# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and # The Centre National de la Recherche Scientifique, 2003 data_global _journal_coden_Cambridge 440 loop_ _publ_author_name 'Ingmar Persson' 'Camelia Hagfeldt' 'Vadim Kessler' _publ_contact_author_name 'Prof Ingmar Persson' _publ_contact_author_address ; Department of Chemistry Swedish University of Agricultural P.O.Box 7015 Uppsala SE-750 07 SWEDEN ; _publ_contact_author_email INGMAR.PERSSON@KEMI.SLU.SE _publ_requested_journal 'New Journal of Chemistry' _publ_section_title ; The discovery of the N,N-dimethylthioformamidium ion. A structural study of ((CH3)2NCHSH))2[HfCl6] in solid state and solution ; data_hfdmtf0m _database_code_CSD 201373 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common 'N,N-Dimethylthioformamidium hexachlorohafniate(IV)' _chemical_melting_point ? _chemical_formula_moiety ((CH3)2NCHSH)2(HfCl6( _chemical_formula_sum 'C6 H16 Cl6 Hf N2 S2' _chemical_formula_weight 571.52 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' S S 0.1246 0.1234 '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' Hf Hf -0.5830 6.1852 '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' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1)/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 8.0963(9) _cell_length_b 15.2585(17) _cell_length_c 8.2235(9) _cell_angle_alpha 90.00 _cell_angle_beta 113.024(2) _cell_angle_gamma 90.00 _cell_volume 934.98(18) _cell_formula_units_Z 2 _cell_measurement_temperature 295(2) _cell_measurement_reflns_used '2695 (I>2s(I))' _cell_measurement_theta_min 2.67 _cell_measurement_theta_max 28.02 _exptl_crystal_description Rod _exptl_crystal_colour 'Pale yellow' _exptl_crystal_size_max 0.5 _exptl_crystal_size_mid 0.3 _exptl_crystal_size_min 0.2 _exptl_crystal_density_meas 2.0 _exptl_crystal_density_diffrn 2.030 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 544 _exptl_absorpt_coefficient_mu 6.642 _exptl_absorpt_correction_type Empirical _exptl_absorpt_correction_T_min 0.2875 _exptl_absorpt_correction_T_max 0.5564 _exptl_absorpt_process_details 'Bruker SADABS' _exptl_special_details ; ? ; _diffrn_ambient_temperature 295(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker Smart CCD 1k' _diffrn_measurement_method 'Bruker Smart' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 5283 _diffrn_reflns_av_R_equivalents 0.0233 _diffrn_reflns_av_sigmaI/netI 0.0367 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -19 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 3.04 _diffrn_reflns_theta_max 28.02 _reflns_number_total 2074 _reflns_number_gt 1454 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker Smart' _computing_cell_refinement 'Bruker Saintplus' _computing_data_reduction 'Bruker Saintplus' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL-NT' _computing_publication_material 'Bruker SHELXTL-NT' _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^)+(0.0293P)^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 SHELXL _refine_ls_extinction_coef 0.0060(4) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 2074 _refine_ls_number_parameters 88 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0390 _refine_ls_R_factor_gt 0.0199 _refine_ls_wR_factor_ref 0.0459 _refine_ls_wR_factor_gt 0.0430 _refine_ls_goodness_of_fit_ref 0.772 _refine_ls_restrained_S_all 0.772 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Hf1 Hf 0.0000 0.0000 0.5000 0.04041(9) Uani 1 2 d S . . Cl1 Cl 0.29883(13) 0.06194(6) 0.57578(14) 0.0589(3) Uani 1 1 d . . . Cl2 Cl -0.06763(14) 0.11006(6) 0.68261(12) 0.0563(3) Uani 1 1 d . . . Cl3 Cl -0.12241(15) 0.09885(6) 0.24618(13) 0.0601(3) Uani 1 1 d . . . S11 S 0.56770(15) 0.24137(7) 0.91263(15) 0.0643(3) Uani 1 1 d . . . N3 N 0.3469(4) 0.35599(18) 0.6928(4) 0.0444(7) Uani 1 1 d . . . C4 C 0.4977(6) 0.3417(2) 0.8190(5) 0.0495(9) Uani 1 1 d . . . C5 C 0.2130(5) 0.2883(2) 0.6202(6) 0.0622(11) Uani 1 1 d . . . H5A H 0.2582 0.2338 0.6791 0.093 Uiso 1 1 calc R . . H5B H 0.1858 0.2820 0.4962 0.093 Uiso 1 1 calc R . . H5C H 0.1060 0.3041 0.6370 0.093 Uiso 1 1 calc R . . C6 C 0.2980(6) 0.4441(3) 0.6163(5) 0.0694(12) Uani 1 1 d . . . H6A H 0.3955 0.4838 0.6739 0.104 Uiso 1 1 calc R . . H6B H 0.1931 0.4640 0.6327 0.104 Uiso 1 1 calc R . . H6C H 0.2735 0.4421 0.4923 0.104 Uiso 1 1 calc R . . H1 H 0.723(6) 0.276(3) 1.021(6) 0.113(16) Uiso 1 1 d . . . H4A H 0.574(5) 0.384(3) 0.863(5) 0.078(14) Uiso 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Hf1 0.04235(13) 0.03115(11) 0.04081(13) 0.00185(11) 0.00878(8) 0.00116(11) Cl1 0.0461(5) 0.0439(5) 0.0794(7) -0.0022(5) 0.0167(5) -0.0050(4) Cl2 0.0630(6) 0.0481(5) 0.0501(5) -0.0073(4) 0.0139(5) 0.0080(4) Cl3 0.0698(7) 0.0525(5) 0.0537(6) 0.0182(5) 0.0194(5) 0.0143(5) S11 0.0598(7) 0.0549(6) 0.0654(7) 0.0097(5) 0.0108(6) 0.0007(5) N3 0.0449(18) 0.0415(16) 0.0429(17) -0.0005(14) 0.0130(15) -0.0028(13) C4 0.055(3) 0.044(2) 0.050(2) 0.0007(18) 0.021(2) -0.0080(19) C5 0.052(2) 0.050(2) 0.069(3) -0.004(2) 0.006(2) -0.0031(19) C6 0.079(3) 0.047(2) 0.067(3) 0.007(2) 0.012(2) -0.001(2) _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 Hf1 Cl1 2.4404(10) . ? Hf1 Cl1 2.4404(10) 3_556 ? Hf1 Cl2 2.4532(9) 3_556 ? Hf1 Cl2 2.4532(9) . ? Hf1 Cl3 2.4486(9) . ? Hf1 Cl3 2.4486(9) 3_556 ? S11 C4 1.707(4) . ? S11 H1 1.33(5) . ? N3 C4 1.274(5) . ? N3 C5 1.447(4) . ? N3 C6 1.472(4) . ? 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 Cl1 Hf1 Cl1 180.0 . 3_556 ? Cl1 Hf1 Cl2 89.15(3) . 3_556 ? Cl1 Hf1 Cl2 90.85(3) 3_556 3_556 ? Cl1 Hf1 Cl2 90.85(3) . . ? Cl1 Hf1 Cl2 89.15(3) 3_556 . ? Cl1 Hf1 Cl3 90.54(4) . . ? Cl1 Hf1 Cl3 89.46(4) 3_556 . ? Cl1 Hf1 Cl3 89.46(4) . 3_556 ? Cl1 Hf1 Cl3 90.54(4) 3_556 3_556 ? Cl2 Hf1 Cl2 180.0 3_556 . ? Cl2 Hf1 Cl3 89.27(3) . . ? Cl2 Hf1 Cl3 90.73(3) 3_556 . ? Cl2 Hf1 Cl3 90.73(3) . 3_556 ? Cl2 Hf1 Cl3 89.27(3) 3_556 3_556 ? Cl3 Hf1 Cl3 180.00(5) . 3_556 ? C4 S11 H1 90.0(19) . . ? C4 N3 C5 122.6(3) . . ? C4 N3 C6 121.1(3) . . ? C5 N3 C6 116.3(3) . . ? N3 C4 S11 124.4(3) . . ? _diffrn_measured_fraction_theta_max 0.921 _diffrn_reflns_theta_full 28.02 _diffrn_measured_fraction_theta_full 0.921 _refine_diff_density_max 0.427 _refine_diff_density_min -0.653 _refine_diff_density_rms 0.076