Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2006 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Norberto Masciocchi' _publ_contact_author_address ; Dipartimento di Scienze Chimiche e Ambientali University of Insubria via Valleggio 11 Como 22100 ITALY ; _publ_contact_author_email NORBERTO.MASCIOCCHI@UNINSUBRIA.IT _publ_section_title ; The competition between acetate and pyrazolate in the formation of polynuclear Zn(II) coordination complexes ; loop_ _publ_author_name 'Norberto Masciocchi' 'Augusto Cingolani' 'Simona Galli' 'Luciano Pandolfo' 'Claudio Pettinari' ; A.Sironi ; # Attachment 'Compound_1.cif' data_Compound_1 _database_code_depnum_ccdc_archive 'CCDC 288509' _audit_creation_method SHELXL-97 _chemical_name_systematic ; bis-pyrazole bis-mu-pyrazolate bis-acetato dizinc(ii) ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C16 H20 N8 O4 Zn2' _chemical_formula_sum 'C16 H20 N8 O4 Zn2' _chemical_formula_weight 519.04 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' Zn Zn 0.2839 1.4301 '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' _symmetry_space_group_name_Hall '-P 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 8.197(4) _cell_length_b 8.300(4) _cell_length_c 9.256(4) _cell_angle_alpha 105.22(3) _cell_angle_beta 106.98(3) _cell_angle_gamma 103.84(4) _cell_volume 546.1(4) _cell_formula_units_Z 1 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 9 _cell_measurement_theta_max 12 _exptl_crystal_description prism _exptl_crystal_colour colorless _exptl_crystal_size_max 0.10 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.579 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 264 _exptl_absorpt_coefficient_mu 2.235 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_method omega-scan _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count 14400 _diffrn_standards_interval_time 300 _diffrn_standards_decay_% 0 _diffrn_reflns_number 2100 _diffrn_reflns_av_R_equivalents 0.0107 _diffrn_reflns_av_sigmaI/netI 0.0241 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 3.14 _diffrn_reflns_theta_max 25.24 _reflns_number_total 1969 _reflns_number_gt 1682 _reflns_threshold_expression >2sigma(I) _computing_data_collection CAD4 _computing_cell_refinement CAD4 _computing_data_reduction local _computing_structure_solution SIR97 _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics WINGX _computing_publication_material CIF _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^)+(0.0518P)^2^+0.1251P] 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 1969 _refine_ls_number_parameters 136 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0440 _refine_ls_R_factor_gt 0.0343 _refine_ls_wR_factor_ref 0.0860 _refine_ls_wR_factor_gt 0.0811 _refine_ls_goodness_of_fit_ref 1.034 _refine_ls_restrained_S_all 1.034 _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 Zn Zn 0.39110(5) 0.60181(5) 0.86850(4) 0.04562(15) Uani 1 1 d . . . O1 O 0.4802(3) 0.7065(3) 0.7284(3) 0.0587(6) Uani 1 1 d . . . O2 O 0.2044(3) 0.5565(4) 0.5506(3) 0.0677(7) Uani 1 1 d . . . N1 N 0.3384(3) 0.3441(3) 0.8099(3) 0.0458(6) Uani 1 1 d . . . N2 N 0.4124(4) 0.2671(3) 0.9130(3) 0.0501(7) Uani 1 1 d . . . N3 N 0.1808(4) 0.6722(4) 0.8989(3) 0.0483(6) Uani 1 1 d . . . N4 N 0.0208(4) 0.6394(4) 0.7844(3) 0.0554(7) Uani 1 1 d . . . H4n H -0.0083 0.5850 0.6828 0.067 Uiso 1 1 calc R . . C1 C 0.2187(5) 0.2141(5) 0.6743(4) 0.0607(9) Uani 1 1 d . . . H1 H 0.1495 0.2307 0.5836 0.073 Uiso 1 1 calc R . . C2 C 0.2116(5) 0.0522(5) 0.6871(5) 0.0676(10) Uani 1 1 d . . . H2 H 0.1387 -0.0597 0.6103 0.081 Uiso 1 1 calc R . . C3 C 0.3350(5) 0.0917(5) 0.8370(5) 0.0675(11) Uani 1 1 d . . . H3 H 0.3618 0.0080 0.8808 0.081 Uiso 1 1 calc R . . C4 C 0.1696(5) 0.7572(5) 1.0361(5) 0.0649(10) Uani 1 1 d . . . H4 H 0.2621 0.7979 1.1375 0.078 Uiso 1 1 calc R . . C5 C 0.0029(6) 0.7771(6) 1.0088(6) 0.0806(13) Uani 1 1 d . . . H5 H -0.0385 0.8312 1.0854 0.097 Uiso 1 1 calc R . . C6 C -0.0879(5) 0.7016(6) 0.8475(6) 0.0732(11) Uani 1 1 d . . . H6 H -0.2052 0.6943 0.7906 0.088 Uiso 1 1 calc R . . C7 C 0.3582(5) 0.6583(5) 0.5900(4) 0.0532(8) Uani 1 1 d . . . C8 C 0.4113(7) 0.7347(7) 0.4745(6) 0.0884(14) Uani 1 1 d . . . H8A H 0.5361 0.8110 0.5257 0.133 Uiso 0.50 1 calc PR . . H8B H 0.3360 0.8019 0.4433 0.133 Uiso 0.50 1 calc PR . . H8C H 0.3960 0.6402 0.3803 0.133 Uiso 0.50 1 calc PR . . H8D H 0.3093 0.6910 0.3738 0.133 Uiso 0.50 1 calc PR . . H8E H 0.5094 0.7002 0.4562 0.133 Uiso 0.50 1 calc PR . . H8F H 0.4494 0.8619 0.5192 0.133 Uiso 0.50 1 calc PR . . 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 Zn 0.0406(2) 0.0478(2) 0.0466(2) 0.01614(16) 0.01088(15) 0.01973(16) O1 0.0496(13) 0.0700(16) 0.0572(15) 0.0265(12) 0.0178(12) 0.0205(12) O2 0.0513(15) 0.094(2) 0.0525(14) 0.0260(14) 0.0185(12) 0.0180(14) N1 0.0411(14) 0.0457(14) 0.0430(14) 0.0107(12) 0.0098(11) 0.0155(11) N2 0.0460(15) 0.0402(14) 0.0528(16) 0.0110(12) 0.0062(12) 0.0170(12) N3 0.0455(14) 0.0599(17) 0.0435(14) 0.0182(13) 0.0169(12) 0.0251(13) N4 0.0472(15) 0.0670(18) 0.0506(16) 0.0180(14) 0.0125(13) 0.0277(14) C1 0.055(2) 0.060(2) 0.0448(19) 0.0100(16) 0.0036(16) 0.0098(17) C2 0.057(2) 0.048(2) 0.064(2) -0.0034(17) 0.0064(18) 0.0055(16) C3 0.059(2) 0.0441(19) 0.083(3) 0.0162(19) 0.008(2) 0.0194(17) C4 0.067(2) 0.080(3) 0.048(2) 0.0156(18) 0.0242(18) 0.030(2) C5 0.080(3) 0.093(3) 0.080(3) 0.018(2) 0.049(3) 0.041(3) C6 0.049(2) 0.088(3) 0.090(3) 0.029(2) 0.030(2) 0.036(2) C7 0.055(2) 0.065(2) 0.051(2) 0.0244(17) 0.0257(17) 0.0301(18) C8 0.101(3) 0.103(4) 0.075(3) 0.048(3) 0.045(3) 0.027(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 Zn O1 1.952(3) . ? Zn N1 1.967(3) . ? Zn N2 1.993(3) 2_667 ? Zn N3 2.017(3) . ? O1 C7 1.262(4) . ? O2 C7 1.223(4) . ? N1 C1 1.329(4) . ? N1 N2 1.362(4) . ? N2 C3 1.333(4) . ? N2 Zn 1.993(3) 2_667 ? N3 C4 1.322(4) . ? N3 N4 1.336(4) . ? N4 C6 1.329(5) . ? C1 C2 1.368(5) . ? C2 C3 1.356(5) . ? C4 C5 1.374(6) . ? C5 C6 1.346(6) . ? C7 C8 1.493(5) . ? 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 Zn N1 115.60(11) . . ? O1 Zn N2 103.94(12) . 2_667 ? N1 Zn N2 110.66(11) . 2_667 ? O1 Zn N3 111.41(11) . . ? N1 Zn N3 111.85(12) . . ? N2 Zn N3 102.25(11) 2_667 . ? C7 O1 Zn 111.7(2) . . ? C1 N1 N2 107.4(3) . . ? C1 N1 Zn 128.5(2) . . ? N2 N1 Zn 123.87(19) . . ? C3 N2 N1 107.2(3) . . ? C3 N2 Zn 127.7(2) . 2_667 ? N1 N2 Zn 125.1(2) . 2_667 ? C4 N3 N4 105.0(3) . . ? C4 N3 Zn 127.7(2) . . ? N4 N3 Zn 127.3(2) . . ? C6 N4 N3 111.4(3) . . ? N1 C1 C2 110.3(3) . . ? C3 C2 C1 104.4(3) . . ? N2 C3 C2 110.7(3) . . ? N3 C4 C5 110.9(4) . . ? C6 C5 C4 105.3(3) . . ? N4 C6 C5 107.5(3) . . ? O2 C7 O1 123.1(3) . . ? O2 C7 C8 121.0(4) . . ? O1 C7 C8 116.0(4) . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 25.24 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.377 _refine_diff_density_min -0.440 _refine_diff_density_rms 0.062 # Attachment 'B515630K_Cpd_2.cif' data_Compound_2 _database_code_depnum_ccdc_archive 'CCDC 288510' _audit_creation_method SHELXL-97 _chemical_name_systematic ; bis-pyrazole bis-acetato zinc(ii) acetic acid solvate ; _chemical_name_common 'bis-pyrazole bis-acetato zinc(ii) acetic acid solvate' _chemical_melting_point ? _chemical_formula_moiety 'C10 H14 N4 O4 Zn, C2 H4 O2 ' _chemical_formula_sum 'C12 H18 N4 O6 Zn' _chemical_formula_weight 379.67 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' Zn Zn 0.2839 1.4301 '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' _symmetry_space_group_name_Hall '-P 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 7.997(1) _cell_length_b 8.294(1) _cell_length_c 14.449(1) _cell_angle_alpha 99.10(1) _cell_angle_beta 105.98(1) _cell_angle_gamma 101.57(1) _cell_volume 879.14(16) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 9 _cell_measurement_theta_max 12 _exptl_crystal_description prism _exptl_crystal_colour colorless _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.434 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 392 _exptl_absorpt_coefficient_mu 1.429 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.89 _exptl_absorpt_correction_T_max 1.00 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type CAD4 _diffrn_measurement_method omega-scan _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count 14400 _diffrn_standards_interval_time 300 _diffrn_standards_decay_% 38 _diffrn_reflns_number 3435 _diffrn_reflns_av_R_equivalents 0.0136 _diffrn_reflns_av_sigmaI/netI 0.0132 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 3.01 _diffrn_reflns_theta_max 25.25 _reflns_number_total 3189 _reflns_number_gt 2928 _reflns_threshold_expression >2sigma(I) _computing_data_collection CAD4 _computing_cell_refinement CAD4 _computing_data_reduction local _computing_structure_solution SIR97 _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics WINGX _computing_publication_material CIF _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^)+(0.0424P)^2^+0.4109P] 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 3189 _refine_ls_number_parameters 212 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0336 _refine_ls_R_factor_gt 0.0298 _refine_ls_wR_factor_ref 0.0808 _refine_ls_wR_factor_gt 0.0783 _refine_ls_goodness_of_fit_ref 1.064 _refine_ls_restrained_S_all 1.064 _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 Zn Zn 0.34200(3) -0.00168(3) 0.687997(19) 0.04442(11) Uani 1 1 d . . . O1 O 0.5183(3) -0.0552(2) 0.79556(13) 0.0626(5) Uani 1 1 d . . . O2 O 0.5732(5) 0.1830(3) 0.89920(17) 0.1101(10) Uani 1 1 d . . . O3 O 0.3948(2) -0.1370(2) 0.57994(12) 0.0513(4) Uani 1 1 d . . . O4 O 0.1627(2) -0.0636(2) 0.49324(13) 0.0564(4) Uani 1 1 d . . . N1 N 0.3532(3) 0.2424(2) 0.68924(14) 0.0465(4) Uani 1 1 d . . . N2 N 0.4588(3) 0.3732(2) 0.76355(15) 0.0519(5) Uani 1 1 d . . . H2N H 0.5305 0.3633 0.8177 0.062 Uiso 1 1 calc R . . N3 N 0.1086(2) -0.1140(2) 0.70491(13) 0.0436(4) Uani 1 1 d . . . N4 N -0.0552(3) -0.0975(3) 0.65808(15) 0.0518(5) Uani 1 1 d . . . H4N H -0.0760 -0.0378 0.6147 0.062 Uiso 1 1 calc R . . C1 C 0.4382(4) 0.5194(3) 0.7427(2) 0.0644(7) Uani 1 1 d . . . H1 H 0.4975 0.6261 0.7832 0.077 Uiso 1 1 calc R . . C2 C 0.3159(5) 0.4855(4) 0.6523(3) 0.0735(8) Uani 1 1 d . . . H2 H 0.2745 0.5632 0.6181 0.088 Uiso 1 1 calc R . . C3 C 0.2644(4) 0.3107(3) 0.6207(2) 0.0625(7) Uani 1 1 d . . . H3 H 0.1802 0.2506 0.5605 0.075 Uiso 1 1 calc R . . C4 C -0.1808(4) -0.1858(4) 0.6876(2) 0.0658(7) Uani 1 1 d . . . H4 H -0.3035 -0.1936 0.6652 0.079 Uiso 1 1 calc R . . C5 C -0.0973(4) -0.2627(4) 0.7568(2) 0.0675(7) Uani 1 1 d . . . H5 H -0.1501 -0.3326 0.7910 0.081 Uiso 1 1 calc R . . C6 C 0.0815(3) -0.2146(3) 0.76511(18) 0.0526(6) Uani 1 1 d . . . H6 H 0.1720 -0.2482 0.8074 0.063 Uiso 1 1 calc R . . C7 C 0.5979(4) 0.0419(3) 0.87810(18) 0.0539(6) Uani 1 1 d . . . C8 C 0.7219(5) -0.0208(4) 0.9543(2) 0.0793(9) Uani 1 1 d . . . H8A H 0.7307 -0.1299 0.9251 0.119 Uiso 1 1 calc R . . H8B H 0.6752 -0.0296 1.0083 0.119 Uiso 1 1 calc R . . H8C H 0.8390 0.0569 0.9781 0.119 Uiso 1 1 calc R . . C9 C 0.2787(3) -0.1447(3) 0.49840(17) 0.0454(5) Uani 1 1 d . . . C10 C 0.2813(5) -0.2600(5) 0.4085(2) 0.0805(9) Uani 1 1 d . . . H10A H 0.3800 -0.3109 0.4259 0.121 Uiso 1 1 calc R . . H10B H 0.2954 -0.1966 0.3598 0.121 Uiso 1 1 calc R . . H10C H 0.1703 -0.3467 0.3820 0.121 Uiso 1 1 calc R . . O5 O 0.7636(5) 0.5695(4) 0.95528(19) 0.1178(10) Uani 1 1 d . . . O6 O 0.7551(5) 0.4115(3) 1.06046(18) 0.1189(12) Uani 1 1 d . . . C11 C 0.8046(5) 0.5547(4) 1.0389(2) 0.0754(8) Uani 1 1 d . . . C12 C 0.9142(6) 0.6911(5) 1.1265(3) 0.1002(12) Uani 1 1 d . . . H12A H 0.9014 0.6571 1.1852 0.150 Uiso 1 1 calc R . . H12B H 0.8739 0.7919 1.1215 0.150 Uiso 1 1 calc R . . H12C H 1.0384 0.7129 1.1296 0.150 Uiso 1 1 calc R . . H H 0.700(9) 0.327(8) 0.998(5) 0.20(3) Uiso 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 Zn 0.04781(17) 0.03500(16) 0.05145(17) 0.01332(11) 0.01289(12) 0.01406(11) O1 0.0662(11) 0.0527(10) 0.0537(10) 0.0050(8) -0.0055(9) 0.0214(9) O2 0.186(3) 0.0589(14) 0.0599(13) 0.0068(10) -0.0118(15) 0.0503(16) O3 0.0513(9) 0.0563(10) 0.0475(9) 0.0146(7) 0.0080(7) 0.0250(8) O4 0.0565(10) 0.0657(11) 0.0516(10) 0.0203(8) 0.0107(8) 0.0294(9) N1 0.0526(11) 0.0351(10) 0.0508(11) 0.0121(8) 0.0122(9) 0.0130(8) N2 0.0575(12) 0.0420(11) 0.0527(12) 0.0095(9) 0.0126(10) 0.0130(9) N3 0.0450(10) 0.0462(10) 0.0400(10) 0.0161(8) 0.0080(8) 0.0153(8) N4 0.0510(11) 0.0600(12) 0.0484(11) 0.0232(9) 0.0098(9) 0.0230(10) C1 0.0715(18) 0.0368(13) 0.082(2) 0.0105(13) 0.0238(15) 0.0109(12) C2 0.095(2) 0.0468(15) 0.083(2) 0.0296(14) 0.0196(18) 0.0298(15) C3 0.0743(18) 0.0479(14) 0.0598(16) 0.0173(12) 0.0052(13) 0.0220(13) C4 0.0482(14) 0.0785(19) 0.0772(19) 0.0268(15) 0.0210(14) 0.0221(13) C5 0.0658(17) 0.0767(19) 0.0739(18) 0.0372(16) 0.0325(15) 0.0186(15) C6 0.0599(15) 0.0552(14) 0.0489(13) 0.0256(11) 0.0148(11) 0.0213(12) C7 0.0583(15) 0.0488(14) 0.0492(14) 0.0139(11) 0.0085(12) 0.0119(11) C8 0.087(2) 0.079(2) 0.0577(17) 0.0162(15) -0.0055(15) 0.0308(18) C9 0.0461(12) 0.0478(13) 0.0453(12) 0.0163(10) 0.0151(10) 0.0137(10) C10 0.089(2) 0.093(2) 0.0593(18) 0.0023(16) 0.0234(16) 0.0332(19) O5 0.182(3) 0.0911(18) 0.0684(16) 0.0362(14) 0.0145(17) 0.0291(19) O6 0.212(3) 0.0673(15) 0.0522(13) 0.0189(11) 0.0063(17) 0.0246(18) C11 0.102(2) 0.070(2) 0.0598(18) 0.0207(15) 0.0217(16) 0.0346(18) C12 0.117(3) 0.086(3) 0.079(2) 0.0092(19) 0.018(2) 0.012(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 Zn O1 1.9656(17) . ? Zn O3 1.9684(17) . ? Zn N1 2.0051(18) . ? Zn N3 2.0092(19) . ? O1 C7 1.244(3) . ? O2 C7 1.231(3) . ? O3 C9 1.266(3) . ? O4 C9 1.244(3) . ? N1 C3 1.326(3) . ? N1 N2 1.345(3) . ? N2 C1 1.325(3) . ? N3 C6 1.327(3) . ? N3 N4 1.344(3) . ? N4 C4 1.329(3) . ? C1 C2 1.346(5) . ? C2 C3 1.388(4) . ? C4 C5 1.363(4) . ? C5 C6 1.371(4) . ? C7 C8 1.501(4) . ? C9 C10 1.494(4) . ? O5 C11 1.195(4) . ? O6 C11 1.288(4) . ? C11 C12 1.479(5) . ? 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 Zn O3 95.73(7) . . ? O1 Zn N1 118.01(8) . . ? O3 Zn N1 118.34(8) . . ? O1 Zn N3 101.54(8) . . ? O3 Zn N3 112.02(8) . . ? N1 Zn N3 109.53(8) . . ? C7 O1 Zn 124.14(17) . . ? C9 O3 Zn 109.42(14) . . ? C3 N1 N2 105.45(19) . . ? C3 N1 Zn 129.40(18) . . ? N2 N1 Zn 125.15(15) . . ? C1 N2 N1 111.4(2) . . ? C6 N3 N4 105.19(19) . . ? C6 N3 Zn 128.61(16) . . ? N4 N3 Zn 126.18(15) . . ? C4 N4 N3 111.0(2) . . ? N2 C1 C2 107.6(3) . . ? C1 C2 C3 105.8(3) . . ? N1 C3 C2 109.8(3) . . ? N4 C4 C5 107.7(2) . . ? C4 C5 C6 105.0(2) . . ? N3 C6 C5 111.1(2) . . ? O2 C7 O1 122.1(2) . . ? O2 C7 C8 120.0(3) . . ? O1 C7 C8 117.8(2) . . ? O4 C9 O3 121.5(2) . . ? O4 C9 C10 120.8(2) . . ? O3 C9 C10 117.6(2) . . ? O5 C11 O6 121.2(3) . . ? O5 C11 C12 125.5(3) . . ? O6 C11 C12 113.3(3) . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 25.25 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.426 _refine_diff_density_min -0.311 _refine_diff_density_rms 0.047 # Attachment 'B415630K_Cpd_4.cif' data_Compound_4 _database_code_depnum_ccdc_archive 'CCDC 288511' # Note: CIF generated from an ab-initio Powder Diffraction Study. # Most single-crystal experimental parameters or data analysis # treatment methods do not apply # The significant and pertinent experimental details are reported in the # paper in tabular form. _audit_creation_method TOPAS _chemical_name_systematic ; catena mu-pyrazolato mu-acetato zinc(ii) ; _chemical_name_mineral '[Zn(pz)(ac)]n' _chemical_formula_moiety ' C5 H6 N2 O2 Zn' _chemical_formula_sum ' C5 H6 N2 O2 Zn' _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_weight 191.50 _cell_length_a 13.63122(39) _cell_length_b 15.23971(48) _cell_length_c 6.47958(19) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 1346.041(69) _cell_formula_units_Z 8 _cell_measurement_temperature 298 _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P b c a' _symmetry_space_group_name_Hall '-P 2ac 2ab' _exptl_crystal_density_diffrn 1.890 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 768.0 _exptl_absorpt_coefficient_mu 4.59 _exptl_absorpt_correction_type none _exptl_absorpt_process_details ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ? _diffrn_ambient_temperature 298 _diffrn_radiation_type 'Cu K\a' _diffrn_radiation_wavelength 1.5418 _diffrn_radiation_monochromator 'diffracted, graphite 002' _diffrn_measurement_device_type 'Bruker AXS D8 Advance' _diffrn_reflns_number 775 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 6 _refine_special_details ; ; _refine_ls_matrix_type full _refine_ls_goodness_of_fit_all 2.68 _refine_ls_number_parameters 43 _refine_ls_number_restraints ? _refine_ls_number_constraints ? _refine_ls_hydrogen_treatment ? _refine_ls_weighting_scheme sigma _refine_ls_weighting_details 1/\s(Y~obs~)^2^ _refine_ls_shift/su_max 0.005 _refine_diff_density_max ? _refine_diff_density_min ? _refine_ls_extinction_method none _refine_ls_extinction_coef ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_source C C 'International Tables Vol C Table 6.1.1.4' H H 'International Tables Vol C Table 6.1.1.4' N N 'International Tables Vol C Table 6.1.1.4' O O 'International Tables Vol C Table 6.1.1.4' Zn Zn 'International Tables Vol C Table 6.1.1.4' _computing_data_collection 'DIFFRAC plus XRD Commander (Kienle & Jacob, 2003)' _computing_data_reduction 'TOPAS (Coelho, 2003)' _computing_structure_solution 'TOPAS (Coelho, 2003)' _computing_structure_refinement 'TOPAS (Coelho, 2003)' _computing_publication_material 'enCifer (Allen et al., 2004)' loop_ _symmetry_equiv_pos_as_xyz '-x, -y, -z' '-x, y+1/2, -z+1/2' '-x+1/2, -y, z+1/2' '-x+1/2, y+1/2, z' 'x, -y+1/2, z+1/2' 'x, y, z' 'x+1/2, -y+1/2, -z' 'x+1/2, y, -z+1/2' loop_ _atom_site_label _atom_site_type_symbol _atom_site_symmetry_multiplicity _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_B_iso_or_equiv Zn Zn 8 0.87531(19) 0.53032(18) 0.05840(38) 1 4.012(80) C1 C 8 0.99956 0.34783 0.44385 1 6.012(80) C2 C 8 0.93113 0.40656 0.39684 1 6.012(80) N3 N 8 0.95751 0.44588 0.22255 1 6.012(80) N4 N 8 1.04224 0.41146 0.16184 1 6.012(80) C5 C 8 1.06822 0.35086 0.29862 1 6.012(80) H1 H 8 0.99941 0.31021 0.56096 1 6.012(80) H2 H 8 0.87338 0.41838 0.47437 1 6.012(80) H5 H 8 1.12588 0.31579 0.29347 1 6.012(80) C21 C 8 0.73939 0.60945 0.33214 1 6.012(80) C22 C 8 0.68713 0.68009 0.43406 1 6.012(80) O21 O 8 0.72446 0.53353 0.38264 1 6.012(80) O22 O 8 0.79829 0.62594 0.19589 1 6.012(80) _geom_special_details ; The structure solution was achieved by simulated annealing, using independent metal ions, and acetate/pyrazolate rigid fragments; final refinements were carried out by the Rietveld method (as implemented in the TOPAS suite of programs), keeping idealized rigid body moieties, helping convergence and stability. As a consequence, statistically significant su's are available only for the zinc atom and for the location and orientation of the two rigid bodies, but not for individual atoms, nor for derived geometrical parameters. Bond distances, angles etc. have been calculated using the fractional coordinates above. Since the ligands were treated as rigid bodies, no su's on the bond distances and angles can be estimated. Indeed, only the su's of the centers of mass and rotational angles are available from the variances of the (full) variance-covariance matrix. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag Zn O22 . . 2.0048 no Zn N3 . . 2.0107 no Zn O21a . . 2.0232 no Zn N4c . . 2.0216 no O21 C21 . . 1.2195 no O22 C21 . . 1.2195 no N3 N4 . . 1.3281 no N3 C2 . . 1.3281 no N4 C5 . . 1.3281 no C1 C2 . . 1.3281 no C1 C5 . . 1.3281 no C21 C22 . . 1.4500 no C1 H1 . . 0.9511 no C2 H2 . . 0.9511 no C5 H5 . . 0.9511 no loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_publ_flag O22 Zn N3 121.46 no O22 Zn O21a 104.34 no O22 Zn N4c 106.61 no N3 Zn O21a 111.38 no N3 Zn N4c 110.15 no O21a Zn N4c 100.80 no C21 O21 Znb 136.02 no Zn O22 C21 121.11 no Zn N3 N4 125.50 no Zn N3 C2 126.00 no N4 N3 C2 108.00 no N3 N4 N5 108.00 no N3 N4 Znc 121.28 no C5 N4 Znc 128.90 no C2 C1 C5 108.00 no N3 C2 C1 108.00 no N4 C5 C1 108.00 no O21 C21 O22 120.00 no O22 C21 C22 120.00 no _chemical_name_common 'catena mu-pyrazolato mu-acetato zinc(ii)'