# Supplementary Material (ESI) for New Journal of Chemistry # This journal is (c) The Royal Society of Chemistry and # The Centre National de la Recherche Scientifique, 2007 data_global _journal_name_full 'New J.Chem.' _journal_coden_cambridge 0440 _publ_section_title ;Synthesis and characterization of a family of tetranuclear manganese(III) phosphonate complexes ; _publ_contact_author_name 'Chang-Neng Chen' _publ_contact_author_email CCN@FJIRSM.AC.CN loop_ _publ_author_name 'Chang-Neng Chen' 'Ming-Qiang Hu' 'Qiutian Liu' 'Chengbing Ma' 'Mei Wang' 'Da-Qiang Yuan' # Attachment 'B706514K_cpds1-4.CIF' data_compound-1 _database_code_depnum_ccdc_archive 'CCDC 635082' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C38 H50 Mn4 N4 O24 P2' _chemical_formula_weight 1228.52 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' 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' P P 0.1023 0.0942 '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' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M C2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 17.8554(9) _cell_length_b 15.7085(9) _cell_length_c 17.7912(9) _cell_angle_alpha 90.00 _cell_angle_beta 96.224(3) _cell_angle_gamma 90.00 _cell_volume 4960.7(5) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 6413 _cell_measurement_theta_min 2.84 _cell_measurement_theta_max 27.48 _exptl_crystal_description prism _exptl_crystal_colour brown _exptl_crystal_size_max .45 _exptl_crystal_size_mid .30 _exptl_crystal_size_min .25 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.645 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2512 _exptl_absorpt_coefficient_mu 1.147 _exptl_absorpt_correction_type empirical _exptl_absorpt_process_details 'SADABS (Sheldrick, 1996)' _exptl_absorpt_correction_T_min .6674 _exptl_absorpt_correction_T_max 0.7527 _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 P4' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number none _diffrn_standards_interval_count none _diffrn_standards_interval_time none _diffrn_standards_decay_% none _diffrn_reflns_number 18157 _diffrn_reflns_av_R_equivalents 0.0167 _diffrn_reflns_av_sigmaI/netI 0.0170 _diffrn_reflns_limit_h_min -23 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 2.84 _diffrn_reflns_theta_max 27.48 _reflns_number_total 5679 _reflns_number_gt 5192 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Siemens SMART' _computing_cell_refinement 'Siemens SMART & SAINT' _computing_data_reduction 'Siemens XPREP' _computing_structure_solution 'Siemens SHELXTL' _computing_structure_refinement 'Siemens SHELXTL' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0689P)^2^+9.5681P] 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 5679 _refine_ls_number_parameters 329 _refine_ls_number_restraints 0 _refine_ls_R_factor_ref 0.0441 _refine_ls_R_factor_gt 0.0400 _refine_ls_wR_factor_ref 0.1134 _refine_ls_wR_factor_gt 0.1101 _refine_ls_goodness_of_fit_ref 1.004 _refine_ls_restrained_S_all 1.004 _refine_ls_shift/su_max 0.001 _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 Mn1 Mn 0.695939(19) 0.30978(2) 0.522766(18) 0.02371(10) Uani 1 1 d . . . Mn2 Mn 0.807606(18) 0.21937(2) 0.664998(18) 0.02255(10) Uani 1 1 d . . . P1 P 0.87193(3) 0.35353(4) 0.57023(3) 0.02607(14) Uani 1 1 d . . . O1 O 0.75941(9) 0.22109(9) 0.56711(8) 0.0229(3) Uani 1 1 d . . . O2 O 0.63663(11) 0.40531(11) 0.48118(10) 0.0368(4) Uani 1 1 d . . . O3 O 0.61569(11) 0.38214(12) 0.35704(10) 0.0390(4) Uani 1 1 d . . . O4 O 0.89012(9) 0.28908(11) 0.51062(9) 0.0288(3) Uani 1 1 d . . . O5 O 0.87505(9) 0.30991(10) 0.64912(9) 0.0288(3) Uani 1 1 d . . . O6 O 0.79618(9) 0.39782(10) 0.55103(10) 0.0301(3) Uani 1 1 d . . . O7 O 0.72735(11) 0.30185(12) 0.71412(10) 0.0384(4) Uani 1 1 d . . . O8 O 0.64865(11) 0.33629(13) 0.61272(10) 0.0394(4) Uani 1 1 d . . . O9 O 0.51774(18) 0.1687(2) 0.59407(19) 0.0846(9) Uani 1 1 d . . . H9B H 0.5378 0.1928 0.5606 0.127 Uiso 1 1 calc R . . O10 O 0.4453(2) 0.2810(2) 0.5837(2) 0.1090(14) Uani 1 1 d . . . O11 O 0.75209(16) 0.54165(18) 0.4786(2) 0.0842(10) Uani 1 1 d . . . H11D H 0.7761 0.5032 0.5012 0.126 Uiso 1 1 calc R . . O12 O 0.8653(2) 0.5932(3) 0.4768(3) 0.1245(16) Uani 1 1 d . . . N1 N 0.85494(11) 0.19759(13) 0.77372(11) 0.0280(4) Uani 1 1 d . . . N2 N 0.74139(11) 0.12174(12) 0.69760(11) 0.0279(4) Uani 1 1 d . . . C1 C 0.91466(15) 0.23956(18) 0.80722(15) 0.0368(5) Uani 1 1 d . . . H1A H 0.9342 0.2850 0.7821 0.044 Uiso 1 1 calc R . . C2 C 0.94832(18) 0.2171(2) 0.87853(17) 0.0478(7) Uani 1 1 d . . . H2A H 0.9897 0.2472 0.9010 0.057 Uiso 1 1 calc R . . C3 C 0.91969(19) 0.1500(2) 0.91511(17) 0.0513(8) Uani 1 1 d . . . H3A H 0.9412 0.1345 0.9631 0.062 Uiso 1 1 calc R . . C4 C 0.85861(18) 0.1053(2) 0.88066(15) 0.0441(6) Uani 1 1 d . . . H4A H 0.8391 0.0591 0.9049 0.053 Uiso 1 1 calc R . . C5 C 0.82698(14) 0.13030(15) 0.80941(13) 0.0304(5) Uani 1 1 d . . . C6 C 0.76222(14) 0.08795(15) 0.76656(13) 0.0299(5) Uani 1 1 d . . . C7 C 0.72480(17) 0.01794(17) 0.79208(16) 0.0409(6) Uani 1 1 d . . . H7A H 0.7399 -0.0056 0.8393 0.049 Uiso 1 1 calc R . . C8 C 0.66545(18) -0.01596(18) 0.74681(18) 0.0468(7) Uani 1 1 d . . . H8A H 0.6407 -0.0637 0.7626 0.056 Uiso 1 1 calc R . . C9 C 0.64231(17) 0.0206(2) 0.67782(17) 0.0467(7) Uani 1 1 d . . . H9A H 0.6008 -0.0006 0.6475 0.056 Uiso 1 1 calc R . . C10 C 0.68246(15) 0.08969(18) 0.65465(15) 0.0374(6) Uani 1 1 d . . . H10A H 0.6678 0.1143 0.6078 0.045 Uiso 1 1 calc R . . C11 C 0.94565(16) 0.43173(18) 0.58002(18) 0.0425(6) Uani 1 1 d . . . H11A H 0.9470 0.4613 0.5330 0.064 Uiso 1 1 calc R . . H11B H 0.9931 0.4041 0.5936 0.064 Uiso 1 1 calc R . . H11C H 0.9363 0.4716 0.6188 0.064 Uiso 1 1 calc R . . C12 C 0.66824(14) 0.33374(16) 0.68317(14) 0.0317(5) Uani 1 1 d . . . C13 C 0.6137(2) 0.3751(2) 0.73114(18) 0.0559(9) Uani 1 1 d . . . H13A H 0.6260 0.3586 0.7830 0.084 Uiso 1 1 calc R . . H13B H 0.5634 0.3571 0.7140 0.084 Uiso 1 1 calc R . . H13C H 0.6171 0.4359 0.7269 0.084 Uiso 1 1 calc R . . C14 C 0.60912(14) 0.42459(15) 0.41455(14) 0.0297(5) Uani 1 1 d . . . C15 C 0.56505(19) 0.50642(19) 0.40683(17) 0.0477(7) Uani 1 1 d . . . H15A H 0.5425 0.5126 0.3556 0.072 Uiso 1 1 calc R . . H15B H 0.5982 0.5535 0.4197 0.072 Uiso 1 1 calc R . . H15C H 0.5263 0.5054 0.4402 0.072 Uiso 1 1 calc R . . C16 C 0.4601(2) 0.2116(3) 0.6092(2) 0.0625(9) Uani 1 1 d . . . C17 C 0.4128(3) 0.1687(3) 0.6609(3) 0.1008(19) Uani 1 1 d . . . H17A H 0.3888 0.2107 0.6893 0.151 Uiso 1 1 calc R . . H17B H 0.4437 0.1325 0.6949 0.151 Uiso 1 1 calc R . . H17C H 0.3751 0.1351 0.6320 0.151 Uiso 1 1 calc R . . C18 C 0.7961(2) 0.6004(2) 0.4646(2) 0.0620(9) Uani 1 1 d . . . C19 C 0.7616(3) 0.6730(3) 0.4200(3) 0.0823(13) Uani 1 1 d . . . H19A H 0.7871 0.7247 0.4364 0.123 Uiso 1 1 calc R . . H19B H 0.7093 0.6774 0.4275 0.123 Uiso 1 1 calc R . . H19C H 0.7662 0.6640 0.3674 0.123 Uiso 1 1 calc R . . 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 0.02791(18) 0.02450(18) 0.01906(17) 0.00077(12) 0.00404(13) 0.00176(12) Mn2 0.02633(18) 0.02279(18) 0.01831(17) 0.00120(11) 0.00151(12) -0.00291(12) P1 0.0273(3) 0.0241(3) 0.0269(3) 0.0002(2) 0.0035(2) -0.0060(2) O1 0.0266(7) 0.0234(7) 0.0185(7) 0.0009(5) 0.0023(6) -0.0020(6) O2 0.0481(10) 0.0319(9) 0.0304(9) 0.0010(7) 0.0039(8) 0.0116(8) O3 0.0432(10) 0.0408(10) 0.0319(9) -0.0045(8) -0.0012(8) 0.0136(8) O4 0.0279(8) 0.0318(8) 0.0271(8) -0.0008(6) 0.0052(6) -0.0046(6) O5 0.0315(8) 0.0293(8) 0.0247(8) 0.0001(6) -0.0003(6) -0.0084(6) O6 0.0322(8) 0.0246(8) 0.0333(9) 0.0001(6) 0.0028(7) -0.0020(6) O7 0.0438(10) 0.0436(10) 0.0277(9) -0.0041(7) 0.0040(7) 0.0123(8) O8 0.0379(9) 0.0548(11) 0.0265(9) 0.0001(8) 0.0088(7) 0.0115(9) O9 0.078(2) 0.088(2) 0.093(2) 0.0271(18) 0.0358(17) 0.0126(17) O10 0.122(3) 0.078(2) 0.135(4) 0.040(2) 0.051(3) 0.018(2) O11 0.0650(17) 0.0627(17) 0.127(3) 0.0380(17) 0.0185(17) 0.0016(14) O12 0.086(2) 0.107(3) 0.171(4) 0.046(3) -0.031(3) -0.028(2) N1 0.0294(10) 0.0307(10) 0.0239(9) -0.0007(7) 0.0021(7) 0.0011(8) N2 0.0322(10) 0.0262(9) 0.0254(9) 0.0035(7) 0.0032(7) -0.0041(8) C1 0.0352(13) 0.0405(14) 0.0330(13) -0.0008(11) -0.0034(10) -0.0035(11) C2 0.0445(16) 0.0567(18) 0.0388(15) -0.0049(13) -0.0116(12) -0.0047(13) C3 0.0582(18) 0.0620(19) 0.0301(14) 0.0053(13) -0.0112(13) 0.0062(15) C4 0.0533(16) 0.0486(16) 0.0295(13) 0.0102(11) -0.0003(11) 0.0017(13) C5 0.0355(12) 0.0320(12) 0.0237(11) 0.0030(9) 0.0034(9) 0.0038(10) C6 0.0367(12) 0.0277(11) 0.0259(11) 0.0041(9) 0.0058(9) 0.0014(9) C7 0.0558(16) 0.0328(13) 0.0352(14) 0.0111(11) 0.0095(12) -0.0038(12) C8 0.0569(18) 0.0352(14) 0.0505(17) 0.0058(12) 0.0159(14) -0.0153(13) C9 0.0466(16) 0.0471(16) 0.0461(16) 0.0007(13) 0.0032(12) -0.0205(13) C10 0.0403(13) 0.0412(14) 0.0297(12) 0.0034(10) -0.0005(10) -0.0117(11) C11 0.0388(14) 0.0364(13) 0.0523(17) -0.0013(12) 0.0049(12) -0.0169(11) C12 0.0369(12) 0.0318(12) 0.0279(12) 0.0008(9) 0.0108(10) 0.0017(10) C13 0.0587(19) 0.074(2) 0.0378(16) -0.0018(15) 0.0186(14) 0.0249(17) C14 0.0312(11) 0.0275(11) 0.0313(12) 0.0018(9) 0.0076(9) 0.0024(9) C15 0.0632(19) 0.0392(14) 0.0415(15) 0.0062(12) 0.0098(13) 0.0214(14) C16 0.065(2) 0.059(2) 0.066(2) 0.0035(17) 0.0179(18) 0.0015(17) C17 0.114(4) 0.083(3) 0.118(4) 0.003(3) 0.069(4) -0.002(3) C18 0.066(2) 0.0486(19) 0.070(2) 0.0031(16) 0.0003(18) -0.0073(16) C19 0.099(3) 0.054(2) 0.096(3) 0.024(2) 0.019(3) -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 Mn1 O1 1.9115(16) . ? Mn1 O1 1.9245(15) 7_656 ? Mn1 O8 1.9341(17) . ? Mn1 O2 1.9368(18) . ? Mn1 O4 2.2199(17) 7_656 ? Mn1 O6 2.2746(17) . ? Mn1 Mn1 2.8722(7) 7_656 ? Mn1 Mn2 3.3618(5) . ? Mn2 O1 1.8572(15) . ? Mn2 O5 1.9044(16) . ? Mn2 N1 2.054(2) . ? Mn2 N2 2.0579(19) . ? Mn2 O3 2.1653(18) 7_656 ? Mn2 O7 2.1834(18) . ? P1 O6 1.5264(18) . ? P1 O4 1.5264(17) . ? P1 O5 1.5575(17) . ? P1 C11 1.795(3) . ? O1 Mn1 1.9245(15) 7_656 ? O2 C14 1.270(3) . ? O3 C14 1.237(3) . ? O3 Mn2 2.1653(18) 7_656 ? O4 Mn1 2.2199(17) 7_656 ? O7 C12 1.242(3) . ? O8 C12 1.265(3) . ? O9 C16 1.283(5) . ? O9 H9B 0.8200 . ? O10 C16 1.199(5) . ? O11 C18 1.255(4) . ? O11 H11D 0.8200 . ? O12 C18 1.236(5) . ? N1 C1 1.338(3) . ? N1 C5 1.356(3) . ? N2 C10 1.330(3) . ? N2 C6 1.351(3) . ? C1 C2 1.389(4) . ? C1 H1A 0.9300 . ? C2 C3 1.366(5) . ? C2 H2A 0.9300 . ? C3 C4 1.384(4) . ? C3 H3A 0.9300 . ? C4 C5 1.388(3) . ? C4 H4A 0.9300 . ? C5 C6 1.473(3) . ? C6 C7 1.388(3) . ? C7 C8 1.368(4) . ? C7 H7A 0.9300 . ? C8 C9 1.377(4) . ? C8 H8A 0.9300 . ? C9 C10 1.388(4) . ? C9 H9A 0.9300 . ? C10 H10A 0.9300 . ? C11 H11A 0.9600 . ? C11 H11B 0.9600 . ? C11 H11C 0.9600 . ? C12 C13 1.509(3) . ? C13 H13A 0.9600 . ? C13 H13B 0.9600 . ? C13 H13C 0.9600 . ? C14 C15 1.506(3) . ? C15 H15A 0.9600 . ? C15 H15B 0.9600 . ? C15 H15C 0.9600 . ? C16 C17 1.477(6) . ? C17 H17A 0.9600 . ? C17 H17B 0.9600 . ? C17 H17C 0.9600 . ? C18 C19 1.484(6) . ? C19 H19A 0.9600 . ? C19 H19B 0.9600 . ? C19 H19C 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 Mn1 O1 83.04(7) . 7_656 ? O1 Mn1 O8 96.20(7) . . ? O1 Mn1 O8 177.55(8) 7_656 . ? O1 Mn1 O2 176.00(8) . . ? O1 Mn1 O2 97.84(7) 7_656 . ? O8 Mn1 O2 83.08(8) . . ? O1 Mn1 O4 87.87(7) . 7_656 ? O1 Mn1 O4 86.47(6) 7_656 7_656 ? O8 Mn1 O4 91.17(8) . 7_656 ? O2 Mn1 O4 96.07(8) . 7_656 ? O1 Mn1 O6 86.26(6) . . ? O1 Mn1 O6 87.13(6) 7_656 . ? O8 Mn1 O6 95.15(8) . . ? O2 Mn1 O6 89.88(7) . . ? O4 Mn1 O6 171.80(6) 7_656 . ? O1 Mn1 Mn1 41.69(5) . 7_656 ? O1 Mn1 Mn1 41.35(5) 7_656 7_656 ? O8 Mn1 Mn1 137.84(6) . 7_656 ? O2 Mn1 Mn1 139.05(6) . 7_656 ? O4 Mn1 Mn1 86.22(5) 7_656 7_656 ? O6 Mn1 Mn1 85.59(4) . 7_656 ? O1 Mn1 Mn2 26.46(5) . . ? O1 Mn1 Mn2 104.69(5) 7_656 . ? O8 Mn1 Mn2 75.20(6) . . ? O2 Mn1 Mn2 150.46(6) . . ? O4 Mn1 Mn2 104.05(5) 7_656 . ? O6 Mn1 Mn2 72.67(4) . . ? Mn1 Mn1 Mn2 64.795(13) 7_656 . ? O1 Mn2 O5 94.94(7) . . ? O1 Mn2 N1 170.77(7) . . ? O5 Mn2 N1 93.55(8) . . ? O1 Mn2 N2 93.05(7) . . ? O5 Mn2 N2 171.99(8) . . ? N1 Mn2 N2 78.51(8) . . ? O1 Mn2 O3 94.52(7) . 7_656 ? O5 Mn2 O3 95.77(8) . 7_656 ? N1 Mn2 O3 81.03(7) . 7_656 ? N2 Mn2 O3 84.05(8) . 7_656 ? O1 Mn2 O7 96.27(7) . . ? O5 Mn2 O7 93.97(8) . . ? N1 Mn2 O7 86.72(7) . . ? N2 Mn2 O7 84.68(8) . . ? O3 Mn2 O7 164.78(7) 7_656 . ? O1 Mn2 Mn1 27.29(5) . . ? O5 Mn2 Mn1 84.60(5) . . ? N1 Mn2 Mn1 158.31(6) . . ? N2 Mn2 Mn1 102.41(6) . . ? O3 Mn2 Mn1 120.66(5) 7_656 . ? O7 Mn2 Mn1 71.89(5) . . ? O6 P1 O4 113.39(10) . . ? O6 P1 O5 110.28(10) . . ? O4 P1 O5 110.16(10) . . ? O6 P1 C11 109.42(12) . . ? O4 P1 C11 108.20(12) . . ? O5 P1 C11 105.03(12) . . ? Mn2 O1 Mn1 126.25(8) . . ? Mn2 O1 Mn1 125.72(8) . 7_656 ? Mn1 O1 Mn1 96.96(7) . 7_656 ? C14 O2 Mn1 132.97(16) . . ? C14 O3 Mn2 131.69(17) . 7_656 ? P1 O4 Mn1 117.17(9) . 7_656 ? P1 O5 Mn2 120.06(10) . . ? P1 O6 Mn1 115.42(9) . . ? C12 O7 Mn2 128.69(16) . . ? C12 O8 Mn1 135.61(17) . . ? C16 O9 H9B 109.5 . . ? C18 O11 H11D 109.5 . . ? C1 N1 C5 119.5(2) . . ? C1 N1 Mn2 124.35(18) . . ? C5 N1 Mn2 115.86(16) . . ? C10 N2 C6 119.7(2) . . ? C10 N2 Mn2 124.26(17) . . ? C6 N2 Mn2 116.01(16) . . ? N1 C1 C2 121.8(3) . . ? N1 C1 H1A 119.1 . . ? C2 C1 H1A 119.1 . . ? C3 C2 C1 118.9(3) . . ? C3 C2 H2A 120.5 . . ? C1 C2 H2A 120.5 . . ? C2 C3 C4 119.9(3) . . ? C2 C3 H3A 120.1 . . ? C4 C3 H3A 120.1 . . ? C3 C4 C5 118.9(3) . . ? C3 C4 H4A 120.5 . . ? C5 C4 H4A 120.5 . . ? N1 C5 C4 121.0(2) . . ? N1 C5 C6 114.7(2) . . ? C4 C5 C6 124.3(2) . . ? N2 C6 C7 120.9(2) . . ? N2 C6 C5 114.6(2) . . ? C7 C6 C5 124.5(2) . . ? C8 C7 C6 119.0(3) . . ? C8 C7 H7A 120.5 . . ? C6 C7 H7A 120.5 . . ? C7 C8 C9 120.1(3) . . ? C7 C8 H8A 120.0 . . ? C9 C8 H8A 120.0 . . ? C8 C9 C10 118.4(3) . . ? C8 C9 H9A 120.8 . . ? C10 C9 H9A 120.8 . . ? N2 C10 C9 121.8(2) . . ? N2 C10 H10A 119.1 . . ? C9 C10 H10A 119.1 . . ? P1 C11 H11A 109.5 . . ? P1 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? P1 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? O7 C12 O8 125.6(2) . . ? O7 C12 C13 119.5(2) . . ? O8 C12 C13 114.9(2) . . ? C12 C13 H13A 109.5 . . ? C12 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C12 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? O3 C14 O2 125.6(2) . . ? O3 C14 C15 118.7(2) . . ? O2 C14 C15 115.7(2) . . ? C14 C15 H15A 109.5 . . ? C14 C15 H15B 109.5 . . ? H15A C15 H15B 109.5 . . ? C14 C15 H15C 109.5 . . ? H15A C15 H15C 109.5 . . ? H15B C15 H15C 109.5 . . ? O10 C16 O9 123.1(4) . . ? O10 C16 C17 122.2(4) . . ? O9 C16 C17 114.7(4) . . ? C16 C17 H17A 109.5 . . ? C16 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? C16 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 109.5 . . ? O12 C18 O11 122.2(4) . . ? O12 C18 C19 120.9(4) . . ? O11 C18 C19 116.1(4) . . ? C18 C19 H19A 109.5 . . ? C18 C19 H19B 109.5 . . ? H19A C19 H19B 109.5 . . ? C18 C19 H19C 109.5 . . ? H19A C19 H19C 109.5 . . ? H19B C19 H19C 109.5 . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 1.044 _refine_diff_density_min -0.649 _refine_diff_density_rms 0.076 _publ_section_references ; Sheldrick G.M.(1996), SADABS, Absorption Correction Program, University of Goeltingen, German Siemens(1994), SAINT Software Reference Manual, Siemens Energy & Automation Inc., Madison, Wisconsin, USA Siemens(1996), SMART Software Reference Manual, Siemens Energy & Automation Inc., Madison, Wisconsin, USA Siemens(1994), SHELXTL^TM^ Version 5 Reference Manual, Siemens Energy & Automation Inc., Madison, Wisconsin, USA ; #========== data_compound-2 _database_code_depnum_ccdc_archive 'CCDC 635083' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C32 H52 Mn4 N4 O23 P2' _chemical_formula_weight 1142.48 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' 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' P P 0.1023 0.0942 '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' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 10.080(3) _cell_length_b 11.084(3) _cell_length_c 11.559(3) _cell_angle_alpha 64.798(5) _cell_angle_beta 81.789(7) _cell_angle_gamma 82.715(6) _cell_volume 1153.4(6) _cell_formula_units_Z 1 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 3090 _cell_measurement_theta_min 2.97 _cell_measurement_theta_max 27.48 _exptl_crystal_description prism _exptl_crystal_colour brown _exptl_crystal_size_max .60 _exptl_crystal_size_mid .45 _exptl_crystal_size_min .40 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.645 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 586 _exptl_absorpt_coefficient_mu 1.225 _exptl_absorpt_correction_type empirical _exptl_absorpt_process_details 'SADABS (Sheldrick, 1996)' _exptl_absorpt_correction_T_min .520 _exptl_absorpt_correction_T_max .619 _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 P4' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number none _diffrn_standards_interval_count none _diffrn_standards_interval_time none _diffrn_standards_decay_% none _diffrn_reflns_number 8763 _diffrn_reflns_av_R_equivalents 0.0120 _diffrn_reflns_av_sigmaI/netI 0.0200 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 8 _diffrn_reflns_theta_min 2.97 _diffrn_reflns_theta_max 27.48 _reflns_number_total 5144 _reflns_number_gt 4613 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Siemens SMART' _computing_cell_refinement 'Siemens SMART & SAINT' _computing_data_reduction 'Siemens XPREP' _computing_structure_solution 'Siemens SHELXTL' _computing_structure_refinement 'Siemens SHELXTL' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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.Six DFIX instructions were applied to restrain bond distances of solvate water moleculars (O9, O10 and O11). ; _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^)+(0.0589P)^2^+0.4342P] 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 5144 _refine_ls_number_parameters 322 _refine_ls_number_restraints 6 _refine_ls_R_factor_ref 0.0356 _refine_ls_R_factor_gt 0.0316 _refine_ls_wR_factor_ref 0.0887 _refine_ls_wR_factor_gt 0.0855 _refine_ls_goodness_of_fit_ref 0.997 _refine_ls_restrained_S_all 0.997 _refine_ls_shift/su_max 0.001 _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 Mn1 Mn 0.04142(2) 0.89219(2) 0.61388(2) 0.02150(8) Uani 1 1 d . . . Mn2 Mn 0.22684(2) 0.91059(3) 0.34242(2) 0.02303(9) Uani 1 1 d . . . P1 P 0.25779(4) 1.10583(5) 0.44793(4) 0.02509(11) Uani 1 1 d . . . N1 N 0.38799(16) 0.86419(16) 0.23497(15) 0.0282(3) Uani 1 1 d . . . N2 N 0.15518(16) 0.76115(15) 0.31180(15) 0.0284(3) Uani 1 1 d . . . C1 C 0.4996(2) 0.9296(2) 0.1939(2) 0.0363(4) Uani 1 1 d . . . H1A H 0.5083 0.9979 0.2182 0.044 Uiso 1 1 calc R . . C2 C 0.6033(2) 0.8985(2) 0.1158(2) 0.0447(5) Uani 1 1 d . . . H2A H 0.6804 0.9453 0.0879 0.054 Uiso 1 1 calc R . . C3 C 0.5897(2) 0.7972(3) 0.0804(2) 0.0485(6) Uani 1 1 d . . . H3A H 0.6574 0.7751 0.0274 0.058 Uiso 1 1 calc R . . C4 C 0.4746(2) 0.7285(2) 0.1242(2) 0.0431(5) Uani 1 1 d . . . H4A H 0.4648 0.6588 0.1022 0.052 Uiso 1 1 calc R . . C5 C 0.3737(2) 0.76396(19) 0.20137(18) 0.0312(4) Uani 1 1 d . . . C6 C 0.2445(2) 0.70081(18) 0.25051(18) 0.0299(4) Uani 1 1 d . . . C7 C 0.2137(2) 0.5885(2) 0.2383(2) 0.0422(5) Uani 1 1 d . . . H7A H 0.2763 0.5466 0.1973 0.051 Uiso 1 1 calc R . . C8 C 0.0884(3) 0.5397(2) 0.2881(2) 0.0459(5) Uani 1 1 d . . . H8A H 0.0663 0.4638 0.2820 0.055 Uiso 1 1 calc R . . C9 C -0.0027(2) 0.6043(2) 0.3466(2) 0.0427(5) Uani 1 1 d . . . H9A H -0.0881 0.5741 0.3781 0.051 Uiso 1 1 calc R . . C10 C 0.0333(2) 0.7149(2) 0.3584(2) 0.0356(4) Uani 1 1 d . . . H10A H -0.0280 0.7577 0.3993 0.043 Uiso 1 1 calc R . . C11 C 0.3883(2) 1.1992(2) 0.4521(2) 0.0354(4) Uani 1 1 d . . . H11A H 0.4625 1.1374 0.4921 0.042 Uiso 1 1 calc R . . H11B H 0.4211 1.2557 0.3647 0.042 Uiso 1 1 calc R . . C12 C 0.3429(3) 1.2866(3) 0.5253(3) 0.0466(5) Uani 1 1 d . . . H12A H 0.4171 1.3335 0.5245 0.070 Uiso 1 1 calc R . . H12B H 0.3119 1.2312 0.6125 0.070 Uiso 1 1 calc R . . H12C H 0.2712 1.3499 0.4849 0.070 Uiso 1 1 calc R . . C13 C -0.0548(2) 0.88331(19) 0.87470(18) 0.0306(4) Uani 1 1 d . . . C14 C -0.0213(3) 0.8223(3) 1.0114(2) 0.0589(7) Uani 1 1 d . . . H14A H -0.0861 0.8565 1.0615 0.088 Uiso 1 1 calc R . . H14B H 0.0667 0.8446 1.0144 0.088 Uiso 1 1 calc R . . H14C H -0.0232 0.7269 1.0457 0.088 Uiso 1 1 calc R . . C15 C 0.24863(19) 0.67578(18) 0.61588(19) 0.0297(4) Uani 1 1 d . . . C16 C 0.3134(2) 0.5423(2) 0.6996(2) 0.0457(5) Uani 1 1 d . . . H16A H 0.3481 0.4941 0.6483 0.069 Uiso 1 1 calc R . . H16B H 0.2479 0.4920 0.7660 0.069 Uiso 1 1 calc R . . H16C H 0.3856 0.5558 0.7377 0.069 Uiso 1 1 calc R . . O1 O 0.06704(12) 0.94087(12) 0.43257(11) 0.0222(2) Uani 1 1 d . . . O2 O 0.02788(14) 0.84886(14) 0.79760(13) 0.0337(3) Uani 1 1 d . . . O3 O -0.15696(15) 0.95965(15) 0.84582(13) 0.0374(3) Uani 1 1 d . . . O4 O 0.14136(13) 1.20105(12) 0.38147(13) 0.0280(3) Uani 1 1 d . . . O5 O 0.32468(13) 1.03215(14) 0.36304(13) 0.0303(3) Uani 1 1 d . . . O6 O 0.21656(13) 1.00587(13) 0.58441(13) 0.0302(3) Uani 1 1 d . . . O7 O 0.30322(15) 0.73820(15) 0.50634(14) 0.0378(3) Uani 1 1 d . . . O8 O 0.14067(14) 0.71563(13) 0.66575(14) 0.0346(3) Uani 1 1 d . . . O9 O 0.2170(2) 1.3489(2) 0.1118(2) 0.0617(5) Uani 1 1 d D . . H9B H 0.193(4) 1.306(4) 0.194(2) 0.109(15) Uiso 1 1 d D . . H9C H 0.175(6) 1.419(4) 0.054(5) 0.20(3) Uiso 1 1 d D . . O10 O 0.3260(2) 0.8237(3) 0.8119(2) 0.0715(6) Uani 1 1 d D . . H10B H 0.306(4) 0.883(3) 0.736(2) 0.083(11) Uiso 1 1 d D . . H10C H 0.250(6) 0.791(6) 0.852(5) 0.14(2) Uiso 1 1 d . . . O11 O 0.5248(2) 0.6043(2) 0.8868(2) 0.0699(6) Uani 1 1 d D . . H11C H 0.599(2) 0.647(4) 0.870(4) 0.099 Uiso 1 1 d D . . H11D H 0.458(2) 0.657(3) 0.890(4) 0.085 Uiso 1 1 d D . . O12 O 0.0464(5) 1.5341(5) -0.0538(5) 0.0910(16) Uani 0.50 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 Mn1 0.02124(14) 0.02171(14) 0.02024(14) -0.00823(10) -0.00292(9) 0.00220(9) Mn2 0.02103(14) 0.02574(15) 0.02584(15) -0.01526(11) -0.00010(10) 0.00017(10) P1 0.0223(2) 0.0270(2) 0.0289(2) -0.01408(19) -0.00261(17) -0.00289(17) N1 0.0269(7) 0.0298(8) 0.0272(8) -0.0133(6) -0.0011(6) 0.0036(6) N2 0.0323(8) 0.0272(7) 0.0297(8) -0.0161(6) -0.0026(6) -0.0007(6) C1 0.0306(10) 0.0408(11) 0.0364(10) -0.0175(9) 0.0028(8) 0.0001(8) C2 0.0325(10) 0.0519(13) 0.0420(12) -0.0168(10) 0.0072(9) 0.0019(9) C3 0.0430(12) 0.0567(14) 0.0396(12) -0.0220(11) 0.0077(10) 0.0126(10) C4 0.0483(12) 0.0436(12) 0.0410(12) -0.0265(10) 0.0013(9) 0.0102(10) C5 0.0360(10) 0.0306(9) 0.0266(9) -0.0141(7) -0.0038(7) 0.0078(7) C6 0.0392(10) 0.0267(9) 0.0257(9) -0.0138(7) -0.0069(7) 0.0057(7) C7 0.0546(13) 0.0340(11) 0.0449(12) -0.0246(9) -0.0058(10) 0.0043(9) C8 0.0668(15) 0.0327(11) 0.0469(13) -0.0220(10) -0.0122(11) -0.0061(10) C9 0.0479(12) 0.0411(12) 0.0437(12) -0.0197(10) -0.0038(10) -0.0131(10) C10 0.0376(10) 0.0362(10) 0.0387(11) -0.0209(9) -0.0011(8) -0.0055(8) C11 0.0290(9) 0.0398(11) 0.0444(11) -0.0231(9) -0.0016(8) -0.0088(8) C12 0.0459(13) 0.0502(13) 0.0589(15) -0.0346(12) -0.0123(11) -0.0049(10) C13 0.0346(10) 0.0315(9) 0.0242(9) -0.0105(7) -0.0040(7) 0.0000(8) C14 0.0607(16) 0.0799(19) 0.0294(11) -0.0199(12) -0.0134(11) 0.0185(14) C15 0.0295(9) 0.0263(9) 0.0361(10) -0.0149(8) -0.0104(7) 0.0035(7) C16 0.0471(13) 0.0312(11) 0.0516(14) -0.0115(10) -0.0126(10) 0.0105(9) O1 0.0210(5) 0.0233(6) 0.0242(6) -0.0125(5) -0.0009(4) 0.0001(4) O2 0.0328(7) 0.0398(7) 0.0245(6) -0.0111(6) -0.0051(5) 0.0055(6) O3 0.0386(8) 0.0417(8) 0.0271(7) -0.0129(6) -0.0027(6) 0.0075(6) O4 0.0264(6) 0.0252(6) 0.0320(7) -0.0109(5) -0.0036(5) -0.0028(5) O5 0.0238(6) 0.0364(7) 0.0369(7) -0.0218(6) 0.0020(5) -0.0053(5) O6 0.0278(6) 0.0335(7) 0.0301(7) -0.0131(6) -0.0053(5) -0.0027(5) O7 0.0335(7) 0.0408(8) 0.0340(7) -0.0132(6) -0.0048(6) 0.0081(6) O8 0.0334(7) 0.0267(7) 0.0358(7) -0.0076(6) -0.0017(6) 0.0034(5) O9 0.0683(13) 0.0578(12) 0.0500(11) -0.0140(10) -0.0008(10) -0.0097(10) O10 0.0584(13) 0.0769(15) 0.0676(14) -0.0127(12) -0.0293(11) -0.0027(11) O11 0.0621(13) 0.0749(15) 0.0717(14) -0.0302(12) -0.0030(11) -0.0065(11) O12 0.090(4) 0.064(3) 0.078(3) 0.006(2) -0.011(3) 0.009(3) _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 1.9152(13) . ? Mn1 O1 1.9277(12) 2_576 ? Mn1 O2 1.9556(14) . ? Mn1 O8 1.9662(14) . ? Mn1 O6 2.2016(14) . ? Mn1 O4 2.2074(14) 2_576 ? Mn1 Mn1 2.8466(7) 2_576 ? Mn2 O1 1.8640(12) . ? Mn2 O5 1.8769(13) . ? Mn2 N1 2.0497(16) . ? Mn2 N2 2.0655(16) . ? Mn2 O7 2.1896(15) . ? Mn2 O3 2.1942(15) 2_576 ? Mn2 P1 2.9658(7) . ? P1 O6 1.5265(14) . ? P1 O4 1.5278(14) . ? P1 O5 1.5614(14) . ? P1 C11 1.792(2) . ? N1 C1 1.333(3) . ? N1 C5 1.353(3) . ? N2 C10 1.340(3) . ? N2 C6 1.352(2) . ? C1 C2 1.390(3) . ? C1 H1A 0.9300 . ? C2 C3 1.377(4) . ? C2 H2A 0.9300 . ? C3 C4 1.382(4) . ? C3 H3A 0.9300 . ? C4 C5 1.386(3) . ? C4 H4A 0.9300 . ? C5 C6 1.480(3) . ? C6 C7 1.388(3) . ? C7 C8 1.385(4) . ? C7 H7A 0.9300 . ? C8 C9 1.372(3) . ? C8 H8A 0.9300 . ? C9 C10 1.387(3) . ? C9 H9A 0.9300 . ? C10 H10A 0.9300 . ? C11 C12 1.530(3) . ? C11 H11A 0.9700 . ? C11 H11B 0.9700 . ? C12 H12A 0.9600 . ? C12 H12B 0.9600 . ? C12 H12C 0.9600 . ? C13 O3 1.235(2) . ? C13 O2 1.277(2) . ? C13 C14 1.501(3) . ? C14 H14A 0.9600 . ? C14 H14B 0.9600 . ? C14 H14C 0.9600 . ? C15 O7 1.239(2) . ? C15 O8 1.276(2) . ? C15 C16 1.506(3) . ? C16 H16A 0.9600 . ? C16 H16B 0.9600 . ? C16 H16C 0.9600 . ? O1 Mn1 1.9277(12) 2_576 ? O3 Mn2 2.1942(15) 2_576 ? O4 Mn1 2.2074(13) 2_576 ? O9 H9B 0.874(19) . ? O9 H9C 0.89(5) . ? O10 H10B 0.880(19) . ? O10 H10C 0.87(5) . ? O11 H11C 0.886(18) . ? O11 H11D 0.844(17) . ? O12 O12 1.428(10) 2_585 ? 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 84.41(5) . 2_576 ? O1 Mn1 O2 175.64(6) . . ? O1 Mn1 O2 95.84(6) 2_576 . ? O1 Mn1 O8 96.75(6) . . ? O1 Mn1 O8 176.09(5) 2_576 . ? O2 Mn1 O8 83.29(6) . . ? O1 Mn1 O6 86.35(5) . . ? O1 Mn1 O6 87.50(5) 2_576 . ? O2 Mn1 O6 89.30(6) . . ? O8 Mn1 O6 96.29(6) . . ? O1 Mn1 O4 87.53(5) . 2_576 ? O1 Mn1 O4 87.37(5) 2_576 2_576 ? O2 Mn1 O4 96.83(6) . 2_576 ? O8 Mn1 O4 88.95(6) . 2_576 ? O6 Mn1 O4 172.37(5) . 2_576 ? O1 Mn1 Mn1 42.37(4) . 2_576 ? O1 Mn1 Mn1 42.03(4) 2_576 2_576 ? O2 Mn1 Mn1 137.70(4) . 2_576 ? O8 Mn1 Mn1 139.00(5) . 2_576 ? O6 Mn1 Mn1 85.85(4) . 2_576 ? O4 Mn1 Mn1 86.56(4) 2_576 2_576 ? O1 Mn2 O5 96.52(6) . . ? O1 Mn2 N1 172.43(6) . . ? O5 Mn2 N1 90.87(6) . . ? O1 Mn2 N2 93.95(6) . . ? O5 Mn2 N2 168.95(6) . . ? N1 Mn2 N2 78.78(7) . . ? O1 Mn2 O7 95.37(6) . . ? O5 Mn2 O7 93.98(6) . . ? N1 Mn2 O7 85.72(6) . . ? N2 Mn2 O7 81.49(6) . . ? O1 Mn2 O3 93.52(6) . 2_576 ? O5 Mn2 O3 99.06(6) . 2_576 ? N1 Mn2 O3 83.66(6) . 2_576 ? N2 Mn2 O3 83.79(6) . 2_576 ? O7 Mn2 O3 163.27(6) . 2_576 ? O1 Mn2 P1 69.16(4) . . ? O5 Mn2 P1 27.44(4) . . ? N1 Mn2 P1 118.27(5) . . ? N2 Mn2 P1 162.22(5) . . ? O7 Mn2 P1 94.21(5) . . ? O3 Mn2 P1 102.20(5) 2_576 . ? O6 P1 O4 113.54(8) . . ? O6 P1 O5 110.90(8) . . ? O4 P1 O5 108.86(8) . . ? O6 P1 C11 109.00(9) . . ? O4 P1 C11 110.01(9) . . ? O5 P1 C11 104.11(9) . . ? O6 P1 Mn2 91.45(6) . . ? O4 P1 Mn2 93.83(5) . . ? C11 P1 Mn2 137.59(7) . . ? C1 N1 C5 120.05(17) . . ? C1 N1 Mn2 124.07(13) . . ? C5 N1 Mn2 115.82(13) . . ? C10 N2 C6 119.90(17) . . ? C10 N2 Mn2 124.16(13) . . ? C6 N2 Mn2 115.65(13) . . ? N1 C1 C2 121.8(2) . . ? N1 C1 H1A 119.1 . . ? C2 C1 H1A 119.1 . . ? C3 C2 C1 118.7(2) . . ? C3 C2 H2A 120.6 . . ? C1 C2 H2A 120.6 . . ? C2 C3 C4 119.4(2) . . ? C2 C3 H3A 120.3 . . ? C4 C3 H3A 120.3 . . ? C3 C4 C5 119.6(2) . . ? C3 C4 H4A 120.2 . . ? C5 C4 H4A 120.2 . . ? N1 C5 C4 120.4(2) . . ? N1 C5 C6 115.10(16) . . ? C4 C5 C6 124.49(19) . . ? N2 C6 C7 121.0(2) . . ? N2 C6 C5 114.24(16) . . ? C7 C6 C5 124.75(18) . . ? C8 C7 C6 119.0(2) . . ? C8 C7 H7A 120.5 . . ? C6 C7 H7A 120.5 . . ? C9 C8 C7 119.4(2) . . ? C9 C8 H8A 120.3 . . ? C7 C8 H8A 120.3 . . ? C8 C9 C10 119.5(2) . . ? C8 C9 H9A 120.2 . . ? C10 C9 H9A 120.2 . . ? N2 C10 C9 121.1(2) . . ? N2 C10 H10A 119.4 . . ? C9 C10 H10A 119.4 . . ? C12 C11 P1 113.46(15) . . ? C12 C11 H11A 108.9 . . ? P1 C11 H11A 108.9 . . ? C12 C11 H11B 108.9 . . ? P1 C11 H11B 108.9 . . ? H11A C11 H11B 107.7 . . ? C11 C12 H12A 109.5 . . ? C11 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C11 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? O3 C13 O2 125.68(17) . . ? O3 C13 C14 119.24(18) . . ? O2 C13 C14 115.07(19) . . ? C13 C14 H14A 109.5 . . ? C13 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? C13 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? O7 C15 O8 125.31(17) . . ? O7 C15 C16 118.64(18) . . ? O8 C15 C16 116.04(18) . . ? C15 C16 H16A 109.5 . . ? C15 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? C15 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? Mn2 O1 Mn1 125.20(7) . . ? Mn2 O1 Mn1 125.83(6) . 2_576 ? Mn1 O1 Mn1 95.59(5) . 2_576 ? C13 O2 Mn1 134.80(13) . . ? C13 O3 Mn2 130.81(12) . 2_576 ? P1 O4 Mn1 116.27(7) . 2_576 ? P1 O5 Mn2 118.93(8) . . ? P1 O6 Mn1 117.59(8) . . ? C15 O7 Mn2 130.58(13) . . ? C15 O8 Mn1 131.43(13) . . ? H9B O9 H9C 129(5) . . ? H10B O10 H10C 105(4) . . ? H11C O11 H11D 108(2) . . ? _diffrn_measured_fraction_theta_max 0.974 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 0.974 _refine_diff_density_max 0.555 _refine_diff_density_min -0.362 _refine_diff_density_rms 0.062 _publ_section_references ; Sheldrick G.M.(1996), SADABS, Absorption Correction Program, University of Goeltingen, German Siemens(1994), SAINT Software Reference Manual, Siemens Energy & Automation Inc., Madison, Wisconsin, USA Siemens(1996), SMART Software Reference Manual, Siemens Energy & Automation Inc., Madison, Wisconsin, USA Siemens(1994), SHELXTL^TM^ Version 5 Reference Manual, Siemens Energy & Automation Inc., Madison, Wisconsin, USA ; #========== data_compound-3 _database_code_depnum_ccdc_archive 'CCDC 635084' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C38 H54 Mn4 N4 O24 P2' _chemical_formula_weight 1232.55 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' 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' P P 0.1023 0.0942 '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' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 11.4387(14) _cell_length_b 11.4850(12) _cell_length_c 11.9747(11) _cell_angle_alpha 100.4590(10) _cell_angle_beta 103.024(4) _cell_angle_gamma 113.282(3) _cell_volume 1342.0(3) _cell_formula_units_Z 1 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 2894 _cell_measurement_theta_min 2.85 _cell_measurement_theta_max 27.48 _exptl_crystal_description prism _exptl_crystal_colour brown _exptl_crystal_size_max .40 _exptl_crystal_size_mid .22 _exptl_crystal_size_min .15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.525 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 632 _exptl_absorpt_coefficient_mu 1.060 _exptl_absorpt_correction_type empirical _exptl_absorpt_process_details 'SADABS (Sheldrick, 1996)' _exptl_absorpt_correction_T_min .7600 _exptl_absorpt_correction_T_max .8540 _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 P4' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number none _diffrn_standards_interval_count none _diffrn_standards_interval_time none _diffrn_standards_decay_% none _diffrn_reflns_number 10383 _diffrn_reflns_av_R_equivalents 0.0175 _diffrn_reflns_av_sigmaI/netI 0.0324 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 2.85 _diffrn_reflns_theta_max 27.48 _reflns_number_total 6053 _reflns_number_gt 4684 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Siemens SMART' _computing_cell_refinement 'Siemens SMART & SAINT' _computing_data_reduction 'Siemens XPREP' _computing_structure_solution 'Siemens SHELXTL' _computing_structure_refinement 'Siemens SHELXTL' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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.Five restraints of DFIX instructions were used to improve the geometry of the distorted solvate oxalic acid molecular in compound 3, and the O14-O15-C19-C20-O16-O17 unit (r.m.s. deviation 0.0006 . ?) was retrained to be flat by the FLAT 0.01 instruction (three restraints). ; _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^)+(0.0943P)^2^+1.2510P] 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 6053 _refine_ls_number_parameters 360 _refine_ls_number_restraints 8 _refine_ls_R_factor_ref 0.0735 _refine_ls_R_factor_gt 0.0558 _refine_ls_wR_factor_ref 0.1726 _refine_ls_wR_factor_gt 0.1564 _refine_ls_goodness_of_fit_ref 1.053 _refine_ls_restrained_S_all 1.086 _refine_ls_shift/su_max 0.008 _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 Mn2 Mn 0.26191(5) 1.16048(5) 0.21109(5) 0.04163(18) Uani 1 1 d . . . Mn1 Mn -0.00581(5) 0.88027(5) 0.02097(4) 0.03811(17) Uani 1 1 d . . . P1 P -0.00718(11) 1.09280(10) 0.23717(9) 0.0481(3) Uani 1 1 d . . . N1 N 0.4152(3) 1.1817(3) 0.1409(3) 0.0495(8) Uani 1 1 d . . . N2 N 0.4278(3) 1.2713(3) 0.3624(3) 0.0505(8) Uani 1 1 d . . . O1 O 0.1256(2) 1.0620(2) 0.0636(2) 0.0371(5) Uani 1 1 d . . . O2 O -0.1443(3) 0.7018(3) -0.0055(2) 0.0518(7) Uani 1 1 d . . . O3 O -0.2984(3) 0.6474(3) -0.1821(3) 0.0580(8) Uani 1 1 d . . . O4 O -0.0452(3) 1.1582(3) 0.1436(2) 0.0497(6) Uani 1 1 d . . . O5 O 0.1478(3) 1.1610(3) 0.3010(2) 0.0541(7) Uani 1 1 d . . . O6 O -0.0591(3) 0.9435(3) 0.1833(2) 0.0509(7) Uani 1 1 d . . . O7 O 0.2812(3) 0.9902(3) 0.2490(3) 0.0627(8) Uani 1 1 d . . . O8 O 0.1136(3) 0.8164(3) 0.1016(3) 0.0564(7) Uani 1 1 d . . . O11 O 0.0058(6) 1.4203(5) 0.2270(8) 0.175(3) Uani 1 1 d . . . O12 O 1.0000 1.5000 0.5000 0.177(5) Uani 1 2 d S . . O13 O -0.0266(15) 1.4841(13) 0.0341(11) 0.139(5) Uani 0.50 1 d P . . O14 O -0.107(2) 0.6048(12) 0.3472(11) 0.286(15) Uani 0.50 1 d PD . . O15 O -0.0254(14) 0.7763(12) 0.2965(8) 0.158(5) Uani 0.50 1 d PD . . H15A H -0.0509 0.8198 0.2591 0.237 Uiso 0.50 1 calc PRD . . O16 O -0.3288(15) 0.5913(13) 0.2656(10) 0.149(5) Uani 0.50 1 d PD . . O17 O -0.2709(9) 0.7518(9) 0.2110(9) 0.113(3) Uani 0.50 1 d PD . . H17A H -0.2020 0.8078 0.2061 0.169 Uiso 0.50 1 calc PR . . C1 C 0.3988(5) 1.1319(5) 0.0270(4) 0.0620(11) Uani 1 1 d . . . H1A H 0.3118 1.0820 -0.0275 0.074 Uiso 1 1 calc R . . C2 C 0.5074(5) 1.1516(6) -0.0140(5) 0.0750(14) Uani 1 1 d . . . H2A H 0.4935 1.1151 -0.0946 0.090 Uiso 1 1 calc R . . C3 C 0.6359(5) 1.2263(6) 0.0670(6) 0.0780(15) Uani 1 1 d . . . H3A H 0.7103 1.2408 0.0418 0.094 Uiso 1 1 calc R . . C4 C 0.6527(5) 1.2789(6) 0.1854(5) 0.0753(14) Uani 1 1 d . . . H4A H 0.7390 1.3299 0.2409 0.090 Uiso 1 1 calc R . . C5 C 0.5430(4) 1.2565(4) 0.2216(4) 0.0582(11) Uani 1 1 d . . . C6 C 0.5488(4) 1.3065(4) 0.3463(4) 0.0563(10) Uani 1 1 d . . . C7 C 0.6654(5) 1.3839(5) 0.4427(5) 0.0770(15) Uani 1 1 d . . . H7A H 0.7489 1.4082 0.4320 0.092 Uiso 1 1 calc R . . C8 C 0.6577(6) 1.4251(5) 0.5547(5) 0.0833(17) Uani 1 1 d . . . H8A H 0.7361 1.4769 0.6202 0.100 Uiso 1 1 calc R . . C9 C 0.5364(6) 1.3903(5) 0.5698(5) 0.0774(16) Uani 1 1 d . . . H9A H 0.5301 1.4185 0.6451 0.093 Uiso 1 1 calc R . . C10 C 0.4213(5) 1.3119(5) 0.4709(4) 0.0620(12) Uani 1 1 d . . . H10A H 0.3374 1.2870 0.4808 0.074 Uiso 1 1 calc R . . C11 C -0.0740(6) 1.1196(6) 0.3563(5) 0.0783(16) Uani 1 1 d . . . H11A H -0.0448 1.0817 0.4164 0.094 Uiso 1 1 calc R . . H11B H -0.0360 1.2146 0.3941 0.094 Uiso 1 1 calc R . . C12 C -0.2203(7) 1.0631(8) 0.3186(7) 0.116(3) Uani 1 1 d . . . H12A H -0.2598 0.9706 0.2711 0.139 Uiso 1 1 calc R . . H12B H -0.2498 1.1103 0.2683 0.139 Uiso 1 1 calc R . . C13 C -0.2702(15) 1.0724(11) 0.4281(13) 0.241(9) Uani 1 1 d . . . H13A H -0.1935 1.1004 0.4994 0.290 Uiso 1 1 calc R . . H13B H -0.2964 1.1434 0.4339 0.290 Uiso 1 1 calc R . . C14 C -0.3586(18) 0.9797(13) 0.4330(12) 0.272(11) Uani 1 1 d . . . H14B H -0.3724 1.0000 0.5089 0.409 Uiso 1 1 calc R . . H14C H -0.3369 0.9066 0.4253 0.409 Uiso 1 1 calc R . . H14D H -0.4393 0.9560 0.3689 0.409 Uiso 1 1 calc R . . C15 C -0.2538(4) 0.6246(4) -0.0890(4) 0.0458(8) Uani 1 1 d . . . C16 C -0.3351(6) 0.4955(5) -0.0698(5) 0.0760(15) Uani 1 1 d . . . H16A H -0.3923 0.4302 -0.1462 0.114 Uiso 1 1 calc R . . H16B H -0.3894 0.5080 -0.0229 0.114 Uiso 1 1 calc R . . H16C H -0.2756 0.4658 -0.0281 0.114 Uiso 1 1 calc R . . C17 C 0.2170(4) 0.8710(4) 0.1964(4) 0.0485(9) Uani 1 1 d . . . C18 C 0.2599(6) 0.7763(5) 0.2434(5) 0.0734(14) Uani 1 1 d . . . H18A H 0.3461 0.7916 0.2359 0.110 Uiso 1 1 calc R . . H18B H 0.1947 0.6865 0.1980 0.110 Uiso 1 1 calc R . . H18C H 0.2663 0.7904 0.3266 0.110 Uiso 1 1 calc R . . C19 C -0.1215(11) 0.6856(8) 0.3019(6) 0.074(3) Uani 0.50 1 d PD . . C20 C -0.2441(9) 0.6748(7) 0.2588(6) 0.055(2) Uani 0.50 1 d PD . . 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 Mn2 0.0401(3) 0.0336(3) 0.0314(3) 0.0035(2) 0.0000(2) 0.0068(2) Mn1 0.0399(3) 0.0284(3) 0.0318(3) 0.0055(2) 0.0033(2) 0.0080(2) P1 0.0544(6) 0.0428(5) 0.0343(5) 0.0040(4) 0.0156(4) 0.0127(5) N1 0.0418(17) 0.0429(18) 0.0463(18) 0.0107(14) 0.0052(14) 0.0088(14) N2 0.0508(19) 0.0341(16) 0.0407(17) 0.0039(13) -0.0054(14) 0.0085(14) O1 0.0384(12) 0.0293(11) 0.0295(11) 0.0051(9) 0.0051(9) 0.0069(10) O2 0.0547(16) 0.0334(13) 0.0431(14) 0.0109(11) 0.0023(12) 0.0044(12) O3 0.0659(19) 0.0348(14) 0.0461(15) 0.0054(12) -0.0026(13) 0.0110(13) O4 0.0529(16) 0.0442(15) 0.0425(14) 0.0038(12) 0.0136(12) 0.0181(13) O5 0.0540(16) 0.0551(17) 0.0328(13) 0.0035(12) 0.0071(12) 0.0132(14) O6 0.0607(17) 0.0428(15) 0.0378(13) 0.0099(11) 0.0187(12) 0.0122(13) O7 0.0643(19) 0.0413(16) 0.0538(17) 0.0089(13) -0.0095(14) 0.0142(14) O8 0.0616(18) 0.0412(15) 0.0491(15) 0.0050(12) -0.0037(13) 0.0221(13) O11 0.126(5) 0.070(3) 0.281(9) -0.010(4) 0.025(5) 0.050(3) O12 0.099(6) 0.137(8) 0.282(13) 0.017(8) 0.074(7) 0.056(6) O13 0.162(12) 0.104(9) 0.110(10) 0.048(7) -0.004(8) 0.038(8) O14 0.42(3) 0.087(9) 0.141(13) 0.038(9) -0.011(16) -0.037(14) O15 0.218(15) 0.233(16) 0.085(7) 0.095(9) 0.046(8) 0.144(14) O16 0.149(11) 0.140(11) 0.166(12) 0.060(10) 0.065(10) 0.059(9) O17 0.092(6) 0.092(7) 0.136(8) 0.019(6) 0.066(6) 0.016(5) C1 0.048(2) 0.060(3) 0.057(3) 0.010(2) 0.011(2) 0.011(2) C2 0.066(3) 0.081(4) 0.074(3) 0.021(3) 0.030(3) 0.026(3) C3 0.053(3) 0.085(4) 0.091(4) 0.030(3) 0.029(3) 0.023(3) C4 0.043(2) 0.076(3) 0.087(4) 0.026(3) 0.010(2) 0.014(2) C5 0.041(2) 0.047(2) 0.066(3) 0.018(2) 0.0010(19) 0.0085(18) C6 0.047(2) 0.041(2) 0.055(2) 0.0109(18) -0.0050(18) 0.0087(18) C7 0.047(3) 0.070(3) 0.071(3) 0.011(3) -0.013(2) 0.007(2) C8 0.076(4) 0.061(3) 0.059(3) 0.005(2) -0.022(3) 0.009(3) C9 0.082(4) 0.057(3) 0.048(3) 0.003(2) -0.011(2) 0.010(3) C10 0.066(3) 0.050(2) 0.041(2) 0.0044(18) -0.0037(19) 0.014(2) C11 0.103(4) 0.069(3) 0.060(3) 0.009(2) 0.048(3) 0.029(3) C12 0.106(5) 0.104(5) 0.131(6) 0.008(5) 0.079(5) 0.031(4) C13 0.301(17) 0.133(9) 0.293(17) 0.013(10) 0.266(16) 0.033(10) C14 0.37(2) 0.157(11) 0.178(11) -0.003(9) 0.204(14) -0.026(12) C15 0.047(2) 0.0295(17) 0.048(2) 0.0052(15) 0.0103(17) 0.0105(15) C16 0.078(3) 0.044(2) 0.068(3) 0.019(2) 0.008(3) -0.001(2) C17 0.051(2) 0.042(2) 0.046(2) 0.0137(17) 0.0088(17) 0.0192(18) C18 0.083(4) 0.056(3) 0.067(3) 0.014(2) -0.004(3) 0.036(3) C19 0.097(8) 0.033(4) 0.051(5) 0.023(4) 0.005(5) -0.005(5) C20 0.069(6) 0.034(4) 0.065(5) 0.025(4) 0.045(5) 0.010(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 Mn2 O1 1.863(2) . ? Mn2 O5 1.870(3) . ? Mn2 N2 2.051(3) . ? Mn2 N1 2.059(4) . ? Mn2 O7 2.167(3) . ? Mn2 O3 2.186(3) 2_575 ? Mn2 P1 2.9675(13) . ? Mn1 O1 1.914(2) . ? Mn1 O1 1.918(2) 2_575 ? Mn1 O2 1.945(3) . ? Mn1 O8 1.947(3) . ? Mn1 O4 2.197(3) 2_575 ? Mn1 O6 2.246(3) . ? Mn1 Mn1 2.8419(11) 2_575 ? P1 O6 1.526(3) . ? P1 O4 1.533(3) . ? P1 O5 1.554(3) . ? P1 C11 1.797(5) . ? N1 C1 1.319(6) . ? N1 C5 1.370(5) . ? N2 C10 1.327(6) . ? N2 C6 1.350(6) . ? O1 Mn1 1.918(2) 2_575 ? O2 C15 1.261(5) . ? O3 C15 1.236(5) . ? O3 Mn2 2.186(3) 2_575 ? O4 Mn1 2.197(3) 2_575 ? O7 C17 1.222(5) . ? O8 C17 1.277(5) . ? O13 O13 1.15(2) 2_585 ? O14 C19 1.205(14) . ? O15 C19 1.203(12) . ? O15 H15A 0.8200 . ? O16 C20 1.093(14) . ? O17 C20 1.234(11) . ? O17 H17A 0.8200 . ? C1 C2 1.388(7) . ? C1 H1A 0.9300 . ? C2 C3 1.377(7) . ? C2 H2A 0.9300 . ? C3 C4 1.373(8) . ? C3 H3A 0.9300 . ? C4 C5 1.364(7) . ? C4 H4A 0.9300 . ? C5 C6 1.476(7) . ? C6 C7 1.378(6) . ? C7 C8 1.374(9) . ? C7 H7A 0.9300 . ? C8 C9 1.348(9) . ? C8 H8A 0.9300 . ? C9 C10 1.385(6) . ? C9 H9A 0.9300 . ? C10 H10A 0.9300 . ? C11 C12 1.456(9) . ? C11 H11A 0.9700 . ? C11 H11B 0.9700 . ? C12 C13 1.547(10) . ? C12 H12A 0.9700 . ? C12 H12B 0.9700 . ? C13 C14 1.166(13) . ? C13 H13A 0.9700 . ? C13 H13B 0.9700 . ? C14 H14B 0.9600 . ? C14 H14C 0.9600 . ? C14 H14D 0.9600 . ? C15 C16 1.498(6) . ? C16 H16A 0.9600 . ? C16 H16B 0.9600 . ? C16 H16C 0.9600 . ? C17 C18 1.504(6) . ? C18 H18A 0.9600 . ? C18 H18B 0.9600 . ? C18 H18C 0.9600 . ? C19 C20 1.328(12) . ? 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 Mn2 O5 96.11(11) . . ? O1 Mn2 N2 173.19(13) . . ? O5 Mn2 N2 90.67(14) . . ? O1 Mn2 N1 94.24(12) . . ? O5 Mn2 N1 169.63(13) . . ? N2 Mn2 N1 78.98(14) . . ? O1 Mn2 O7 94.64(11) . . ? O5 Mn2 O7 95.09(14) . . ? N2 Mn2 O7 85.31(12) . . ? N1 Mn2 O7 84.75(14) . . ? O1 Mn2 O3 94.32(10) . 2_575 ? O5 Mn2 O3 95.65(14) . 2_575 ? N2 Mn2 O3 84.40(12) . 2_575 ? N1 Mn2 O3 82.85(13) . 2_575 ? O7 Mn2 O3 165.19(13) . 2_575 ? O1 Mn2 P1 69.11(8) . . ? O5 Mn2 P1 27.01(9) . . ? N2 Mn2 P1 117.66(11) . . ? N1 Mn2 P1 163.28(10) . . ? O7 Mn2 P1 97.65(10) . . ? O3 Mn2 P1 96.55(9) 2_575 . ? O1 Mn1 O1 84.27(11) . 2_575 ? O1 Mn1 O2 173.28(11) . . ? O1 Mn1 O2 95.55(11) 2_575 . ? O1 Mn1 O8 97.06(12) . . ? O1 Mn1 O8 177.92(11) 2_575 . ? O2 Mn1 O8 83.32(12) . . ? O1 Mn1 O4 88.38(10) . 2_575 ? O1 Mn1 O4 87.37(10) 2_575 2_575 ? O2 Mn1 O4 98.33(11) . 2_575 ? O8 Mn1 O4 91.07(12) . 2_575 ? O1 Mn1 O6 86.38(10) . . ? O1 Mn1 O6 86.51(11) 2_575 . ? O2 Mn1 O6 86.90(11) . . ? O8 Mn1 O6 95.16(12) . . ? O4 Mn1 O6 172.31(10) 2_575 . ? O1 Mn1 Mn1 42.19(7) . 2_575 ? O1 Mn1 Mn1 42.07(7) 2_575 2_575 ? O2 Mn1 Mn1 137.23(9) . 2_575 ? O8 Mn1 Mn1 139.23(9) . 2_575 ? O4 Mn1 Mn1 87.13(8) 2_575 2_575 ? O6 Mn1 Mn1 85.20(8) . 2_575 ? O6 P1 O4 112.56(16) . . ? O6 P1 O5 110.06(18) . . ? O4 P1 O5 110.95(17) . . ? O6 P1 C11 108.7(2) . . ? O4 P1 C11 109.9(2) . . ? O5 P1 C11 104.3(2) . . ? O6 P1 Mn2 93.68(12) . . ? O4 P1 Mn2 92.98(11) . . ? C11 P1 Mn2 137.4(2) . . ? C1 N1 C5 119.3(4) . . ? C1 N1 Mn2 125.3(3) . . ? C5 N1 Mn2 115.4(3) . . ? C10 N2 C6 120.0(4) . . ? C10 N2 Mn2 123.8(3) . . ? C6 N2 Mn2 116.1(3) . . ? Mn2 O1 Mn1 126.02(12) . . ? Mn2 O1 Mn1 125.49(13) . 2_575 ? Mn1 O1 Mn1 95.73(11) . 2_575 ? C15 O2 Mn1 133.2(3) . . ? C15 O3 Mn2 128.5(2) . 2_575 ? P1 O4 Mn1 116.59(15) . 2_575 ? P1 O5 Mn2 119.85(16) . . ? P1 O6 Mn1 116.31(15) . . ? C17 O7 Mn2 132.1(3) . . ? C17 O8 Mn1 132.8(3) . . ? C19 O15 H15A 109.5 . . ? C20 O17 H17A 109.5 . . ? N1 C1 C2 122.0(4) . . ? N1 C1 H1A 119.0 . . ? C2 C1 H1A 119.0 . . ? C3 C2 C1 118.8(5) . . ? C3 C2 H2A 120.6 . . ? C1 C2 H2A 120.6 . . ? C2 C3 C4 119.1(5) . . ? C2 C3 H3A 120.4 . . ? C4 C3 H3A 120.4 . . ? C5 C4 C3 120.0(5) . . ? C5 C4 H4A 120.0 . . ? C3 C4 H4A 120.0 . . ? C4 C5 N1 120.7(5) . . ? C4 C5 C6 124.8(4) . . ? N1 C5 C6 114.5(4) . . ? N2 C6 C7 119.9(5) . . ? N2 C6 C5 115.0(3) . . ? C7 C6 C5 125.1(5) . . ? C8 C7 C6 119.7(5) . . ? C8 C7 H7A 120.1 . . ? C6 C7 H7A 120.1 . . ? C9 C8 C7 120.0(5) . . ? C9 C8 H8A 120.0 . . ? C7 C8 H8A 120.0 . . ? C8 C9 C10 118.7(5) . . ? C8 C9 H9A 120.6 . . ? C10 C9 H9A 120.6 . . ? N2 C10 C9 121.7(5) . . ? N2 C10 H10A 119.1 . . ? C9 C10 H10A 119.1 . . ? C12 C11 P1 114.8(4) . . ? C12 C11 H11A 108.6 . . ? P1 C11 H11A 108.6 . . ? C12 C11 H11B 108.6 . . ? P1 C11 H11B 108.6 . . ? H11A C11 H11B 107.5 . . ? C11 C12 C13 111.3(8) . . ? C11 C12 H12A 109.4 . . ? C13 C12 H12A 109.4 . . ? C11 C12 H12B 109.4 . . ? C13 C12 H12B 109.4 . . ? H12A C12 H12B 108.0 . . ? C14 C13 C12 120.0(11) . . ? C14 C13 H13A 107.3 . . ? C12 C13 H13A 107.3 . . ? C14 C13 H13B 107.3 . . ? C12 C13 H13B 107.3 . . ? H13A C13 H13B 106.9 . . ? C13 C14 H14B 109.5 . . ? C13 C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? C13 C14 H14D 109.5 . . ? H14B C14 H14D 109.5 . . ? H14C C14 H14D 109.5 . . ? O3 C15 O2 125.8(4) . . ? O3 C15 C16 118.7(4) . . ? O2 C15 C16 115.5(4) . . ? C15 C16 H16A 109.5 . . ? C15 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? C15 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? O7 C17 O8 125.8(4) . . ? O7 C17 C18 119.4(4) . . ? O8 C17 C18 114.9(4) . . ? C17 C18 H18A 109.5 . . ? C17 C18 H18B 109.5 . . ? H18A C18 H18B 109.5 . . ? C17 C18 H18C 109.5 . . ? H18A C18 H18C 109.5 . . ? H18B C18 H18C 109.5 . . ? O14 C19 O15 120.1(15) . . ? O14 C19 C20 119.8(13) . . ? O15 C19 C20 120.2(9) . . ? O16 C20 O17 116.8(12) . . ? O16 C20 C19 118.1(12) . . ? O17 C20 C19 125.2(8) . . ? _diffrn_measured_fraction_theta_max 0.984 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 0.984 _refine_diff_density_max 0.977 _refine_diff_density_min -0.447 _refine_diff_density_rms 0.084 _publ_section_references ; Sheldrick G.M.(1996), SADABS, Absorption Correction Program, University of Goeltingen, German Siemens(1994), SAINT Software Reference Manual, Siemens Energy & Automation Inc., Madison, Wisconsin, USA Siemens(1996), SMART Software Reference Manual, Siemens Energy & Automation Inc., Madison, Wisconsin, USA Siemens(1994), SHELXTL^TM^ Version 5 Reference Manual, Siemens Energy & Automation Inc., Madison, Wisconsin, USA ; #========== data_compound-4 _database_code_depnum_ccdc_archive 'CCDC 635085' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C86 H72 Mn4 N6 O24 P2' _chemical_formula_weight 1855.20 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' P P 0.1023 0.0942 '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 P2(1)/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 18.0431(7) _cell_length_b 11.0649(3) _cell_length_c 21.7461(9) _cell_angle_alpha 90.00 _cell_angle_beta 91.002(2) _cell_angle_gamma 90.00 _cell_volume 4340.8(3) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 7272 _cell_measurement_theta_min 2.63 _cell_measurement_theta_max 27.48 _exptl_crystal_description PRISM _exptl_crystal_colour BROWN _exptl_crystal_size_max .80 _exptl_crystal_size_mid .40 _exptl_crystal_size_min .30 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.419 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1904 _exptl_absorpt_coefficient_mu 0.683 _exptl_absorpt_correction_type empirical _exptl_absorpt_process_details 'SADABS (Sheldrick, 1996)' _exptl_absorpt_correction_T_min .7010 _exptl_absorpt_correction_T_max 1.0000 _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 P4' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number none _diffrn_standards_interval_count none _diffrn_standards_interval_time none _diffrn_standards_decay_% none _diffrn_reflns_number 31627 _diffrn_reflns_av_R_equivalents 0.0214 _diffrn_reflns_av_sigmaI/netI 0.0235 _diffrn_reflns_limit_h_min -23 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -28 _diffrn_reflns_limit_l_max 28 _diffrn_reflns_theta_min 2.63 _diffrn_reflns_theta_max 27.48 _reflns_number_total 9889 _reflns_number_gt 8838 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Siemens SMART' _computing_cell_refinement 'Siemens SMART & SAINT' _computing_data_reduction 'Siemens XPREP' _computing_structure_solution 'Siemens SHELXTL' _computing_structure_refinement 'Siemens SHELXTL' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0787P)^2^+1.2153P] 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 9889 _refine_ls_number_parameters 550 _refine_ls_number_restraints 0 _refine_ls_R_factor_ref 0.0471 _refine_ls_R_factor_gt 0.0409 _refine_ls_wR_factor_ref 0.1208 _refine_ls_wR_factor_gt 0.1143 _refine_ls_goodness_of_fit_ref 1.005 _refine_ls_restrained_S_all 1.005 _refine_ls_shift/su_max 0.001 _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 P1 P 0.52970(3) 0.70434(4) 0.08076(2) 0.03405(11) Uani 1 1 d . . . Mn1 Mn 0.561085(14) 0.53374(2) -0.037273(11) 0.03153(9) Uani 1 1 d . . . Mn2 Mn 0.430040(15) 0.74390(2) -0.028200(12) 0.03252(9) Uani 1 1 d . . . O1 O 0.46264(6) 0.58443(11) -0.02458(5) 0.0308(2) Uani 1 1 d . . . O2 O 0.66351(7) 0.49217(13) -0.04722(7) 0.0427(3) Uani 1 1 d . . . O3 O 0.67326(8) 0.29946(14) -0.01771(7) 0.0490(4) Uani 1 1 d . . . O4 O 0.48226(7) 0.60056(13) 0.10511(6) 0.0391(3) Uani 1 1 d . . . O5 O 0.48085(8) 0.79503(12) 0.04317(6) 0.0400(3) Uani 1 1 d . . . O6 O 0.59359(7) 0.65838(12) 0.04214(6) 0.0366(3) Uani 1 1 d . . . O7 O 0.51645(8) 0.81607(14) -0.08789(7) 0.0489(3) Uani 1 1 d . . . O8 O 0.57960(9) 0.64645(14) -0.10437(6) 0.0481(3) Uani 1 1 d . . . O9 O 0.42483(10) 0.6013(2) 0.21270(8) 0.0806(6) Uani 1 1 d . . . H9B H 0.4471 0.6000 0.1801 0.121 Uiso 1 1 calc R . . O10 O 0.53730(11) 0.5685(2) 0.25281(9) 0.0745(5) Uani 1 1 d . . . O11 O 0.26603(11) 0.31075(19) -0.15979(9) 0.0703(5) Uani 1 1 d . . . O12 O 0.27177(9) 0.42047(17) -0.07421(7) 0.0593(4) Uani 1 1 d . . . H12A H 0.3129 0.3896 -0.0707 0.089 Uiso 1 1 calc R . . N1 N 0.37367(9) 0.90534(14) -0.03820(7) 0.0374(3) Uani 1 1 d . . . N2 N 0.37256(8) 0.70988(14) -0.10879(7) 0.0348(3) Uani 1 1 d . . . N3 N -0.0858(2) 0.8072(4) 0.0944(2) 0.1143(12) Uani 1 1 d . . . C1 C 0.37669(12) 1.00184(19) -0.00220(10) 0.0447(4) Uani 1 1 d . . . H1A H 0.4137 1.0069 0.0280 0.054 Uiso 1 1 calc R . . C2 C 0.32584(13) 1.09586(19) -0.00848(11) 0.0507(5) Uani 1 1 d . . . H2A H 0.3291 1.1626 0.0174 0.061 Uiso 1 1 calc R . . C3 C 0.27095(13) 1.0901(2) -0.05286(11) 0.0506(5) Uani 1 1 d . . . H3A H 0.2366 1.1525 -0.0568 0.061 Uiso 1 1 calc R . . C4 C 0.26669(11) 0.98984(19) -0.09231(10) 0.0432(4) Uani 1 1 d . . . C5 C 0.21235(13) 0.9733(2) -0.14107(11) 0.0544(6) Uani 1 1 d . . . H5A H 0.1759 1.0316 -0.1473 0.065 Uiso 1 1 calc R . . C6 C 0.21323(13) 0.8756(2) -0.17768(11) 0.0531(5) Uani 1 1 d . . . H6B H 0.1772 0.8676 -0.2085 0.064 Uiso 1 1 calc R . . C7 C 0.26840(11) 0.78347(19) -0.17023(9) 0.0414(4) Uani 1 1 d . . . C8 C 0.27658(12) 0.6826(2) -0.20880(9) 0.0482(5) Uani 1 1 d . . . H8A H 0.2442 0.6712 -0.2420 0.058 Uiso 1 1 calc R . . C9 C 0.33196(13) 0.6015(2) -0.19757(10) 0.0483(5) Uani 1 1 d . . . H9A H 0.3388 0.5368 -0.2242 0.058 Uiso 1 1 calc R . . C10 C 0.37870(11) 0.61576(18) -0.14582(9) 0.0404(4) Uani 1 1 d . . . H10A H 0.4148 0.5578 -0.1374 0.049 Uiso 1 1 calc R . . C11 C 0.31996(10) 0.79492(17) -0.12163(8) 0.0345(4) Uani 1 1 d . . . C12 C 0.31981(10) 0.89935(17) -0.08310(9) 0.0363(4) Uani 1 1 d . . . C13 C 0.69951(10) 0.39490(19) -0.03745(8) 0.0399(4) Uani 1 1 d . . . C14 C 0.78068(11) 0.4010(2) -0.04982(10) 0.0477(5) Uani 1 1 d . . . C15 C 0.82361(14) 0.2976(3) -0.04432(14) 0.0685(7) Uani 1 1 d . . . H15A H 0.8013 0.2237 -0.0361 0.082 Uiso 1 1 calc R . . C16 C 0.89974(16) 0.3041(4) -0.05098(18) 0.0886(10) Uani 1 1 d . . . H16A H 0.9284 0.2347 -0.0467 0.106 Uiso 1 1 calc R . . C17 C 0.93294(16) 0.4124(4) -0.06381(19) 0.0946(11) Uani 1 1 d . . . H17A H 0.9841 0.4168 -0.0676 0.114 Uiso 1 1 calc R . . C18 C 0.89077(16) 0.5138(3) -0.07100(18) 0.0869(10) Uani 1 1 d . . . H18A H 0.9133 0.5867 -0.0810 0.104 Uiso 1 1 calc R . . C19 C 0.81465(13) 0.5095(3) -0.06359(13) 0.0619(6) Uani 1 1 d . . . H19A H 0.7865 0.5795 -0.0679 0.074 Uiso 1 1 calc R . . C20 C 0.56282(11) 0.75536(19) -0.11584(9) 0.0397(4) Uani 1 1 d . . . C21 C 0.60412(12) 0.8129(3) -0.16764(10) 0.0567(6) Uani 1 1 d . . . C22 C 0.59592(17) 0.9351(3) -0.17908(17) 0.0854(10) Uani 1 1 d . . . H22A H 0.5657 0.9824 -0.1546 0.102 Uiso 1 1 calc R . . C23 C 0.6339(2) 0.9863(5) -0.2281(2) 0.127(2) Uani 1 1 d . . . H23A H 0.6291 1.0686 -0.2361 0.152 Uiso 1 1 calc R . . C24 C 0.6777(2) 0.9170(6) -0.2643(2) 0.137(2) Uani 1 1 d . . . H24A H 0.7024 0.9523 -0.2970 0.164 Uiso 1 1 calc R . . C25 C 0.6857(2) 0.7962(6) -0.25311(18) 0.1179(17) Uani 1 1 d . . . H25A H 0.7156 0.7494 -0.2781 0.141 Uiso 1 1 calc R . . C26 C 0.64907(17) 0.7435(4) -0.20424(13) 0.0807(9) Uani 1 1 d . . . H26A H 0.6549 0.6614 -0.1962 0.097 Uiso 1 1 calc R . . C27 C 0.56371(12) 0.7915(2) 0.14459(9) 0.0467(5) Uani 1 1 d . . . H27A H 0.5948 0.7418 0.1704 0.070 Uiso 1 1 calc R . . H27B H 0.5227 0.8209 0.1678 0.070 Uiso 1 1 calc R . . H27C H 0.5919 0.8587 0.1297 0.070 Uiso 1 1 calc R . . C28 C 0.47231(14) 0.5867(2) 0.25876(10) 0.0558(6) Uani 1 1 d . . . C29 C 0.43738(15) 0.5947(3) 0.32038(11) 0.0636(7) Uani 1 1 d . . . C30 C 0.3622(2) 0.6051(6) 0.32568(16) 0.132(2) Uani 1 1 d . . . H30A H 0.3316 0.6071 0.2908 0.158 Uiso 1 1 calc R . . C31 C 0.3768(3) 0.6122(7) 0.43497(18) 0.161(3) Uani 1 1 d . . . H31A H 0.3561 0.6190 0.4737 0.193 Uiso 1 1 calc R . . C32 C 0.3323(3) 0.6126(9) 0.3842(2) 0.204(4) Uani 1 1 d . . . H32A H 0.2812 0.6180 0.3885 0.245 Uiso 1 1 calc R . . C33 C 0.4506(3) 0.6022(4) 0.42994(14) 0.1003(12) Uani 1 1 d . . . H33A H 0.4808 0.6013 0.4650 0.120 Uiso 1 1 calc R . . C34 C 0.48149(18) 0.5934(3) 0.37224(12) 0.0689(7) Uani 1 1 d . . . H34A H 0.5326 0.5864 0.3687 0.083 Uiso 1 1 calc R . . C35 C 0.24144(12) 0.3890(2) -0.12729(10) 0.0469(5) Uani 1 1 d . . . C36 C 0.17446(12) 0.4616(2) -0.14442(10) 0.0456(5) Uani 1 1 d . . . C37 C 0.14167(15) 0.4439(3) -0.20161(12) 0.0637(7) Uani 1 1 d . . . H37A H 0.1597 0.3847 -0.2277 0.076 Uiso 1 1 calc R . . C38 C 0.08170(18) 0.5147(3) -0.21996(14) 0.0776(8) Uani 1 1 d . . . H38A H 0.0604 0.5038 -0.2588 0.093 Uiso 1 1 calc R . . C39 C 0.05410(17) 0.5991(3) -0.18196(17) 0.0823(9) Uani 1 1 d . . . H39A H 0.0134 0.6451 -0.1945 0.099 Uiso 1 1 calc R . . C40 C 0.08563(17) 0.6175(3) -0.12524(16) 0.0791(8) Uani 1 1 d . . . H40A H 0.0665 0.6761 -0.0993 0.095 Uiso 1 1 calc R . . C41 C 0.14627(15) 0.5488(3) -0.10621(13) 0.0620(6) Uani 1 1 d . . . H41A H 0.1678 0.5618 -0.0676 0.074 Uiso 1 1 calc R . . C42 C -0.0001(3) 0.7781(4) 0.1901(2) 0.1177(15) Uani 1 1 d . . . C43 C -0.0491(2) 0.7947(3) 0.1359(2) 0.0889(10) 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 P1 0.0340(2) 0.0379(3) 0.0300(2) -0.00609(18) -0.00741(17) 0.00318(19) Mn1 0.02887(14) 0.03566(16) 0.02996(14) 0.00074(10) -0.00230(10) 0.00355(10) Mn2 0.03161(15) 0.03230(16) 0.03334(15) -0.00184(10) -0.00809(11) 0.00436(10) O1 0.0302(6) 0.0326(6) 0.0294(5) -0.0019(5) -0.0056(4) 0.0043(5) O2 0.0308(6) 0.0482(8) 0.0493(7) 0.0011(6) 0.0022(6) 0.0037(6) O3 0.0383(7) 0.0478(8) 0.0611(9) 0.0062(7) 0.0084(7) 0.0068(6) O4 0.0412(7) 0.0455(8) 0.0304(6) -0.0043(5) -0.0023(5) 0.0001(6) O5 0.0421(7) 0.0379(7) 0.0397(7) -0.0079(5) -0.0116(5) 0.0053(6) O6 0.0337(6) 0.0413(7) 0.0347(6) -0.0059(5) -0.0040(5) 0.0014(5) O7 0.0460(8) 0.0459(8) 0.0548(8) 0.0070(7) 0.0016(7) -0.0034(7) O8 0.0530(8) 0.0508(9) 0.0406(7) 0.0085(6) 0.0056(6) 0.0048(7) O9 0.0578(10) 0.143(2) 0.0417(8) -0.0096(11) 0.0053(8) 0.0027(12) O10 0.0564(11) 0.1106(16) 0.0566(10) 0.0026(10) 0.0069(8) 0.0104(11) O11 0.0670(11) 0.0790(13) 0.0640(10) -0.0202(10) -0.0214(9) 0.0279(10) O12 0.0482(9) 0.0762(11) 0.0528(9) -0.0131(8) -0.0145(7) 0.0159(8) N1 0.0347(8) 0.0346(8) 0.0429(8) 0.0008(6) -0.0042(6) 0.0017(6) N2 0.0343(7) 0.0352(8) 0.0347(7) 0.0019(6) -0.0082(6) 0.0012(6) N3 0.081(2) 0.123(3) 0.139(3) 0.010(2) 0.006(2) 0.033(2) C1 0.0456(11) 0.0390(10) 0.0492(11) -0.0035(9) -0.0019(9) 0.0003(9) C2 0.0573(13) 0.0351(11) 0.0598(13) -0.0022(9) 0.0045(10) 0.0024(9) C3 0.0505(12) 0.0385(11) 0.0630(13) 0.0082(10) 0.0061(10) 0.0093(9) C4 0.0395(10) 0.0407(10) 0.0493(11) 0.0117(9) 0.0009(8) 0.0069(8) C5 0.0445(11) 0.0585(14) 0.0600(13) 0.0172(11) -0.0085(10) 0.0168(10) C6 0.0477(12) 0.0591(14) 0.0518(12) 0.0131(11) -0.0177(9) 0.0061(10) C7 0.0395(10) 0.0451(11) 0.0392(9) 0.0107(8) -0.0095(8) -0.0013(8) C8 0.0517(12) 0.0542(12) 0.0380(10) 0.0046(9) -0.0171(9) -0.0075(10) C9 0.0603(13) 0.0438(11) 0.0402(10) -0.0054(8) -0.0122(9) -0.0014(10) C10 0.0439(10) 0.0376(10) 0.0395(9) -0.0008(8) -0.0094(8) 0.0030(8) C11 0.0327(8) 0.0346(9) 0.0360(9) 0.0075(7) -0.0054(7) 0.0000(7) C12 0.0334(9) 0.0348(9) 0.0406(9) 0.0080(7) -0.0031(7) 0.0005(7) C13 0.0328(9) 0.0513(12) 0.0355(9) -0.0028(8) 0.0009(7) 0.0048(8) C14 0.0339(10) 0.0621(14) 0.0472(11) -0.0040(10) 0.0065(8) 0.0067(9) C15 0.0464(13) 0.0716(17) 0.0879(19) 0.0024(15) 0.0136(13) 0.0143(12) C16 0.0487(15) 0.097(2) 0.120(3) 0.005(2) 0.0217(17) 0.0283(16) C17 0.0360(13) 0.115(3) 0.134(3) -0.013(2) 0.0221(16) 0.0068(16) C18 0.0472(14) 0.095(2) 0.120(3) -0.010(2) 0.0269(16) -0.0115(15) C19 0.0414(12) 0.0697(16) 0.0751(16) -0.0046(13) 0.0130(11) -0.0009(11) C20 0.0349(9) 0.0486(11) 0.0353(9) 0.0068(8) -0.0081(7) -0.0055(8) C21 0.0421(11) 0.0822(17) 0.0455(11) 0.0248(11) -0.0085(9) -0.0091(11) C22 0.0631(17) 0.097(2) 0.095(2) 0.0567(19) -0.0085(15) -0.0117(16) C23 0.085(3) 0.162(4) 0.133(4) 0.105(4) -0.007(3) -0.024(3) C24 0.082(3) 0.237(7) 0.093(3) 0.092(4) 0.002(2) -0.041(3) C25 0.085(2) 0.200(5) 0.070(2) 0.039(3) 0.0247(18) -0.009(3) C26 0.0669(17) 0.121(3) 0.0542(15) 0.0132(16) 0.0136(13) -0.0036(17) C27 0.0480(11) 0.0521(12) 0.0395(10) -0.0141(9) -0.0113(8) 0.0012(9) C28 0.0556(13) 0.0672(15) 0.0449(11) -0.0026(10) 0.0075(10) -0.0036(11) C29 0.0636(15) 0.0845(19) 0.0429(11) -0.0040(12) 0.0107(11) -0.0088(14) C30 0.0623(19) 0.273(7) 0.0601(18) -0.020(3) 0.0145(15) 0.003(3) C31 0.128(4) 0.299(8) 0.057(2) -0.016(3) 0.040(2) -0.015(5) C32 0.082(3) 0.451(13) 0.080(3) -0.028(5) 0.039(2) -0.006(5) C33 0.126(3) 0.132(3) 0.0428(14) -0.0002(17) 0.0021(17) -0.022(3) C34 0.0802(18) 0.0749(18) 0.0515(13) -0.0002(12) 0.0008(13) -0.0088(15) C35 0.0428(11) 0.0540(13) 0.0438(10) 0.0017(9) -0.0067(8) 0.0009(9) C36 0.0405(10) 0.0497(12) 0.0466(11) 0.0080(9) -0.0022(8) 0.0023(9) C37 0.0598(14) 0.0761(17) 0.0547(13) 0.0012(12) -0.0140(11) 0.0114(13) C38 0.0733(18) 0.093(2) 0.0652(17) 0.0173(16) -0.0207(14) 0.0152(17) C39 0.0619(17) 0.083(2) 0.101(2) 0.0230(19) -0.0089(16) 0.0250(16) C40 0.0631(16) 0.080(2) 0.094(2) -0.0018(17) 0.0001(15) 0.0254(15) C41 0.0542(13) 0.0695(16) 0.0621(14) -0.0023(12) -0.0046(11) 0.0131(12) C42 0.127(4) 0.094(3) 0.131(4) -0.004(3) -0.029(3) 0.008(3) C43 0.069(2) 0.074(2) 0.124(3) 0.001(2) 0.012(2) 0.0186(17) _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 P1 O6 1.5253(13) . ? P1 O4 1.5322(15) . ? P1 O5 1.5578(14) . ? P1 C27 1.7899(19) . ? Mn1 O1 1.8876(12) . ? Mn1 O2 1.9204(13) . ? Mn1 O1 1.9292(12) 3_665 ? Mn1 O8 1.9526(14) . ? Mn1 O4 2.2262(13) 3_665 ? Mn1 O6 2.2788(12) . ? Mn1 Mn1 2.8582(5) 3_665 ? Mn2 O1 1.8612(12) . ? Mn2 O5 1.8761(13) . ? Mn2 N2 2.0555(15) . ? Mn2 N1 2.0652(16) . ? Mn2 O3 2.1831(15) 3_665 ? Mn2 O7 2.1963(15) . ? O1 Mn1 1.9292(12) 3_665 ? O2 C13 1.273(2) . ? O3 C13 1.237(3) . ? O3 Mn2 2.1831(15) 3_665 ? O4 Mn1 2.2262(13) 3_665 ? O7 C20 1.240(3) . ? O8 C20 1.266(3) . ? O9 C28 1.316(3) . ? O9 H9B 0.8200 . ? O10 C28 1.199(3) . ? O11 C35 1.207(3) . ? O12 C35 1.316(3) . ? O12 H12A 0.8200 . ? N1 C1 1.325(3) . ? N1 C12 1.367(2) . ? N2 C10 1.322(3) . ? N2 C11 1.362(2) . ? N3 C43 1.119(5) . ? C1 C2 1.392(3) . ? C1 H1A 0.9300 . ? C2 C3 1.372(3) . ? C2 H2A 0.9300 . ? C3 C4 1.404(3) . ? C3 H3A 0.9300 . ? C4 C12 1.398(3) . ? C4 C5 1.443(3) . ? C5 C6 1.343(4) . ? C5 H5A 0.9300 . ? C6 C7 1.432(3) . ? C6 H6B 0.9300 . ? C7 C11 1.401(3) . ? C7 C8 1.406(3) . ? C8 C9 1.362(3) . ? C8 H8A 0.9300 . ? C9 C10 1.403(3) . ? C9 H9A 0.9300 . ? C10 H10A 0.9300 . ? C11 C12 1.427(3) . ? C13 C14 1.495(3) . ? C14 C19 1.383(4) . ? C14 C15 1.386(4) . ? C15 C16 1.386(4) . ? C15 H15A 0.9300 . ? C16 C17 1.371(5) . ? C16 H16A 0.9300 . ? C17 C18 1.363(5) . ? C17 H17A 0.9300 . ? C18 C19 1.386(4) . ? C18 H18A 0.9300 . ? C19 H19A 0.9300 . ? C20 C21 1.503(3) . ? C21 C26 1.380(4) . ? C21 C22 1.383(4) . ? C22 C23 1.397(5) . ? C22 H22A 0.9300 . ? C23 C24 1.362(8) . ? C23 H23A 0.9300 . ? C24 C25 1.366(8) . ? C24 H24A 0.9300 . ? C25 C26 1.390(4) . ? C25 H25A 0.9300 . ? C26 H26A 0.9300 . ? C27 H27A 0.9600 . ? C27 H27B 0.9600 . ? C27 H27C 0.9600 . ? C28 C29 1.493(3) . ? C29 C30 1.368(4) . ? C29 C34 1.369(4) . ? C30 C32 1.394(5) . ? C30 H30A 0.9300 . ? C31 C33 1.343(6) . ? C31 C32 1.353(7) . ? C31 H31A 0.9300 . ? C32 H32A 0.9300 . ? C33 C34 1.385(4) . ? C33 H33A 0.9300 . ? C34 H34A 0.9300 . ? C35 C36 1.493(3) . ? C36 C41 1.377(3) . ? C36 C37 1.382(3) . ? C37 C38 1.389(4) . ? C37 H37A 0.9300 . ? C38 C39 1.349(5) . ? C38 H38A 0.9300 . ? C39 C40 1.364(5) . ? C39 H39A 0.9300 . ? C40 C41 1.389(4) . ? C40 H40A 0.9300 . ? C41 H41A 0.9300 . ? C42 C43 1.474(6) . ? 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 O6 P1 O4 111.87(8) . . ? O6 P1 O5 110.61(8) . . ? O4 P1 O5 110.47(8) . . ? O6 P1 C27 110.76(9) . . ? O4 P1 C27 108.78(9) . . ? O5 P1 C27 104.06(9) . . ? O1 Mn1 O2 176.00(6) . . ? O1 Mn1 O1 83.03(5) . 3_665 ? O2 Mn1 O1 98.16(6) . 3_665 ? O1 Mn1 O8 95.35(6) . . ? O2 Mn1 O8 83.76(6) . . ? O1 Mn1 O8 175.37(6) 3_665 . ? O1 Mn1 O4 88.55(5) . 3_665 ? O2 Mn1 O4 95.34(6) . 3_665 ? O1 Mn1 O4 85.98(5) 3_665 3_665 ? O8 Mn1 O4 89.65(6) . 3_665 ? O1 Mn1 O6 86.54(5) . . ? O2 Mn1 O6 89.71(5) . . ? O1 Mn1 O6 86.51(5) 3_665 . ? O8 Mn1 O6 97.74(6) . . ? O4 Mn1 O6 171.48(5) 3_665 . ? O1 Mn1 Mn1 42.07(4) . 3_665 ? O2 Mn1 Mn1 138.99(5) . 3_665 ? O1 Mn1 Mn1 40.96(4) 3_665 3_665 ? O8 Mn1 Mn1 137.25(5) . 3_665 ? O4 Mn1 Mn1 86.33(4) 3_665 3_665 ? O6 Mn1 Mn1 85.36(3) . 3_665 ? O1 Mn2 O5 95.82(5) . . ? O1 Mn2 N2 90.97(6) . . ? O5 Mn2 N2 173.00(6) . . ? O1 Mn2 N1 168.29(6) . . ? O5 Mn2 N1 93.38(6) . . ? N2 Mn2 N1 80.12(6) . . ? O1 Mn2 O3 92.52(6) . 3_665 ? O5 Mn2 O3 95.55(6) . 3_665 ? N2 Mn2 O3 85.85(6) . 3_665 ? N1 Mn2 O3 79.36(6) . 3_665 ? O1 Mn2 O7 98.20(6) . . ? O5 Mn2 O7 92.16(6) . . ? N2 Mn2 O7 85.15(6) . . ? N1 Mn2 O7 88.66(6) . . ? O3 Mn2 O7 166.10(6) 3_665 . ? Mn2 O1 Mn1 124.96(7) . . ? Mn2 O1 Mn1 126.75(7) . 3_665 ? Mn1 O1 Mn1 96.97(5) . 3_665 ? C13 O2 Mn1 132.29(13) . . ? C13 O3 Mn2 132.95(13) . 3_665 ? P1 O4 Mn1 117.59(7) . 3_665 ? P1 O5 Mn2 120.24(8) . . ? P1 O6 Mn1 115.60(7) . . ? C20 O7 Mn2 125.78(13) . . ? C20 O8 Mn1 135.37(14) . . ? C28 O9 H9B 109.5 . . ? C35 O12 H12A 109.5 . . ? C1 N1 C12 118.86(17) . . ? C1 N1 Mn2 128.31(14) . . ? C12 N1 Mn2 112.08(12) . . ? C10 N2 C11 119.00(16) . . ? C10 N2 Mn2 128.10(13) . . ? C11 N2 Mn2 112.81(12) . . ? N1 C1 C2 121.6(2) . . ? N1 C1 H1A 119.2 . . ? C2 C1 H1A 119.2 . . ? C3 C2 C1 120.0(2) . . ? C3 C2 H2A 120.0 . . ? C1 C2 H2A 120.0 . . ? C2 C3 C4 119.9(2) . . ? C2 C3 H3A 120.1 . . ? C4 C3 H3A 120.1 . . ? C12 C4 C3 116.64(19) . . ? C12 C4 C5 118.0(2) . . ? C3 C4 C5 125.4(2) . . ? C6 C5 C4 121.5(2) . . ? C6 C5 H5A 119.2 . . ? C4 C5 H5A 119.2 . . ? C5 C6 C7 121.4(2) . . ? C5 C6 H6B 119.3 . . ? C7 C6 H6B 119.3 . . ? C11 C7 C8 116.52(18) . . ? C11 C7 C6 118.2(2) . . ? C8 C7 C6 125.29(19) . . ? C9 C8 C7 120.04(18) . . ? C9 C8 H8A 120.0 . . ? C7 C8 H8A 120.0 . . ? C8 C9 C10 119.9(2) . . ? C8 C9 H9A 120.1 . . ? C10 C9 H9A 120.1 . . ? N2 C10 C9 121.43(19) . . ? N2 C10 H10A 119.3 . . ? C9 C10 H10A 119.3 . . ? N2 C11 C7 122.90(18) . . ? N2 C11 C12 116.58(16) . . ? C7 C11 C12 120.51(17) . . ? N1 C12 C4 123.00(18) . . ? N1 C12 C11 116.73(16) . . ? C4 C12 C11 120.27(17) . . ? O3 C13 O2 125.60(18) . . ? O3 C13 C14 118.89(19) . . ? O2 C13 C14 115.48(19) . . ? C19 C14 C15 119.1(2) . . ? C19 C14 C13 121.2(2) . . ? C15 C14 C13 119.7(2) . . ? C16 C15 C14 120.1(3) . . ? C16 C15 H15A 119.9 . . ? C14 C15 H15A 119.9 . . ? C17 C16 C15 120.3(3) . . ? C17 C16 H16A 119.9 . . ? C15 C16 H16A 119.9 . . ? C18 C17 C16 119.9(3) . . ? C18 C17 H17A 120.1 . . ? C16 C17 H17A 120.1 . . ? C17 C18 C19 120.7(3) . . ? C17 C18 H18A 119.7 . . ? C19 C18 H18A 119.7 . . ? C14 C19 C18 119.9(3) . . ? C14 C19 H19A 120.0 . . ? C18 C19 H19A 120.0 . . ? O7 C20 O8 125.43(19) . . ? O7 C20 C21 119.0(2) . . ? O8 C20 C21 115.5(2) . . ? C26 C21 C22 120.2(3) . . ? C26 C21 C20 120.0(3) . . ? C22 C21 C20 119.8(3) . . ? C21 C22 C23 118.8(4) . . ? C21 C22 H22A 120.6 . . ? C23 C22 H22A 120.6 . . ? C24 C23 C22 120.7(5) . . ? C24 C23 H23A 119.7 . . ? C22 C23 H23A 119.7 . . ? C23 C24 C25 120.6(4) . . ? C23 C24 H24A 119.7 . . ? C25 C24 H24A 119.7 . . ? C24 C25 C26 119.8(5) . . ? C24 C25 H25A 120.1 . . ? C26 C25 H25A 120.1 . . ? C21 C26 C25 120.0(4) . . ? C21 C26 H26A 120.0 . . ? C25 C26 H26A 120.0 . . ? P1 C27 H27A 109.5 . . ? P1 C27 H27B 109.5 . . ? H27A C27 H27B 109.5 . . ? P1 C27 H27C 109.5 . . ? H27A C27 H27C 109.5 . . ? H27B C27 H27C 109.5 . . ? O10 C28 O9 124.3(2) . . ? O10 C28 C29 122.4(2) . . ? O9 C28 C29 113.3(2) . . ? C30 C29 C34 119.6(3) . . ? C30 C29 C28 121.0(3) . . ? C34 C29 C28 119.3(3) . . ? C29 C30 C32 118.8(4) . . ? C29 C30 H30A 120.6 . . ? C32 C30 H30A 120.6 . . ? C33 C31 C32 120.6(3) . . ? C33 C31 H31A 119.7 . . ? C32 C31 H31A 119.7 . . ? C31 C32 C30 120.7(4) . . ? C31 C32 H32A 119.6 . . ? C30 C32 H32A 119.6 . . ? C31 C33 C34 119.7(4) . . ? C31 C33 H33A 120.2 . . ? C34 C33 H33A 120.2 . . ? C29 C34 C33 120.5(3) . . ? C29 C34 H34A 119.7 . . ? C33 C34 H34A 119.7 . . ? O11 C35 O12 123.5(2) . . ? O11 C35 C36 123.0(2) . . ? O12 C35 C36 113.5(2) . . ? C41 C36 C37 119.1(2) . . ? C41 C36 C35 122.2(2) . . ? C37 C36 C35 118.7(2) . . ? C36 C37 C38 119.9(3) . . ? C36 C37 H37A 120.1 . . ? C38 C37 H37A 120.1 . . ? C39 C38 C37 120.6(3) . . ? C39 C38 H38A 119.7 . . ? C37 C38 H38A 119.7 . . ? C38 C39 C40 120.3(3) . . ? C38 C39 H39A 119.8 . . ? C40 C39 H39A 119.8 . . ? C39 C40 C41 120.1(3) . . ? C39 C40 H40A 119.9 . . ? C41 C40 H40A 119.9 . . ? C36 C41 C40 120.1(3) . . ? C36 C41 H41A 120.0 . . ? C40 C41 H41A 120.0 . . ? N3 C43 C42 179.4(5) . . ? _diffrn_measured_fraction_theta_max 0.992 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 0.992 _refine_diff_density_max 0.492 _refine_diff_density_min -0.322 _refine_diff_density_rms 0.052 _publ_section_references ; Sheldrick G.M.(1996), SADABS, Absorption Correction Program, University of Goeltingen, German Siemens(1994), SAINT Software Reference Manual, Siemens Energy & Automation Inc., Madison, Wisconsin, USA Siemens(1996), SMART Software Reference Manual, Siemens Energy & Automation Inc., Madison, Wisconsin, USA Siemens(1994), SHELXTL^TM^ Version 5 Reference Manual, Siemens Energy & Automation Inc., Madison, Wisconsin, USA ;