# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2008 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'David Rankin' _publ_contact_author_email D.W.H.RANKIN@ED.AC.UK _publ_section_title ; Highly asymmetric coordination of trimethylsilyl groups to tetrazole and triazole rings: an experimental and computational study in gaseous and crystalline phases ; loop_ _publ_author_name 'David Rankin' 'Thomas Foerster' 'Ingo Gronde' 'Stuart A Hayes' 'Sarah Masters' 'Norbert Mitzel' ; H.E.Robertson ; 'Derek A Wann' # Attachment 'compound_1_XRD.CIF' data_ingo2 _database_code_depnum_ccdc_archive 'CCDC 679183' _audit_creation_method SHELXL-97 _chemical_name_systematic ; 2-Trimethylsilyltetrazole ; _chemical_name_common 2-Trimethylsilyltetrazole _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C4 H10 N4 Si' _chemical_formula_weight 142.25 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' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Si Si 0.0817 0.0704 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 5.916(1) _cell_length_b 10.577(1) _cell_length_c 6.624(1) _cell_angle_alpha 90.00 _cell_angle_beta 105.35(1) _cell_angle_gamma 90.00 _cell_volume 399.7(1) _cell_formula_units_Z 2 _cell_measurement_temperature 133(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 13 _cell_measurement_theta_max 21 _exptl_crystal_description Cylinder _exptl_crystal_colour Colourless _exptl_crystal_size_max 1 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.25 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.182 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 152 _exptl_absorpt_coefficient_mu 0.220 _exptl_absorpt_correction_type None _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; Crystal grown in situ from the melt The structure was tested for higher symmetry with PLATON' ADDSYM program. A structure solution in P21/m is possible, but in this case the refinement does not produce the H atom at N and does not reflect the different N-N and N-C bond lengths to N(1), which are confirmed by GED and calculations ; _diffrn_ambient_temperature 133(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 'four circle diffractometer CAD4' _diffrn_measurement_method 'omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 60 _diffrn_standards_decay_% None _diffrn_reflns_number 2397 _diffrn_reflns_av_R_equivalents 0.0937 _diffrn_reflns_av_sigmaI/netI 0.0742 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -6 _diffrn_reflns_limit_l_max 3 _diffrn_reflns_theta_min 3.19 _diffrn_reflns_theta_max 27.11 _reflns_number_total 1628 _reflns_number_gt 1430 _reflns_threshold_expression >2sigma(I) _computing_data_collection CAD4-Software _computing_cell_refinement CAD4-Software _computing_data_reduction CADSHEL _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics SHELXTL _computing_publication_material 'SHELXL-93 (Sheldrick, 1993)' _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^)+(0.0814P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.3(2) _refine_ls_number_reflns 1628 _refine_ls_number_parameters 101 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0564 _refine_ls_R_factor_gt 0.0471 _refine_ls_wR_factor_ref 0.1193 _refine_ls_wR_factor_gt 0.1141 _refine_ls_goodness_of_fit_ref 1.029 _refine_ls_restrained_S_all 1.029 _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 N1 N 0.1588(3) 0.7726(3) 0.5489(3) 0.0319(4) Uani 1 1 d . . . N2 N 0.0520(7) 0.8822(3) 0.4702(5) 0.0498(9) Uani 1 1 d . . . N3 N -0.1246(7) 0.8526(3) 0.3196(5) 0.0547(9) Uani 1 1 d . . . N4 N -0.1455(6) 0.7270(3) 0.2904(5) 0.0482(8) Uani 1 1 d . . . C5 C 0.0333(7) 0.6808(3) 0.4324(6) 0.0422(8) Uani 1 1 d . . . H51 H 0.061(9) 0.596(5) 0.460(7) 0.071(12) Uiso 1 1 d . . . Si6 Si 0.40500(9) 0.76937(6) 0.78274(9) 0.0299(2) Uani 1 1 d . . . C7 C 0.5632(7) 0.6218(3) 0.7616(7) 0.0418(9) Uani 1 1 d . . . H71 H 0.692(5) 0.6154(17) 0.873(5) 0.084(19) Uiso 1 1 calc R . . H72 H 0.609(6) 0.6227(15) 0.640(5) 0.08(2) Uiso 1 1 calc R . . H73 H 0.466(4) 0.554(2) 0.761(6) 0.09(2) Uiso 1 1 calc R . . C8 C 0.5727(8) 0.9133(4) 0.7674(8) 0.0489(11) Uani 1 1 d . . . H81 H 0.699(4) 0.9194(15) 0.886(4) 0.056(13) Uiso 1 1 calc R . . H82 H 0.476(3) 0.9837(18) 0.760(5) 0.051(13) Uiso 1 1 calc R . . H83 H 0.629(5) 0.9100(14) 0.648(4) 0.08(2) Uiso 1 1 calc R . . C9 C 0.2667(4) 0.7706(6) 1.0014(4) 0.0457(6) Uani 1 1 d . . . H91 H 0.384(2) 0.778(4) 1.130(2) 0.056(8) Uiso 1 1 calc R . . H92 H 0.183(6) 0.694(2) 1.001(4) 0.068(17) Uiso 1 1 calc R . . H93 H 0.162(6) 0.840(2) 0.986(3) 0.065(17) Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 N1 0.0395(8) 0.0267(8) 0.0307(9) 0.0060(15) 0.0112(7) 0.0057(14) N2 0.061(2) 0.0358(13) 0.0454(17) -0.0009(13) 0.0009(14) 0.0188(14) N3 0.056(2) 0.0596(19) 0.0418(15) 0.0008(14) 0.0013(15) 0.0215(15) N4 0.0427(14) 0.0605(17) 0.0392(15) -0.0016(12) 0.0069(11) -0.0007(13) C5 0.051(2) 0.0344(14) 0.0389(18) 0.0015(12) 0.0082(15) -0.0075(13) Si6 0.0340(3) 0.0279(3) 0.0292(4) -0.0007(4) 0.0109(2) -0.0021(4) C7 0.041(2) 0.034(2) 0.0485(19) -0.0028(15) 0.0090(16) 0.0076(14) C8 0.055(3) 0.044(2) 0.046(2) -0.0007(16) 0.010(2) -0.0150(18) C9 0.0429(11) 0.0629(16) 0.0338(12) 0.000(2) 0.0146(9) -0.002(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 N1 C5 1.337(4) . ? N1 N2 1.357(4) . ? N1 Si6 1.8238(18) . ? N2 N3 1.278(5) . ? N3 N4 1.343(5) . ? N4 C5 1.309(5) . ? C5 H51 0.92(5) . ? Si6 C8 1.835(4) . ? Si6 C9 1.842(2) . ? Si6 C7 1.844(4) . ? C7 H71 0.9152 . ? C7 H72 0.9152 . ? C7 H73 0.9152 . ? C8 H81 0.9320 . ? C8 H82 0.9320 . ? C8 H83 0.9320 . ? C9 H91 0.9506 . ? C9 H92 0.9506 . ? C9 H93 0.9506 . ? 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 C5 N1 N2 105.5(2) . . ? C5 N1 Si6 132.4(2) . . ? N2 N1 Si6 121.9(2) . . ? N3 N2 N1 107.0(3) . . ? N2 N3 N4 112.3(4) . . ? C5 N4 N3 103.9(4) . . ? N4 C5 N1 111.3(3) . . ? N4 C5 H51 125(3) . . ? N1 C5 H51 123(3) . . ? N1 Si6 C8 105.04(16) . . ? N1 Si6 C9 104.26(9) . . ? C8 Si6 C9 113.4(2) . . ? N1 Si6 C7 104.97(15) . . ? C8 Si6 C7 113.92(13) . . ? C9 Si6 C7 113.9(2) . . ? Si6 C7 H71 109.5 . . ? Si6 C7 H72 109.5 . . ? H71 C7 H72 109.5 . . ? Si6 C7 H73 109.5 . . ? H71 C7 H73 109.5 . . ? H72 C7 H73 109.5 . . ? Si6 C8 H81 109.5 . . ? Si6 C8 H82 109.5 . . ? H81 C8 H82 109.5 . . ? Si6 C8 H83 109.5 . . ? H81 C8 H83 109.5 . . ? H82 C8 H83 109.5 . . ? Si6 C9 H91 109.5 . . ? Si6 C9 H92 109.5 . . ? H91 C9 H92 109.5 . . ? Si6 C9 H93 109.5 . . ? H91 C9 H93 109.5 . . ? H92 C9 H93 109.5 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C5 N1 N2 N3 0.6(3) . . . . ? Si6 N1 N2 N3 -174.3(3) . . . . ? N1 N2 N3 N4 0.1(6) . . . . ? N2 N3 N4 C5 -0.8(7) . . . . ? N3 N4 C5 N1 1.2(6) . . . . ? N2 N1 C5 N4 -1.2(4) . . . . ? Si6 N1 C5 N4 173.0(2) . . . . ? C5 N1 Si6 C8 150.6(3) . . . . ? N2 N1 Si6 C8 -36.0(3) . . . . ? C5 N1 Si6 C9 -89.9(4) . . . . ? N2 N1 Si6 C9 83.5(3) . . . . ? C5 N1 Si6 C7 30.2(3) . . . . ? N2 N1 Si6 C7 -156.4(3) . . . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A C5 H51 N2 0.92(5) 2.44(5) 3.289(4) 154(4) 2_546 _diffrn_measured_fraction_theta_max 0.916 _diffrn_reflns_theta_full 27.11 _diffrn_measured_fraction_theta_full 0.916 _refine_diff_density_max 0.309 _refine_diff_density_min -0.282 _refine_diff_density_rms 0.055