Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2002 data_global _journal_coden_Cambridge 1145 _publ_requested_journal 'Journal of Materials Chemistry' loop_ _publ_author_name 'Rojo, T.' 'Arriortua, M. Isabel' 'Larranaga, Aitor' 'Mesa, Jose L.' 'Olazcuaga, R.' 'Pizarro, Jose L.' _publ_contact_author_name 'Prof T Rojo' _publ_contact_author_address ; Departamento Quimica Inorganica Facultad de Ciencias Universidad del Pais Vasco Apdo 644 Bilbao E-48080 SPAIN ; _publ_contact_author_email 'QIPROAPT@LG.EHU.ES' _publ_section_title ; Hydrothermal synthesis, crystal structure, spectroscopic and magnetic properties of the Mn4(SeO3)4.3H2O and Mn3(SeO3)3.H2O compounds ; data_tocho _database_code_CSD 181273 _audit_creation_method SHELXL-97 _chemical_formula_sum 'H2 Mn3 O10 Se3' _chemical_formula_weight 563.72 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' 'Mn' 'Mn' 0.3368 0.7283 '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' 'Se' 'Se' -0.0929 2.2259 '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 8.266(3) _cell_length_b 8.350(3) _cell_length_c 9.008(3) _cell_angle_alpha 65.24(3) _cell_angle_beta 68.82(4) _cell_angle_gamma 67.77(4) _cell_volume 507.2(3) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _exptl_crystal_density_diffrn 3.691 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 518 _exptl_absorpt_coefficient_mu 14.478 _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_reflns_number 3221 _diffrn_reflns_av_R_equivalents 0.0247 _diffrn_reflns_av_sigmaI/netI 0.0387 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 2.57 _diffrn_reflns_theta_max 24.71 _reflns_number_total 1620 _reflns_number_gt 1344 _reflns_threshold_expression >2sigma(I) _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0277P)^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 SHELXL _refine_ls_extinction_coef 0.0821(18) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 1620 _refine_ls_number_parameters 156 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0313 _refine_ls_R_factor_gt 0.0222 _refine_ls_wR_factor_ref 0.0491 _refine_ls_wR_factor_gt 0.0472 _refine_ls_goodness_of_fit_ref 0.969 _refine_ls_restrained_S_all 0.969 _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 Se1 Se 0.21245(7) 0.57159(7) 0.21898(6) 0.00745(15) Uani 1 1 d . . . Se2 Se 0.33340(7) 0.83502(7) 0.69038(6) 0.00737(15) Uani 1 1 d . . . Se3 Se -0.33754(7) 0.78072(7) 1.09999(6) 0.00759(15) Uani 1 1 d . . . Mn1 Mn 0.03631(11) 0.65868(10) 0.79791(9) 0.0082(2) Uani 1 1 d . . . Mn2 Mn 0.5000 0.5000 0.5000 0.0065(2) Uani 1 2 d S . . Mn3 Mn 0.0000 1.0000 1.0000 0.0080(3) Uani 1 2 d S . . Mn4 Mn 0.17163(11) 0.30098(10) 0.58209(10) 0.0101(2) Uani 1 1 d . . . O1 O 0.3185(5) 0.4960(5) 0.3733(5) 0.0141(8) Uani 1 1 d . . . O2 O 0.0585(5) 0.4440(5) 0.3333(5) 0.0127(8) Uani 1 1 d . . . O3 O 0.0683(5) 0.7738(5) 0.2355(4) 0.0114(8) Uani 1 1 d . . . O4 O 0.2951(5) 0.7050(5) 0.6093(4) 0.0110(8) Uani 1 1 d . . . O5 O 0.1488(5) 0.8181(5) 0.8560(4) 0.0106(8) Uani 1 1 d . . . O6 O 0.2717(5) 1.0460(5) 0.5540(4) 0.0129(8) Uani 1 1 d . . . O7 O -0.1574(5) 0.6136(5) 1.0408(5) 0.0151(8) Uani 1 1 d . . . O8 O -0.3598(5) 0.6936(5) 1.3125(4) 0.0132(8) Uani 1 1 d . . . O9 O -0.2529(5) 0.9516(5) 1.0532(5) 0.0186(9) Uani 1 1 d . . . O10 O -0.1540(7) 0.9252(5) 0.7022(6) 0.0263(10) Uani 1 1 d D . . H1 H -0.109(12) 1.019(9) 0.691(11) 0.066(19) Uiso 1 1 d D . . H2 H -0.192(12) 0.974(11) 0.602(7) 0.066(19) Uiso 1 1 d 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 Se1 0.0061(3) 0.0079(3) 0.0059(3) -0.0017(2) -0.0004(2) -0.0009(2) Se2 0.0065(3) 0.0057(3) 0.0091(3) -0.0027(2) -0.0008(2) -0.0015(2) Se3 0.0064(3) 0.0073(3) 0.0079(3) -0.0013(2) -0.0022(2) -0.0016(2) Mn1 0.0100(4) 0.0085(4) 0.0067(4) -0.0025(4) -0.0007(3) -0.0044(3) Mn2 0.0057(6) 0.0065(5) 0.0064(6) -0.0028(5) 0.0022(4) -0.0033(4) Mn3 0.0111(6) 0.0053(5) 0.0048(6) -0.0017(5) 0.0006(4) -0.0014(5) Mn4 0.0083(4) 0.0079(4) 0.0132(5) -0.0035(4) 0.0002(3) -0.0037(3) O1 0.014(2) 0.0160(19) 0.015(2) -0.0017(18) -0.0095(16) -0.0052(17) O2 0.015(2) 0.0135(19) 0.012(2) -0.0034(18) -0.0048(15) -0.0061(17) O3 0.011(2) 0.0042(17) 0.010(2) 0.0005(16) -0.0010(15) 0.0016(15) O4 0.0112(19) 0.0100(17) 0.013(2) -0.0090(17) 0.0007(15) -0.0020(15) O5 0.0110(19) 0.0118(18) 0.0076(19) -0.0053(17) 0.0038(14) -0.0049(16) O6 0.019(2) 0.0058(17) 0.010(2) -0.0003(17) -0.0037(16) -0.0020(16) O7 0.018(2) 0.0069(17) 0.011(2) -0.0041(17) 0.0054(16) -0.0008(16) O8 0.017(2) 0.0130(19) 0.008(2) -0.0001(17) 0.0001(15) -0.0083(16) O9 0.017(2) 0.0122(19) 0.023(2) -0.0060(19) 0.0031(17) -0.0082(17) O10 0.043(3) 0.012(2) 0.027(3) -0.002(2) -0.026(2) 0.001(2) _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 Se1 O1 1.682(4) . ? Se1 O3 1.689(3) . ? Se1 O2 1.724(4) . ? Se2 O6 1.683(4) . ? Se2 O4 1.704(3) . ? Se2 O5 1.708(4) . ? Se2 Mn1 2.9933(15) . ? Se3 O9 1.656(4) . ? Se3 O8 1.705(4) . ? Se3 O7 1.711(3) . ? Mn1 O7 2.174(4) . ? Mn1 O2 2.185(3) 2_566 ? Mn1 O5 2.187(3) . ? Mn1 O7 2.201(4) 2_567 ? Mn1 O10 2.212(4) . ? Mn1 O4 2.250(4) . ? Mn2 O8 2.127(4) 1_654 ? Mn2 O8 2.127(4) 2_567 ? Mn2 O4 2.186(3) . ? Mn2 O4 2.186(3) 2_666 ? Mn2 O1 2.205(3) . ? Mn2 O1 2.205(3) 2_666 ? Mn3 O9 2.125(4) 2_577 ? Mn3 O9 2.125(4) . ? Mn3 O5 2.141(3) 2_577 ? Mn3 O5 2.141(3) . ? Mn3 O3 2.256(4) 1_556 ? Mn3 O3 2.256(4) 2_576 ? Mn4 O6 2.061(3) 1_545 ? Mn4 O8 2.116(4) 2_567 ? Mn4 O3 2.178(4) 2_566 ? Mn4 O1 2.223(4) . ? Mn4 O2 2.398(4) . ? Mn4 O2 2.445(4) 2_566 ? O2 Mn1 2.185(3) 2_566 ? O2 Mn4 2.445(4) 2_566 ? O3 Mn4 2.178(4) 2_566 ? O3 Mn3 2.256(4) 1_554 ? O6 Mn4 2.061(3) 1_565 ? O7 Mn1 2.201(4) 2_567 ? O8 Mn4 2.116(4) 2_567 ? O8 Mn2 2.127(4) 1_456 ? O10 H1 0.94(2) . ? O10 H2 0.94(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 O1 Se1 O3 103.58(17) . . ? O1 Se1 O2 95.27(18) . . ? O3 Se1 O2 96.13(17) . . ? O6 Se2 O4 101.27(17) . . ? O6 Se2 O5 104.46(19) . . ? O4 Se2 O5 94.21(16) . . ? O6 Se2 Mn1 107.33(14) . . ? O4 Se2 Mn1 48.18(12) . . ? O5 Se2 Mn1 46.08(11) . . ? O9 Se3 O8 99.81(18) . . ? O9 Se3 O7 104.81(19) . . ? O8 Se3 O7 99.55(18) . . ? O7 Mn1 O2 101.07(14) . 2_566 ? O7 Mn1 O5 92.57(13) . . ? O2 Mn1 O5 163.35(14) 2_566 . ? O7 Mn1 O7 74.17(15) . 2_567 ? O2 Mn1 O7 95.22(14) 2_566 2_567 ? O5 Mn1 O7 97.66(14) . 2_567 ? O7 Mn1 O10 88.79(17) . . ? O2 Mn1 O10 86.23(14) 2_566 . ? O5 Mn1 O10 84.56(15) . . ? O7 Mn1 O10 162.87(16) 2_567 . ? O7 Mn1 O4 157.86(14) . . ? O2 Mn1 O4 99.63(13) 2_566 . ? O5 Mn1 O4 68.56(12) . . ? O7 Mn1 O4 96.25(15) 2_567 . ? O10 Mn1 O4 100.34(17) . . ? O7 Mn1 Se2 126.20(10) . . ? O2 Mn1 Se2 132.66(11) 2_566 . ? O5 Mn1 Se2 34.22(9) . . ? O7 Mn1 Se2 99.57(11) 2_567 . ? O10 Mn1 Se2 91.81(13) . . ? O4 Mn1 Se2 34.37(8) . . ? O8 Mn2 O8 180.0 1_654 2_567 ? O8 Mn2 O4 92.99(14) 1_654 . ? O8 Mn2 O4 87.01(14) 2_567 . ? O8 Mn2 O4 87.01(14) 1_654 2_666 ? O8 Mn2 O4 92.99(14) 2_567 2_666 ? O4 Mn2 O4 180.0 . 2_666 ? O8 Mn2 O1 103.67(14) 1_654 . ? O8 Mn2 O1 76.32(14) 2_567 . ? O4 Mn2 O1 93.05(14) . . ? O4 Mn2 O1 86.95(14) 2_666 . ? O8 Mn2 O1 76.32(14) 1_654 2_666 ? O8 Mn2 O1 103.68(14) 2_567 2_666 ? O4 Mn2 O1 86.95(14) . 2_666 ? O4 Mn2 O1 93.05(14) 2_666 2_666 ? O1 Mn2 O1 179.999(2) . 2_666 ? O9 Mn3 O9 179.999(1) 2_577 . ? O9 Mn3 O5 95.79(14) 2_577 2_577 ? O9 Mn3 O5 84.21(14) . 2_577 ? O9 Mn3 O5 84.21(14) 2_577 . ? O9 Mn3 O5 95.79(14) . . ? O5 Mn3 O5 180.0 2_577 . ? O9 Mn3 O3 87.19(15) 2_577 1_556 ? O9 Mn3 O3 92.81(15) . 1_556 ? O5 Mn3 O3 89.57(13) 2_577 1_556 ? O5 Mn3 O3 90.43(13) . 1_556 ? O9 Mn3 O3 92.81(15) 2_577 2_576 ? O9 Mn3 O3 87.19(15) . 2_576 ? O5 Mn3 O3 90.43(13) 2_577 2_576 ? O5 Mn3 O3 89.56(13) . 2_576 ? O3 Mn3 O3 179.999(2) 1_556 2_576 ? O6 Mn4 O8 103.23(15) 1_545 2_567 ? O6 Mn4 O3 90.66(14) 1_545 2_566 ? O8 Mn4 O3 114.72(14) 2_567 2_566 ? O6 Mn4 O1 110.75(15) 1_545 . ? O8 Mn4 O1 76.14(14) 2_567 . ? O3 Mn4 O1 153.71(14) 2_566 . ? O6 Mn4 O2 93.88(13) 1_545 . ? O8 Mn4 O2 141.82(14) 2_567 . ? O3 Mn4 O2 98.70(14) 2_566 . ? O1 Mn4 O2 65.87(13) . . ? O6 Mn4 O2 156.00(14) 1_545 2_566 ? O8 Mn4 O2 93.12(13) 2_567 2_566 ? O3 Mn4 O2 66.33(13) 2_566 2_566 ? O1 Mn4 O2 90.00(13) . 2_566 ? O2 Mn4 O2 83.47(12) . 2_566 ? Se1 O1 Mn2 155.2(2) . . ? Se1 O1 Mn4 103.43(18) . . ? Mn2 O1 Mn4 100.61(15) . . ? Se1 O2 Mn1 119.09(18) . 2_566 ? Se1 O2 Mn4 95.42(15) . . ? Mn1 O2 Mn4 132.71(16) 2_566 . ? Se1 O2 Mn4 92.71(14) . 2_566 ? Mn1 O2 Mn4 111.76(16) 2_566 2_566 ? Mn4 O2 Mn4 96.52(12) . 2_566 ? Se1 O3 Mn4 103.80(17) . 2_566 ? Se1 O3 Mn3 118.78(17) . 1_554 ? Mn4 O3 Mn3 111.37(16) 2_566 1_554 ? Se2 O4 Mn2 125.95(19) . . ? Se2 O4 Mn1 97.45(15) . . ? Mn2 O4 Mn1 124.06(16) . . ? Se2 O5 Mn3 128.60(19) . . ? Se2 O5 Mn1 99.70(14) . . ? Mn3 O5 Mn1 125.67(17) . . ? Se2 O6 Mn4 131.77(19) . 1_565 ? Se3 O7 Mn1 124.4(2) . . ? Se3 O7 Mn1 128.2(2) . 2_567 ? Mn1 O7 Mn1 105.83(15) . 2_567 ? Se3 O8 Mn4 120.4(2) . 2_567 ? Se3 O8 Mn2 129.94(18) . 1_456 ? Mn4 O8 Mn2 106.81(16) 2_567 1_456 ? Se3 O9 Mn3 139.6(2) . . ? Mn1 O10 H1 108(6) . . ? Mn1 O10 H2 129(5) . . ? H1 O10 H2 101(8) . . ? _diffrn_measured_fraction_theta_max 0.935 _diffrn_reflns_theta_full 24.71 _diffrn_measured_fraction_theta_full 0.935 _refine_diff_density_max 0.581 _refine_diff_density_min -0.812 _refine_diff_density_rms 0.152 data_mnt2pnab _database_code_CSD 181274 _audit_creation_date 2002-06-13T15:45:34-00:00 _audit_creation_method 'WinGX routine CIF_UPDATE' _audit_conform_dict_name cif_core.dic _audit_conform_dict_version 2.1 _audit_conform_dict_location ftp://ftp.iucr.org/cifdics/cif_core.dic _publ_requested_category FI #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'H6 Mn4 O15 Se4' _chemical_formula_structural 'H6 MN4 O15 SE4' _chemical_formula_sum 'H6 Mn4 O15 Se4' _chemical_formula_weight 781.65 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21' _symmetry_space_group_name_Hall 'P 2yb' _symmetry_Int_Tables_number 4 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 9.181(2) _cell_length_b 8.602(3) _cell_length_c 9.852(4) _cell_angle_alpha 90 _cell_angle_beta 116.63(2) _cell_angle_gamma 90 _cell_volume 695.5(4) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 6 _cell_measurement_theta_max 13 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description acicular _exptl_crystal_colour 'pale pink' _exptl_crystal_size_max 0.4 _exptl_crystal_size_mid 0.07 _exptl_crystal_size_min 0.02 _exptl_crystal_density_meas 3.6 _exptl_crystal_density_diffrn 3.732 _exptl_crystal_density_method 'Picnometry' _exptl_crystal_F_000 724 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 14.093 _exptl_absorpt_factor_muR 1.126 _exptl_absorpt_correction_type psi-scan _exptl_absorpt_process_details ; North A.C.T., Phillips D.C. & Mathews F.S. (1968) Acta. Cryst. A24, 351 Number of psi-scan sets used was 8 Theta correction was applied. Weighted transmission curves were used. No Fourier smoothing was applied. ; _exptl_absorpt_correction_T_min 0.1927 _exptl_absorpt_correction_T_max 0.3206 _exptl_absorpt_correction_T_ave 0.2615 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_source 'Enraf Nonius FR590' _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.7107 _diffrn_radiation_type MoK\a _diffrn_radiation_monochromator graphite _diffrn_radiation_probe x-ray _diffrn_detector 'scintillation LiI' _diffrn_detector_dtime 1.195 _diffrn_orient_matrix_type ; x-axis points to radiation source the matrix is specified in reciprocal space ; _diffrn_orient_matrix_ub_11 0.98039E-1 _diffrn_orient_matrix_ub_12 0.5158E-2 _diffrn_orient_matrix_ub_13 0.8459E-2 _diffrn_orient_matrix_ub_21 0.19951E-1 _diffrn_orient_matrix_ub_22 -0.5749E-2 _diffrn_orient_matrix_ub_23 -0.29692E-1 _diffrn_orient_matrix_ub_31 -0.3369E-2 _diffrn_orient_matrix_ub_32 0.116068 _diffrn_orient_matrix_ub_33 -0.1846E-2 _diffrn_measurement_device '\k-geometry diffractometer' _diffrn_measurement_device_type 'Enraf Nonius CAD4' _diffrn_measurement_method 'non-profiled omega/2theta scans' _diffrn_standards_number 2 _diffrn_standards_interval_count 94 _diffrn_standards_interval_time 60 _diffrn_standards_decay_% 0 _diffrn_standards_decay_corr_max 1 _diffrn_standards_decay_corr_min 1 loop_ _diffrn_standard_refln_index_h _diffrn_standard_refln_index_k _diffrn_standard_refln_index_l 0 2 -8 2 2 -4 _diffrn_reflns_number 1334 _diffrn_reflns_av_R_equivalents 0.0444 _diffrn_reflns_av_unetI/netI 0.083 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 5 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 0 _diffrn_reflns_limit_l_min -5 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 2.31 _diffrn_reflns_theta_max 24.98 _diffrn_reflns_theta_full 24.98 _diffrn_measured_fraction_theta_full 0.986 _diffrn_measured_fraction_theta_max 0.986 _reflns_number_total 1290 _reflns_number_gt 1204 _reflns_threshold_expression >2sigma(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'CAD4 Express (Enraf Nonius, 1994)' _computing_cell_refinement 'CAD4 Express (Enraf Nonius, 1994)' _computing_data_reduction 'XCAD4 (Harms & Wocadlo, 1995)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _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^)+(0.0857P)^2^+11.9607P] 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_number_reflns 1290 _refine_ls_number_parameters 133 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0597 _refine_ls_R_factor_gt 0.0563 _refine_ls_wR_factor_ref 0.1562 _refine_ls_wR_factor_gt 0.152 _refine_ls_goodness_of_fit_ref 1.06 _refine_ls_restrained_S_all 1.06 _refine_ls_shift/su_max 0 _refine_ls_shift/su_mean 0 _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.16(4) _refine_diff_density_max 2.065 _refine_diff_density_min -1.55 _refine_diff_density_rms 0.39 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# 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 0.006 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Se Se -0.0929 2.2259 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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 Se1 Se 0.2424(2) 0.3287(3) 0.66976(18) 0.0077(4) Uani 1 1 d . . . Se2 Se 0.3632(2) 0.3311(3) 1.33762(19) 0.0092(4) Uani 1 1 d . . . Se3 Se 0.3343(2) 0.8290(3) 0.76844(18) 0.0070(4) Uani 1 1 d . . . Se4 Se 0.0349(2) 0.7010(3) 1.0064(2) 0.0088(5) Uani 1 1 d . . . Mn1 Mn 0.3186(4) 0.5187(4) 1.0079(4) 0.0083(7) Uani 1 1 d . . . Mn2 Mn 0.3239(4) 0.1302(4) 0.9928(4) 0.0097(7) Uani 1 1 d . . . Mn3 Mn 0.0353(4) 0.5288(4) 1.3404(4) 0.0092(7) Uani 1 1 d . . . Mn4 Mn 0.0183(4) 0.1317(4) 1.3486(4) 0.0101(7) Uani 1 1 d . . . O1 O 0.2677(15) 0.330(2) 0.8526(14) 0.013(3) Uiso 1 1 d . . . O2 O 0.3133(15) 0.309(2) 1.1477(14) 0.011(3) Uiso 1 1 d . . . O3 O 0.2404(16) 0.6794(18) 1.1325(15) 0.011(3) Uiso 1 1 d . . . O4 O 0.0440(18) 0.5640(18) 0.8831(18) 0.009(3) Uiso 1 1 d . . . O5 O 0.4103(17) 0.692(2) 0.9112(15) 0.013(3) Uiso 1 1 d . . . O6 O 0.4097(17) 0.9926(17) 0.8640(15) 0.009(3) Uiso 1 1 d . . . O7 O -0.056(2) 0.595(2) 1.0996(19) 0.017(4) Uiso 1 1 d . . . O8 O 0.1844(15) 0.314(2) 1.3434(13) 0.009(3) Uiso 1 1 d . . . O9 O 0.0837(18) 0.193(2) 0.5897(16) 0.017(3) Uiso 1 1 d . . . O10 O -0.1367(15) 0.336(2) 1.2644(13) 0.011(3) Uiso 1 1 d . . . O11 O 0.1431(17) 0.4930(17) 0.5991(15) 0.007(3) Uiso 1 1 d . . . O12 O 0.4401(17) 0.1454(18) 1.4040(16) 0.012(3) Uiso 1 1 d . . . O13W O 0.3909(19) -0.043(2) 1.1658(17) 0.019(3) Uiso 1 1 d . . . O14W O 0.2503(16) 0.6706(17) 1.3946(15) 0.011(3) Uiso 1 1 d . . . O15W O 0.225(2) -0.021(2) 1.4509(18) 0.021(4) 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 Se1 0.0078(8) 0.0054(8) 0.0105(8) -0.0008(10) 0.0046(7) -0.0002(10) Se2 0.0071(8) 0.0091(9) 0.0122(9) -0.0010(10) 0.0051(7) 0.0011(10) Se3 0.0068(8) 0.0046(8) 0.0101(8) -0.0008(9) 0.0043(7) 0.0003(9) Se4 0.0084(9) 0.0079(9) 0.0128(9) 0.0019(8) 0.0072(7) 0.0026(8) Mn1 0.0067(16) 0.0056(17) 0.0119(16) 0.0016(13) 0.0035(13) 0.0016(13) Mn2 0.0093(16) 0.0071(17) 0.0143(16) 0.0019(14) 0.0067(13) 0.0001(12) Mn3 0.0111(16) 0.0049(15) 0.0124(17) -0.0006(14) 0.0059(13) 0.0007(12) Mn4 0.0098(16) 0.0084(16) 0.0114(16) 0.0004(14) 0.0040(13) 0.0008(13) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _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 Se1 O11 1.656(14) . ? Se1 O1 1.710(13) . ? Se1 O9 1.754(16) . ? Se2 O8 1.674(12) . ? Se2 O2 1.726(12) . ? Se2 O12 1.751(15) . ? Se3 O6 1.662(15) . ? Se3 O10 1.696(13) 2_557 ? Se3 O5 1.724(15) . ? Se4 O4 1.721(16) . ? Se4 O3 1.742(13) . ? Se4 O7 1.751(17) . ? Se4 Mn1 3.034(4) . ? Mn1 O1 2.131(18) . ? Mn1 O5 2.135(16) . ? Mn1 O3 2.173(15) . ? Mn1 O6 2.246(14) 2_647 ? Mn1 O4 2.289(15) . ? Mn1 O2 2.285(16) . ? Mn2 O6 2.128(14) 1_545 ? Mn2 O13W 2.136(17) . ? Mn2 O1 2.122(19) . ? Mn2 O2 2.199(15) . ? Mn2 O7 2.227(17) 2_547 ? Mn2 O5 2.250(15) 2_647 ? Mn3 O9 2.083(17) 2_557 ? Mn3 O14W 2.174(15) . ? Mn3 O10 2.176(17) . ? Mn3 O7 2.206(17) . ? Mn3 O8 2.295(17) . ? Mn3 O11 2.305(13) 1_556 ? Mn4 O11 2.137(15) 2_547 ? Mn4 O15W 2.150(17) . ? Mn4 O4 2.170(16) 2_547 ? Mn4 O10 2.180(17) . ? Mn4 O8 2.201(16) . ? Mn4 O9 2.237(15) 1_556 ? O4 Mn4 2.170(16) 2_557 ? O5 Mn2 2.250(15) 2_657 ? O6 Mn2 2.128(14) 1_565 ? O6 Mn1 2.246(14) 2_657 ? O7 Mn2 2.227(17) 2_557 ? O9 Mn3 2.083(17) 2_547 ? O9 Mn4 2.237(15) 1_554 ? O10 Se3 1.696(13) 2_547 ? O11 Mn4 2.137(14) 2_557 ? O11 Mn3 2.305(13) 1_554 ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O11 Se1 O1 103.0(8) . . ? O11 Se1 O9 100.9(8) . . ? O1 Se1 O9 99.9(8) . . ? O8 Se2 O2 103.8(6) . . ? O8 Se2 O12 98.2(8) . . ? O2 Se2 O12 99.8(7) . . ? O6 Se3 O10 102.4(8) . 2_557 ? O6 Se3 O5 101.7(8) . . ? O10 Se3 O5 100.9(7) 2_557 . ? O4 Se4 O3 92.9(7) . . ? O4 Se4 O7 101.4(8) . . ? O3 Se4 O7 100.9(7) . . ? O4 Se4 Mn1 48.4(5) . . ? O3 Se4 Mn1 44.7(5) . . ? O7 Se4 Mn1 109.8(6) . . ? O1 Mn1 O5 102.4(6) . . ? O1 Mn1 O3 150.1(5) . . ? O5 Mn1 O3 96.0(6) . . ? O1 Mn1 O6 99.1(5) . 2_647 ? O5 Mn1 O6 76.1(5) . 2_647 ? O3 Mn1 O6 108.1(5) . 2_647 ? O1 Mn1 O4 84.8(5) . . ? O5 Mn1 O4 101.6(6) . . ? O3 Mn1 O4 68.4(5) . . ? O6 Mn1 O4 175.8(6) 2_647 . ? O1 Mn1 O2 77.0(6) . . ? O5 Mn1 O2 160.1(5) . . ? O3 Mn1 O2 93.5(6) . . ? O6 Mn1 O2 84.3(5) 2_647 . ? O4 Mn1 O2 98.2(5) . . ? O1 Mn1 Se4 118.5(4) . . ? O5 Mn1 Se4 98.4(4) . . ? O3 Mn1 Se4 34.3(3) . . ? O6 Mn1 Se4 142.1(4) 2_647 . ? O4 Mn1 Se4 34.2(4) . . ? O2 Mn1 Se4 99.3(4) . . ? O6 Mn2 O13W 92.1(6) 1_545 . ? O6 Mn2 O1 96.3(6) 1_545 . ? O13W Mn2 O1 170.0(7) . . ? O6 Mn2 O2 161.1(6) 1_545 . ? O13W Mn2 O2 91.2(6) . . ? O1 Mn2 O2 79.1(6) . . ? O6 Mn2 O7 108.4(6) 1_545 2_547 ? O13W Mn2 O7 95.8(6) . 2_547 ? O1 Mn2 O7 86.7(6) . 2_547 ? O2 Mn2 O7 89.7(6) . 2_547 ? O6 Mn2 O5 76.2(5) 1_545 2_647 ? O13W Mn2 O5 87.7(6) . 2_647 ? O1 Mn2 O5 89.0(6) . 2_647 ? O2 Mn2 O5 85.4(5) . 2_647 ? O7 Mn2 O5 174.1(6) 2_547 2_647 ? O9 Mn3 O14W 95.2(6) 2_557 . ? O9 Mn3 O10 102.9(6) 2_557 . ? O14W Mn3 O10 161.9(6) . . ? O9 Mn3 O7 100.2(6) 2_557 . ? O14W Mn3 O7 89.2(6) . . ? O10 Mn3 O7 87.6(6) . . ? O9 Mn3 O8 160.3(6) 2_557 . ? O14W Mn3 O8 88.8(5) . . ? O10 Mn3 O8 74.2(6) . . ? O7 Mn3 O8 99.1(5) . . ? O9 Mn3 O11 75.7(5) 2_557 1_556 ? O14W Mn3 O11 84.9(5) . 1_556 ? O10 Mn3 O11 99.5(5) . 1_556 ? O7 Mn3 O11 172.5(6) . 1_556 ? O8 Mn3 O11 85.4(5) . 1_556 ? O11 Mn4 O15W 96.2(6) 2_547 . ? O11 Mn4 O4 102.7(6) 2_547 2_547 ? O15W Mn4 O4 95.2(6) . 2_547 ? O11 Mn4 O10 97.9(5) 2_547 . ? O15W Mn4 O10 163.6(6) . . ? O4 Mn4 O10 89.8(5) 2_547 . ? O11 Mn4 O8 164.7(5) 2_547 . ? O15W Mn4 O8 88.3(6) . . ? O4 Mn4 O8 91.4(5) 2_547 . ? O10 Mn4 O8 76.0(6) . . ? O11 Mn4 O9 76.2(5) 2_547 1_556 ? O15W Mn4 O9 83.5(6) . 1_556 ? O4 Mn4 O9 178.1(7) 2_547 1_556 ? O10 Mn4 O9 91.8(6) . 1_556 ? O8 Mn4 O9 89.9(5) . 1_556 ? Se1 O1 Mn2 123.9(11) . . ? Se1 O1 Mn1 130.2(11) . . ? Mn2 O1 Mn1 103.8(5) . . ? Se2 O2 Mn2 139.2(9) . . ? Se2 O2 Mn1 119.9(8) . . ? Mn2 O2 Mn1 96.6(5) . . ? Se4 O3 Mn1 101.0(6) . . ? Se4 O4 Mn4 119.0(8) . 2_557 ? Se4 O4 Mn1 97.3(7) . . ? Mn4 O4 Mn1 108.5(6) 2_557 . ? Se3 O5 Mn1 138.1(8) . . ? Se3 O5 Mn2 118.1(7) . 2_657 ? Mn1 O5 Mn2 102.6(6) . 2_657 ? Se3 O6 Mn2 129.6(8) . 1_565 ? Se3 O6 Mn1 118.6(7) . 2_657 ? Mn2 O6 Mn1 102.9(6) 1_565 2_657 ? Se4 O7 Mn3 131.1(9) . . ? Se4 O7 Mn2 114.4(8) . 2_557 ? Mn3 O7 Mn2 107.0(7) . 2_557 ? Se2 O8 Mn4 139.9(10) . . ? Se2 O8 Mn3 121.0(9) . . ? Mn4 O8 Mn3 99.1(5) . . ? Se1 O9 Mn3 139.1(8) . 2_547 ? Se1 O9 Mn4 114.1(8) . 1_554 ? Mn3 O9 Mn4 105.1(7) 2_547 1_554 ? Se3 O10 Mn3 130.1(10) 2_547 . ? Se3 O10 Mn4 120.1(9) 2_547 . ? Mn3 O10 Mn4 103.6(5) . . ? Se1 O11 Mn4 133.3(8) . 2_557 ? Se1 O11 Mn3 117.5(7) . 1_554 ? Mn4 O11 Mn3 101.0(6) 2_557 1_554 ?