Fe2 O11 2.108(6) . ? Fe2 O6 2.110(7) . ? Fe3 O1 1.893(6) . ? Fe3 O2 1.995(6) . ? Fe3 O5 2.014(6) . ? Fe3 O3 2.015(6) . ? Fe3 O7 2.045(7) . ? Fe3 N1 2.248(8) . ? O2 C1 1.398(12) . ? O3 C4 1.426(12) . ? O3 Fe2 1.984(6) 2_665 ? O4 C6 1.393(14) . ? O5 C12 1.283(11) . ? O6 C12 1.262(12) . ? O7 C7 1.239(12) . ? O8 C7 1.302(12) . ? O9 C17 1.237(11) . ? O10 C17 1.274(12) . ? N1 C3 1.476(12) . ? N1 C2 1.490(12) . ? N1 C5 1.508(13) . ? C1 C2 1.493(15) . ? C3 C4 1.520(12) . ? C5 C6 1.511(15) . ? C7 C8 1.500(14) . ? C8 C9 1.501(17) . ? C8 C10 1.533(16) . ? C8 C11 1.556(17) . ? C12 C13 1.521(14) . ? C13 C15 1.496(15) . ? C13 C16 1.510(16) . ? C13 C14 1.524(15) . ? C17 C18 1.537(15) . ? C18 C20 1.491(15) . ? C18 C19 1.495(17) . ? C18 C21 1.523(17) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Fe1 O1 90.0(3) . 3_565 ? O1 Fe1 O1 90.0(3) . 2_665 ? O1 Fe1 O1 90.0(3) 3_565 2_665 ? O1 Fe1 O2 102.7(3) . 3_565 ? O1 Fe1 O2 78.0(2) 3_565 3_565 ? O1 Fe1 O2 162.4(3) 2_665 3_565 ? O1 Fe1 O2 78.0(2) . . ? O1 Fe1 O2 162.4(3) 3_565 . ? O1 Fe1 O2 102.7(3) 2_665 . ? O2 Fe1 O2 92.0(2) 3_565 . ? O1 Fe1 O2 162.4(3) . 2_665 ? O1 Fe1 O2 102.7(3) 3_565 2_665 ? O1 Fe1 O2 78.0(2) 2_665 2_665 ? O2 Fe1 O2 92.0(2) 3_565 2_665 ? O2 Fe1 O2 92.0(2) . 2_665 ? O1 Fe2 O3 95.3(3) . 3_565 ? O1 Fe2 O8 97.7(3) . . ? O3 Fe2 O8 90.9(3) 3_565 . ? O1 Fe2 O9 174.5(3) . . ? O3 Fe2 O9 88.8(3) 3_565 . ? O8 Fe2 O9 85.8(2) . . ? O1 Fe2 O11 91.3(3) . . ? O3 Fe2 O11 96.3(3) 3_565 . ? O8 Fe2 O11 168.0(3) . . ? O9 Fe2 O11 84.7(3) . . ? O1 Fe2 O6 91.3(3) . . ? O3 Fe2 O6 173.4(3) 3_565 . ? O8 Fe2 O6 88.1(3) . . ? O9 Fe2 O6 84.6(3) . . ? O11 Fe2 O6 83.7(3) . . ? O1 Fe3 O2 80.9(3) . . ? O1 Fe3 O5 101.5(3) . . ? O2 Fe3 O5 175.4(3) . . ? O1 Fe3 O3 96.7(3) . . ? O2 Fe3 O3 95.8(3) . . ? O5 Fe3 O3 87.9(3) . . ? O1 Fe3 O7 97.7(3) . . ? O2 Fe3 O7 91.1(3) . . ? O5 Fe3 O7 84.7(3) . . ? O3 Fe3 O7 164.8(3) . . ? O1 Fe3 N1 160.1(3) . . ? O2 Fe3 N1 79.9(3) . . ? O5 Fe3 N1 98.1(3) . . ? O3 Fe3 N1 80.5(3) . . ? O7 Fe3 N1 87.5(3) . . ? Fe2 O1 Fe3 118.8(3) . . ? Fe2 O1 Fe1 134.7(3) . . ? Fe3 O1 Fe1 100.0(3) . . ? C1 O2 Fe3 117.2(6) . . ? C1 O2 Fe1 138.2(6) . . ? Fe3 O2 Fe1 96.6(3) . . ? C4 O3 Fe2 121.1(6) . 2_665 ? C4 O3 Fe3 110.1(5) . . ? Fe2 O3 Fe3 128.4(3) 2_665 . ? C12 O5 Fe3 128.2(6) . . ? C12 O6 Fe2 131.0(6) . . ? C7 O7 Fe3 127.0(6) . . ? C7 O8 Fe2 134.9(6) . . ? C17 O9 Fe2 137.6(7) . . ? C3 N1 C2 112.1(8) . . ? C3 N1 C5 112.3(8) . . ? C2 N1 C5 112.0(8) . . ? C3 N1 Fe3 105.8(5) . . ? C2 N1 Fe3 102.5(5) . . ? C5 N1 Fe3 111.6(6) . . ? O2 C1 C2 109.6(8) . . ? N1 C2 C1 109.9(8) . . ? N1 C3 C4 109.8(7) . . ? O3 C4 C3 108.1(8) . . ? N1 C5 C6 116.9(9) . . ? O4 C6 C5 112.5(9) . . ? O7 C7 O8 123.5(9) . . ? O7 C7 C8 121.0(10) . . ? O8 C7 C8 115.5(9) . . ? C7 C8 C9 109.5(10) . . ? C7 C8 C10 113.5(10) . . ? C9 C8 C10 108.9(11) . . ? C7 C8 C11 105.9(9) . . ? C9 C8 C11 111.1(13) . . ? C10 C8 C11 107.9(10) . . ? O6 C12 O5 122.9(8) . . ? O6 C12 C13 119.8(9) . . ? O5 C12 C13 117.3(9) . . ? C15 C13 C16 110.7(10) . . ? C15 C13 C12 111.2(9) . . ? C16 C13 C12 109.4(9) . . ? C15 C13 C14 109.8(9) . . ? C16 C13 C14 110.0(10) . . ? C12 C13 C14 105.8(9) . . ? O9 C17 O10 123.8(10) . . ? O9 C17 C18 115.9(9) . . ? O10 C17 C18 120.3(9) . . ? C20 C18 C19 110.0(11) . . ? C20 C18 C21 109.2(11) . . ? C19 C18 C21 110.4(12) . . ? C20 C18 C17 105.9(9) . . ? C19 C18 C17 109.1(9) . . ? C21 C18 C17 112.2(10) . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O4 H4 O10 0.84 2.42 2.843(11) 112.3 4_454 _diffrn_measured_fraction_theta_max 0.992 _diffrn_reflns_theta_full 25.05 _diffrn_measured_fraction_theta_full 0.992 _refine_diff_density_max 0.660 _refine_diff_density_min -0.466 _refine_diff_density_rms 0.097