# Supplementary Material (ESI) for ChemComm # This journal is © The Royal Society of Chemistry 1999 # CCDC Number: 182/1437 # ---------------------------------------------------------------- # Electronic CIF files associated with manuscript "The # organo-pillared porous magnetic framework # Co4(SO4)(OH)6(H2NC2H4NH2)0.5 . 3(H2O)" submitted to Chem. # Commun. # ---------------------------------------------------------------- data_Co8(SO4)2(OH)12(en).6(H2O) _publ_contact_author ; Matthew J. Rosseinsky Inorganic Chemistry Laboratory University of Oxford South Parks Road Oxford OX1 3QR UK ; _publ_contact_author_phone '(44) 1865 272695' _publ_contact_author_fax '(44) 1865 272690' _publ_contact_author_email matthew.rosseinsky@chem.ox.ac.uk _publ_requested_journal 'Chem. Commun.' loop_ _publ_author_name _publ_author_address 'Rujiwatra, Apinpus' ; Inorganic Chemistry Laboratory University of Oxford South Parks Road Oxford OX1 3QR UK ; 'Kepert, Cameron J. ' ; School of Chemistry University of Sydney NSW 2006 Australia ; 'Rosseinsky, Matthew J.' ; Inorganic Chemistry Laboratory University of Oxford South Parks Road Oxford OX1 3QR UK ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; mu-ethylenediaminododecahydroxodisulfatooctacobalt(II)-6-water ; _chemical_name_common 'en-pillared namuwite' _chemical_melting_point ? _chemical_formula_moiety 'C H10 Co4 N O10 S, 3(H2 O)' _chemical_formula_sum 'C H16 Co4 N O13 S' _chemical_formula_weight 517.93 _chemical_compound_source ; 'hydrothermal synthesis at 180 deg C for 4 days' ; 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' 'S' 'S' 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Co' 'Co' 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting trigonal _symmetry_space_group_name_H-M 'P -3' _symmetry_Int_Tables_number 147 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' _cell_length_a 8.298(1) _cell_length_b 8.298(1) _cell_length_c 10.519(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 627.3(2) _cell_formula_units_Z 2 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 11099 _cell_measurement_theta_min 2.83 _cell_measurement_theta_max 26.58 _exptl_crystal_description 'transparent platelets' _exptl_crystal_colour blue _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.05 _exptl_crystal_density_diffrn 2.742 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 514 _exptl_absorpt_coefficient_mu 5.432 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min 1.0 _exptl_absorpt_correction_T_max 1.0 _exptl_special_details ; ? ; _diffrn_ambient_environment ; 'In thin film of perfluorpolyether oil on mohair fibre' ; _diffrn_crystal_treatment 'Flash cooled in nitrogen stream' _diffrn_ambient_temperature 150(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 'Enraf-Nonius DIP2000 diffractometer' _diffrn_detector 'Eu/Ba image plate' _diffrn_measurement_method 'Ninety 2-degree oscillations in phi' _diffrn_standards_decay_% 0 _diffrn_reflns_number 3396 _diffrn_reflns_av_R_equivalents 0.054 _diffrn_reflns_av_sigmaI/netI 0.0265 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 2.83 _diffrn_reflns_theta_max 26.58 _reflns_number_total 875 _reflns_number_gt 839 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CAD-4 software (Enraf-Nonius, 1989)' _computing_cell_refinement 'CAD-4 software (Enraf-Nonius, 1989)' _computing_data_reduction 'RC93 (Watkin et al., 1994)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'XPMA/ZORTEP' _computing_publication_material 'CIFTAB' _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. The ethylenediamine molecule is disordered about a 3-fold axis and has an occupation of one third. The nitrogen and carbon atoms of this group were modelled isotropically, their orientations subject to bond length restraints: from the analysis of structures within the Cambridge Crystallographic Database containing ethylenediamine molecules the restraints C-C = 1.49(2), C-N = 1.48(2) were derived. The disorder of the ethylenediamine pillar imparts disorder to the solvent water molecule, which was modelled as the sum of three 1/3-occupied oxygen atoms having isotropic thermal parameters constrained to be equal. Of these, O11A and O11B form short hydrogen bonding contacts to the amine hydrogen atoms of the pillar, whereas O11C, which lies in the vicinity of the ethylene group of the pillar, sits much closer to the inorganic layer and forms a short hydrogen bond to O1-H1. No hydrogen atoms were added to the water molecule sites. The four largest peaks in the difference Fourier map lie ca. 1A away from the cobalt atoms. ; _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^)+(0.0718P)^2^+12.8917P] 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_number_reflns 875 _refine_ls_number_parameters 64 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0881 _refine_ls_R_factor_gt 0.0859 _refine_ls_wR_factor_ref 0.2193 _refine_ls_wR_factor_gt 0.2179 _refine_ls_goodness_of_fit_ref 1.321 _refine_ls_restrained_S_all 1.320 _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 Co1 Co 0.42215(16) 0.13693(16) 0.00161(14) 0.0188(5) Uani 1 1 d . . . Co2 Co 0.0000 0.0000 0.1641(2) 0.0171(6) Uani 1 3 d S . . S1 S 0.6667 0.3333 0.2711(6) 0.0327(12) Uani 1 3 d S . . O1 O 0.3753(8) -0.1025(8) 0.0933(7) 0.0188(15) Uani 1 1 d . . . H1 H 0.3743 -0.1039 0.1750 0.023 Uiso 1 1 calc R . . O2 O 0.2501(9) 0.1959(8) 0.1158(7) 0.0177(15) Uani 1 1 d . . . H2 H 0.3099 0.2437 0.1852 0.021 Uiso 1 1 calc R . . O3 O 0.6667 0.3333 0.1229(13) 0.022(3) Uani 1 3 d S . . O4 O 0.5056(12) 0.3444(14) 0.3138(10) 0.045(2) Uani 1 1 d . . . N1 N 0.019(6) 0.042(3) 0.3532(18) 0.021(7) Uiso 0.33 1 d PD . . H2A H 0.1358 0.0545 0.3791 0.027 Uiso 0.33 1 calc PR . . H2B H 0.0288 0.1610 0.3670 0.027 Uiso 0.33 1 calc PR . . C1 C -0.123(6) -0.089(7) 0.4430(15) 0.082(17) Uiso 0.33 1 d PD . . H3A H -0.2008 -0.2051 0.4007 0.102 Uiso 0.33 1 calc PR . . H3B H -0.1995 -0.0395 0.4705 0.102 Uiso 0.33 1 calc PR . . O11A O 0.291(10) -0.101(10) 0.419(8) 0.099(10) Uiso 0.33 1 d P . . O11B O 0.118(11) 0.452(10) 0.416(8) 0.099(10) Uiso 0.33 1 d P . . O11C O -0.457(9) -0.320(9) 0.353(5) 0.099(10) Uiso 0.33 1 d P . . 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 0.0085(7) 0.0073(7) 0.0408(9) -0.0001(5) 0.0001(5) 0.0041(5) Co2 0.0107(7) 0.0107(7) 0.0299(12) 0.000 0.000 0.0053(4) S1 0.0238(15) 0.0238(15) 0.051(3) 0.000 0.000 0.0119(7) O1 0.009(3) 0.008(3) 0.036(4) 0.001(3) -0.001(3) 0.002(2) O2 0.012(3) 0.008(3) 0.034(4) -0.004(3) -0.002(3) 0.005(2) O3 0.008(3) 0.008(3) 0.051(8) 0.000 0.000 0.0038(16) O4 0.032(5) 0.051(6) 0.058(6) -0.005(5) -0.004(4) 0.025(5) _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 O1 2.051(7) 6 ? Co1 O1 2.063(6) . ? Co1 O1 2.094(7) 4_655 ? Co1 O2 2.102(7) . ? Co1 O2 2.142(7) 5 ? Co1 O3 2.257(8) . ? Co2 O2 1.958(6) 3 ? Co2 O2 1.958(6) . ? Co2 O2 1.958(6) 2 ? Co2 N1 2.012(19) . ? Co2 N1 2.012(19) 3 ? Co2 N1 2.012(19) 2 ? S1 O4 1.456(9) 2_655 ? S1 O4 1.456(9) 3_665 ? S1 O4 1.456(9) . ? S1 O3 1.558(15) . ? O1 Co1 2.051(7) 5 ? O1 Co1 2.094(7) 4_655 ? O1 H1 0.8600 . ? O2 Co1 2.142(7) 6 ? O2 H2 0.8600 . ? O3 Co1 2.257(8) 2_655 ? O3 Co1 2.257(8) 3_665 ? N1 C1 1.48(2) . ? N1 H2A 0.9600 . ? N1 H2B 0.9600 . ? C1 C1 1.51(2) 6_556 ? C1 H3A 0.9600 . ? C1 H3B 0.9600 . ? 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 Co1 O1 177.7(3) 6 . ? O1 Co1 O1 95.2(4) 6 4_655 ? O1 Co1 O1 82.5(3) . 4_655 ? O1 Co1 O2 84.6(3) 6 . ? O1 Co1 O2 97.7(3) . . ? O1 Co1 O2 171.6(3) 4_655 . ? O1 Co1 O2 97.2(3) 6 5 ? O1 Co1 O2 83.3(3) . 5 ? O1 Co1 O2 95.2(3) 4_655 5 ? O2 Co1 O2 93.2(4) . 5 ? O1 Co1 O3 83.8(3) 6 . ? O1 Co1 O3 95.7(3) . . ? O1 Co1 O3 82.8(3) 4_655 . ? O2 Co1 O3 88.8(3) . . ? O2 Co1 O3 177.9(2) 5 . ? O2 Co2 O2 113.52(19) 3 . ? O2 Co2 O2 113.52(19) 3 2 ? O2 Co2 O2 113.52(19) . 2 ? O2 Co2 N1 113.4(8) 3 . ? O2 Co2 N1 98.8(11) . . ? O2 Co2 N1 102.7(14) 2 . ? O2 Co2 N1 98.8(11) 3 3 ? O2 Co2 N1 102.7(14) . 3 ? O2 Co2 N1 113.4(8) 2 3 ? O2 Co2 N1 102.7(14) 3 2 ? O2 Co2 N1 113.4(8) . 2 ? O2 Co2 N1 98.8(11) 2 2 ? O4 S1 O4 110.9(4) 2_655 3_665 ? O4 S1 O4 110.9(4) 2_655 . ? O4 S1 O4 110.9(4) 3_665 . ? O4 S1 O3 108.0(4) 2_655 . ? O4 S1 O3 108.0(4) 3_665 . ? O4 S1 O3 108.0(4) . . ? Co1 O1 Co1 97.6(3) 5 . ? Co1 O1 Co1 102.1(3) 5 4_655 ? Co1 O1 Co1 97.5(3) . 4_655 ? Co1 O1 H1 118.5 5 . ? Co1 O1 H1 118.5 . . ? Co1 O1 H1 118.5 4_655 . ? Co2 O2 Co1 121.1(3) . . ? Co2 O2 Co1 120.0(3) . 6 ? Co1 O2 Co1 93.7(3) . 6 ? Co2 O2 H2 106.9 . . ? Co1 O2 H2 106.9 . . ? Co1 O2 H2 106.9 6 . ? S1 O3 Co1 124.4(3) . 2_655 ? S1 O3 Co1 124.4(3) . . ? Co1 O3 Co1 91.2(4) 2_655 . ? S1 O3 Co1 124.4(3) . 3_665 ? Co1 O3 Co1 91.2(4) 2_655 3_665 ? Co1 O3 Co1 91.2(4) . 3_665 ? C1 N1 Co2 122.7(17) . . ? C1 N1 H2A 106.7 . . ? Co2 N1 H2A 106.7 . . ? C1 N1 H2B 106.7 . . ? Co2 N1 H2B 106.7 . . ? H2A N1 H2B 106.6 . . ? N1 C1 C1 111.2(16) . 6_556 ? N1 C1 H3A 109.4 . . ? C1 C1 H3A 109.4 6_556 . ? N1 C1 H3B 109.4 . . ? C1 C1 H3B 109.4 6_556 . ? H3A C1 H3B 108.0 . . ? 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 O11A 0.86 2.66 3.50(8) 164.8 . N1 H2A O11A 0.96 2.27 3.11(8) 145.0 . O1 H1 O11B 0.86 2.56 3.41(9) 173.8 3 N1 H2B O11B 0.96 2.21 3.15(8) 166.2 . O1 H1 O11C 0.86 1.91 2.76(6) 168.7 2 C1 H3A O11C 0.96 1.91 2.64(7) 130.3 . O2 H2 O4 0.86 1.95 2.782(12) 161.9 . _diffrn_measured_fraction_theta_max 0.984 _diffrn_reflns_theta_full 26.58 _diffrn_measured_fraction_theta_full 0.984 _refine_diff_density_max 1.938 _refine_diff_density_min -1.332 _refine_diff_density_rms 0.239