# Supplementary Material (ESI) for Journal of Materials Chemistry # This journal is (C) The Royal Society of Chemistry 2009 data_33 _audit_creation_method SHELXL-97 _chemical_name_systematic ; '(TAMS)Bi2Cl8' ; _chemical_name_common '(TAMS)Bi2Cl8' _chemical_melting_point 'not measured' _chemical_formula_moiety '(TAMS)Bi2Cl8' _chemical_formula_sum 'C17 H22 Bi2 Cl8 N2' _chemical_formula_weight 955.93 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' 'Cl' 'Cl' 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Bi' 'Bi' -4.1077 10.2566 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting 'orthorhombic' _symmetry_space_group_name_H-M 'Pna2(1)' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z+1/2' 'x+1/2, -y+1/2, z' '-x+1/2, y+1/2, z+1/2' _cell_length_a 32.458(4) _cell_length_b 7.1893(9) _cell_length_c 11.7654(17) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2745.5(6) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 5132 _cell_measurement_theta_min 3.0494 _cell_measurement_theta_max 27.4835 _exptl_crystal_description 'Prism' _exptl_crystal_colour 'brown' _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 2.313 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1760 _exptl_absorpt_coefficient_mu 13.589 _exptl_absorpt_correction_type 'Numerical' _exptl_absorpt_correction_T_min 0.2903 _exptl_absorpt_correction_T_max 0.5598 _exptl_absorpt_process_details 'Sphere (Rigaku CrystalClear)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'rotating-anode generator' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Rigaku Mercury CCD ' _diffrn_measurement_method '\w ' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 16529 _diffrn_reflns_av_R_equivalents 0.0432 _diffrn_reflns_av_sigmaI/netI 0.0410 _diffrn_reflns_limit_h_min -39 _diffrn_reflns_limit_h_max 31 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 3.05 _diffrn_reflns_theta_max 25.49 _reflns_number_total 4999 _reflns_number_gt 4372 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrystalClear (Rigaku Corp., 2002)' _computing_cell_refinement 'CrystalClear (Rigaku Corp., 2002)' _computing_data_reduction 'CrystalClear (Rigaku Corp., 2002)' _computing_structure_solution 'Siemens SHELXTL^TM^ 5' _computing_structure_refinement 'Siemens SHELXTL^TM^ 5' _computing_molecular_graphics ? _computing_publication_material 'Siemens SHELXTL^TM^ 5' _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^)+(0.0907P)^2^+14.8695P] 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 constr _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 0.008(15) _refine_ls_number_reflns 4999 _refine_ls_number_parameters 263 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0674 _refine_ls_R_factor_gt 0.0591 _refine_ls_wR_factor_ref 0.1552 _refine_ls_wR_factor_gt 0.1487 _refine_ls_goodness_of_fit_ref 1.076 _refine_ls_restrained_S_all 1.076 _refine_ls_shift/su_max 0.005 _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 Bi1 Bi 0.833590(5) 0.33236(2) 0.476279(14) 0.04727(4) Uani 1 1 d . . . Bi2 Bi 0.899044(5) -0.16826(2) 0.547933(12) 0.04752(4) Uani 1 1 d . . . Cl1 Cl 0.79785(5) 0.2167(2) 0.29931(12) 0.0728(4) Uani 1 1 d . . . Cl2 Cl 0.85357(4) 0.65555(17) 0.36584(10) 0.0585(4) Uani 1 1 d . . . Cl3 Cl 0.76966(4) 0.47176(18) 0.56092(12) 0.0625(4) Uani 1 1 d . . . Cl4 Cl 0.91098(4) 0.13714(17) 0.41565(12) 0.0652(4) Uani 1 1 d . . . Cl5 Cl 0.82040(4) 0.02463(18) 0.60566(12) 0.0705(4) Uani 1 1 d . . . Cl6 Cl 0.93473(6) -0.0559(2) 0.72773(11) 0.0815(5) Uani 1 1 d . . . Cl7 Cl 0.96659(4) -0.2882(2) 0.46902(15) 0.0788(4) Uani 1 1 d . . . Cl8 Cl 0.88291(4) -0.49142(19) 0.65591(9) 0.0622(4) Uani 1 1 d . . . C1 C 1.2347(2) 1.6904(7) 0.3728(6) 0.089(2) Uani 1 1 d . . . H1A H 1.2228 1.7986 0.4078 0.133 Uiso 1 1 calc R . . H1B H 1.2315 1.6985 0.2919 0.133 Uiso 1 1 calc R . . H1C H 1.2634 1.6836 0.3913 0.133 Uiso 1 1 calc R . . C2 C 1.19756(17) 1.3935(8) 0.3432(4) 0.0629(17) Uani 1 1 d . . . H2A H 1.1998 1.4145 0.2654 0.075 Uiso 1 1 calc R . . C3 C 1.17818(17) 1.2332(9) 0.3825(4) 0.0646(16) Uani 1 1 d . . . H3A H 1.1688 1.1463 0.3300 0.078 Uiso 1 1 calc R . . C4 C 1.17258(14) 1.1997(7) 0.4951(4) 0.0567(14) Uani 1 1 d . . . C5 C 1.18804(17) 1.3466(7) 0.5673(5) 0.0760(17) Uani 1 1 d . . . H5A H 1.1844 1.3360 0.6455 0.091 Uiso 1 1 calc R . . C6 C 1.20736(16) 1.4976(7) 0.5267(5) 0.0748(17) Uani 1 1 d . . . H6A H 1.2168 1.5885 0.5765 0.090 Uiso 1 1 calc R . . C7 C 1.15198(16) 1.0433(8) 0.5437(4) 0.0684(17) Uani 1 1 d . . . H7A H 1.1513 1.0311 0.6223 0.082 Uiso 1 1 calc R . . C8 C 1.13387(15) 0.9152(7) 0.4804(4) 0.0613(14) Uani 1 1 d . . . H8A H 1.1370 0.9302 0.4023 0.074 Uiso 1 1 calc R . . C9 C 1.10954(15) 0.7525(7) 0.5154(4) 0.0477(13) Uani 1 1 d . . . C10 C 1.09316(19) 0.6321(8) 0.4337(4) 0.0661(18) Uani 1 1 d . . . H10A H 1.0993 0.6520 0.3574 0.079 Uiso 1 1 calc R . . C11 C 1.06785(19) 0.4827(10) 0.4638(5) 0.081(2) Uani 1 1 d . . . H11A H 1.0563 0.4072 0.4081 0.097 Uiso 1 1 calc R . . C12 C 1.06055(14) 0.4498(7) 0.5737(4) 0.0552(14) Uani 1 1 d . . . C13 C 1.07681(16) 0.5585(7) 0.6581(4) 0.0581(16) Uani 1 1 d . . . H13A H 1.0705 0.5369 0.7340 0.070 Uiso 1 1 calc R . . C14 C 1.10256(18) 0.6991(9) 0.6273(5) 0.0717(19) Uani 1 1 d . . . H14A H 1.1163 0.7633 0.6845 0.086 Uiso 1 1 calc R . . C15 C 1.0541(2) 0.1612(8) 0.6785(6) 0.079(2) Uani 1 1 d . . . H15A H 1.0663 0.2237 0.7422 0.118 Uiso 1 1 calc R . . H15B H 1.0753 0.1029 0.6341 0.118 Uiso 1 1 calc R . . H15C H 1.0352 0.0683 0.7053 0.118 Uiso 1 1 calc R . . C16 C 0.99662(16) 0.3803(8) 0.6791(7) 0.082(2) Uani 1 1 d . . . H16A H 1.0079 0.4414 0.7447 0.122 Uiso 1 1 calc R . . H16B H 0.9784 0.2827 0.7030 0.122 Uiso 1 1 calc R . . H16C H 0.9816 0.4688 0.6341 0.122 Uiso 1 1 calc R . . C17 C 1.0131(2) 0.1978(10) 0.5113(6) 0.105(3) Uani 1 1 d . . . H17A H 1.0342 0.1368 0.4681 0.157 Uiso 1 1 calc R . . H17B H 0.9988 0.2849 0.4636 0.157 Uiso 1 1 calc R . . H17C H 0.9940 0.1069 0.5394 0.157 Uiso 1 1 calc R . . N1 N 1.21298(14) 1.5176(7) 0.4162(4) 0.0685(15) Uani 1 1 d . . . N2 N 1.03188(13) 0.2971(6) 0.6077(4) 0.0629(14) Uani 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 Bi1 0.05237(8) 0.04480(7) 0.04464(8) 0.00767(9) -0.00111(8) 0.00079(7) Bi2 0.05564(8) 0.04605(8) 0.04087(7) 0.00531(8) -0.00034(8) 0.00575(7) Cl1 0.0797(8) 0.0876(9) 0.0512(7) -0.0042(7) -0.0061(7) -0.0212(7) Cl2 0.0751(7) 0.0581(7) 0.0421(6) 0.0116(5) -0.0034(5) -0.0036(6) Cl3 0.0585(6) 0.0675(7) 0.0615(7) 0.0054(7) 0.0047(6) 0.0036(6) Cl4 0.0712(7) 0.0571(6) 0.0671(7) 0.0204(6) 0.0151(6) 0.0072(6) Cl5 0.0830(7) 0.0592(7) 0.0693(7) 0.0238(6) 0.0309(6) 0.0069(6) Cl6 0.1122(11) 0.0912(10) 0.0410(6) -0.0021(7) -0.0145(7) -0.0245(8) Cl7 0.0716(7) 0.0898(8) 0.0749(8) 0.0112(8) 0.0130(8) 0.0282(6) Cl8 0.0790(7) 0.0674(7) 0.0404(5) 0.0166(6) -0.0045(6) 0.0012(7) C1 0.123(5) 0.060(3) 0.083(4) -0.026(3) 0.013(4) -0.028(3) C2 0.074(3) 0.081(3) 0.034(2) -0.004(2) 0.001(2) -0.015(3) C3 0.063(3) 0.091(4) 0.040(2) 0.003(3) -0.015(2) -0.002(3) C4 0.052(2) 0.069(3) 0.049(2) -0.029(2) -0.016(2) 0.007(2) C5 0.076(3) 0.098(3) 0.054(3) -0.032(3) -0.005(3) 0.041(3) C6 0.071(3) 0.068(3) 0.085(3) -0.051(2) 0.005(3) -0.006(3) C7 0.071(3) 0.094(4) 0.039(2) 0.015(3) -0.019(2) 0.006(3) C8 0.068(3) 0.066(3) 0.051(2) 0.002(3) 0.023(3) 0.023(2) C9 0.053(2) 0.061(2) 0.0289(19) -0.002(2) 0.0086(17) 0.001(2) C10 0.091(4) 0.083(4) 0.024(2) -0.011(2) 0.014(2) -0.010(3) C11 0.085(3) 0.109(4) 0.049(3) 0.018(3) 0.011(3) 0.013(4) C12 0.048(2) 0.068(3) 0.050(3) 0.017(2) -0.005(2) 0.004(2) C13 0.066(3) 0.068(3) 0.040(2) -0.002(2) 0.008(2) 0.001(2) C14 0.071(3) 0.101(4) 0.043(2) 0.016(3) 0.000(3) 0.001(3) C15 0.085(4) 0.070(3) 0.080(4) 0.011(3) 0.009(3) 0.028(3) C16 0.047(3) 0.075(3) 0.122(5) 0.013(4) -0.008(3) 0.018(3) C17 0.128(5) 0.128(5) 0.059(4) 0.011(4) -0.019(4) -0.054(4) N1 0.066(3) 0.079(3) 0.061(2) -0.002(3) 0.005(2) 0.001(2) N2 0.058(2) 0.078(3) 0.053(2) 0.013(2) -0.005(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 Bi1 Cl3 2.5103(13) . ? Bi1 Cl1 2.5243(15) . ? Bi1 Cl5 2.7194(14) . ? Bi1 Cl2 2.7399(13) . ? Bi1 Cl8 2.9384(13) 1_565 ? Bi1 Cl4 2.9647(14) . ? Bi2 Cl7 2.5320(15) . ? Bi2 Cl6 2.5435(15) . ? Bi2 Cl8 2.6992(13) . ? Bi2 Cl4 2.7190(14) . ? Bi2 Cl2 2.8937(13) 1_545 ? Bi2 Cl5 2.9834(14) . ? Cl2 Bi2 2.8937(13) 1_565 ? Cl8 Bi1 2.9384(13) 1_545 ? C1 N1 1.517(8) . ? C1 H1A 0.9600 . ? C1 H1B 0.9600 . ? C1 H1C 0.9600 . ? C2 N1 1.336(7) . ? C2 C3 1.392(8) . ? C2 H2A 0.9300 . ? C3 C4 1.358(7) . ? C3 H3A 0.9300 . ? C4 C7 1.428(7) . ? C4 C5 1.446(7) . ? C5 C6 1.341(8) . ? C5 H5A 0.9300 . ? C6 N1 1.320(7) . ? C6 H6A 0.9300 . ? C7 C8 1.322(7) . ? C7 H7A 0.9300 . ? C8 C9 1.470(7) . ? C8 H8A 0.9300 . ? C9 C14 1.390(7) . ? C9 C10 1.398(7) . ? C10 C11 1.398(9) . ? C10 H10A 0.9300 . ? C11 C12 1.336(7) . ? C11 H11A 0.9300 . ? C12 C13 1.369(7) . ? C12 N2 1.493(7) . ? C13 C14 1.361(8) . ? C13 H13A 0.9300 . ? C14 H14A 0.9300 . ? C15 N2 1.474(8) . ? C15 H15A 0.9600 . ? C15 H15B 0.9600 . ? C15 H15C 0.9600 . ? C16 N2 1.541(8) . ? C16 H16A 0.9600 . ? C16 H16B 0.9600 . ? C16 H16C 0.9600 . ? C17 N2 1.472(8) . ? C17 H17A 0.9600 . ? C17 H17B 0.9600 . ? C17 H17C 0.9600 . ? 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 Cl3 Bi1 Cl1 94.52(5) . . ? Cl3 Bi1 Cl5 88.43(4) . . ? Cl1 Bi1 Cl5 96.98(5) . . ? Cl3 Bi1 Cl2 92.59(4) . . ? Cl1 Bi1 Cl2 89.82(4) . . ? Cl5 Bi1 Cl2 173.03(4) . . ? Cl3 Bi1 Cl8 89.59(4) . 1_565 ? Cl1 Bi1 Cl8 170.27(4) . 1_565 ? Cl5 Bi1 Cl8 91.95(4) . 1_565 ? Cl2 Bi1 Cl8 81.17(4) . 1_565 ? Cl3 Bi1 Cl4 170.01(4) . . ? Cl1 Bi1 Cl4 92.01(5) . . ? Cl5 Bi1 Cl4 83.28(4) . . ? Cl2 Bi1 Cl4 94.98(4) . . ? Cl8 Bi1 Cl4 85.15(4) 1_565 . ? Cl7 Bi2 Cl6 91.08(6) . . ? Cl7 Bi2 Cl8 92.72(5) . . ? Cl6 Bi2 Cl8 88.30(5) . . ? Cl7 Bi2 Cl4 86.65(5) . . ? Cl6 Bi2 Cl4 98.89(5) . . ? Cl8 Bi2 Cl4 172.79(4) . . ? Cl7 Bi2 Cl2 91.21(5) . 1_545 ? Cl6 Bi2 Cl2 170.80(4) . 1_545 ? Cl8 Bi2 Cl2 82.69(4) . 1_545 ? Cl4 Bi2 Cl2 90.14(4) . 1_545 ? Cl7 Bi2 Cl5 169.28(5) . . ? Cl6 Bi2 Cl5 93.01(5) . . ? Cl8 Bi2 Cl5 97.29(4) . . ? Cl4 Bi2 Cl5 82.93(4) . . ? Cl2 Bi2 Cl5 86.30(4) 1_545 . ? Bi1 Cl2 Bi2 98.10(4) . 1_565 ? Bi2 Cl4 Bi1 97.11(4) . . ? Bi1 Cl5 Bi2 96.66(4) . . ? Bi2 Cl8 Bi1 97.95(4) . 1_545 ? N1 C1 H1A 109.5 . . ? N1 C1 H1B 109.5 . . ? H1A C1 H1B 109.5 . . ? N1 C1 H1C 109.5 . . ? H1A C1 H1C 109.5 . . ? H1B C1 H1C 109.5 . . ? N1 C2 C3 120.5(5) . . ? N1 C2 H2A 119.7 . . ? C3 C2 H2A 119.7 . . ? C4 C3 C2 122.1(5) . . ? C4 C3 H3A 119.0 . . ? C2 C3 H3A 119.0 . . ? C3 C4 C7 126.4(5) . . ? C3 C4 C5 113.4(5) . . ? C7 C4 C5 120.2(5) . . ? C6 C5 C4 123.0(5) . . ? C6 C5 H5A 118.5 . . ? C4 C5 H5A 118.5 . . ? N1 C6 C5 120.2(5) . . ? N1 C6 H6A 119.9 . . ? C5 C6 H6A 119.9 . . ? C8 C7 C4 122.1(5) . . ? C8 C7 H7A 119.0 . . ? C4 C7 H7A 119.0 . . ? C7 C8 C9 129.4(5) . . ? C7 C8 H8A 115.3 . . ? C9 C8 H8A 115.3 . . ? C14 C9 C10 114.7(5) . . ? C14 C9 C8 124.9(5) . . ? C10 C9 C8 120.3(4) . . ? C11 C10 C9 121.7(5) . . ? C11 C10 H10A 119.2 . . ? C9 C10 H10A 119.2 . . ? C12 C11 C10 119.0(5) . . ? C12 C11 H11A 120.5 . . ? C10 C11 H11A 120.5 . . ? C11 C12 C13 122.2(5) . . ? C11 C12 N2 119.9(5) . . ? C13 C12 N2 117.8(4) . . ? C14 C13 C12 117.9(5) . . ? C14 C13 H13A 121.1 . . ? C12 C13 H13A 121.1 . . ? C13 C14 C9 123.9(5) . . ? C13 C14 H14A 118.1 . . ? C9 C14 H14A 118.1 . . ? N2 C15 H15A 109.5 . . ? N2 C15 H15B 109.5 . . ? H15A C15 H15B 109.5 . . ? N2 C15 H15C 109.5 . . ? H15A C15 H15C 109.5 . . ? H15B C15 H15C 109.5 . . ? N2 C16 H16A 109.5 . . ? N2 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? N2 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? N2 C17 H17A 109.5 . . ? N2 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? N2 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 109.5 . . ? C6 N1 C2 120.6(5) . . ? C6 N1 C1 119.0(5) . . ? C2 N1 C1 120.3(5) . . ? C17 N2 C15 108.5(5) . . ? C17 N2 C12 114.2(4) . . ? C15 N2 C12 109.5(4) . . ? C17 N2 C16 107.5(5) . . ? C15 N2 C16 108.2(5) . . ? C12 N2 C16 108.9(4) . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 25.49 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 1.789 _refine_diff_density_min -1.549 _refine_diff_density_rms 0.167