Supplementary material (ESI) for Dalton Trans. This journal is (c) The Royal Society of Chemistry 2008 data_global _journal_name_full 'Dalton Trans.' _journal_coden_cambridge 0222 _journal_year ? _journal_volume ? _journal_page_first ? loop_ _publ_author_name A.Schnepf I.Krossing G.Santiso-Quinones C.Schenk _publ_contact_author_name 'Andreas Schnepf' _publ_contact_author_email SCHNEPF@CHEMIE.UNI-KARLSRUHE.DE data_cs68p-3 _database_code_depnum_ccdc_archive 'CCDC 665707' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C78 H210 Ag Ge18 Li O6 Si24' _chemical_formula_weight 3340.05 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' Li Li -0.0003 0.0001 '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' Si Si 0.0817 0.0704 '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' Ag Ag -0.8971 1.1015 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting rhombohedral _symmetry_space_group_name_H-M R-3 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'z, x, y' 'y, z, x' '-x, -y, -z' '-z, -x, -y' '-y, -z, -x' _cell_length_a 15.6343(18) _cell_length_b 15.6343(18) _cell_length_c 15.6343(18) _cell_angle_alpha 97.049(17) _cell_angle_beta 97.049(17) _cell_angle_gamma 97.049(17) _cell_volume 3727.0(7) _cell_formula_units_Z 1 _cell_measurement_temperature 149(2) _cell_measurement_reflns_used 18451 _cell_measurement_theta_min 1.705 _cell_measurement_theta_max 25.955 _exptl_crystal_description fragment _exptl_crystal_colour orange-red _exptl_crystal_size_max 0.3 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.2 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.488 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1688 _exptl_absorpt_coefficient_mu 3.925 _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_T_min 0.4022 _exptl_absorpt_correction_T_max 0.4943 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 149(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 ? _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 13286 _diffrn_reflns_av_R_equivalents 0.0513 _diffrn_reflns_av_sigmaI/netI 0.0453 _diffrn_reflns_limit_h_min -19 _diffrn_reflns_limit_h_max 19 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 2.00 _diffrn_reflns_theta_max 25.94 _reflns_number_total 4833 _reflns_number_gt 3990 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0420P)^2^+2.8876P] 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 4833 _refine_ls_number_parameters 195 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0461 _refine_ls_R_factor_gt 0.0348 _refine_ls_wR_factor_ref 0.0882 _refine_ls_wR_factor_gt 0.0838 _refine_ls_goodness_of_fit_ref 1.038 _refine_ls_restrained_S_all 1.038 _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 Ag1 Ag 0.5000 0.5000 0.5000 0.03367(15) Uani 1 6 d S . . Ge1 Ge 0.30882(3) 0.43613(3) 0.26417(3) 0.03642(11) Uani 1 1 d . . . Ge2 Ge 0.32698(2) 0.46254(2) 0.42753(2) 0.03087(10) Uani 1 1 d . . . Ge3 Ge 0.19038(2) 0.31609(3) 0.28333(3) 0.03456(11) Uani 1 1 d . . . Si1 Si 0.26436(7) 0.54330(6) 0.18036(6) 0.0321(2) Uani 1 1 d . . . Si2 Si 0.23213(8) 0.47924(7) 0.03436(7) 0.0409(3) Uani 1 1 d . . . Si3 Si 0.37963(8) 0.65810(7) 0.20031(8) 0.0459(3) Uani 1 1 d . . . Si4 Si 0.13891(8) 0.58786(9) 0.23136(9) 0.0505(3) Uani 1 1 d . . . C2C C 0.1929(4) 0.5618(3) -0.0336(3) 0.0712(16) Uani 1 1 d . . . H2CA H 0.1793 0.5354 -0.0948 0.107 Uiso 1 1 calc R . . H2CB H 0.2385 0.6119 -0.0280 0.107 Uiso 1 1 calc R . . H2CC H 0.1406 0.5810 -0.0135 0.107 Uiso 1 1 calc R . . C2B C 0.1419(3) 0.3869(3) 0.0216(3) 0.0604(13) Uani 1 1 d . . . H2BA H 0.1290 0.3607 -0.0396 0.091 Uiso 1 1 calc R . . H2BB H 0.0898 0.4084 0.0403 0.091 Uiso 1 1 calc R . . H2BC H 0.1593 0.3431 0.0575 0.091 Uiso 1 1 calc R . . C2A C 0.3296(4) 0.4386(4) -0.0068(3) 0.0659(14) Uani 1 1 d . . . H2AA H 0.3140 0.4123 -0.0678 0.099 Uiso 1 1 calc R . . H2AB H 0.3493 0.3950 0.0281 0.099 Uiso 1 1 calc R . . H2AC H 0.3765 0.4873 -0.0023 0.099 Uiso 1 1 calc R . . C3C C 0.4746(3) 0.6235(4) 0.1503(5) 0.0789(17) Uani 1 1 d . . . H3CA H 0.5219 0.6724 0.1594 0.118 Uiso 1 1 calc R . . H3CB H 0.4572 0.6050 0.0877 0.118 Uiso 1 1 calc R . . H3CC H 0.4946 0.5749 0.1775 0.118 Uiso 1 1 calc R . . C3B C 0.4138(5) 0.6948(4) 0.3179(4) 0.098(3) Uani 1 1 d . . . H3BA H 0.4620 0.7427 0.3259 0.148 Uiso 1 1 calc R . . H3BB H 0.4329 0.6463 0.3460 0.148 Uiso 1 1 calc R . . H3BC H 0.3647 0.7147 0.3442 0.148 Uiso 1 1 calc R . . C3A C 0.3449(4) 0.7513(3) 0.1467(4) 0.0685(15) Uani 1 1 d . . . H3AA H 0.3935 0.7989 0.1554 0.103 Uiso 1 1 calc R . . H3AB H 0.2957 0.7716 0.1724 0.103 Uiso 1 1 calc R . . H3AC H 0.3274 0.7322 0.0843 0.103 Uiso 1 1 calc R . . C4B C 0.1632(7) 0.6261(11) 0.3479(5) 0.234(9) Uani 1 1 d . . . H4BA H 0.1110 0.6447 0.3692 0.352 Uiso 1 1 calc R . . H4BB H 0.2102 0.6754 0.3585 0.352 Uiso 1 1 calc R . . H4BC H 0.1813 0.5789 0.3785 0.352 Uiso 1 1 calc R . . C4C C 0.1013(4) 0.6753(5) 0.1730(6) 0.112(3) Uani 1 1 d . . . H4CA H 0.0491 0.6930 0.1951 0.168 Uiso 1 1 calc R . . H4CB H 0.0875 0.6540 0.1106 0.168 Uiso 1 1 calc R . . H4CC H 0.1473 0.7254 0.1824 0.168 Uiso 1 1 calc R . . C4A C 0.0464(4) 0.4980(5) 0.2112(7) 0.129(4) Uani 1 1 d . . . H4AA H -0.0044 0.5189 0.2332 0.193 Uiso 1 1 calc R . . H4AB H 0.0625 0.4496 0.2413 0.193 Uiso 1 1 calc R . . H4AC H 0.0324 0.4781 0.1486 0.193 Uiso 1 1 calc R . . O100 O -0.0322(2) 0.1197(2) 0.0649(2) 0.0508(7) Uani 1 1 d . . . C100 C -0.0796(4) 0.1836(3) 0.0304(3) 0.0614(12) Uani 1 1 d . . . H10A H -0.1418 0.1596 0.0130 0.074 Uiso 1 1 calc R . . H10B H -0.0556 0.2022 -0.0212 0.074 Uiso 1 1 calc R . . C101 C -0.0697(5) 0.2585(4) 0.1016(4) 0.0801(17) Uani 1 1 d . . . H10C H -0.0186 0.3014 0.0981 0.096 Uiso 1 1 calc R . . H10D H -0.1223 0.2880 0.0987 0.096 Uiso 1 1 calc R . . C102 C -0.0576(4) 0.2181(4) 0.1820(4) 0.0657(14) Uani 1 1 d . . . H10E H -0.1142 0.1951 0.1985 0.079 Uiso 1 1 calc R . . H10F H -0.0247 0.2602 0.2310 0.079 Uiso 1 1 calc R . . C103 C -0.0066(3) 0.1459(3) 0.1568(3) 0.0617(13) Uani 1 1 d . . . H10G H 0.0567 0.1667 0.1695 0.074 Uiso 1 1 calc R . . H10H H -0.0201 0.0965 0.1892 0.074 Uiso 1 1 calc R . . Li1 Li 0.0000 0.0000 0.0000 0.050(4) Uani 1 6 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 Ag1 0.03274(15) 0.03274(15) 0.03274(15) 0.00093(15) 0.00093(15) 0.00093(15) Ge1 0.0394(2) 0.0340(2) 0.0358(2) 0.00897(16) 0.00109(16) 0.00507(16) Ge2 0.03200(19) 0.02966(19) 0.03127(19) 0.00319(14) 0.00518(15) 0.00589(14) Ge3 0.02719(19) 0.0390(2) 0.0380(2) 0.00917(16) 0.00320(15) 0.00434(15) Si1 0.0344(5) 0.0310(5) 0.0317(5) 0.0075(4) 0.0026(4) 0.0068(4) Si2 0.0490(6) 0.0414(6) 0.0314(5) 0.0078(4) 0.0008(5) 0.0044(5) Si3 0.0498(6) 0.0365(6) 0.0479(6) 0.0126(5) -0.0040(5) -0.0038(5) Si4 0.0505(7) 0.0560(7) 0.0535(7) 0.0130(6) 0.0140(5) 0.0281(6) C2C 0.104(4) 0.059(3) 0.049(3) 0.018(2) -0.009(3) 0.014(3) C2B 0.067(3) 0.054(3) 0.053(3) 0.003(2) -0.001(2) -0.006(2) C2A 0.073(3) 0.079(4) 0.046(3) 0.000(2) 0.018(2) 0.010(3) C3C 0.043(3) 0.078(4) 0.117(5) 0.026(3) 0.012(3) 0.000(3) C3B 0.123(6) 0.084(4) 0.064(4) 0.008(3) -0.021(4) -0.046(4) C3A 0.074(3) 0.041(2) 0.092(4) 0.028(3) 0.004(3) 0.001(2) C4B 0.169(9) 0.47(2) 0.070(5) -0.078(9) -0.016(5) 0.226(13) C4C 0.074(4) 0.093(5) 0.207(9) 0.087(5) 0.062(5) 0.056(4) C4A 0.072(4) 0.073(4) 0.265(12) 0.034(6) 0.089(6) 0.026(3) O100 0.0565(18) 0.0487(17) 0.0461(16) 0.0046(13) 0.0005(14) 0.0124(14) C100 0.065(3) 0.060(3) 0.063(3) 0.017(2) 0.009(2) 0.017(2) C101 0.099(5) 0.053(3) 0.089(4) 0.008(3) 0.016(4) 0.016(3) C102 0.061(3) 0.067(3) 0.065(3) -0.008(3) 0.007(2) 0.013(2) C103 0.064(3) 0.064(3) 0.052(3) -0.007(2) -0.001(2) 0.011(2) Li1 0.048(4) 0.048(4) 0.048(4) 0.002(5) 0.002(5) 0.002(5) _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 Ag1 Ge2 2.7641(8) 6_666 ? Ag1 Ge2 2.7641(7) 2 ? Ag1 Ge2 2.7641(7) 4_666 ? Ag1 Ge2 2.7641(7) . ? Ag1 Ge2 2.7641(7) 5_666 ? Ag1 Ge2 2.7641(7) 3 ? Ge1 Si1 2.3684(11) . ? Ge1 Ge2 2.5080(6) 3 ? Ge1 Ge2 2.5116(7) . ? Ge1 Ge3 2.5421(7) . ? Ge1 Ge3 2.5442(7) 3 ? Ge2 Ge1 2.5080(6) 2 ? Ge2 Ge2 2.8554(8) 3 ? Ge2 Ge2 2.8554(8) 2 ? Ge3 Ge1 2.5442(7) 2 ? Ge3 Ge3 2.6462(8) 3 ? Ge3 Ge3 2.6462(8) 2 ? Si1 Si3 2.3445(16) . ? Si1 Si2 2.3452(15) . ? Si1 Si4 2.3561(16) . ? Si2 C2B 1.865(5) . ? Si2 C2A 1.876(6) . ? Si2 C2C 1.882(5) . ? Si3 C3B 1.849(6) . ? Si3 C3C 1.867(6) . ? Si3 C3A 1.871(5) . ? Si4 C4B 1.824(7) . ? Si4 C4C 1.850(6) . ? Si4 C4A 1.855(7) . ? O100 C100 1.434(6) . ? O100 C103 1.437(6) . ? O100 Li1 2.162(3) . ? C100 C101 1.493(8) . ? C101 C102 1.478(8) . ? C102 C103 1.503(7) . ? Li1 O100 2.162(3) 4 ? Li1 O100 2.162(3) 3 ? Li1 O100 2.162(3) 5 ? Li1 O100 2.162(3) 2 ? Li1 O100 2.162(3) 6 ? 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 Ge2 Ag1 Ge2 117.80(3) 6_666 2 ? Ge2 Ag1 Ge2 62.20(3) 6_666 4_666 ? Ge2 Ag1 Ge2 117.80(3) 2 4_666 ? Ge2 Ag1 Ge2 117.80(3) 6_666 . ? Ge2 Ag1 Ge2 62.20(3) 2 . ? Ge2 Ag1 Ge2 180.000(7) 4_666 . ? Ge2 Ag1 Ge2 62.20(3) 6_666 5_666 ? Ge2 Ag1 Ge2 180.0 2 5_666 ? Ge2 Ag1 Ge2 62.20(3) 4_666 5_666 ? Ge2 Ag1 Ge2 117.80(3) . 5_666 ? Ge2 Ag1 Ge2 180.000(1) 6_666 3 ? Ge2 Ag1 Ge2 62.20(3) 2 3 ? Ge2 Ag1 Ge2 117.80(3) 4_666 3 ? Ge2 Ag1 Ge2 62.20(3) . 3 ? Ge2 Ag1 Ge2 117.80(3) 5_666 3 ? Si1 Ge1 Ge2 125.41(3) . 3 ? Si1 Ge1 Ge2 121.08(3) . . ? Ge2 Ge1 Ge2 69.34(3) 3 . ? Si1 Ge1 Ge3 116.27(3) . . ? Ge2 Ge1 Ge3 118.22(3) 3 . ? Ge2 Ge1 Ge3 83.10(3) . . ? Si1 Ge1 Ge3 120.12(3) . 3 ? Ge2 Ge1 Ge3 83.13(3) 3 3 ? Ge2 Ge1 Ge3 118.12(3) . 3 ? Ge3 Ge1 Ge3 62.70(3) . 3 ? Ge1 Ge2 Ge1 92.33(3) 2 . ? Ge1 Ge2 Ag1 112.27(3) 2 . ? Ge1 Ge2 Ag1 112.15(3) . . ? Ge1 Ge2 Ge2 98.812(14) 2 3 ? Ge1 Ge2 Ge2 55.272(18) . 3 ? Ag1 Ge2 Ge2 58.901(13) . 3 ? Ge1 Ge2 Ge2 55.388(18) 2 2 ? Ge1 Ge2 Ge2 98.728(14) . 2 ? Ag1 Ge2 Ge2 58.901(13) . 2 ? Ge2 Ge2 Ge2 60.0 3 2 ? Ge1 Ge3 Ge1 90.77(3) . 2 ? Ge1 Ge3 Ge3 58.690(19) . 3 ? Ge1 Ge3 Ge3 101.018(15) 2 3 ? Ge1 Ge3 Ge3 101.074(15) . 2 ? Ge1 Ge3 Ge3 58.611(18) 2 2 ? Ge3 Ge3 Ge3 60.0 3 2 ? Si3 Si1 Si2 111.55(7) . . ? Si3 Si1 Si4 111.91(6) . . ? Si2 Si1 Si4 110.49(6) . . ? Si3 Si1 Ge1 107.50(5) . . ? Si2 Si1 Ge1 107.97(5) . . ? Si4 Si1 Ge1 107.19(5) . . ? C2B Si2 C2A 109.2(3) . . ? C2B Si2 C2C 107.0(3) . . ? C2A Si2 C2C 109.7(3) . . ? C2B Si2 Si1 110.24(17) . . ? C2A Si2 Si1 111.55(17) . . ? C2C Si2 Si1 109.04(18) . . ? C3B Si3 C3C 109.1(4) . . ? C3B Si3 C3A 109.3(3) . . ? C3C Si3 C3A 107.6(3) . . ? C3B Si3 Si1 109.8(2) . . ? C3C Si3 Si1 110.91(19) . . ? C3A Si3 Si1 110.11(18) . . ? C4B Si4 C4C 110.0(6) . . ? C4B Si4 C4A 109.2(7) . . ? C4C Si4 C4A 105.7(4) . . ? C4B Si4 Si1 109.4(3) . . ? C4C Si4 Si1 110.7(2) . . ? C4A Si4 Si1 111.8(2) . . ? C100 O100 C103 108.9(4) . . ? C100 O100 Li1 129.8(3) . . ? C103 O100 Li1 121.3(3) . . ? O100 C100 C101 106.1(4) . . ? C102 C101 C100 103.9(5) . . ? C101 C102 C103 102.6(5) . . ? O100 C103 C102 106.1(4) . . ? O100 Li1 O100 87.58(11) 4 3 ? O100 Li1 O100 92.42(11) 4 5 ? O100 Li1 O100 87.58(11) 3 5 ? O100 Li1 O100 180.0(2) 4 . ? O100 Li1 O100 92.42(11) 3 . ? O100 Li1 O100 87.58(11) 5 . ? O100 Li1 O100 87.58(11) 4 2 ? O100 Li1 O100 92.42(11) 3 2 ? O100 Li1 O100 180.00(16) 5 2 ? O100 Li1 O100 92.42(11) . 2 ? O100 Li1 O100 92.42(11) 4 6 ? O100 Li1 O100 180.00(17) 3 6 ? O100 Li1 O100 92.42(11) 5 6 ? O100 Li1 O100 87.58(11) . 6 ? O100 Li1 O100 87.58(11) 2 6 ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 25.94 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.498 _refine_diff_density_min -0.936 _refine_diff_density_rms 0.081 # Attachment 'CS75R-3B.CIF' data_cs75r-3b _database_code_depnum_ccdc_archive 'CCDC 665708' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C78 H210 Cu Ge18 Li O6 Si24' _chemical_formula_weight 3295.72 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' Li Li -0.0003 0.0001 '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' Si Si 0.0817 0.0704 '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' Ge Ge 0.1547 1.8001 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting rhombohedral _symmetry_space_group_name_H-M R-3 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'z, x, y' 'y, z, x' '-x, -y, -z' '-z, -x, -y' '-y, -z, -x' _cell_length_a 15.6548(18) _cell_length_b 15.6548(18) _cell_length_c 15.6548(18) _cell_angle_alpha 97.309(17) _cell_angle_beta 97.309(17) _cell_angle_gamma 97.309(17) _cell_volume 3734.2(7) _cell_formula_units_Z 1 _cell_measurement_temperature 149(2) _cell_measurement_reflns_used 10596 _cell_measurement_theta_min 1.285 _cell_measurement_theta_max 23.93 _exptl_crystal_description plate _exptl_crystal_colour orange-red _exptl_crystal_size_max 0.2 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.1 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.466 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1670 _exptl_absorpt_coefficient_mu 3.928 _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_T_min 0.7262 _exptl_absorpt_correction_T_max 0.8191 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 149(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 ? _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 15371 _diffrn_reflns_av_R_equivalents 0.0673 _diffrn_reflns_av_sigmaI/netI 0.0559 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 1.73 _diffrn_reflns_theta_max 24.01 _reflns_number_total 3883 _reflns_number_gt 2733 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0443P)^2^+0.0000P] 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 3883 _refine_ls_number_parameters 194 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0710 _refine_ls_R_factor_gt 0.0403 _refine_ls_wR_factor_ref 0.0869 _refine_ls_wR_factor_gt 0.0782 _refine_ls_goodness_of_fit_ref 0.963 _refine_ls_restrained_S_all 0.963 _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 Ge1 Ge 0.43383(4) 0.46974(4) 0.33470(4) 0.03352(16) Uani 1 1 d . . . Ge2 Ge 0.44181(4) 0.31576(4) 0.26982(4) 0.03530(16) Uani 1 1 d . . . Ge3 Ge 0.32158(4) 0.19631(4) 0.28801(4) 0.03697(17) Uani 1 1 d . . . Cu1 Cu 0.5000 0.5000 0.5000 0.0231(3) Uani 1 6 d S . . Si1 Si 0.54460(9) 0.26780(10) 0.18194(10) 0.0321(3) Uani 1 1 d . . . Si10 Si 0.58657(13) 0.14088(12) 0.23005(12) 0.0507(5) Uani 1 1 d . . . Si11 Si 0.66249(11) 0.37944(12) 0.19895(12) 0.0473(4) Uani 1 1 d . . . Si12 Si 0.47650(11) 0.23688(11) 0.03673(10) 0.0415(4) Uani 1 1 d . . . C10C C 0.4960(6) 0.0487(6) 0.2095(9) 0.130(5) Uani 1 1 d . . . H10A H 0.5166 -0.0024 0.2306 0.195 Uiso 1 1 calc R . . H10B H 0.4752 0.0351 0.1469 0.195 Uiso 1 1 calc R . . H10C H 0.4482 0.0648 0.2401 0.195 Uiso 1 1 calc R . . C10B C 0.6714(7) 0.1018(7) 0.1712(9) 0.142(6) Uani 1 1 d . . . H10D H 0.6876 0.0490 0.1925 0.213 Uiso 1 1 calc R . . H10E H 0.7226 0.1468 0.1809 0.213 Uiso 1 1 calc R . . H10F H 0.6493 0.0886 0.1088 0.213 Uiso 1 1 calc R . . C10A C 0.6259(14) 0.1624(9) 0.3463(7) 0.245(12) Uani 1 1 d . . . H10G H 0.6434 0.1093 0.3659 0.367 Uiso 1 1 calc R . . H10H H 0.5795 0.1807 0.3777 0.367 Uiso 1 1 calc R . . H10I H 0.6761 0.2086 0.3578 0.367 Uiso 1 1 calc R . . C11C C 0.7519(4) 0.3414(5) 0.1417(5) 0.068(2) Uani 1 1 d . . . H11A H 0.8009 0.3886 0.1493 0.102 Uiso 1 1 calc R . . H11B H 0.7303 0.3242 0.0795 0.102 Uiso 1 1 calc R . . H11C H 0.7712 0.2914 0.1663 0.102 Uiso 1 1 calc R . . C11B C 0.6303(6) 0.4751(5) 0.1510(7) 0.094(3) Uani 1 1 d . . . H11D H 0.6807 0.5209 0.1590 0.141 Uiso 1 1 calc R . . H11E H 0.5839 0.4970 0.1801 0.141 Uiso 1 1 calc R . . H11F H 0.6093 0.4579 0.0888 0.141 Uiso 1 1 calc R . . C11A C 0.7051(6) 0.4119(7) 0.3153(6) 0.111(4) Uani 1 1 d . . . H11G H 0.7545 0.4586 0.3220 0.166 Uiso 1 1 calc R . . H11H H 0.7243 0.3617 0.3398 0.166 Uiso 1 1 calc R . . H11I H 0.6592 0.4325 0.3461 0.166 Uiso 1 1 calc R . . C12C C 0.4374(5) 0.3343(5) -0.0028(5) 0.069(2) Uani 1 1 d . . . H12A H 0.4095 0.3188 -0.0635 0.103 Uiso 1 1 calc R . . H12B H 0.4869 0.3804 0.0010 0.103 Uiso 1 1 calc R . . H12C H 0.3953 0.3549 0.0333 0.103 Uiso 1 1 calc R . . C12B C 0.3833(4) 0.1479(5) 0.0240(4) 0.0606(18) Uani 1 1 d . . . H12D H 0.3558 0.1359 -0.0370 0.091 Uiso 1 1 calc R . . H12E H 0.3407 0.1655 0.0610 0.091 Uiso 1 1 calc R . . H12F H 0.4042 0.0953 0.0412 0.091 Uiso 1 1 calc R . . C12A C 0.5568(5) 0.1967(6) -0.0327(5) 0.073(2) Uani 1 1 d . . . H12G H 0.5294 0.1835 -0.0936 0.109 Uiso 1 1 calc R . . H12H H 0.5754 0.1439 -0.0133 0.109 Uiso 1 1 calc R . . H12I H 0.6076 0.2417 -0.0272 0.109 Uiso 1 1 calc R . . O100 O 0.1229(3) -0.0303(3) 0.0611(3) 0.0512(11) Uani 1 1 d . . . C100 C 0.1851(5) -0.0776(5) 0.0236(5) 0.0629(19) Uani 1 1 d . . . H10J H 0.2044 -0.0506 -0.0259 0.075 Uiso 1 1 calc R . . H10K H 0.1586 -0.1386 0.0019 0.075 Uiso 1 1 calc R . . C101 C 0.2600(5) -0.0749(7) 0.0926(6) 0.081(2) Uani 1 1 d . . . H10L H 0.3072 -0.0276 0.0888 0.097 Uiso 1 1 calc R . . H10M H 0.2833 -0.1309 0.0881 0.097 Uiso 1 1 calc R . . C102 C 0.2229(5) -0.0582(5) 0.1752(5) 0.0645(19) Uani 1 1 d . . . H10N H 0.1975 -0.1133 0.1929 0.077 Uiso 1 1 calc R . . H10O H 0.2679 -0.0266 0.2229 0.077 Uiso 1 1 calc R . . C103 C 0.1546(5) -0.0038(5) 0.1528(4) 0.0632(19) Uani 1 1 d . . . H10P H 0.1068 -0.0135 0.1878 0.076 Uiso 1 1 calc R . . H10Q H 0.1792 0.0587 0.1641 0.076 Uiso 1 1 calc R . . Li1 Li 0.0000 0.0000 0.0000 0.039(5) Uani 1 6 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 Ge1 0.0342(3) 0.0337(3) 0.0359(3) 0.0109(2) 0.0091(2) 0.0073(2) Ge2 0.0332(3) 0.0398(4) 0.0352(4) 0.0043(2) 0.0120(2) 0.0083(3) Ge3 0.0428(4) 0.0310(3) 0.0407(4) 0.0077(3) 0.0137(3) 0.0091(3) Cu1 0.0224(3) 0.0224(3) 0.0224(3) 0.0004(4) 0.0004(4) 0.0004(4) Si1 0.0305(8) 0.0352(9) 0.0326(8) 0.0037(6) 0.0100(6) 0.0082(6) Si10 0.0577(11) 0.0491(11) 0.0538(11) 0.0141(8) 0.0135(9) 0.0278(9) Si11 0.0386(10) 0.0493(10) 0.0502(11) -0.0051(8) 0.0152(8) -0.0040(8) Si12 0.0401(10) 0.0518(10) 0.0328(9) 0.0034(7) 0.0083(7) 0.0068(8) C10C 0.085(7) 0.074(7) 0.257(15) 0.093(8) 0.034(8) 0.027(5) C10B 0.134(10) 0.100(8) 0.260(16) 0.104(9) 0.141(11) 0.082(7) C10A 0.49(3) 0.162(13) 0.079(8) -0.017(8) -0.109(13) 0.208(18) C11C 0.045(4) 0.071(5) 0.091(6) 0.005(4) 0.032(4) 0.002(3) C11B 0.091(7) 0.045(5) 0.152(9) 0.019(5) 0.049(6) -0.002(4) C11A 0.089(7) 0.145(9) 0.068(6) -0.022(6) 0.007(5) -0.054(6) C12C 0.088(6) 0.075(5) 0.048(4) 0.026(4) 0.008(4) 0.018(4) C12B 0.049(4) 0.082(5) 0.044(4) 0.001(3) 0.001(3) -0.002(4) C12A 0.058(5) 0.103(6) 0.053(5) -0.009(4) 0.023(4) 0.004(4) O100 0.051(3) 0.058(3) 0.044(3) 0.002(2) 0.005(2) 0.014(2) C100 0.055(4) 0.074(5) 0.061(5) 0.001(4) 0.011(4) 0.017(4) C101 0.053(5) 0.112(7) 0.082(6) 0.022(5) 0.007(4) 0.025(4) C102 0.061(5) 0.073(5) 0.059(5) 0.006(4) 0.000(4) 0.021(4) C103 0.066(5) 0.070(5) 0.048(4) -0.003(3) -0.010(3) 0.019(4) Li1 0.039(6) 0.039(6) 0.039(6) 0.007(7) 0.007(7) 0.007(7) _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 Ge2 2.5186(9) . ? Ge1 Ge2 2.5217(9) 2 ? Ge1 Cu1 2.6221(8) . ? Ge1 Ge1 2.8475(10) 3 ? Ge1 Ge1 2.8475(10) 2 ? Ge2 Si1 2.3777(15) . ? Ge2 Ge1 2.5217(9) 3 ? Ge2 Ge3 2.5489(9) . ? Ge2 Ge3 2.5508(9) 2 ? Ge3 Ge2 2.5508(9) 3 ? Ge3 Ge3 2.6400(11) 3 ? Ge3 Ge3 2.6400(11) 2 ? Cu1 Ge1 2.6221(8) 4_666 ? Cu1 Ge1 2.6221(8) 3 ? Cu1 Ge1 2.6221(8) 6_666 ? Cu1 Ge1 2.6221(8) 2 ? Cu1 Ge1 2.6221(8) 5_666 ? Si1 Si11 2.338(2) . ? Si1 Si12 2.347(2) . ? Si1 Si10 2.352(2) . ? Si10 C10A 1.819(10) . ? Si10 C10B 1.833(8) . ? Si10 C10C 1.855(10) . ? Si11 C11A 1.841(9) . ? Si11 C11B 1.855(9) . ? Si11 C11C 1.875(6) . ? Si12 C12B 1.857(7) . ? Si12 C12C 1.861(7) . ? Si12 C12A 1.879(7) . ? O100 C100 1.435(8) . ? O100 C103 1.446(8) . ? O100 Li1 2.173(4) . ? C100 C101 1.482(10) . ? C101 C102 1.491(11) . ? C102 C103 1.484(9) . ? Li1 O100 2.173(4) 5 ? Li1 O100 2.173(4) 3 ? Li1 O100 2.173(4) 4 ? Li1 O100 2.173(4) 2 ? Li1 O100 2.173(4) 6 ? 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 Ge2 Ge1 Ge2 91.99(4) . 2 ? Ge2 Ge1 Cu1 111.15(3) . . ? Ge2 Ge1 Cu1 111.05(3) 2 . ? Ge2 Ge1 Ge1 55.65(2) . 3 ? Ge2 Ge1 Ge1 98.84(2) 2 3 ? Cu1 Ge1 Ge1 57.112(15) . 3 ? Ge2 Ge1 Ge1 98.915(19) . 2 ? Ge2 Ge1 Ge1 55.55(2) 2 2 ? Cu1 Ge1 Ge1 57.112(15) . 2 ? Ge1 Ge1 Ge1 60.0 3 2 ? Si1 Ge2 Ge1 127.24(5) . . ? Si1 Ge2 Ge1 122.50(4) . 3 ? Ge1 Ge2 Ge1 68.80(3) . 3 ? Si1 Ge2 Ge3 114.37(5) . . ? Ge1 Ge2 Ge3 118.20(3) . . ? Ge1 Ge2 Ge3 83.50(4) 3 . ? Si1 Ge2 Ge3 118.43(5) . 2 ? Ge1 Ge2 Ge3 83.52(4) . 2 ? Ge1 Ge2 Ge3 118.11(3) 3 2 ? Ge3 Ge2 Ge3 62.35(3) . 2 ? Ge2 Ge3 Ge2 90.61(4) . 3 ? Ge2 Ge3 Ge3 101.17(2) . 3 ? Ge2 Ge3 Ge3 58.79(3) 3 3 ? Ge2 Ge3 Ge3 58.86(3) . 2 ? Ge2 Ge3 Ge3 101.12(2) 3 2 ? Ge3 Ge3 Ge3 60.0 3 2 ? Ge1 Cu1 Ge1 114.23(3) 4_666 3 ? Ge1 Cu1 Ge1 65.78(3) 4_666 6_666 ? Ge1 Cu1 Ge1 180.000(10) 3 6_666 ? Ge1 Cu1 Ge1 114.23(3) 4_666 2 ? Ge1 Cu1 Ge1 65.78(3) 3 2 ? Ge1 Cu1 Ge1 114.22(3) 6_666 2 ? Ge1 Cu1 Ge1 180.0 4_666 . ? Ge1 Cu1 Ge1 65.78(3) 3 . ? Ge1 Cu1 Ge1 114.22(3) 6_666 . ? Ge1 Cu1 Ge1 65.78(3) 2 . ? Ge1 Cu1 Ge1 65.78(3) 4_666 5_666 ? Ge1 Cu1 Ge1 114.22(3) 3 5_666 ? Ge1 Cu1 Ge1 65.78(3) 6_666 5_666 ? Ge1 Cu1 Ge1 180.0 2 5_666 ? Ge1 Cu1 Ge1 114.22(3) . 5_666 ? Si11 Si1 Si12 111.10(9) . . ? Si11 Si1 Si10 111.75(9) . . ? Si12 Si1 Si10 110.30(9) . . ? Si11 Si1 Ge2 107.91(7) . . ? Si12 Si1 Ge2 108.27(7) . . ? Si10 Si1 Ge2 107.35(7) . . ? C10A Si10 C10B 109.7(8) . . ? C10A Si10 C10C 108.5(8) . . ? C10B Si10 C10C 104.9(6) . . ? C10A Si10 Si1 109.8(4) . . ? C10B Si10 Si1 111.2(3) . . ? C10C Si10 Si1 112.6(3) . . ? C11A Si11 C11B 109.8(5) . . ? C11A Si11 C11C 108.5(5) . . ? C11B Si11 C11C 107.4(4) . . ? C11A Si11 Si1 109.9(3) . . ? C11B Si11 Si1 111.0(3) . . ? C11C Si11 Si1 110.2(2) . . ? C12B Si12 C12C 109.2(4) . . ? C12B Si12 C12A 106.9(4) . . ? C12C Si12 C12A 109.6(4) . . ? C12B Si12 Si1 110.7(2) . . ? C12C Si12 Si1 111.9(3) . . ? C12A Si12 Si1 108.4(3) . . ? C100 O100 C103 108.1(5) . . ? C100 O100 Li1 129.4(4) . . ? C103 O100 Li1 122.4(4) . . ? O100 C100 C101 107.5(6) . . ? C100 C101 C102 104.0(6) . . ? C103 C102 C101 103.3(6) . . ? O100 C103 C102 106.2(5) . . ? O100 Li1 O100 87.54(15) 5 3 ? O100 Li1 O100 87.54(15) 5 . ? O100 Li1 O100 92.46(15) 3 . ? O100 Li1 O100 92.46(15) 5 4 ? O100 Li1 O100 87.54(15) 3 4 ? O100 Li1 O100 180.0(3) . 4 ? O100 Li1 O100 180.0(3) 5 2 ? O100 Li1 O100 92.46(15) 3 2 ? O100 Li1 O100 92.46(15) . 2 ? O100 Li1 O100 87.54(15) 4 2 ? O100 Li1 O100 92.46(15) 5 6 ? O100 Li1 O100 180.0(2) 3 6 ? O100 Li1 O100 87.54(15) . 6 ? O100 Li1 O100 92.46(15) 4 6 ? O100 Li1 O100 87.54(15) 2 6 ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 24.01 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 1.092 _refine_diff_density_min -0.335 _refine_diff_density_rms 0.089