Supplementary Material (ESI) for J. Mater. Chem. This journal is (C) The Royal Society of Chemistry 2002 data_global # 1. SUBMISSION DETAILS _publ_contact_autor ; C. Ruiz-Valero Instituto de Ciencia de Materiales CSIC Campus de Cantoblanco 28049 MADRID Spain ; _publ_contact_author_phone '34 1 334-9026' _publ_contact_author_fax '34 1 372-0623' _publ_contact_author_email crvalero@icmm.csic.es _publ_requested_journal 'Journal of Materials Chemistry.' _journal_coden_Cambridge 1145 _publ_requested_coeditor_name ? #========================================================================== # 3. TITLE AND AUTHOR LIST _publ_section_title 'New Catalitycally Active Neodymium Sulfate' loop_ _publ_author_name _publ_author_address 'Caridad Ruiz-Valero' ? 'Enrique Gutierrez-Puebla' ; Instituto de Ciencia de Materiales CSIC Campus de Cantoblanco 28049 MADRID Spain ; 'Berta Gomez-Lor' ; Instituto de Ciencia de Materiales CSIC Campus de Cantoblanco 28049 MADRID Spain ; 'M. Angeles Monge' ; Instituto de Ciencia de Materiales CSIC Campus de Cantoblanco 28049 MADRID Spain ; 'Concepcion Cascales' ; Instituto de Ciencia de Materiales CSIC Campus de Cantoblanco 28049 MADRID Spain. ; 'Marta Iglesias' ; Instituto de Ciencia de Materiales CSIC Campus de Cantoblanco 28049 MADRID Spain ; 'Natalia Snejko' ; Instituto de Ciencia de Materiales CSIC Campus de Cantoblanco 28049 MADRID Spain ; #=========================================================================== # 4. TEXT _publ_section_abstract ; Abstract: Two novel isotypic rare earth sulfates, R(SO4)2.NH4 (R = Nd, Eu), have been synthesized hydrothermally at 170 o C for 5 days. The crystal structure of these compounds have been established by single crystal X-ray diffraction in the monoclinic space group P21/c with a = 8.867(1), b = 7.187(1), c = 10.804(2) A, B= 91.653(3)o, Z = 4, for Nd(SO4)2.NH4. The structure can be conceived as formed by parallel layers [R(SO4)2]- , in which a honey comb (6, 3) layer of [RO9] sharing edges polyhedra is bonded to different isolated SO4 tetrahedra. Inside the inter-block space a row of NH4+ ions are hosted, which connect the layers through hydrogen bonds. The magnetic measurements, and catalytic studies of the Nd(SO4)2.NH4 in alkenes hydrogenation, and selective oxidation of organic sulfides are reported. This material shows a good activity and selectivity, and can be reused at least four cycles without significant loss in the catalytic activity. ; _publ_section_comment ; ; _publ_section_experimental ; ; _publ_section_references ; ; _publ_section_figure_captions ; ; _publ_section_acknowledgements ? data_snd _database_code_CSD 186877 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ' Neodymium sulfate amonium' _chemical_melting_point ? _chemical_formula_moiety ' Nd S2 O8 N H4' _chemical_formula_sum 'H4 N Nd O8 S2' _chemical_formula_weight 354.40 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source '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' 'S' 'S' 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Nd' 'Nd' -0.1943 3.0179 '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' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P21/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 8.8667(14) _cell_length_b 7.1872(11) _cell_length_c 10.8038(17) _cell_angle_alpha 90.00 _cell_angle_beta 91.653(3) _cell_angle_gamma 90.00 _cell_volume 688.20(19) _cell_formula_units_Z 4 _cell_measurement_temperature 143(2) _cell_measurement_reflns_used 75 _cell_measurement_theta_min 3.40 _cell_measurement_theta_max 25.48 _exptl_crystal_description prismatic _exptl_crystal_colour colorless _exptl_crystal_size_max 0.1 _exptl_crystal_size_mid 0.1 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 3.420 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 668 _exptl_absorpt_coefficient_mu 8.164 _exptl_absorpt_correction_type Sadabs _exptl_absorpt_correction_T_min 0.008 _exptl_absorpt_correction_T_max 0.035 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 143(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 ? _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_% none _diffrn_reflns_number 1819 _diffrn_reflns_av_R_equivalents 0.0829 _diffrn_reflns_av_sigmaI/netI 0.1186 _diffrn_reflns_limit_h_min -2 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 6 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 3.40 _diffrn_reflns_theta_max 26.58 _reflns_number_total 1064 _reflns_number_gt 767 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker Smart' _computing_cell_refinement 'Bruker Smart' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXL-97 (Sheldrick, 1997)' _computing_publication_material '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^)+(0.0788P)^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 1064 _refine_ls_number_parameters 122 _refine_ls_number_restraints 10 _refine_ls_R_factor_all 0.0865 _refine_ls_R_factor_gt 0.0658 _refine_ls_wR_factor_ref 0.1618 _refine_ls_wR_factor_gt 0.1536 _refine_ls_goodness_of_fit_ref 0.965 _refine_ls_restrained_S_all 0.960 _refine_ls_shift/su_max 0.416 _refine_ls_shift/su_mean 0.035 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 Nd1 Nd 0.94647(9) 0.17116(15) 0.65079(8) 0.0169(4) Uani 1 1 d . . . S1 S 0.7335(4) 0.1630(7) 0.4126(4) 0.0173(10) Uani 1 1 d . . . S2 S 1.1762(4) 0.1687(8) 0.8869(4) 0.0194(10) Uani 1 1 d . . . O1 O 0.6106(12) 0.044(2) 0.3755(10) 0.025(3) Uani 1 1 d . . . O2 O 0.7097(12) 0.256(2) 0.5321(11) 0.021(3) Uani 1 1 d . . . O3 O 0.8728(13) 0.0527(19) 0.4396(10) 0.022(3) Uani 1 1 d . . . O4 O 0.7663(13) 0.3028(19) 0.3168(12) 0.025(3) Uani 1 1 d . . . O5 O 1.1148(13) 0.178(2) 1.0115(11) 0.023(3) Uani 1 1 d . . . O6 O 1.1270(12) 0.3397(18) 0.8132(10) 0.020(3) Uani 1 1 d . . . O7 O 1.1004(12) 0.014(2) 0.8191(10) 0.022(3) Uani 1 1 d . . . O8 O 1.3362(13) 0.149(2) 0.8903(12) 0.028(3) Uani 1 1 d . . . N1 N 0.4346(16) 0.353(3) 0.6559(14) 0.034(5) Uani 1 1 d D . . H11 H 0.451(15) 0.304(18) 0.735(9) 0.050 Uiso 1 1 d D . . H12 H 0.502(14) 0.450(16) 0.644(13) 0.050 Uiso 1 1 d D . . H14 H 0.337(11) 0.40(2) 0.649(12) 0.050 Uiso 1 1 d D . . H13 H 0.449(16) 0.261(16) 0.598(11) 0.050 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 Nd1 0.0216(5) 0.0119(7) 0.0174(6) -0.0005(5) 0.0030(3) 0.0005(5) S1 0.023(2) 0.014(3) 0.016(2) 0.002(2) 0.0026(14) 0.002(2) S2 0.021(2) 0.018(3) 0.019(2) -0.004(2) 0.0031(15) -0.002(2) O1 0.023(6) 0.024(10) 0.028(7) -0.007(7) 0.005(5) -0.004(6) O2 0.019(6) 0.017(9) 0.028(7) -0.002(6) 0.002(5) -0.002(5) O3 0.035(7) 0.019(10) 0.013(6) -0.007(6) 0.000(5) 0.010(6) O4 0.023(6) 0.010(9) 0.043(8) 0.005(7) 0.002(5) 0.007(5) O5 0.026(6) 0.021(9) 0.023(7) 0.000(6) 0.004(5) 0.009(6) O6 0.033(7) 0.005(9) 0.020(6) 0.002(6) 0.002(5) 0.004(6) O7 0.021(6) 0.029(10) 0.017(6) 0.004(7) 0.001(4) 0.007(6) O8 0.027(6) 0.019(10) 0.037(8) 0.005(7) 0.000(5) 0.004(6) N1 0.032(9) 0.029(13) 0.040(10) 0.000(9) 0.004(7) -0.004(8) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Nd1 O5 2.409(12) 4_565 ? Nd1 O4 2.444(12) 4_566 ? Nd1 O3 2.490(12) 3_756 ? Nd1 O2 2.503(11) . ? Nd1 O3 2.504(11) . ? Nd1 O6 2.503(13) 2_746 ? Nd1 O7 2.510(11) . ? Nd1 O7 2.520(15) 2_756 ? Nd1 O6 2.636(11) . ? Nd1 S1 3.148(4) . ? Nd1 S2 3.219(4) . ? S1 O1 1.434(13) . ? S1 O2 1.473(13) . ? S1 O4 1.477(14) . ? S1 O3 1.489(12) . ? S2 O8 1.425(12) . ? S2 O5 1.467(12) . ? S2 O7 1.484(14) . ? S2 O6 1.522(13) . ? O3 Nd1 2.490(12) 3_756 ? O4 Nd1 2.444(12) 4_565 ? O5 Nd1 2.409(12) 4_566 ? O6 Nd1 2.503(13) 2_756 ? O7 Nd1 2.520(15) 2_746 ? N1 H11 0.93(9) . ? N1 H12 0.93(9) . ? N1 H14 0.92(9) . ? N1 H13 0.92(9) . ? 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 O5 Nd1 O4 148.6(5) 4_565 4_566 ? O5 Nd1 O3 68.2(5) 4_565 3_756 ? O4 Nd1 O3 141.2(4) 4_566 3_756 ? O5 Nd1 O2 95.5(4) 4_565 . ? O4 Nd1 O2 78.5(4) 4_566 . ? O3 Nd1 O2 119.7(4) 3_756 . ? O5 Nd1 O3 74.6(4) 4_565 . ? O4 Nd1 O3 122.4(4) 4_566 . ? O3 Nd1 O3 65.0(4) 3_756 . ? O2 Nd1 O3 54.7(4) . . ? O5 Nd1 O6 134.1(4) 4_565 2_746 ? O4 Nd1 O6 77.3(4) 4_566 2_746 ? O3 Nd1 O6 67.6(4) 3_756 2_746 ? O2 Nd1 O6 95.3(4) . 2_746 ? O3 Nd1 O6 75.9(4) . 2_746 ? O5 Nd1 O7 108.8(4) 4_565 . ? O4 Nd1 O7 81.7(4) 4_566 . ? O3 Nd1 O7 69.6(4) 3_756 . ? O2 Nd1 O7 155.6(4) . . ? O3 Nd1 O7 129.0(4) . . ? O6 Nd1 O7 66.2(4) 2_746 . ? O5 Nd1 O7 75.4(4) 4_565 2_756 ? O4 Nd1 O7 73.5(4) 4_566 2_756 ? O3 Nd1 O7 142.4(4) 3_756 2_756 ? O2 Nd1 O7 72.0(4) . 2_756 ? O3 Nd1 O7 114.2(4) . 2_756 ? O6 Nd1 O7 149.9(4) 2_746 2_756 ? O7 Nd1 O7 115.8(3) . 2_756 ? O5 Nd1 O6 80.4(4) 4_565 . ? O4 Nd1 O6 82.7(4) 4_566 . ? O3 Nd1 O6 100.0(4) 3_756 . ? O2 Nd1 O6 135.6(4) . . ? O3 Nd1 O6 154.2(4) . . ? O6 Nd1 O6 119.3(3) 2_746 . ? O7 Nd1 O6 54.4(4) . . ? O7 Nd1 O6 64.1(4) 2_756 . ? O5 Nd1 S1 82.3(3) 4_565 . ? O4 Nd1 S1 102.2(3) 4_566 . ? O3 Nd1 S1 92.6(3) 3_756 . ? O2 Nd1 S1 27.3(3) . . ? O3 Nd1 S1 27.7(3) . . ? O6 Nd1 S1 87.5(3) 2_746 . ? O7 Nd1 S1 152.2(3) . . ? O7 Nd1 S1 91.5(2) 2_756 . ? O6 Nd1 S1 153.0(3) . . ? O5 Nd1 S2 96.2(3) 4_565 . ? O4 Nd1 S2 80.3(3) 4_566 . ? O3 Nd1 S2 84.7(3) 3_756 . ? O2 Nd1 S2 155.5(3) . . ? O3 Nd1 S2 149.6(3) . . ? O6 Nd1 S2 91.9(3) 2_746 . ? O7 Nd1 S2 26.5(3) . . ? O7 Nd1 S2 90.3(3) 2_756 . ? O6 Nd1 S2 27.9(3) . . ? S1 Nd1 S2 177.24(11) . . ? O1 S1 O2 112.8(7) . . ? O1 S1 O4 112.0(7) . . ? O2 S1 O4 110.0(8) . . ? O1 S1 O3 110.8(8) . . ? O2 S1 O3 102.0(7) . . ? O4 S1 O3 108.7(7) . . ? O1 S1 Nd1 132.2(6) . . ? O2 S1 Nd1 51.2(5) . . ? O4 S1 Nd1 115.8(5) . . ? O3 S1 Nd1 51.3(4) . . ? O8 S2 O5 112.1(7) . . ? O8 S2 O7 112.1(8) . . ? O5 S2 O7 108.1(8) . . ? O8 S2 O6 111.2(8) . . ? O5 S2 O6 109.7(7) . . ? O7 S2 O6 103.2(7) . . ? O8 S2 Nd1 128.9(6) . . ? O5 S2 Nd1 118.9(5) . . ? O7 S2 Nd1 49.1(5) . . ? O6 S2 Nd1 54.2(5) . . ? S1 O2 Nd1 101.5(6) . . ? S1 O3 Nd1 143.7(6) . 3_756 ? S1 O3 Nd1 101.0(6) . . ? Nd1 O3 Nd1 115.0(4) 3_756 . ? S1 O4 Nd1 135.4(7) . 4_565 ? S2 O5 Nd1 147.7(8) . 4_566 ? S2 O6 Nd1 139.4(7) . 2_756 ? S2 O6 Nd1 97.9(6) . . ? Nd1 O6 Nd1 112.7(4) 2_756 . ? S2 O7 Nd1 104.4(7) . . ? S2 O7 Nd1 138.0(7) . 2_746 ? Nd1 O7 Nd1 116.5(5) . 2_746 ? H11 N1 H12 109(3) . . ? H11 N1 H14 109(3) . . ? H12 N1 H14 109(3) . . ? H11 N1 H13 110(3) . . ? H12 N1 H13 110(3) . . ? H14 N1 H13 111(3) . . ? _diffrn_measured_fraction_theta_max 0.741 _diffrn_reflns_theta_full 26.58 _diffrn_measured_fraction_theta_full 0.741 _refine_diff_density_max 1.762 _refine_diff_density_min -3.402 _refine_diff_density_rms 0.455 data_seu2 _database_code_CSD 186878 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ' Europium Sulfate Ammonium' _chemical_melting_point ? _chemical_formula_moiety ' Eu S2 O8 N H4' _chemical_formula_sum 'H4 Eu N O8 S2' _chemical_formula_weight 362.12 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' 'S' 'S' 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Eu' 'Eu' -0.1578 3.6682 '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' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P21/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 8.8605(8) _cell_length_b 7.1183(7) _cell_length_c 10.6690(10) _cell_angle_alpha 90.00 _cell_angle_beta 91.324(2) _cell_angle_gamma 90.00 _cell_volume 672.73(11) _cell_formula_units_Z 4 _cell_measurement_temperature 296(2) _cell_measurement_reflns_used 60 _cell_measurement_theta_min 3.40 _cell_measurement_theta_max 28.54 _exptl_crystal_description prismatic _exptl_crystal_colour colorless _exptl_crystal_size_max 0.1 _exptl_crystal_size_mid 0.06 _exptl_crystal_size_min 0.02 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 3.575 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 680 _exptl_absorpt_coefficient_mu 9.957 _exptl_absorpt_correction_type Sadabs _exptl_absorpt_correction_T_min 0.65 _exptl_absorpt_correction_T_max 1.0 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 296(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 ? _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_% none _diffrn_reflns_number 3066 _diffrn_reflns_av_R_equivalents 0.0444 _diffrn_reflns_av_sigmaI/netI 0.0514 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 3 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 3.44 _diffrn_reflns_theta_max 31.94 _reflns_number_total 1590 _reflns_number_gt 1310 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXL-97 (Sheldrick, 1997)' _computing_publication_material '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^)+(0.0459P)^2^+0.6113P] 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 1590 _refine_ls_number_parameters 122 _refine_ls_number_restraints 10 _refine_ls_R_factor_all 0.0531 _refine_ls_R_factor_gt 0.0376 _refine_ls_wR_factor_ref 0.0881 _refine_ls_wR_factor_gt 0.0823 _refine_ls_goodness_of_fit_ref 1.067 _refine_ls_restrained_S_all 1.064 _refine_ls_shift/su_max 0.378 _refine_ls_shift/su_mean 0.025 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 Eu1 Eu 0.94754(4) 0.17006(4) 0.65143(3) 0.00766(13) Uani 1 1 d . . . S1 S 0.7374(2) 0.1633(2) 0.41458(15) 0.0085(4) Uani 1 1 d . . . S2 S 1.1744(2) 0.1674(2) 0.88723(15) 0.0083(4) Uani 1 1 d . . . O1 O 0.6122(7) 0.0489(7) 0.3758(5) 0.0185(13) Uani 1 1 d . . . O2 O 0.7148(6) 0.2593(7) 0.5366(5) 0.0127(12) Uani 1 1 d . . . O3 O 0.8759(6) 0.0484(6) 0.4412(4) 0.0112(11) Uani 1 1 d . . . O4 O 0.7716(7) 0.3053(6) 0.3189(5) 0.0133(11) Uani 1 1 d . . . O5 O 1.1113(7) 0.1733(6) 1.0133(5) 0.0156(12) Uani 1 1 d . . . O6 O 1.1262(6) 0.3375(6) 0.8098(5) 0.0103(10) Uani 1 1 d . . . O7 O 1.1000(6) 0.0114(6) 0.8155(4) 0.0090(10) Uani 1 1 d . . . O8 O 1.3361(7) 0.1495(6) 0.8900(5) 0.0161(12) Uani 1 1 d . . . N1 N 0.4339(9) 0.3528(8) 0.6569(6) 0.0204(16) Uani 1 1 d D . . H14 H 0.358(8) 0.443(10) 0.653(8) 0.050 Uiso 1 1 d D . . H11 H 0.460(9) 0.331(11) 0.740(6) 0.050 Uiso 1 1 d D . . H13 H 0.518(8) 0.396(11) 0.614(7) 0.050 Uiso 1 1 d D . . H12 H 0.400(9) 0.242(9) 0.620(7) 0.050 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 Eu1 0.0123(2) 0.00552(14) 0.00522(19) 0.00003(12) 0.00093(14) 0.00068(13) S1 0.0106(10) 0.0081(6) 0.0070(8) 0.0003(6) 0.0003(7) 0.0009(6) S2 0.0122(10) 0.0066(6) 0.0060(8) -0.0009(5) -0.0005(7) 0.0007(6) O1 0.020(4) 0.019(2) 0.016(3) -0.0045(19) -0.003(3) -0.007(2) O2 0.014(3) 0.013(2) 0.012(3) -0.0057(18) 0.001(2) 0.0042(19) O3 0.019(3) 0.011(2) 0.004(2) -0.0011(16) 0.004(2) 0.0043(18) O4 0.013(3) 0.015(2) 0.011(3) 0.0049(18) 0.003(2) 0.0048(18) O5 0.025(4) 0.013(2) 0.009(3) 0.0008(19) 0.002(2) 0.003(2) O6 0.013(3) 0.0075(19) 0.011(2) 0.0009(18) 0.001(2) 0.0009(18) O7 0.013(3) 0.0101(19) 0.004(2) -0.0010(17) -0.0002(19) -0.0018(19) O8 0.017(3) 0.013(2) 0.018(3) 0.0032(19) -0.001(2) 0.003(2) N1 0.023(4) 0.019(3) 0.020(4) 0.002(2) -0.004(3) -0.002(3) _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 Eu1 O5 2.370(6) 4_565 ? Eu1 O4 2.405(6) 4_566 ? Eu1 O3 2.432(5) 3_756 ? Eu1 O2 2.458(5) . ? Eu1 O7 2.461(4) . ? Eu1 O3 2.474(5) . ? Eu1 O7 2.493(5) 2_756 ? Eu1 O6 2.493(4) 2_746 ? Eu1 O6 2.580(5) . ? Eu1 S1 3.1045(16) . ? Eu1 S2 3.1836(16) . ? Eu1 Eu1 4.1600(7) 3_756 ? S1 O1 1.430(6) . ? S1 O4 1.473(5) . ? S1 O2 1.488(5) . ? S1 O3 1.497(5) . ? S2 O8 1.438(6) . ? S2 O5 1.469(6) . ? S2 O7 1.493(5) . ? S2 O6 1.521(5) . ? O3 Eu1 2.432(5) 3_756 ? O4 Eu1 2.405(6) 4_565 ? O5 Eu1 2.370(6) 4_566 ? O6 Eu1 2.493(4) 2_756 ? O7 Eu1 2.493(4) 2_746 ? N1 H14 0.93(6) . ? N1 H11 0.93(6) . ? N1 H13 0.93(6) . ? N1 H12 0.93(6) . ? 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 O5 Eu1 O4 147.59(15) 4_565 4_566 ? O5 Eu1 O3 68.87(17) 4_565 3_756 ? O4 Eu1 O3 141.51(16) 4_566 3_756 ? O5 Eu1 O2 95.01(19) 4_565 . ? O4 Eu1 O2 78.49(18) 4_566 . ? O3 Eu1 O2 120.21(16) 3_756 . ? O5 Eu1 O7 108.91(19) 4_565 . ? O4 Eu1 O7 81.93(18) 4_566 . ? O3 Eu1 O7 69.37(16) 3_756 . ? O2 Eu1 O7 156.02(19) . . ? O5 Eu1 O3 75.46(18) 4_565 . ? O4 Eu1 O3 122.82(18) 4_566 . ? O3 Eu1 O3 64.0(2) 3_756 . ? O2 Eu1 O3 56.20(17) . . ? O7 Eu1 O3 127.56(15) . . ? O5 Eu1 O7 74.77(18) 4_565 2_756 ? O4 Eu1 O7 73.09(16) 4_566 2_756 ? O3 Eu1 O7 142.50(19) 3_756 2_756 ? O2 Eu1 O7 71.10(15) . 2_756 ? O7 Eu1 O7 116.00(11) . 2_756 ? O3 Eu1 O7 115.40(14) . 2_756 ? O5 Eu1 O6 135.76(18) 4_565 2_746 ? O4 Eu1 O6 76.65(16) 4_566 2_746 ? O3 Eu1 O6 68.51(17) 3_756 2_746 ? O2 Eu1 O6 96.19(17) . 2_746 ? O7 Eu1 O6 65.66(16) . 2_746 ? O3 Eu1 O6 75.83(15) . 2_746 ? O7 Eu1 O6 148.92(19) 2_756 2_746 ? O5 Eu1 O6 79.32(17) 4_565 . ? O4 Eu1 O6 83.01(18) 4_566 . ? O3 Eu1 O6 99.82(17) 3_756 . ? O2 Eu1 O6 134.59(15) . . ? O7 Eu1 O6 55.09(14) . . ? O3 Eu1 O6 153.67(19) . . ? O7 Eu1 O6 63.90(15) 2_756 . ? O6 Eu1 O6 119.29(11) 2_746 . ? O5 Eu1 S1 82.28(14) 4_565 . ? O4 Eu1 S1 102.64(13) 4_566 . ? O3 Eu1 S1 92.23(12) 3_756 . ? O2 Eu1 S1 28.08(12) . . ? O7 Eu1 S1 151.77(11) . . ? O3 Eu1 S1 28.35(12) . . ? O7 Eu1 S1 91.72(10) 2_756 . ? O6 Eu1 S1 88.04(11) 2_746 . ? O6 Eu1 S1 152.56(10) . . ? O5 Eu1 S2 96.29(14) 4_565 . ? O4 Eu1 S2 79.73(13) 4_566 . ? O3 Eu1 S2 85.23(12) 3_756 . ? O2 Eu1 S2 154.49(12) . . ? O7 Eu1 S2 27.00(11) . . ? O3 Eu1 S2 149.17(12) . . ? O7 Eu1 S2 89.97(10) 2_756 . ? O6 Eu1 S2 91.51(11) 2_746 . ? O6 Eu1 S2 28.20(10) . . ? S1 Eu1 S2 177.41(5) . . ? O5 Eu1 Eu1 68.90(12) 4_565 3_756 ? O4 Eu1 Eu1 141.25(11) 4_566 3_756 ? O3 Eu1 Eu1 32.32(11) 3_756 3_756 ? O2 Eu1 Eu1 87.90(12) . 3_756 ? O7 Eu1 Eu1 99.01(11) . 3_756 ? O3 Eu1 Eu1 31.70(12) . 3_756 ? O7 Eu1 Eu1 135.96(11) 2_756 3_756 ? O6 Eu1 Eu1 68.92(12) 2_746 3_756 ? O6 Eu1 Eu1 129.25(12) . 3_756 ? S1 Eu1 Eu1 59.96(3) . 3_756 ? S2 Eu1 Eu1 117.52(3) . 3_756 ? O1 S1 O4 111.2(3) . . ? O1 S1 O2 113.3(3) . . ? O4 S1 O2 109.0(3) . . ? O1 S1 O3 111.8(3) . . ? O4 S1 O3 109.0(3) . . ? O2 S1 O3 102.2(3) . . ? O1 S1 Eu1 133.7(2) . . ? O4 S1 Eu1 115.1(2) . . ? O2 S1 Eu1 51.0(2) . . ? O3 S1 Eu1 51.71(18) . . ? O8 S2 O5 112.6(3) . . ? O8 S2 O7 111.9(3) . . ? O5 S2 O7 108.5(3) . . ? O8 S2 O6 110.4(3) . . ? O5 S2 O6 111.5(3) . . ? O7 S2 O6 101.5(3) . . ? O8 S2 Eu1 128.8(2) . . ? O5 S2 Eu1 118.5(3) . . ? O7 S2 Eu1 48.42(18) . . ? O6 S2 Eu1 53.28(19) . . ? S1 O2 Eu1 100.9(3) . . ? S1 O3 Eu1 143.6(3) . 3_756 ? S1 O3 Eu1 99.9(2) . . ? Eu1 O3 Eu1 116.0(2) 3_756 . ? S1 O4 Eu1 135.4(3) . 4_565 ? S2 O5 Eu1 146.5(3) . 4_566 ? S2 O6 Eu1 137.5(3) . 2_756 ? S2 O6 Eu1 98.5(2) . . ? Eu1 O6 Eu1 112.84(19) 2_756 . ? S2 O7 Eu1 104.6(2) . . ? S2 O7 Eu1 136.6(3) . 2_746 ? Eu1 O7 Eu1 117.14(18) . 2_746 ? H14 N1 H11 109(3) . . ? H14 N1 H13 109(3) . . ? H11 N1 H13 110(3) . . ? H14 N1 H12 110(3) . . ? H11 N1 H12 110(3) . . ? H13 N1 H12 109(3) . . ? _diffrn_measured_fraction_theta_max 0.686 _diffrn_reflns_theta_full 31.94 _diffrn_measured_fraction_theta_full 0.686 _refine_diff_density_max 1.371 _refine_diff_density_min -1.489 _refine_diff_density_rms 0.302 #END