# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2002 data_rnb _database_code_CSD 182/1886 _journal_coden_Cambridge 182 _journal_volume ? _journal_year 2001 _journal_page_first 323 loop_ _publ_author_name 'G.Das' 'P.K.Bharadwaj' 'D.Ghosh' 'B.Chaudhuri' 'R.Banerjee' _publ_contact_author_name 'Dr Rupendranath Banerjee' _publ_contact_author_address ; Department of Chemistry Jadavpur University Calcutta 700 032 INDIA ; _publ_contact_author_email 'dsthcr28@cal2.vsnl.net.in' _publ_requested_journal 'Chemical Communications' _publ_section_title ; Synthesis and structure for [MnIV(biguandie)3]4+ ion: The simplest source for stable manganese(IV) in aqueous solution. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C6 H27 Mn N18 O14 S0.50' _chemical_formula_sum 'C6 H27 Mn N18 O14 S0.50' _chemical_formula_weight 646.43 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' 'Mn' 'Mn' 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M I2/a loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y, -z' 'x+1/2, y+1/2, z+1/2' '-x+1, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y, z' '-x+1/2, -y+1/2, -z+1/2' 'x, -y+1/2, z+1/2' _cell_length_a 17.2338(17) _cell_length_b 15.8698(16) _cell_length_c 18.3355(18) _cell_angle_alpha 90.00 _cell_angle_beta 103.07(1) _cell_angle_gamma 90.00 _cell_volume 4884.772(46) _cell_formula_units_Z 8 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 8.2 _cell_measurement_theta_max 14.3 _exptl_crystal_description 'Rectangular plates' _exptl_crystal_colour Red _exptl_crystal_size_max 0.3 _exptl_crystal_size_mid 0.2 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.758 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2672 _exptl_absorpt_coefficient_mu 0.685 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _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 'Enraf Nonius TurboCAD4' _diffrn_measurement_method 'theta-2theta scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time 'every hour' _diffrn_standards_decay_% ? _diffrn_reflns_number 4430 _diffrn_reflns_av_R_equivalents 0.0301 _diffrn_reflns_av_sigmaI/netI 0.0710 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 20 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 1.72 _diffrn_reflns_theta_max 24.96 _reflns_number_total 4272 _reflns_number_gt 2425 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CAD4 Express (Enraf Nonius, 1994)' _computing_cell_refinement 'CAD4 Express (Enraf Nonius, 1994)' _computing_data_reduction 'XCAD4 (Harms & Wocadlo, 1995)' _computing_structure_solution 'SIR 92' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material ? _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^)+(0.2000P)^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 4272 _refine_ls_number_parameters 323 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1614 _refine_ls_R_factor_gt 0.0943 _refine_ls_wR_factor_ref 0.3235 _refine_ls_wR_factor_gt 0.2755 _refine_ls_goodness_of_fit_ref 1.166 _refine_ls_restrained_S_all 1.166 _refine_ls_shift/su_max 0.062 _refine_ls_shift/su_mean 0.005 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 Mn Mn 0.63707(7) 0.03958(7) 0.24907(6) 0.0332(4) Uani 1 1 d . . . N3 N 0.5467(4) 0.0483(4) 0.2943(3) 0.0371(15) Uani 1 1 d . . . H3 H 0.5489 0.0163 0.3326 0.045 Uiso 1 1 calc R . . N13 N 0.6898(4) 0.1357(4) 0.3022(4) 0.0406(16) Uani 1 1 d . . . H13 H 0.6720 0.1834 0.2832 0.049 Uiso 1 1 calc R . . N6 N 0.5920(4) -0.0614(4) 0.1978(4) 0.0435(17) Uani 1 1 d . . . H6 H 0.5496 -0.0790 0.2104 0.052 Uiso 1 1 calc R . . N2 N 0.4656(4) 0.1418(5) 0.2143(4) 0.0517(19) Uani 1 1 d . . . H2 H 0.4208 0.1680 0.2051 0.062 Uiso 1 1 calc R . . N11 N 0.6937(4) -0.0272(4) 0.3326(4) 0.0415(16) Uani 1 1 d . . . H11 H 0.6751 -0.0771 0.3352 0.050 Uiso 1 1 calc R . . N7 N 0.6827(4) -0.0905(5) 0.1249(4) 0.060(2) Uani 1 1 d . . . H7 H 0.6940 -0.1234 0.0915 0.072 Uiso 1 1 calc R . . N8 N 0.7222(4) 0.0286(4) 0.1960(4) 0.0455(17) Uani 1 1 d . . . H8 H 0.7573 0.0679 0.2053 0.055 Uiso 1 1 calc R . . N5 N 0.4283(5) 0.0965(6) 0.3177(5) 0.062(2) Uani 1 1 d . . . H5A H 0.4348 0.0663 0.3576 0.075 Uiso 1 1 calc R . . H5B H 0.3867 0.1278 0.3046 0.075 Uiso 1 1 calc R . . N14 N 0.7974(5) -0.0659(6) 0.4299(5) 0.067(2) Uani 1 1 d . . . H14A H 0.7843 -0.1182 0.4245 0.081 Uiso 1 1 calc R . . H14B H 0.8379 -0.0508 0.4642 0.081 Uiso 1 1 calc R . . C2 C 0.4826(5) 0.0950(5) 0.2764(4) 0.0404(19) Uiso 1 1 d . . . N9 N 0.5732(5) -0.1748(5) 0.1158(5) 0.065(2) Uani 1 1 d . . . H9A H 0.5300 -0.1889 0.1287 0.078 Uiso 1 1 calc R . . H9B H 0.5898 -0.2038 0.0827 0.078 Uiso 1 1 calc R . . N1 N 0.5797(4) 0.1131(4) 0.1712(4) 0.0451(17) Uani 1 1 d . . . H1 H 0.6029 0.1214 0.1349 0.054 Uiso 1 1 calc R . . N12 N 0.7811(5) 0.0730(5) 0.3971(5) 0.064(2) Uani 1 1 d . . . H12 H 0.8238 0.0808 0.4312 0.076 Uiso 1 1 calc R . . C3 C 0.6144(5) -0.1081(5) 0.1469(5) 0.0426(19) Uani 1 1 d . . . N10 N 0.7998(5) -0.0290(5) 0.1232(5) 0.069(3) Uani 1 1 d . . . H10A H 0.8067 -0.0681 0.0928 0.082 Uiso 1 1 calc R . . H10B H 0.8355 0.0093 0.1365 0.082 Uiso 1 1 calc R . . C5 C 0.7555(5) -0.0086(6) 0.3855(5) 0.045(2) Uani 1 1 d . . . N15 N 0.7782(5) 0.2149(5) 0.3892(5) 0.072(3) Uani 1 1 d . . . H15A H 0.7598 0.2613 0.3677 0.086 Uiso 1 1 calc R . . H15B H 0.8163 0.2160 0.4286 0.086 Uiso 1 1 calc R . . N4 N 0.4828(6) 0.2058(7) 0.1065(6) 0.085(3) Uiso 1 1 d . . . H4A H 0.5093 0.2149 0.0728 0.102 Uiso 0.51 1 calc PR . . H4B H 0.4378 0.2304 0.1038 0.102 Uiso 0.51 1 calc PR . . C4 C 0.7352(5) -0.0278(5) 0.1491(5) 0.044(2) Uani 1 1 d . . . C1 C 0.5121(6) 0.1521(6) 0.1643(5) 0.056(3) Uani 1 1 d . . . C6 C 0.7475(5) 0.1415(6) 0.3616(5) 0.048(2) Uani 1 1 d . . . S S 0.2500 0.2230(3) 0.0000 0.0920(16) Uani 1 2 d S . . O1 O 0.2500 0.1489(10) 0.0000 0.41(3) Uani 1 2 d S . . O2 O 0.2252(14) 0.2604(9) 0.0526(10) 0.232(10) Uani 1 1 d . . . N1A N 0.5993(5) 0.3387(6) 0.2960(6) 0.071(3) Uani 1 1 d . . . O1A O 0.6652(4) 0.3258(4) 0.2797(4) 0.0638(19) Uani 1 1 d . . . O2A O 0.5756(4) 0.4130(5) 0.2961(6) 0.086(3) Uani 1 1 d . . . O3A O 0.5606(5) 0.2784(5) 0.3132(6) 0.096(3) Uani 1 1 d . . . N1B N 0.4815(5) 0.4152(6) 0.0490(4) 0.062(2) Uani 1 1 d . . . O1B O 0.5477(4) 0.4425(6) 0.0798(5) 0.094(3) Uani 1 1 d . . . O2B O 0.4711(4) 0.3610(5) -0.0011(5) 0.076(2) Uani 1 1 d . . . O3B O 0.4234(4) 0.4488(7) 0.0654(5) 0.100(3) Uani 1 1 d . . . N1C N 0.6030(19) 0.066(2) -0.0111(18) 0.273(14) Uiso 1 1 d . . . O1C O 0.6819(14) 0.1433(14) -0.0504(12) 0.246(9) Uiso 1 1 d . . . O2C O 0.5529(14) -0.0233(15) -0.0272(12) 0.254(10) Uiso 1 1 d . . . O3C O 0.6194(11) 0.1402(13) 0.0184(10) 0.197(7) Uiso 1 1 d . . . O1W O 0.2796(6) 0.1950(7) 0.2697(10) 0.193(8) Uani 1 1 d . . . O2W O 0.3453(8) 0.2716(6) 0.1864(7) 0.139(4) Uani 1 1 d . . . O3W O 0.6212(5) 0.3384(6) -0.0366(4) 0.086(2) Uani 1 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 Mn 0.0292(7) 0.0349(7) 0.0366(7) -0.0002(5) 0.0097(5) -0.0005(5) N3 0.032(3) 0.046(4) 0.035(3) 0.008(3) 0.010(3) 0.004(3) N13 0.040(4) 0.032(3) 0.049(4) -0.001(3) 0.008(3) 0.004(3) N6 0.032(4) 0.047(4) 0.055(4) -0.010(3) 0.016(3) -0.009(3) N2 0.035(4) 0.050(4) 0.064(5) 0.008(4) 0.000(4) 0.010(3) N11 0.029(4) 0.043(4) 0.051(4) 0.008(3) 0.007(3) -0.003(3) N7 0.043(4) 0.071(5) 0.070(5) -0.032(4) 0.025(4) -0.013(4) N8 0.040(4) 0.044(4) 0.058(4) -0.005(3) 0.023(3) -0.007(3) N5 0.044(5) 0.083(6) 0.067(5) -0.001(5) 0.027(4) 0.022(4) N14 0.048(5) 0.071(6) 0.072(5) 0.027(4) -0.007(4) 0.007(4) N9 0.042(5) 0.066(5) 0.088(6) -0.035(5) 0.019(4) -0.011(4) N1 0.041(4) 0.055(4) 0.038(4) 0.011(3) 0.005(3) 0.001(3) N12 0.040(4) 0.066(5) 0.071(5) -0.004(4) -0.017(4) -0.011(4) C3 0.032(4) 0.048(5) 0.047(5) -0.005(4) 0.009(4) -0.005(4) N10 0.058(5) 0.079(6) 0.081(6) -0.033(5) 0.041(5) -0.013(4) C5 0.032(4) 0.053(5) 0.049(5) 0.009(4) 0.007(4) 0.006(4) N15 0.065(6) 0.058(5) 0.081(6) -0.014(4) -0.010(5) -0.013(4) C4 0.035(4) 0.052(5) 0.048(5) -0.016(4) 0.012(4) -0.001(4) C1 0.053(6) 0.053(5) 0.049(5) 0.019(4) -0.012(4) -0.001(5) C6 0.042(5) 0.050(5) 0.049(5) -0.001(4) 0.006(4) -0.006(4) S 0.154(5) 0.060(3) 0.069(3) 0.000 0.039(3) 0.000 O1 1.10(11) 0.056(10) 0.170(19) 0.000 0.36(4) 0.000 O2 0.40(3) 0.112(10) 0.256(17) -0.004(10) 0.230(19) 0.099(13) N1A 0.036(5) 0.053(5) 0.124(8) -0.021(5) 0.020(5) -0.002(4) O1A 0.039(4) 0.065(4) 0.096(5) 0.002(4) 0.035(4) 0.003(3) O2A 0.047(4) 0.051(4) 0.159(8) -0.009(5) 0.022(5) 0.006(4) O3A 0.054(5) 0.053(4) 0.192(10) -0.017(5) 0.050(6) -0.015(4) N1B 0.053(5) 0.085(6) 0.049(5) -0.008(4) 0.016(4) -0.001(5) O1B 0.041(4) 0.142(8) 0.093(6) -0.042(5) 0.003(4) -0.003(5) O2B 0.061(5) 0.086(5) 0.080(5) -0.017(4) 0.014(4) -0.001(4) O3B 0.044(4) 0.171(10) 0.085(6) -0.051(6) 0.016(4) 0.011(5) O1W 0.069(7) 0.099(8) 0.36(2) 0.043(11) -0.051(10) 0.004(6) O2W 0.164(11) 0.080(7) 0.154(10) -0.007(6) -0.002(8) 0.047(7) O3W 0.067(5) 0.120(7) 0.067(5) -0.014(5) 0.008(4) 0.020(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 Mn N8 1.943(7) . ? Mn N11 1.935(6) . ? Mn N13 1.923(7) . ? Mn N1 1.934(7) . ? Mn N3 1.928(6) . ? Mn N6 1.930(7) . ? N3 C2 1.309(10) . ? N13 C6 1.302(10) . ? N6 C3 1.315(10) . ? N2 C1 1.358(12) . ? N2 C2 1.334(11) . ? N11 C5 1.302(10) . ? N7 C4 1.350(11) . ? N7 C3 1.358(11) . ? N8 C4 1.296(10) . ? N5 C2 1.331(11) . ? N14 C5 1.320(11) . ? N9 C3 1.328(11) . ? N1 C1 1.299(12) . ? N12 C5 1.369(12) . ? N12 C6 1.332(12) . ? N10 C4 1.305(11) . ? N15 C6 1.331(11) . ? N4 C1 1.364(12) . ? S O1 1.175(16) . ? S O2 1.285(11) 2 ? S O2 1.285(11) . ? N1A O3A 1.247(11) . ? N1A O2A 1.249(10) . ? N1A O1A 1.255(10) . ? N1B O1B 1.231(11) . ? N1B O3B 1.230(10) . ? N1B O2B 1.241(11) . ? N1C O2C 1.65(4) . ? N1C O3C 1.30(3) . ? N1C O1C 2.08(4) . ? 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 N8 Mn N11 92.5(3) . . ? N8 Mn N13 90.1(3) . . ? N11 Mn N13 86.4(3) . . ? N8 Mn N1 90.1(3) . . ? N11 Mn N1 175.5(3) . . ? N13 Mn N1 90.0(3) . . ? N8 Mn N3 175.4(3) . . ? N11 Mn N3 90.6(3) . . ? N13 Mn N3 93.5(3) . . ? N1 Mn N3 87.0(3) . . ? N8 Mn N6 87.0(3) . . ? N11 Mn N6 90.4(3) . . ? N13 Mn N6 175.6(3) . . ? N1 Mn N6 93.4(3) . . ? N3 Mn N6 89.6(3) . . ? C2 N3 Mn 130.5(6) . . ? C6 N13 Mn 131.6(6) . . ? C3 N6 Mn 131.5(6) . . ? C1 N2 C2 126.4(8) . . ? C5 N11 Mn 130.4(6) . . ? C4 N7 C3 128.0(8) . . ? C4 N8 Mn 131.2(6) . . ? N3 C2 N5 122.0(8) . . ? N3 C2 N2 122.7(8) . . ? N5 C2 N2 115.3(8) . . ? C1 N1 Mn 131.0(7) . . ? C5 N12 C6 127.4(7) . . ? N6 C3 N9 122.7(8) . . ? N6 C3 N7 120.5(7) . . ? N9 C3 N7 116.8(8) . . ? N11 C5 N12 120.6(7) . . ? N11 C5 N14 123.1(9) . . ? N12 C5 N14 116.3(8) . . ? N7 C4 N10 115.7(8) . . ? N7 C4 N8 121.6(8) . . ? N10 C4 N8 122.8(8) . . ? N1 C1 N2 122.1(8) . . ? N1 C1 N4 122.6(10) . . ? N2 C1 N4 115.4(9) . . ? N13 C6 N15 122.9(9) . . ? N13 C6 N12 121.1(8) . . ? N15 C6 N12 115.9(8) . . ? O1 S O2 117.6(7) . 2 ? O1 S O2 117.6(7) . . ? O2 S O2 124.9(15) 2 . ? O3A N1A O2A 122.1(9) . . ? O3A N1A O1A 120.0(8) . . ? O2A N1A O1A 117.9(9) . . ? O1B N1B O3B 117.2(9) . . ? O1B N1B O2B 123.1(9) . . ? O3B N1B O2B 119.4(9) . . ? O2C N1C O3C 155(3) . . ? O2C N1C O1C 143(2) . . ? O3C N1C O1C 60.7(18) . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 24.96 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 2.065 _refine_diff_density_min -0.923 _refine_diff_density_rms 0.143