# Electronic Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2012 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _journal_volume ? _journal_page_first ? _journal_year ? loop_ _publ_author_name _publ_author_address _publ_author_footnote _publ_author_email K.Konidaris ; Department of Chemistry, University of Patras, 265 04 Patras, Greece ; . . V.Mpekiari ; Department of Aquaculture, Technological Educational Institute of Messolonghi, 30 200 Messolonghi, Greece ; . . E.Katsoulakou ; Department of Chemistry, University of Patras, 265 04 Patras, Greece ; . . C.Raptopoulou ; Institute of Materials Science, NCSR Demokritos, 153 10 Aghia Paraskevi Attikis, Greece ; . . V.Psycharis ; Institute of Materials Science, NCSR Demokritos, 153 10 Aghia Paraskevi Attikis, Greece ; . . E.Manessi-Zoupa ; Department of Chemistry, University of Patras, 265 04 Patras, Greece ; . . G.Kostakis ; Institute of Nanotechnology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz Platz 1, 76344 Eggenstein-Leopoldshafen, Germany. ; . . S.Perlepes ; Department of Chemistry, University of Patras, 265 04 Patras, Greece ; . . _publ_contact_author_name 'Dr Spyros Perlepes' _publ_contact_author_address ; Department of Chemistry, University of Patras, 265 04 Patras, Greece ; _publ_contact_author_email perlepes@patreas.upatras.gr _publ_contact_author_phone '0030 2610 996730' _publ_section_title ; Investigation of the zinc(II)/benzoate/2-pyridinealdoxime reaction system: a mononuclear compound, an inverse 12-metallacrown-4 complex and a dodecanuclear cluster with a "tetrahedron-in-cube" topology ; _publ_contact_letter ; Please consider this CIF for publication. I certify that this contibution is the original work of those listed as authors; that it has not been published before (in any language or medium) and is not being considered for publication elsewhere; that all authors concur with and are aware of the submission; that all workers involved in the study are listed as authors or given proper credit in the acknowledgements; that I have obtained permission for and acknowledged the source of any excerpts from other copyright works; and that to the best of my knowledge the paper contains no statements which are libellous, unlawful or in any way actionable. All coauthors have made significant scientific contributions to the work reported, including the ideas and their execution, and share responsibility and accountability for the results. ; # The loop structure below should contain the names and addresses of all # authors, in the required order of publication. Repeat as necessary. # NB if using publCIF, the Author database tool might prove useful # (see the Tools menu in publCIF) # Attachment '- Complex 3. MeOH.cif' #============================================================================== #TrackingRef '- Complex 3. MeOH.cif' #============================================================================== data_pekk342 _database_code_depnum_ccdc_archive 'CCDC 844926' #TrackingRef '- Complex 3. MeOH.cif' _audit_update_record ; 2011-09-19 # Formatted by publCIF ; _audit_creation_method SHELXL-97 _chemical_name_systematic ? _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C25 H26 N14 O7 Zn4' _chemical_formula_weight 896.08 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Zn Zn -1.5491 0.6778 '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 9.25740(10) _cell_length_b 9.88540(10) _cell_length_c 10.35700(10) _cell_angle_alpha 76.4260(10) _cell_angle_beta 68.6370(10) _cell_angle_gamma 76.0430(10) _cell_volume 845.238(15) _cell_formula_units_Z 1 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 10306 _cell_measurement_theta_min 7.11 _cell_measurement_theta_max 71.95 _exptl_crystal_description parallelepiped _exptl_crystal_colour colorless _exptl_crystal_size_max 0.35 _exptl_crystal_size_mid 0.27 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.760 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 450 _exptl_absorpt_coefficient_mu 3.783 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.677 _exptl_absorpt_correction_T_max 1.000 _exptl_absorpt_process_details 'CrystalClear, Rigaku MSC, 2005' _exptl_special_details ? _diffrn_ambient_temperature 180(2) _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Rigaku R-AXIS SPIDER IPDS' _diffrn_measurement_method '\q scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 10952 _diffrn_reflns_av_R_equivalents 0.0317 _diffrn_reflns_av_sigmaI/netI 0.0309 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 7.58 _diffrn_reflns_theta_max 64.96 _reflns_number_total 2636 _reflns_number_gt 2376 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrystalClear, Rigaku MSC, 2005' _computing_cell_refinement 'CrystalClear, Rigaku MSC, 2005' _computing_data_reduction 'CrystalClear, Rigaku MSC, 2005' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0718P)^2^+1.8046P] 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 refall _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2636 _refine_ls_number_parameters 229 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0470 _refine_ls_R_factor_gt 0.0432 _refine_ls_wR_factor_ref 0.1278 _refine_ls_wR_factor_gt 0.1241 _refine_ls_goodness_of_fit_ref 1.055 _refine_ls_restrained_S_all 1.055 _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 Zn1 Zn 0.85647(6) 0.12683(5) 0.56095(6) 0.0310(2) Uani 1 1 d . . . Zn2 Zn 0.85814(7) -0.19545(6) 0.74409(6) 0.0340(2) Uani 1 1 d . . . O1 O 0.6478(4) -0.0935(3) 0.7507(3) 0.0419(8) Uani 1 1 d . . . N1 N 0.6835(5) 0.2630(4) 0.4696(4) 0.0368(9) Uani 1 1 d . . . N2 N 0.6604(4) 0.0199(4) 0.6460(4) 0.0355(9) Uani 1 1 d . . . O11 O 1.0985(4) 0.3240(3) 0.3885(3) 0.0359(8) Uani 1 1 d . . . N11 N 0.7745(5) 0.2164(4) 0.7585(4) 0.0390(10) Uani 1 1 d . . . N12 N 0.9957(4) 0.2835(3) 0.5155(4) 0.0304(8) Uani 1 1 d . . . N21 N 0.8848(6) -0.3005(5) 0.9198(5) 0.0590(13) Uani 1 1 d . . . N22 N 0.8301(5) -0.2760(5) 1.0357(4) 0.0495(11) Uani 1 1 d . . . N23 N 0.7832(8) -0.2597(7) 1.1510(5) 0.0860(19) Uani 1 1 d . . . O31 O 1.0003(3) -0.0558(3) 0.6349(3) 0.0344(7) Uani 1 1 d . . . C1 C 0.6967(6) 0.3826(5) 0.3771(5) 0.0402(12) Uani 1 1 d . . . H1 H 0.7927 0.4178 0.3456 0.052 Uiso 1 1 calc R . . C2 C 0.5787(7) 0.4572(5) 0.3253(5) 0.0474(13) Uani 1 1 d . . . H2 H 0.5910 0.5444 0.2633 0.062 Uiso 1 1 calc R . . C3 C 0.4424(7) 0.4038(6) 0.3644(6) 0.0489(13) Uani 1 1 d . . . H3 H 0.3603 0.4520 0.3275 0.064 Uiso 1 1 calc R . . C4 C 0.4263(6) 0.2782(5) 0.4589(6) 0.0454(13) Uani 1 1 d . . . H4 H 0.3333 0.2388 0.4875 0.059 Uiso 1 1 calc R . . C5 C 0.5482(5) 0.2121(5) 0.5103(5) 0.0379(11) Uani 1 1 d . . . C6 C 0.5377(6) 0.0820(5) 0.6138(5) 0.0400(12) Uani 1 1 d . . . H6 H 0.4423 0.0452 0.6556 0.052 Uiso 1 1 calc R . . C11 C 0.6586(7) 0.1882(7) 0.8778(6) 0.068(2) Uani 1 1 d . . . H11 H 0.6000 0.1185 0.8850 0.088 Uiso 1 1 calc R . . C12 C 0.6201(10) 0.2549(9) 0.9908(7) 0.105(3) Uani 1 1 d . . . H12 H 0.5350 0.2333 1.0734 0.137 Uiso 1 1 calc R . . C13 C 0.7068(9) 0.3537(8) 0.9828(7) 0.091(3) Uani 1 1 d . . . H13 H 0.6837 0.4001 1.0604 0.118 Uiso 1 1 calc R . . C14 C 0.8284(7) 0.3843(5) 0.8596(5) 0.0515(15) Uani 1 1 d . . . H14 H 0.8896 0.4525 0.8509 0.067 Uiso 1 1 calc R . . C15 C 0.8584(5) 0.3140(4) 0.7506(5) 0.0355(11) Uani 1 1 d . . . C16 C 0.9805(5) 0.3453(4) 0.6162(4) 0.0313(10) Uani 1 1 d . . . H16 H 1.0472 0.4101 0.6040 0.041 Uiso 1 1 calc R . . O1M O 1.0980(12) -0.0314(11) 0.7185(11) 0.086(3) Uiso 0.50 1 d P . . C1M C 1.162(2) 0.0273(18) 0.757(2) 0.013(5) Uiso 0.25 1 d P . . C2M C 1.133(2) 0.0269(18) 0.786(2) 0.015(5) Uiso 0.25 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 Zn1 0.0300(4) 0.0281(3) 0.0340(4) -0.0100(2) -0.0005(3) -0.0144(3) Zn2 0.0389(4) 0.0309(3) 0.0301(3) -0.0093(2) 0.0001(3) -0.0157(3) O1 0.0369(18) 0.0339(16) 0.0456(19) -0.0034(14) 0.0026(15) -0.0174(14) N1 0.041(2) 0.034(2) 0.037(2) -0.0129(16) -0.0056(18) -0.0158(17) N2 0.033(2) 0.0307(19) 0.039(2) -0.0135(16) 0.0033(18) -0.0157(17) O11 0.0392(17) 0.0340(16) 0.0315(15) -0.0092(13) 0.0033(14) -0.0204(14) N11 0.041(2) 0.037(2) 0.036(2) -0.0143(16) 0.0032(18) -0.0175(17) N12 0.0298(19) 0.0267(17) 0.0314(18) -0.0074(15) -0.0007(16) -0.0108(15) N21 0.094(4) 0.041(2) 0.039(3) -0.0087(19) -0.018(2) -0.011(2) N22 0.058(3) 0.054(3) 0.040(3) -0.004(2) -0.012(2) -0.026(2) N23 0.099(5) 0.118(5) 0.040(3) -0.017(3) -0.009(3) -0.035(4) O31 0.0342(16) 0.0320(15) 0.0347(16) -0.0112(13) -0.0002(13) -0.0135(13) C1 0.045(3) 0.036(2) 0.039(3) -0.011(2) -0.009(2) -0.013(2) C2 0.057(3) 0.042(3) 0.043(3) -0.015(2) -0.015(3) -0.004(3) C3 0.048(3) 0.052(3) 0.052(3) -0.022(3) -0.022(3) 0.005(2) C4 0.038(3) 0.046(3) 0.057(3) -0.021(2) -0.013(3) -0.008(2) C5 0.031(2) 0.039(2) 0.046(3) -0.019(2) -0.007(2) -0.006(2) C6 0.030(2) 0.041(3) 0.049(3) -0.017(2) 0.000(2) -0.017(2) C11 0.075(4) 0.073(4) 0.049(3) -0.028(3) 0.021(3) -0.049(3) C12 0.126(6) 0.119(6) 0.060(4) -0.053(4) 0.048(4) -0.088(6) C13 0.116(6) 0.101(5) 0.052(3) -0.045(4) 0.029(4) -0.069(5) C14 0.071(4) 0.047(3) 0.037(3) -0.017(2) -0.001(3) -0.028(3) C15 0.042(3) 0.028(2) 0.034(2) -0.0096(18) -0.003(2) -0.012(2) C16 0.039(2) 0.027(2) 0.031(2) -0.0063(17) -0.0069(19) -0.0162(19) _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 Zn1 N12 2.112(3) . ? Zn1 N2 2.124(3) . ? Zn1 O31 2.134(3) . ? Zn1 O31 2.151(3) 2_756 ? Zn1 N1 2.176(4) . ? Zn1 N11 2.223(4) . ? Zn2 N21 1.941(5) . ? Zn2 O1 1.950(3) . ? Zn2 O11 1.958(3) 2_756 ? Zn2 O31 1.994(3) . ? O1 N2 1.359(5) . ? N1 C1 1.336(6) . ? N1 C5 1.350(6) . ? N2 C6 1.274(6) . ? O11 N12 1.350(4) . ? O11 Zn2 1.958(3) 2_756 ? N11 C11 1.332(6) . ? N11 C15 1.348(5) . ? N12 C16 1.278(5) . ? N21 N22 1.179(6) . ? N22 N23 1.150(6) . ? O31 O1M 1.549(11) . ? O31 Zn1 2.151(3) 2_756 ? C1 C2 1.370(8) . ? C1 H1 0.9500 . ? C2 C3 1.372(8) . ? C2 H2 0.9500 . ? C3 C4 1.391(7) . ? C3 H3 0.9500 . ? C4 C5 1.379(7) . ? C4 H4 0.9500 . ? C5 C6 1.466(7) . ? C6 H6 0.9500 . ? C11 C12 1.370(8) . ? C11 H11 0.9500 . ? C12 C13 1.377(9) . ? C12 H12 0.9500 . ? C13 C14 1.387(7) . ? C13 H13 0.9500 . ? C14 C15 1.372(6) . ? C14 H14 0.9500 . ? C15 C16 1.460(6) . ? C16 H16 0.9500 . ? O1M C1M 1.131(19) . ? O1M C2M 1.18(2) . ? 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 N12 Zn1 N2 160.78(13) . . ? N12 Zn1 O31 101.46(13) . . ? N2 Zn1 O31 90.32(13) . . ? N12 Zn1 O31 89.83(11) . 2_756 ? N2 Zn1 O31 107.29(12) . 2_756 ? O31 Zn1 O31 80.03(13) . 2_756 ? N12 Zn1 N1 94.67(14) . . ? N2 Zn1 N1 76.32(15) . . ? O31 Zn1 N1 162.14(12) . . ? O31 Zn1 N1 92.52(13) 2_756 . ? N12 Zn1 N11 75.70(13) . . ? N2 Zn1 N11 88.44(13) . . ? O31 Zn1 N11 94.29(14) . . ? O31 Zn1 N11 163.19(13) 2_756 . ? N1 Zn1 N11 97.09(15) . . ? N21 Zn2 O1 117.12(18) . . ? N21 Zn2 O11 110.35(16) . 2_756 ? O1 Zn2 O11 102.46(14) . 2_756 ? N21 Zn2 O31 117.33(18) . . ? O1 Zn2 O31 104.74(13) . . ? O11 Zn2 O31 102.96(11) 2_756 . ? N2 O1 Zn2 109.0(2) . . ? C1 N1 C5 117.7(5) . . ? C1 N1 Zn1 129.2(3) . . ? C5 N1 Zn1 113.0(3) . . ? C6 N2 O1 118.2(3) . . ? C6 N2 Zn1 116.5(3) . . ? O1 N2 Zn1 124.1(3) . . ? N12 O11 Zn2 112.7(2) . 2_756 ? C11 N11 C15 117.8(4) . . ? C11 N11 Zn1 129.9(3) . . ? C15 N11 Zn1 112.3(3) . . ? C16 N12 O11 117.5(3) . . ? C16 N12 Zn1 117.3(3) . . ? O11 N12 Zn1 125.2(2) . . ? N22 N21 Zn2 132.0(4) . . ? N23 N22 N21 175.6(7) . . ? O1M O31 Zn2 112.5(4) . . ? O1M O31 Zn1 116.3(4) . . ? Zn2 O31 Zn1 106.23(14) . . ? O1M O31 Zn1 113.2(4) . 2_756 ? Zn2 O31 Zn1 107.63(12) . 2_756 ? Zn1 O31 Zn1 99.97(13) . 2_756 ? N1 C1 C2 123.3(5) . . ? N1 C1 H1 118.3 . . ? C2 C1 H1 118.3 . . ? C1 C2 C3 118.9(5) . . ? C1 C2 H2 120.5 . . ? C3 C2 H2 120.5 . . ? C2 C3 C4 119.0(5) . . ? C2 C3 H3 120.5 . . ? C4 C3 H3 120.5 . . ? C5 C4 C3 118.6(5) . . ? C5 C4 H4 120.7 . . ? C3 C4 H4 120.7 . . ? N1 C5 C4 122.4(5) . . ? N1 C5 C6 115.8(5) . . ? C4 C5 C6 121.8(4) . . ? N2 C6 C5 118.0(4) . . ? N2 C6 H6 121.0 . . ? C5 C6 H6 121.0 . . ? N11 C11 C12 123.1(5) . . ? N11 C11 H11 118.5 . . ? C12 C11 H11 118.5 . . ? C11 C12 C13 118.9(5) . . ? C11 C12 H12 120.5 . . ? C13 C12 H12 120.5 . . ? C12 C13 C14 118.9(5) . . ? C12 C13 H13 120.6 . . ? C14 C13 H13 120.6 . . ? C15 C14 C13 118.6(5) . . ? C15 C14 H14 120.7 . . ? C13 C14 H14 120.7 . . ? N11 C15 C14 122.7(4) . . ? N11 C15 C16 116.0(4) . . ? C14 C15 C16 121.3(4) . . ? N12 C16 C15 118.4(4) . . ? N12 C16 H16 120.8 . . ? C15 C16 H16 120.8 . . ? C1M O1M C2M 16.0(13) . . ? C1M O1M O31 158.5(13) . . ? C2M O1M O31 157.4(13) . . ? _diffrn_measured_fraction_theta_max 0.917 _diffrn_reflns_theta_full 64.96 _diffrn_measured_fraction_theta_full 0.917 _refine_diff_density_max 1.278 _refine_diff_density_min -0.430 _refine_diff_density_rms 0.097 # start Validation Reply Form _vrf_PLAT029_pekk342 ; PROBLEM: _diffrn_measured_fraction_theta_full Low ....... 0.92 RESPONSE: This alert is usually generated when trying to collect data for triclinic space groups by using Cu-radiation. Complete data set to 2theta=143 \% was collected and only the data to 2theta=130 \% were used in the refinement, ensuring that the data-to-parameters criterion (> 10) is valid, thus no further action was taken. ; _vrf_PLAT220_pekk342 ; PROBLEM: Large Non-Solvent C Ueq(max)/Ueq(min) ... 8.08 Ratio RESPONSE: Some of the carbon atoms of the ligand present unusually high thermal parameters, however their atom type assignment is unambiguous. Their large thermal motion is probably due to the pure quality of the crystals, which were not improved upon repeating crystallization efforts. No further action was taken. ; # end Validation Reply Form