Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2003 data_global _journal_coden_Cambridge 186 loop_ _publ_author_name 'C. N. R. Rao' 'Srinivasan Natarajan' 'R. Vaidhyanathan' _publ_contact_author_name 'Prof C. N. R. Rao' _publ_contact_author_address ; Chemistry and Physics of Materials Unit Jawaharlal Nehru Centre for Advanced Scientific Research Jakkur, P. O. Bangalore 560 064 INDIA ; _publ_contact_author_email CNRRAO@JNCASR.AC.IN _publ_requested_journal 'Dalton Transactions' _publ_section_title ; Aliphatic dicarboxylates with three-dimentional metal-organic frameworks possessing hydrophobic channels ; data_sad1 _database_code_CSD 199941 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C3 H6 Cd N0 O6' _chemical_formula_weight 250.48 _chemical_melting_point ? _chemical_compound_source ? 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' Cd Cd -0.8075 1.2024 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Rhombohedral _symmetry_space_group_name_H-M R-3 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 17.0685(2) _cell_length_b 17.0685(2) _cell_length_c 12.4302(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 3136.17(9) _cell_formula_units_Z 18 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max 0.14 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.06 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.387 _exptl_crystal_density_method ? _exptl_crystal_F_000 2160 _exptl_absorpt_coefficient_mu 3.107 _exptl_absorpt_correction_type SADABS _exptl_absorpt_correction_T_min 0.721591 _exptl_absorpt_correction_T_max 1.000000 _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 'Siemens P4' _diffrn_measurement_method '\w scans' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 4504 _diffrn_reflns_av_R_equivalents 0.0459 _diffrn_reflns_av_sigmaI/netI 0.0274 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.14 _diffrn_reflns_theta_max 23.29 _reflns_number_total 1012 _reflns_number_observed 990 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens XSCANS' _computing_cell_refinement 'Siemens XSCANS' _computing_data_reduction 'Siemens SHELXTL' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'Siemens SHELXTL' _computing_publication_material 'Siemens SHELXTL' _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^)+(0.0000P)^2^+72.3680P] 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 ? _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1012 _refine_ls_number_parameters 107 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0344 _refine_ls_R_factor_obs 0.0336 _refine_ls_wR_factor_all 0.0901 _refine_ls_wR_factor_obs 0.0898 _refine_ls_goodness_of_fit_all 1.443 _refine_ls_goodness_of_fit_obs 1.456 _refine_ls_restrained_S_all 1.443 _refine_ls_restrained_S_obs 1.456 _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 Cd1 Cd 0.39981(4) 0.06511(4) 0.84954(5) 0.0250(2) Uani 1 d . . C1 C 0.4718(5) 0.2272(5) 0.9622(6) 0.021(2) Uani 1 d . . C2 C 0.3431(5) -0.1068(5) 0.9312(7) 0.027(2) Uani 1 d . . C3 C 0.3100(6) -0.2042(5) 0.9667(7) 0.029(2) Uani 1 d . . H2A H 0.2966(6) -0.2416(5) 0.9030(7) 0.035 Uiso 1 calc R . H2B H 0.3586(6) -0.2060(5) 1.0049(7) 0.035 Uiso 1 calc R . O1 O 0.5425(4) 0.1043(4) 0.7936(5) 0.0312(13) Uani 1 d . . O2 O 0.3797(4) 0.0764(4) 0.6690(5) 0.0326(14) Uani 1 d . . O3 O 0.4750(4) 0.1593(4) 0.9929(4) 0.0301(13) Uani 1 d . . O4 O 0.3504(4) -0.0880(4) 0.8331(4) 0.0344(14) Uani 1 d . . O10 O 0.2523(4) 0.0311(5) 0.8606(6) 0.0318(14) Uani 1 d . . O100 O 0.1435(5) -0.1290(6) 0.9555(6) 0.063(2) Uani 1 d . . H101 H 0.1073(45) -0.0937(44) 0.9713(54) 0.003(16) Uiso 1 d . . H11 H 0.2315(73) 0.0252(71) 0.7946(100) 0.055(33) Uiso 1 d . . H10 H 0.2138(76) -0.0087(74) 0.8809(90) 0.045(37) Uiso 1 d . . H100 H 0.0811(86) -0.1728(84) 0.9220(100) 0.075(38) 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 Cd1 0.0254(4) 0.0262(4) 0.0201(3) -0.0001(2) 0.0021(2) 0.0105(3) C1 0.016(4) 0.023(4) 0.023(4) 0.003(3) 0.008(3) 0.009(3) C2 0.022(4) 0.028(4) 0.032(5) 0.002(4) 0.004(3) 0.013(4) C3 0.032(4) 0.028(4) 0.026(4) 0.002(4) 0.008(4) 0.015(4) O1 0.029(3) 0.040(3) 0.026(3) 0.008(3) 0.003(3) 0.018(3) O2 0.026(3) 0.041(3) 0.026(3) 0.002(3) 0.002(3) 0.014(3) O3 0.041(3) 0.029(3) 0.027(3) 0.001(2) 0.001(3) 0.023(3) O4 0.042(4) 0.034(3) 0.021(3) 0.003(3) 0.008(3) 0.014(3) O10 0.028(4) 0.035(4) 0.028(4) -0.002(3) -0.001(3) 0.012(3) O100 0.053(5) 0.064(5) 0.043(4) 0.011(4) -0.002(4) 0.007(4) _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 Cd1 O10 2.288(7) . ? Cd1 O1 2.288(5) . ? Cd1 O2 2.293(6) . ? Cd1 O3 2.312(6) . ? Cd1 O4 2.319(6) . ? Cd1 O2 2.535(6) 6 ? Cd1 O1 2.545(5) 17_556 ? C1 O3 1.247(9) . ? C1 O1 1.258(10) 17_556 ? C1 C3 1.509(11) 12_557 ? C2 O4 1.251(10) . ? C2 O2 1.269(10) 6 ? C2 C3 1.528(11) . ? C3 C1 1.509(11) 11_557 ? C3 H2A 0.97 . ? C3 H2B 0.97 . ? O1 C1 1.258(10) 18_546 ? O1 Cd1 2.545(5) 18_546 ? O2 C2 1.269(10) 8_544 ? O2 Cd1 2.535(6) 8_544 ? O10 H11 0.88(12) . ? O10 H10 0.71(11) . ? O100 H101 1.07(7) . ? O100 H100 1.03(13) . ? 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 O10 Cd1 O1 165.5(2) . . ? O10 Cd1 O2 83.6(2) . . ? O1 Cd1 O2 82.0(2) . . ? O10 Cd1 O3 106.7(2) . . ? O1 Cd1 O3 83.8(2) . . ? O2 Cd1 O3 138.6(2) . . ? O10 Cd1 O4 89.2(2) . . ? O1 Cd1 O4 92.1(2) . . ? O2 Cd1 O4 91.3(2) . . ? O3 Cd1 O4 127.9(2) . . ? O10 Cd1 O2 86.5(2) . 6 ? O1 Cd1 O2 105.8(2) . 6 ? O2 Cd1 O2 143.6(2) . 6 ? O3 Cd1 O2 77.7(2) . 6 ? O4 Cd1 O2 53.6(2) . 6 ? O10 Cd1 O1 85.1(2) . 17_556 ? O1 Cd1 O1 93.7(3) . 17_556 ? O2 Cd1 O1 89.3(2) . 17_556 ? O3 Cd1 O1 53.2(2) . 17_556 ? O4 Cd1 O1 174.2(2) . 17_556 ? O2 Cd1 O1 124.7(2) 6 17_556 ? O3 C1 O1 121.4(7) . 17_556 ? O3 C1 C3 117.9(7) . 12_557 ? O1 C1 C3 120.7(7) 17_556 12_557 ? O4 C2 O2 121.2(7) . 6 ? O4 C2 C3 119.7(7) . . ? O2 C2 C3 119.1(7) 6 . ? C1 C3 C2 114.8(6) 11_557 . ? C1 C3 H2A 108.6(4) 11_557 . ? C2 C3 H2A 108.6(5) . . ? C1 C3 H2B 108.6(4) 11_557 . ? C2 C3 H2B 108.6(4) . . ? H2A C3 H2B 107.6 . . ? C1 O1 Cd1 126.7(5) 18_546 . ? C1 O1 Cd1 87.1(4) 18_546 18_546 ? Cd1 O1 Cd1 143.1(2) . 18_546 ? C2 O2 Cd1 127.7(5) 8_544 . ? C2 O2 Cd1 87.3(5) 8_544 8_544 ? Cd1 O2 Cd1 142.8(2) . 8_544 ? C1 O3 Cd1 98.3(5) . . ? C2 O4 Cd1 97.9(5) . . ? Cd1 O10 H11 107.6(71) . . ? Cd1 O10 H10 129.4(90) . . ? H11 O10 H10 95.4(100) . . ? H101 O100 H100 78.8(71) . . ? _refine_diff_density_max 0.908 _refine_diff_density_min -1.055 _refine_diff_density_rms 0.127 data_sad1b _database_code_CSD 199942 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C5 H6 Mn O4' _chemical_formula_weight 185.04 _chemical_melting_point ? _chemical_compound_source ? 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' 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' _symmetry_cell_setting Rhombohedral _symmetry_space_group_name_H-M R-3 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 11.29440(10) _cell_length_b 11.29440(10) _cell_length_c 29.4830(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 3257.08(6) _cell_formula_units_Z 18 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max 0.12 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.698 _exptl_crystal_density_method ? _exptl_crystal_F_000 1674 _exptl_absorpt_coefficient_mu 1.775 _exptl_absorpt_correction_type SADABS _exptl_absorpt_correction_T_min 0.645501 _exptl_absorpt_correction_T_max 1.000000 _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 'Siemens P4' _diffrn_measurement_method '\w scans' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 4523 _diffrn_reflns_av_R_equivalents 0.0516 _diffrn_reflns_av_sigmaI/netI 0.0312 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 32 _diffrn_reflns_theta_min 2.07 _diffrn_reflns_theta_max 23.24 _reflns_number_total 1045 _reflns_number_observed 957 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens XSCANS' _computing_cell_refinement 'Siemens XSCANS' _computing_data_reduction 'Siemens SHELXTL' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'Siemens SHELXTL' _computing_publication_material 'Siemens SHELXTL' _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^)+(0.0189P)^2^+2.2708P] 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 ? _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.00117(9) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 1045 _refine_ls_number_parameters 118 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0228 _refine_ls_R_factor_obs 0.0205 _refine_ls_wR_factor_all 0.0507 _refine_ls_wR_factor_obs 0.0500 _refine_ls_goodness_of_fit_all 1.091 _refine_ls_goodness_of_fit_obs 1.131 _refine_ls_restrained_S_all 1.091 _refine_ls_restrained_S_obs 1.131 _refine_ls_shift/esd_max 0.000 _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 Mn1 Mn 0.0000 0.0000 0.13868(2) 0.0210(2) Uani 1 d S . Mn2 Mn 0.0000 0.0000 0.0000 0.0200(2) Uani 1 d S . Mn3 Mn -0.1667 -0.3333 0.1667 0.0215(2) Uani 1 d S . O1 O -0.13985(14) -0.19909(13) 0.10914(4) 0.0269(3) Uani 1 d . . O2 O 0.02990(13) -0.14809(13) 0.18302(4) 0.0281(3) Uani 1 d . . O3 O -0.17089(14) -0.12582(15) 0.04308(4) 0.0298(4) Uani 1 d . . O4 O -0.0622(2) -0.41728(14) 0.13195(5) 0.0386(4) Uani 1 d . . C1 C -0.1875(2) -0.2196(2) 0.06871(6) 0.0273(5) Uani 1 d . . C2 C -0.0621(2) -0.5272(2) 0.13185(7) 0.0289(5) Uani 1 d . . C3 C -0.2739(3) -0.3650(3) 0.05234(9) 0.0526(8) Uani 1 d . . C4 C 0.0532(3) -0.5295(3) 0.10678(10) 0.0490(7) Uani 1 d . . C5 C -0.4253(3) -0.4115(3) 0.05765(10) 0.0694(10) Uani 1 d . . H1 H 0.0773(24) -0.5882(26) 0.1232(7) 0.043(7) Uiso 1 d . . H3 H -0.2477(28) -0.4170(29) 0.0679(9) 0.053(8) Uiso 1 d . . H2 H 0.1283(32) -0.4383(33) 0.1062(9) 0.074(9) Uiso 1 d . . H4 H -0.2458(28) -0.3642(27) 0.0195(10) 0.060(8) Uiso 1 d . . H5 H -0.4491(32) -0.3560(34) 0.0399(11) 0.082(10) Uiso 1 d . . H6 H -0.4738(34) -0.5046(34) 0.0425(11) 0.081(10) 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 Mn1 0.0168(2) 0.0168(2) 0.0295(3) 0.000 0.000 0.00840(10) Mn2 0.0206(3) 0.0206(3) 0.0189(4) 0.000 0.000 0.01030(13) Mn3 0.0220(3) 0.0148(2) 0.0269(3) 0.0014(2) 0.0015(2) 0.0087(2) O1 0.0316(8) 0.0210(8) 0.0225(7) 0.0008(6) -0.0016(6) 0.0091(6) O2 0.0213(8) 0.0201(8) 0.0388(8) 0.0052(6) -0.0055(6) 0.0073(6) O3 0.0271(8) 0.0285(8) 0.0299(8) 0.0103(6) 0.0047(6) 0.0111(7) O4 0.0465(10) 0.0235(9) 0.0515(9) 0.0078(7) 0.0204(7) 0.0217(7) C1 0.0266(12) 0.0261(12) 0.0240(11) 0.0020(9) 0.0041(9) 0.0092(9) C2 0.0305(13) 0.0241(12) 0.0340(11) 0.0035(9) 0.0081(9) 0.0151(10) C3 0.080(2) 0.0296(14) 0.0266(14) -0.0006(10) -0.0057(13) 0.0117(14) C4 0.044(2) 0.0271(14) 0.079(2) 0.0156(13) 0.0321(14) 0.0206(13) C5 0.066(2) 0.038(2) 0.055(2) 0.0165(14) -0.035(2) -0.0103(15) _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 Mn1 O1 2.1812(13) 2 ? Mn1 O1 2.1812(13) . ? Mn1 O1 2.1813(13) 3 ? Mn1 O2 2.2772(13) . ? Mn1 O2 2.2772(13) 2 ? Mn1 O2 2.2773(13) 3 ? Mn2 O3 2.1482(13) . ? Mn2 O3 2.1483(13) 2 ? Mn2 O3 2.1483(13) 12 ? Mn2 O3 2.1483(13) 10 ? Mn2 O3 2.1483(13) 3 ? Mn2 O3 2.1483(13) 11 ? Mn3 O4 2.1118(14) 13_445 ? Mn3 O4 2.1117(14) . ? Mn3 O1 2.1927(13) 13_445 ? Mn3 O1 2.1926(13) . ? Mn3 O2 2.2122(13) . ? Mn3 O2 2.2122(13) 13_445 ? O1 C1 1.281(2) . ? O2 C2 1.278(2) 14 ? O3 C1 1.237(2) . ? O4 C2 1.242(2) . ? C1 C3 1.509(3) . ? C2 O2 1.278(2) 15_445 ? C2 C4 1.509(3) . ? C3 C5 1.526(5) . ? C4 C5 1.526(4) 3_545 ? C5 C4 1.526(4) 2_445 ? 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 Mn1 O1 105.12(4) 2 . ? O1 Mn1 O1 105.12(4) 2 3 ? O1 Mn1 O1 105.12(4) . 3 ? O1 Mn1 O2 86.89(5) 2 . ? O1 Mn1 O2 76.64(5) . . ? O1 Mn1 O2 166.64(5) 3 . ? O1 Mn1 O2 76.64(5) 2 2 ? O1 Mn1 O2 166.64(5) . 2 ? O1 Mn1 O2 86.89(5) 3 2 ? O2 Mn1 O2 90.33(5) . 2 ? O1 Mn1 O2 166.64(5) 2 3 ? O1 Mn1 O2 86.89(5) . 3 ? O1 Mn1 O2 76.64(5) 3 3 ? O2 Mn1 O2 90.33(5) . 3 ? O2 Mn1 O2 90.32(5) 2 3 ? O3 Mn2 O3 88.61(5) . 2 ? O3 Mn2 O3 91.39(5) . 12 ? O3 Mn2 O3 91.40(5) 2 12 ? O3 Mn2 O3 180.0 . 10 ? O3 Mn2 O3 91.40(5) 2 10 ? O3 Mn2 O3 88.61(5) 12 10 ? O3 Mn2 O3 88.61(5) . 3 ? O3 Mn2 O3 88.60(5) 2 3 ? O3 Mn2 O3 180.0 12 3 ? O3 Mn2 O3 91.39(5) 10 3 ? O3 Mn2 O3 91.39(5) . 11 ? O3 Mn2 O3 180.0 2 11 ? O3 Mn2 O3 88.60(5) 12 11 ? O3 Mn2 O3 88.60(5) 10 11 ? O3 Mn2 O3 91.39(5) 3 11 ? O4 Mn3 O4 180.0 13_445 . ? O4 Mn3 O1 91.17(5) 13_445 13_445 ? O4 Mn3 O1 88.83(5) . 13_445 ? O4 Mn3 O1 88.82(5) 13_445 . ? O4 Mn3 O1 91.18(5) . . ? O1 Mn3 O1 180.0 13_445 . ? O4 Mn3 O2 89.52(6) 13_445 . ? O4 Mn3 O2 90.48(6) . . ? O1 Mn3 O2 102.22(5) 13_445 . ? O1 Mn3 O2 77.78(5) . . ? O4 Mn3 O2 90.48(6) 13_445 13_445 ? O4 Mn3 O2 89.52(6) . 13_445 ? O1 Mn3 O2 77.78(5) 13_445 13_445 ? O1 Mn3 O2 102.22(5) . 13_445 ? O2 Mn3 O2 180.0 . 13_445 ? C1 O1 Mn1 125.50(12) . . ? C1 O1 Mn3 133.99(12) . . ? Mn1 O1 Mn3 100.52(5) . . ? C2 O2 Mn3 132.14(13) 14 . ? C2 O2 Mn1 128.82(12) 14 . ? Mn3 O2 Mn1 97.02(5) . . ? C1 O3 Mn2 129.01(13) . . ? C2 O4 Mn3 136.86(13) . . ? O3 C1 O1 122.9(2) . . ? O3 C1 C3 118.4(2) . . ? O1 C1 C3 118.6(2) . . ? O4 C2 O2 123.7(2) . 15_445 ? O4 C2 C4 116.7(2) . . ? O2 C2 C4 119.5(2) 15_445 . ? C1 C3 C5 110.2(3) . . ? C2 C4 C5 111.2(2) . 3_545 ? C3 C5 C4 113.9(2) . 2_445 ? _refine_diff_density_max 0.198 _refine_diff_density_min -0.218 _refine_diff_density_rms 0.046