data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Ulrich Abram' _publ_contact_author_address # Name and address of author for correspondence ; Ulrich Abram Free University of Berlin Institute of Chemistry Fabeckstrasse 34-36 D-14195 Berlin Germany ; _publ_contact_author_phone '0049 (0)30 838 54002' _publ_contact_author_fax '0049 (0)30 838 52676' _publ_contact_author_email abram@chemie.fu-berlin.de #============================================================================ # 2. TITLE AND AUTHOR LIST _publ_section_title ; [TcCl4(H2O)2] and [Cl3(H2O)2TcOTc(H2O)2Cl3] - Two Molecular Intermediates of the Hydrolysis of Technetium(IV) ; # The loop structure below should contain the names and addresses of all # authors, in the required order of publication. Repeat as necessary. loop_ _publ_author_name _publ_author_address U.Abram ; Free University of Berlin Institute of Chemistry Fabeckstrasse 34-36 D-14195 Berlin Germany ; E.Yegen ; Free University of Berlin Institute of Chemistry Fabeckstrasse 34-36 D-14195 Berlin Germany ; A.Hagenbach ; Free University of Berlin Institute of Chemistry Fabeckstrasse 34-36 D-14195 Berlin Germany ; #=============== STRUCTURE I ============================ data_tccl4an2 _database_code_depnum_ccdc_archive 'CCDC 278683' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Bis(acetonitril)tetrachlorotechnetium(VI) Acetonitril solvate ; _chemical_name_common 'Bis(acetonitril)tetrachlorotechnetium(VI) Acetonitril solvate' _chemical_melting_point ? _chemical_formula_moiety 'TcCl4(AN)2 * AN' _chemical_formula_sum 'C6 H9 Cl4 N3 Tc' _chemical_formula_weight 362.96 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' Cl Cl 0.1484 0.1585 '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' Tc Tc -1.4390 0.7593 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M Pnma loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z+1/2' '-x, y+1/2, -z' '-x, -y, -z' 'x-1/2, y, -z-1/2' '-x-1/2, y-1/2, z-1/2' 'x, -y-1/2, z' _cell_length_a 10.325(5) _cell_length_b 13.531(5) _cell_length_c 9.720(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1358.0(11) _cell_formula_units_Z 4 _cell_measurement_temperature 193(2) _cell_measurement_reflns_used 1274 _cell_measurement_theta_min 2.58 _cell_measurement_theta_max 27.10 _exptl_crystal_description Plate _exptl_crystal_colour yellow _exptl_crystal_size_max 0.2 _exptl_crystal_size_mid 0.1 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.775 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 708 _exptl_absorpt_coefficient_mu 1.816 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 193(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'STOE IPDS 2T' _diffrn_measurement_method 'rotation method' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0.1 _diffrn_reflns_number 4069 _diffrn_reflns_av_R_equivalents 0.0920 _diffrn_reflns_av_sigmaI/netI 0.0847 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 3.25 _diffrn_reflns_theta_max 26.80 _reflns_number_total 1486 _reflns_number_gt 1027 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'STOE X-AREA' _computing_cell_refinement 'STOE X-AREA' _computing_data_reduction 'STOE X-RED' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _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^)+(0.0481P)^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 'riding model' _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1486 _refine_ls_number_parameters 69 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0836 _refine_ls_R_factor_gt 0.0460 _refine_ls_wR_factor_ref 0.0992 _refine_ls_wR_factor_gt 0.0877 _refine_ls_goodness_of_fit_ref 0.921 _refine_ls_restrained_S_all 0.921 _refine_ls_shift/su_max 0.030 _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 Tc1 Tc 0.94277(6) 0.7500 0.01432(6) 0.02140(19) Uani 1 2 d S . . Cl1 Cl 1.0959(2) 0.7500 0.1894(2) 0.0376(5) Uani 1 2 d S . . Cl2 Cl 1.04589(15) 0.87334(11) -0.10179(14) 0.0373(4) Uani 1 1 d . . . Cl3 Cl 0.7671(2) 0.7500 -0.1325(2) 0.0375(5) Uani 1 2 d S . . N1 N 0.8440(5) 0.8591(4) 0.1311(5) 0.0307(10) Uani 1 1 d . . . C1 C 0.7915(6) 0.9149(5) 0.1956(6) 0.0381(14) Uani 1 1 d . . . C2 C 0.7230(8) 0.9864(6) 0.2797(8) 0.062(2) Uani 1 1 d . . . H2A H 0.7840 1.0316 0.3197 0.093 Uiso 1 1 calc R . . H2B H 0.6771 0.9526 0.3516 0.093 Uiso 1 1 calc R . . H2C H 0.6627 1.0222 0.2236 0.093 Uiso 1 1 calc R . . C10 C 0.9250(13) 0.7707(12) 0.5284(13) 0.063(4) Uiso 0.50 1 d P A -1 H10A H 0.9493 0.7918 0.6191 0.095 Uiso 0.50 1 calc PR A -1 H10B H 0.8346 0.7836 0.5140 0.095 Uiso 0.50 1 calc PR A -1 H10C H 0.9749 0.8064 0.4614 0.095 Uiso 0.50 1 calc PR A -1 C11 C 0.955(2) 0.6426(16) 0.511(2) 0.082(5) Uiso 0.50 1 d P A -1 N11 N 0.980(2) 0.5595(15) 0.500(2) 0.105(6) Uiso 0.50 1 d P A -1 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 Tc1 0.0210(3) 0.0201(3) 0.0231(3) 0.000 0.0016(3) 0.000 Cl1 0.0364(11) 0.0371(12) 0.0393(10) 0.000 -0.0144(9) 0.000 Cl2 0.0366(8) 0.0335(8) 0.0417(7) 0.0082(6) 0.0092(7) -0.0064(6) Cl3 0.0325(11) 0.0379(12) 0.0421(11) 0.000 -0.0106(9) 0.000 N1 0.032(3) 0.023(2) 0.038(2) 0.000(2) 0.005(2) 0.002(2) C1 0.040(4) 0.028(3) 0.046(3) 0.002(3) 0.012(3) -0.005(3) C2 0.072(5) 0.040(4) 0.074(5) -0.013(4) 0.044(4) 0.003(4) _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 Tc1 N1 2.123(5) . ? Tc1 N1 2.123(5) 8_575 ? Tc1 Cl2 2.2787(16) 8_575 ? Tc1 Cl2 2.2787(16) . ? Tc1 Cl3 2.308(2) . ? Tc1 Cl1 2.323(2) . ? N1 C1 1.121(7) . ? C1 C2 1.450(9) . ? C10 C11 1.77(3) . ? C11 N11 1.16(3) . ? 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 N1 Tc1 N1 88.1(3) . 8_575 ? N1 Tc1 Cl2 176.83(13) . 8_575 ? N1 Tc1 Cl2 88.84(13) 8_575 8_575 ? N1 Tc1 Cl2 88.84(13) . . ? N1 Tc1 Cl2 176.83(13) 8_575 . ? Cl2 Tc1 Cl2 94.17(9) 8_575 . ? N1 Tc1 Cl3 87.31(14) . . ? N1 Tc1 Cl3 87.31(14) 8_575 . ? Cl2 Tc1 Cl3 93.49(6) 8_575 . ? Cl2 Tc1 Cl3 93.49(6) . . ? N1 Tc1 Cl1 86.29(14) . . ? N1 Tc1 Cl1 86.29(14) 8_575 . ? Cl2 Tc1 Cl1 92.57(6) 8_575 . ? Cl2 Tc1 Cl1 92.57(6) . . ? Cl3 Tc1 Cl1 171.09(9) . . ? C1 N1 Tc1 178.0(5) . . ? N1 C1 C2 179.5(7) . . ? N11 C11 C10 177(2) . . ? _diffrn_measured_fraction_theta_max 0.983 _diffrn_reflns_theta_full 26.80 _diffrn_measured_fraction_theta_full 0.983 _refine_diff_density_max 0.859 _refine_diff_density_min -0.955 _refine_diff_density_rms 0.133 ################################## STRUCTURE 2 ################################ data_tccl4h2omono _database_code_depnum_ccdc_archive 'CCDC 278684' _audit_creation_method SHELXL-97 _chemical_name_systematic ; cis-Diaquatetrachlorotechnetium(IV) dioxane solvate ; _chemical_name_common 'cis-Diaquatetrachlorotechnetium(IV) dioxane solvate' _chemical_melting_point ? _chemical_formula_moiety 'TcCl4H2O x 2dioxane' _chemical_formula_sum 'C8 H20 Cl4 O6 Tc' _chemical_formula_weight 452.04 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' Cl Cl 0.1484 0.1585 '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' Tc Tc -1.4390 0.7593 '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 18.495(8) _cell_length_b 25.730(5) _cell_length_c 7.023(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3342(3) _cell_formula_units_Z 8 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 99 _cell_measurement_theta_min 3.20 _cell_measurement_theta_max 25.67 _exptl_crystal_description block _exptl_crystal_colour pale-green _exptl_crystal_size_max 0.05 _exptl_crystal_size_mid 0.04 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.797 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1816 _exptl_absorpt_coefficient_mu 1.516 _exptl_absorpt_correction_type integration _exptl_absorpt_correction_T_min 0.7953 _exptl_absorpt_correction_T_max 0.8386 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 173(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type CuKalpha _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'STOE IPDS 2T' _diffrn_measurement_method 'rotation method' _diffrn_detector_area_resol_mean 6.67 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 1957 _diffrn_reflns_av_R_equivalents 0.0282 _diffrn_reflns_av_sigmaI/netI 0.0589 _diffrn_reflns_limit_h_min -21 _diffrn_reflns_limit_h_max 23 _diffrn_reflns_limit_k_min -28 _diffrn_reflns_limit_k_max 7 _diffrn_reflns_limit_l_min -8 _diffrn_reflns_limit_l_max 8 _diffrn_reflns_theta_min 2.68 _diffrn_reflns_theta_max 26.38 _reflns_number_total 1318 _reflns_number_gt 1081 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'STOE X-AREA' _computing_cell_refinement 'STOE X-AREA' _computing_data_reduction 'STOE X-AREA' _computing_structure_solution SHELXS _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ORTEP _computing_publication_material WINGX _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^)+(0.0661P)^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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.38(12) _refine_ls_number_reflns 1318 _refine_ls_number_parameters 88 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0390 _refine_ls_R_factor_gt 0.0282 _refine_ls_wR_factor_ref 0.1163 _refine_ls_wR_factor_gt 0.0923 _refine_ls_goodness_of_fit_ref 1.102 _refine_ls_restrained_S_all 1.102 _refine_ls_shift/su_max 0.006 _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 Tc Tc 0.2500 -0.2500 -0.29292(11) 0.0273(3) Uani 1 2 d S . . Cl1 Cl 0.16033(9) -0.31323(11) -0.3197(3) 0.0403(6) Uani 1 1 d . . . Cl2 Cl 0.18367(11) -0.20541(19) -0.0728(5) 0.0828(15) Uani 1 1 d . . . O10 O 0.1964(3) -0.2108(4) -0.5132(12) 0.051(3) Uani 1 1 d . . . H10B H 0.2090 -0.1745 -0.5096 0.077 Uiso 1 1 d . . . H10C H 0.1448 -0.2141 -0.4954 0.077 Uiso 1 1 d . . . O1 O 0.0593(3) -0.2088(3) -0.5992(7) 0.0328(18) Uani 1 1 d . . . C2 C 0.0018(4) -0.2173(5) -0.4625(12) 0.035(2) Uani 1 1 d . . . H2A H 0.0095 -0.2502 -0.3985 0.041 Uiso 1 1 calc R . . H2B H -0.0441 -0.2192 -0.5290 0.041 Uiso 1 1 calc R . . C3 C -0.0015(4) -0.1744(5) -0.3165(12) 0.038(3) Uani 1 1 d . . . H3A H -0.0415 -0.1805 -0.2303 0.046 Uiso 1 1 calc R . . H3B H 0.0428 -0.1741 -0.2426 0.046 Uiso 1 1 calc R . . O4 O -0.0106(3) -0.1259(3) -0.4098(9) 0.0352(19) Uani 1 1 d . . . C5 C 0.0482(4) -0.1181(4) -0.5391(15) 0.036(2) Uani 1 1 d . . . H5A H 0.0934 -0.1187 -0.4694 0.044 Uiso 1 1 calc R . . H5B H 0.0435 -0.0842 -0.5987 0.044 Uiso 1 1 calc R . . C6 C 0.0492(5) -0.1590(6) -0.6884(12) 0.036(3) Uani 1 1 d . . . H6A H 0.0041 -0.1587 -0.7585 0.043 Uiso 1 1 calc R . . H6B H 0.0883 -0.1524 -0.7773 0.043 Uiso 1 1 calc R . . 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 Tc 0.0206(3) 0.0331(7) 0.0283(4) 0.000 0.000 0.0030(5) Cl1 0.0302(9) 0.036(2) 0.0548(13) 0.0031(12) 0.0115(9) -0.0053(8) Cl2 0.0323(11) 0.132(4) 0.084(2) -0.076(3) 0.0084(13) -0.0040(13) O10 0.029(3) 0.044(7) 0.081(5) 0.029(5) -0.020(3) -0.007(3) O1 0.029(3) 0.035(6) 0.035(3) 0.000(3) 0.000(2) 0.001(3) C2 0.031(4) 0.027(9) 0.046(4) 0.002(4) 0.002(4) 0.001(4) C3 0.031(4) 0.043(9) 0.041(5) -0.003(4) 0.003(4) 0.003(3) O4 0.032(3) 0.026(7) 0.048(3) -0.002(3) -0.001(2) 0.005(3) C5 0.031(4) 0.029(8) 0.049(4) 0.002(5) -0.002(4) 0.005(3) C6 0.038(4) 0.039(10) 0.032(4) 0.003(4) -0.001(3) 0.004(4) _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 Tc O10 2.096(7) . ? Tc O10 2.096(7) 14_545 ? Tc Cl2 2.283(3) 14_545 ? Tc Cl2 2.283(3) . ? Tc Cl1 2.331(2) . ? Tc Cl1 2.331(2) 14_545 ? O10 H10B 0.9625 . ? O10 H10C 0.9654 . ? O1 C6 1.438(15) . ? O1 C2 1.450(10) . ? C2 C3 1.506(15) . ? C2 H2A 0.9700 . ? C2 H2B 0.9700 . ? C3 O4 1.421(15) . ? C3 H3A 0.9700 . ? C3 H3B 0.9700 . ? O4 C5 1.430(10) . ? C5 C6 1.487(16) . ? C5 H5A 0.9700 . ? C5 H5B 0.9700 . ? C6 H6A 0.9700 . ? C6 H6B 0.9700 . ? 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 O10 Tc O10 84.9(5) . 14_545 ? O10 Tc Cl2 174.8(2) . 14_545 ? O10 Tc Cl2 90.2(3) 14_545 14_545 ? O10 Tc Cl2 90.2(3) . . ? O10 Tc Cl2 174.8(2) 14_545 . ? Cl2 Tc Cl2 94.8(2) 14_545 . ? O10 Tc Cl1 86.5(2) . . ? O10 Tc Cl1 86.6(2) 14_545 . ? Cl2 Tc Cl1 94.94(12) 14_545 . ? Cl2 Tc Cl1 91.31(11) . . ? O10 Tc Cl1 86.6(2) . 14_545 ? O10 Tc Cl1 86.5(2) 14_545 14_545 ? Cl2 Tc Cl1 91.31(11) 14_545 14_545 ? Cl2 Tc Cl1 94.94(12) . 14_545 ? Cl1 Tc Cl1 170.76(12) . 14_545 ? Tc O10 H10B 109.4 . . ? Tc O10 H10C 109.2 . . ? H10B O10 H10C 108.8 . . ? C6 O1 C2 109.1(7) . . ? O1 C2 C3 111.7(8) . . ? O1 C2 H2A 109.3 . . ? C3 C2 H2A 109.3 . . ? O1 C2 H2B 109.3 . . ? C3 C2 H2B 109.3 . . ? H2A C2 H2B 107.9 . . ? O4 C3 C2 109.5(7) . . ? O4 C3 H3A 109.8 . . ? C2 C3 H3A 109.8 . . ? O4 C3 H3B 109.8 . . ? C2 C3 H3B 109.8 . . ? H3A C3 H3B 108.2 . . ? C3 O4 C5 109.0(7) . . ? O4 C5 C6 111.0(8) . . ? O4 C5 H5A 109.4 . . ? C6 C5 H5A 109.4 . . ? O4 C5 H5B 109.4 . . ? C6 C5 H5B 109.4 . . ? H5A C5 H5B 108.0 . . ? O1 C6 C5 109.0(7) . . ? O1 C6 H6A 109.9 . . ? C5 C6 H6A 109.9 . . ? O1 C6 H6B 109.9 . . ? C5 C6 H6B 109.9 . . ? H6A C6 H6B 108.3 . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O10 H10C O1 0.97 1.75 2.607(7) 146.4 . O10 H10B O4 0.96 1.76 2.582(12) 140.7 12_444 _diffrn_measured_fraction_theta_max 0.774 _diffrn_reflns_theta_full 26.38 _diffrn_measured_fraction_theta_full 0.774 _refine_diff_density_max 0.497 _refine_diff_density_min -0.882 _refine_diff_density_rms 0.242 ########################################STRUCTURE 3 ################ data_tccl4h2odi _database_code_depnum_ccdc_archive 'CCDC 278685' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Tetraaquahexachloro(mu-oxo)ditechnetium(V) dioxane solvate ; _chemical_name_common 'Tetraaquahexachloro(mu-oxo)ditechnetium(V) dioxane solvate' _chemical_melting_point ? _chemical_formula_moiety Tc2Cl6(H2O)4O _chemical_formula_sum 'C12 H28 Cl3 O8.50 Tc' _chemical_formula_weight 512.69 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' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Tc Tc -1.4390 0.7593 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 10.054(5) _cell_length_b 10.138(5) _cell_length_c 10.519(5) _cell_angle_alpha 98.823(5) _cell_angle_beta 102.258(5) _cell_angle_gamma 91.989(5) _cell_volume 1032.8(9) _cell_formula_units_Z 2 _cell_measurement_temperature 193(2) _cell_measurement_reflns_used 3526 _cell_measurement_theta_min 2.55 _cell_measurement_theta_max 28.66 _exptl_crystal_description block _exptl_crystal_colour 'golden brown' _exptl_crystal_size_max .2 _exptl_crystal_size_mid .1 _exptl_crystal_size_min .05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.649 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 524 _exptl_absorpt_coefficient_mu 1.120 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 193(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 'STOE IPDS 2T' _diffrn_measurement_method rotation _diffrn_detector_area_resol_mean 6.67 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 9898 _diffrn_reflns_av_R_equivalents 0.0756 _diffrn_reflns_av_sigmaI/netI 0.2661 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 2.55 _diffrn_reflns_theta_max 29.21 _reflns_number_total 5410 _reflns_number_gt 2188 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'STOE X-AREA' _computing_cell_refinement 'STOE X-AREA' _computing_data_reduction 'STOE X-AREA' _computing_structure_solution SHELXS _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ORTEP _computing_publication_material WINGX _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^)+(0.0000P)^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 5410 _refine_ls_number_parameters 223 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1255 _refine_ls_R_factor_gt 0.0401 _refine_ls_wR_factor_ref 0.0728 _refine_ls_wR_factor_gt 0.0570 _refine_ls_goodness_of_fit_ref 0.588 _refine_ls_restrained_S_all 0.588 _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 Tc Tc 0.62978(5) 0.09237(5) 0.63348(6) 0.01873(11) Uani 1 1 d . . . O10 O 0.5000 0.0000 0.5000 0.0217(12) Uani 1 2 d S . . Cl1 Cl 0.61673(13) 0.28951(12) 0.54192(14) 0.0281(3) Uani 1 1 d . . . Cl2 Cl 0.69377(13) -0.09169(12) 0.73750(15) 0.0294(3) Uani 1 1 d . . . Cl3 Cl 0.47604(14) 0.15299(14) 0.76422(15) 0.0305(3) Uani 1 1 d . . . O20 O 0.7858(3) 0.1980(3) 0.7892(3) 0.0231(8) Uani 1 1 d . . . H20A H 0.7814 0.1663 0.8701 0.035 Uiso 1 1 d . . . H20B H 0.7703 0.2922 0.7995 0.035 Uiso 1 1 d . . . O30 O 0.7853(3) 0.0468(3) 0.5294(4) 0.0242(9) Uani 1 1 d . . . H30A H 0.7844 -0.0490 0.5048 0.036 Uiso 1 1 d . . . H30B H 0.7680 0.0864 0.4503 0.036 Uiso 1 1 d . . . O1 O 0.8292(3) -0.2042(3) 0.4520(4) 0.0291(9) Uani 1 1 d . . . C2 C 0.8925(5) -0.2194(5) 0.3417(6) 0.0288(13) Uani 1 1 d . . . H2A H 0.9518 -0.1404 0.3466 0.035 Uiso 1 1 calc R . . H2B H 0.8231 -0.2288 0.2606 0.035 Uiso 1 1 calc R . . C3 C 0.9751(5) -0.3420(5) 0.3411(6) 0.0351(14) Uani 1 1 d . . . H3A H 1.0168 -0.3523 0.2653 0.042 Uiso 1 1 calc R . . H3B H 1.0474 -0.3304 0.4201 0.042 Uiso 1 1 calc R . . O4 O 0.8899(4) -0.4590(3) 0.3358(4) 0.0320(9) Uani 1 1 d . . . C5 C 0.8261(5) -0.4428(5) 0.4463(6) 0.0314(13) Uani 1 1 d . . . H5A H 0.8954 -0.4330 0.5275 0.038 Uiso 1 1 calc R . . H5B H 0.7670 -0.5218 0.4419 0.038 Uiso 1 1 calc R . . C6 C 0.7443(5) -0.3224(5) 0.4467(6) 0.0338(14) Uani 1 1 d . . . H6A H 0.6721 -0.3344 0.3676 0.041 Uiso 1 1 calc R . . H6B H 0.7025 -0.3124 0.5224 0.041 Uiso 1 1 calc R . . O11 O 0.8009(4) 0.1374(4) 0.3035(4) 0.0388(10) Uani 1 1 d . . . C12 C 0.9217(6) 0.1712(7) 0.2607(6) 0.0448(16) Uani 1 1 d . . . H12A H 1.0002 0.1414 0.3173 0.054 Uiso 1 1 calc R . . H12B H 0.9339 0.2676 0.2683 0.054 Uiso 1 1 calc R . . C13 C 0.9136(6) 0.1076(6) 0.1205(6) 0.0478(17) Uani 1 1 d . . . H13A H 0.9959 0.1326 0.0932 0.057 Uiso 1 1 calc R . . H13B H 0.9055 0.0109 0.1129 0.057 Uiso 1 1 calc R . . O14 O 0.7970(4) 0.1518(4) 0.0377(4) 0.0452(11) Uani 1 1 d . . . C15 C 0.6754(6) 0.1186(7) 0.0797(7) 0.0513(18) Uani 1 1 d . . . H15A H 0.6615 0.0222 0.0702 0.062 Uiso 1 1 calc R . . H15B H 0.5977 0.1506 0.0238 0.062 Uiso 1 1 calc R . . C16 C 0.6839(6) 0.1790(6) 0.2186(7) 0.0464(17) Uani 1 1 d . . . H16A H 0.6901 0.2758 0.2269 0.056 Uiso 1 1 calc R . . H16B H 0.6018 0.1522 0.2454 0.056 Uiso 1 1 calc R . . O21 O 0.8194(4) 0.4668(3) 0.8673(4) 0.0347(10) Uani 1 1 d . . . C22 C 0.7564(6) 0.5632(5) 0.7903(6) 0.0386(15) Uani 1 1 d . . . H22A H 0.7545 0.5331 0.6978 0.046 Uiso 1 1 calc R . . H22B H 0.8094 0.6484 0.8176 0.046 Uiso 1 1 calc R . . C23 C 0.6153(6) 0.5798(6) 0.8085(7) 0.0471(17) Uani 1 1 d . . . H23A H 0.5740 0.6443 0.7557 0.056 Uiso 1 1 calc R . . H23B H 0.5618 0.4951 0.7773 0.056 Uiso 1 1 calc R . . O24 O 0.6117(4) 0.6237(4) 0.9421(6) 0.0580(14) Uani 1 1 d . . . C25 C 0.6731(7) 0.5263(7) 1.0198(7) 0.0512(18) Uani 1 1 d . . . H25A H 0.6195 0.4414 0.9919 0.061 Uiso 1 1 calc R . . H25B H 0.6739 0.5564 1.1121 0.061 Uiso 1 1 calc R . . C26 C 0.8176(6) 0.5080(6) 1.0033(6) 0.0434(16) Uani 1 1 d . . . H26A H 0.8726 0.5916 1.0367 0.052 Uiso 1 1 calc R . . H26B H 0.8568 0.4411 1.0540 0.052 Uiso 1 1 calc R . . 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 Tc 0.0203(2) 0.0187(2) 0.0160(3) 0.00277(18) 0.00173(18) -0.00017(17) O10 0.024(3) 0.016(2) 0.025(3) 0.006(2) 0.006(2) 0.000(2) Cl1 0.0331(7) 0.0218(7) 0.0298(9) 0.0080(6) 0.0053(6) 0.0008(5) Cl2 0.0351(8) 0.0251(7) 0.0284(9) 0.0100(6) 0.0033(6) 0.0046(6) Cl3 0.0278(7) 0.0395(8) 0.0260(9) 0.0062(6) 0.0085(6) 0.0072(6) O20 0.0280(19) 0.0219(19) 0.016(2) 0.0012(15) 0.0004(16) -0.0068(15) O30 0.030(2) 0.0202(18) 0.019(2) 0.0038(15) -0.0027(16) 0.0004(15) O1 0.032(2) 0.0248(18) 0.031(2) 0.0021(16) 0.0110(17) 0.0032(15) C2 0.030(3) 0.029(3) 0.029(4) 0.004(2) 0.009(3) 0.002(2) C3 0.027(3) 0.037(3) 0.043(4) 0.006(3) 0.010(3) 0.003(2) O4 0.038(2) 0.0234(18) 0.036(3) 0.0031(17) 0.0149(19) -0.0006(16) C5 0.029(3) 0.031(3) 0.037(4) 0.010(3) 0.010(3) 0.006(2) C6 0.028(3) 0.035(3) 0.041(4) 0.010(3) 0.011(3) 0.000(2) O11 0.033(2) 0.062(3) 0.025(2) 0.017(2) 0.0078(18) 0.0035(19) C12 0.032(3) 0.078(5) 0.026(4) 0.012(3) 0.006(3) 0.004(3) C13 0.050(4) 0.056(4) 0.038(4) 0.002(3) 0.014(3) 0.004(3) O14 0.046(3) 0.069(3) 0.018(2) 0.013(2) 0.0007(19) -0.011(2) C15 0.037(4) 0.081(5) 0.032(4) 0.016(3) -0.002(3) -0.020(3) C16 0.033(3) 0.068(4) 0.040(4) 0.022(3) 0.003(3) 0.006(3) O21 0.043(2) 0.031(2) 0.031(3) -0.0002(17) 0.0122(19) 0.0075(17) C22 0.050(4) 0.028(3) 0.040(4) 0.006(3) 0.014(3) 0.003(3) C23 0.050(4) 0.032(3) 0.060(5) 0.011(3) 0.012(4) 0.003(3) O24 0.048(3) 0.052(3) 0.077(4) -0.005(3) 0.030(3) 0.008(2) C25 0.048(4) 0.068(5) 0.037(5) 0.000(4) 0.017(4) -0.010(4) C26 0.047(4) 0.055(4) 0.025(4) -0.011(3) 0.015(3) -0.007(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 Tc O10 1.8124(8) . ? Tc O30 2.116(4) . ? Tc O20 2.132(3) . ? Tc Cl3 2.3169(17) . ? Tc Cl1 2.3440(18) . ? Tc Cl2 2.3460(17) . ? O10 Tc 1.8124(8) 2_656 ? O1 C2 1.428(6) . ? O1 C6 1.434(6) . ? C2 C3 1.519(6) . ? C3 O4 1.426(6) . ? O4 C5 1.434(6) . ? C5 C6 1.495(6) . ? O11 C12 1.430(6) . ? O11 C16 1.435(6) . ? C12 C13 1.500(8) . ? C13 O14 1.434(7) . ? O14 C15 1.431(7) . ? C15 C16 1.479(9) . ? O21 C26 1.432(7) . ? O21 C22 1.441(6) . ? C22 C23 1.484(8) . ? C23 O24 1.415(8) . ? O24 C25 1.449(8) . ? C25 C26 1.513(8) . ? 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 O10 Tc O30 92.02(10) . . ? O10 Tc O20 178.67(9) . . ? O30 Tc O20 86.82(14) . . ? O10 Tc Cl3 93.58(6) . . ? O30 Tc Cl3 174.40(11) . . ? O20 Tc Cl3 87.58(11) . . ? O10 Tc Cl1 93.72(5) . . ? O30 Tc Cl1 85.70(11) . . ? O20 Tc Cl1 86.85(10) . . ? Cl3 Tc Cl1 94.14(6) . . ? O10 Tc Cl2 95.97(5) . . ? O30 Tc Cl2 86.17(10) . . ? O20 Tc Cl2 83.31(10) . . ? Cl3 Tc Cl2 93.04(6) . . ? Cl1 Tc Cl2 167.55(5) . . ? Tc O10 Tc 180.0 2_656 . ? C2 O1 C6 109.7(4) . . ? O1 C2 C3 110.0(4) . . ? O4 C3 C2 110.5(4) . . ? C3 O4 C5 109.6(4) . . ? O4 C5 C6 110.5(4) . . ? O1 C6 C5 110.7(4) . . ? C12 O11 C16 109.7(5) . . ? O11 C12 C13 111.2(5) . . ? O14 C13 C12 108.9(5) . . ? C15 O14 C13 110.3(5) . . ? O14 C15 C16 111.2(5) . . ? O11 C16 C15 110.8(5) . . ? C26 O21 C22 109.9(4) . . ? O21 C22 C23 110.1(5) . . ? O24 C23 C22 112.2(5) . . ? C23 O24 C25 108.7(5) . . ? O24 C25 C26 110.3(6) . . ? O21 C26 C25 110.6(5) . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O20 H20A O14 0.96 1.77 2.706(6) 164.2 1_556 O20 H20B O21 0.97 1.81 2.711(5) 153.1 . O30 H30A O1 0.97 1.70 2.632(5) 162.5 . O30 H30B O11 0.96 1.79 2.708(6) 157.5 . _diffrn_measured_fraction_theta_max 0.967 _diffrn_reflns_theta_full 29.21 _diffrn_measured_fraction_theta_full 0.967 _refine_diff_density_max 0.898 _refine_diff_density_min -1.312 _refine_diff_density_rms 0.130 #----END