# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2010 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Thomas Vaid' _publ_contact_author_email TPVAID@UA.EDU _publ_section_title ; Cadmium and Zinc Thiolate and Selenolate Metal-Organic Frameworks ; loop_ _publ_author_name 'Thomas Vaid' 'P. W. Stephens' 'Kevin H. Stone' 'Dayna L. Turner' # Attachment 'Cd_thiolates.cif' data_[Cd(en)3][Cd(SC6H4S)2] _database_code_depnum_ccdc_archive 'CCDC 704799' #TrackingRef 'Cd_thiolates.cif' # 5. CHEMICAL DATA _chemical_name_systematic ; ??? ; _chemical_name_common (Cd(en)3)(Cd(SC6H4S)2) _chemical_formula_moiety ? _chemical_formula_structural '[Cd(en)3][Cd(SC6H4S)2]' _chemical_formula_analytical ? _chemical_formula_sum 'C18 H32 Cd2 N6 S4' _chemical_formula_weight 685.568 _chemical_melting_point ? _chemical_compound_source ? # for minerals and # natural products loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source _atom_type_scat_length_neutron # include if applicable ? ? ? ? ? ? #============================================================================== # 6. POWDER SPECIMEN AND CRYSTAL DATA _space_group_crystal_system Monoclinic _space_group_name_H-M_alt 'C 2/c' #_symmetry_space_group_name_Hall '-C 2yc' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, 1/2-z' '-x, -y, -z' 'x, -y, 1/2+z' '1/2+x, 1/2+y, z' '1/2-x, 1/2+y, 1/2-z' '1/2-x, 1/2-y, -z' '1/2+x, 1/2-y, 1/2+z' _cell_length_a 12.01279(11) _cell_length_b 14.83093(15) _cell_length_c 14.57556(13) _cell_angle_alpha 90 _cell_angle_beta 90.21712(43) _cell_angle_gamma 90 _cell_volume 2596.78(4) _cell_formula_units_Z 4 _cell_measurement_temperature 298 # The next three fields give the specimen dimensions in mm. The equatorial # plane contains the incident and diffracted beam. _pd_spec_size_axial 4 # perpendicular to # equatorial plane _pd_spec_size_equat ? # parallel to # scattering vector # in transmission _pd_spec_size_thick 0.5 # parallel to # scattering vector # in reflection # The next five fields are character fields that describe the specimen. _pd_spec_mounting # This field should be # used to give details of the # container. ; Sample was loaded into a quartz zero background flat plate sample holder ; _pd_spec_mount_mode reflection # options are 'reflection' # or 'transmission' _pd_spec_shape flat_sheet # options are 'cylinder' # 'flat_sheet' or 'irregular' _pd_char_particle_morphology ? _pd_char_colour ? # use ICDD colour descriptions # The following three fields describe the preparation of the specimen. # The cooling rate is in K/min. The pressure at which the sample was # prepared is in kPa. The temperature of preparation is in K. _pd_prep_cool_rate ? _pd_prep_pressure ? _pd_prep_temperature ? # The next four fields are normally only needed for transmission experiments. _exptl_absorpt_coefficient_mu ? _exptl_absorpt_correction_type ? # include if applicable _exptl_absorpt_process_details ? # include if applicable _exptl_absorpt_correction_T_min ? # include if applicable _exptl_absorpt_correction_T_max ? # include if applicable #============================================================================== # 7. EXPERIMENTAL DATA _exptl_special_details ; ? ; # The following item is used to identify the equipment used to record # the powder pattern when the diffractogram was measured at a laboratory # other than the authors' home institution, e.g. when neutron or synchrotron # radiation is used. _pd_instr_location ; X16C, National Synchrotron Light Source, Brookhaven National Laboratory ; _pd_calibration_special_details # description of the method used # to calibrate the instrument ; NIST standard reference material 1976(sintered plate of Al2O3). 7 reflections were used to calibrate wavelength and detector zero. ; _diffrn_ambient_temperature 298 _diffrn_source synchrotron _diffrn_source_target ? _diffrn_source_type ? _diffrn_radiation_type ? _diffrn_measurement_device_type 'Huber diffractometer' _diffrn_detector 'NaI scintillation counter' _diffrn_detector_type ? # make or model of detector _pd_meas_scan_method step # options are 'step', 'cont', # 'tof', 'fixed' or # 'disp' (= dispersive) _pd_meas_special_details ; ? ; # The following six items are used for angular dispersive measurements only. _diffrn_radiation_wavelength 0.696745 _diffrn_radiation_monochromator 'double Si(111)' # The following four items give details of the measured (not processed) # powder pattern. Angles are in degrees. _pd_meas_number_of_points 8800 _pd_meas_2theta_range_min 1 _pd_meas_2theta_range_max 45 _pd_meas_2theta_range_inc 0.005 # The following three items are used for time-of-flight measurements only. _pd_instr_dist_src/spec ? _pd_instr_dist_spec/detc ? _pd_meas_2theta_fixed ? #============================================================================== # 8. REFINEMENT DATA # Use the next field to give any special details about the fitting of the # powder pattern. _pd_proc_ls_special_details ; A slightly different geometry was implemented above 22 degrees in 2theta, so the fit was performed on two datasets simultaneously to account for the mismatch between the two geometries at that angle. ; # The next three items are given as text. _pd_proc_ls_profile_function ; Simple_Axial_Model(7.66(2)) function with Rp=9999,Rs=300 in TOPAS-Academic ; _pd_proc_ls_background_function ; Chebyshev polynomial with 15 coeffecients ; _pd_proc_ls_pref_orient_corr ; none ; _pd_proc_ls_prof_R_factor ? _pd_proc_ls_prof_wR_factor 5.356 _pd_proc_ls_prof_wR_expected 3.007 _refine_ls_R_I_factor ? _refine_ls_R_Fsqd_factor ? _refine_ls_R_factor_all ? _refine_special_details ; The structure was refined as four rigid bodies and four free atoms. The two Cd atoms, and two independent S atoms were treated as single atoms, with the Cd atoms being located on the 2-fold axis and the S atoms on general positions. There are two independed aromatic rings, both located on inversion centers, and so modeled as only half of the rings. The ethylenediamine molecules were treated as two independed rigid bodies, with one being located on a general position while the other was modeled as only half of the molecule with a dummy atom located midway between the C-C bond and located on the 2-fold axis. Internal degrees of freedom for the rigid bodies were parameterized as a single bond length for the aromatic rings, which was refined to a value of 1.407(3) Angstroms. The N-C and C-C bonds within the ethylenediameine molecules were both refined to values of 1.458(5) and 1.570(8) Angstroms respectively. The only refined torsion angle was that of the full en rigid body, which was refined to a value of 303.4(9) degrees. All hydrogen atoms were tethered to their respective heavier atoms with a distance of 1 Angstrom and ideal geometry. Two illuminated volume corrections were applied, one to account for the change in the illuminated length of the sample as theta was increased, and another to account for the change in effective depth of the sample as theta was increased. An anisotropic strain broadening model based on that developed in Stephens, P. W., J. Appl. Cryst. (1999). 32, 281-289 was applied as well. ; _refine_ls_matrix_type ? _refine_ls_weighting_scheme sigma # options are 'sigma'(based on measured su's) # or 'calc' (calculated weights) _refine_ls_weighting_details ? _refine_ls_hydrogen_treatment ? _refine_ls_extinction_method ? _refine_ls_extinction_coef ? _refine_ls_number_parameters 87 _refine_ls_number_restraints ? _refine_ls_number_constraints ? # The following item is the same as CHI, the square root of 'CHI squared' _refine_ls_goodness_of_fit_all 1.781 _refine_ls_restrained_S_all ? _refine_ls_shift/su_max 0.1 _refine_ls_shift/su_mean ? # The following four items apply to angular dispersive measurements. # 2theta minimum, maximum and increment (in degrees) are for the # intensities used in the refinement. _pd_proc_2theta_range_min 1 _pd_proc_2theta_range_max 45 _pd_proc_2theta_range_inc 0.005 _pd_proc_wavelength 0.696745 _pd_block_diffractogram_id DLT3-25 # The id used for the block containing # the powder pattern profile (section 11) # Give appropriate details in the next two text fields. _pd_proc_info_excluded_regions ? _pd_proc_info_data_reduction ? # The following items are used to identify the programs used. _computing_data_collection EPICS _computing_cell_refinement 'TOPAS Academic' _computing_data_reduction ? _computing_structure_solution 'TOPAS Academic' _computing_structure_refinement 'TOPAS Academic' _computing_molecular_graphics ? _computing_publication_material ? # 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS loop_ _atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_calc_flag _atom_site_refinement_flags Cd1 Cd Uiso 0.50000 0.22989(9) 0.25000 1.000 0.0540(7) . . S1 S Uiso 0.3749(3) 0.3400(3) 0.3321(2) 1.000 0.0540(7) . . S2 S Uiso 0.3888(3) 0.1294(3) 0.1427(2) 1.000 0.0540(7) . . C1A C Uiso 0.23814 0.15564 0.00054 1.000 0.0540(7) . . C1B C Uiso 0.21268 0.33203 0.46244 1.000 0.0540(7) . . C2A C Uiso 0.32639 0.29172 0.05982 1.000 0.0540(7) . . C2B C Uiso 0.34407 0.20687 0.46317 1.000 0.0540(7) . . C3A C Uiso 0.31453 0.19736 0.06036 1.000 0.0540(7) . . C3B C Uiso 0.30675 0.28890 0.42560 1.000 0.0540(7) . . Cd2 Cd Uiso 0.00000 0.16806(8) 0.25000 1.000 0.0540(7) . . N1A N Uiso 0.03491 0.13144 0.40392 1.000 0.0540(7) . . N1B N Uiso 0.11854 0.29192 0.21487 1.000 0.0540(7) . . N2A N Uiso 0.14922 0.06376 0.24665 1.000 0.0540(7) . . C7A C Uiso 0.09142 0.04451 0.40821 1.000 0.0540(7) . . C7B C Uiso 0.04667 0.37114 0.21279 1.000 0.0540(7) . . C8A C Uiso 0.19079 0.04372 0.33855 1.000 0.0540(7) . . H1A H Uiso 0.22971 0.08856 0.00092 1.000 0.0540(7) . . H1B H Uiso 0.18616 0.39035 0.43573 1.000 0.0540(7) . . H2A H Uiso 0.38069 0.32138 0.10234 1.000 0.0540(7) . . H2B H Uiso 0.41094 0.17621 0.43698 1.000 0.0540(7) . . H3A H Uiso 0.04122 -0.00784 0.39549 1.000 0.0540(7) . . H3B H Uiso 0.01165 0.38224 0.15147 1.000 0.0540(7) . . H4A H Uiso 0.11957 0.02901 0.47091 1.000 0.0540(7) . . H4B H Uiso 0.08761 0.42906 0.22268 1.000 0.0540(7) . . H5A H Uiso 0.24988 0.08638 0.35999 1.000 0.0540(7) . . H5B H Uiso 0.17799 0.29830 0.16747 1.000 0.0540(7) . . H6A H Uiso 0.23090 -0.01522 0.34280 1.000 0.0540(7) . . H6B H Uiso 0.16386 0.29226 0.27256 1.000 0.0540(7) . . H7A H Uiso -0.02838 0.13194 0.44828 1.000 0.0540(7) . . H8A H Uiso 0.08415 0.17911 0.43069 1.000 0.0540(7) . . H9A H Uiso 0.21252 0.06325 0.20229 1.000 0.0540(7) . . H10A H Uiso 0.10392 0.01181 0.22374 1.000 0.0540(7) . . #=============================================================================== # 10. MOLECULAR GEOMETRY _geom_special_details ; Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag Cd1 S1 2.524(4) . . yes Cd1 S2 2.537(4) . . yes 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_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag S1 Cd1 S2 111.06(12) . . . yes S1 Cd1 S1 99.37(14) . . 2_655 yes S1 Cd1 S2 113.63(11) . . 2_655 yes S1 Cd1 S2 113.63(11) 2_655 . . yes S2 Cd1 S2 108.04(14) . . 2_655 yes S1 Cd1 S2 111.06(12) 2_655 . 2_655 yes data_[Mg(en)3][Cd(SC6H4S)2] _database_code_depnum_ccdc_archive 'CCDC 704800' #TrackingRef 'Cd_thiolates.cif' # 5. CHEMICAL DATA _chemical_name_systematic ; ??? ; _chemical_name_common (Mg(en)3)(Cd(SC6H4S)2) _chemical_formula_moiety ? _chemical_formula_structural '[Mg(en)3][Cd(SC6H4S)2]' _chemical_formula_analytical ? _chemical_formula_sum 'Mg0.813 Cd1.187 S4 C18 N6 H32' _chemical_formula_weight 613.673 _chemical_melting_point ? _chemical_compound_source ? # for minerals and # natural products loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source _atom_type_scat_length_neutron # include if applicable ? ? ? ? ? ? #============================================================================== # 6. POWDER SPECIMEN AND CRYSTAL DATA _space_group_crystal_system Monoclinic _space_group_name_H-M_alt C2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, 1/2-z' '-x, -y, -z' 'x, -y, 1/2+z' '1/2+x, 1/2+y, z' '1/2-x, 1/2+y, 1/2-z' '1/2-x, 1/2-y, -z' '1/2+x, 1/2-y, 1/2+z' _cell_length_a 11.87713(27) _cell_length_b 14.71177(43) _cell_length_c 14.62618(29) _cell_angle_alpha 90 _cell_angle_beta 90.41268(95) _cell_angle_gamma 90 _cell_volume 2555.62(11) _cell_measurement_temperature 298 _cell_formula_units_Z 4 # The next three fields give the specimen dimensions in mm. The equatorial # plane contains the incident and diffracted beam. _pd_spec_size_axial 8 # perpendicular to # equatorial plane _pd_spec_size_equat 0.7 # parallel to # scattering vector # in transmission _pd_spec_size_thick ? # parallel to # scattering vector # in reflection # The next five fields are character fields that describe the specimen. _pd_spec_mounting # This field should be # used to give details of the # container. ; Sample was loaded into a thin walled glass capillary ; _pd_spec_mount_mode transmission # options are 'reflection' # or 'transmission' _pd_spec_shape cylinder # options are 'cylinder' # 'flat_sheet' or 'irregular' _pd_char_particle_morphology ? _pd_char_colour ? # use ICDD colour descriptions # The following three fields describe the preparation of the specimen. # The cooling rate is in K/min. The pressure at which the sample was # prepared is in kPa. The temperature of preparation is in K. _pd_prep_cool_rate ? _pd_prep_pressure ? _pd_prep_temperature ? # The next four fields are normally only needed for transmission experiments. _exptl_absorpt_coefficient_mu ? _exptl_absorpt_correction_type none # include if applicable _exptl_absorpt_process_details ? # include if applicable _exptl_absorpt_correction_T_min ? # include if applicable _exptl_absorpt_correction_T_max ? # include if applicable #============================================================================== # 7. EXPERIMENTAL DATA _exptl_special_details ; ? ; # The following item is used to identify the equipment used to record # the powder pattern when the diffractogram was measured at a laboratory # other than the authors' home institution, e.g. when neutron or synchrotron # radiation is used. _pd_instr_location ; X16C, National Synchrotron Light Source, Brookhaven National Laboratory ; _pd_calibration_special_details # description of the method used # to calibrate the instrument ; NIST standard reference material 1976(sintered plate of Al2O3). 7 reflections were used to calibrate wavelength and detector zero. ; _diffrn_ambient_temperature 298 _diffrn_source synchrotron _diffrn_source_target ? _diffrn_source_type ? _diffrn_radiation_type ? _diffrn_measurement_device_type 'Huber diffractometer' _diffrn_detector 'NaI scintillation counter' _diffrn_detector_type ? # make or model of detector _pd_meas_scan_method step # options are 'step', 'cont', # 'tof', 'fixed' or # 'disp' (= dispersive) _pd_meas_special_details ; ? ; # The following six items are used for angular dispersive measurements only. _diffrn_radiation_wavelength 0.698525 _diffrn_radiation_monochromator 'double Si(111)' # The following four items give details of the measured (not processed) # powder pattern. Angles are in degrees. _pd_meas_number_of_points 7600 _pd_meas_2theta_range_min 2 _pd_meas_2theta_range_max 40 _pd_meas_2theta_range_inc 0.005 # The following three items are used for time-of-flight measurements only. _pd_instr_dist_src/spec ? _pd_instr_dist_spec/detc ? _pd_meas_2theta_fixed ? #============================================================================== # 8. REFINEMENT DATA # Use the next field to give any special details about the fitting of the # powder pattern. _pd_proc_ls_special_details ; ? ; # The next three items are given as text. _pd_proc_ls_profile_function ; Simple_Axial_Model(8.41(2)) function with Rp=9999,Rs=300 in TOPAS-Academic ; _pd_proc_ls_background_function ; Chebyshev polynomial with 12 coeffecients ; _pd_proc_ls_pref_orient_corr ; none ; _pd_proc_ls_prof_R_factor ? _pd_proc_ls_prof_wR_factor 4.524 _pd_proc_ls_prof_wR_expected 3.420 _refine_ls_R_I_factor ? _refine_ls_R_Fsqd_factor ? _refine_ls_R_factor_all ? _refine_special_details ; The structure was modeled as 4 rigid bodies and 6 free atoms. The sites with either Mg or Cd were occupied by one atom of each, with the occupancies refined and constrained so that a total of one atom was present on each site. The nominally Cd site was found to be fully occupied by Cd and unoccupied by Mg. The nominally Mg site was found to be 0.813(3) occupied by Mg and 0.187(3) by Cd. Both sites are located on a 2-fold axis. The S atoms were placed on general positions. There are two independed aromatic rings, both located on inversion centers, and so modeled as only half of the rings. The ethylenediamine molecules were treated as two independed rigid bodies, with one being located on a general position while the other was modeled as only half of the molecule with a dummy atom located midway between the C-C bond and located on the 2-fold axis. Internal degrees of freedom for the rigid bodies were parameterized as a single bond length for the aromatic rings, which was refined to a value of 1.406(4) Angstroms. The N-C and C-C bonds within the ethylenediameine molecules were both refined to values of 1.401(7) and 1.680(9) Angstroms respectively. The only refined torsion angle was that of the full en rigid body, which was refined to a value of 315(1) degrees. All Hydrogen atoms were tethered to their respective heavier atoms with a distance of 1 Angstrom. An anisotropic strain broadening model based on that developed in Stephens, P. W., J. Appl. Cryst. (1999). 32, 281-289 was applied as well. ; _refine_ls_matrix_type ? _refine_ls_weighting_scheme sigma # options are 'sigma'(based on measured su's) # or 'calc' (calculated weights) _refine_ls_weighting_details ? _refine_ls_hydrogen_treatment ? _refine_ls_extinction_method ? _refine_ls_extinction_coef ? _refine_ls_number_parameters 61 _refine_ls_number_restraints ? _refine_ls_number_constraints ? # The following item is the same as CHI, the square root of 'CHI squared' _refine_ls_goodness_of_fit_all 1.323 _refine_ls_restrained_S_all ? _refine_ls_shift/su_max ? _refine_ls_shift/su_mean ? # The following four items apply to angular dispersive measurements. # 2theta minimum, maximum and increment (in degrees) are for the # intensities used in the refinement. _pd_proc_2theta_range_min 2 _pd_proc_2theta_range_max 40 _pd_proc_2theta_range_inc 0.005 _pd_proc_wavelength 0.698525 _pd_block_diffractogram_id DLT3-268 # The id used for the block containing # the powder pattern profile (section 11) # Give appropriate details in the next two text fields. _pd_proc_info_excluded_regions ? _pd_proc_info_data_reduction ? # The following items are used to identify the programs used. _computing_data_collection EPICS _computing_cell_refinement 'TOPAS Academic' _computing_data_reduction ? _computing_structure_solution 'TOPAS Academic' _computing_structure_refinement 'TOPAS Academic' _computing_molecular_graphics ? _computing_publication_material ? # 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS loop_ _atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_calc_flag _atom_site_refinement_flags Cd1 Cd Uiso 0.50000 0.22608(12) 0.25000 1.000(10) 0.0277(6) . . S1 S Uiso 0.3779(3) 0.3411(3) 0.3345(3) 1.000 0.0277(6) . . S2 S Uiso 0.3869(3) 0.1231(3) 0.1425(3) 1.000 0.0277(6) . . C1 C Uiso 0.23826 0.15498 -0.00382 1.000 0.0277(6) . . C2 C Uiso 0.32635 0.28949 0.06223 1.000 0.0277(6) . . C3 C Uiso 0.31460 0.19448 0.05841 1.000 0.0277(6) . . C4 C Uiso 0.20823 0.33168 0.46317 1.000 0.0277(6) . . C5 C Uiso 0.34626 0.20930 0.46244 1.000 0.0277(6) . . C6 C Uiso 0.30449 0.29098 0.42561 1.000 0.0277(6) . . N1 N Uiso 0.02852 0.12641 0.39728 1.000 0.0277(6) . . N2 N Uiso 0.15132 0.06388 0.24721 1.000 0.0277(6) . . C7 C Uiso 0.09292 0.04795 0.41179 1.000 0.0277(6) . . C8 C Uiso 0.19563 0.04262 0.33355 1.000 0.0277(6) . . N3 N Uiso 0.11180 0.28967 0.22676 1.000 0.0277(6) . . C9 C Uiso 0.04090 0.36267 0.20497 1.000 0.0277(6) . . Cd2 Cd Uiso 0.00000 0.1631(3) 0.25000 0.188(6) 0.0277(6) . . Mg2 Mg Uiso 0.00000 0.1631(3) 0.25000 0.812(6) 0.0277(6) . . H1 H Uiso 0.22990 0.08740 -0.00654 1.000 0.0277(6) . . H2 H Uiso 0.38065 0.31758 0.10650 1.000 0.0277(6) . . H3 H Uiso 0.17852 0.38978 0.43697 1.000 0.0277(6) . . H4 H Uiso 0.41473 0.18036 0.43572 1.000 0.0277(6) . . H5 H Uiso 0.04771 -0.00937 0.40987 1.000 0.0277(6) . . H6 H Uiso 0.12670 0.04432 0.47451 1.000 0.0277(6) . . H7 H Uiso 0.25936 0.08295 0.35265 1.000 0.0277(6) . . H8 H Uiso 0.23242 -0.01848 0.33629 1.000 0.0277(6) . . H9 H Uiso -0.03260 0.12958 0.44384 1.000 0.0277(6) . . H10 H Uiso 0.07412 0.18122 0.41379 1.000 0.0277(6) . . H11 H Uiso 0.21245 0.06070 0.20065 1.000 0.0277(6) . . H12 H Uiso 0.10079 0.01360 0.22612 1.000 0.0277(6) . . H13 H Uiso -0.00752 0.35144 0.14990 1.000 0.0277(6) . . H14 H Uiso 0.08237 0.41861 0.18587 1.000 0.0277(6) . . H15 H Uiso 0.16048 0.27531 0.17316 1.000 0.0277(6) . . H16 H Uiso 0.16940 0.30976 0.27270 1.000 0.0277(6) . . #============================================================================== data_[Cd(en)3][Cd(SeC6H4Se)2] _database_code_depnum_ccdc_archive 'CCDC 704801' #TrackingRef 'Cd_thiolates.cif' # 5. CHEMICAL DATA _chemical_name_systematic ; ??? ; _chemical_name_common (Cd(en)3)(Cd(SeC6H4Se)2) _chemical_formula_moiety ? _chemical_formula_structural '[Cd(en)3][Cd(SeC6H4Se)2]' _chemical_formula_analytical ? _chemical_formula_sum 'C18 H32 Cd2 N6 Se4' _chemical_formula_weight 873.16 _chemical_melting_point ? _chemical_compound_source ? # for minerals and # natural products loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source _atom_type_scat_length_neutron # include if applicable ? ? ? ? ? ? #============================================================================== # 6. POWDER SPECIMEN AND CRYSTAL DATA _space_group_crystal_system Monoclinic _space_group_name_H-M_alt C2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, 1/2-z' '-x, -y, -z' 'x, -y, 1/2+z' '1/2+x, 1/2+y, z' '1/2-x, 1/2+y, 1/2-z' '1/2-x, 1/2-y, -z' '1/2+x, 1/2-y, 1/2+z' _cell_length_a 12.01276(26) _cell_length_b 14.67424(34) _cell_length_c 15.20217(31) _cell_angle_alpha 90 _cell_angle_beta 89.11913(94) _cell_angle_gamma 90 _cell_volume 2679.49(10) _cell_measurement_temperature 298 _cell_formula_units_Z 4 # The next three fields give the specimen dimensions in mm. The equatorial # plane contains the incident and diffracted beam. _pd_spec_size_axial 4 # perpendicular to # equatorial plane _pd_spec_size_equat ? # parallel to # scattering vector # in transmission _pd_spec_size_thick 0.5 # parallel to # scattering vector # in reflection # The next five fields are character fields that describe the specimen. _pd_spec_mounting # This field should be # used to give details of the # container. ; Sample was loaded into a quartz zero background flat plate sample holder ; _pd_spec_mount_mode reflection # options are 'reflection' # or 'transmission' _pd_spec_shape flat_sheet # options are 'cylinder' # 'flat_sheet' or 'irregular' _pd_char_particle_morphology ? _pd_char_colour ? # use ICDD colour descriptions # The following three fields describe the preparation of the specimen. # The cooling rate is in K/min. The pressure at which the sample was # prepared is in kPa. The temperature of preparation is in K. _pd_prep_cool_rate ? _pd_prep_pressure ? _pd_prep_temperature ? # The next four fields are normally only needed for transmission experiments. _exptl_absorpt_coefficient_mu ? _exptl_absorpt_correction_type ? # include if applicable _exptl_absorpt_process_details ? # include if applicable _exptl_absorpt_correction_T_min ? # include if applicable _exptl_absorpt_correction_T_max ? # include if applicable #============================================================================== # 7. EXPERIMENTAL DATA _exptl_special_details ; ? ; # The following item is used to identify the equipment used to record # the powder pattern when the diffractogram was measured at a laboratory # other than the authors' home institution, e.g. when neutron or synchrotron # radiation is used. _pd_instr_location ; X16C, National Synchrotron Light Source, Brookhaven National Laboratory ; _pd_calibration_special_details # description of the method used # to calibrate the instrument ; NIST standard reference material 1976(sintered plate of Al2O3). 7 reflections were used to calibrate wavelength and detector zero. ; _diffrn_ambient_temperature 298 _diffrn_source synchrotron _diffrn_source_target ? _diffrn_source_type ? _diffrn_radiation_type ? _diffrn_measurement_device_type 'Huber diffractometer' _diffrn_detector 'NaI scintillation counter' _diffrn_detector_type ? # make or model of detector _pd_meas_scan_method step # options are 'step', 'cont', # 'tof', 'fixed' or # 'disp' (= dispersive) _pd_meas_special_details ; ? ; # The following six items are used for angular dispersive measurements only. _diffrn_radiation_wavelength 0.696942 _diffrn_radiation_monochromator 'double Si(111)' # The following four items give details of the measured (not processed) # powder pattern. Angles are in degrees. _pd_meas_number_of_points 6788 _pd_meas_2theta_range_min 1 _pd_meas_2theta_range_max 34.940 _pd_meas_2theta_range_inc 0.005 # The following three items are used for time-of-flight measurements only. _pd_instr_dist_src/spec ? _pd_instr_dist_spec/detc ? _pd_meas_2theta_fixed ? #============================================================================== # 8. REFINEMENT DATA # Use the next field to give any special details about the fitting of the # powder pattern. _pd_proc_ls_special_details ; ? ; # The next three items are given as text. _pd_proc_ls_profile_function ; Simple_Axial_Model(6.62(4)) function with Rp=9999,Rs=300 in TOPAS-Academic ; _pd_proc_ls_background_function ; Chebyshev polynomial with 8 coeffecients ; _pd_proc_ls_pref_orient_corr ; none ; _pd_proc_ls_prof_R_factor ? _pd_proc_ls_prof_wR_factor 4.111 _pd_proc_ls_prof_wR_expected 2.839 _refine_ls_R_I_factor ? _refine_ls_R_Fsqd_factor ? _refine_ls_R_factor_all ? _refine_special_details ; The structure was refined as four rigid bodies and four free atoms. The two Cd atoms, and two independent Se atoms were treated as single atoms, with the Cd atoms being located on the 2-fold axis and the Se atoms on general positions. There are two independed aromatic rings, both located on inversion centers, and so modeled as only half of the rings. The ethylenediamine molecules were treated as two independed rigid bodies, with one being located on a general position while the other was modeled as only half of the molecule with a dummy atom located midway between the C-C bond and located on the 2-fold axis. Internal degrees of freedom for the rigid bodies were parameterized as a single bond length for the aromatic rings, which was refined to a value of 1.404(5) Angstroms. The N-C and C-C bonds within the ethylenediameine molecules were both refined to values of 1.41(1) and 1.56(1) Angstroms respectively. The only refined torsion angle was that of the full en rigid body, which was refined to a value of 300(2) degrees. All Hydrogen atoms were tethered to their respective heavier atoms with a distance of 1 Angstrom. Two illuminated volume corrections were applied, one to account for the change in the illuminated length of the sample as theta was increased, and another to account for the change in effective depth of the sample as theta was increased. An anisotropic strain broadening model based on that developed in Stephens, P. W., J. Appl. Cryst. (1999). 32, 281-289 was applied as well. ; _refine_ls_matrix_type ? _refine_ls_weighting_scheme sigma # options are 'sigma'(based on measured su's) # or 'calc' (calculated weights) _refine_ls_weighting_details ? _refine_ls_hydrogen_treatment ? _refine_ls_extinction_method ? _refine_ls_extinction_coef ? _refine_ls_number_parameters 61 _refine_ls_number_restraints ? _refine_ls_number_constraints ? # The following item is the same as CHI, the square root of 'CHI squared' _refine_ls_goodness_of_fit_all 1.448 _refine_ls_restrained_S_all ? _refine_ls_shift/su_max ? _refine_ls_shift/su_mean ? # The following four items apply to angular dispersive measurements. # 2theta minimum, maximum and increment (in degrees) are for the # intensities used in the refinement. _pd_proc_2theta_range_min 1 _pd_proc_2theta_range_max 34.940 _pd_proc_2theta_range_inc 0.005 _pd_proc_wavelength 0.696951 _pd_block_diffractogram_id DLT3-207 # The id used for the block containing # the powder pattern profile (section 11) # Give appropriate details in the next two text fields. _pd_proc_info_excluded_regions ? _pd_proc_info_data_reduction ? # The following items are used to identify the programs used. _computing_data_collection EPICS _computing_cell_refinement 'TOPAS Academic' _computing_data_reduction ? _computing_structure_solution 'TOPAS Academic' _computing_structure_refinement 'TOPAS Academic' _computing_molecular_graphics ? _computing_publication_material ? # 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS loop_ _atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_calc_flag _atom_site_refinement_flags Cd1 Cd Uiso 0.50000 0.2785(2) 0.25000 1.000 0.0593(14) . . Se1 Se Uiso 0.3719(2) 0.15759(18) 0.17446(19) 1.000 0.0593(14) . . Se2 Se Uiso 0.3893(3) 0.38503(18) 0.3599(2) 1.000 0.0593(14) . . C1 C Uiso 0.29832 0.20648 0.07223 1.000 0.0593(14) . . C2 C Uiso 0.34566 0.28678 0.03823 1.000 0.0593(14) . . C3 C Uiso 0.20266 0.16970 0.03400 1.000 0.0593(14) . . C4 C Uiso 0.32441 0.21020 0.43916 1.000 0.0593(14) . . C5 C Uiso 0.31093 0.30519 0.44121 1.000 0.0593(14) . . C6 C Uiso 0.23651 0.34499 0.50205 1.000 0.0593(14) . . Cd2 Cd Uiso 0.00000 0.32707(19) 0.25000 1.000 0.0593(14) . . N1 N Uiso 0.15038 0.42293 0.24861 1.000 0.0593(14) . . N2 N Uiso 0.01329 0.39158 0.10148 1.000 0.0593(14) . . N3 N Uiso -0.11472 0.19654 0.19623 1.000 0.0593(14) . . C7 C Uiso 0.19365 0.42957 0.16201 1.000 0.0593(14) . . C8 C Uiso 0.09856 0.45771 0.09829 1.000 0.0593(14) . . C9 C Uiso -0.02986 0.13083 0.20516 1.000 0.0593(14) . . H1 H Uiso 0.41381 0.31299 0.06547 1.000 0.0593(14) . . H2 H Uiso 0.16893 0.11248 0.05822 1.000 0.0593(14) . . H3 H Uiso 0.37743 0.18184 0.39582 1.000 0.0593(14) . . H4 H Uiso 0.22691 0.41267 0.50351 1.000 0.0593(14) . . H5 H Uiso 0.22945 0.37208 0.14042 1.000 0.0593(14) . . H6 H Uiso 0.25688 0.47357 0.15599 1.000 0.0593(14) . . H7 H Uiso 0.07215 0.52051 0.11332 1.000 0.0593(14) . . H8 H Uiso 0.13044 0.46754 0.03788 1.000 0.0593(14) . . H9 H Uiso 0.21116 0.40495 0.28933 1.000 0.0593(14) . . H10 H Uiso 0.13159 0.48518 0.27110 1.000 0.0593(14) . . H11 H Uiso -0.04750 0.40957 0.06075 1.000 0.0593(14) . . H12 H Uiso 0.04044 0.33406 0.07315 1.000 0.0593(14) . . H13 H Uiso 0.02650 0.13200 0.15607 1.000 0.0593(14) . . H14 H Uiso -0.05733 0.06665 0.20128 1.000 0.0593(14) . . H15 H Uiso -0.15289 0.18741 0.13890 1.000 0.0593(14) . . H16 H Uiso -0.17669 0.18304 0.23893 1.000 0.0593(14) . . data_[Zn(en)3][Zn(SC6H4S)2] _database_code_depnum_ccdc_archive 'CCDC 704802' #TrackingRef 'Cd_thiolates.cif' # 5. CHEMICAL DATA _chemical_name_systematic ; ??? ; _chemical_name_common (Zn(en)3)(Zn(SC6H4S)2) _chemical_formula_moiety ? _chemical_formula_structural '[Zn(en)3][Zn(SC6H4S)2]' _chemical_formula_analytical ? _chemical_formula_sum 'C18 H32 N6 S4 Zn2' _chemical_formula_weight 591.56 _chemical_melting_point ? _chemical_compound_source ? # for minerals and # natural products loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source _atom_type_scat_length_neutron # include if applicable ? ? ? ? ? ? #============================================================================== # 6. POWDER SPECIMEN AND CRYSTAL DATA _space_group_crystal_system Monoclinic _space_group_name_H-M_alt C2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, 1/2-z' '-x, -y, -z' 'x, -y, 1/2+z' '1/2+x, 1/2+y, z' '1/2-x, 1/2+y, 1/2-z' '1/2-x, 1/2-y, -z' '1/2+x, 1/2-y, 1/2+z' _cell_length_a 11.65582(32) _cell_length_b 15.24511(54) _cell_length_c 14.21869(40) _cell_angle_alpha 90 _cell_angle_beta 90.6517(13) _cell_angle_gamma 90 _cell_volume 2526.42(13) _cell_measurement_temperature 298 _cell_formula_units_Z 4 # The next three fields give the specimen dimensions in mm. The equatorial # plane contains the incident and diffracted beam. _pd_spec_size_axial 8 # perpendicular to # equatorial plane _pd_spec_size_equat ? # parallel to # scattering vector # in transmission _pd_spec_size_thick 0.5 # parallel to # scattering vector # in reflection # The next five fields are character fields that describe the specimen. _pd_spec_mounting # This field should be # used to give details of the # container. ; Sample was loaded into a quartz zero background flat plate sample holder ; _pd_spec_mount_mode reflection # options are 'reflection' # or 'transmission' _pd_spec_shape flat_sheet # options are 'cylinder' # 'flat_sheet' or 'irregular' _pd_char_particle_morphology ? _pd_char_colour ? # use ICDD colour descriptions # The following three fields describe the preparation of the specimen. # The cooling rate is in K/min. The pressure at which the sample was # prepared is in kPa. The temperature of preparation is in K. _pd_prep_cool_rate ? _pd_prep_pressure ? _pd_prep_temperature ? # The next four fields are normally only needed for transmission experiments. _exptl_absorpt_coefficient_mu ? _exptl_absorpt_correction_type ? # include if applicable _exptl_absorpt_process_details ? # include if applicable _exptl_absorpt_correction_T_min ? # include if applicable _exptl_absorpt_correction_T_max ? # include if applicable #============================================================================== # 7. EXPERIMENTAL DATA _exptl_special_details ; ? ; # The following item is used to identify the equipment used to record # the powder pattern when the diffractogram was measured at a laboratory # other than the authors' home institution, e.g. when neutron or synchrotron # radiation is used. _pd_instr_location ; X16C, National Synchrotron Light Source, Brookhaven National Laboratory ; _pd_calibration_special_details # description of the method used # to calibrate the instrument ; NIST standard reference material 1976(sintered plate of Al2O3). 7 reflections were used to calibrate wavelength and detector zero. ; _diffrn_ambient_temperature 298 _diffrn_source synchrotron _diffrn_source_target ? _diffrn_source_type ? _diffrn_radiation_type ? _diffrn_measurement_device_type 'Huber diffractometer' _diffrn_detector 'NaI scintillation counter' _diffrn_detector_type ? # make or model of detector _pd_meas_scan_method step # options are 'step', 'cont', # 'tof', 'fixed' or # 'disp' (= dispersive) _pd_meas_special_details ; ? ; # The following six items are used for angular dispersive measurements only. _diffrn_radiation_wavelength 0.696951 _diffrn_radiation_monochromator 'double Si(111)' # The following four items give details of the measured (not processed) # powder pattern. Angles are in degrees. _pd_meas_number_of_points 3800 _pd_meas_2theta_range_min 1 _pd_meas_2theta_range_max 20 _pd_meas_2theta_range_inc 0.005 # The following three items are used for time-of-flight measurements only. _pd_instr_dist_src/spec ? _pd_instr_dist_spec/detc ? _pd_meas_2theta_fixed ? #============================================================================== # 8. REFINEMENT DATA # Use the next field to give any special details about the fitting of the # powder pattern. _pd_proc_ls_special_details ; ? ; # The next three items are given as text. _pd_proc_ls_profile_function ; Simple_Axial_Model(8.478(29)) function with Rp=9999,Rs=300 in TOPAS-Academic ; _pd_proc_ls_background_function ; Chebyshev polynomial with 12 coeffecients ; _pd_proc_ls_pref_orient_corr ; none ; _pd_proc_ls_prof_R_factor ? _pd_proc_ls_prof_wR_factor 11.428 _pd_proc_ls_prof_wR_expected 5.249 _refine_ls_R_I_factor ? _refine_ls_R_Fsqd_factor ? _refine_ls_R_factor_all ? _refine_special_details ; The structure was refined as four rigid bodies and four free atoms. The two Zn atoms, and two independent S atoms were treated as single atoms, with the Zn atoms being located on the 2-fold axis and the S atoms on general positions. There are two independed aromatic rings, both located on inversion centers, and so modeled as only half of the rings. The ethylenediamine molecules were treated as two independed rigid bodies, with one being located on a general position while the other was modeled as only half of the molecule with a dummy atom located midway between the C-C bond and located on the 2-fold axis. Internal degrees of freedom for the rigid bodies were parameterized as a single bond length for the aromatic rings, which was refined to a value of 1.364(4) Angstroms. The N-C and C-C bonds within the ethylenediameine molecules were both refined to values of 1.55(1) and 1.60(1) Angstroms respectively. The only refined torsion angle was that of the full en rigid body, which was refined to a value of 299(2) degrees. All Hydrogen atoms were tethered to their respective heavier atoms with a distance of 1 Angstrom. Two illuminated volume corrections were applied, one to account for the change in the illuminated length of the sample as theta was increased, and another to account for the change in effective depth of the sample as theta was increased. An anisotropic strain broadening model based on that developed in Stephens, P. W., J. Appl. Cryst. (1999). 32, 281-289 was applied as well. ; _refine_ls_matrix_type ? _refine_ls_weighting_scheme sigma # options are 'sigma'(based on measured su's) # or 'calc' (calculated weights) _refine_ls_weighting_details ? _refine_ls_hydrogen_treatment ? _refine_ls_extinction_method ? _refine_ls_extinction_coef ? _refine_ls_number_parameters 61 _refine_ls_number_restraints ? _refine_ls_number_constraints ? # The following item is the same as CHI, the square root of 'CHI squared' _refine_ls_goodness_of_fit_all 2.177 _refine_ls_restrained_S_all ? _refine_ls_shift/su_max ? _refine_ls_shift/su_mean ? # The following four items apply to angular dispersive measurements. # 2theta minimum, maximum and increment (in degrees) are for the # intensities used in the refinement. _pd_proc_2theta_range_min 1 _pd_proc_2theta_range_max 20 _pd_proc_2theta_range_inc 0.005 _pd_proc_wavelength 0.696951 _pd_block_diffractogram_id DLT3-214 # The id used for the block containing # the powder pattern profile (section 11) # Give appropriate details in the next two text fields. _pd_proc_info_excluded_regions ? _pd_proc_info_data_reduction ? # The following items are used to identify the programs used. _computing_data_collection EPICS _computing_cell_refinement 'TOPAS Academic' _computing_data_reduction ? _computing_structure_solution 'TOPAS Academic' _computing_structure_refinement 'TOPAS Academic' _computing_molecular_graphics ? _computing_publication_material ? # 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS loop_ _atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_calc_flag _atom_site_refinement_flags Zn1 Zn Uiso 0.50000 0.2364(3) 0.25000 1.000 0.084(3) . . S1 S Uiso 0.39281 0.14302 0.14640 1.000 0.084(3) . . S2 S Uiso 0.38877 0.32897 0.33083 1.000 0.050(3) . . C1 C Uiso 0.31261 0.20310 0.06418 1.000 0.084(3) . . C2 C Uiso 0.25653 0.16092 -0.00739 1.000 0.050(3) . . C3 C Uiso 0.30608 0.29218 0.07157 1.000 0.050(3) . . C4 C Uiso 0.20952 0.32210 0.45348 1.000 0.050(3) . . C5 C Uiso 0.35053 0.21207 0.47332 1.000 0.050(3) . . C6 C Uiso 0.31005 0.28417 0.42679 1.000 0.050(3) . . Zn2 Zn Uiso 0.00000 0.1484(3) 0.25000 1.000 0.050(3) . . N1 N Uiso 0.01924 0.14311 0.40122 1.000 0.084(3) . . N2 N Uiso 0.15592 0.06248 0.24408 1.000 0.050(3) . . N3 N Uiso 0.13668 0.25479 0.22249 1.000 0.050(3) . . C7 C Uiso 0.08282 0.05475 0.41372 1.000 0.050(3) . . C8 C Uiso 0.19357 0.05332 0.34828 1.000 0.050(3) . . C9 C Uiso 0.04148 0.32387 0.20558 1.000 0.050(3) . . H1 H Uiso 0.26131 0.09562 -0.01281 1.000 0.084(3) . . H2 H Uiso 0.34718 0.32310 0.12403 1.000 0.050(3) . . H3 H Uiso 0.17985 0.37495 0.41938 1.000 0.050(3) . . H4 H Uiso 0.42421 0.18427 0.45376 1.000 0.050(3) . . H5 H Uiso 0.03378 0.00251 0.39940 1.000 0.050(3) . . H6 H Uiso 0.10630 0.04241 0.48027 1.000 0.050(3) . . H7 H Uiso 0.24856 0.09984 0.36945 1.000 0.050(3) . . H8 H Uiso 0.23922 -0.00094 0.36142 1.000 0.050(3) . . H9 H Uiso -0.04998 0.14401 0.44212 1.000 0.050(3) . . H10 H Uiso 0.06610 0.19128 0.43000 1.000 0.050(3) . . H11 H Uiso 0.22514 0.06158 0.20318 1.000 0.050(3) . . H12 H Uiso 0.11599 0.00764 0.22329 1.000 0.050(3) . . H13 H Uiso -0.00497 0.31312 0.14715 1.000 0.050(3) . . H14 H Uiso 0.07178 0.38408 0.19315 1.000 0.050(3) . . H15 H Uiso 0.18853 0.25310 0.16697 1.000 0.050(3) . . H16 H Uiso 0.19054 0.27606 0.27276 1.000 0.050(3) . . data_[NMe4]2[Cd2(SC6H4S)3] _database_code_depnum_ccdc_archive 'CCDC 704803' #TrackingRef 'Cd_thiolates.cif' # 5. CHEMICAL DATA _chemical_name_systematic ; ??? ; _chemical_name_common (NMe4)2(Cd2(SC6H4S)3) _chemical_formula_moiety ? _chemical_formula_structural '[NMe4]2[Cd2(SC6H4S)3]' _chemical_formula_analytical ? _chemical_formula_sum 'C13 H18 Cd N S3' _chemical_formula_weight 396.90 _chemical_melting_point ? _chemical_compound_source ? # for minerals and # natural products loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source _atom_type_scat_length_neutron # include if applicable ? ? ? ? ? ? #============================================================================== # 6. POWDER SPECIMEN AND CRYSTAL DATA _space_group_crystal_system Triclinic _space_group_name_H-M_alt P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 11.49545(56) _cell_length_b 10.67562(51) _cell_length_c 8.70190(36) _cell_angle_alpha 58.5230(20) _cell_angle_beta 106.4984(32) _cell_angle_gamma 110.9806(28) _cell_volume 844.045(71) _cell_measurement_temperature 298 _cell_formula_units_Z 2 # The next three fields give the specimen dimensions in mm. The equatorial # plane contains the incident and diffracted beam. _pd_spec_size_axial 8 # perpendicular to # equatorial plane _pd_spec_size_equat ? # parallel to # scattering vector # in transmission _pd_spec_size_thick 0.5 # parallel to # scattering vector # in reflection # The next five fields are character fields that describe the specimen. _pd_spec_mounting # This field should be # used to give details of the # container. ; Sample was loaded into zero background quartz sample holder ; _pd_spec_mount_mode reflection # options are 'reflection' # or 'transmission' _pd_spec_shape flat_sheet # options are 'cylinder' # 'flat_sheet' or 'irregular' _pd_char_particle_morphology ? _pd_char_colour ? # use ICDD colour descriptions # The following three fields describe the preparation of the specimen. # The cooling rate is in K/min. The pressure at which the sample was # prepared is in kPa. The temperature of preparation is in K. _pd_prep_cool_rate ? _pd_prep_pressure ? _pd_prep_temperature ? # The next four fields are normally only needed for transmission experiments. _exptl_absorpt_coefficient_mu ? _exptl_absorpt_correction_type ? # include if applicable _exptl_absorpt_process_details ? # include if applicable _exptl_absorpt_correction_T_min ? # include if applicable _exptl_absorpt_correction_T_max ? # include if applicable #============================================================================== # 7. EXPERIMENTAL DATA _exptl_special_details ; ? ; # The following item is used to identify the equipment used to record # the powder pattern when the diffractogram was measured at a laboratory # other than the authors' home institution, e.g. when neutron or synchrotron # radiation is used. _pd_instr_location ; X16C, National Synchrotron Light Source, Brookhaven National Laboratory ; _pd_calibration_special_details # description of the method used # to calibrate the instrument ; NIST standard reference material 1976(sintered plate of Al2O3). 7 reflections were used to calibrate wavelength and detector zero. ; _diffrn_ambient_temperature 298 _diffrn_source synchrotron _diffrn_source_target ? _diffrn_source_type ? _diffrn_radiation_type ? _diffrn_measurement_device_type 'Huber diffractometer' _diffrn_detector 'NaI scintillation counter' _diffrn_detector_type ? # make or model of detector _pd_meas_scan_method step # options are 'step', 'cont', # 'tof', 'fixed' or # 'disp' (= dispersive) _pd_meas_special_details ; ? ; # The following six items are used for angular dispersive measurements only. _diffrn_radiation_wavelength 0.697907 _diffrn_radiation_monochromator 'double Si(111)' # The following four items give details of the measured (not processed) # powder pattern. Angles are in degrees. _pd_meas_number_of_points 6600 _pd_meas_2theta_range_min 2 _pd_meas_2theta_range_max 35 _pd_meas_2theta_range_inc 0.005 # The following three items are used for time-of-flight measurements only. _pd_instr_dist_src/spec ? _pd_instr_dist_spec/detc ? _pd_meas_2theta_fixed ? #============================================================================== # 8. REFINEMENT DATA # Use the next field to give any special details about the fitting of the # powder pattern. _pd_proc_ls_special_details ; ? ; # The next three items are given as text. _pd_proc_ls_profile_function ; Simple_Axial_Model(7.42(4)) function with Rp=9999,Rs=300 in TOPAS-Academic ; _pd_proc_ls_background_function ; Chebyshev polynomial with 14 coeffecients ; _pd_proc_ls_pref_orient_corr ; none ; _pd_proc_ls_prof_R_factor ? _pd_proc_ls_prof_wR_factor 6.703 _pd_proc_ls_prof_wR_expected 2.675 _refine_ls_R_I_factor ? _refine_ls_R_Fsqd_factor ? _refine_ls_R_factor_all ? _refine_special_details ; The structure was refined as 4 rigid bodies. Three half rings were modeled as rigid bodies and also placed on inversion centers. There is a single independent molecule of NMe4 which was modeled as a rigid body and placed on a general position, giving the other molecule present in the structure from symmetry. Paramters relating to the structure internal to the rigid bodies were a single bond length for the aromatic rings, which was refined to a value of 1.367(5) Angstroms. The NMe4 molecule was refined with a single internal parameter for the N-C bond length, which was refined to a value of 1.51(1) Angstroms. The Cd atoms were given their own isotropic thermal parameter. Because of the possibility for some disorder in the NMe4 ion, all atoms composing that ion were given a different isotropic thermal parameter, which refined to a higher value than all that for the other atoms. All remaining atoms were given a third isotropic thermal paramter. All Hydrogen atoms were tethered to their respective heavier atoms with a distance of 1 Angstrom. Two illuminated volume corrections were applied, one to account for the change in the illuminated length of the sample as theta was increased, and another to account for the change in effective depth of the sample as theta was increased. An anisotropic strain broadening model based on that developed in Stephens, P. W., J. Appl. Cryst. (1999). 32, 281-289 was applied as well. ; _refine_ls_matrix_type ? _refine_ls_weighting_scheme sigma # options are 'sigma'(based on measured su's) # or 'calc' (calculated weights) _refine_ls_weighting_details ? _refine_ls_hydrogen_treatment ? _refine_ls_extinction_method ? _refine_ls_extinction_coef ? _refine_ls_number_parameters 71 _refine_ls_number_restraints ? _refine_ls_number_constraints ? # The following item is the same as CHI, the square root of 'CHI squared' _refine_ls_goodness_of_fit_all 2.506 _refine_ls_restrained_S_all ? _refine_ls_shift/su_max ? _refine_ls_shift/su_mean ? # The following four items apply to angular dispersive measurements. # 2theta minimum, maximum and increment (in degrees) are for the # intensities used in the refinement. _pd_proc_2theta_range_min 2 _pd_proc_2theta_range_max 35 _pd_proc_2theta_range_inc 0.005 _pd_proc_wavelength 0.697907 _pd_block_diffractogram_id DLT4-98 # The id used for the block containing # the powder pattern profile (section 11) # Give appropriate details in the next two text fields. _pd_proc_info_excluded_regions ? _pd_proc_info_data_reduction ? # The following items are used to identify the programs used. _computing_data_collection EPICS _computing_cell_refinement 'TOPAS Academic' _computing_data_reduction ? _computing_structure_solution 'TOPAS Academic' _computing_structure_refinement 'TOPAS Academic' _computing_molecular_graphics ? _computing_publication_material ? # 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS loop_ _atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_calc_flag _atom_site_refinement_flags Cd1 Cd Uiso 0.15569 0.11661 0.97645 1.000 0.1169(57) . . S1 S Uiso 0.03308 -0.11616 0.93426 1.000 0.0742(52) . . S2 S Uiso 0.33517 0.03562 1.20534 1.000 0.0742(52) . . S3 S Uiso 0.22588 0.35553 0.72429 1.000 0.0742(52) . . C11 C Uiso 0.01379 -0.04844 0.68108 1.000 0.0742(52) . . C12 C Uiso 0.10615 -0.04023 0.60522 1.000 0.0742(52) . . C13 C Uiso -0.09235 -0.00821 0.57586 1.000 0.0742(52) . . C21 C Uiso 0.52875 -0.04609 1.18090 1.000 0.0742(52) . . C22 C Uiso 0.40078 0.06132 0.90688 1.000 0.0742(52) . . C23 C Uiso 0.42954 0.01523 1.08778 1.000 0.0742(52) . . C31 C Uiso -0.01337 0.35086 0.55826 1.000 0.0742(52) . . C32 C Uiso 0.09804 0.43729 0.59735 1.000 0.0742(52) . . C33 C Uiso 0.11141 0.58643 0.53909 1.000 0.0742(52) . . N1 N Uiso 0.29935 0.53382 0.16186 1.000 0.253(11) . . C7 C Uiso 0.31406 0.57706 -0.02784 1.000 0.253(11) . . C8 C Uiso 0.29382 0.67105 0.16596 1.000 0.253(11) . . C9 C Uiso 0.40254 0.46834 0.30299 1.000 0.253(11) . . C10 C Uiso 0.17744 0.41183 0.19218 1.000 0.253(11) . . H12 H Uiso 0.18436 -0.06987 0.68276 1.000 0.0742(52) . . H13 H Uiso -0.16041 -0.01426 0.63176 1.000 0.0742(52) . . H21 H Uiso 0.54994 -0.08005 1.31421 1.000 0.0742(52) . . H22 H Uiso 0.32767 0.10650 0.83826 1.000 0.0742(52) . . H31 H Uiso -0.02323 0.24095 0.60119 1.000 0.0742(52) . . H33 H Uiso 0.19352 0.65013 0.56790 1.000 0.0742(52) . . H7A H Uiso 0.33427 0.49260 -0.02600 1.000 0.253(11) . . H7B H Uiso 0.23683 0.60472 -0.11123 1.000 0.253(11) . . H7C H Uiso 0.37835 0.67636 -0.07839 1.000 0.253(11) . . H8A H Uiso 0.33675 0.66800 0.28477 1.000 0.253(11) . . H8B H Uiso 0.33006 0.76539 0.05846 1.000 0.253(11) . . H8C H Uiso 0.20450 0.67558 0.14001 1.000 0.253(11) . . H9A H Uiso 0.40969 0.48327 0.40992 1.000 0.253(11) . . H9B H Uiso 0.38635 0.35956 0.33450 1.000 0.253(11) . . H9C H Uiso 0.48224 0.51447 0.24692 1.000 0.253(11) . . H10A H Uiso 0.16294 0.36177 0.32185 1.000 0.253(11) . . H10B H Uiso 0.10799 0.45682 0.10371 1.000 0.253(11) . . H10C H Uiso 0.17881 0.33950 0.15296 1.000 0.253(11) . . #============================================================================== #============================================================================== data_[NEt4]2[Cd2(SC6H4S)3] _database_code_depnum_ccdc_archive 'CCDC 704804' #TrackingRef 'Cd_thiolates.cif' # 5. CHEMICAL DATA _chemical_name_systematic ; ??? ; _chemical_name_common (NEt4)2(Cd2(SC6H4S)3) _chemical_formula_moiety ? _chemical_formula_structural '[NEt4]2[Cd2(SC6H4S)3]' _chemical_formula_analytical ? _chemical_formula_sum 'C17 H26 Cd N S3' _chemical_formula_weight 453.01 _chemical_melting_point ? _chemical_compound_source ? # for minerals and # natural products loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source _atom_type_scat_length_neutron # include if applicable ? ? ? ? ? ? #============================================================================== # 6. POWDER SPECIMEN AND CRYSTAL DATA _space_group_crystal_system Triclinic _space_group_name_H-M_alt P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 9.04393(76) _cell_length_b 9.60952(71) _cell_length_c 12.1736(11) _cell_angle_alpha 94.7168(68) _cell_angle_beta 80.1422(79) _cell_angle_gamma 68.6195(69) _cell_volume 958.49(15) _cell_measurement_temperature 298 _cell_formula_units_Z 2 # The next three fields give the specimen dimensions in mm. The equatorial # plane contains the incident and diffracted beam. _pd_spec_size_axial 8 # perpendicular to # equatorial plane _pd_spec_size_equat 0.7 # parallel to # scattering vector # in transmission _pd_spec_size_thick ? # parallel to # scattering vector # in reflection # The next five fields are character fields that describe the specimen. _pd_spec_mounting # This field should be # used to give details of the # container. ; Sample was loaded into a thin walled glass capillary ; _pd_spec_mount_mode transmission # options are 'reflection' # or 'transmission' _pd_spec_shape cylinder # options are 'cylinder' # 'flat_sheet' or 'irregular' _pd_char_particle_morphology ? _pd_char_colour ? # use ICDD colour descriptions # The following three fields describe the preparation of the specimen. # The cooling rate is in K/min. The pressure at which the sample was # prepared is in kPa. The temperature of preparation is in K. _pd_prep_cool_rate ? _pd_prep_pressure ? _pd_prep_temperature ? # The next four fields are normally only needed for transmission experiments. _exptl_absorpt_coefficient_mu ? _exptl_absorpt_correction_type ? # include if applicable _exptl_absorpt_process_details ? # include if applicable _exptl_absorpt_correction_T_min ? # include if applicable _exptl_absorpt_correction_T_max ? # include if applicable #============================================================================== # 7. EXPERIMENTAL DATA _exptl_special_details ; ? ; # The following item is used to identify the equipment used to record # the powder pattern when the diffractogram was measured at a laboratory # other than the authors' home institution, e.g. when neutron or synchrotron # radiation is used. _pd_instr_location ; X16C, National Synchrotron Light Source, Brookhaven National Laboratory ; _pd_calibration_special_details # description of the method used # to calibrate the instrument ; NIST standard reference material 1976(sintered plate of Al2O3). 7 reflections were used to calibrate wavelength and detector zero. ; _diffrn_ambient_temperature 298 _diffrn_source synchrotron _diffrn_source_target ? _diffrn_source_type ? _diffrn_radiation_type ? _diffrn_measurement_device_type 'Huber diffractometer' _diffrn_detector 'NaI scintillation counter' _diffrn_detector_type ? # make or model of detector _pd_meas_scan_method step # options are 'step', 'cont', # 'tof', 'fixed' or # 'disp' (= dispersive) _pd_meas_special_details ; ? ; # The following six items are used for angular dispersive measurements only. _diffrn_radiation_wavelength 0.598191 _diffrn_radiation_monochromator 'double Si(111)' # The following four items give details of the measured (not processed) # powder pattern. Angles are in degrees. _pd_meas_number_of_points 6600 _pd_meas_2theta_range_min 2 _pd_meas_2theta_range_max 35 _pd_meas_2theta_range_inc 0.005 # The following three items are used for time-of-flight measurements only. _pd_instr_dist_src/spec ? _pd_instr_dist_spec/detc ? _pd_meas_2theta_fixed ? #============================================================================== # 8. REFINEMENT DATA # Use the next field to give any special details about the fitting of the # powder pattern. _pd_proc_ls_special_details ; ? ; # The next three items are given as text. _pd_proc_ls_profile_function ; Simple_Axial_Model(8.00(4)) function with Rp=9999,Rs=300 in TOPAS-Academic ; _pd_proc_ls_background_function ; Chebyshev polynomial with 11 coeffecients ; _pd_proc_ls_pref_orient_corr ; none ; _pd_proc_ls_prof_R_factor ? _pd_proc_ls_prof_wR_factor 7.384 _pd_proc_ls_prof_wR_expected 4.850 _refine_ls_R_I_factor ? _refine_ls_R_Fsqd_factor ? _refine_ls_R_factor_all ? _refine_special_details ; The structure was refined as 4 rigid bodies. Three half rings were modeled as rigid bodies and also placed on inversion centers. There is a single independent molecule of NEt4 which was modeled as a rigid body and placed on a general position, giving the other molecule present in the structure from symmetry. Parameters relating to the structure internal to the rigid bodies were a single bond length for the aromatic rings, which was refined to a value of 1.35(1) Angstroms. The NEt4 molecule was refined with two internal parameters for the N-C bond length and C-C bond length, which were refined to values of 1.67(1) Angstroms and 1.42(2) Angstroms respectively. All atoms were given a single isotropic thermal parameter, and Hydrogen atoms were tethered to their respective heavier atoms with a distance of 1 Angstrom. An anisotropic strain broadening model based on that developed in Stephens, P. W., J. Appl. Cryst. (1999). 32, 281-289 was applied as well. ; _refine_ls_matrix_type ? _refine_ls_weighting_scheme sigma # options are 'sigma'(based on measured su's) # or 'calc' (calculated weights) _refine_ls_weighting_details ? _refine_ls_hydrogen_treatment ? _refine_ls_extinction_method ? _refine_ls_extinction_coef ? _refine_ls_number_parameters 74 _refine_ls_number_restraints ? _refine_ls_number_constraints ? # The following item is the same as CHI, the square root of 'CHI squared' _refine_ls_goodness_of_fit_all 1.522 _refine_ls_restrained_S_all ? _refine_ls_shift/su_max ? _refine_ls_shift/su_mean ? # The following four items apply to angular dispersive measurements. # 2theta minimum, maximum and increment (in degrees) are for the # intensities used in the refinement. _pd_proc_2theta_range_min 2 _pd_proc_2theta_range_max 35 _pd_proc_2theta_range_inc 0.005 _pd_proc_wavelength 0.598191 _pd_block_diffractogram_id DLT4-231 # The id used for the block containing # the powder pattern profile (section 11) # Give appropriate details in the next two text fields. _pd_proc_info_excluded_regions ? _pd_proc_info_data_reduction ? # The following items are used to identify the programs used. _computing_data_collection EPICS _computing_cell_refinement 'TOPAS Academic' _computing_data_reduction ? _computing_structure_solution 'TOPAS Academic' _computing_structure_refinement 'TOPAS Academic' _computing_molecular_graphics ? _computing_publication_material ? # 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS loop_ _atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_calc_flag _atom_site_refinement_flags Cd1 Cd Uiso -0.06694 0.09047 0.14503 1.000 0.0916(27) . . S1 S Uiso 0.20415 -0.10188 0.02467 1.000 0.0916(27) . . S2 S Uiso -0.15279 -0.02517 0.29976 1.000 0.0916(27) . . S3 S Uiso -0.06265 0.33793 0.21575 1.000 0.0916(27) . . C11 C Uiso 0.06681 0.02063 0.39803 1.000 0.0916(27) . . C12 C Uiso -0.13465 -0.03181 0.51307 1.000 0.0916(27) . . C13 C Uiso -0.06783 -0.01118 0.41110 1.000 0.0916(27) . . C21 C Uiso -0.02611 0.43245 0.08993 1.000 0.0916(27) . . C22 C Uiso -0.07395 0.58408 0.10270 1.000 0.0916(27) . . C23 C Uiso 0.04783 0.34837 -0.01277 1.000 0.0916(27) . . C31 C Uiso 0.42221 0.00318 -0.08534 1.000 0.0916(27) . . C32 C Uiso 0.45107 -0.04682 0.09591 1.000 0.0916(27) . . C33 C Uiso 0.37328 -0.04364 0.01057 1.000 0.0916(27) . . N1 N Uiso 0.35979 0.43988 0.27491 1.000 0.0916(27) . . C1 C Uiso 0.50642 0.49246 0.30523 1.000 0.0916(27) . . C2 C Uiso 0.38066 0.27522 0.31851 1.000 0.0916(27) . . C3 C Uiso 0.37298 0.42086 0.13582 1.000 0.0916(27) . . C4 C Uiso 0.17911 0.57088 0.34003 1.000 0.0916(27) . . C5 C Uiso 0.45597 0.65207 0.31097 1.000 0.0916(27) . . C6 C Uiso 0.38339 0.28790 0.43549 1.000 0.0916(27) . . C7 C Uiso 0.27716 0.56128 0.10688 1.000 0.0916(27) . . C8 C Uiso 0.18839 0.62942 0.44887 1.000 0.0916(27) . . H11 H Uiso 0.11641 0.03595 0.32232 1.000 0.0916(27) . . H12 H Uiso -0.23461 -0.05542 0.52278 1.000 0.0916(27) . . H22 H Uiso -0.12885 0.64650 0.17894 1.000 0.0916(27) . . H23 H Uiso 0.08335 0.23579 -0.02225 1.000 0.0916(27) . . H31 H Uiso 0.36445 0.00554 -0.14871 1.000 0.0916(27) . . H32 H Uiso 0.41474 -0.08158 0.16712 1.000 0.0916(27) . . H1A H Uiso 0.52868 0.46374 0.37967 1.000 0.0916(27) . . H1B H Uiso 0.60753 0.44060 0.24496 1.000 0.0916(27) . . H1C H Uiso 0.37119 0.68930 0.26550 1.000 0.0916(27) . . H1D H Uiso 0.40970 0.70206 0.39145 1.000 0.0916(27) . . H1E H Uiso 0.55161 0.67686 0.27997 1.000 0.0916(27) . . H2A H Uiso 0.28719 0.24813 0.30652 1.000 0.0916(27) . . H2B H Uiso 0.48475 0.19466 0.27448 1.000 0.0916(27) . . H2C H Uiso 0.44217 0.18542 0.45409 1.000 0.0916(27) . . H2D H Uiso 0.44055 0.35585 0.45308 1.000 0.0916(27) . . H2E H Uiso 0.26935 0.33134 0.48138 1.000 0.0916(27) . . H3A H Uiso 0.48904 0.39002 0.09593 1.000 0.0916(27) . . H3B H Uiso 0.33214 0.34166 0.11264 1.000 0.0916(27) . . H3C H Uiso 0.16819 0.56137 0.10099 1.000 0.0916(27) . . H3D H Uiso 0.26302 0.64585 0.16663 1.000 0.0916(27) . . H3E H Uiso 0.33303 0.57516 0.03270 1.000 0.0916(27) . . H4A H Uiso 0.14732 0.65480 0.29444 1.000 0.0916(27) . . H4B H Uiso 0.09603 0.52439 0.34822 1.000 0.0916(27) . . H4C H Uiso 0.13378 0.58682 0.50783 1.000 0.0916(27) . . H4D H Uiso 0.30509 0.60027 0.45300 1.000 0.0916(27) . . H4E H Uiso 0.13282 0.74224 0.46216 1.000 0.0916(27) . . data_[NMe4]2[Cd2(SeC6H4Se)3] _database_code_depnum_ccdc_archive 'CCDC 704805' #TrackingRef 'Cd_thiolates.cif' # 5. CHEMICAL DATA _chemical_name_systematic ; ??? ; _chemical_name_common (NMe4)2(Cd2(SeC6H4Se)3) _chemical_formula_moiety ? _chemical_formula_structural '[NMe4]2[Cd2(SeC6H4Se)3]' _chemical_formula_analytical ? _chemical_formula_sum 'C13 H18 Cd N Se3' _chemical_formula_weight 537.57 _chemical_melting_point ? _chemical_compound_source ? # for minerals and # natural products loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source _atom_type_scat_length_neutron # include if applicable ? ? ? ? ? ? #============================================================================== # 6. POWDER SPECIMEN AND CRYSTAL DATA _space_group_crystal_system Triclinic _space_group_name_H-M_alt P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 11.76130(51) _cell_length_b 10.84000(47) _cell_length_c 8.85827(35) _cell_angle_alpha 58.4655(23) _cell_angle_beta 106.7092(35) _cell_angle_gamma 111.8351(33) _cell_volume 887.334(70) _cell_measurement_temperature 298 _cell_formula_units_Z 2 # The next three fields give the specimen dimensions in mm. The equatorial # plane contains the incident and diffracted beam. _pd_spec_size_axial 8 # perpendicular to # equatorial plane _pd_spec_size_equat 0.7 # parallel to # scattering vector # in transmission _pd_spec_size_thick ? # parallel to # scattering vector # in reflection # The next five fields are character fields that describe the specimen. _pd_spec_mounting # This field should be # used to give details of the # container. ; Sample was loaded into a thin walled glass capillary ; _pd_spec_mount_mode transmission # options are 'reflection' # or 'transmission' _pd_spec_shape cylinder # options are 'cylinder' # 'flat_sheet' or 'irregular' _pd_char_particle_morphology ? _pd_char_colour ? # use ICDD colour descriptions # The following three fields describe the preparation of the specimen. # The cooling rate is in K/min. The pressure at which the sample was # prepared is in kPa. The temperature of preparation is in K. _pd_prep_cool_rate ? _pd_prep_pressure ? _pd_prep_temperature ? # The next four fields are normally only needed for transmission experiments. _exptl_absorpt_coefficient_mu ? _exptl_absorpt_correction_type ? # include if applicable _exptl_absorpt_process_details ? # include if applicable _exptl_absorpt_correction_T_min ? # include if applicable _exptl_absorpt_correction_T_max ? # include if applicable #============================================================================== # 7. EXPERIMENTAL DATA _exptl_special_details ; ? ; # The following item is used to identify the equipment used to record # the powder pattern when the diffractogram was measured at a laboratory # other than the authors' home institution, e.g. when neutron or synchrotron # radiation is used. _pd_instr_location ; X16C, National Synchrotron Light Source, Brookhaven National Laboratory ; _pd_calibration_special_details # description of the method used # to calibrate the instrument ; NIST standard reference material 1976(sintered plate of Al2O3). 7 reflections were used to calibrate wavelength and detector zero. ; _diffrn_ambient_temperature 298 _diffrn_source synchrotron _diffrn_source_target ? _diffrn_source_type ? _diffrn_radiation_type ? _diffrn_measurement_device_type 'Huber diffractometer' _diffrn_detector 'NaI scintillation counter' _diffrn_detector_type ? # make or model of detector _pd_meas_scan_method step # options are 'step', 'cont', # 'tof', 'fixed' or # 'disp' (= dispersive) _pd_meas_special_details ; ? ; # The following six items are used for angular dispersive measurements only. _diffrn_radiation_wavelength 0.698092 _diffrn_radiation_monochromator 'double Si(111)' # The following four items give details of the measured (not processed) # powder pattern. Angles are in degrees. _pd_meas_number_of_points 8000 _pd_meas_2theta_range_min 2 _pd_meas_2theta_range_max 42 _pd_meas_2theta_range_inc 0.005 # The following three items are used for time-of-flight measurements only. _pd_instr_dist_src/spec ? _pd_instr_dist_spec/detc ? _pd_meas_2theta_fixed ? #============================================================================== # 8. REFINEMENT DATA # Use the next field to give any special details about the fitting of the # powder pattern. _pd_proc_ls_special_details ; ? ; # The next three items are given as text. _pd_proc_ls_profile_function ; Simple_Axial_Model(8.37(4)) function with Rp=9999,Rs=300 in TOPAS-Academic ; _pd_proc_ls_background_function ; Chebyshev polynomial with 12 coeffecients ; _pd_proc_ls_pref_orient_corr ; none ; _pd_proc_ls_prof_R_factor ? _pd_proc_ls_prof_wR_factor 4.241 _pd_proc_ls_prof_wR_expected 2.373 _refine_ls_R_I_factor ? _refine_ls_R_Fsqd_factor ? _refine_ls_R_factor_all ? _refine_special_details ; The structure was refined as 4 rigid bodies. Three half rings were modeled as rigid bodies and also placed on inversion centers. There is a single independent molecule of NMe4 which was modeled as a rigid body and placed on a general position, giving the other molecule present in the structure from symmetry. Paramters relating to the structure internal to the rigid bodies were a single bond length for the aromatic rings, which was refined to a value of 1.350(8) Angstroms. The NMe4 molecule was refined with a single internal parameter for the N-C bond length, which was refined to a value of 1.61(1) Angstroms. All atoms were given a single isotropic thermal parameter, and all Hydrogen atoms were tethered to their respective heavier atoms with a distance of 1 Angstrom. ; _refine_ls_matrix_type ? _refine_ls_weighting_scheme sigma # options are 'sigma'(based on measured su's) # or 'calc' (calculated weights) _refine_ls_weighting_details ? _refine_ls_hydrogen_treatment ? _refine_ls_extinction_method ? _refine_ls_extinction_coef ? _refine_ls_number_parameters 50 _refine_ls_number_restraints ? _refine_ls_number_constraints ? # The following item is the same as CHI, the square root of 'CHI squared' _refine_ls_goodness_of_fit_all 1.787 _refine_ls_restrained_S_all ? _refine_ls_shift/su_max ? _refine_ls_shift/su_mean ? # The following four items apply to angular dispersive measurements. # 2theta minimum, maximum and increment (in degrees) are for the # intensities used in the refinement. _pd_proc_2theta_range_min 2 _pd_proc_2theta_range_max 42 _pd_proc_2theta_range_inc 0.005 _pd_proc_wavelength 0.698092 _pd_block_diffractogram_id DLT4-151 # The id used for the block containing # the powder pattern profile (section 11) # Give appropriate details in the next two text fields. _pd_proc_info_excluded_regions ? _pd_proc_info_data_reduction ? # The following items are used to identify the programs used. _computing_data_collection EPICS _computing_cell_refinement 'TOPAS Academic' _computing_data_reduction ? _computing_structure_solution 'TOPAS Academic' _computing_structure_refinement 'TOPAS Academic' _computing_molecular_graphics ? _computing_publication_material ? # 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS loop_ _atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_calc_flag _atom_site_refinement_flags Cd1 Cd Uiso 0.16341 0.11589 0.98307 1.000 0.0447(8) . . Se1 Se Uiso -0.03206 0.13179 1.06204 1.000 0.0447(8) . . Se2 Se Uiso 0.34177 0.04171 1.22322 1.000 0.0500(8) . . Se3 Se Uiso 0.24021 0.36610 0.69402 1.000 0.0500(8) . . C11 C Uiso -0.01306 0.05367 1.32164 1.000 0.0447(8) . . C12 C Uiso 0.08943 0.01142 1.42241 1.000 0.0500(8) . . C13 C Uiso -0.10248 0.04225 1.39923 1.000 0.0500(8) . . C21 C Uiso 0.39937 0.05208 0.91627 1.000 0.0500(8) . . C22 C Uiso 0.43631 0.01679 1.08986 1.000 0.0500(8) . . C23 C Uiso 0.53693 -0.03529 1.17359 1.000 0.0500(8) . . C31 C Uiso 0.11284 0.59306 0.51161 1.000 0.0500(8) . . C32 C Uiso -0.01363 0.35163 0.56852 1.000 0.0500(8) . . C33 C Uiso 0.09921 0.44470 0.58013 1.000 0.0500(8) . . N1 N Uiso 0.30604 0.54368 0.11729 1.000 0.0447(8) . . C7 C Uiso 0.28437 0.36783 0.26033 1.000 0.0500(8) . . C8 C Uiso 0.33743 0.64104 0.22010 1.000 0.0500(8) . . C9 C Uiso 0.18284 0.56912 -0.02120 1.000 0.0500(8) . . C10 C Uiso 0.41947 0.59679 0.00991 1.000 0.0500(8) . . H12 H Uiso 0.15565 0.01987 1.36496 1.000 0.0447(8) . . H13 H Uiso -0.17837 0.07354 1.32460 1.000 0.0500(8) . . H21 H Uiso 0.32486 0.09065 0.85426 1.000 0.0500(8) . . H23 H Uiso 0.56428 -0.06143 1.30213 1.000 0.0500(8) . . H31 H Uiso 0.19640 0.66198 0.52021 1.000 0.0500(8) . . H32 H Uiso -0.02372 0.24177 0.61926 1.000 0.0500(8) . . H7A H Uiso 0.24925 0.30604 0.19615 1.000 0.0500(8) . . H7B H Uiso 0.36484 0.34880 0.33104 1.000 0.0500(8) . . H7C H Uiso 0.22558 0.33976 0.34238 1.000 0.0500(8) . . H8A H Uiso 0.29419 0.72233 0.15048 1.000 0.0500(8) . . H8B H Uiso 0.30904 0.57401 0.34118 1.000 0.0500(8) . . H8C H Uiso 0.42849 0.68706 0.23233 1.000 0.0500(8) . . H9A H Uiso 0.17903 0.67425 -0.06969 1.000 0.0500(8) . . H9B H Uiso 0.18444 0.55249 -0.12138 1.000 0.0500(8) . . H9C H Uiso 0.10875 0.49640 0.04171 1.000 0.0500(8) . . H10A H Uiso 0.42224 0.69888 -0.09432 1.000 0.0500(8) . . H10B H Uiso 0.49855 0.60067 0.09087 1.000 0.0500(8) . . H10C H Uiso 0.40788 0.52370 -0.03332 1.000 0.0500(8) . . #============================================================================== data_[Zn(dien)2]3[Zn2(SC6H4S)5] _database_code_depnum_ccdc_archive 'CCDC 757366' #TrackingRef 'Cd_thiolates.cif' # 5. CHEMICAL DATA _chemical_name_systematic ; ??? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural '[Zn(dien)2]3[Zn2(SC6H4S)5]' _chemical_formula_analytical ? _chemical_formula_sum 'Zn5 S10 C54 N18 H98' _chemical_formula_weight 1647.154 _chemical_melting_point ? _chemical_compound_source ? # for minerals and # natural products loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source _atom_type_scat_length_neutron # include if applicable ? ? ? ? ? ? #============================================================================== # 6. POWDER SPECIMEN AND CRYSTAL DATA _space_group_crystal_system Monoclinic _space_group_name_H-M_alt 'C 2/c' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, 1/2-z' '-x, -y, -z' 'x, -y, 1/2+z' '1/2+x, 1/2+y, z' '1/2-x, 1/2+y, 1/2-z' '1/2-x, 1/2-y, -z' '1/2+x, 1/2-y, 1/2+z' _cell_length_a 43.68499(25) _cell_length_b 8.815705(44) _cell_length_c 18.89291(11) _cell_angle_alpha 90 _cell_angle_beta 73.86574(36) _cell_angle_gamma 90 _cell_volume 6989.351(68) _cell_measurement_temperature 298 _cell_formula_units_Z 4 # The next three fields give the specimen dimensions in mm. The equatorial # plane contains the incident and diffracted beam. _pd_spec_size_axial 4 # perpendicular to # equatorial plane _pd_spec_size_equat ? # parallel to # scattering vector # in transmission _pd_spec_size_thick 0.7 # parallel to # scattering vector # in reflection # The next five fields are character fields that describe the specimen. _pd_spec_mounting # This field should be # used to give details of the # container. ; Sample was loaded into a quartz zero background flat plate sample holder ; _pd_spec_mount_mode transmission # options are 'reflection' # or 'transmission' _pd_spec_shape cylinder # options are 'cylinder' # 'flat_sheet' or 'irregular' _pd_char_particle_morphology ? _pd_char_colour ? # use ICDD colour descriptions # The following three fields describe the preparation of the specimen. # The cooling rate is in K/min. The pressure at which the sample was # prepared is in kPa. The temperature of preparation is in K. _pd_prep_cool_rate ? _pd_prep_pressure ? _pd_prep_temperature ? # The next four fields are normally only needed for transmission experiments. _exptl_absorpt_coefficient_mu ? _exptl_absorpt_correction_type ? # include if applicable _exptl_absorpt_process_details ? # include if applicable _exptl_absorpt_correction_T_min ? # include if applicable _exptl_absorpt_correction_T_max ? # include if applicable #============================================================================== # 7. EXPERIMENTAL DATA _exptl_special_details ; ? ; # The following item is used to identify the equipment used to record # the powder pattern when the diffractogram was measured at a laboratory # other than the authors' home institution, e.g. when neutron or synchrotron # radiation is used. _pd_instr_location ; X16C, National Synchrotron Light Source, Brookhaven National Laboratory ; _pd_calibration_special_details # description of the method used # to calibrate the instrument ; NIST standard reference material 1976(sintered plate of Al2O3). 7 reflections were used to calibrate wavelength and detector zero. ; _diffrn_ambient_temperature 298 _diffrn_source synchrotron _diffrn_source_target ? _diffrn_source_type ? _diffrn_radiation_type ? _diffrn_measurement_device_type 'Huber diffractometer' _diffrn_detector 'NaI scintillation counter' _diffrn_detector_type ? # make or model of detector _pd_meas_scan_method step # options are 'step', 'cont', # 'tof', 'fixed' or # 'disp' (= dispersive) _pd_meas_special_details ; ? ; # The following six items are used for angular dispersive measurements only. _diffrn_radiation_wavelength 0.698431 _diffrn_radiation_monochromator 'double Si(111)' # The following four items give details of the measured (not processed) # powder pattern. Angles are in degrees. _pd_meas_number_of_points 7800 _pd_meas_2theta_range_min 1 _pd_meas_2theta_range_max 40 _pd_meas_2theta_range_inc 0.005 # The following three items are used for time-of-flight measurements only. _pd_instr_dist_src/spec ? _pd_instr_dist_spec/detc ? _pd_meas_2theta_fixed ? #============================================================================== # 8. REFINEMENT DATA # Use the next field to give any special details about the fitting of the # powder pattern. _pd_proc_ls_special_details ; ; # The next three items are given as text. _pd_proc_ls_profile_function ; Simple_Axial_Model(8.60(2)) function with Rp=9999,Rs=300 in TOPAS-Academic ; _pd_proc_ls_background_function ; Chebyshev polynomial with 12 coeffecients ; _pd_proc_ls_pref_orient_corr ; none ; _pd_proc_ls_prof_R_factor ? _pd_proc_ls_prof_wR_factor 6.333 _pd_proc_ls_prof_wR_expected 3.611 _refine_ls_R_I_factor ? _refine_ls_R_Fsqd_factor ? _refine_ls_R_factor_all ? _refine_special_details ; The final structure was refined as Z-matrices for the phenol rings and for the Zn(dien)2 moieties. The other Zn atom and the S atoms were refined as free atoms. Hydrogen atoms were tethered to their respective heavy atoms at a distance of 1 Angstrom. ; _refine_ls_matrix_type ? _refine_ls_weighting_scheme sigma # options are 'sigma'(based on measured su's) # or 'calc' (calculated weights) _refine_ls_weighting_details ? _refine_ls_hydrogen_treatment ? _refine_ls_extinction_method ? _refine_ls_extinction_coef ? _refine_ls_number_parameters 93 _refine_ls_number_restraints ? _refine_ls_number_constraints ? # The following item is the same as CHI, the square root of 'CHI squared' _refine_ls_goodness_of_fit_all 1.754 _refine_ls_restrained_S_all ? _refine_ls_shift/su_max ? _refine_ls_shift/su_mean ? # The following four items apply to angular dispersive measurements. # 2theta minimum, maximum and increment (in degrees) are for the # intensities used in the refinement. _pd_proc_2theta_range_min 1 _pd_proc_2theta_range_max 40 _pd_proc_2theta_range_inc 0.005 _pd_proc_wavelength 0.698431 _pd_block_diffractogram_id DLT3-284 # The id used for the block containing # the powder pattern profile (section 11) # Give appropriate details in the next two text fields. _pd_proc_info_excluded_regions ? _pd_proc_info_data_reduction ? # The following items are used to identify the programs used. _computing_data_collection EPICS _computing_cell_refinement 'TOPAS Academic' _computing_data_reduction ? _computing_structure_solution Superflip _computing_structure_refinement 'TOPAS Academic' _computing_molecular_graphics ? _computing_publication_material ? # 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS loop_ _atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_calc_flag _atom_site_refinement_flags Zn3 Zn Uiso 0.08426(7) 0.8922(3) 0.10003(16) 1.000 0.0370(6) . . S1A S Uiso 0.07966(17) 0.7950(7) 0.2180(4) 1.000 0.0370(6) . . S1B S Uiso 0.12968(15) 1.0579(7) 0.0709(4) 1.000 0.0370(6) . . S1C S Uiso 0.03323(16) 1.0088(7) 0.1280(3) 1.000 0.0370(6) . . S2A S Uiso 0.08674(16) 0.7157(8) 0.0011(4) 1.000 0.0370(6) . . S2B S Uiso 0.20816(16) 0.5847(8) 0.2897(3) 1.000 0.0370(6) . . C1A C Uiso 0.11663 0.74258 0.23813 1.000 0.0370(6) . . C1B C Uiso 0.12267 1.51681 0.05812 1.000 0.0370(6) . . C1C C Uiso -0.01710 0.99933 0.07444 1.000 0.0370(6) . . C2A C Uiso 0.11637 0.68698 0.30754 1.000 0.0370(6) . . C2B C Uiso 0.13278 1.37108 0.07004 1.000 0.0370(6) . . C2C C Uiso 0.01617 1.00445 0.05421 1.000 0.0370(6) . . C3A C Uiso 0.14456 0.63493 0.32034 1.000 0.0370(6) . . C3B C Uiso 0.11855 1.24440 0.04797 1.000 0.0370(6) . . C3C C Uiso 0.03327 1.00511 -0.02022 1.000 0.0370(6) . . C4A C Uiso 0.17302 0.63849 0.26372 1.000 0.0370(6) . . C4B C Uiso 0.09420 1.26345 0.01397 1.000 0.0370(6) . . C5A C Uiso 0.17329 0.69409 0.19431 1.000 0.0370(6) . . C5B C Uiso 0.08409 1.40919 0.00205 1.000 0.0370(6) . . C6A C Uiso 0.14509 0.74614 0.18151 1.000 0.0370(6) . . C6B C Uiso 0.09832 0.53587 0.02413 1.000 0.0370(6) . . Zn2 Zn Uiso 0.18471 0.07790 0.35222 1.000 0.0370(6) . . N1D N Uiso 0.17096 0.25329 0.43432 1.000 0.0370(6) . . N2D N Uiso 0.23264 0.12928 0.37501 1.000 0.0370(6) . . N3D N Uiso 0.19290 -0.11519 0.40928 1.000 0.0370(6) . . N4D N Uiso 0.13562 0.02000 0.36425 1.000 0.0370(6) . . N5D N Uiso 0.17349 0.24184 0.26873 1.000 0.0370(6) . . N6D N Uiso 0.21028 -0.02201 0.24927 1.000 0.0370(6) . . C7D C Uiso 0.19598 0.27216 0.47198 1.000 0.0370(6) . . C8D C Uiso 0.22798 0.27284 0.41620 1.000 0.0370(6) . . C9D C Uiso 0.24421 -0.00545 0.40554 1.000 0.0370(6) . . C10D C Uiso 0.21639 -0.09403 0.45106 1.000 0.0370(6) . . C11D C Uiso 0.12477 0.09466 0.30596 1.000 0.0370(6) . . C12D C Uiso 0.13853 0.25129 0.29327 1.000 0.0370(6) . . C13D C Uiso 0.18963 0.18856 0.19394 1.000 0.0370(6) . . C14D C Uiso 0.21894 0.10140 0.19505 1.000 0.0370(6) . . Zn1 Zn Uiso 0.00000 0.4830(5) 0.25000 1.000 0.0370(6) . . N1E N Uiso 0.05098 0.42351 0.19040 1.000 0.0370(6) . . N2E N Uiso 0.01656 0.34977 0.33257 1.000 0.0370(6) . . N3E N Uiso 0.00895 0.65167 0.32660 1.000 0.0370(6) . . C7E C Uiso 0.06697 0.34089 0.23763 1.000 0.0370(6) . . C8E C Uiso 0.04288 0.25035 0.29365 1.000 0.0370(6) . . C9E C Uiso 0.01898 0.43691 0.39713 1.000 0.0370(6) . . C10E C Uiso 0.00142 0.58396 0.40054 1.000 0.0370(6) . . H1B H Uiso 0.13286 1.60748 0.07393 1.000 0.0370(6) . . H1C H Uiso -0.02934 0.99886 0.12771 1.000 0.0370(6) . . H2A H Uiso 0.09599 0.68443 0.34807 1.000 0.0370(6) . . H2B H Uiso 0.15021 1.35743 0.09438 1.000 0.0370(6) . . H3A H Uiso 0.14438 0.59513 0.37002 1.000 0.0370(6) . . H3C H Uiso 0.05709 1.00877 -0.03469 1.000 0.0370(6) . . H4B H Uiso 0.08401 1.17278 -0.00184 1.000 0.0370(6) . . H5A H Uiso 0.19366 0.69664 0.15378 1.000 0.0370(6) . . H5B H Uiso 0.06666 1.42283 -0.02229 1.000 0.0370(6) . . H6A H Uiso 0.14528 0.78593 0.13183 1.000 0.0370(6) . . H1D1 H Uiso 0.16610 0.34854 0.41080 1.000 0.0370(6) . . H1D2 H Uiso 0.14959 0.22886 0.46850 1.000 0.0370(6) . . H2D H Uiso 0.25129 0.13889 0.33039 1.000 0.0370(6) . . H7D1 H Uiso 0.19164 0.36562 0.50318 1.000 0.0370(6) . . H7D2 H Uiso 0.19371 0.19168 0.51039 1.000 0.0370(6) . . H8D1 H Uiso 0.22987 0.36448 0.38407 1.000 0.0370(6) . . H5D H Uiso 0.18282 0.34265 0.27537 1.000 0.0370(6) . . H8D2 H Uiso 0.24488 0.29370 0.44137 1.000 0.0370(6) . . H9D1 H Uiso 0.25846 -0.06571 0.36461 1.000 0.0370(6) . . H9D2 H Uiso 0.25952 0.02633 0.43343 1.000 0.0370(6) . . H10D1 H Uiso 0.22410 -0.19144 0.46712 1.000 0.0370(6) . . H10D2 H Uiso 0.20750 -0.04218 0.49951 1.000 0.0370(6) . . H3D1 H Uiso 0.19937 -0.20304 0.37488 1.000 0.0370(6) . . H3D2 H Uiso 0.17247 -0.15360 0.44296 1.000 0.0370(6) . . H4D1 H Uiso 0.13326 -0.09285 0.36472 1.000 0.0370(6) . . H4D2 H Uiso 0.12251 0.04636 0.41512 1.000 0.0370(6) . . H11D1 H Uiso 0.13028 0.02994 0.26071 1.000 0.0370(6) . . H11D2 H Uiso 0.10096 0.09283 0.31927 1.000 0.0370(6) . . H12D1 H Uiso 0.12918 0.30633 0.25791 1.000 0.0370(6) . . H12D2 H Uiso 0.13025 0.31342 0.33887 1.000 0.0370(6) . . H13D1 H Uiso 0.17432 0.12895 0.17425 1.000 0.0370(6) . . H13D2 H Uiso 0.19403 0.27680 0.15932 1.000 0.0370(6) . . H14D1 H Uiso 0.22997 0.06552 0.14413 1.000 0.0370(6) . . H14D2 H Uiso 0.23523 0.17248 0.20443 1.000 0.0370(6) . . H6D1 H Uiso 0.19826 -0.10192 0.23057 1.000 0.0370(6) . . H6D2 H Uiso 0.22989 -0.07907 0.25064 1.000 0.0370(6) . . H2E H Uiso 0.00655 0.24683 0.33862 1.000 0.0370(6) . . H1E1 H Uiso 0.05996 0.52833 0.18121 1.000 0.0370(6) . . H1E2 H Uiso 0.05283 0.36429 0.14425 1.000 0.0370(6) . . H7E1 H Uiso 0.08464 0.27802 0.20628 1.000 0.0370(6) . . H7E2 H Uiso 0.07916 0.41402 0.25986 1.000 0.0370(6) . . H8E1 H Uiso 0.03582 0.16186 0.26902 1.000 0.0370(6) . . H8E2 H Uiso 0.05359 0.19777 0.32718 1.000 0.0370(6) . . H9E1 H Uiso 0.01121 0.37357 0.44249 1.000 0.0370(6) . . H9E2 H Uiso 0.04193 0.44995 0.39528 1.000 0.0370(6) . . H10E1 H Uiso -0.02188 0.56651 0.42301 1.000 0.0370(6) . . H10E2 H Uiso 0.00655 0.65164 0.43817 1.000 0.0370(6) . . H3E1 H Uiso -0.01073 0.69814 0.31870 1.000 0.0370(6) . . H3E2 H Uiso 0.02694 0.72510 0.32047 1.000 0.0370(6) . .