# 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 'Richard Robson' 'Brendan F. Abrahams' 'Marissa G. Haywood' _publ_contact_author_name 'Prof Richard Robson' _publ_contact_author_address ; School of Chemistry University of Melbourne Parkville Victoria 3010 AUSTRALIA ; _publ_contact_author_email R.ROBSON@UNIMELB.EDU.AU _publ_requested_journal 'Chemical Communications' _publ_section_title ; [Co(NH3)6]3[Cu4(OH)(CO3)8].2H2O - A New Carbonato-Copper(II) Anion Stabilized by Extensive Hydrogen Bonding ; data_bacur31a _database_code_depnum_ccdc_archive 'CCDC 228199' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ; _chemical_name_common ; Hexaamminecobalt(III) octacarbonatohydroxotetracuprate(II)dihydrate ; _chemical_melting_point ? _chemical_formula_moiety ; (Co1 N6 H18 +3)3 (Cu4 O25 H1 C8 -9) (H2 O1)2 ; _chemical_formula_sum 'C8 H59 Co3 Cu4 N18 O27' _chemical_formula_weight 1270.68 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' Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cu Cu 0.3201 1.2651 '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' _symmetry_cell_setting Tetragonal _symmetry_space_group_name_H-M I4/mmm loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x, -y, -z' '-x, -y, z' '-x, y, -z' 'y, x, -z' 'y, -x, z' '-y, x, z' '-y, -x, -z' 'x+1/2, y+1/2, z+1/2' 'x+1/2, -y+1/2, -z+1/2' '-x+1/2, -y+1/2, z+1/2' '-x+1/2, y+1/2, -z+1/2' 'y+1/2, x+1/2, -z+1/2' 'y+1/2, -x+1/2, z+1/2' '-y+1/2, x+1/2, z+1/2' '-y+1/2, -x+1/2, -z+1/2' '-x, -y, -z' '-x, y, z' 'x, y, -z' 'x, -y, z' '-y, -x, z' '-y, x, -z' 'y, -x, -z' 'y, x, z' '-x+1/2, -y+1/2, -z+1/2' '-x+1/2, y+1/2, z+1/2' 'x+1/2, y+1/2, -z+1/2' 'x+1/2, -y+1/2, z+1/2' '-y+1/2, -x+1/2, z+1/2' '-y+1/2, x+1/2, -z+1/2' 'y+1/2, -x+1/2, -z+1/2' 'y+1/2, x+1/2, z+1/2' _cell_length_a 10.4090(6) _cell_length_b 10.4090(6) _cell_length_c 17.1883(19) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1862.3(3) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 1304 _cell_measurement_theta_min 2.29 _cell_measurement_theta_max 26.33 _exptl_crystal_description 'square plate' _exptl_crystal_colour yellow-green _exptl_crystal_size_max 0.10 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.025 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.266 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1292 _exptl_absorpt_coefficient_mu 3.663 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.822 _exptl_absorpt_correction_T_max 1.000 _exptl_absorpt_process_details ; Sheldrick, G. M. SADABS ; _exptl_special_details ; ? ; _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_measurement_device_type 'Bruker CCD area detector' _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_% 1 _diffrn_reflns_number 5828 _diffrn_reflns_av_R_equivalents 0.0406 _diffrn_reflns_av_sigmaI/netI 0.0309 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 2.29 _diffrn_reflns_theta_max 27.50 _reflns_number_total 664 _reflns_number_gt 566 _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, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Carbonate ions are disordered over two orientations that are related by mirror symmetry. The non-coordinating oxygen atom and carbon atom are common to both orientations. Given the disorder, hydrogen atoms of the hexaaminecobalt(III) cation were not included in the model. The hydroxide ion at the centre of the anion was also disordered over two sites. The position of the hydrogen atom of the hydroxide group was refined. 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^)+(0.0732P)^2^+13.4600P] 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 664 _refine_ls_number_parameters 62 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0605 _refine_ls_R_factor_gt 0.0486 _refine_ls_wR_factor_ref 0.1441 _refine_ls_wR_factor_gt 0.1359 _refine_ls_goodness_of_fit_ref 1.180 _refine_ls_restrained_S_all 1.180 _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 O4 O 0.5000 0.5000 0.7966(8) 0.067(4) Uani 1 8 d S . . O1 O 0.6432(6) 0.7886(6) 0.9389(4) 0.0283(14) Uani 0.50 1 d P . . O2 O 0.7275(9) 0.5999(7) 0.9034(4) 0.0378(18) Uani 0.50 1 d P . . Co3 Co 0.5000 0.5000 0.5000 0.0220(6) Uani 1 16 d S . . N3 N 0.6878(8) 0.5000 0.5000 0.037(2) Uani 1 4 d S . . N4 N 0.5000 0.5000 0.6137(7) 0.049(4) Uani 1 8 d S . . Cu1 Cu 0.5000 0.71430(11) 1.0000 0.0246(4) Uani 1 4 d S . . Co1 Co 0.5000 0.0000 0.7500 0.0148(4) Uani 1 8 d S . . N2 N 0.5000 -0.1887(5) 0.7481(3) 0.0263(12) Uani 1 2 d S . . N1 N 0.5000 0.0000 0.8640(4) 0.0303(18) Uani 1 4 d S . . O3 O 0.7918(4) 0.7918(4) 0.8544(3) 0.0431(13) Uani 1 2 d S . . C1 C 0.7245(4) 0.7245(4) 0.8981(3) 0.0228(13) Uani 1 2 d S . . O5 O 0.5000 0.5000 0.9886(18) 0.043(6) Uiso 0.50 8 d SP . . H1 H 0.5000 0.5000 0.92(2) 0.051 Uiso 0.50 8 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 O4 0.072(6) 0.072(6) 0.058(8) 0.000 0.000 0.000 O1 0.021(3) 0.029(3) 0.034(4) 0.008(3) 0.005(3) 0.005(3) O2 0.070(6) 0.020(3) 0.023(3) -0.004(3) 0.010(4) 0.004(3) Co3 0.0233(8) 0.0233(8) 0.0193(11) 0.000 0.000 0.000 N3 0.025(4) 0.032(4) 0.055(6) 0.000 0.000 0.000 N4 0.064(6) 0.064(6) 0.018(6) 0.000 0.000 0.000 Cu1 0.0199(6) 0.0346(7) 0.0194(6) 0.000 0.000 0.000 Co1 0.0164(5) 0.0164(5) 0.0117(7) 0.000 0.000 0.000 N2 0.028(3) 0.016(2) 0.036(3) -0.002(2) 0.000 0.000 N1 0.049(5) 0.028(4) 0.013(3) 0.000 0.000 0.000 O3 0.046(2) 0.046(2) 0.038(3) 0.0071(17) 0.0071(17) -0.011(3) C1 0.0263(19) 0.0263(19) 0.016(3) -0.0023(17) -0.0023(17) 0.002(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 O1 C1 1.286(7) . ? O1 Cu1 1.980(6) . ? O2 C1 1.301(8) . ? O2 Cu1 1.965(7) 5_557 ? Co3 N4 1.955(12) 17_666 ? Co3 N4 1.955(12) . ? Co3 N3 1.955(9) . ? Co3 N3 1.955(9) 17_666 ? Co3 N3 1.955(9) 5_556 ? Co3 N3 1.955(9) 21_665 ? Cu1 O2 1.965(7) 5_557 ? Cu1 O2 1.965(7) 7_655 ? Cu1 O2 1.965(7) 22_657 ? Cu1 O2 1.965(7) 24 ? Cu1 O1 1.980(6) 19_557 ? Cu1 O1 1.980(6) 18_655 ? Cu1 O1 1.980(6) 4_657 ? Cu1 O5 2.239(3) . ? Cu1 O5 2.239(3) 17_667 ? Co1 N1 1.960(7) 13_546 ? Co1 N1 1.960(7) . ? Co1 N2 1.964(5) . ? Co1 N2 1.964(5) 30_546 ? Co1 N2 1.964(5) 3_655 ? Co1 N2 1.964(5) 13_546 ? O3 C1 1.242(8) . ? C1 O1 1.286(7) 24 ? C1 O2 1.301(8) 24 ? O5 Cu1 2.239(3) 5_557 ? O5 Cu1 2.239(3) 17_667 ? O5 Cu1 2.239(3) 21_665 ? 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 C1 O1 Cu1 125.6(5) . . ? C1 O2 Cu1 125.8(5) . 5_557 ? N4 Co3 N4 180.000(1) 17_666 . ? N4 Co3 N3 90.000(2) 17_666 . ? N4 Co3 N3 90.000(2) . . ? N4 Co3 N3 90.000(2) 17_666 17_666 ? N4 Co3 N3 90.000(2) . 17_666 ? N3 Co3 N3 180.000(2) . 17_666 ? N4 Co3 N3 90.000(1) 17_666 5_556 ? N4 Co3 N3 90.000(1) . 5_556 ? N3 Co3 N3 90.000(1) . 5_556 ? N3 Co3 N3 90.000(1) 17_666 5_556 ? N4 Co3 N3 90.000(1) 17_666 21_665 ? N4 Co3 N3 90.000(1) . 21_665 ? N3 Co3 N3 90.000(1) . 21_665 ? N3 Co3 N3 90.000(3) 17_666 21_665 ? N3 Co3 N3 180.000(4) 5_556 21_665 ? O2 Cu1 O2 172.0(5) 5_557 7_655 ? O2 Cu1 O2 172.0(5) 22_657 24 ? O2 Cu1 O1 85.6(3) 22_657 19_557 ? O2 Cu1 O1 91.3(4) 24 19_557 ? O2 Cu1 O1 91.3(4) 22_657 18_655 ? O2 Cu1 O1 85.6(3) 24 18_655 ? O1 Cu1 O1 134.0(4) 19_557 18_655 ? O2 Cu1 O1 91.3(4) 5_557 . ? O2 Cu1 O1 85.6(3) 7_655 . ? O2 Cu1 O1 85.6(3) 5_557 4_657 ? O2 Cu1 O1 91.3(4) 7_655 4_657 ? O1 Cu1 O1 134.0(4) . 4_657 ? O2 Cu1 O5 98.3(7) 5_557 . ? O2 Cu1 O5 89.7(7) 7_655 . ? O2 Cu1 O5 98.3(7) 22_657 . ? O2 Cu1 O5 89.7(7) 24 . ? O1 Cu1 O5 115.8(5) 19_557 . ? O1 Cu1 O5 110.0(5) 18_655 . ? O1 Cu1 O5 110.0(5) . . ? O1 Cu1 O5 115.8(5) 4_657 . ? O2 Cu1 O5 89.7(7) 5_557 17_667 ? O2 Cu1 O5 98.3(7) 7_655 17_667 ? O2 Cu1 O5 89.7(7) 22_657 17_667 ? O2 Cu1 O5 98.3(7) 24 17_667 ? O1 Cu1 O5 110.0(5) 19_557 17_667 ? O1 Cu1 O5 115.8(5) 18_655 17_667 ? O1 Cu1 O5 115.8(5) . 17_667 ? O1 Cu1 O5 110.0(5) 4_657 17_667 ? N1 Co1 N1 180.000(2) 13_546 . ? N1 Co1 N2 89.06(16) 13_546 . ? N1 Co1 N2 90.94(16) . . ? N1 Co1 N2 90.94(16) 13_546 30_546 ? N1 Co1 N2 89.06(16) . 30_546 ? N2 Co1 N2 90.016(6) . 30_546 ? N1 Co1 N2 89.06(16) 13_546 3_655 ? N1 Co1 N2 90.94(16) . 3_655 ? N2 Co1 N2 178.1(3) . 3_655 ? N2 Co1 N2 90.016(7) 30_546 3_655 ? N1 Co1 N2 90.94(16) 13_546 13_546 ? N1 Co1 N2 89.06(16) . 13_546 ? N2 Co1 N2 90.016(7) . 13_546 ? N2 Co1 N2 178.1(3) 30_546 13_546 ? N2 Co1 N2 90.016(6) 3_655 13_546 ? O3 C1 O1 114.1(5) . . ? O3 C1 O1 114.1(5) . 24 ? O3 C1 O2 126.2(4) . . ? O1 C1 O2 119.7(7) . . ? O3 C1 O2 126.2(4) . 24 ? O1 C1 O2 119.7(7) 24 24 ? Cu1 O5 Cu1 89.56(14) . 5_557 ? Cu1 O5 Cu1 169.9(15) . 17_667 ? Cu1 O5 Cu1 89.56(14) 5_557 17_667 ? Cu1 O5 Cu1 89.56(14) . 21_665 ? Cu1 O5 Cu1 169.9(15) 5_557 21_665 ? Cu1 O5 Cu1 89.56(14) 17_667 21_665 ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 1.152 _refine_diff_density_min -0.574 _refine_diff_density_rms 0.201