# 1. SUBMISSION DETAILS _publ_contact_author_name 'Maria Kirsanova' _publ_contact_author_address ; Moscow State University Department of Chemistry Leninskie Gory 1 build. 3 GSP-1 119991 Moscow Russia ; _publ_contact_author_phone '007 495 939-1200' _publ_contact_author_fax ? _publ_contact_author_email 'kirsanova@inorg.chem.msu.ru' _publ_requested_journal ? _publ_requested_coeditor_name ? _publ_contact_letter ; ? ; #============================================================================== # 3. TITLE AND AUTHOR LIST _publ_section_title ; Synthesis, structure, and transport properties of type-I clathrates Ge46–xPxSe8–y (x » 15.4; y = 0–2.65) with diverse host-guest bonding ; loop_ _publ_author_name _publ_author_address 'Maria A. Kirsanova' ; Moscow State University Department of Chemistry Leninskie Gory 1 build. 3 GSP-1 119991 Moscow Russia ; 'Andrei V. Olenev' ; ”SineTheta” Ltd. Department of Chemistry Leninskie Gory scientific park of Lomonosov Moscow State University, 1-77 119991 Moscow Russia ; 'Artem M. Abakumov' ; EMAT, University of Antwerp Groenenborgerlaan 171, B-2020 Antwerp, Belgium ; 'Andrei V. Shevelkov' ; Moscow State University Department of Chemistry Leninskie Gory 1 build. 3 GSP-1 119991 Moscow Russia ; #============================================================================== # 4. TEXT _publ_section_abstract ; ; _publ_section_comment ; ; _publ_section_experimental ; ; _publ_section_references ; ; _publ_section_figure_captions ; ; _publ_section_acknowledgements ; ; #============================================================================== data_xl _audit_creation_method SHELXL-97 _chemical_name_systematic ; 'germanium-phosphor selenide' ; _chemical_name_common 'germanium-phosphor selenide' _chemical_melting_point 'not measured' _chemical_formula_moiety 'Ge30.71 P15.29 Se5.38' _chemical_formula_sum 'Ge30.71 P15.29 Se5.38' _chemical_formula_weight 3127.23 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'P' 'P' 0.1023 0.0942 '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' 'Se' 'Se' -0.0929 2.2259 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting cubic _symmetry_space_group_name_H-M 'Fm-3' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-x, y, -z' 'x, -y, -z' 'z, x, y' 'z, -x, -y' '-z, -x, y' '-z, x, -y' 'y, z, x' '-y, z, -x' 'y, -z, -x' '-y, -z, x' 'x, y+1/2, z+1/2' '-x, -y+1/2, z+1/2' '-x, y+1/2, -z+1/2' 'x, -y+1/2, -z+1/2' 'z, x+1/2, y+1/2' 'z, -x+1/2, -y+1/2' '-z, -x+1/2, y+1/2' '-z, x+1/2, -y+1/2' 'y, z+1/2, x+1/2' '-y, z+1/2, -x+1/2' 'y, -z+1/2, -x+1/2' '-y, -z+1/2, x+1/2' 'x+1/2, y, z+1/2' '-x+1/2, -y, z+1/2' '-x+1/2, y, -z+1/2' 'x+1/2, -y, -z+1/2' 'z+1/2, x, y+1/2' 'z+1/2, -x, -y+1/2' '-z+1/2, -x, y+1/2' '-z+1/2, x, -y+1/2' 'y+1/2, z, x+1/2' '-y+1/2, z, -x+1/2' 'y+1/2, -z, -x+1/2' '-y+1/2, -z, x+1/2' 'x+1/2, y+1/2, z' '-x+1/2, -y+1/2, z' '-x+1/2, y+1/2, -z' 'x+1/2, -y+1/2, -z' 'z+1/2, x+1/2, y' 'z+1/2, -x+1/2, -y' '-z+1/2, -x+1/2, y' '-z+1/2, x+1/2, -y' 'y+1/2, z+1/2, x' '-y+1/2, z+1/2, -x' 'y+1/2, -z+1/2, -x' '-y+1/2, -z+1/2, x' '-x, -y, -z' 'x, y, -z' 'x, -y, z' '-x, y, z' '-z, -x, -y' '-z, x, y' 'z, x, -y' 'z, -x, y' '-y, -z, -x' 'y, -z, x' '-y, z, x' 'y, z, -x' '-x, -y+1/2, -z+1/2' 'x, y+1/2, -z+1/2' 'x, -y+1/2, z+1/2' '-x, y+1/2, z+1/2' '-z, -x+1/2, -y+1/2' '-z, x+1/2, y+1/2' 'z, x+1/2, -y+1/2' 'z, -x+1/2, y+1/2' '-y, -z+1/2, -x+1/2' 'y, -z+1/2, x+1/2' '-y, z+1/2, x+1/2' 'y, z+1/2, -x+1/2' '-x+1/2, -y, -z+1/2' 'x+1/2, y, -z+1/2' 'x+1/2, -y, z+1/2' '-x+1/2, y, z+1/2' '-z+1/2, -x, -y+1/2' '-z+1/2, x, y+1/2' 'z+1/2, x, -y+1/2' 'z+1/2, -x, y+1/2' '-y+1/2, -z, -x+1/2' 'y+1/2, -z, x+1/2' '-y+1/2, z, x+1/2' 'y+1/2, z, -x+1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, y+1/2, -z' 'x+1/2, -y+1/2, z' '-x+1/2, y+1/2, z' '-z+1/2, -x+1/2, -y' '-z+1/2, x+1/2, y' 'z+1/2, x+1/2, -y' 'z+1/2, -x+1/2, y' '-y+1/2, -z+1/2, -x' 'y+1/2, -z+1/2, x' '-y+1/2, z+1/2, x' 'y+1/2, z+1/2, -x' _cell_length_a 20.310(2) _cell_length_b 20.310(2) _cell_length_c 20.310(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 8377.3(16) _cell_formula_units_Z 8 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 24 _cell_measurement_theta_min 16.47 _cell_measurement_theta_max 16.49 _exptl_crystal_description pyramid _exptl_crystal_colour 'dark gray' _exptl_crystal_size_max 0.04 _exptl_crystal_size_mid 0.03 _exptl_crystal_size_min 0.02 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 4.959 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 11159 _exptl_absorpt_coefficient_mu 26.918 _exptl_absorpt_correction_type 'psi-scan corrections' _exptl_absorpt_correction_T_min 0.4123 _exptl_absorpt_correction_T_max 0.6151 _exptl_absorpt_process_details ? _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 'Nonius CAD4' _diffrn_measurement_method \w--2\q _diffrn_detector_area_resol_mean ? _diffrn_standards_number 1 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 120 _diffrn_standards_decay_% ? _diffrn_reflns_number 2752 _diffrn_reflns_av_R_equivalents 0.0440 _diffrn_reflns_av_sigmaI/netI 0.0554 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 26 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 26 _diffrn_reflns_limit_l_min -26 _diffrn_reflns_limit_l_max 0 _diffrn_reflns_theta_min 3.33 _diffrn_reflns_theta_max 27.92 _reflns_number_total 918 _reflns_number_gt 622 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CAD4 (Nonius)' _computing_cell_refinement 'CAD4 (Nonius)' _computing_data_reduction 'XCAD7 (P.McArdle, 1999)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXL-97 (Sheldrick, 1997)' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0152P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens 'none' _refine_ls_hydrogen_treatment 'none' _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.000036(3) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 918 _refine_ls_number_parameters 59 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0661 _refine_ls_R_factor_gt 0.0344 _refine_ls_wR_factor_ref 0.0688 _refine_ls_wR_factor_gt 0.0628 _refine_ls_goodness_of_fit_ref 1.063 _refine_ls_restrained_S_all 1.063 _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_symetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Se1 Se 0.0000 0.0000 0.0000 0.0211(18) Uani 0.83(2) 24 d SP . . Se2 Se 0.0000 0.5000 0.0000 0.0165(17) Uani 0.822(19) 24 d SP . . Se3 Se 0.2500 0.2500 0.2500 0.0236(6) Uani 1 12 d S . . Se4 Se 0.24914(9) 0.12075(8) 0.5000 0.0169(5) Uani 0.592(4) 2 d SP . . Ge1 Ge 0.74972(4) 0.40804(3) 0.19001(3) 0.00804(17) Uani 1 1 d . . . Ge2 Ge 0.5000 0.43935(5) 0.15806(5) 0.0099(2) Uani 1 2 d S . . Ge3 Ge 0.0000 0.34343(5) 0.06057(5) 0.0082(2) Uani 1 2 d S . . P4 P 0.5000 0.37836(10) 0.25707(12) 0.0057(4) Uani 1 2 d S . . Ge5 Ge 0.90817(7) 0.40817(7) 0.09183(7) 0.0079(10) Uani 0.165(7) 3 d SP . . P5 P 0.90817(7) 0.40817(7) 0.09183(7) 0.0079(10) Uani 0.83 3 d SP . . Ge6 Ge 0.84188(4) 0.34188(4) 0.15812(4) 0.0101(6) Uani 0.699(7) 3 d SP . . P6 P 0.84188(4) 0.34188(4) 0.15812(4) 0.0101(6) Uani 0.30 3 d SP . . Ge7 Ge 0.65781(5) 0.34219(5) 0.15781(5) 0.0105(7) Uani 0.490(7) 3 d SP . . P7 P 0.65781(5) 0.34219(5) 0.15781(5) 0.0105(7) Uani 0.51 3 d SP . . Ge8 Ge 0.59214(6) 0.40786(6) 0.09214(6) 0.0070(8) Uani 0.323(7) 3 d SP . . P8 P 0.59214(6) 0.40786(6) 0.09214(6) 0.0070(8) Uani 0.68 3 d SP . . 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 Se1 0.0211(18) 0.0211(18) 0.0211(18) 0.000 0.000 0.000 Se2 0.0165(17) 0.0165(17) 0.0165(17) 0.000 0.000 0.000 Se3 0.0236(6) 0.0236(6) 0.0236(6) 0.000 0.000 0.000 Se4 0.0143(8) 0.0158(8) 0.0206(9) 0.000 0.000 -0.0034(8) Ge1 0.0081(3) 0.0087(3) 0.0073(3) 0.0005(2) -0.0001(3) 0.0015(3) Ge2 0.0093(5) 0.0077(4) 0.0126(5) 0.0016(4) 0.000 0.000 Ge3 0.0070(4) 0.0103(5) 0.0071(4) 0.0004(4) 0.000 0.000 P4 0.0047(9) 0.0045(9) 0.0080(11) 0.0007(9) 0.000 0.000 Ge5 0.0079(10) 0.0079(10) 0.0079(10) -0.0020(5) -0.0020(5) 0.0020(5) P5 0.0079(10) 0.0079(10) 0.0079(10) -0.0020(5) -0.0020(5) 0.0020(5) Ge6 0.0101(6) 0.0101(6) 0.0101(6) -0.0013(4) -0.0013(4) 0.0013(4) P6 0.0101(6) 0.0101(6) 0.0101(6) -0.0013(4) -0.0013(4) 0.0013(4) Ge7 0.0105(7) 0.0105(7) 0.0105(7) 0.0000(4) 0.0000(4) 0.0000(4) P7 0.0105(7) 0.0105(7) 0.0105(7) 0.0000(4) 0.0000(4) 0.0000(4) Ge8 0.0070(8) 0.0070(8) 0.0070(8) -0.0011(5) 0.0011(5) -0.0011(5) P8 0.0070(8) 0.0070(8) 0.0070(8) -0.0011(5) 0.0011(5) -0.0011(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 Se4 Ge3 2.242(2) 34 ? Ge1 P4 2.3321(14) 30_565 ? Ge1 Ge7 2.3877(9) . ? Ge1 Ge6 2.3934(9) . ? Ge1 Ge1 2.4366(12) 27_655 ? Ge2 P4 2.362(3) . ? Ge2 P8 2.3882(9) 52_655 ? Ge2 Ge8 2.3882(9) 52_655 ? Ge2 Ge8 2.3882(9) . ? Ge2 Ge2 2.4634(19) 2_665 ? Ge3 Se4 2.242(2) 43 ? Ge3 P5 2.3686(10) 52_655 ? Ge3 Ge5 2.3686(10) 52_655 ? Ge3 P5 2.3686(10) 1_455 ? Ge3 Ge5 2.3686(10) 1_455 ? Ge3 Ge3 2.4605(19) 50 ? P4 Ge1 2.3321(14) 70_554 ? P4 Ge1 2.3321(14) 24_654 ? Ge5 Ge6 2.332(3) . ? Ge5 Ge3 2.3686(10) 65_655 ? Ge5 Ge3 2.3686(10) 1_655 ? Ge5 Ge3 2.3686(10) 94 ? Ge6 Ge1 2.3934(9) 47_556 ? Ge6 Ge1 2.3934(9) 20_645 ? Ge7 Ge8 2.310(3) . ? Ge7 Ge1 2.3877(9) 30_565 ? Ge7 Ge1 2.3877(9) 24_654 ? Ge8 Ge2 2.3882(9) 69_655 ? Ge8 Ge2 2.3882(9) 30_565 ? 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 P4 Ge1 Ge7 109.60(7) 30_565 . ? P4 Ge1 Ge6 103.80(7) 30_565 . ? Ge7 Ge1 Ge6 102.87(4) . . ? P4 Ge1 Ge1 126.52(4) 30_565 27_655 ? Ge7 Ge1 Ge1 106.12(4) . 27_655 ? Ge6 Ge1 Ge1 105.48(4) . 27_655 ? P4 Ge2 P8 109.68(6) . 52_655 ? P4 Ge2 Ge8 109.68(6) . 52_655 ? P8 Ge2 Ge8 0.00(9) 52_655 52_655 ? P4 Ge2 Ge8 109.68(6) . . ? P8 Ge2 Ge8 103.18(7) 52_655 . ? Ge8 Ge2 Ge8 103.18(7) 52_655 . ? P4 Ge2 Ge2 121.64(6) . 2_665 ? P8 Ge2 Ge2 105.54(4) 52_655 2_665 ? Ge8 Ge2 Ge2 105.54(4) 52_655 2_665 ? Ge8 Ge2 Ge2 105.54(4) . 2_665 ? Se4 Ge3 P5 108.62(7) 43 52_655 ? Se4 Ge3 Ge5 108.62(7) 43 52_655 ? P5 Ge3 Ge5 0.00(5) 52_655 52_655 ? Se4 Ge3 P5 108.62(7) 43 1_455 ? P5 Ge3 P5 103.89(8) 52_655 1_455 ? Ge5 Ge3 P5 103.89(8) 52_655 1_455 ? Se4 Ge3 Ge5 108.62(7) 43 1_455 ? P5 Ge3 Ge5 103.89(8) 52_655 1_455 ? Ge5 Ge3 Ge5 103.89(8) 52_655 1_455 ? P5 Ge3 Ge5 0.00(11) 1_455 1_455 ? Se4 Ge3 Ge3 123.03(5) 43 50 ? P5 Ge3 Ge3 105.55(4) 52_655 50 ? Ge5 Ge3 Ge3 105.55(4) 52_655 50 ? P5 Ge3 Ge3 105.55(4) 1_455 50 ? Ge5 Ge3 Ge3 105.55(4) 1_455 50 ? Ge1 P4 Ge1 106.42(9) 70_554 24_654 ? Ge1 P4 Ge2 104.94(7) 70_554 . ? Ge1 P4 Ge2 104.94(7) 24_654 . ? Ge6 Ge5 Ge3 106.79(6) . 65_655 ? Ge6 Ge5 Ge3 106.79(6) . 1_655 ? Ge3 Ge5 Ge3 112.01(6) 65_655 1_655 ? Ge6 Ge5 Ge3 106.79(6) . 94 ? Ge3 Ge5 Ge3 112.01(6) 65_655 94 ? Ge3 Ge5 Ge3 112.01(6) 1_655 94 ? Ge5 Ge6 Ge1 106.47(4) . 47_556 ? Ge5 Ge6 Ge1 106.47(4) . 20_645 ? Ge1 Ge6 Ge1 112.30(3) 47_556 20_645 ? Ge5 Ge6 Ge1 106.47(4) . . ? Ge1 Ge6 Ge1 112.30(3) 47_556 . ? Ge1 Ge6 Ge1 112.30(3) 20_645 . ? Ge8 Ge7 Ge1 106.63(4) . . ? Ge8 Ge7 Ge1 106.63(4) . 30_565 ? Ge1 Ge7 Ge1 112.16(4) . 30_565 ? Ge8 Ge7 Ge1 106.63(4) . 24_654 ? Ge1 Ge7 Ge1 112.16(4) . 24_654 ? Ge1 Ge7 Ge1 112.16(4) 30_565 24_654 ? Ge7 Ge8 Ge2 106.46(5) . 69_655 ? Ge7 Ge8 Ge2 106.46(5) . . ? Ge2 Ge8 Ge2 112.31(5) 69_655 . ? Ge7 Ge8 Ge2 106.46(5) . 30_565 ? Ge2 Ge8 Ge2 112.31(5) 69_655 30_565 ? Ge2 Ge8 Ge2 112.31(5) . 30_565 ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 27.92 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 1.035 _refine_diff_density_min -1.940 _refine_diff_density_rms 0.229 data_xl2 _audit_creation_method SHELXL-97 _chemical_name_systematic ; 'germanium-phosphor selenide' ; _chemical_name_common 'germanium-phosphor selenide' _chemical_melting_point 'not measured' _chemical_formula_moiety 'Ge30.54 P15.46 Se7.97' _chemical_formula_sum 'Ge30.54 P15.46 Se7.97' _chemical_formula_weight 3324.61 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'P' 'P' 0.1023 0.0942 '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' 'Se' 'Se' -0.0929 2.2259 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting cubic _symmetry_space_group_name_H-M 'Fm-3' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-x, y, -z' 'x, -y, -z' 'z, x, y' 'z, -x, -y' '-z, -x, y' '-z, x, -y' 'y, z, x' '-y, z, -x' 'y, -z, -x' '-y, -z, x' 'x, y+1/2, z+1/2' '-x, -y+1/2, z+1/2' '-x, y+1/2, -z+1/2' 'x, -y+1/2, -z+1/2' 'z, x+1/2, y+1/2' 'z, -x+1/2, -y+1/2' '-z, -x+1/2, y+1/2' '-z, x+1/2, -y+1/2' 'y, z+1/2, x+1/2' '-y, z+1/2, -x+1/2' 'y, -z+1/2, -x+1/2' '-y, -z+1/2, x+1/2' 'x+1/2, y, z+1/2' '-x+1/2, -y, z+1/2' '-x+1/2, y, -z+1/2' 'x+1/2, -y, -z+1/2' 'z+1/2, x, y+1/2' 'z+1/2, -x, -y+1/2' '-z+1/2, -x, y+1/2' '-z+1/2, x, -y+1/2' 'y+1/2, z, x+1/2' '-y+1/2, z, -x+1/2' 'y+1/2, -z, -x+1/2' '-y+1/2, -z, x+1/2' 'x+1/2, y+1/2, z' '-x+1/2, -y+1/2, z' '-x+1/2, y+1/2, -z' 'x+1/2, -y+1/2, -z' 'z+1/2, x+1/2, y' 'z+1/2, -x+1/2, -y' '-z+1/2, -x+1/2, y' '-z+1/2, x+1/2, -y' 'y+1/2, z+1/2, x' '-y+1/2, z+1/2, -x' 'y+1/2, -z+1/2, -x' '-y+1/2, -z+1/2, x' '-x, -y, -z' 'x, y, -z' 'x, -y, z' '-x, y, z' '-z, -x, -y' '-z, x, y' 'z, x, -y' 'z, -x, y' '-y, -z, -x' 'y, -z, x' '-y, z, x' 'y, z, -x' '-x, -y+1/2, -z+1/2' 'x, y+1/2, -z+1/2' 'x, -y+1/2, z+1/2' '-x, y+1/2, z+1/2' '-z, -x+1/2, -y+1/2' '-z, x+1/2, y+1/2' 'z, x+1/2, -y+1/2' 'z, -x+1/2, y+1/2' '-y, -z+1/2, -x+1/2' 'y, -z+1/2, x+1/2' '-y, z+1/2, x+1/2' 'y, z+1/2, -x+1/2' '-x+1/2, -y, -z+1/2' 'x+1/2, y, -z+1/2' 'x+1/2, -y, z+1/2' '-x+1/2, y, z+1/2' '-z+1/2, -x, -y+1/2' '-z+1/2, x, y+1/2' 'z+1/2, x, -y+1/2' 'z+1/2, -x, y+1/2' '-y+1/2, -z, -x+1/2' 'y+1/2, -z, x+1/2' '-y+1/2, z, x+1/2' 'y+1/2, z, -x+1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, y+1/2, -z' 'x+1/2, -y+1/2, z' '-x+1/2, y+1/2, z' '-z+1/2, -x+1/2, -y' '-z+1/2, x+1/2, y' 'z+1/2, x+1/2, -y' 'z+1/2, -x+1/2, y' '-y+1/2, -z+1/2, -x' 'y+1/2, -z+1/2, x' '-y+1/2, z+1/2, x' 'y+1/2, z+1/2, -x' _cell_length_a 20.406(2) _cell_length_b 20.406(2) _cell_length_c 20.406(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 8496.8(17) _cell_formula_units_Z 8 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 3591 _cell_measurement_theta_min 2.82 _cell_measurement_theta_max 35.06 _exptl_crystal_description cubic _exptl_crystal_colour 'black' _exptl_crystal_size_max 0.03 _exptl_crystal_size_mid 0.03 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 5.192 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 11828 _exptl_absorpt_coefficient_mu 28.594 _exptl_absorpt_correction_type 'multi-scan' _exptl_absorpt_correction_T_min 0.4809 _exptl_absorpt_correction_T_max 0.4809 _exptl_absorpt_process_details ? _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 'Bruker APEX-II CCD' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 8498 _diffrn_reflns_av_R_equivalents 0.0418 _diffrn_reflns_av_sigmaI/netI 0.0329 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 32 _diffrn_reflns_limit_k_min -23 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -29 _diffrn_reflns_limit_l_max 25 _diffrn_reflns_theta_min 2.00 _diffrn_reflns_theta_max 35.06 _reflns_number_total 1683 _reflns_number_gt 1459 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker APEX2' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0325P)^2^+51.1297P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens 'none' _refine_ls_hydrogen_treatment 'none' _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.000040(5) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 1683 _refine_ls_number_parameters 58 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0321 _refine_ls_R_factor_gt 0.0254 _refine_ls_wR_factor_ref 0.0686 _refine_ls_wR_factor_gt 0.0660 _refine_ls_goodness_of_fit_ref 1.080 _refine_ls_restrained_S_all 1.080 _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_symetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Se1 Se 0.0000 0.0000 0.0000 0.0082(7) Uani 0.986(10) 24 d SP . . Se2 Se 0.5000 0.0000 0.0000 0.0104(7) Uani 0.948(10) 24 d SP . . Se3 Se 0.2500 0.2500 0.7500 0.0086(2) Uani 1 12 d S . . Se4 Se 0.25100(3) 0.0000 0.87804(3) 0.00827(10) Uani 1 2 d S . . Ge1 Ge 0.250385(16) 0.809961(17) 0.092269(18) 0.00330(8) Uani 1 1 d . . . Ge2 Ge 0.34229(2) 0.93935(2) 0.0000 0.00404(11) Uani 1 2 d S . . Ge3 Ge 0.15509(2) 0.0000 0.93988(2) 0.00324(10) Uani 1 2 d S . . Ge4 Ge 0.24376(5) 0.87809(6) 0.0000 0.0034(3) Uani 0.052(3) 2 d SP . . P4 P 0.24376(5) 0.87809(6) 0.0000 0.0034(3) Uani 0.95 2 d SP . . Ge5 Ge 0.09216(4) 0.90784(4) 0.90784(4) 0.0018(4) Uani 0.187(3) 3 d SP . . P5 P 0.09216(4) 0.90784(4) 0.90784(4) 0.0018(4) Uani 0.81 3 d SP . . Ge6 Ge 0.15827(3) 0.84173(3) 0.84173(3) 0.0024(3) Uani 0.638(3) 3 d SP . . P6 P 0.15827(3) 0.84173(3) 0.84173(3) 0.0024(3) Uani 0.36 3 d SP . . Ge7 Ge 0.34225(4) 0.84225(4) 0.84225(4) 0.0026(3) Uani 0.414(3) 3 d SP . . P7 P 0.34225(4) 0.84225(4) 0.84225(4) 0.0026(3) Uani 0.59 3 d SP . . Ge8 Ge 0.40772(4) 0.90772(4) 0.09228(4) 0.0025(3) Uani 0.318(3) 3 d SP . . P8 P 0.40772(4) 0.90772(4) 0.09228(4) 0.0025(3) Uani 0.68 3 d SP . . 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 Se1 0.0082(7) 0.0082(7) 0.0082(7) 0.000 0.000 0.000 Se2 0.0104(7) 0.0104(7) 0.0104(7) 0.000 0.000 0.000 Se3 0.0086(2) 0.0086(2) 0.0086(2) 0.000 0.000 0.000 Se4 0.0061(2) 0.0126(2) 0.0061(2) 0.000 0.00334(17) 0.000 Ge1 0.00341(16) 0.00261(15) 0.00388(16) 0.00055(11) 0.00060(10) -0.00006(10) Ge2 0.0058(2) 0.0027(2) 0.0036(2) 0.000 0.000 -0.00106(16) Ge3 0.0041(2) 0.0033(2) 0.0023(2) 0.000 0.00038(16) 0.000 Ge4 0.0038(5) 0.0041(5) 0.0023(5) 0.000 0.000 0.0007(4) P4 0.0038(5) 0.0041(5) 0.0023(5) 0.000 0.000 0.0007(4) Ge5 0.0018(4) 0.0018(4) 0.0018(4) 0.0003(3) -0.0003(3) -0.0003(3) P5 0.0018(4) 0.0018(4) 0.0018(4) 0.0003(3) -0.0003(3) -0.0003(3) Ge6 0.0024(3) 0.0024(3) 0.0024(3) 0.00078(19) -0.00078(19) -0.00078(19) P6 0.0024(3) 0.0024(3) 0.0024(3) 0.00078(19) -0.00078(19) -0.00078(19) Ge7 0.0026(3) 0.0026(3) 0.0026(3) 0.0008(2) 0.0008(2) 0.0008(2) P7 0.0026(3) 0.0026(3) 0.0026(3) 0.0008(2) 0.0008(2) 0.0008(2) Ge8 0.0025(3) 0.0025(3) 0.0025(3) -0.0006(3) -0.0006(3) 0.0006(3) P8 0.0025(3) 0.0025(3) 0.0025(3) -0.0006(3) -0.0006(3) 0.0006(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 Se4 Ge3 2.3287(8) . ? Ge1 Ge4 2.3444(9) . ? Ge1 P7 2.3944(6) 50_556 ? Ge1 Ge7 2.3944(6) 50_556 ? Ge1 Ge6 2.4015(5) 50_556 ? Ge1 P6 2.4015(5) 50_556 ? Ge1 Ge1 2.4471(8) 38_565 ? Ge2 Ge4 2.3674(14) . ? Ge2 Ge8 2.3969(6) . ? Ge2 P8 2.3969(6) 50 ? Ge2 Ge8 2.3969(6) 50 ? Ge2 Ge2 2.4753(10) 51_575 ? Ge3 P5 2.3692(6) 1_545 ? Ge3 Ge5 2.3692(6) 1_545 ? Ge3 P5 2.3692(6) 51_565 ? Ge3 Ge5 2.3692(6) 51_565 ? Ge3 Ge3 2.4534(10) 50_557 ? Ge4 Ge1 2.3444(9) 50 ? Ge5 Ge6 2.3366(19) . ? Ge5 Ge3 2.3692(6) 1_565 ? Ge5 Ge3 2.3692(6) 10_556 ? Ge5 Ge3 2.3692(6) 53_666 ? Ge6 Ge1 2.4015(5) 50_556 ? Ge6 Ge1 2.4015(5) 57_666 ? Ge6 Ge1 2.4015(5) 56_565 ? Ge7 P8 2.3140(19) 50_556 ? Ge7 Ge8 2.3140(19) 50_556 ? Ge7 Ge1 2.3944(6) 90 ? Ge7 Ge1 2.3944(6) 82_465 ? Ge7 Ge1 2.3944(6) 50_556 ? Ge8 P7 2.3140(19) 50_556 ? Ge8 Ge7 2.3140(19) 50_556 ? Ge8 Ge2 2.3969(6) 35_465 ? Ge8 Ge2 2.3969(6) 91_556 ? 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 Ge4 Ge1 P7 109.28(4) . 50_556 ? Ge4 Ge1 Ge7 109.28(4) . 50_556 ? P7 Ge1 Ge7 0.000(4) 50_556 50_556 ? Ge4 Ge1 Ge6 104.19(4) . 50_556 ? P7 Ge1 Ge6 103.03(2) 50_556 50_556 ? Ge7 Ge1 Ge6 103.03(2) 50_556 50_556 ? Ge4 Ge1 P6 104.19(4) . 50_556 ? P7 Ge1 P6 103.03(2) 50_556 50_556 ? Ge7 Ge1 P6 103.03(2) 50_556 50_556 ? Ge6 Ge1 P6 0.000(18) 50_556 50_556 ? Ge4 Ge1 Ge1 126.35(3) . 38_565 ? P7 Ge1 Ge1 106.27(2) 50_556 38_565 ? Ge7 Ge1 Ge1 106.27(2) 50_556 38_565 ? Ge6 Ge1 Ge1 105.36(2) 50_556 38_565 ? P6 Ge1 Ge1 105.36(2) 50_556 38_565 ? Ge4 Ge2 Ge8 109.32(4) . . ? Ge4 Ge2 P8 109.32(4) . 50 ? Ge8 Ge2 P8 103.56(4) . 50 ? Ge4 Ge2 Ge8 109.32(4) . 50 ? Ge8 Ge2 Ge8 103.56(4) . 50 ? P8 Ge2 Ge8 0.00(6) 50 50 ? Ge4 Ge2 Ge2 121.87(3) . 51_575 ? Ge8 Ge2 Ge2 105.62(2) . 51_575 ? P8 Ge2 Ge2 105.62(2) 50 51_575 ? Ge8 Ge2 Ge2 105.62(2) 50 51_575 ? Se4 Ge3 P5 107.82(4) . 1_545 ? Se4 Ge3 Ge5 107.82(4) . 1_545 ? P5 Ge3 Ge5 0.000(10) 1_545 1_545 ? Se4 Ge3 P5 107.82(4) . 51_565 ? P5 Ge3 P5 105.07(5) 1_545 51_565 ? Ge5 Ge3 P5 105.07(5) 1_545 51_565 ? Se4 Ge3 Ge5 107.82(4) . 51_565 ? P5 Ge3 Ge5 105.07(5) 1_545 51_565 ? Ge5 Ge3 Ge5 105.07(5) 1_545 51_565 ? P5 Ge3 Ge5 0.000(5) 51_565 51_565 ? Se4 Ge3 Ge3 122.815(19) . 50_557 ? P5 Ge3 Ge3 106.02(2) 1_545 50_557 ? Ge5 Ge3 Ge3 106.02(2) 1_545 50_557 ? P5 Ge3 Ge3 106.02(2) 51_565 50_557 ? Ge5 Ge3 Ge3 106.02(2) 51_565 50_557 ? Ge1 Ge4 Ge1 106.86(5) 50 . ? Ge1 Ge4 Ge2 105.32(3) 50 . ? Ge1 Ge4 Ge2 105.32(3) . . ? Ge6 Ge5 Ge3 107.74(4) . 1_565 ? Ge6 Ge5 Ge3 107.74(4) . 10_556 ? Ge3 Ge5 Ge3 111.15(3) 1_565 10_556 ? Ge6 Ge5 Ge3 107.74(4) . 53_666 ? Ge3 Ge5 Ge3 111.15(3) 1_565 53_666 ? Ge3 Ge5 Ge3 111.15(3) 10_556 53_666 ? Ge5 Ge6 Ge1 106.50(2) . 50_556 ? Ge5 Ge6 Ge1 106.50(2) . 57_666 ? Ge1 Ge6 Ge1 112.27(2) 50_556 57_666 ? Ge5 Ge6 Ge1 106.50(3) . 56_565 ? Ge1 Ge6 Ge1 112.27(2) 50_556 56_565 ? Ge1 Ge6 Ge1 112.27(2) 57_666 56_565 ? P8 Ge7 Ge8 0.00(6) 50_556 50_556 ? P8 Ge7 Ge1 106.78(3) 50_556 90 ? Ge8 Ge7 Ge1 106.78(3) 50_556 90 ? P8 Ge7 Ge1 106.78(3) 50_556 82_465 ? Ge8 Ge7 Ge1 106.78(3) 50_556 82_465 ? Ge1 Ge7 Ge1 112.03(3) 90 82_465 ? P8 Ge7 Ge1 106.78(3) 50_556 50_556 ? Ge8 Ge7 Ge1 106.78(3) 50_556 50_556 ? Ge1 Ge7 Ge1 112.03(3) 90 50_556 ? Ge1 Ge7 Ge1 112.03(3) 82_465 50_556 ? P7 Ge8 Ge7 0.00(6) 50_556 50_556 ? P7 Ge8 Ge2 106.71(3) 50_556 35_465 ? Ge7 Ge8 Ge2 106.71(3) 50_556 35_465 ? P7 Ge8 Ge2 106.71(3) 50_556 . ? Ge7 Ge8 Ge2 106.71(3) 50_556 . ? Ge2 Ge8 Ge2 112.09(3) 35_465 . ? P7 Ge8 Ge2 106.71(3) 50_556 91_556 ? Ge7 Ge8 Ge2 106.71(3) 50_556 91_556 ? Ge2 Ge8 Ge2 112.09(3) 35_465 91_556 ? Ge2 Ge8 Ge2 112.09(3) . 91_556 ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 35.06 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 2.104 _refine_diff_density_min -1.455 _refine_diff_density_rms 0.280 data_xl1 _audit_creation_method SHELXL-97 _chemical_name_systematic ; 'germanium-phosphor selenide' ; _chemical_name_common 'germanium-phosphor selenide' _chemical_melting_point 'not measured' _chemical_formula_moiety 'Ge30.70 P15.30 Se7.97' _chemical_formula_sum 'Ge30.70 P15.30 Se7.97' _chemical_formula_weight 3331.82 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'P' 'P' 0.1023 0.0942 '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' 'Se' 'Se' -0.0929 2.2259 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting cubic _symmetry_space_group_name_H-M 'Fm-3' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-x, y, -z' 'x, -y, -z' 'z, x, y' 'z, -x, -y' '-z, -x, y' '-z, x, -y' 'y, z, x' '-y, z, -x' 'y, -z, -x' '-y, -z, x' 'x, y+1/2, z+1/2' '-x, -y+1/2, z+1/2' '-x, y+1/2, -z+1/2' 'x, -y+1/2, -z+1/2' 'z, x+1/2, y+1/2' 'z, -x+1/2, -y+1/2' '-z, -x+1/2, y+1/2' '-z, x+1/2, -y+1/2' 'y, z+1/2, x+1/2' '-y, z+1/2, -x+1/2' 'y, -z+1/2, -x+1/2' '-y, -z+1/2, x+1/2' 'x+1/2, y, z+1/2' '-x+1/2, -y, z+1/2' '-x+1/2, y, -z+1/2' 'x+1/2, -y, -z+1/2' 'z+1/2, x, y+1/2' 'z+1/2, -x, -y+1/2' '-z+1/2, -x, y+1/2' '-z+1/2, x, -y+1/2' 'y+1/2, z, x+1/2' '-y+1/2, z, -x+1/2' 'y+1/2, -z, -x+1/2' '-y+1/2, -z, x+1/2' 'x+1/2, y+1/2, z' '-x+1/2, -y+1/2, z' '-x+1/2, y+1/2, -z' 'x+1/2, -y+1/2, -z' 'z+1/2, x+1/2, y' 'z+1/2, -x+1/2, -y' '-z+1/2, -x+1/2, y' '-z+1/2, x+1/2, -y' 'y+1/2, z+1/2, x' '-y+1/2, z+1/2, -x' 'y+1/2, -z+1/2, -x' '-y+1/2, -z+1/2, x' '-x, -y, -z' 'x, y, -z' 'x, -y, z' '-x, y, z' '-z, -x, -y' '-z, x, y' 'z, x, -y' 'z, -x, y' '-y, -z, -x' 'y, -z, x' '-y, z, x' 'y, z, -x' '-x, -y+1/2, -z+1/2' 'x, y+1/2, -z+1/2' 'x, -y+1/2, z+1/2' '-x, y+1/2, z+1/2' '-z, -x+1/2, -y+1/2' '-z, x+1/2, y+1/2' 'z, x+1/2, -y+1/2' 'z, -x+1/2, y+1/2' '-y, -z+1/2, -x+1/2' 'y, -z+1/2, x+1/2' '-y, z+1/2, x+1/2' 'y, z+1/2, -x+1/2' '-x+1/2, -y, -z+1/2' 'x+1/2, y, -z+1/2' 'x+1/2, -y, z+1/2' '-x+1/2, y, z+1/2' '-z+1/2, -x, -y+1/2' '-z+1/2, x, y+1/2' 'z+1/2, x, -y+1/2' 'z+1/2, -x, y+1/2' '-y+1/2, -z, -x+1/2' 'y+1/2, -z, x+1/2' '-y+1/2, z, x+1/2' 'y+1/2, z, -x+1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, y+1/2, -z' 'x+1/2, -y+1/2, z' '-x+1/2, y+1/2, z' '-z+1/2, -x+1/2, -y' '-z+1/2, x+1/2, y' 'z+1/2, x+1/2, -y' 'z+1/2, -x+1/2, y' '-y+1/2, -z+1/2, -x' 'y+1/2, -z+1/2, x' '-y+1/2, z+1/2, x' 'y+1/2, z+1/2, -x' _cell_length_a 20.351(2) _cell_length_b 20.351(2) _cell_length_c 20.351(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 8429.3(16) _cell_formula_units_Z 8 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 9913 _cell_measurement_theta_min 2.83 _cell_measurement_theta_max 45.00 _exptl_crystal_description cubic _exptl_crystal_colour 'black' _exptl_crystal_size_max 0.03 _exptl_crystal_size_mid 0.03 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 5.251 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 11864 _exptl_absorpt_coefficient_mu 28.992 _exptl_absorpt_correction_type 'multi-scan' _exptl_absorpt_correction_T_min 0.4767 _exptl_absorpt_correction_T_max 0.4767 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 173(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 'Bruker APEX-II CCD' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 39918 _diffrn_reflns_av_R_equivalents 0.0623 _diffrn_reflns_av_sigmaI/netI 0.0322 _diffrn_reflns_limit_h_min -32 _diffrn_reflns_limit_h_max 35 _diffrn_reflns_limit_k_min -39 _diffrn_reflns_limit_k_max 39 _diffrn_reflns_limit_l_min -40 _diffrn_reflns_limit_l_max 30 _diffrn_reflns_theta_min 1.73 _diffrn_reflns_theta_max 45.21 _reflns_number_total 3101 _reflns_number_gt 2699 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker APEX2' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0075P)^2^+140.3254P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens 'none' _refine_ls_hydrogen_treatment 'none' _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.000035(2) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 3101 _refine_ls_number_parameters 58 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0381 _refine_ls_R_factor_gt 0.0290 _refine_ls_wR_factor_ref 0.0560 _refine_ls_wR_factor_gt 0.0541 _refine_ls_goodness_of_fit_ref 1.099 _refine_ls_restrained_S_all 1.099 _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_symetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Se1 Se 0.0000 0.0000 0.0000 0.0061(3) Uani 1 24 d S . . Se2 Se 0.5000 0.0000 0.0000 0.0070(4) Uani 0.940(9) 24 d SP . . Se3 Se 0.2500 0.2500 0.7500 0.00543(13) Uani 1 12 d S . . Se4 Se 0.251028(19) 0.0000 0.878068(18) 0.00488(5) Uani 1 2 d S . . Ge1 Ge 0.250412(12) 0.809933(11) 0.092320(11) 0.00149(4) Uani 1 1 d . . . Ge2 Ge 0.342257(17) 0.939337(17) 0.0000 0.00186(5) Uani 1 2 d S . . Ge3 Ge 0.155112(16) 0.0000 0.939936(17) 0.00144(5) Uani 1 2 d S . . Ge4 Ge 0.24368(4) 0.87821(4) 0.0000 0.00205(18) Uani 0.054(2) 2 d SP . . P4 P 0.24368(4) 0.87821(4) 0.0000 0.00205(18) Uani 0.95 2 d SP . . Ge5 Ge 0.09219(3) 0.90781(3) 0.90781(3) 0.0007(2) Uani 0.184(3) 3 d SP . . P5 P 0.09219(3) 0.90781(3) 0.90781(3) 0.0007(2) Uani 0.82 3 d SP . . Ge6 Ge 0.15824(2) 0.84176(2) 0.84176(2) 0.00106(15) Uani 0.653(3) 3 d SP . . P6 P 0.15824(2) 0.84176(2) 0.84176(2) 0.00106(15) Uani 0.35 3 d SP . . Ge7 Ge 0.34218(2) 0.84218(2) 0.84218(2) 0.00169(19) Uani 0.431(3) 3 d SP . . P7 P 0.34218(2) 0.84218(2) 0.84218(2) 0.00169(19) Uani 0.57 3 d SP . . Ge8 Ge 0.40771(3) 0.90771(3) 0.09229(3) 0.00138(19) Uani 0.328(3) 3 d SP . . P8 P 0.40771(3) 0.90771(3) 0.09229(3) 0.00138(19) Uani 0.67 3 d SP . . 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 Se1 0.0061(3) 0.0061(3) 0.0061(3) 0.000 0.000 0.000 Se2 0.0070(4) 0.0070(4) 0.0070(4) 0.000 0.000 0.000 Se3 0.00543(13) 0.00543(13) 0.00543(13) 0.000 0.000 0.000 Se4 0.00402(12) 0.00732(13) 0.00332(11) 0.000 0.00224(10) 0.000 Ge1 0.00135(8) 0.00104(8) 0.00207(9) 0.00014(6) 0.00043(6) -0.00008(6) Ge2 0.00301(12) 0.00092(12) 0.00164(13) 0.000 0.000 -0.00045(10) Ge3 0.00210(12) 0.00111(12) 0.00113(12) 0.000 0.00002(9) 0.000 Ge4 0.0029(3) 0.0021(3) 0.0011(3) 0.000 0.000 0.0000(2) P4 0.0029(3) 0.0021(3) 0.0011(3) 0.000 0.000 0.0000(2) Ge5 0.0007(2) 0.0007(2) 0.0007(2) 0.00039(17) -0.00039(17) -0.00039(17) P5 0.0007(2) 0.0007(2) 0.0007(2) 0.00039(17) -0.00039(17) -0.00039(17) Ge6 0.00106(15) 0.00106(15) 0.00106(15) 0.00041(11) -0.00041(11) -0.00041(11) P6 0.00106(15) 0.00106(15) 0.00106(15) 0.00041(11) -0.00041(11) -0.00041(11) Ge7 0.00169(19) 0.00169(19) 0.00169(19) 0.00057(14) 0.00057(14) 0.00057(14) P7 0.00169(19) 0.00169(19) 0.00169(19) 0.00057(14) 0.00057(14) 0.00057(14) Ge8 0.00138(19) 0.00138(19) 0.00138(19) -0.00043(15) -0.00043(15) 0.00043(15) P8 0.00138(19) 0.00138(19) 0.00138(19) -0.00043(15) -0.00043(15) 0.00043(15) _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 Se4 Ge3 2.3229(6) . ? Ge1 Ge4 2.3409(6) . ? Ge1 P7 2.3865(4) 50_556 ? Ge1 Ge7 2.3865(4) 50_556 ? Ge1 Ge6 2.3954(4) 50_556 ? Ge1 P6 2.3954(4) 50_556 ? Ge1 Ge1 2.4395(5) 38_565 ? Ge2 Ge4 2.3606(10) . ? Ge2 Ge8 2.3909(4) . ? Ge2 P8 2.3909(4) 50 ? Ge2 Ge8 2.3909(4) 50 ? Ge2 Ge2 2.4692(7) 51_575 ? Ge3 P5 2.3637(5) 1_545 ? Ge3 Ge5 2.3637(5) 1_545 ? Ge3 P5 2.3637(5) 51_565 ? Ge3 Ge5 2.3637(5) 51_565 ? Ge3 Ge3 2.4448(7) 50_557 ? Ge4 Ge1 2.3409(6) 50 ? Ge5 Ge6 2.3284(13) . ? Ge5 Ge3 2.3637(5) 1_565 ? Ge5 Ge3 2.3637(5) 53_666 ? Ge5 Ge3 2.3637(5) 10_556 ? Ge6 Ge1 2.3954(4) 50_556 ? Ge6 Ge1 2.3954(4) 56_565 ? Ge6 Ge1 2.3954(4) 57_666 ? Ge7 P8 2.3101(13) 50_556 ? Ge7 Ge8 2.3101(13) 50_556 ? Ge7 Ge1 2.3865(4) 90 ? Ge7 Ge1 2.3865(4) 82_465 ? Ge7 Ge1 2.3865(4) 50_556 ? Ge8 P7 2.3101(13) 50_556 ? Ge8 Ge7 2.3101(13) 50_556 ? Ge8 Ge2 2.3909(4) 35_465 ? Ge8 Ge2 2.3909(4) 91_556 ? 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 Ge4 Ge1 P7 109.32(3) . 50_556 ? Ge4 Ge1 Ge7 109.32(3) . 50_556 ? P7 Ge1 Ge7 0.000(3) 50_556 50_556 ? Ge4 Ge1 Ge6 104.07(3) . 50_556 ? P7 Ge1 Ge6 103.040(14) 50_556 50_556 ? Ge7 Ge1 Ge6 103.040(14) 50_556 50_556 ? Ge4 Ge1 P6 104.07(3) . 50_556 ? P7 Ge1 P6 103.040(14) 50_556 50_556 ? Ge7 Ge1 P6 103.040(14) 50_556 50_556 ? Ge6 Ge1 P6 0.000(12) 50_556 50_556 ? Ge4 Ge1 Ge1 126.385(18) . 38_565 ? P7 Ge1 Ge1 106.280(16) 50_556 38_565 ? Ge7 Ge1 Ge1 106.280(16) 50_556 38_565 ? Ge6 Ge1 Ge1 105.368(15) 50_556 38_565 ? P6 Ge1 Ge1 105.368(15) 50_556 38_565 ? Ge4 Ge2 Ge8 109.37(3) . . ? Ge4 Ge2 P8 109.37(3) . 50 ? Ge8 Ge2 P8 103.54(3) . 50 ? Ge4 Ge2 Ge8 109.37(3) . 50 ? Ge8 Ge2 Ge8 103.54(3) . 50 ? P8 Ge2 Ge8 0.00(4) 50 50 ? Ge4 Ge2 Ge2 121.80(2) . 51_575 ? Ge8 Ge2 Ge2 105.616(15) . 51_575 ? P8 Ge2 Ge2 105.616(15) 50 51_575 ? Ge8 Ge2 Ge2 105.616(15) 50 51_575 ? Se4 Ge3 P5 107.78(3) . 1_545 ? Se4 Ge3 Ge5 107.78(3) . 1_545 ? P5 Ge3 Ge5 0.000(7) 1_545 1_545 ? Se4 Ge3 P5 107.78(3) . 51_565 ? P5 Ge3 P5 105.07(3) 1_545 51_565 ? Ge5 Ge3 P5 105.07(3) 1_545 51_565 ? Se4 Ge3 Ge5 107.78(3) . 51_565 ? P5 Ge3 Ge5 105.07(3) 1_545 51_565 ? Ge5 Ge3 Ge5 105.07(3) 1_545 51_565 ? P5 Ge3 Ge5 0.000(4) 51_565 51_565 ? Se4 Ge3 Ge3 122.823(13) . 50_557 ? P5 Ge3 Ge3 106.055(16) 1_545 50_557 ? Ge5 Ge3 Ge3 106.055(16) 1_545 50_557 ? P5 Ge3 Ge3 106.055(16) 51_565 50_557 ? Ge5 Ge3 Ge3 106.055(16) 51_565 50_557 ? Ge1 Ge4 Ge1 106.76(4) 50 . ? Ge1 Ge4 Ge2 105.25(2) 50 . ? Ge1 Ge4 Ge2 105.25(2) . . ? Ge6 Ge5 Ge3 107.76(3) . 1_565 ? Ge6 Ge5 Ge3 107.76(3) . 53_666 ? Ge3 Ge5 Ge3 111.12(2) 1_565 53_666 ? Ge6 Ge5 Ge3 107.76(3) . 10_556 ? Ge3 Ge5 Ge3 111.12(2) 1_565 10_556 ? Ge3 Ge5 Ge3 111.12(2) 53_666 10_556 ? Ge5 Ge6 Ge1 106.553(17) . 50_556 ? Ge5 Ge6 Ge1 106.553(17) . 56_565 ? Ge1 Ge6 Ge1 112.225(15) 50_556 56_565 ? Ge5 Ge6 Ge1 106.553(17) . 57_666 ? Ge1 Ge6 Ge1 112.225(15) 50_556 57_666 ? Ge1 Ge6 Ge1 112.225(15) 56_565 57_666 ? P8 Ge7 Ge8 0.00(5) 50_556 50_556 ? P8 Ge7 Ge1 106.74(2) 50_556 90 ? Ge8 Ge7 Ge1 106.74(2) 50_556 90 ? P8 Ge7 Ge1 106.74(2) 50_556 82_465 ? Ge8 Ge7 Ge1 106.74(2) 50_556 82_465 ? Ge1 Ge7 Ge1 112.058(19) 90 82_465 ? P8 Ge7 Ge1 106.74(2) 50_556 50_556 ? Ge8 Ge7 Ge1 106.74(2) 50_556 50_556 ? Ge1 Ge7 Ge1 112.057(19) 90 50_556 ? Ge1 Ge7 Ge1 112.058(19) 82_465 50_556 ? P7 Ge8 Ge7 0.00(4) 50_556 50_556 ? P7 Ge8 Ge2 106.69(2) 50_556 35_465 ? Ge7 Ge8 Ge2 106.69(2) 50_556 35_465 ? P7 Ge8 Ge2 106.69(2) 50_556 . ? Ge7 Ge8 Ge2 106.69(2) 50_556 . ? Ge2 Ge8 Ge2 112.10(2) 35_465 . ? P7 Ge8 Ge2 106.69(2) 50_556 91_556 ? Ge7 Ge8 Ge2 106.69(2) 50_556 91_556 ? Ge2 Ge8 Ge2 112.10(2) 35_465 91_556 ? Ge2 Ge8 Ge2 112.10(2) . 91_556 ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 45.21 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 2.174 _refine_diff_density_min -2.320 _refine_diff_density_rms 0.325