Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2005 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Prof A.K.Powell' _publ_contact_author_address ; Inst fuer Anorganische Chemie Universitaet Karlsruhe Engesserstrasse Geb. 30.45 Karlsruhe D76128 GERMANY ; _publ_contact_author_email powell@chemie.uni-karlsruhe.de _publ_contact_author_phone '+44 721 608 2135' _publ_section_title ; Crystal structure and magnetic properties of a pseudo cubic close-packed array of oxalate-linked {FeII6(\m3-OH)6}6+ clusters ; loop_ _publ_author_name _publ_author_address 'Bao-Li Fei.' ; Institut fur Anorganische Chemie Universitat Karlsruhe Engesserstr. Geb. 30.45 D-76128 Karlsruhe Germany ; 'Rodolphe Clerac' ; Centre de Recherche Paul Pascal CNRS UPR 8641 Avenur Dr. A. Schweitzer 33600 Pessac France ; 'Christopher E. Anson' ; Institut fur Anorganische Chemie Universitat Karlsruhe Engesserstr. Geb. 30.45 D-76128 Karlsruhe Germany ; 'Annie K. Powell' ; Institut fur Anorganische Chemie Universitat Karlsruhe Engesserstr. Geb. 30.45 D-76128 Karlsruhe Germany ; #======================================================================= data_3314-25r _database_code_depnum_ccdc_archive 'CCDC 244359' _audit_creation_method SHELXL-97 _chemical_name_systematic ; [Diaquo-hexaoxalato-tetrabarium(II)-hexakis(hexa-\m3-hydroxohexairon(II))] dibromide tetrahydrate ; _chemical_name_common ; (Diaquo-hexaoxalato-tetrabarium(ii)-hexakis(hexa-mu3- hydroxohexairon(ii))) dibromide tetrahydrate ; _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C12 H18 Ba4 Br2 Fe6 O36' _chemical_formula_weight 1782.54 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' 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' Ba Ba -0.3244 2.2819 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting trigonal _symmetry_space_group_name_H-M 'R -3 m' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'y, x, -z' 'x-y, -y, -z' '-x, -x+y, -z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'y+2/3, x+1/3, -z+1/3' 'x-y+2/3, -y+1/3, -z+1/3' '-x+2/3, -x+y+1/3, -z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' 'y+1/3, x+2/3, -z+2/3' 'x-y+1/3, -y+2/3, -z+2/3' '-x+1/3, -x+y+2/3, -z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-y, -x, z' '-x+y, y, z' 'x, x-y, z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-y+2/3, -x+1/3, z+1/3' '-x+y+2/3, y+1/3, z+1/3' 'x+2/3, x-y+1/3, z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' '-y+1/3, -x+2/3, z+2/3' '-x+y+1/3, y+2/3, z+2/3' 'x+1/3, x-y+2/3, z+2/3' _cell_length_a 11.1818(7) _cell_length_b 11.1818(7) _cell_length_c 27.412(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 2968.3(4) _cell_formula_units_Z 3 _cell_measurement_temperature 200(2) _cell_measurement_reflns_used 8000 _cell_measurement_theta_min 2.23 _cell_measurement_theta_max 25.73 _exptl_crystal_description block _exptl_crystal_colour yellow _exptl_crystal_size_max 0.13 _exptl_crystal_size_mid 0.09 _exptl_crystal_size_min 0.09 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.992 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2484 _exptl_absorpt_coefficient_mu 8.172 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.366 _exptl_absorpt_correction_T_max 0.479 _exptl_absorpt_process_details 'XPREP: SHELXTL 5.1 (Bruker AXS Inc., 1997)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 200(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Stoe IPDS' _diffrn_measurement_method 'area detector' _diffrn_detector_area_resol_mean 6.667 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6494 _diffrn_reflns_av_R_equivalents 0.0320 _diffrn_reflns_av_sigmaI/netI 0.0131 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -33 _diffrn_reflns_limit_l_max 33 _diffrn_reflns_theta_min 2.23 _diffrn_reflns_theta_max 25.94 _reflns_number_total 752 _reflns_number_gt 703 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'IPDS 2.92 (Stoe & Cie GmbH, 1999)' _computing_cell_refinement 'IPDS 2.92 (Stoe & Cie GmbH, 1999)' _computing_data_reduction 'IPDS 2.92 (Stoe & Cie GmbH, 1999)' _computing_structure_solution 'SHELXTL 5.1 (Bruker AXS Inc., 1997)' _computing_structure_refinement 'SHELXTL 5.1 (Bruker AXS Inc., 1997)' _computing_molecular_graphics 'SHELXTL 5.1 (Bruker AXS Inc., 1997)' _computing_publication_material 'SHELXTL 5.1 (Bruker AXS Inc., 1997)' _refine_special_details ; The oxalate "cage" centred at 2/3, 1/3, 1/3 contains two bromide counterions and four non-coordinated water molecules. Br(1) and O(11) thus have occupancies 33% and 67% respectively. Although separated by only ca. 1 \%A, Br(1) and O(11) could both be freely refined anisotropically, resulting in sensible hydrogen-bonding geometries. No attempt was made to locate the hydrogens on these disordered lattice waters. 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^)+(0.0652P)^2^+20.4818P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 752 _refine_ls_number_parameters 71 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0339 _refine_ls_R_factor_gt 0.0324 _refine_ls_wR_factor_ref 0.0865 _refine_ls_wR_factor_gt 0.0850 _refine_ls_goodness_of_fit_ref 1.061 _refine_ls_restrained_S_all 1.061 _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 Ba1 Ba 0.6667 0.3333 0.11406(2) 0.0164(2) Uani 1 6 d S . . Ba2 Ba 0.3333 0.6667 0.29062(2) 0.0177(2) Uani 1 6 d S . . Fe1 Fe 0.46077(4) 0.53923(4) 0.13493(3) 0.0153(2) Uani 1 2 d S . . O1 O 0.4287(2) 0.5713(2) 0.20701(14) 0.0164(8) Uani 1 2 d SD . . H1 H 0.461(4) 0.539(4) 0.225(3) 0.05(3) Uiso 1 2 d SD . . O2 O 0.4255(3) 0.3326(3) 0.14228(11) 0.0226(6) Uani 1 1 d . . . C1 C 0.3333 0.2366(5) 0.1667 0.0173(11) Uani 1 2 d S . . O3 O 0.4672(2) 0.5328(2) 0.05929(16) 0.0281(10) Uani 1 2 d S . . O4 O 0.5761(2) 0.4239(2) 0.03375(15) 0.0311(10) Uani 1 2 d S . . C2 C 0.5139(3) 0.4861(3) 0.02724(19) 0.0190(11) Uani 1 2 d S . . O5 O 0.6667 0.3333 0.2214(5) 0.081(4) Uani 1 6 d SD . . H5 H 0.627(6) 0.255(12) 0.237(7) 0.121 Uiso 0.67 2 d SPD . . Br1 Br 0.52729(12) 0.47271(12) 0.30788(10) 0.0421(6) Uani 0.33 2 d SP . . O11 O 0.5448(5) 0.4552(5) 0.2706(5) 0.069(3) Uani 0.67 2 d SP . . 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 Ba1 0.0157(3) 0.0157(3) 0.0177(4) 0.000 0.000 0.00786(13) Ba2 0.0180(3) 0.0180(3) 0.0171(3) 0.000 0.000 0.00898(13) Fe1 0.0159(3) 0.0159(3) 0.0144(4) -0.00040(15) 0.00040(15) 0.0082(3) O1 0.0147(13) 0.0147(13) 0.0165(18) 0.0019(8) -0.0019(8) 0.0050(16) O2 0.0213(14) 0.0172(14) 0.0297(14) 0.0045(12) 0.0051(13) 0.0099(11) C1 0.015(3) 0.016(2) 0.021(3) 0.0003(10) 0.001(2) 0.0076(13) O3 0.040(2) 0.040(2) 0.0161(19) -0.0015(9) 0.0015(9) 0.028(2) O4 0.049(2) 0.049(2) 0.0167(19) 0.0011(9) -0.0011(9) 0.040(3) C2 0.023(2) 0.023(2) 0.014(3) -0.0003(11) 0.0003(11) 0.013(2) O5 0.105(7) 0.105(7) 0.033(6) 0.000 0.000 0.052(4) Br1 0.0471(10) 0.0471(10) 0.0396(13) 0.0042(5) -0.0042(5) 0.0290(11) O11 0.067(6) 0.067(6) 0.091(9) 0.006(3) -0.006(3) 0.046(6) _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 Ba1 O2 2.802(3) 23_655 ? Ba1 O2 2.802(3) 2_655 ? Ba1 O2 2.802(3) 3_665 ? Ba1 O2 2.802(3) 24 ? Ba1 O2 2.802(3) 22_665 ? Ba1 O2 2.802(3) . ? Ba1 O4 2.815(4) 2_655 ? Ba1 O4 2.815(4) 3_665 ? Ba1 O4 2.815(4) . ? Ba1 O5 2.943(13) . ? Ba1 Ba2 4.2976(9) 13_544 ? Ba2 O3 2.632(4) 26_455 ? Ba2 O3 2.632(4) 27 ? Ba2 O3 2.632(4) 25_565 ? Ba2 O4 2.734(4) 9_565 ? Ba2 O4 2.734(4) 8 ? Ba2 O4 2.734(4) 7_455 ? Ba2 O1 2.943(4) 3_565 ? Ba2 O1 2.943(4) 2_665 ? Ba2 O1 2.943(4) . ? Fe1 O1 2.071(4) . ? Fe1 O3 2.077(4) . ? Fe1 O2 2.150(3) 22_665 ? Fe1 O2 2.150(3) . ? Fe1 O1 2.2361(13) 26_455 ? Fe1 O1 2.2361(13) 27 ? O1 Fe1 2.2361(13) 26_455 ? O1 Fe1 2.2361(13) 27 ? O1 H1 0.80(5) . ? O2 C1 1.247(4) . ? C1 O2 1.247(4) 12 ? C1 C1 1.565(10) 25 ? O3 C2 1.261(7) . ? O3 Ba2 2.632(4) 25_565 ? O4 C2 1.217(7) . ? O4 Ba2 2.734(4) 13_544 ? C2 C2 1.587(10) 19_665 ? O5 H5 0.86(5) . ? Br1 O11 1.077(14) . ? 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 Ba1 O2 57.18(11) 23_655 2_655 ? O2 Ba1 O2 57.71(11) 23_655 3_665 ? O2 Ba1 O2 112.68(6) 2_655 3_665 ? O2 Ba1 O2 112.68(6) 23_655 24 ? O2 Ba1 O2 57.71(11) 2_655 24 ? O2 Ba1 O2 147.94(13) 3_665 24 ? O2 Ba1 O2 112.68(6) 23_655 22_665 ? O2 Ba1 O2 147.94(13) 2_655 22_665 ? O2 Ba1 O2 57.18(11) 3_665 22_665 ? O2 Ba1 O2 112.68(6) 24 22_665 ? O2 Ba1 O2 147.94(13) 23_655 . ? O2 Ba1 O2 112.68(6) 2_655 . ? O2 Ba1 O2 112.68(6) 3_665 . ? O2 Ba1 O2 57.18(11) 24 . ? O2 Ba1 O2 57.71(11) 22_665 . ? O2 Ba1 O4 102.38(6) 23_655 2_655 ? O2 Ba1 O4 72.41(10) 2_655 2_655 ? O2 Ba1 O4 137.35(9) 3_665 2_655 ? O2 Ba1 O4 72.41(10) 24 2_655 ? O2 Ba1 O4 137.35(9) 22_665 2_655 ? O2 Ba1 O4 102.38(6) . 2_655 ? O2 Ba1 O4 72.41(10) 23_655 3_665 ? O2 Ba1 O4 102.38(6) 2_655 3_665 ? O2 Ba1 O4 72.41(10) 3_665 3_665 ? O2 Ba1 O4 137.35(9) 24 3_665 ? O2 Ba1 O4 102.38(6) 22_665 3_665 ? O2 Ba1 O4 137.35(9) . 3_665 ? O4 Ba1 O4 65.34(14) 2_655 3_665 ? O2 Ba1 O4 137.35(9) 23_655 . ? O2 Ba1 O4 137.35(9) 2_655 . ? O2 Ba1 O4 102.38(6) 3_665 . ? O2 Ba1 O4 102.38(6) 24 . ? O2 Ba1 O4 72.41(10) 22_665 . ? O2 Ba1 O4 72.41(10) . . ? O4 Ba1 O4 65.34(14) 2_655 . ? O4 Ba1 O4 65.34(14) 3_665 . ? O2 Ba1 O5 73.97(6) 23_655 . ? O2 Ba1 O5 73.97(6) 2_655 . ? O2 Ba1 O5 73.97(6) 3_665 . ? O2 Ba1 O5 73.97(6) 24 . ? O2 Ba1 O5 73.97(6) 22_665 . ? O2 Ba1 O5 73.97(6) . . ? O4 Ba1 O5 141.44(9) 2_655 . ? O4 Ba1 O5 141.44(9) 3_665 . ? O4 Ba1 O5 141.44(9) . . ? O3 Ba2 O3 117.08(5) 26_455 27 ? O3 Ba2 O3 117.08(6) 26_455 25_565 ? O3 Ba2 O3 117.08(6) 27 25_565 ? O3 Ba2 O4 116.65(8) 26_455 9_565 ? O3 Ba2 O4 60.00(13) 27 9_565 ? O3 Ba2 O4 116.65(8) 25_565 9_565 ? O3 Ba2 O4 60.00(13) 26_455 8 ? O3 Ba2 O4 116.65(8) 27 8 ? O3 Ba2 O4 116.65(8) 25_565 8 ? O4 Ba2 O4 67.56(14) 9_565 8 ? O3 Ba2 O4 116.65(8) 26_455 7_455 ? O3 Ba2 O4 116.65(8) 27 7_455 ? O3 Ba2 O4 60.00(13) 25_565 7_455 ? O4 Ba2 O4 67.55(14) 9_565 7_455 ? O4 Ba2 O4 67.55(14) 8 7_455 ? O3 Ba2 O1 63.68(8) 26_455 3_565 ? O3 Ba2 O1 118.92(12) 27 3_565 ? O3 Ba2 O1 63.68(8) 25_565 3_565 ? O4 Ba2 O1 178.92(12) 9_565 3_565 ? O4 Ba2 O1 113.31(10) 8 3_565 ? O4 Ba2 O1 113.31(10) 7_455 3_565 ? O3 Ba2 O1 118.92(12) 26_455 2_665 ? O3 Ba2 O1 63.68(8) 27 2_665 ? O3 Ba2 O1 63.68(8) 25_565 2_665 ? O4 Ba2 O1 113.31(10) 9_565 2_665 ? O4 Ba2 O1 178.92(12) 8 2_665 ? O4 Ba2 O1 113.31(10) 7_455 2_665 ? O1 Ba2 O1 65.83(12) 3_565 2_665 ? O3 Ba2 O1 63.68(8) 26_455 . ? O3 Ba2 O1 63.68(8) 27 . ? O3 Ba2 O1 118.92(12) 25_565 . ? O4 Ba2 O1 113.31(10) 9_565 . ? O4 Ba2 O1 113.31(10) 8 . ? O4 Ba2 O1 178.92(12) 7_455 . ? O1 Ba2 O1 65.83(12) 3_565 . ? O1 Ba2 O1 65.83(12) 2_665 . ? O1 Fe1 O3 165.97(16) . . ? O1 Fe1 O2 98.17(12) . 22_665 ? O3 Fe1 O2 92.72(13) . 22_665 ? O1 Fe1 O2 98.17(12) . . ? O3 Fe1 O2 92.72(13) . . ? O2 Fe1 O2 77.95(16) 22_665 . ? O1 Fe1 O1 83.88(15) . 26_455 ? O3 Fe1 O1 86.33(13) . 26_455 ? O2 Fe1 O1 173.19(13) 22_665 26_455 ? O2 Fe1 O1 95.35(12) . 26_455 ? O1 Fe1 O1 83.88(15) . 27 ? O3 Fe1 O1 86.33(13) . 27 ? O2 Fe1 O1 95.35(12) 22_665 27 ? O2 Fe1 O1 173.19(13) . 27 ? O1 Fe1 O1 91.3(2) 26_455 27 ? Fe1 O1 Fe1 88.94(10) . 26_455 ? Fe1 O1 Fe1 88.94(10) . 27 ? Fe1 O1 Fe1 145.85(19) 26_455 27 ? Fe1 O1 Ba2 158.60(18) . . ? Fe1 O1 Ba2 84.85(10) 26_455 . ? Fe1 O1 Ba2 84.85(10) 27 . ? Fe1 O1 H1 111(7) . . ? Fe1 O1 H1 106.3(6) 26_455 . ? Fe1 O1 H1 106.3(6) 27 . ? Ba2 O1 H1 90(7) . . ? C1 O2 Fe1 127.1(3) . . ? C1 O2 Ba1 122.0(3) . . ? Fe1 O2 Ba1 108.18(10) . . ? O2 C1 O2 126.8(5) . 12 ? O2 C1 C1 116.6(2) . 25 ? O2 C1 C1 116.6(2) 12 25 ? C2 O3 Fe1 137.6(4) . . ? C2 O3 Ba2 125.9(4) . 25_565 ? Fe1 O3 Ba2 96.51(16) . 25_565 ? C2 O4 Ba2 121.5(4) . 13_544 ? C2 O4 Ba1 137.0(4) . . ? Ba2 O4 Ba1 101.50(14) 13_544 . ? O4 C2 O3 127.4(5) . . ? O4 C2 C2 118.3(6) . 19_665 ? O3 C2 C2 114.3(6) . 19_665 ? Ba1 O5 H5 119(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 O1 H1 Br1 0.80(5) 2.60(6) 3.360(4) 158(9) . O1 H1 O11 0.80(5) 2.04(5) 2.845(12) 179(9) . O5 H5 Br1 0.86(5) 2.76(8) 3.592(9) 163(19) 2_655 O5 H5 O11 0.86(5) 1.85(5) 2.717(14) 178(19) 2_655 _diffrn_measured_fraction_theta_max 0.989 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.988 _refine_diff_density_max 1.332 _refine_diff_density_min -0.699 _refine_diff_density_rms 0.171 #======================================================================= data_3324-29 _database_code_depnum_ccdc_archive 'CCDC 265043' _audit_creation_method SHELXL-97 _chemical_name_systematic ; [Diaquo-hexaoxalato-tetrabarium(II)-hexakis(hexa-\m3-hydroxohexairon(II))] diiodide tetrahydrate ; _chemical_name_common ; (Diaquo-hexaoxalato-tetrabarium(ii)-hexakis(hexa-mu3- hydroxohexairon(ii))) diiodide tetrahydrate ; _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C12 H18 Ba4 Fe6 I2 O36' _chemical_formula_weight 1876.52 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' 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' Ba Ba -0.3244 2.2819 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' I I -0.4742 1.8119 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting trigonal _symmetry_space_group_name_H-M 'R -3 m' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'y, x, -z' 'x-y, -y, -z' '-x, -x+y, -z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'y+2/3, x+1/3, -z+1/3' 'x-y+2/3, -y+1/3, -z+1/3' '-x+2/3, -x+y+1/3, -z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' 'y+1/3, x+2/3, -z+2/3' 'x-y+1/3, -y+2/3, -z+2/3' '-x+1/3, -x+y+2/3, -z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-y, -x, z' '-x+y, y, z' 'x, x-y, z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-y+2/3, -x+1/3, z+1/3' '-x+y+2/3, y+1/3, z+1/3' 'x+2/3, x-y+1/3, z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' '-y+1/3, -x+2/3, z+2/3' '-x+y+1/3, y+2/3, z+2/3' 'x+1/3, x-y+2/3, z+2/3' _cell_length_a 11.1999(12) _cell_length_b 11.1999(12) _cell_length_c 27.428(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 2979.6(6) _cell_formula_units_Z 3 _cell_measurement_temperature 200(2) _cell_measurement_reflns_used 8000 _cell_measurement_theta_min 2.31 _cell_measurement_theta_max 25.21 _exptl_crystal_description block _exptl_crystal_colour yellow _exptl_crystal_size_max 0.27 _exptl_crystal_size_mid 0.13 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 3.137 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2592 _exptl_absorpt_coefficient_mu 7.684 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.370 _exptl_absorpt_correction_T_max 0.742 _exptl_absorpt_process_details 'SHELXTL 5.1 (Bruker AXS Inc., 1997)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 200(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Stoe IPDS' _diffrn_measurement_method 'area detector' _diffrn_detector_area_resol_mean 6.667 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 4722 _diffrn_reflns_av_R_equivalents 0.1476 _diffrn_reflns_av_sigmaI/netI 0.0656 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -33 _diffrn_reflns_limit_l_max 33 _diffrn_reflns_theta_min 2.23 _diffrn_reflns_theta_max 25.79 _reflns_number_total 752 _reflns_number_gt 668 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'IPDS 2.92 (Stoe & Cie GmbH, 1999)' _computing_cell_refinement 'IPDS 2.92 (Stoe & Cie GmbH, 1999)' _computing_data_reduction 'IPDS 2.92 (Stoe & Cie GmbH, 1999)' _computing_structure_solution 'SHELXTL 5.1 (Bruker AXS Inc., 1997)' _computing_structure_refinement 'SHELXTL 5.1 (Bruker AXS Inc., 1997)' _computing_molecular_graphics 'SHELXTL 5.1 (Bruker AXS Inc., 1997)' _computing_publication_material 'SHELXTL 5.1 (Bruker AXS Inc., 1997)' _refine_special_details ; The oxalate "cage" centred at 2/3, 1/3, 1/3 contains two iodide counterions and four non-coordinated water molecules. I(1) and O(11) thus have occupancies 33% and 67% respectively. Although separated by only ca. 1 \%A, I(1) and O(11) could both be freely refined anisotropically, resulting in sensible hydrogen-bonding geometries. No attempt was made to locate the hydrogens on these disordered lattice waters. 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^)+(0.1350P)^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 752 _refine_ls_number_parameters 71 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0669 _refine_ls_R_factor_gt 0.0642 _refine_ls_wR_factor_ref 0.1642 _refine_ls_wR_factor_gt 0.1607 _refine_ls_goodness_of_fit_ref 1.029 _refine_ls_restrained_S_all 1.028 _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 Ba1 Ba 0.6667 0.3333 0.11278(3) 0.0233(4) Uani 1 6 d S . . Ba2 Ba 0.3333 0.6667 0.29079(3) 0.0246(4) Uani 1 6 d S . . Fe1 Fe 0.46051(7) 0.53949(7) 0.13444(5) 0.0225(5) Uani 1 2 d S . . O1 O 0.4282(3) 0.5718(3) 0.2065(2) 0.0247(14) Uani 1 2 d SD . . H1 H 0.459(7) 0.541(7) 0.229(5) 0.08(6) Uiso 1 2 d SD . . O2 O 0.4240(5) 0.3322(5) 0.14168(18) 0.0278(10) Uani 1 1 d . . . C1 C 0.3333 0.2362(8) 0.1667 0.0259(19) Uani 1 2 d S . . O3 O 0.4678(4) 0.5322(4) 0.0595(3) 0.0345(16) Uani 1 2 d S . . O4 O 0.5760(4) 0.4240(4) 0.0332(3) 0.0358(16) Uani 1 2 d S . . C2 C 0.5144(5) 0.4856(5) 0.0273(3) 0.028(2) Uani 1 2 d S . . O5 O 0.6667 0.3333 0.2159(6) 0.064(5) Uani 1 6 d SD . . H5 H 0.641(11) 0.28(2) 0.241(6) 0.095 Uiso 0.67 2 d SPD . . I1 I 0.53696(14) 0.46304(14) 0.30851(11) 0.0558(8) Uani 0.33 2 d SP . . O11 O 0.5422(11) 0.4578(11) 0.2725(9) 0.090(6) Uani 0.67 2 d SP . . 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 Ba1 0.0208(5) 0.0208(5) 0.0284(7) 0.000 0.000 0.0104(2) Ba2 0.0225(5) 0.0225(5) 0.0289(6) 0.000 0.000 0.0112(2) Fe1 0.0204(6) 0.0204(6) 0.0267(8) -0.0001(3) 0.0001(3) 0.0103(5) O1 0.023(2) 0.023(2) 0.029(3) 0.0011(12) -0.0011(12) 0.012(3) O2 0.024(2) 0.021(2) 0.040(2) 0.0036(19) 0.005(2) 0.0131(17) C1 0.019(4) 0.023(4) 0.035(5) 0.0018(18) 0.004(4) 0.010(2) O3 0.043(3) 0.043(3) 0.028(3) -0.0005(14) 0.0005(14) 0.030(4) O4 0.045(3) 0.045(3) 0.032(4) 0.0022(14) -0.0022(14) 0.034(4) C2 0.024(3) 0.024(3) 0.032(5) 0.000(2) 0.000(2) 0.009(4) O5 0.080(8) 0.080(8) 0.031(7) 0.000 0.000 0.040(4) I1 0.0678(14) 0.0678(14) 0.0458(15) 0.0052(6) -0.0052(6) 0.0445(14) O11 0.090(11) 0.090(11) 0.105(15) 0.017(6) -0.017(6) 0.056(12) _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 Ba1 O4 2.802(7) 2_655 ? Ba1 O4 2.802(7) 3_665 ? Ba1 O4 2.802(7) . ? Ba1 O2 2.825(5) 2_655 ? Ba1 O2 2.825(5) 23_655 ? Ba1 O2 2.825(5) 3_665 ? Ba1 O2 2.825(5) 24 ? Ba1 O2 2.825(5) 22_665 ? Ba1 O2 2.825(5) . ? Ba1 O5 2.828(16) . ? Ba1 Ba2 4.2603(13) 13_544 ? Ba2 O3 2.650(7) 26_455 ? Ba2 O3 2.650(7) 27 ? Ba2 O3 2.650(7) 25_565 ? Ba2 O4 2.723(7) 9_565 ? Ba2 O4 2.723(7) 8 ? Ba2 O4 2.723(7) 7_455 ? Ba2 O1 2.954(6) 3_565 ? Ba2 O1 2.954(6) 2_665 ? Ba2 O1 2.954(6) . ? Ba2 Fe1 3.5269(16) 25_565 ? Ba2 Fe1 3.5269(16) 26_455 ? Ba2 Fe1 3.5269(16) 27 ? Fe1 O3 2.060(7) . ? Fe1 O1 2.074(6) . ? Fe1 O2 2.155(5) 22_665 ? Fe1 O2 2.155(5) . ? Fe1 O1 2.231(2) 26_455 ? Fe1 O1 2.231(2) 27 ? Fe1 Ba2 3.5269(16) 25_565 ? O1 Fe1 2.231(2) 26_455 ? O1 Fe1 2.231(2) 27 ? O1 H1 0.86(5) . ? O2 C1 1.251(6) . ? C1 O2 1.251(6) 12 ? C1 C1 1.558(17) 25 ? O3 C2 1.264(12) . ? O3 Ba2 2.650(7) 25_565 ? O4 C2 1.207(12) . ? O4 Ba2 2.723(7) 13_544 ? C2 C2 1.596(19) 19_665 ? O5 H5 0.85(5) . ? I1 O11 0.99(2) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O4 Ba1 O4 65.8(2) 2_655 3_665 ? O4 Ba1 O4 65.8(2) 2_655 . ? O4 Ba1 O4 65.8(2) 3_665 . ? O4 Ba1 O2 72.42(17) 2_655 2_655 ? O4 Ba1 O2 102.48(10) 3_665 2_655 ? O4 Ba1 O2 137.84(14) . 2_655 ? O4 Ba1 O2 102.48(10) 2_655 23_655 ? O4 Ba1 O2 72.42(17) 3_665 23_655 ? O4 Ba1 O2 137.84(14) . 23_655 ? O2 Ba1 O2 56.93(18) 2_655 23_655 ? O4 Ba1 O2 137.84(14) 2_655 3_665 ? O4 Ba1 O2 72.42(17) 3_665 3_665 ? O4 Ba1 O2 102.48(10) . 3_665 ? O2 Ba1 O2 112.45(9) 2_655 3_665 ? O2 Ba1 O2 57.79(18) 23_655 3_665 ? O4 Ba1 O2 72.42(17) 2_655 24 ? O4 Ba1 O2 137.84(14) 3_665 24 ? O4 Ba1 O2 102.48(10) . 24 ? O2 Ba1 O2 57.79(18) 2_655 24 ? O2 Ba1 O2 112.45(9) 23_655 24 ? O2 Ba1 O2 147.4(2) 3_665 24 ? O4 Ba1 O2 137.84(13) 2_655 22_665 ? O4 Ba1 O2 102.48(10) 3_665 22_665 ? O4 Ba1 O2 72.42(17) . 22_665 ? O2 Ba1 O2 147.4(2) 2_655 22_665 ? O2 Ba1 O2 112.45(9) 23_655 22_665 ? O2 Ba1 O2 56.93(18) 3_665 22_665 ? O2 Ba1 O2 112.45(9) 24 22_665 ? O4 Ba1 O2 102.48(10) 2_655 . ? O4 Ba1 O2 137.84(13) 3_665 . ? O4 Ba1 O2 72.42(17) . . ? O2 Ba1 O2 112.45(9) 2_655 . ? O2 Ba1 O2 147.4(2) 23_655 . ? O2 Ba1 O2 112.45(9) 3_665 . ? O2 Ba1 O2 56.93(18) 24 . ? O2 Ba1 O2 57.79(18) 22_665 . ? O4 Ba1 O5 141.13(15) 2_655 . ? O4 Ba1 O5 141.13(15) 3_665 . ? O4 Ba1 O5 141.13(15) . . ? O2 Ba1 O5 73.71(10) 2_655 . ? O2 Ba1 O5 73.71(10) 23_655 . ? O2 Ba1 O5 73.71(10) 3_665 . ? O2 Ba1 O5 73.71(10) 24 . ? O2 Ba1 O5 73.71(10) 22_665 . ? O2 Ba1 O5 73.71(10) . . ? O3 Ba2 O3 116.99(9) 26_455 27 ? O3 Ba2 O3 116.98(9) 26_455 25_565 ? O3 Ba2 O3 116.98(9) 27 25_565 ? O3 Ba2 O4 116.87(13) 26_455 9_565 ? O3 Ba2 O4 59.9(2) 27 9_565 ? O3 Ba2 O4 116.87(13) 25_565 9_565 ? O3 Ba2 O4 59.9(2) 26_455 8 ? O3 Ba2 O4 116.87(13) 27 8 ? O3 Ba2 O4 116.87(13) 25_565 8 ? O4 Ba2 O4 68.0(2) 9_565 8 ? O3 Ba2 O4 116.87(13) 26_455 7_455 ? O3 Ba2 O4 116.87(13) 27 7_455 ? O3 Ba2 O4 59.9(2) 25_565 7_455 ? O4 Ba2 O4 68.0(2) 9_565 7_455 ? O4 Ba2 O4 68.0(2) 8 7_455 ? O3 Ba2 O1 63.65(13) 26_455 3_565 ? O3 Ba2 O1 118.4(2) 27 3_565 ? O3 Ba2 O1 63.65(13) 25_565 3_565 ? O4 Ba2 O1 178.28(19) 9_565 3_565 ? O4 Ba2 O1 113.34(15) 8 3_565 ? O4 Ba2 O1 113.34(15) 7_455 3_565 ? O3 Ba2 O1 118.4(2) 26_455 2_665 ? O3 Ba2 O1 63.65(13) 27 2_665 ? O3 Ba2 O1 63.65(13) 25_565 2_665 ? O4 Ba2 O1 113.34(15) 9_565 2_665 ? O4 Ba2 O1 178.28(19) 8 2_665 ? O4 Ba2 O1 113.34(15) 7_455 2_665 ? O1 Ba2 O1 65.3(2) 3_565 2_665 ? O3 Ba2 O1 63.65(13) 26_455 . ? O3 Ba2 O1 63.65(13) 27 . ? O3 Ba2 O1 118.4(2) 25_565 . ? O4 Ba2 O1 113.34(15) 9_565 . ? O4 Ba2 O1 113.34(15) 8 . ? O4 Ba2 O1 178.28(19) 7_455 . ? O1 Ba2 O1 65.3(2) 3_565 . ? O1 Ba2 O1 65.3(2) 2_665 . ? O3 Fe1 O1 166.3(3) . . ? O3 Fe1 O2 92.2(2) . 22_665 ? O1 Fe1 O2 98.31(18) . 22_665 ? O3 Fe1 O2 92.2(2) . . ? O1 Fe1 O2 98.31(18) . . ? O2 Fe1 O2 78.6(2) 22_665 . ? O3 Fe1 O1 87.4(2) . 26_455 ? O1 Fe1 O1 83.1(2) . 26_455 ? O2 Fe1 O1 173.7(2) 22_665 26_455 ? O2 Fe1 O1 95.12(19) . 26_455 ? O3 Fe1 O1 87.4(2) . 27 ? O1 Fe1 O1 83.1(2) . 27 ? O2 Fe1 O1 95.12(19) 22_665 27 ? O2 Fe1 O1 173.7(2) . 27 ? O1 Fe1 O1 91.2(3) 26_455 27 ? Fe1 O1 Fe1 89.59(17) . 26_455 ? Fe1 O1 Fe1 89.59(17) . 27 ? Fe1 O1 Fe1 146.6(3) 26_455 27 ? Fe1 O1 Ba2 159.1(3) . . ? Fe1 O1 Ba2 84.50(16) 26_455 . ? Fe1 O1 Ba2 84.50(16) 27 . ? Fe1 O1 H1 119(10) . . ? Fe1 O1 H1 104.8(17) 26_455 . ? Fe1 O1 H1 104.8(17) 27 . ? Ba2 O1 H1 82(10) . . ? C1 O2 Fe1 127.7(4) . . ? C1 O2 Ba1 121.5(4) . . ? Fe1 O2 Ba1 107.78(17) . . ? O2 C1 O2 126.1(8) . 12 ? O2 C1 C1 117.0(4) . 25 ? O2 C1 C1 117.0(4) 12 25 ? C2 O3 Fe1 138.3(6) . . ? C2 O3 Ba2 125.5(6) . 25_565 ? Fe1 O3 Ba2 96.2(3) . 25_565 ? C2 O4 Ba2 122.4(6) . 13_544 ? C2 O4 Ba1 136.7(6) . . ? Ba2 O4 Ba1 100.9(2) 13_544 . ? O4 C2 O3 127.8(9) . . ? O4 C2 C2 118.2(11) . 19_665 ? O3 C2 C2 113.9(10) . 19_665 ? Ba1 O5 H5 144(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 O1 H1 I1 0.86(5) 2.65(6) 3.504(7) 172(16) . O1 H1 O11 0.86(5) 2.01(7) 2.86(2) 170(17) . O5 H5 I1 0.85(5) 2.74(8) 3.576(12) 168(19) 2_655 O5 H5 O11 0.85(5) 2.11(14) 2.87(3) 150(19) 2_655 _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 4.013 _refine_diff_density_min -1.215 _refine_diff_density_rms 0.398