# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2010 data_global _journal_coden_Cambridge 222 loop_ _publ_author_name 'Nishikiori, Shinichi' 'Dan, Hiroki' 'Yamamuro, Osamu' _publ_contact_author_name 'Nishikiori, Shin-ichi' _publ_contact_author_email cnskor@mail.ecc.u-tokyo.ac.jp _publ_section_title ; Tridymite-like host clathrate [K(H2O)n][CuZn(CN)4]:crystal structure, guest molecular motion and properties ; # Attachment 'KCuZnCN.cif' data_KCuZnCN _database_code_depnum_ccdc_archive 'CCDC 798630' #TrackingRef 'KCuZnCN.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_structural '(K (H2 O)11.2) (Cu Zn (C N)4)' _chemical_formula_sum 'C4 H22.4 Cu K N4 O11.2 Zn' _chemical_formula_weight 473.88 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cu Cu 0.3201 1.2651 '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' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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' _symmetry_cell_setting hexagonal _symmetry_space_group_name_H-M 'P 63 m c' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z+1/2' 'x-y, x, z+1/2' '-x+y, -x, z' '-y, x-y, z' 'y, -x+y, z+1/2' '-y, -x, z' 'y, x, z+1/2' '-x, -x+y, z+1/2' 'x-y, -y, z+1/2' 'x, x-y, z' '-x+y, y, z' _cell_length_a 8.2737(8) _cell_length_b 8.2737(8) _cell_length_c 13.4002(13) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 794.40(13) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 6691 _cell_measurement_theta_min 3.04 _cell_measurement_theta_max 31.92 _exptl_crystal_description 'hexagonal prism' _exptl_crystal_colour colorless _exptl_crystal_size_max 0.39 _exptl_crystal_size_mid 0.35 _exptl_crystal_size_min 0.34 _exptl_crystal_density_meas 1.98 _exptl_crystal_density_diffrn 1.98 _exptl_crystal_density_method 'floatation in CHBr3-ethylbenzene mixture' _exptl_crystal_F_000 484 _exptl_absorpt_coefficient_mu 3.17 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.2437 _exptl_absorpt_correction_T_max 0.3403 _exptl_absorpt_process_details ; HIGASHI, T. (1995). Abscor - Empirical Absorption Correction based on Fourier Series Approximation. Rigaku Corporation, Tokyo, Japan. ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.710747 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Rigaku RAXIS-RAPID imaging-plate' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 10.0 _diffrn_reflns_number 17662 _diffrn_reflns_av_R_equivalents 0.0414 _diffrn_reflns_av_sigmaI/netI 0.0158 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -6 _diffrn_reflns_limit_k_max 6 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 3.04 _diffrn_reflns_theta_max 31.92 _reflns_number_total 1068 _reflns_number_gt 645 _reflns_threshold_expression >2\s(I) _computing_data_collection 'PROCESS-AUTO (Rigaku, 1998)' _computing_cell_refinement 'PROCESS-AUTO (Rigaku, 1998)' _computing_data_reduction 'PROCESS-AUTO (Rigaku, 1998)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep3 for Windows (Farrugia, 1997)' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997), PLATON (Spek, 2003)' _refine_special_details ; This clathrate [K(H2O)n][CuZn(CN)4] is comprised of a 3D metal complex framework host[CnZn(CN)4]- and water molecules together with K+ as guests. Solid-state NMR revealed that the water molecules are in a dynamic disordered state. The inside of the host is supposed to be a kind of K+ aqueous solution at room temperature. Therefore, the positions of the guest species could not bedetermined from a D map and refinement including the guest species was impossible. In this analysis, the SQUEEZE procedure, which is implemented in the PLATON program, was used for therefinement of the host part, and the disordered guest part was untouched. (P. v.d. Sluis, A. L. Spek,Acta Cryst. A46, (1990), 194-201) The content of the water molecules (n) varies between 1.2 and11.2 depending on conditions where the clathrate is placed. In the case of a fresh single crystal, the n value was the maximum value of 11.2. Based on n = 11.2, values of various data were calculated and they fill in this CIF. On the other hand, CheckCIF estimates the values based on only the host part which was included in the refinement. This causes large discrepancy between the values in CIF and those CheckCIF estimated, and CheckCIF reported many ALERTs. Such ALERTs have no meaning. Measurement of diffraction data at low temperaturewas filed due to a phase transition at 240K. 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^)+(0.0938P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary heavy _atom_sites_solution_secondary difmap _refine_ls_hydrogen_treatment noref _refine_ls_extinction_method none _refine_ls_abs_structure_details 'Flack (1983), 501 Freidel pairs' _refine_ls_abs_structure_Flack 0.33(11) _refine_ls_number_reflns 1068 _refine_ls_number_parameters 25 _refine_ls_number_restraints 1 _refine_ls_R_factor_gt 0.049 _refine_ls_wR_factor_ref 0.151 _refine_ls_goodness_of_fit_ref 1.044 _refine_ls_shift/su_max 0.005 _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 Zn Zn 0.3333 0.6667 0.79652(6) 0.0813(6) Uani 1 6 d S . . Cu Cu 0.3333 0.6667 0.41879(5) 0.0785(6) Uani 1 6 d S . . C1 C 0.3333 0.6667 0.5609(15) 0.082(5) Uani 1 6 d S . . N1 N 0.3333 0.6667 0.6436(12) 0.097(6) Uani 1 6 d S . . C2 C 0.4559(5) 0.5441(5) 0.3710(10) 0.094(2) Uani 1 2 d S . . N2 N 0.4664(3) 0.5336(3) 0.8434(9) 0.094(2) Uani 1 2 d S . . 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 0.0819(8) 0.0819(8) 0.0802(13) 0.000 0.000 0.0410(4) Cu 0.0847(8) 0.0847(8) 0.0660(9) 0.000 0.000 0.0423(4) C1 0.086(7) 0.086(7) 0.075(7) 0.000 0.000 0.043(3) N1 0.118(9) 0.118(9) 0.056(5) 0.000 0.000 0.059(4) C2 0.098(3) 0.098(3) 0.086(5) 0.0043(15) -0.0043(15) 0.047(4) N2 0.098(2) 0.098(2) 0.103(6) 0.0093(12) -0.0093(12) 0.061(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 N2 2.008(5) 5_665 ? Zn N2 2.008(5) 4_565 ? Zn N2 2.008(5) . ? Zn N1 2.049(16) . ? Cu C2 1.870(6) 4_565 ? Cu C2 1.870(6) 5_665 ? Cu C2 1.870(6) . ? Cu C1 1.90(2) . ? C1 N1 1.11(3) . ? C2 N2 1.173(7) 2_664 ? 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 N2 Zn N2 110.7(2) 5_665 4_565 ? N2 Zn N2 110.7(2) 5_665 . ? N2 Zn N2 110.7(2) 4_565 . ? N2 Zn N1 108.2(3) 5_665 . ? N2 Zn N1 108.2(3) 4_565 . ? N2 Zn N1 108.2(3) . . ? C2 Cu C2 108.9(3) 4_565 5_665 ? C2 Cu C2 108.9(3) 4_565 . ? C2 Cu C2 108.9(3) 5_665 . ? C2 Cu C1 110.0(4) 4_565 . ? C2 Cu C1 110.0(4) 5_665 . ? C2 Cu C1 110.0(4) . . ? N1 C1 Cu 180.00(6) . . ? C1 N1 Zn 180.00(6) . . ? N2 C2 Cu 178.3(12) 2_664 . ? C2 N2 Zn 179.9(11) 2_665 . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 31.92 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.295 _refine_diff_density_min -0.566 _refine_diff_density_rms 0.076 # SQUEEZE RESULTS (APPEND TO CIF) # Note: Data are Listed for all Voids in the P1 Unit Cell # i.e. Centre of Gravity, Solvent Accessible Volume, # Recovered number of Electrons in the Void and # Details about the Squeezed Material _platon_squeeze_void_nr 1 _platon_squeeze_void_average_x -0.014 _platon_squeeze_void_average_y -0.010 _platon_squeeze_void_average_z -0.059 _platon_squeeze_void_volume 517 _platon_squeeze_void_count_electrons 101 _platon_squeeze_void_content 'K+ ions and water molecules' _platon_squeeze_details ; ;