# Electronic Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2011 data_global _journal_coden_Cambridge 222 loop_ _publ_author_name 'Keene, Tony' 'Murphy, Michael' 'Price, Jason' 'Price, David' 'Kepert, Cameron' _publ_contact_author_name 'Kepert, Cameron' _publ_contact_author_email c.kepert@chem.usyd.edu.au _publ_section_title ; A new modification of an old framework: Hofmann layers with unusual tetracyanidometallate groups ; # Attachment '- compound1.cif' data_compound1 _database_code_depnum_ccdc_archive 'CCDC 831130' #TrackingRef '- compound1.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; {[Mn(H~2~O)(bpy)~0.5~][Mo(O)(CN)~4~(bpy)~0.5~] .2H~2~O ; _chemical_name_common 'MoMn(bpy) Hofmann' _chemical_melting_point N/A _chemical_formula_moiety 'C14 H10 Mn Mo N6 O2, 2(H2 O)' _chemical_formula_sum 'C14 H14 Mn Mo N6 O4' _chemical_formula_weight 481.19 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' Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Mo Mo -1.6832 0.6857 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21/c' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 7.3707(14) _cell_length_b 17.234(4) _cell_length_c 14.422(3) _cell_angle_alpha 90.00 _cell_angle_beta 91.646(10) _cell_angle_gamma 90.00 _cell_volume 1831.2(6) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 8413 _cell_measurement_theta_min 2.75 _cell_measurement_theta_max 31.18 _exptl_crystal_description block _exptl_crystal_colour blue _exptl_crystal_size_max 0.10 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.745 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 956 _exptl_absorpt_coefficient_mu 1.406 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.6869 _exptl_absorpt_correction_T_max 0.7462 _exptl_absorpt_process_details SADABS-2007/4 _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker-Nonius FR591 Kappa APEX II' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 31333 _diffrn_reflns_av_R_equivalents 0.0487 _diffrn_reflns_av_sigmaI/netI 0.0476 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -24 _diffrn_reflns_limit_k_max 25 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 1.84 _diffrn_reflns_theta_max 31.37 _reflns_number_total 5919 _reflns_number_gt 4523 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'APEX2 Ver. 2009.3-0 (Bruker-AXS, 2009)' _computing_cell_refinement 'SAINT Ver. 7.60A (Bruker-AXS, 2009)' _computing_data_reduction 'SAINT Ver. 7.60A' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Diamond 3.2g (Crystal Impact, 2011)' _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 'w=1/[\s^2^(Fo^2^)+(0.0401P)^2^] 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 5919 _refine_ls_number_parameters 259 _refine_ls_number_restraints 9 _refine_ls_R_factor_all 0.0563 _refine_ls_R_factor_gt 0.0296 _refine_ls_wR_factor_ref 0.0846 _refine_ls_wR_factor_gt 0.0637 _refine_ls_goodness_of_fit_ref 1.151 _refine_ls_restrained_S_all 1.150 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group H1W H 0.633(2) 0.4783(12) 0.3891(14) 0.014(8) Uiso 1 1 d D . . H2W H 0.746(3) 0.4874(12) 0.4683(13) 0.023(9) Uiso 1 1 d D . . H5W H 0.666(3) 0.5028(14) 0.658(2) 0.065(14) Uiso 1 1 d D . . H3W H 0.9703(12) 0.5543(16) 0.591(3) 0.055(13) Uiso 1 1 d D . . H4W H 0.817(4) 0.5983(6) 0.565(3) 0.050(13) Uiso 1 1 d D . . H6W H 0.573(4) 0.4325(10) 0.646(2) 0.043(12) Uiso 1 1 d D . . Mo1 Mo 0.16746(3) 0.207726(12) 0.215825(14) 0.00677(6) Uani 1 1 d . . . Mn1 Mn 0.65803(5) 0.32970(2) 0.44539(3) 0.00764(8) Uani 1 1 d . . . O1 O 0.2052(2) 0.12489(11) 0.27533(12) 0.0135(4) Uani 1 1 d . . . N10 N 0.1109(3) 0.32749(12) 0.12844(14) 0.0090(4) Uani 1 1 d . . . C11 C 0.0915(3) 0.32710(15) 0.03493(17) 0.0111(5) Uani 1 1 d . . . H11 H 0.1071 0.2794 0.0032 0.013 Uiso 1 1 calc R . . C12 C 0.0500(3) 0.39295(15) -0.01717(18) 0.0121(5) Uani 1 1 d . . . H12 H 0.0397 0.3896 -0.0829 0.015 Uiso 1 1 calc R . . C13 C 0.0235(3) 0.46405(14) 0.02680(16) 0.0085(4) Uani 1 1 d . . . C14 C 0.0443(4) 0.46457(15) 0.12407(18) 0.0140(5) Uani 1 1 d . . . H14 H 0.0284 0.5115 0.1575 0.017 Uiso 1 1 calc R . . C15 C 0.0881(4) 0.39636(15) 0.17149(18) 0.0137(5) Uani 1 1 d . . . H15 H 0.1027 0.3983 0.2371 0.016 Uiso 1 1 calc R . . C2 C -0.0156(3) 0.26525(15) 0.30920(17) 0.0096(5) Uani 1 1 d . . . C3 C 0.3309(3) 0.17952(14) 0.09767(17) 0.0092(4) Uani 1 1 d . . . C1 C 0.3728(3) 0.28358(15) 0.27831(17) 0.0107(5) Uani 1 1 d . . . C4 C -0.0600(3) 0.17275(15) 0.12774(17) 0.0105(5) Uani 1 1 d . . . N2 N -0.1088(3) 0.29615(13) 0.36066(15) 0.0128(4) Uani 1 1 d . . . N4 N -0.1758(3) 0.15727(13) 0.07494(15) 0.0127(4) Uani 1 1 d . . . N3 N 0.4140(3) 0.15899(13) 0.03472(15) 0.0126(4) Uani 1 1 d . . . N1 N 0.4762(3) 0.32147(13) 0.32029(15) 0.0129(4) Uani 1 1 d . . . O1W O 0.7197(3) 0.45541(11) 0.42224(13) 0.0146(4) Uani 1 1 d D . . N20 N 0.6264(3) 0.19913(12) 0.47143(15) 0.0102(4) Uani 1 1 d . . . C25 C 0.6075(3) 0.15013(15) 0.39868(19) 0.0134(5) Uani 1 1 d . . . H25 H 0.6291 0.1699 0.3385 0.016 Uiso 1 1 calc R . . C24 C 0.5584(3) 0.07266(15) 0.40644(18) 0.0127(5) Uani 1 1 d . . . H24 H 0.5455 0.0411 0.3526 0.015 Uiso 1 1 calc R . . C21 C 0.6024(3) 0.16828(15) 0.55686(19) 0.0135(5) Uani 1 1 d . . . H21 H 0.6194 0.2009 0.6095 0.016 Uiso 1 1 calc R . . C22 C 0.5541(3) 0.09133(15) 0.57121(18) 0.0128(5) Uani 1 1 d . . . H22 H 0.5387 0.0725 0.6324 0.015 Uiso 1 1 calc R . . C23 C 0.5279(3) 0.04128(15) 0.49440(18) 0.0108(5) Uani 1 1 d . . . O2W O 0.8539(3) 0.55050(12) 0.57626(14) 0.0191(4) Uani 1 1 d D . . O3W O 0.5703(3) 0.47721(12) 0.67570(14) 0.0194(4) Uani 1 1 d 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 Mo1 0.00682(9) 0.00871(10) 0.00481(9) 0.00024(8) 0.00062(6) 0.00029(7) Mn1 0.00718(16) 0.00954(19) 0.00623(18) -0.00026(14) 0.00079(13) -0.00033(13) O1 0.0157(8) 0.0131(9) 0.0116(9) 0.0032(7) 0.0019(7) 0.0016(7) N10 0.0099(9) 0.0090(10) 0.0082(10) 0.0000(8) -0.0004(7) -0.0015(7) C11 0.0151(11) 0.0114(12) 0.0070(11) -0.0008(9) 0.0006(9) 0.0013(9) C12 0.0167(12) 0.0134(13) 0.0061(11) 0.0010(9) 0.0007(9) 0.0023(9) C13 0.0092(10) 0.0097(11) 0.0066(11) -0.0001(9) 0.0016(8) -0.0014(8) C14 0.0250(13) 0.0085(12) 0.0083(12) -0.0014(9) 0.0003(10) 0.0012(10) C15 0.0234(13) 0.0112(13) 0.0063(11) -0.0004(9) -0.0021(10) 0.0004(10) C2 0.0093(10) 0.0100(11) 0.0094(11) 0.0009(9) -0.0010(9) -0.0022(9) C3 0.0088(10) 0.0089(11) 0.0097(11) 0.0020(9) -0.0006(9) -0.0012(8) C1 0.0110(10) 0.0127(12) 0.0084(11) 0.0034(9) 0.0025(9) 0.0032(9) C4 0.0111(11) 0.0108(12) 0.0099(12) 0.0022(9) 0.0041(9) 0.0012(9) N2 0.0127(9) 0.0140(11) 0.0119(10) 0.0014(9) 0.0019(8) 0.0000(8) N4 0.0148(10) 0.0117(11) 0.0116(11) 0.0003(8) -0.0013(8) -0.0021(8) N3 0.0106(9) 0.0134(11) 0.0141(11) 0.0004(9) 0.0020(8) 0.0006(8) N1 0.0131(10) 0.0153(11) 0.0102(11) 0.0037(9) 0.0001(8) 0.0017(8) O1W 0.0192(9) 0.0112(9) 0.0133(9) 0.0001(7) -0.0020(7) -0.0017(7) N20 0.0103(9) 0.0094(10) 0.0109(10) 0.0003(8) 0.0003(8) 0.0004(7) C25 0.0134(11) 0.0151(13) 0.0116(12) 0.0008(10) 0.0013(9) 0.0003(9) C24 0.0142(11) 0.0112(12) 0.0127(12) 0.0004(10) 0.0000(9) -0.0003(9) C21 0.0148(11) 0.0131(13) 0.0126(13) -0.0024(10) 0.0006(10) -0.0002(9) C22 0.0153(11) 0.0127(12) 0.0104(12) 0.0003(10) 0.0021(9) 0.0010(10) C23 0.0085(10) 0.0112(12) 0.0127(12) 0.0010(10) 0.0004(9) 0.0023(9) O2W 0.0190(10) 0.0163(10) 0.0219(11) -0.0007(9) 0.0011(8) -0.0022(8) O3W 0.0236(10) 0.0169(11) 0.0176(10) -0.0012(8) 0.0008(8) -0.0023(8) _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 Mo1 O1 1.6847(18) . ? Mo1 C4 2.160(3) . ? Mo1 C3 2.170(2) . ? Mo1 C2 2.173(2) . ? Mo1 C1 2.176(3) . ? Mo1 N10 2.448(2) . ? Mn1 N2 2.214(2) 1_655 ? Mn1 N4 2.216(2) 4_666 ? Mn1 N1 2.221(2) . ? Mn1 O1W 2.2405(19) . ? Mn1 N3 2.251(2) 4_566 ? Mn1 N20 2.294(2) . ? N10 C11 1.352(3) . ? N10 C15 1.352(3) . ? C11 C12 1.390(3) . ? C11 H11 0.9500 . ? C12 C13 1.396(3) . ? C12 H12 0.9500 . ? C13 C14 1.407(3) . ? C13 C13 1.496(5) 3_565 ? C14 C15 1.393(4) . ? C14 H14 0.9500 . ? C15 H15 0.9500 . ? C2 N2 1.156(3) . ? C3 N3 1.164(3) . ? C1 N1 1.160(3) . ? C4 N4 1.158(3) . ? N2 Mn1 2.214(2) 1_455 ? N4 Mn1 2.216(2) 4_465 ? N3 Mn1 2.251(2) 4_565 ? O1W H1W 0.8798(10) . ? O1W H2W 0.8798(10) . ? N20 C25 1.351(3) . ? N20 C21 1.358(3) . ? C25 C24 1.389(4) . ? C25 H25 0.9500 . ? C24 C23 1.403(3) . ? C24 H24 0.9500 . ? C21 C22 1.390(4) . ? C21 H21 0.9500 . ? C22 C23 1.413(4) . ? C22 H22 0.9500 . ? C23 C23 1.491(5) 3_656 ? O2W H3W 0.8799(11) . ? O2W H4W 0.8798(10) . ? O3W H5W 0.8799(10) . ? O3W H6W 0.8799(10) . ? 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 Mo1 C4 100.20(9) . . ? O1 Mo1 C3 97.07(9) . . ? C4 Mo1 C3 85.11(9) . . ? O1 Mo1 C2 99.63(9) . . ? C4 Mo1 C2 90.37(9) . . ? C3 Mo1 C2 163.23(9) . . ? O1 Mo1 C1 101.27(9) . . ? C4 Mo1 C1 158.48(9) . . ? C3 Mo1 C1 93.70(9) . . ? C2 Mo1 C1 84.61(9) . . ? O1 Mo1 N10 179.51(8) . . ? C4 Mo1 N10 79.32(8) . . ? C3 Mo1 N10 82.81(8) . . ? C2 Mo1 N10 80.49(8) . . ? C1 Mo1 N10 79.21(8) . . ? N2 Mn1 N4 94.17(8) 1_655 4_666 ? N2 Mn1 N1 89.71(8) 1_655 . ? N4 Mn1 N1 175.94(8) 4_666 . ? N2 Mn1 O1W 90.36(8) 1_655 . ? N4 Mn1 O1W 85.30(8) 4_666 . ? N1 Mn1 O1W 93.50(8) . . ? N2 Mn1 N3 169.82(8) 1_655 4_566 ? N4 Mn1 N3 86.57(8) 4_666 4_566 ? N1 Mn1 N3 89.82(8) . 4_566 ? O1W Mn1 N3 99.81(7) . 4_566 ? N2 Mn1 N20 85.31(8) 1_655 . ? N4 Mn1 N20 91.01(8) 4_666 . ? N1 Mn1 N20 90.49(8) . . ? O1W Mn1 N20 174.10(7) . . ? N3 Mn1 N20 84.53(8) 4_566 . ? C11 N10 C15 116.8(2) . . ? C11 N10 Mo1 121.39(16) . . ? C15 N10 Mo1 121.69(17) . . ? N10 C11 C12 123.4(2) . . ? N10 C11 H11 118.3 . . ? C12 C11 H11 118.3 . . ? C11 C12 C13 120.2(2) . . ? C11 C12 H12 119.9 . . ? C13 C12 H12 119.9 . . ? C12 C13 C14 116.5(2) . . ? C12 C13 C13 121.7(3) . 3_565 ? C14 C13 C13 121.8(3) . 3_565 ? C15 C14 C13 120.1(2) . . ? C15 C14 H14 120.0 . . ? C13 C14 H14 120.0 . . ? N10 C15 C14 123.0(2) . . ? N10 C15 H15 118.5 . . ? C14 C15 H15 118.5 . . ? N2 C2 Mo1 178.0(2) . . ? N3 C3 Mo1 175.1(2) . . ? N1 C1 Mo1 173.0(2) . . ? N4 C4 Mo1 174.6(2) . . ? C2 N2 Mn1 163.7(2) . 1_455 ? C4 N4 Mn1 155.5(2) . 4_465 ? C3 N3 Mn1 150.1(2) . 4_565 ? C1 N1 Mn1 146.3(2) . . ? Mn1 O1W H1W 111.6(16) . . ? Mn1 O1W H2W 122.3(19) . . ? H1W O1W H2W 105.43(17) . . ? C25 N20 C21 116.5(2) . . ? C25 N20 Mn1 119.65(17) . . ? C21 N20 Mn1 123.30(17) . . ? N20 C25 C24 124.0(2) . . ? N20 C25 H25 118.0 . . ? C24 C25 H25 118.0 . . ? C25 C24 C23 119.5(2) . . ? C25 C24 H24 120.3 . . ? C23 C24 H24 120.3 . . ? N20 C21 C22 123.3(2) . . ? N20 C21 H21 118.3 . . ? C22 C21 H21 118.3 . . ? C21 C22 C23 119.7(2) . . ? C21 C22 H22 120.2 . . ? C23 C22 H22 120.2 . . ? C24 C23 C22 116.9(2) . . ? C24 C23 C23 121.2(3) . 3_656 ? C22 C23 C23 122.0(3) . 3_656 ? H3W O2W H4W 105.43(17) . . ? H5W O3W H6W 105.41(17) . . ? _diffrn_measured_fraction_theta_max 0.982 _diffrn_reflns_theta_full 31.37 _diffrn_measured_fraction_theta_full 0.982 _refine_diff_density_max 0.804 _refine_diff_density_min -0.860 _refine_diff_density_rms 0.194 # start Validation Reply Form _vrf_PLAT731_I ; PROBLEM: Bond Calc 0.880(18), Rep 0.8798(10) ...... 9.90 su-Ra RESPONSE: Bond distances and angles were fixed to literature values. ; _vrf_PLAT732_I ; PROBLEM: Angle Calc 105.6(19), Rep 105.43(17) ...... 9.90 su-Ra RESPONSE: Bond distances and angles were fixed to literature values. ; # end Validation Reply Form # Attachment '- compound2.cif' data_pc _database_code_depnum_ccdc_archive 'CCDC 831131' #TrackingRef '- compound2.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; {[Mn(H~2~O)(bpy)~0.5~][Mn(N)(CN)~4~(bpy)~0.5~] .2H~2~O ; _chemical_name_common 'MnMn(bpy) Hofmann' _chemical_melting_point N/A _chemical_formula_moiety 'C14 H8 Mn2 N7 O, 2(O)' _chemical_formula_sum 'C14 H8 Mn2 N7 O3' _chemical_formula_weight 432.14 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' Mn Mn 0.3368 0.7283 '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' 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 'P 21/c' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 7.3620(15) _cell_length_b 18.015(4) _cell_length_c 13.908(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.52(3) _cell_angle_gamma 90.00 _cell_volume 1844.5(7) _cell_formula_units_Z 4 _cell_measurement_temperature 273(2) _cell_measurement_reflns_used 4468 _cell_measurement_theta_min 3.32 _cell_measurement_theta_max 13.27 _exptl_crystal_description block _exptl_crystal_colour orange _exptl_crystal_size_max 0.08 _exptl_crystal_size_mid 0.05 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.556 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 860 _exptl_absorpt_coefficient_mu 1.397 _exptl_absorpt_correction_type sphere _exptl_absorpt_process_details ; Interpolation using Int.Tab. Vol. C (1992) p. 523,Tab. 6.3.3.3 for values of muR in the range 0-2.5, and Int.Tab. Vol.II (1959) p.302; Table 5.3.6 B for muR in the range 2.6-10.0. The interpolation procedure of C.W.Dwiggins Jr (Acta Cryst.(1975) A31,146-148) is used with some modification. ; _exptl_absorpt_correction_T_min 0.8614 _exptl_absorpt_correction_T_max 0.8619 _diffrn_ambient_temperature 273(2) _diffrn_radiation_wavelength 0.71246 _diffrn_radiation_type synchrotron _diffrn_radiation_source 'Australian Synchrotron MX-1' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'ADSC Quantum 210r Detector' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 25461 _diffrn_reflns_av_R_equivalents 0.0765 _diffrn_reflns_av_sigmaI/netI 0.0465 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 22 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 1.85 _diffrn_reflns_theta_max 26.92 _reflns_number_total 3784 _reflns_number_gt 3770 _reflns_threshold_expression >2\s(I) _computing_data_collection 'BluIce (McPhilips et al. 2002)' _computing_cell_refinement 'XDS (Kabsch, 2010)' _computing_data_reduction 'XDS (Kabsch, 2010)' _computing_structure_solution 'SIR 92 (Altomare, 1994)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Diamond 3.2g (Crystal Impact, 2011)' _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^ > 2\s(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 'w=1/[\s^2^(Fo^2^)+(0.0000P)^2^+20.7701P] 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 3784 _refine_ls_number_parameters 234 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0810 _refine_ls_R_factor_gt 0.0809 _refine_ls_wR_factor_ref 0.2104 _refine_ls_wR_factor_gt 0.2103 _refine_ls_goodness_of_fit_ref 1.330 _refine_ls_restrained_S_all 1.330 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Mn1 Mn -0.10103(11) 0.31409(5) 0.08000(6) 0.0097(3) Uani 1 1 d . . . Mn2 Mn 0.39429(12) 0.20829(5) 0.31249(6) 0.0135(3) Uani 1 1 d . . . N5 N 0.3782(8) 0.1341(4) 0.2610(4) 0.0282(14) Uani 1 1 d . . . N10 N 0.4192(7) 0.3245(3) 0.3889(4) 0.0151(10) Uani 1 1 d . . . N20 N -0.0803(8) 0.1921(3) 0.0442(5) 0.0267(13) Uani 1 1 d . . . N3 N 0.6749(8) 0.2816(4) 0.1748(4) 0.0266(13) Uani 1 1 d . . . N4 N 0.7048(8) 0.1694(3) 0.4582(4) 0.0222(12) Uani 1 1 d . . . N2 N 0.1228(8) 0.1676(3) 0.4763(4) 0.0220(12) Uani 1 1 d . . . N1 N 0.0973(8) 0.2955(4) 0.1956(4) 0.0295(14) Uani 1 1 d . . . C2 C 0.2204(8) 0.1831(4) 0.4157(4) 0.0160(12) Uani 1 1 d . . . C4 C 0.5937(8) 0.1829(3) 0.4027(4) 0.0155(12) Uani 1 1 d . . . C3 C 0.5741(9) 0.2543(4) 0.2253(4) 0.0203(13) Uani 1 1 d . . . C1 C 0.2022(8) 0.2626(4) 0.2399(4) 0.0195(13) Uani 1 1 d . . . C11 C 0.4321(10) 0.3885(4) 0.3381(4) 0.0226(14) Uani 1 1 d . . . H11 H 0.4184 0.3857 0.2716 0.027 Uiso 1 1 calc R . . C12 C 0.4336(10) 0.3317(4) 0.4843(4) 0.0207(13) Uani 1 1 d . . . H12 H 0.4221 0.2893 0.5219 0.025 Uiso 1 1 calc R . . C13 C 0.4636(11) 0.4564(4) 0.3775(5) 0.0270(15) Uani 1 1 d . . . H13 H 0.4730 0.4979 0.3381 0.032 Uiso 1 1 calc R . . C14 C 0.4648(10) 0.3987(4) 0.5303(4) 0.0218(14) Uani 1 1 d . . . H14 H 0.4745 0.4002 0.5969 0.026 Uiso 1 1 calc R . . C15 C 0.4819(8) 0.4639(3) 0.4774(4) 0.0168(12) Uani 1 1 d . . . C21 C -0.0692(11) 0.1411(4) 0.1151(5) 0.0272(15) Uani 1 1 d . . . H21 H -0.0845 0.1577 0.1778 0.033 Uiso 1 1 calc R . . C22 C -0.0672(10) 0.1654(4) -0.0454(5) 0.0251(14) Uani 1 1 d . . . H22 H -0.0802 0.1982 -0.0966 0.030 Uiso 1 1 calc R . . C23 C -0.0376(11) 0.0678(4) 0.1024(5) 0.0289(16) Uani 1 1 d . . . H23 H -0.0291 0.0362 0.1552 0.035 Uiso 1 1 calc R . . C24 C -0.0352(10) 0.0912(4) -0.0652(5) 0.0250(14) Uani 1 1 d . . . H24 H -0.0252 0.0757 -0.1287 0.030 Uiso 1 1 calc R . . C25 C -0.0178(9) 0.0396(3) 0.0090(5) 0.0215(13) Uani 1 1 d . . . O1W O -0.1375(10) 0.4339(4) 0.1146(8) 0.078(3) Uani 1 1 d . . . O2W O 0.8564(16) 0.0263(5) 0.3490(10) 0.109(4) Uani 1 1 d . . . O3WA O 0.490(3) 0.0377(12) 0.5787(15) 0.074(6) Uiso 0.50 1 d P . . O3WB O 0.429(3) 0.0613(13) 0.5844(15) 0.078(6) Uiso 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 0.0100(4) 0.0095(4) 0.0096(4) -0.0001(3) -0.0002(3) 0.0003(3) Mn2 0.0103(4) 0.0236(5) 0.0066(4) -0.0012(3) -0.0002(3) -0.0008(4) N5 0.027(3) 0.039(4) 0.018(3) -0.011(3) 0.006(2) -0.009(3) N10 0.021(3) 0.014(2) 0.010(2) -0.0019(19) -0.0022(19) 0.000(2) N20 0.024(3) 0.022(3) 0.034(3) -0.003(2) 0.007(3) 0.001(2) N3 0.022(3) 0.039(4) 0.019(3) -0.001(2) 0.008(2) -0.008(3) N4 0.025(3) 0.020(3) 0.021(3) -0.006(2) -0.009(2) 0.003(2) N2 0.021(3) 0.029(3) 0.016(3) 0.004(2) 0.011(2) 0.002(2) N1 0.022(3) 0.044(4) 0.022(3) 0.005(3) -0.008(2) -0.007(3) C2 0.014(3) 0.021(3) 0.013(3) -0.002(2) -0.005(2) 0.005(2) C4 0.011(3) 0.021(3) 0.015(3) -0.005(2) 0.002(2) 0.000(2) C3 0.018(3) 0.029(3) 0.014(3) 0.000(3) -0.003(2) 0.005(3) C1 0.014(3) 0.032(4) 0.013(3) 0.004(3) -0.001(2) -0.005(3) C11 0.039(4) 0.022(3) 0.006(3) 0.001(2) -0.003(3) -0.001(3) C12 0.035(4) 0.014(3) 0.013(3) 0.001(2) 0.004(3) 0.001(3) C13 0.043(4) 0.026(4) 0.012(3) 0.003(3) -0.004(3) -0.005(3) C14 0.042(4) 0.016(3) 0.007(3) 0.002(2) 0.002(3) 0.004(3) C15 0.020(3) 0.018(3) 0.012(3) -0.002(2) 0.000(2) 0.003(2) C21 0.040(4) 0.013(3) 0.028(4) -0.003(3) 0.010(3) 0.005(3) C22 0.033(4) 0.013(3) 0.029(4) -0.002(3) 0.002(3) -0.001(3) C23 0.045(4) 0.012(3) 0.030(4) -0.002(3) 0.002(3) 0.000(3) C24 0.032(4) 0.013(3) 0.029(4) -0.006(3) 0.006(3) 0.001(3) C25 0.018(3) 0.011(3) 0.036(4) -0.005(3) 0.004(3) -0.001(2) O1W 0.047(4) 0.023(3) 0.163(9) -0.042(4) 0.003(5) 0.002(3) O2W 0.103(8) 0.051(5) 0.172(12) -0.010(6) -0.015(8) 0.031(5) _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 N1 2.187(6) . ? Mn1 N3 2.201(6) 1_455 ? Mn1 N2 2.224(5) 4_565 ? Mn1 N4 2.227(5) 4_465 ? Mn1 O1W 2.227(6) . ? Mn1 N20 2.259(6) . ? Mn2 N5 1.521(6) . ? Mn2 C4 1.976(6) . ? Mn2 C3 1.985(7) . ? Mn2 C2 1.985(6) . ? Mn2 C1 1.987(6) . ? Mn2 N10 2.354(5) . ? N10 C12 1.337(8) . ? N10 C11 1.356(8) . ? N20 C22 1.339(9) . ? N20 C21 1.349(9) . ? N3 C3 1.138(9) . ? N3 Mn1 2.201(6) 1_655 ? N4 C4 1.146(8) . ? N4 Mn1 2.227(5) 4_666 ? N2 C2 1.147(9) . ? N2 Mn1 2.224(5) 4_566 ? N1 C1 1.148(9) . ? C11 C13 1.359(10) . ? C11 H11 0.9300 . ? C12 C14 1.384(9) . ? C12 H12 0.9300 . ? C13 C15 1.401(9) . ? C13 H13 0.9300 . ? C14 C15 1.392(9) . ? C14 H14 0.9300 . ? C15 C15 1.469(12) 3_666 ? C21 C23 1.353(9) . ? C21 H21 0.9300 . ? C22 C24 1.386(9) . ? C22 H22 0.9300 . ? C23 C25 1.402(10) . ? C23 H23 0.9300 . ? C24 C25 1.394(10) . ? C24 H24 0.9300 . ? C25 C25 1.474(12) 3 ? O3WA O3WB 0.62(3) . ? 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 N1 Mn1 N3 91.0(2) . 1_455 ? N1 Mn1 N2 90.3(2) . 4_565 ? N3 Mn1 N2 172.7(2) 1_455 4_565 ? N1 Mn1 N4 177.6(2) . 4_465 ? N3 Mn1 N4 90.7(2) 1_455 4_465 ? N2 Mn1 N4 87.8(2) 4_565 4_465 ? N1 Mn1 O1W 94.1(3) . . ? N3 Mn1 O1W 92.1(3) 1_455 . ? N2 Mn1 O1W 95.0(3) 4_565 . ? N4 Mn1 O1W 87.5(3) 4_465 . ? N1 Mn1 N20 88.1(2) . . ? N3 Mn1 N20 85.7(2) 1_455 . ? N2 Mn1 N20 87.1(2) 4_565 . ? N4 Mn1 N20 90.4(2) 4_465 . ? O1W Mn1 N20 176.9(3) . . ? N5 Mn2 C4 98.6(3) . . ? N5 Mn2 C3 97.4(3) . . ? C4 Mn2 C3 89.4(2) . . ? N5 Mn2 C2 95.2(3) . . ? C4 Mn2 C2 88.2(2) . . ? C3 Mn2 C2 167.3(3) . . ? N5 Mn2 C1 98.1(3) . . ? C4 Mn2 C1 163.3(3) . . ? C3 Mn2 C1 87.7(3) . . ? C2 Mn2 C1 91.1(2) . . ? N5 Mn2 N10 178.7(3) . . ? C4 Mn2 N10 82.3(2) . . ? C3 Mn2 N10 81.6(2) . . ? C2 Mn2 N10 85.7(2) . . ? C1 Mn2 N10 81.0(2) . . ? C12 N10 C11 115.5(5) . . ? C12 N10 Mn2 122.6(4) . . ? C11 N10 Mn2 121.8(4) . . ? C22 N20 C21 115.5(6) . . ? C22 N20 Mn1 124.0(5) . . ? C21 N20 Mn1 120.3(5) . . ? C3 N3 Mn1 168.9(6) . 1_655 ? C4 N4 Mn1 159.1(5) . 4_666 ? C2 N2 Mn1 155.9(5) . 4_566 ? C1 N1 Mn1 156.2(6) . . ? N2 C2 Mn2 178.5(6) . . ? N4 C4 Mn2 177.0(6) . . ? N3 C3 Mn2 178.8(6) . . ? N1 C1 Mn2 176.9(6) . . ? N10 C11 C13 124.6(6) . . ? N10 C11 H11 117.7 . . ? C13 C11 H11 117.7 . . ? N10 C12 C14 123.6(6) . . ? N10 C12 H12 118.2 . . ? C14 C12 H12 118.2 . . ? C11 C13 C15 120.0(6) . . ? C11 C13 H13 120.0 . . ? C15 C13 H13 120.0 . . ? C12 C14 C15 120.5(6) . . ? C12 C14 H14 119.8 . . ? C15 C14 H14 119.8 . . ? C14 C15 C13 115.8(6) . . ? C14 C15 C15 122.6(7) . 3_666 ? C13 C15 C15 121.7(7) . 3_666 ? N20 C21 C23 125.4(7) . . ? N20 C21 H21 117.3 . . ? C23 C21 H21 117.3 . . ? N20 C22 C24 123.0(7) . . ? N20 C22 H22 118.5 . . ? C24 C22 H22 118.5 . . ? C21 C23 C25 119.5(7) . . ? C21 C23 H23 120.2 . . ? C25 C23 H23 120.2 . . ? C22 C24 C25 120.7(7) . . ? C22 C24 H24 119.7 . . ? C25 C24 H24 119.7 . . ? C24 C25 C23 115.8(6) . . ? C24 C25 C25 122.3(8) . 3 ? C23 C25 C25 121.9(8) . 3 ? _diffrn_measured_fraction_theta_max 0.952 _diffrn_reflns_theta_full 26.92 _diffrn_measured_fraction_theta_full 0.952 _refine_diff_density_max 1.054 _refine_diff_density_min -1.387 _refine_diff_density_rms 0.160 # start Validation Reply Form _vrf_PLAT306_I ; PROBLEM: Isolated Oxygen Atom (H-atoms Missing ?) ....... O2W RESPONSE: Hydrogen atoms could not be located from difference maps, probably due to only one axis of rotation during collection (a function of the diffractometer at MX-1). ; # end Validation Reply Form # Attachment '- compound5.cif' data_compound5 _database_code_depnum_ccdc_archive 'CCDC 831132' #TrackingRef '- compound5.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; {[Mn(H~2~O)~2~]~0.5~[Mn(bpa)~2~]~0.5~ [Mo(O)(CN)~4~(bpa)~0.5~]}.MeOH ; _chemical_name_common 'MoMn(bpa) Hofmann' _chemical_melting_point N/A _chemical_formula_moiety 'C22 H14 Mn Mo N7 O2, 2(C0.50 H2 O0.50)' _chemical_formula_sum 'C23 H18 Mn Mo N7 O3' _chemical_formula_weight 591.32 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' Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Mo Mo -1.6832 0.6857 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 1 2/m 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z' '-x, -y, -z' 'x, -y, z' _cell_length_a 12.2987(7) _cell_length_b 7.6559(3) _cell_length_c 14.6269(6) _cell_angle_alpha 90.00 _cell_angle_beta 106.545(5) _cell_angle_gamma 90.00 _cell_volume 1320.21(11) _cell_formula_units_Z 2 _cell_measurement_temperature 150.0 _cell_measurement_reflns_used 5412 _cell_measurement_theta_min 2.8997 _cell_measurement_theta_max 29.2499 _exptl_crystal_description block _exptl_crystal_colour green _exptl_crystal_size_max 0.12 _exptl_crystal_size_mid 0.07 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.488 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 592 _exptl_absorpt_coefficient_mu 0.989 _exptl_absorpt_correction_T_min 0.74777 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 150.0 _diffrn_radiation_wavelength 0.7107 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_source 'SuperNova (Mo) X-ray Source' _diffrn_radiation_monochromator mirror _diffrn_measurement_device_type 'SuperNova, Dual, Cu at zero, Atlas' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 10.5861 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 11530 _diffrn_reflns_av_R_equivalents 0.0552 _diffrn_reflns_av_sigmaI/netI 0.0426 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 7 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 2.91 _diffrn_reflns_theta_max 24.99 _reflns_number_total 2515 _reflns_number_gt 2104 _reflns_threshold_expression >2\s(I) _computing_data_collection ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _computing_cell_refinement ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _computing_data_reduction ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _computing_structure_solution 'SIR-92 (Altomare, 1994)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Diamond 3.2g (Crystal Impact, 2011)' _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^ > 2\s(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 'w=1/[\s^2^(Fo^2^)+(0.1231P)^2^+5.9471P] 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 2515 _refine_ls_number_parameters 170 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0835 _refine_ls_R_factor_gt 0.0718 _refine_ls_wR_factor_ref 0.2038 _refine_ls_wR_factor_gt 0.1921 _refine_ls_goodness_of_fit_ref 1.068 _refine_ls_restrained_S_all 1.068 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Mo1 Mo -0.09884(6) 0.5000 0.23261(4) 0.0245(3) Uani 1 2 d S . . Mn1 Mn 0.0000 1.0000 0.0000 0.0243(5) Uani 1 4 d S . . O1W O 0.1890(6) 1.0000 0.0470(5) 0.0456(18) Uani 1 2 d S . . H1W1 H 0.2170 1.0295 -0.0060 0.068 Uiso 0.25 1 calc PR . . H1W2 H 0.2159 0.8861 0.0703 0.068 Uiso 0.50 1 calc PR . . H1W3 H 0.2155 1.0844 0.0969 0.068 Uiso 0.25 1 calc PR . . N2 N -0.0107(5) 0.7961(7) 0.1051(4) 0.0345(13) Uani 1 1 d . . . O1 O -0.2372(6) 0.5000 0.1748(5) 0.0445(17) Uani 1 2 d S . . N11 N 0.1020(6) 0.5000 0.3238(5) 0.0300(17) Uani 1 2 d S . . C16 C 0.4502(9) 0.5000 0.4781(8) 0.048(3) Uani 1 2 d S . . N1 N -0.0881(5) 0.2033(7) 0.3981(4) 0.0318(12) Uani 1 1 d . . . C2 C -0.0377(5) 0.6940(9) 0.1518(4) 0.0299(14) Uani 1 1 d . . . C13 C 0.2488(9) 0.5000 0.4719(7) 0.049(3) Uani 1 2 d S . . H13 H 0.2679 0.5000 0.5382 0.059 Uiso 1 2 calc SR . . C11 C 0.1370(8) 0.5000 0.4202(6) 0.041(2) Uani 1 2 d S . . H11 H 0.0824 0.5000 0.4530 0.050 Uiso 1 2 calc SR . . C12 C 0.1856(9) 0.5000 0.2811(8) 0.046(3) Uani 1 2 d S . . H12 H 0.1643 0.5000 0.2148 0.055 Uiso 1 2 calc SR . . C1 C -0.0963(5) 0.3053(8) 0.3388(4) 0.0256(13) Uani 1 1 d . . . C15 C 0.3336(8) 0.5000 0.4275(7) 0.042(2) Uani 1 2 d S . . Mn2 Mn 0.0000 0.0000 0.5000 0.0246(5) Uani 1 4 d S . . N21 N 0.1438(7) 0.0000 0.4311(5) 0.0316(17) Uani 1 2 d S . . C14 C 0.2973(9) 0.5000 0.3266(8) 0.047(3) Uani 1 2 d S . . H14 H 0.3502 0.5000 0.2921 0.056 Uiso 1 2 calc SR . . N22 N 0.7031(10) 0.0506(14) 0.0899(8) 0.044(3) Uiso 0.50 1 d P A -1 C30 C 0.534(2) 0.145(3) 0.1308(18) 0.098(7) Uiso 0.50 1 d P A -1 H30 H 0.4682 0.2123 0.1147 0.118 Uiso 0.50 1 calc PR A -1 C32 C 0.613(2) 0.138(4) 0.073(2) 0.111(9) Uiso 0.50 1 d P A -1 H32 H 0.5947 0.2058 0.0180 0.134 Uiso 0.50 1 calc PR A -1 C28 C 0.5645(11) 0.0457(15) 0.2086(9) 0.038(3) Uiso 0.50 1 d P A -1 C24 C 0.3402(10) 0.0437(14) 0.4470(9) 0.034(3) Uiso 0.50 1 d P A -1 H24 H 0.4131 0.0599 0.4872 0.040 Uiso 0.50 1 calc PR A -1 C22 C 0.2495(9) 0.0381(14) 0.4845(8) 0.030(3) Uiso 0.50 1 d P A -1 H22 H 0.2617 0.0616 0.5490 0.036 Uiso 0.50 1 calc PR A -1 C23 C 0.2136(8) -0.0333(15) 0.2948(7) 0.027(3) Uiso 0.50 1 d P A -1 H23 H 0.2015 -0.0737 0.2327 0.033 Uiso 0.50 1 calc PR A -1 C21 C 0.1267(8) -0.0276(18) 0.3368(7) 0.026(3) Uiso 0.50 1 d P A -1 H21 H 0.0528 -0.0434 0.2985 0.032 Uiso 0.50 1 calc PR A -1 C26 C 0.4156(9) 0.0345(17) 0.3082(8) 0.033(3) Uiso 0.50 1 d P A -1 C27 C 0.4878(10) 0.0389(16) 0.2670(9) 0.037(3) Uiso 0.50 1 d P A -1 C25 C 0.3237(8) 0.025(2) 0.3502(7) 0.029(3) Uiso 0.50 1 d P A -1 C29 C 0.6680(12) -0.038(2) 0.2304(11) 0.053(4) Uiso 0.50 1 d P A -1 H29 H 0.6937 -0.0989 0.2877 0.064 Uiso 0.50 1 calc PR A -1 C31 C 0.7330(10) -0.0336(19) 0.1686(8) 0.053(4) Uiso 0.50 1 d P A -1 H31 H 0.8015 -0.0938 0.1844 0.063 Uiso 0.50 1 calc PR A -1 O91 O 0.2868(10) 0.6614(19) 0.1056(8) 0.140(7) Uiso 0.50 1 d PR A -2 H91 H 0.2461 0.7428 0.0799 0.210 Uiso 0.50 1 calc PR A -2 C92 C 0.240(2) 0.5000 0.0613(19) 0.144(9) Uiso 0.5 2 d S A -2 H92A H 0.2788 0.4037 0.0986 0.216 Uiso 0.50 1 calc PR A -2 H92B H 0.2488 0.4939 -0.0017 0.216 Uiso 0.50 1 calc SR A -2 H92C H 0.1607 0.4946 0.0575 0.216 Uiso 0.50 1 calc SR A -2 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 Mo1 0.0301(5) 0.0361(5) 0.0089(4) 0.000 0.0082(3) 0.000 Mn1 0.0358(11) 0.0314(10) 0.0098(8) 0.000 0.0130(7) 0.000 O1W 0.034(4) 0.083(6) 0.022(3) 0.000 0.010(3) 0.000 N2 0.052(3) 0.041(3) 0.015(2) 0.002(2) 0.016(2) 0.003(3) O1 0.037(4) 0.065(5) 0.028(4) 0.000 0.005(3) 0.000 N11 0.031(4) 0.039(4) 0.023(4) 0.000 0.011(3) 0.000 C16 0.032(5) 0.062(7) 0.048(6) 0.000 0.008(5) 0.000 N1 0.041(3) 0.037(3) 0.021(3) 0.002(2) 0.014(2) 0.001(2) C2 0.044(4) 0.038(4) 0.010(3) 0.000(3) 0.010(3) 0.004(3) C13 0.034(6) 0.085(8) 0.026(5) 0.000 0.005(4) 0.000 C11 0.033(5) 0.075(7) 0.018(5) 0.000 0.010(4) 0.000 C12 0.036(6) 0.075(8) 0.032(5) 0.000 0.017(4) 0.000 C1 0.030(3) 0.034(3) 0.016(3) -0.005(3) 0.012(2) -0.001(3) C15 0.031(5) 0.055(6) 0.038(6) 0.000 0.007(4) 0.000 Mn2 0.0367(11) 0.0304(10) 0.0114(9) 0.000 0.0144(8) 0.000 N21 0.039(4) 0.042(4) 0.018(4) 0.000 0.015(3) 0.000 C14 0.032(5) 0.068(7) 0.045(6) 0.000 0.018(5) 0.000 _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 Mo1 O1 1.670(7) . ? Mo1 C1 2.147(6) 4_565 ? Mo1 C1 2.147(6) . ? Mo1 C2 2.162(6) . ? Mo1 C2 2.162(6) 4_565 ? Mo1 N11 2.451(7) . ? Mn1 N2 2.221(5) 2 ? Mn1 N2 2.221(5) 4_575 ? Mn1 N2 2.221(5) . ? Mn1 N2 2.221(5) 3_575 ? Mn1 O1W 2.228(7) . ? Mn1 O1W 2.228(7) 3_575 ? O1W H1W1 0.9600 . ? O1W H1W2 0.9600 . ? O1W H1W3 0.9600 . ? N2 C2 1.147(8) . ? N11 C12 1.345(12) . ? N11 C11 1.353(11) . ? C16 C16 1.21(2) 3_666 ? C16 C15 1.414(14) . ? N1 C1 1.150(8) . ? N1 Mn2 2.213(5) . ? C13 C11 1.367(14) . ? C13 C15 1.378(14) . ? C13 H13 0.9300 . ? C11 H11 0.9300 . ? C12 C14 1.346(15) . ? C12 H12 0.9300 . ? C15 C14 1.414(15) . ? Mn2 N1 2.213(5) 4 ? Mn2 N1 2.213(5) 2_556 ? Mn2 N1 2.213(5) 3_556 ? Mn2 N21 2.272(7) 3_556 ? Mn2 N21 2.272(7) . ? N21 C22 1.344(13) . ? N21 C22 1.344(13) 4 ? N21 C21 1.351(12) 4 ? N21 C21 1.351(12) . ? C14 H14 0.9300 . ? N22 C32 1.26(3) . ? N22 C31 1.279(16) . ? C30 C28 1.33(3) . ? C30 C32 1.46(3) . ? C30 H30 0.9300 . ? C32 H32 0.9300 . ? C28 C29 1.380(18) . ? C28 C27 1.443(17) . ? C24 C22 1.377(16) . ? C24 C25 1.379(16) . ? C24 H24 0.9300 . ? C22 H22 0.9300 . ? C23 C21 1.376(14) . ? C23 C25 1.438(15) . ? C23 H23 0.9300 . ? C21 H21 0.9300 . ? C26 C27 1.207(16) . ? C26 C25 1.433(14) . ? C29 C31 1.368(18) . ? C29 H29 0.9300 . ? C31 H31 0.9300 . ? O91 C92 1.437(18) . ? O91 H91 0.8200 . ? C92 H92A 0.9600 . ? C92 H92B 0.9600 . ? C92 H92C 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 Mo1 C1 99.7(2) . 4_565 ? O1 Mo1 C1 99.7(2) . . ? C1 Mo1 C1 88.0(3) 4_565 . ? O1 Mo1 C2 100.7(2) . . ? C1 Mo1 C2 89.0(2) 4_565 . ? C1 Mo1 C2 159.5(2) . . ? O1 Mo1 C2 100.7(2) . 4_565 ? C1 Mo1 C2 159.5(2) 4_565 4_565 ? C1 Mo1 C2 89.0(2) . 4_565 ? C2 Mo1 C2 86.8(3) . 4_565 ? O1 Mo1 N11 177.6(3) . . ? C1 Mo1 N11 78.5(2) 4_565 . ? C1 Mo1 N11 78.5(2) . . ? C2 Mo1 N11 81.0(2) . . ? C2 Mo1 N11 81.0(2) 4_565 . ? N2 Mn1 N2 180.00(19) 2 4_575 ? N2 Mn1 N2 90.7(3) 2 . ? N2 Mn1 N2 89.3(3) 4_575 . ? N2 Mn1 N2 89.3(3) 2 3_575 ? N2 Mn1 N2 90.7(3) 4_575 3_575 ? N2 Mn1 N2 180.0(3) . 3_575 ? N2 Mn1 O1W 87.20(19) 2 . ? N2 Mn1 O1W 92.80(19) 4_575 . ? N2 Mn1 O1W 92.80(19) . . ? N2 Mn1 O1W 87.20(19) 3_575 . ? N2 Mn1 O1W 92.80(19) 2 3_575 ? N2 Mn1 O1W 87.20(19) 4_575 3_575 ? N2 Mn1 O1W 87.20(19) . 3_575 ? N2 Mn1 O1W 92.80(19) 3_575 3_575 ? O1W Mn1 O1W 180.0 . 3_575 ? Mn1 O1W H1W1 109.5 . . ? Mn1 O1W H1W2 109.5 . . ? H1W1 O1W H1W2 109.5 . . ? Mn1 O1W H1W3 109.5 . . ? H1W1 O1W H1W3 109.5 . . ? H1W2 O1W H1W3 109.5 . . ? C2 N2 Mn1 167.1(5) . . ? C12 N11 C11 115.2(8) . . ? C12 N11 Mo1 122.1(6) . . ? C11 N11 Mo1 122.7(6) . . ? C16 C16 C15 179.6(16) 3_666 . ? C1 N1 Mn2 155.0(5) . . ? N2 C2 Mo1 176.3(6) . . ? C11 C13 C15 121.1(9) . . ? C11 C13 H13 119.5 . . ? C15 C13 H13 119.5 . . ? N11 C11 C13 123.2(9) . . ? N11 C11 H11 118.4 . . ? C13 C11 H11 118.4 . . ? N11 C12 C14 125.3(10) . . ? N11 C12 H12 117.3 . . ? C14 C12 H12 117.3 . . ? N1 C1 Mo1 175.9(5) . . ? C13 C15 C14 115.9(9) . . ? C13 C15 C16 122.9(10) . . ? C14 C15 C16 121.2(10) . . ? N1 Mn2 N1 180.0(2) 4 2_556 ? N1 Mn2 N1 89.4(3) 4 . ? N1 Mn2 N1 90.6(3) 2_556 . ? N1 Mn2 N1 90.6(3) 4 3_556 ? N1 Mn2 N1 89.4(3) 2_556 3_556 ? N1 Mn2 N1 180.000(1) . 3_556 ? N1 Mn2 N21 90.28(19) 4 3_556 ? N1 Mn2 N21 89.72(19) 2_556 3_556 ? N1 Mn2 N21 90.28(19) . 3_556 ? N1 Mn2 N21 89.72(19) 3_556 3_556 ? N1 Mn2 N21 89.72(19) 4 . ? N1 Mn2 N21 90.28(19) 2_556 . ? N1 Mn2 N21 89.72(19) . . ? N1 Mn2 N21 90.28(19) 3_556 . ? N21 Mn2 N21 180.000(1) 3_556 . ? C22 N21 C22 25.1(10) . 4 ? C22 N21 C21 113.8(8) . 4 ? C22 N21 C21 118.1(8) 4 4 ? C22 N21 C21 118.1(8) . . ? C22 N21 C21 113.8(8) 4 . ? C21 N21 C21 18.0(12) 4 . ? C22 N21 Mn2 119.2(6) . . ? C22 N21 Mn2 119.2(6) 4 . ? C21 N21 Mn2 122.6(6) 4 . ? C21 N21 Mn2 122.6(6) . . ? C12 C14 C15 119.4(9) . . ? C12 C14 H14 120.3 . . ? C15 C14 H14 120.3 . . ? C32 N22 C31 117.0(18) . . ? C28 C30 C32 114(2) . . ? C28 C30 H30 123.2 . . ? C32 C30 H30 123.2 . . ? N22 C32 C30 127(3) . . ? N22 C32 H32 116.5 . . ? C30 C32 H32 116.5 . . ? C30 C28 C29 118.8(16) . . ? C30 C28 C27 116.9(16) . . ? C29 C28 C27 124.2(12) . . ? C22 C24 C25 120.4(11) . . ? C22 C24 H24 119.8 . . ? C25 C24 H24 119.8 . . ? N21 C22 C24 122.3(10) . . ? N21 C22 H22 118.9 . . ? C24 C22 H22 118.9 . . ? C21 C23 C25 117.7(9) . . ? C21 C23 H23 121.1 . . ? C25 C23 H23 121.1 . . ? N21 C21 C23 123.0(9) . . ? N21 C21 H21 118.5 . . ? C23 C21 H21 118.5 . . ? C27 C26 C25 175.5(12) . . ? C26 C27 C28 174.0(13) . . ? C24 C25 C26 122.1(10) . . ? C24 C25 C23 116.7(10) . . ? C26 C25 C23 120.3(10) . . ? C31 C29 C28 120.6(14) . . ? C31 C29 H29 119.7 . . ? C28 C29 H29 119.7 . . ? N22 C31 C29 122.5(13) . . ? N22 C31 H31 118.7 . . ? C29 C31 H31 118.7 . . ? C92 O91 H91 109.5 . . ? O91 C92 H92A 109.5 . . ? O91 C92 H92B 109.5 . . ? H92A C92 H92B 109.5 . . ? O91 C92 H92C 109.5 . . ? H92A C92 H92C 109.5 . . ? H92B C92 H92C 109.5 . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 24.99 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 3.010 _refine_diff_density_min -1.053 _refine_diff_density_rms 0.166