# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2004 data_global _journal_coden_Cambridge 182 loop_ _publ_author_name 'Paul Kruger' 'Paul Jensen' 'Anthea C. Lees' 'Eithne Tynan' _publ_contact_author_name 'Dr Paul Kruger' _publ_contact_author_address ; Department of Chemistry Trinity College Dublin Dublin REPUBLIC OF IRELAND ; _publ_contact_author_phone ' 353 1 608 1422 ' _publ_contact_author_fax ' 353 1 671 2826 ' _publ_contact_author_email ' paul.kruger@tcd.ie ' _publ_requested_journal 'Chemical Communications' _publ_section_title ; Solvent templated synthesis of metal-organic frameworks: structural characterisation and properties of the 3D network isomers {[Mn(dcbp)].½DMF}n and {[Mn(dcbp)].2H2O}n ; data_1 _database_code_depnum_ccdc_archive 'CCDC 225925' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety Mn(dcbp).1/2DMF _chemical_formula_sum 'C13.50 H9.50 Mn N2.50 O4.50' _chemical_formula_weight 333.68 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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' _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 15.6763(10) _cell_length_b 10.2423(6) _cell_length_c 16.7755(10) _cell_angle_alpha 90.00 _cell_angle_beta 102.2490(10) _cell_angle_gamma 90.00 _cell_volume 2632.2(3) _cell_formula_units_Z 8 _cell_measurement_temperature 153(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description plate _exptl_crystal_colour yellow _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.11 _exptl_crystal_size_min 0.02 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.684 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1352 _exptl_absorpt_coefficient_mu 1.026 _exptl_absorpt_correction_type Empirical _exptl_absorpt_correction_T_min 0.714 _exptl_absorpt_correction_T_max 1.000 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 153(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 SMART APEX CCD' _diffrn_measurement_method 'Omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 10077 _diffrn_reflns_av_R_equivalents 0.0414 _diffrn_reflns_av_sigmaI/netI 0.0343 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 2.48 _diffrn_reflns_theta_max 25.00 _reflns_number_total 2312 _reflns_number_gt 2182 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0262P)^2^+8.9300P] 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 calc _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2312 _refine_ls_number_parameters 213 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0522 _refine_ls_R_factor_gt 0.0478 _refine_ls_wR_factor_ref 0.0952 _refine_ls_wR_factor_gt 0.0935 _refine_ls_goodness_of_fit_ref 1.267 _refine_ls_restrained_S_all 1.267 _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 0.14325(3) 0.59899(5) 0.02220(3) 0.01030(15) Uani 1 1 d . . . N1 N 0.14969(17) 0.4685(3) 0.13462(16) 0.0141(6) Uani 1 1 d . . . C1 C 0.1027(2) 0.4908(3) 0.1911(2) 0.0173(7) Uani 1 1 d . . . H1 H 0.0550 0.5498 0.1783 0.021 Uiso 1 1 calc R . . C2 C 0.1201(2) 0.4325(3) 0.2671(2) 0.0179(7) Uani 1 1 d . . . H2 H 0.0851 0.4514 0.3055 0.021 Uiso 1 1 calc R . . C3 C 0.1892(2) 0.3462(3) 0.2862(2) 0.0141(7) Uani 1 1 d . . . C4 C 0.2378(2) 0.3207(3) 0.2274(2) 0.0151(7) Uani 1 1 d . . . H4 H 0.2847 0.2601 0.2383 0.018 Uiso 1 1 calc R . . C5 C 0.2172(2) 0.3845(3) 0.15304(19) 0.0125(7) Uani 1 1 d . . . C6 C 0.2736(2) 0.3733(3) 0.09189(19) 0.0112(7) Uani 1 1 d . . . C7 C 0.3308(2) 0.2701(3) 0.09247(19) 0.0134(7) Uani 1 1 d . . . H7 H 0.3298 0.1974 0.1274 0.016 Uiso 1 1 calc R . . C8 C 0.3894(2) 0.2748(3) 0.0414(2) 0.0132(7) Uani 1 1 d . . . C9 C 0.3888(2) 0.3826(3) -0.0080(2) 0.0186(7) Uani 1 1 d . . . H9 H 0.4305 0.3907 -0.0414 0.022 Uiso 1 1 calc R . . C10 C 0.3271(2) 0.4786(4) -0.0084(2) 0.0208(8) Uani 1 1 d . . . H10 H 0.3260 0.5508 -0.0441 0.025 Uiso 1 1 calc R . . N2 N 0.26846(17) 0.4744(3) 0.03965(16) 0.0148(6) Uani 1 1 d . . . C11 C 0.2155(2) 0.2864(3) 0.3707(2) 0.0129(7) Uani 1 1 d . . . O1 O 0.28864(15) 0.2317(2) 0.38616(14) 0.0163(5) Uani 1 1 d . . . O2 O 0.16373(15) 0.3007(2) 0.41754(13) 0.0168(5) Uani 1 1 d . . . C12 C 0.4542(2) 0.1657(3) 0.04162(19) 0.0128(7) Uani 1 1 d . . . O3 O 0.42993(14) 0.0524(2) 0.05438(13) 0.0146(5) Uani 1 1 d . . . O4 O 0.52733(14) 0.2000(2) 0.03031(14) 0.0177(5) Uani 1 1 d . . . O5 O 0.0000 0.7357(4) 0.2500 0.0468(12) Uani 1 2 d S . . C13 C -0.0247(5) 0.8363(9) 0.2776(5) 0.034(2) Uani 0.50 1 d P A -1 H13 H -0.0559 0.8286 0.3201 0.040 Uiso 0.50 1 calc PR A -1 N3 N -0.010(4) 0.9552(7) 0.252(3) 0.039(6) Uani 0.50 1 d PD A -1 C14 C -0.0487(14) 1.0704(15) 0.2824(10) 0.126(8) Uani 0.50 1 d PD A -1 H14A H -0.0824 1.0435 0.3226 0.189 Uiso 0.50 1 calc PR A -1 H14B H -0.0873 1.1148 0.2369 0.189 Uiso 0.50 1 calc PR A -1 H14C H -0.0020 1.1300 0.3081 0.189 Uiso 0.50 1 calc PR A -1 C15 C 0.0423(8) 0.9716(14) 0.1906(7) 0.065(3) Uani 0.50 1 d PD A -1 H15A H 0.0651 0.8865 0.1782 0.097 Uiso 0.50 1 calc PR A -1 H15B H 0.0911 1.0307 0.2115 0.097 Uiso 0.50 1 calc PR A -1 H15C H 0.0062 1.0085 0.1408 0.097 Uiso 0.50 1 calc PR A -1 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 0.0099(3) 0.0126(3) 0.0091(3) 0.0003(2) 0.00346(18) 0.0015(2) N1 0.0120(14) 0.0167(15) 0.0140(14) 0.0011(11) 0.0039(11) 0.0007(11) C1 0.0138(17) 0.0219(19) 0.0169(18) 0.0024(14) 0.0048(14) 0.0064(14) C2 0.0175(17) 0.027(2) 0.0125(17) 0.0011(14) 0.0098(14) 0.0038(14) C3 0.0150(17) 0.0145(16) 0.0128(17) 0.0002(13) 0.0027(13) -0.0007(13) C4 0.0148(17) 0.0147(17) 0.0165(18) 0.0013(13) 0.0048(14) 0.0041(14) C5 0.0121(16) 0.0138(17) 0.0127(16) -0.0021(13) 0.0050(13) 0.0004(13) C6 0.0092(15) 0.0143(17) 0.0094(16) -0.0016(13) 0.0000(12) -0.0016(12) C7 0.0136(16) 0.0157(17) 0.0097(16) 0.0036(13) 0.0000(13) 0.0017(13) C8 0.0112(16) 0.0152(17) 0.0124(16) -0.0057(13) 0.0008(13) -0.0026(13) C9 0.0182(17) 0.0211(19) 0.0199(18) 0.0043(15) 0.0112(14) 0.0045(14) C10 0.0196(18) 0.025(2) 0.0207(19) 0.0092(15) 0.0096(15) 0.0045(15) N2 0.0142(14) 0.0184(15) 0.0125(14) 0.0009(12) 0.0044(11) 0.0023(12) C11 0.0156(17) 0.0101(16) 0.0128(17) -0.0019(13) 0.0025(13) -0.0023(13) O1 0.0147(12) 0.0207(13) 0.0133(12) 0.0041(10) 0.0025(10) 0.0052(10) O2 0.0196(12) 0.0217(13) 0.0112(12) -0.0008(10) 0.0078(10) 0.0025(10) C12 0.0105(16) 0.0196(18) 0.0078(16) -0.0016(13) 0.0010(12) 0.0018(13) O3 0.0153(12) 0.0149(12) 0.0131(12) -0.0014(9) 0.0018(10) 0.0001(9) O4 0.0130(12) 0.0182(12) 0.0244(13) -0.0010(10) 0.0096(10) 0.0043(10) O5 0.052(3) 0.035(3) 0.056(3) 0.000 0.016(2) 0.000 C13 0.030(5) 0.047(6) 0.022(4) 0.012(4) 0.001(3) 0.003(4) N3 0.05(2) 0.035(3) 0.031(5) 0.005(9) 0.014(9) 0.014(8) C14 0.22(2) 0.076(11) 0.096(12) 0.012(9) 0.071(13) 0.085(13) C15 0.061(7) 0.085(9) 0.047(7) 0.029(6) 0.011(6) -0.029(7) _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 O2 2.117(2) 6_565 ? Mn1 O4 2.120(2) 3_455 ? Mn1 O1 2.158(2) 4 ? Mn1 O3 2.178(2) 7 ? Mn1 N1 2.296(3) . ? Mn1 N2 2.307(3) . ? N1 C1 1.337(4) . ? N1 C5 1.347(4) . ? C1 C2 1.382(5) . ? C2 C3 1.382(5) . ? C3 C4 1.393(5) . ? C3 C11 1.519(4) . ? C4 C5 1.385(4) . ? C5 C6 1.494(4) . ? C6 N2 1.347(4) . ? C6 C7 1.385(4) . ? C7 C8 1.383(5) . ? C8 C9 1.380(5) . ? C8 C12 1.510(4) . ? C9 C10 1.378(5) . ? C10 N2 1.346(4) . ? C11 O2 1.252(4) . ? C11 O1 1.252(4) . ? O1 Mn1 2.158(2) 4_545 ? O2 Mn1 2.117(2) 6_566 ? C12 O4 1.251(4) . ? C12 O3 1.254(4) . ? O3 Mn1 2.178(2) 7 ? O4 Mn1 2.120(2) 3_545 ? O5 C13 1.225(9) . ? O5 C13 1.225(9) 2 ? C13 N3 1.326(13) . ? N3 C14 1.462(12) . ? N3 C15 1.463(16) . ? 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 O2 Mn1 O4 95.69(9) 6_565 3_455 ? O2 Mn1 O1 98.39(9) 6_565 4 ? O4 Mn1 O1 87.02(9) 3_455 4 ? O2 Mn1 O3 90.57(9) 6_565 7 ? O4 Mn1 O3 91.95(9) 3_455 7 ? O1 Mn1 O3 171.04(9) 4 7 ? O2 Mn1 N1 167.37(9) 6_565 . ? O4 Mn1 N1 96.91(9) 3_455 . ? O1 Mn1 N1 81.53(9) 4 . ? O3 Mn1 N1 89.77(9) 7 . ? O2 Mn1 N2 95.69(9) 6_565 . ? O4 Mn1 N2 168.34(9) 3_455 . ? O1 Mn1 N2 88.80(9) 4 . ? O3 Mn1 N2 90.48(9) 7 . ? N1 Mn1 N2 71.69(9) . . ? C1 N1 C5 118.0(3) . . ? C1 N1 Mn1 123.2(2) . . ? C5 N1 Mn1 117.1(2) . . ? N1 C1 C2 123.3(3) . . ? C3 C2 C1 118.8(3) . . ? C2 C3 C4 118.4(3) . . ? C2 C3 C11 121.3(3) . . ? C4 C3 C11 120.2(3) . . ? C5 C4 C3 119.4(3) . . ? N1 C5 C4 122.0(3) . . ? N1 C5 C6 116.2(3) . . ? C4 C5 C6 121.6(3) . . ? N2 C6 C7 122.7(3) . . ? N2 C6 C5 115.2(3) . . ? C7 C6 C5 122.0(3) . . ? C8 C7 C6 118.9(3) . . ? C9 C8 C7 118.7(3) . . ? C9 C8 C12 120.8(3) . . ? C7 C8 C12 120.5(3) . . ? C10 C9 C8 119.2(3) . . ? N2 C10 C9 122.9(3) . . ? C10 N2 C6 117.4(3) . . ? C10 N2 Mn1 125.3(2) . . ? C6 N2 Mn1 116.1(2) . . ? O2 C11 O1 127.5(3) . . ? O2 C11 C3 117.0(3) . . ? O1 C11 C3 115.4(3) . . ? C11 O1 Mn1 136.2(2) . 4_545 ? C11 O2 Mn1 144.0(2) . 6_566 ? O4 C12 O3 127.4(3) . . ? O4 C12 C8 115.4(3) . . ? O3 C12 C8 117.1(3) . . ? C12 O3 Mn1 134.4(2) . 7 ? C12 O4 Mn1 134.2(2) . 3_545 ? C13 O5 C13 65.5(8) . 2 ? O5 C13 N3 124.3(10) . . ? C13 N3 C14 121.3(15) . . ? C13 N3 C15 119.4(10) . . ? C14 N3 C15 119.2(13) . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.425 _refine_diff_density_min -0.352 _refine_diff_density_rms 0.075 #---END data_2 _database_code_depnum_ccdc_archive 'CCDC 225926' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety Mn(dcbp).2(H20) _chemical_formula_sum 'C12 H10 Mn N2 O6' _chemical_formula_weight 333.16 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' _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 11.9505(9) _cell_length_b 14.5679(11) _cell_length_c 9.2494(7) _cell_angle_alpha 90.00 _cell_angle_beta 127.7910(10) _cell_angle_gamma 90.00 _cell_volume 1272.51(17) _cell_formula_units_Z 4 _cell_measurement_temperature 153(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description Needle _exptl_crystal_colour 'Pale yellow' _exptl_crystal_size_max 0.38 _exptl_crystal_size_mid 0.09 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.739 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 676 _exptl_absorpt_coefficient_mu 1.068 _exptl_absorpt_correction_type Empirical _exptl_absorpt_correction_T_min 0.855 _exptl_absorpt_correction_T_max 1.000 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 153(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 SMART APEX CCD' _diffrn_measurement_method 'Omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6153 _diffrn_reflns_av_R_equivalents 0.0259 _diffrn_reflns_av_sigmaI/netI 0.0232 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -19 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.57 _diffrn_reflns_theta_max 28.29 _reflns_number_total 1500 _reflns_number_gt 1439 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0425P)^2^+2.2366P] 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 calc _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1500 _refine_ls_number_parameters 105 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0415 _refine_ls_R_factor_gt 0.0392 _refine_ls_wR_factor_ref 0.0966 _refine_ls_wR_factor_gt 0.0954 _refine_ls_goodness_of_fit_ref 1.219 _refine_ls_restrained_S_all 1.219 _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 0.0000 0.03480(3) 0.2500 0.01142(16) Uani 1 2 d S . . N1 N 0.10607(19) 0.16170(12) 0.2322(3) 0.0143(4) Uani 1 1 d . . . C1 C 0.0651(2) 0.24228(14) 0.2568(3) 0.0129(4) Uani 1 1 d . . . C2 C 0.1406(2) 0.32264(14) 0.2957(3) 0.0143(4) Uani 1 1 d . . . H2 H 0.1134 0.3774 0.3224 0.017 Uiso 1 1 calc R . . C3 C 0.2566(2) 0.32246(15) 0.2952(3) 0.0140(4) Uani 1 1 d . . . C4 C 0.2945(2) 0.24084(15) 0.2584(3) 0.0182(5) Uani 1 1 d . . . H4 H 0.3703 0.2391 0.2511 0.022 Uiso 1 1 calc R . . C5 C 0.2191(2) 0.16164(15) 0.2324(3) 0.0182(5) Uani 1 1 d . . . H5 H 0.2484 0.1051 0.2141 0.022 Uiso 1 1 calc R . . C6 C 0.3334(2) 0.41155(14) 0.3305(3) 0.0141(4) Uani 1 1 d . . . O1 O 0.36425(17) 0.42983(11) 0.2256(2) 0.0187(3) Uani 1 1 d . . . O2 O 0.35439(16) 0.46251(10) 0.4541(2) 0.0167(3) Uani 1 1 d . . . O3 O 0.0626(5) 0.4862(3) -0.0448(6) 0.0360(10) Uani 0.50 1 d P . . O3' O 0.0637(5) 0.4453(5) -0.1067(7) 0.0536(15) 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 0.0127(2) 0.0071(2) 0.0173(3) 0.000 0.0107(2) 0.000 N1 0.0153(9) 0.0110(8) 0.0196(9) 0.0000(7) 0.0122(8) -0.0007(7) C1 0.0139(10) 0.0116(10) 0.0144(10) 0.0010(7) 0.0093(9) 0.0008(7) C2 0.0154(10) 0.0100(10) 0.0190(10) -0.0004(8) 0.0113(9) 0.0002(7) C3 0.0146(10) 0.0125(10) 0.0150(10) 0.0006(8) 0.0092(8) -0.0015(7) C4 0.0194(11) 0.0144(11) 0.0280(12) -0.0029(9) 0.0183(10) -0.0007(8) C5 0.0202(11) 0.0134(11) 0.0289(12) -0.0033(9) 0.0190(10) 0.0001(8) C6 0.0105(9) 0.0108(10) 0.0174(10) 0.0025(8) 0.0067(8) 0.0013(7) O1 0.0230(8) 0.0165(8) 0.0226(8) -0.0023(6) 0.0169(7) -0.0060(6) O2 0.0175(8) 0.0122(7) 0.0187(8) -0.0014(6) 0.0102(7) -0.0008(6) O3 0.032(2) 0.042(3) 0.025(2) 0.0045(19) 0.0127(19) 0.0031(19) O3' 0.031(2) 0.094(5) 0.029(3) 0.006(3) 0.014(2) -0.003(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 2.1383(15) 3_445 ? Mn1 O1 2.1383(15) 4_545 ? Mn1 O2 2.1643(16) 7_556 ? Mn1 O2 2.1643(16) 8_455 ? Mn1 N1 2.3038(18) 2 ? Mn1 N1 2.3038(18) . ? N1 C1 1.344(3) . ? N1 C5 1.349(3) . ? C1 C2 1.384(3) . ? C1 C1 1.482(4) 2 ? C2 C3 1.388(3) . ? C3 C4 1.387(3) . ? C3 C6 1.506(3) . ? C4 C5 1.391(3) . ? C6 O2 1.253(3) . ? C6 O1 1.259(3) . ? O1 Mn1 2.1383(15) 3 ? O2 Mn1 2.1643(16) 7_556 ? O3 O3' 0.832(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 O1 Mn1 O1 88.69(9) 3_445 4_545 ? O1 Mn1 O2 96.69(6) 3_445 7_556 ? O1 Mn1 O2 84.80(6) 4_545 7_556 ? O1 Mn1 O2 84.80(6) 3_445 8_455 ? O1 Mn1 O2 96.69(6) 4_545 8_455 ? O2 Mn1 O2 177.92(8) 7_556 8_455 ? O1 Mn1 N1 99.57(6) 3_445 2 ? O1 Mn1 N1 168.93(7) 4_545 2 ? O2 Mn1 N1 86.91(6) 7_556 2 ? O2 Mn1 N1 91.42(6) 8_455 2 ? O1 Mn1 N1 168.93(6) 3_445 . ? O1 Mn1 N1 99.57(6) 4_545 . ? O2 Mn1 N1 91.42(6) 7_556 . ? O2 Mn1 N1 86.91(6) 8_455 . ? N1 Mn1 N1 73.28(9) 2 . ? C1 N1 C5 117.94(18) . . ? C1 N1 Mn1 114.52(13) . . ? C5 N1 Mn1 126.41(15) . . ? N1 C1 C2 122.36(18) . . ? N1 C1 C1 117.27(12) . 2 ? C2 C1 C1 120.37(12) . 2 ? C1 C2 C3 119.40(19) . . ? C4 C3 C2 118.6(2) . . ? C4 C3 C6 122.98(19) . . ? C2 C3 C6 118.38(19) . . ? C3 C4 C5 118.62(19) . . ? N1 C5 C4 122.8(2) . . ? O2 C6 O1 126.04(19) . . ? O2 C6 C3 117.56(19) . . ? O1 C6 C3 116.30(19) . . ? C6 O1 Mn1 129.13(14) . 3 ? C6 O2 Mn1 136.13(14) . 7_556 ? _diffrn_measured_fraction_theta_max 0.946 _diffrn_reflns_theta_full 28.29 _diffrn_measured_fraction_theta_full 0.946 _refine_diff_density_max 0.497 _refine_diff_density_min -0.244 _refine_diff_density_rms 0.087 #---END data_2a _database_code_depnum_ccdc_archive 'CCDC 225927' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety Mn(dcbp) _chemical_formula_sum 'C12 H6 Mn N2 O4' _chemical_formula_weight 297.13 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' _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 12.1736(10) _cell_length_b 14.6323(12) _cell_length_c 9.0078(8) _cell_angle_alpha 90.00 _cell_angle_beta 131.2100(10) _cell_angle_gamma 90.00 _cell_volume 1207.09(18) _cell_formula_units_Z 4 _cell_measurement_temperature 343(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description needle _exptl_crystal_colour 'pale yellow' _exptl_crystal_size_max 0.28 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.07 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.635 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 596 _exptl_absorpt_coefficient_mu 1.104 _exptl_absorpt_correction_type Empirical _exptl_absorpt_correction_T_min 0.855 _exptl_absorpt_correction_T_max 1.000 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 343(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 SMART APEX CCD' _diffrn_measurement_method 'Omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 4647 _diffrn_reflns_av_R_equivalents 0.0260 _diffrn_reflns_av_sigmaI/netI 0.0225 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 2.62 _diffrn_reflns_theta_max 24.94 _reflns_number_total 1061 _reflns_number_gt 968 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0389P)^2^+2.2842P] 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 calc _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1061 _refine_ls_number_parameters 87 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0438 _refine_ls_R_factor_gt 0.0381 _refine_ls_wR_factor_ref 0.0876 _refine_ls_wR_factor_gt 0.0852 _refine_ls_goodness_of_fit_ref 1.146 _refine_ls_restrained_S_all 1.146 _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 0.0000 0.03211(4) 0.2500 0.0223(2) Uani 1 2 d S . . N1 N 0.0982(2) 0.16317(15) 0.2232(3) 0.0244(5) Uani 1 1 d . . . C1 C 0.0606(3) 0.24413(17) 0.2495(4) 0.0222(6) Uani 1 1 d . . . C2 C 0.1333(3) 0.32420(17) 0.2782(4) 0.0249(6) Uani 1 1 d . . . H2 H 0.1095 0.3784 0.3051 0.030 Uiso 1 1 calc R . . C3 C 0.2411(3) 0.32363(18) 0.2667(4) 0.0243(6) Uani 1 1 d . . . C4 C 0.2730(3) 0.24161(19) 0.2263(5) 0.0321(7) Uani 1 1 d . . . H4 H 0.3409 0.2391 0.2102 0.039 Uiso 1 1 calc R . . C5 C 0.2024(3) 0.16342(19) 0.2103(5) 0.0322(7) Uani 1 1 d . . . H5 H 0.2280 0.1081 0.1895 0.039 Uiso 1 1 calc R . . C6 C 0.3236(3) 0.41090(18) 0.3069(4) 0.0256(6) Uani 1 1 d . . . O1 O 0.3628(2) 0.42421(14) 0.2117(3) 0.0403(6) Uani 1 1 d . . . O2 O 0.3439(2) 0.46344(12) 0.4328(3) 0.0301(5) 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 Mn1 0.0260(3) 0.0154(3) 0.0360(4) 0.000 0.0249(3) 0.000 N1 0.0270(13) 0.0181(11) 0.0359(13) -0.0029(9) 0.0239(12) -0.0012(9) C1 0.0228(14) 0.0197(13) 0.0278(14) 0.0019(11) 0.0183(12) 0.0020(11) C2 0.0269(14) 0.0172(13) 0.0370(16) -0.0007(11) 0.0238(14) 0.0005(11) C3 0.0257(14) 0.0234(14) 0.0281(15) -0.0001(11) 0.0196(13) -0.0023(11) C4 0.0381(17) 0.0270(15) 0.0505(19) -0.0066(13) 0.0375(16) -0.0061(13) C5 0.0370(17) 0.0232(14) 0.053(2) -0.0070(13) 0.0370(17) -0.0025(12) C6 0.0210(14) 0.0198(14) 0.0335(16) 0.0032(12) 0.0168(13) -0.0005(11) O1 0.0540(14) 0.0348(12) 0.0559(14) -0.0086(10) 0.0465(13) -0.0181(11) O2 0.0325(11) 0.0206(10) 0.0363(11) -0.0025(9) 0.0223(10) -0.0010(8) _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 O2 2.1505(19) 7_556 ? Mn1 O2 2.1505(19) 8_455 ? Mn1 O1 2.155(2) 3_445 ? Mn1 O1 2.155(2) 4_545 ? Mn1 N1 2.355(2) . ? Mn1 N1 2.355(2) 2 ? N1 C1 1.346(3) . ? N1 C5 1.348(3) . ? C1 C2 1.386(4) . ? C1 C1 1.482(5) 2 ? C2 C3 1.383(4) . ? C3 C4 1.382(4) . ? C3 C6 1.514(4) . ? C4 C5 1.380(4) . ? C6 O1 1.241(3) . ? C6 O2 1.253(3) . ? O1 Mn1 2.155(2) 3 ? O2 Mn1 2.1505(19) 7_556 ? 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 O2 Mn1 O2 176.53(10) 7_556 8_455 ? O2 Mn1 O1 98.52(8) 7_556 3_445 ? O2 Mn1 O1 84.05(8) 8_455 3_445 ? O2 Mn1 O1 84.05(8) 7_556 4_545 ? O2 Mn1 O1 98.52(8) 8_455 4_545 ? O1 Mn1 O1 85.77(12) 3_445 4_545 ? O2 Mn1 N1 92.73(8) 7_556 . ? O2 Mn1 N1 84.44(8) 8_455 . ? O1 Mn1 N1 166.57(9) 3_445 . ? O1 Mn1 N1 102.76(8) 4_545 . ? O2 Mn1 N1 84.44(8) 7_556 2 ? O2 Mn1 N1 92.73(8) 8_455 2 ? O1 Mn1 N1 102.76(8) 3_445 2 ? O1 Mn1 N1 166.57(9) 4_545 2 ? N1 Mn1 N1 70.93(11) . 2 ? C1 N1 C5 117.4(2) . . ? C1 N1 Mn1 116.42(17) . . ? C5 N1 Mn1 125.52(17) . . ? N1 C1 C2 121.9(2) . . ? N1 C1 C1 117.13(15) . 2 ? C2 C1 C1 120.98(16) . 2 ? C3 C2 C1 120.1(2) . . ? C4 C3 C2 118.0(2) . . ? C4 C3 C6 122.6(2) . . ? C2 C3 C6 119.3(2) . . ? C5 C4 C3 119.0(3) . . ? N1 C5 C4 123.3(3) . . ? O1 C6 O2 126.4(2) . . ? O1 C6 C3 117.6(2) . . ? O2 C6 C3 116.0(2) . . ? C6 O1 Mn1 127.93(19) . 3 ? C6 O2 Mn1 134.11(17) . 7_556 ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 24.94 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.545 _refine_diff_density_min -0.231 _refine_diff_density_rms 0.070