# Electronic Supplementary Material (ESI) for CrystEngComm # This journal is © The Royal Society of Chemistry 2013 data_global _journal_name_full CrystEngComm _journal_coden_cambridge 1350 #TrackingRef '- nebpy.cif' _publ_contact_author ; Wiebcke, Michael Institut f\"ur Anorganische Chemie Leibniz Universit\"at Hannover Callinistrasse 9 30167 Hannover Germany ; _publ_contact_author_email michael.wiebcke@acb.uni-hannover.de _publ_contact_author_phone '049 511 762 3698' _publ_contact_author_fax '049 511 762 3006' loop_ _publ_author_name _publ_author_address C.A.Schroder ; Institut f\"ur Anorganische Chemie Leibniz Universit\"at Hannover Callinstrasse 9 30167 Hannover Germany ; I.A.Baburin ; Institut f\"ur Physikalische Chemie und Elektrochemie Technische Universit\"at Dresden Mommsenstrasse 13 01062 Dresden Germany ; 'L.van Wullen' ; Institut f\"ur Physik' Universit\"at Augsburg Universit\"atsstrasse 1 86159 Augsburg Germany ; M.Wiebcke ; Institut f\"ur Anorganische Chemie Leibniz Universit\"at Hannover Callinistrasse 9 30167 Hannover Germany ; S.Leoni ; Institut f\"ur Physikalische Chemie und Elektrochemie Technische Universit\"at Dresden Mommsenstrasse 13 01062 Dresden Germany ; _publ_section_title ; Subtle Polymorphism of Zinc Imidazolate Frameworks: Temperature-Dependent Ground States in the Energy Landscape Revealed by Experiment and Theory ; _publ_contact_author_name 'Wiebcke, Michael' data_nebpy _database_code_depnum_ccdc_archive 'CCDC 889150' #TrackingRef '- nebpy.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; diimidazolatozinc(II) ; _chemical_name_common diimidazolatozinc(ii) _chemical_melting_point 'ca. 410 C (decomp.)' _chemical_formula_moiety '2(C6 H6 N4 Zn), C5 H5 N' _chemical_formula_sum 'C17 H17 N9 Zn2' _chemical_formula_weight 478.14 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 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' Zn Zn -1.5491 0.6778 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M Fdd2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-x+1/4, y+1/4, z+1/4' 'x+3/4, -y+3/4, z+1/4' 'x, y+1/2, z+1/2' '-x, -y+1/2, z+1/2' '-x+1/4, y+3/4, z+3/4' 'x+3/4, -y+5/4, z+3/4' 'x+1/2, y, z+1/2' '-x+1/2, -y, z+1/2' '-x+3/4, y+1/4, z+3/4' 'x+5/4, -y+3/4, z+3/4' 'x+1/2, y+1/2, z' '-x+1/2, -y+1/2, z' '-x+3/4, y+3/4, z+1/4' 'x+5/4, -y+5/4, z+1/4' _cell_length_a 18.50490(10) _cell_length_b 23.8735(2) _cell_length_c 9.31560(10) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 4115.42(6) _cell_formula_units_Z 8 _cell_measurement_temperature 173 _cell_measurement_reflns_used 8186 _cell_measurement_theta_min 4.772 _cell_measurement_theta_max 65.326 _exptl_crystal_description block _exptl_crystal_colour colorless _exptl_crystal_size_max 0.18 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.543 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1936 _exptl_absorpt_coefficient_mu 3.047 _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_T_min 0.5796 _exptl_absorpt_correction_T_max 0.7386 _exptl_absorpt_process_details 'SADABS (BRUKER, 2006)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 173 _diffrn_radiation_wavelength 1.54184 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'BRUKER Kappa Apex II CCD' _diffrn_measurement_method '\f and \w scan' _diffrn_reflns_number 8941 _diffrn_reflns_av_R_equivalents 0.0566 _diffrn_reflns_av_sigmaI/netI 0.0329 _diffrn_reflns_limit_h_min -21 _diffrn_reflns_limit_h_max 21 _diffrn_reflns_limit_k_min -24 _diffrn_reflns_limit_k_max 27 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 5.63 _diffrn_reflns_theta_max 65.40 _reflns_number_total 1710 _reflns_number_gt 1696 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'APEX2 (BRUKER, 2006)' _computing_cell_refinement 'SAINT (BRUKER, 2006)' _computing_data_reduction 'SAINT (BRUKER, 2006)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _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^)+(0.0479P)^2^+5.3652P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.08(4) _refine_ls_number_reflns 1710 _refine_ls_number_parameters 128 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0284 _refine_ls_R_factor_gt 0.0283 _refine_ls_wR_factor_ref 0.0732 _refine_ls_wR_factor_gt 0.0731 _refine_ls_goodness_of_fit_ref 1.031 _refine_ls_restrained_S_all 1.031 _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 0.045857(17) 0.314894(14) 0.70762(5) 0.03334(14) Uani 1 1 d . . . N1 N -0.00210(14) 0.30293(11) 0.5186(3) 0.0388(5) Uani 1 1 d . . . C2 C -0.01159(15) 0.25280(13) 0.4593(4) 0.0381(6) Uani 1 1 d . . . H2 H -0.0021 0.2194 0.5071 0.046 Uiso 1 1 calc R . . N3 N 0.03582(14) 0.24504(11) 0.8262(3) 0.0393(6) Uani 1 1 d . . . C4 C -0.04229(19) 0.31068(14) 0.2970(4) 0.0475(9) Uani 1 1 d . . . H4 H -0.0584 0.3259 0.2108 0.057 Uiso 1 1 calc R . . C5 C -0.02146(18) 0.34013(13) 0.4139(4) 0.0448(7) Uani 1 1 d . . . H5 H -0.0205 0.3790 0.4218 0.054 Uiso 1 1 calc R . . N6 N -0.00723(13) 0.37203(10) 0.8223(3) 0.0355(5) Uani 1 1 d . . . C7 C -0.07818(15) 0.38148(12) 0.8168(3) 0.0341(6) Uani 1 1 d . . . H7 H -0.1081 0.3669 0.7459 0.041 Uiso 1 1 calc R . . N8 N 0.14815(12) 0.33604(10) 0.6732(3) 0.0338(5) Uani 1 1 d . . . C9 C -0.04194(16) 0.42651(13) 1.0033(4) 0.0396(7) Uani 1 1 d . . . H9 H -0.0407 0.4489 1.0849 0.048 Uiso 1 1 calc R . . C10 C 0.01550(15) 0.40023(13) 0.9417(4) 0.0418(7) Uani 1 1 d . . . H10 H 0.0628 0.4013 0.9756 0.050 Uiso 1 1 calc R . . N11 N 0.0000 0.5000 1.3371(6) 0.0795(18) Uani 1 2 d S . . C12 C -0.0593(3) 0.5011(2) 1.4095(8) 0.0860(19) Uani 1 1 d . . . H12 H -0.1027 0.5022 1.3592 0.103 Uiso 1 1 calc R . . C13 C -0.0620(4) 0.5009(2) 1.5533(9) 0.104(3) Uani 1 1 d . . . H13 H -0.1061 0.5013 1.6010 0.125 Uiso 1 1 calc R . . C14 C 0.0000 0.5000 1.6267(7) 0.108(4) Uani 1 2 d S . . H14 H 0.0000 0.5000 1.7266 0.130 Uiso 1 2 calc SR . . 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 0.02987(19) 0.0371(2) 0.0331(2) -0.00214(16) 0.00544(16) -0.00146(13) N1 0.0390(13) 0.0398(13) 0.0376(13) -0.0023(11) -0.0005(11) -0.0025(11) C2 0.0396(15) 0.0358(13) 0.0389(13) 0.0056(14) -0.0042(14) -0.0030(11) N3 0.0365(12) 0.0415(14) 0.0400(13) 0.0013(11) 0.0087(11) 0.0003(10) C4 0.052(2) 0.047(2) 0.043(2) 0.0024(14) -0.0086(14) 0.0132(13) C5 0.0526(17) 0.0354(16) 0.0465(18) -0.0035(13) -0.0041(15) 0.0073(14) N6 0.0306(12) 0.0359(12) 0.0400(13) -0.0022(11) 0.0013(11) -0.0003(10) C7 0.0314(13) 0.0395(15) 0.0314(14) -0.0050(12) -0.0024(11) -0.0017(11) N8 0.0310(11) 0.0356(11) 0.0349(14) 0.0007(10) 0.0029(10) -0.0011(10) C9 0.0432(17) 0.0396(16) 0.0361(15) -0.0090(13) -0.0027(12) -0.0013(11) C10 0.0297(13) 0.0468(15) 0.0488(18) -0.0087(16) -0.0061(14) 0.0012(11) N11 0.120(5) 0.071(4) 0.047(3) 0.000 0.000 0.037(4) C12 0.058(2) 0.064(3) 0.136(6) -0.012(3) -0.036(3) 0.010(2) C13 0.115(5) 0.058(3) 0.140(7) 0.012(4) 0.085(5) 0.013(3) C14 0.235(14) 0.053(4) 0.036(3) 0.000 0.000 0.038(6) _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 N8 1.985(2) . ? Zn N6 1.992(2) . ? Zn N1 1.992(3) . ? Zn N3 2.009(3) . ? N1 C2 1.330(4) . ? N1 C5 1.367(4) . ? C2 N3 1.320(5) 6_554 ? C2 H2 0.9300 . ? N3 C2 1.320(5) 6 ? N3 C4 1.363(4) 6 ? C4 C5 1.353(5) . ? C4 N3 1.363(4) 6_554 ? C4 H4 0.9300 . ? C5 H5 0.9300 . ? N6 C7 1.333(4) . ? N6 C10 1.367(4) . ? C7 N8 1.332(4) 4_455 ? C7 H7 0.9300 . ? N8 C7 1.332(4) 12_454 ? N8 C9 1.370(4) 12_454 ? C9 C10 1.361(4) . ? C9 N8 1.370(4) 4_455 ? C9 H9 0.9300 . ? C10 H10 0.9300 . ? N11 C12 1.288(7) . ? N11 C12 1.288(7) 2_565 ? C12 C13 1.341(10) . ? C12 H12 0.9300 . ? C13 C14 1.335(9) . ? C13 H13 0.9300 . ? C14 C13 1.335(9) 2_565 ? C14 H14 0.9300 . ? 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 N8 Zn N6 112.51(10) . . ? N8 Zn N1 108.56(11) . . ? N6 Zn N1 110.65(11) . . ? N8 Zn N3 112.84(10) . . ? N6 Zn N3 103.18(11) . . ? N1 Zn N3 109.00(11) . . ? C2 N1 C5 104.7(3) . . ? C2 N1 Zn 123.7(2) . . ? C5 N1 Zn 130.9(2) . . ? N3 C2 N1 113.6(3) 6_554 . ? N3 C2 H2 123.2 6_554 . ? N1 C2 H2 123.2 . . ? C2 N3 C4 104.8(3) 6 6 ? C2 N3 Zn 121.0(2) 6 . ? C4 N3 Zn 133.8(3) 6 . ? C5 C4 N3 108.7(3) . 6_554 ? C5 C4 H4 125.6 . . ? N3 C4 H4 125.6 6_554 . ? C4 C5 N1 108.2(3) . . ? C4 C5 H5 125.9 . . ? N1 C5 H5 125.9 . . ? C7 N6 C10 104.6(2) . . ? C7 N6 Zn 125.50(19) . . ? C10 N6 Zn 128.5(2) . . ? N8 C7 N6 113.2(2) 4_455 . ? N8 C7 H7 123.4 4_455 . ? N6 C7 H7 123.4 . . ? C7 N8 C9 105.4(2) 12_454 12_454 ? C7 N8 Zn 125.58(19) 12_454 . ? C9 N8 Zn 128.9(2) 12_454 . ? C10 C9 N8 107.6(3) . 4_455 ? C10 C9 H9 126.2 . . ? N8 C9 H9 126.2 4_455 . ? C9 C10 N6 109.2(3) . . ? C9 C10 H10 125.4 . . ? N6 C10 H10 125.4 . . ? C12 N11 C12 116.9(7) . 2_565 ? N11 C12 C13 123.7(6) . . ? N11 C12 H12 118.2 . . ? C13 C12 H12 118.2 . . ? C14 C13 C12 118.7(6) . . ? C14 C13 H13 120.7 . . ? C12 C13 H13 120.7 . . ? C13 C14 C13 118.4(7) . 2_565 ? C13 C14 H14 120.8 . . ? C13 C14 H14 120.8 2_565 . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 65.40 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.373 _refine_diff_density_min -0.235 _refine_diff_density_rms 0.061