Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2001 data_global _audit_creation_method 'SHELXL-97' _publ_contact_author 'Dr Susan Bourne' _publ_contact_author_email 'xraysue@psipsy.uct.ac.za' _publ_requested_journal 'Dalton Transactions' _journal_coden_Cambridge 186 _publ_section_title ; One- and two-dimensional coordination polymers of zinc(II) with pyrazine. Solid state reactions and decomposition kinetics of the interconversion reactions. ; loop_ _publ_author_name _publ_author_address 'Susan A. Bourne' ; Department of Chemistry University of Cape Town Rondebosch 7701 South Africa ; ' Mairi Kilkenny' ; Department of Chemistry University of Cape Town Rondebosch 7701 South Africa ; ' Luigi R. Nassimbeni' ; Department of Chemistry University of Cape Town Rondebosch 7701 South Africa ; data_1 _database_code_CSD 154178 _audit_creation_method SHELXL-97 _chemical_name_systematic ; catena-(mu-pyrazine dibromo zinc(II)) ; _chemical_name_common ? _chemical_melting_point 533 _chemical_formula_moiety ? _chemical_formula_sum 'C4 H4 Br2 N2 Zn' _chemical_formula_weight 305.28 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' 'Zn' 'Zn' 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Br' 'Br' -0.2901 2.4595 '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 21/m 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' '-x, -y, -z' 'x, -y-1/2, z' _cell_length_a 6.0068(4) _cell_length_b 9.9518(8) _cell_length_c 6.9936(6) _cell_angle_alpha 90.00 _cell_angle_beta 110.472(5) _cell_angle_gamma 90.00 _cell_volume 391.66(5) _cell_formula_units_Z 2 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 2012 _cell_measurement_theta_min 3.7 _cell_measurement_theta_max 28.3 _exptl_crystal_description plate _exptl_crystal_colour 'pale yellow' _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.28 _exptl_crystal_size_min 0.14 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.589 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 284 _exptl_absorpt_coefficient_mu 13.250 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 298(2) _diffrn_radiation_wavelength 0.71070 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD diffractometer' _diffrn_measurement_method '/f and /w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 2012 _diffrn_reflns_av_R_equivalents 0.0736 _diffrn_reflns_av_sigmaI/netI 0.0604 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 6 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -6 _diffrn_reflns_limit_l_max 9 _diffrn_reflns_theta_min 3.72 _diffrn_reflns_theta_max 28.28 _reflns_number_total 987 _reflns_number_gt 833 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Nonius, 1998)' _computing_cell_refinement 'Collect (Nonius, 1998)' _computing_data_reduction 'DENZO (Owinowski, 1996)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'X-Seed ('Barbour, 2000)' _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^)+(0.1289P)^2^+0.2684P] 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 987 _refine_ls_number_parameters 46 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0758 _refine_ls_R_factor_gt 0.0677 _refine_ls_wR_factor_ref 0.1864 _refine_ls_wR_factor_gt 0.1739 _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 Zn1 Zn 0.62290(14) 0.2500 0.54948(15) 0.0287(4) Uani 1 2 d S . . Br2 Br 0.27193(14) 0.2500 0.26918(15) 0.0409(4) Uani 1 2 d S . . Br1 Br 0.62528(18) 0.2500 0.88337(15) 0.0469(4) Uani 1 2 d S . . N1 N 0.8423(8) 0.0949(4) 0.5211(8) 0.0284(10) Uani 1 1 d . . . C1 C 1.0393(11) 0.0615(6) 0.6769(9) 0.0344(13) Uani 1 1 d . . . H1 H 1.0709 0.1035 0.8024 0.041 Uiso 1 1 calc R . . C2 C 0.8028(11) 0.0340(6) 0.3442(10) 0.0340(12) Uani 1 1 d . . . H2 H 0.6681 0.0555 0.2330 0.041 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Zn1 0.0246(5) 0.0242(5) 0.0407(7) 0.000 0.0157(4) 0.000 Br2 0.0268(5) 0.0482(6) 0.0461(7) 0.000 0.0106(4) 0.000 Br1 0.0479(6) 0.0578(7) 0.0395(7) 0.000 0.0209(5) 0.000 N1 0.026(2) 0.0216(19) 0.040(3) -0.0015(19) 0.0147(19) 0.0016(16) C1 0.036(3) 0.031(3) 0.035(3) -0.003(2) 0.012(3) 0.006(2) C2 0.030(2) 0.028(3) 0.039(3) 0.000(2) 0.007(2) 0.004(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 Zn1 N1 2.084(4) 4_565 ? Zn1 N1 2.084(4) . ? Zn1 Br2 2.3230(12) . ? Zn1 Br1 2.3301(13) . ? N1 C2 1.323(8) . ? N1 C1 1.340(8) . ? C1 C2 1.387(8) 3_756 ? C2 C1 1.387(8) 3_756 ? 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 Zn1 N1 95.6(2) 4_565 . ? N1 Zn1 Br2 109.71(14) 4_565 . ? N1 Zn1 Br2 109.71(14) . . ? N1 Zn1 Br1 108.24(14) 4_565 . ? N1 Zn1 Br1 108.24(14) . . ? Br2 Zn1 Br1 122.09(5) . . ? C2 N1 C1 117.8(5) . . ? C2 N1 Zn1 121.1(4) . . ? C1 N1 Zn1 120.9(4) . . ? N1 C1 C2 121.7(6) . 3_756 ? N1 C2 C1 120.5(6) . 3_756 ? _diffrn_measured_fraction_theta_max 0.967 _diffrn_reflns_theta_full 28.28 _diffrn_measured_fraction_theta_full 0.967 _refine_diff_density_max 2.126 _refine_diff_density_min -1.325 _refine_diff_density_rms 0.304 #===END data_2 _database_code_CSD 154179 _audit_creation_method SHELXL-97 _chemical_name_systematic ; catena-(bis(mu-pyrazine) dibromo zinc(II)) ; _chemical_name_common ? _chemical_melting_point 533 _chemical_formula_moiety ? _chemical_formula_sum 'C8 H8 Br2 N4 Zn' _chemical_formula_weight 385.37 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' 'Br' 'Br' -0.2901 2.4595 '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' 'Zn' 'Zn' 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'C c c a' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y+1/2, z' 'x, -y+1/2, -z+1/2' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, -y+1, z' 'x+1/2, -y+1, -z+1/2' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, y-1/2, -z' '-x, y-1/2, z-1/2' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, y, -z' '-x+1/2, y, z-1/2' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 10.1904(4) _cell_length_b 10.1981(6) _cell_length_c 11.1516(7) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1158.90(11) _cell_formula_units_Z 4 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 3623 _cell_measurement_theta_min 3.3 _cell_measurement_theta_max 27.5 _exptl_crystal_description rod _exptl_crystal_colour 'pale yellow' _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.40 _exptl_crystal_size_min 0.28 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.209 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 736 _exptl_absorpt_coefficient_mu 8.986 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 173(2) _diffrn_radiation_wavelength 0.71070 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD diffractometer' _diffrn_measurement_method '/f and /w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 3623 _diffrn_reflns_av_R_equivalents 0.0619 _diffrn_reflns_av_sigmaI/netI 0.0343 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 3.37 _diffrn_reflns_theta_max 27.48 _reflns_number_total 675 _reflns_number_gt 399 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Nonius, 1998)' _computing_cell_refinement 'Collect (Nonius, 1998)' _computing_data_reduction 'DENZO (Owinowski, 1996)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'X-Seed ('Barbour, 2000)' _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^)+(0.0435P)^2^+1.1038P] 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 675 _refine_ls_number_parameters 56 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0451 _refine_ls_R_factor_gt 0.0301 _refine_ls_wR_factor_ref 0.0840 _refine_ls_wR_factor_gt 0.0736 _refine_ls_goodness_of_fit_ref 1.071 _refine_ls_restrained_S_all 1.071 _refine_ls_shift/su_max 0.007 _refine_ls_shift/su_mean 0.001 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 0.5000 0.2500 0.2500 0.0089(2) Uani 1 4 d S . . Br1 Br 0.5000 0.2500 0.01845(3) 0.01472(19) Uani 1 2 d S . . N1 N 0.6532(2) 0.4033(2) 0.2513(6) 0.0125(5) Uani 1 1 d . . . C1 C 0.7553(10) 0.4018(9) 0.3252(11) 0.018(3) Uani 0.517(11) 1 d P . . H1 H 0.7626 0.3313 0.3805 0.021 Uiso 0.517(11) 1 calc PR . . C2 C 0.7564(9) 0.3950(8) 0.1741(11) 0.010(3) Uani 0.482(10) 1 d P . . H2 H 0.7625 0.3232 0.1201 0.012 Uiso 0.482(10) 1 calc PR . . C3 C 0.6509(8) 0.5050(11) 0.3259(11) 0.011(3) Uani 0.482(10) 1 d P . . H3 H 0.5808 0.5122 0.3816 0.014 Uiso 0.482(10) 1 calc PR . . C4 C 0.6453(8) 0.5064(10) 0.1742(12) 0.017(3) Uani 0.517(11) 1 d P . . H4 H 0.5735 0.5124 0.1201 0.021 Uiso 0.517(11) 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 Zn1 0.0075(3) 0.0066(3) 0.0127(4) 0.000 0.000 0.000 Br1 0.0164(3) 0.0156(3) 0.0121(3) 0.000 0.000 -0.0014(4) N1 0.0112(10) 0.0111(11) 0.0152(12) 0.001(3) 0.001(3) -0.0012(7) C1 0.021(6) 0.016(5) 0.015(7) 0.011(5) -0.003(5) -0.002(4) C2 0.010(5) 0.007(5) 0.014(7) -0.005(5) 0.007(5) -0.004(3) C3 0.008(5) 0.016(6) 0.009(6) -0.006(6) 0.005(4) -0.001(4) C4 0.017(6) 0.009(5) 0.026(8) 0.006(6) -0.004(5) -0.003(4) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Zn1 N1 2.210(2) 2_655 ? Zn1 N1 2.210(2) . ? Zn1 N1 2.210(2) 4_655 ? Zn1 N1 2.210(2) 3 ? Zn1 Br1 2.5821(4) 3 ? Zn1 Br1 2.5821(4) . ? N1 C1 1.327(12) . ? N1 C3 1.329(11) . ? N1 C4 1.360(12) . ? N1 C2 1.361(11) . ? C1 C3 1.348(12) 6_655 ? C1 C1 2.005(17) 6_655 ? C2 C4 1.420(11) 6_655 ? C3 C1 1.348(12) 6_655 ? C3 C3 2.022(16) 6_655 ? C4 C2 1.420(11) 6_655 ? 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 Zn1 N1 179.2(3) 2_655 . ? N1 Zn1 N1 90.09(11) 2_655 4_655 ? N1 Zn1 N1 89.92(11) . 4_655 ? N1 Zn1 N1 89.92(11) 2_655 3 ? N1 Zn1 N1 90.09(11) . 3 ? N1 Zn1 N1 179.2(3) 4_655 3 ? N1 Zn1 Br1 89.61(17) 2_655 3 ? N1 Zn1 Br1 89.61(17) . 3 ? N1 Zn1 Br1 90.39(17) 4_655 3 ? N1 Zn1 Br1 90.39(17) 3 3 ? N1 Zn1 Br1 90.39(17) 2_655 . ? N1 Zn1 Br1 90.39(17) . . ? N1 Zn1 Br1 89.61(17) 4_655 . ? N1 Zn1 Br1 89.61(17) 3 . ? Br1 Zn1 Br1 180.0 3 . ? C1 N1 C3 68.6(6) . . ? C1 N1 C4 116.6(6) . . ? C3 N1 C4 78.0(4) . . ? C1 N1 C2 77.7(4) . . ? C3 N1 C2 117.3(6) . . ? C4 N1 C2 72.2(6) . . ? C1 N1 Zn1 123.4(5) . . ? C3 N1 Zn1 122.9(5) . . ? C4 N1 Zn1 120.0(5) . . ? C2 N1 Zn1 119.8(4) . . ? N1 C1 C3 123.5(9) . 6_655 ? N1 C1 C1 86.9(6) . 6_655 ? C3 C1 C1 48.2(6) 6_655 6_655 ? N1 C2 C4 120.0(9) . 6_655 ? N1 C3 C1 122.3(9) . 6_655 ? N1 C3 C3 86.7(6) . 6_655 ? C1 C3 C3 47.7(6) 6_655 6_655 ? N1 C4 C2 120.3(9) . 6_655 ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.598 _refine_diff_density_min -1.095 _refine_diff_density_rms 0.168 #===END