# Supplementary Material (ESI) for Journal of Materials Chemistry # This journal is © The Royal Society of Chemistry 2001 # CCDC Number: 1145/246 data_global _publ_contact_author_email reisner@jazz.ncnr.nist.gov _publ_contact_author_fax 301-921-9847 _publ_contact_author_phone 301-975-4570 # AUTHORS LIST loop_ _publ_author_name _publ_author_address 'Reisner, Barbara. A.' ; NIST Center for Neutron Research 100 Bureau Drive Gaithersburg, MD 20899-8562 Dept. of Geosciences SUNY, Stony Brook NY 11794-2100 USA ; 'Tripathi, Akhilesh' ; Dept. of Chemistry SUNY, Stony Brook NY 11794-3400 USA ; 'Parise, John. B.' ; Dept. of Chemistry & Dept. of Geosciences SUNY, Stony Brook NY 11794-2100 USA ; _publ_requested_journal ; Journal of Materials Chemistry ; _publ_section_title ;Na~8[Zn~4~Ge~8~O~18~(OH)~12~].2H~2~O: An Interrupted-Framework Zincogermanate Built from [GeO~3~(OH)] and [Ge~2~(OH)~2~] Units ; data_absj30 _computing_data_collection 'SMART (Bruker )' _computing_cell_refinement 'SAINT (Bruker )' _computing_data_reduction 'SAINT and SADABS (Sheldrick, 1996)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXTL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common sodium zinc germanate hydroxide hydrate _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'H4 Ge2 Na2 O8 Zn' _chemical_formula_weight 388.62 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'O' 'O' 0.0106 0.0060 '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' 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Na' 'Na' 0.0362 0.0249 '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' 'Ge' 'Ge' 0.1547 1.8001 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M Pbcn loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y+1/2, z+1/2' '-x, y, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y-1/2, -z-1/2' 'x, -y, z-1/2' '-x-1/2, y-1/2, z' _cell_length_a 13.036(3) _cell_length_b 8.7286(17) _cell_length_c 12.938(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1472.2(5) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 9377 _cell_measurement_theta_min 3.13 _cell_measurement_theta_max 28.25 _exptl_crystal_description tabular _exptl_crystal_colour colorless _exptl_crystal_size_max '0.2 mm' _exptl_crystal_size_mid '0.1 mm' _exptl_crystal_size_min '0.02 mm' _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 3.506 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1472 _exptl_absorpt_coefficient_mu 11.474 _exptl_absorpt_correction_type 'multi-scan' __exptl_absorpt_correction_T_min 0.442433 _exptl_absorpt_correction_T_max .9999 _exptl_absorpt_process_details '(SADABS; Sheldrick, 1996)' _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 'SMART 1K CCD' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean 0.75 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 9377 _diffrn_reflns_av_R_equivalents 0.0602 _diffrn_reflns_av_sigmaI/netI 0.0364 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 3.13 _diffrn_reflns_theta_max 28.25 _reflns_number_total 1712 _reflns_number_gt 1125 _reflns_threshold_expression I>2\s(I) _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^)+(0.0766P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens refined _refine_ls_hydrogen_treatment refined _refine_ls_extinction_method 'SHELXTL (Bruker, 1997)' _refine_ls_extinction_coef 0.0001(2) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 1712 _refine_ls_number_parameters 138 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0595 _refine_ls_R_factor_gt 0.0434 _refine_ls_wR_factor_ref 0.1293 _refine_ls_wR_factor_gt 0.1206 _refine_ls_goodness_of_fit_ref 1.060 _refine_ls_restrained_S_all 1.060 _refine_ls_shift/su_max 0.193 _refine_ls_shift/su_mean 0.018 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 Ge1 Ge 0.37758(4) 0.12596(6) 0.50092(4) 0.0094(2) Uani 1 1 d . . . Ge2 Ge 0.12044(4) -0.11787(5) 0.25133(4) 0.0088(2) Uani 1 1 d . . . Zn1 Zn 0.25098(5) 0.12444(6) 0.12689(4) 0.0098(2) Uani 1 1 d . . . Na1 Na 0.1491(2) 0.2569(2) 0.37489(18) 0.0162(5) Uani 1 1 d . . . Na2 Na 0.0000 0.0000 0.5000 0.0200(9) Uani 1 2 d S . . Na3 Na 0.0000 0.5104(4) 0.2500 0.0191(8) Uani 1 2 d S . . O1 O 0.1312(3) -0.0203(5) 0.3729(3) 0.0131(9) Uani 1 1 d . . . O2 O 0.3690(3) 0.0298(5) 0.3792(3) 0.0134(9) Uani 1 1 d . . . O3 O 0.4992(3) 0.2199(5) 0.5006(3) 0.0147(9) Uani 1 1 d . . . O4 O 0.1213(3) 0.0188(4) 0.1555(3) 0.0120(9) Uani 1 1 d . . . O5 O 0.0000 -0.2119(6) 0.2500 0.0130(12) Uani 1 2 d S . . O6 O 0.3764(4) -0.0094(4) 0.5977(3) 0.0134(9) Uani 1 1 d . . . O7 O 0.2830(3) 0.2647(4) 0.5010(3) 0.0118(8) Uani 1 1 d . . . O8 O 0.2857(3) 0.2422(4) 0.2502(3) 0.0112(8) Uani 1 1 d . . . O9 O 0.0000 0.2392(7) 0.2500 0.0172(13) Uani 1 2 d S . . H(1) H 0.167(7) -0.086(8) 0.420(6) 0.04(2) Uiso 1 1 d . . . H(2) H 0.329(7) 0.091(8) 0.336(7) 0.04(3) Uiso 1 1 d . . . H(3) H 0.542(6) 0.143(7) 0.462(6) 0.03(2) Uiso 1 1 d . . . H(9) H 0.044(7) 0.133(7) 0.218(7) 0.05(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 Ge1 0.0106(4) 0.0068(3) 0.0108(4) 0.00006(19) 0.0001(2) -0.0001(2) Ge2 0.0092(4) 0.0064(3) 0.0107(3) 0.0001(2) 0.0002(2) 0.0002(2) Zn1 0.0105(4) 0.0090(4) 0.0098(4) 0.0000(3) 0.0000(2) -0.0001(2) Na1 0.0165(12) 0.0131(12) 0.0191(12) -0.0016(9) -0.0011(10) -0.0003(10) Na2 0.022(2) 0.0164(18) 0.021(2) -0.0003(12) 0.0052(18) 0.0026(15) Na3 0.022(2) 0.0135(17) 0.0222(19) 0.000 -0.0088(18) 0.000 O1 0.015(2) 0.0093(18) 0.015(2) -0.0012(16) -0.001(2) -0.0026(17) O2 0.016(2) 0.0115(19) 0.013(2) -0.0004(16) 0.000(2) -0.0011(18) O3 0.011(2) 0.014(2) 0.018(2) -0.0010(14) 0.000(2) -0.0019(17) O4 0.008(2) 0.0114(18) 0.017(2) 0.0052(16) -0.0013(18) -0.0031(17) O5 0.006(3) 0.011(3) 0.022(3) 0.000 0.002(3) 0.000 O6 0.012(2) 0.0109(18) 0.018(2) 0.0049(16) -0.0009(19) -0.0010(16) O7 0.014(2) 0.0099(19) 0.0113(18) -0.0010(15) -0.0006(17) 0.0054(18) O8 0.011(2) 0.0082(18) 0.0142(17) -0.0007(17) -0.0007(17) -0.0041(16) O9 0.016(3) 0.014(3) 0.021(3) 0.000 0.002(3) 0.000 _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 Ge1 O6 1.722(4) . ? Ge1 O7 1.728(4) . ? Ge1 O3 1.785(4) . ? Ge1 O2 1.788(4) . ? Ge2 O4 1.721(4) . ? Ge2 O8 1.728(3) 8_655 ? Ge2 O5 1.772(3) . ? Ge2 O1 1.795(4) . ? Zn1 O7 1.946(4) 2_554 ? Zn1 O8 1.951(4) . ? Zn1 O6 1.955(4) 7 ? Zn1 O4 1.960(4) . ? Na1 O7 2.390(5) . ? Na1 O2 2.395(5) 8_665 ? Na1 O8 2.407(5) . ? Na1 O1 2.430(5) . ? Na1 O9 2.533(3) . ? Na1 O3 2.541(5) 4_456 ? Na2 O1 2.379(4) 5_556 ? Na2 O1 2.379(4) . ? Na2 O3 2.445(5) 8_655 ? Na2 O3 2.445(5) 4_456 ? Na2 O4 2.565(4) 3 ? Na2 O4 2.565(4) 7_556 ? Na3 O9 2.367(8) . ? Na3 O2 2.396(4) 8_665 ? Na3 O2 2.396(4) 6_566 ? Na3 O5 2.424(6) 1_565 ? Na3 O6 2.545(4) 4_456 ? Na3 O6 2.545(4) 2_554 ? O1 H(1) 0.96(8) . ? O2 H(2) 0.93(9) . ? O3 H(3) 1.01(8) . ? O9 H(9) 1.17(7) . ? 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 O6 Ge1 O7 118.3(2) . . ? O6 Ge1 O3 109.0(2) . . ? O7 Ge1 O3 108.1(2) . . ? O6 Ge1 O2 108.55(19) . . ? O7 Ge1 O2 106.54(19) . . ? O3 Ge1 O2 105.62(19) . . ? O7 Zn1 O8 118.37(16) 2_554 . ? O7 Zn1 O6 106.53(15) 2_554 7 ? O8 Zn1 O6 103.54(16) . 7 ? O7 Zn1 O4 101.28(16) 2_554 . ? O8 Zn1 O4 107.07(15) . . ? O6 Zn1 O4 121.05(16) 7 . ? O4 Ge2 O8 118.62(19) . 8_655 ? O4 Ge2 O5 108.68(18) . . ? O8 Ge2 O5 107.4(2) 8_655 . ? O4 Ge2 O1 107.57(19) . . ? O8 Ge2 O1 106.73(19) 8_655 . ? O5 Ge2 O1 107.30(16) . . ? O7 Na1 O2 91.60(15) . 8_665 ? O7 Na1 O8 85.33(15) . . ? O2 Na1 O8 98.13(16) 8_665 . ? O7 Na1 O1 96.08(16) . . ? O2 Na1 O1 168.78(17) 8_665 . ? O8 Na1 O1 90.66(15) . . ? O7 Na1 O9 176.20(16) . . ? O2 Na1 O9 89.98(19) 8_665 . ? O8 Na1 O9 97.88(12) . . ? O1 Na1 O9 81.88(19) . . ? O7 Na1 O3 97.29(15) . 4_456 ? O2 Na1 O3 80.21(16) 8_665 4_456 ? O8 Na1 O3 176.92(17) . 4_456 ? O1 Na1 O3 90.68(16) . 4_456 ? O9 Na1 O3 79.56(12) . 4_456 ? O1 Na2 O1 180.0 5_556 . ? O1 Na2 O3 94.32(14) 5_556 8_655 ? O1 Na2 O3 85.68(14) . 8_655 ? O1 Na2 O3 85.68(14) 5_556 4_456 ? O1 Na2 O3 94.32(14) . 4_456 ? O3 Na2 O3 180.0 8_655 4_456 ? O1 Na2 O4 95.40(13) 5_556 3 ? O1 Na2 O4 84.60(13) . 3 ? O3 Na2 O4 93.97(13) 8_655 3 ? O3 Na2 O4 86.03(13) 4_456 3 ? O1 Na2 O4 84.60(13) 5_556 7_556 ? O1 Na2 O4 95.40(13) . 7_556 ? O3 Na2 O4 86.03(13) 8_655 7_556 ? O3 Na2 O4 93.97(13) 4_456 7_556 ? O4 Na2 O4 180.00(10) 3 7_556 ? O9 Na3 O2 94.05(12) . 8_665 ? O9 Na3 O2 94.05(13) . 6_566 ? O2 Na3 O2 171.9(3) 8_665 6_566 ? O9 Na3 O5 180.000(1) . 1_565 ? O2 Na3 O5 85.95(12) 8_665 1_565 ? O2 Na3 O5 85.95(13) 6_566 1_565 ? O9 Na3 O6 89.80(11) . 4_456 ? O2 Na3 O6 84.92(13) 8_665 4_456 ? O2 Na3 O6 95.11(13) 6_566 4_456 ? O5 Na3 O6 90.20(11) 1_565 4_456 ? O9 Na3 O6 89.80(11) . 2_554 ? O2 Na3 O6 95.11(13) 8_665 2_554 ? O2 Na3 O6 84.92(13) 6_566 2_554 ? O5 Na3 O6 90.20(11) 1_565 2_554 ? O6 Na3 O6 179.6(2) 4_456 2_554 ? Ge2 O1 Na2 125.8(2) . . ? Ge2 O1 Na1 119.3(2) . . ? Na2 O1 Na1 89.31(15) . . ? Ge2 O1 H(1) 108(5) . . ? Na2 O1 H(1) 87(5) . . ? Na1 O1 H(1) 123(4) . . ? Ge1 O2 Na3 127.1(2) . 6_656 ? Ge1 O2 Na1 119.6(2) . 8_655 ? Na3 O2 Na1 89.07(17) 6_656 8_655 ? Ge1 O2 H(2) 108(5) . . ? Na3 O2 H(2) 91(6) 6_656 . ? Na1 O2 H(2) 120(5) 8_655 . ? Ge2 O4 Zn1 117.9(2) . . ? Ge2 O4 Na2 121.1(2) . 3 ? Zn1 O4 Na2 114.43(16) . 3 ? Ge1 O3 Na2 117.6(2) . 4_556 ? Ge1 O3 Na1 135.9(2) . 4_556 ? Na2 O3 Na1 85.35(14) 4_556 4_556 ? Ge1 O3 H(3) 101(4) . . ? Na2 O3 H(3) 132(4) 4_556 . ? Na1 O3 H(3) 87(4) 4_556 . ? Ge2 O5 Ge2 124.8(3) . 3 ? Ge2 O5 Na3 117.60(16) . 1_545 ? Ge2 O5 Na3 117.60(16) 3 1_545 ? Ge1 O6 Zn1 120.0(2) . 7_556 ? Ge1 O6 Na3 124.0(2) . 2 ? Zn1 O6 Na3 112.23(17) 7_556 2 ? Ge1 O7 Zn1 120.8(2) . 2 ? Ge1 O7 Na1 120.1(2) . . ? Zn1 O7 Na1 114.77(18) 2 . ? Ge2 O8 Zn1 122.9(2) 8_665 . ? Ge2 O8 Na1 118.72(19) 8_665 . ? Zn1 O8 Na1 113.84(17) . . ? Na3 O9 Na1 86.51(15) . 3 ? Na3 O9 Na1 86.51(15) . . ? Na1 O9 Na1 173.0(3) 3 . ? Na3 O9 H(9) 143(4) . . ? Na1 O9 H(9) 101(5) 3 . ? Na1 O9 H(9) 84(5) . . ? _diffrn_measured_fraction_theta_max 0.938 _diffrn_reflns_theta_full 28.25 _diffrn_measured_fraction_theta_full 0.938 _refine_diff_density_max 3.345 _refine_diff_density_min -1.731 _refine_diff_density_rms 0.318