# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2004 data_global _journal_coden_Cambridge 182 loop_ _publ_author_name 'Serge Vilminot' 'Gilles Andre' 'Mohamedally Kurmoo' 'Tahar Mhiri' 'Mireille Richard-Plouet' 'Mohsen Ben Salah' _publ_contact_author_name 'Dr Serge Vilminot' _publ_contact_author_address ; Institut de Physique et Chimie des Materiaux de Strasbourg 23 rue du loess strasbourg 67034 FRANCE ; _publ_contact_author_email vilminot@ipcms.u-strasbg.fr _publ_contact_author_fax '+33 388 10 72 47' _publ_contact_author_phone '+33 388 10 71 28' _publ_requested_journal 'Chemical Communications' _publ_section_title ; CoII5(OH)6(SO4)2(H2O)4: The first ferromagnet based on a layered cobalt-hydroxide pillared by inorganic OSO3-Co(H2O)4-O3SO ; data_co5 _database_code_depnum_ccdc_archive 'CCDC 245726' _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety Co5(OH)6(SO4)2(H2O)4 _chemical_formula_structural Co5(OH)6(SO4)2(H2O)4 _chemical_formula_analytical Co5O18H14S2 _chemical_formula_sum Co5O18H14S2' _chemical_formula_weight 660.666 _chemical_melting_point 'decomposes at 235C' _chemical_compound_source 'CoSO4.7H2O + NaOH hydrothermal' 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' H H 0.0000 0.0000 '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' Co Co2+ 0.2990 0.9730 '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 5.4698(2) _cell_length_b 6.3435(3) _cell_length_c 20.5471(8) _cell_angle_alpha 90.00 _cell_angle_beta 91.709(2) _cell_angle_gamma 90.00 _cell_volume 712.62(5) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 1761 _cell_measurement_theta_min 0.998 _cell_measurement_theta_max 30.034 _exptl_crystal_description platelet _exptl_crystal_colour 'light pink' _exptl_crystal_size_max ? _exptl_crystal_size_mid ? _exptl_crystal_size_min ? _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 3.079 _exptl_crystal_density_method ? _exptl_crystal_F_000 550 _exptl_absorpt_coefficient_mu 6.060 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device KappaCCD _diffrn_measurement_method '95mm CCD camera on \k-goniostat' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 3417 _diffrn_reflns_av_R_equivalents 0.0391 _diffrn_reflns_av_sigmaI/netI 0.0611 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -28 _diffrn_reflns_limit_l_max 28 _diffrn_reflns_theta_min 3.36 _diffrn_reflns_theta_max 30.04 _reflns_number_total 2035 _reflns_number_observed 1834 _reflns_observed_criterion >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 1997)' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[\s^2^(Fo^2^)+(0.0429P)^2^+5.6320P] 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 yes _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0008(14) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 2035 _refine_ls_number_parameters 144 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0614 _refine_ls_R_factor_obs 0.0535 _refine_ls_wR_factor_all 0.1291 _refine_ls_wR_factor_obs 0.1259 _refine_ls_goodness_of_fit_all 1.111 _refine_ls_goodness_of_fit_obs 1.145 _refine_ls_restrained_S_all 1.111 _refine_ls_restrained_S_obs 1.145 _refine_ls_shift/esd_max -0.001 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Co1 Co2+ -0.00025(10) 0.06128(9) 0.25095(3) 0.0053(2) Uani 1 d . . Co2 Co2+ 0.48877(11) 0.31102(9) 0.25220(3) 0.0053(2) Uani 1 d . . Co3 Co2+ 0.0000 0.0000 0.0000 0.0073(2) Uani 1 d S . S S 0.7973(2) 0.31825(15) 0.11249(5) 0.0054(2) Uani 1 d . . O1 O 0.9535(7) 0.4860(5) 0.0876(2) 0.0137(7) Uani 1 d . . O2 O 0.8220(6) 0.3132(4) 0.1858(2) 0.0068(6) Uani 1 d . . O3 O 0.5415(6) 0.3606(6) 0.0941(2) 0.0163(7) Uani 1 d . . O4 O 0.8758(7) 0.1109(5) 0.0889(2) 0.0149(7) Uani 1 d . . OH1 O 0.3212(6) 0.0562(5) 0.2033(2) 0.0077(6) Uani 1 d . . OH2 O 0.1518(6) 0.3124(4) 0.2984(2) 0.0059(6) Uani 1 d . . OH3 O 0.3258(6) 0.5665(5) 0.2044(2) 0.0074(6) Uani 1 d . . OH4 O 0.2515(7) 0.8240(6) 0.0572(2) 0.0143(7) Uani 1 d . . OH5 O 0.2754(7) 0.2286(6) -0.0091(2) 0.0104(6) Uani 1 d . . H1 H 0.3164(184) 0.0611(140) 0.1708(45) 0.047(29) Uiso 1 d . . H2 H 0.1472(126) 0.3223(90) 0.3364(34) 0.011(16) Uiso 1 d . . H3 H 0.3272(175) 0.5225(137) 0.1733(43) 0.043(26) Uiso 1 d . . H41 H 0.3761(154) 0.8207(113) 0.0420(40) 0.031(22) Uiso 1 d . . H42 H 0.2339(134) 0.7086(114) 0.0670(35) 0.019(18) Uiso 1 d . . H51 H 0.3566(119) 0.2649(99) 0.0189(31) 0.008(14) Uiso 1 d . . H52 H 0.2347(141) 0.3445(119) 0.9761(38) 0.030(20) Uiso 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 Co1 0.0043(3) 0.0031(3) 0.0084(3) -0.0001(2) 0.0004(2) -0.0002(2) Co2 0.0046(3) 0.0022(3) 0.0091(3) 0.0001(2) 0.0005(2) 0.0001(2) Co3 0.0092(4) 0.0059(4) 0.0069(4) -0.0004(3) 0.0009(3) 0.0009(3) S 0.0066(5) 0.0045(4) 0.0050(4) -0.0003(3) 0.0003(3) -0.0001(3) O1 0.020(2) 0.0093(15) 0.0121(15) 0.0046(13) 0.0014(12) -0.0047(14) O2 0.012(2) 0.0063(14) 0.0028(13) -0.0007(10) 0.0014(11) -0.0005(11) O3 0.008(2) 0.029(2) 0.013(2) -0.0018(14) -0.0013(12) 0.0023(15) O4 0.030(2) 0.0047(14) 0.0105(15) -0.0032(12) 0.0045(14) 0.0058(14) OH1 0.010(2) 0.0075(15) 0.0059(14) -0.0003(11) 0.0013(12) -0.0004(11) OH2 0.0062(15) 0.0060(14) 0.0056(14) -0.0005(10) 0.0000(11) 0.0012(11) OH3 0.009(2) 0.0069(14) 0.0059(14) -0.0008(11) 0.0020(11) 0.0014(11) OH4 0.010(2) 0.014(2) 0.019(2) 0.0077(13) 0.0030(14) 0.0030(13) OH5 0.012(2) 0.012(2) 0.0075(15) 0.0017(12) -0.0014(12) -0.0009(13) _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 Co1 OH3 2.028(3) 2_545 ? Co1 OH2 2.033(3) . ? Co1 OH1 2.038(4) . ? Co1 OH2 2.039(3) 2_545 ? Co1 O2 2.245(3) 2_645 ? Co1 O2 2.283(3) 1_455 ? Co2 OH3 2.044(3) 2_645 ? Co2 OH1 2.069(3) 2_655 ? Co2 OH3 2.082(3) . ? Co2 OH2 2.098(3) . ? Co2 OH1 2.100(3) . ? Co2 O2 2.309(3) . ? Co3 O4 2.090(3) 3_655 ? Co3 O4 2.090(3) 1_455 ? Co3 OH4 2.103(4) 3_565 ? Co3 OH4 2.103(4) 1_545 ? Co3 OH5 2.103(4) . ? Co3 OH5 2.103(4) 3 ? S O3 1.463(4) . ? S O1 1.466(3) . ? S O4 1.470(3) . ? S O2 1.509(3) . ? O2 Co1 2.245(3) 2_655 ? O2 Co1 2.283(3) 1_655 ? O4 Co3 2.090(3) 1_655 ? OH1 Co2 2.069(3) 2_645 ? OH2 Co1 2.039(3) 2 ? OH3 Co1 2.028(3) 2 ? OH3 Co2 2.044(3) 2_655 ? OH4 Co3 2.103(4) 1_565 ? 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 OH3 Co1 OH2 97.02(13) 2_545 . ? OH3 Co1 OH1 178.20(13) 2_545 . ? OH2 Co1 OH1 84.06(13) . . ? OH3 Co1 OH2 83.59(13) 2_545 2_545 ? OH2 Co1 OH2 178.84(8) . 2_545 ? OH1 Co1 OH2 95.30(13) . 2_545 ? OH3 Co1 O2 96.98(13) 2_545 2_645 ? OH2 Co1 O2 96.16(12) . 2_645 ? OH1 Co1 O2 84.32(13) . 2_645 ? OH2 Co1 O2 84.74(12) 2_545 2_645 ? OH3 Co1 O2 83.66(13) 2_545 1_455 ? OH2 Co1 O2 83.90(12) . 1_455 ? OH1 Co1 O2 95.04(13) . 1_455 ? OH2 Co1 O2 95.20(12) 2_545 1_455 ? O2 Co1 O2 179.34(3) 2_645 1_455 ? OH3 Co2 OH1 98.11(14) 2_645 2_655 ? OH3 Co2 OH3 175.41(5) 2_645 . ? OH1 Co2 OH3 79.99(14) 2_655 . ? OH3 Co2 OH2 103.69(13) 2_645 . ? OH1 Co2 OH2 103.49(13) 2_655 . ? OH3 Co2 OH2 80.84(12) . . ? OH3 Co2 OH1 80.14(14) 2_645 . ? OH1 Co2 OH1 175.51(5) 2_655 . ? OH3 Co2 OH1 101.45(14) . . ? OH2 Co2 OH1 80.98(13) . . ? OH3 Co2 O2 82.66(12) 2_645 . ? OH1 Co2 O2 82.05(12) 2_655 . ? OH3 Co2 O2 92.92(12) . . ? OH2 Co2 O2 170.69(12) . . ? OH1 Co2 O2 93.60(12) . . ? O4 Co3 O4 180.0 3_655 1_455 ? O4 Co3 OH4 85.11(14) 3_655 3_565 ? O4 Co3 OH4 94.89(14) 1_455 3_565 ? O4 Co3 OH4 94.89(14) 3_655 1_545 ? O4 Co3 OH4 85.11(14) 1_455 1_545 ? OH4 Co3 OH4 180.0 3_565 1_545 ? O4 Co3 OH5 84.38(14) 3_655 . ? O4 Co3 OH5 95.62(14) 1_455 . ? OH4 Co3 OH5 92.43(14) 3_565 . ? OH4 Co3 OH5 87.57(14) 1_545 . ? O4 Co3 OH5 95.62(14) 3_655 3 ? O4 Co3 OH5 84.38(14) 1_455 3 ? OH4 Co3 OH5 87.57(15) 3_565 3 ? OH4 Co3 OH5 92.43(14) 1_545 3 ? OH5 Co3 OH5 180.0 . 3 ? O3 S O1 109.8(2) . . ? O3 S O4 111.4(2) . . ? O1 S O4 110.8(2) . . ? O3 S O2 108.5(2) . . ? O1 S O2 109.2(2) . . ? O4 S O2 107.0(2) . . ? S O2 Co1 126.0(2) . 2_655 ? S O2 Co1 128.6(2) . 1_655 ? Co1 O2 Co1 88.94(12) 2_655 1_655 ? S O2 Co2 122.8(2) . . ? Co1 O2 Co2 89.96(11) 2_655 . ? Co1 O2 Co2 88.83(11) 1_655 . ? S O4 Co3 134.0(2) . 1_655 ? Co1 OH1 Co2 103.22(15) . 2_645 ? Co1 OH1 Co2 97.36(14) . . ? Co2 OH1 Co2 99.23(15) 2_645 . ? Co1 OH2 Co1 102.33(14) . 2 ? Co1 OH2 Co2 97.58(13) . . ? Co1 OH2 Co2 97.35(13) 2 . ? Co1 OH3 Co2 104.21(15) 2 2_655 ? Co1 OH3 Co2 98.22(14) 2 . ? Co2 OH3 Co2 100.64(15) 2_655 . ? _refine_diff_density_max 3.348 _refine_diff_density_min -0.946 _refine_diff_density_rms 0.243