# Supplementary Material (ESI) for Journal of Materials Chemistry # This journal is © The Royal Society of Chemistry 2000 # CCDC Number: 1145/194 # COMPOUND 1 data_1 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical '[{H3N-(CH2)6-NH3}PBI4] ' _chemical_formula_sum 'C6 H18 I4 N2 Pb' _chemical_formula_weight 833.02 _chemical_melting_point ? _chemical_compound_source ? 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' 'I' 'I' -0.4742 1.8119 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Pb' 'Pb' -3.3944 10.1111 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting 'monoclinic' _symmetry_space_group_name_H-M P21/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 11.856(5) _cell_length_b 8.486(4) _cell_length_c 9.043(4) _cell_angle_alpha 90.00 _cell_angle_beta 106.89(1) _cell_angle_gamma 90.00 _cell_volume 870.6(7) _cell_formula_units_Z 2 _cell_measurement_temperature 298 _cell_measurement_reflns_used 25 _cell_measurement_theta_min 5.3 _cell_measurement_theta_max 11.7 _exptl_crystal_description 'parallelipiped' _exptl_crystal_colour 'yellow-orange' _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 3.178 _exptl_crystal_density_method ? _exptl_crystal_F_000 724 _exptl_absorpt_coefficient_mu 16.757 _exptl_absorpt_correction_type 'psi-scan empirical' _exptl_absorpt_correction_T_min 0.52 _exptl_absorpt_correction_T_max 1.00 _exptl_special_details ; ? ; _diffrn_ambient_temperature 298 _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Crystal Logic Dual Goniometer diffractometer' _diffrn_measurement_method 'theta-2theta scans' _diffrn_standards_number 3 _diffrn_standards_interval_count 97 _diffrn_standards_interval_time ? _diffrn_standards_decay_% 2.8 _diffrn_reflns_number 1605 _diffrn_reflns_av_R_equivalents 0.0402 _diffrn_reflns_av_sigmaI/netI 0.0431 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 1.80 _diffrn_reflns_theta_max 24.97 _reflns_number_total 1526 _reflns_number_observed 1472 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Program COLLECT (UCLA Crystallographic package, C.E.Strouse, 1994)' _computing_cell_refinement 'Program LEAST (UCLA Crystallographic package, C.E.Strouse, 1994)' _computing_data_reduction 'Program REDUCE (UCLA Crystallographic package, C.E.Strouse, 1994)' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'ORTEP' _computing_publication_material ? _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[\s^2^(Fo^2^)+(0.0211P)^2^+3.0815P] 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 ? _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0441(13) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 1526 _refine_ls_number_parameters 67 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0298 _refine_ls_R_factor_obs 0.0284 _refine_ls_wR_factor_all 0.0769 _refine_ls_wR_factor_obs 0.0758 _refine_ls_goodness_of_fit_all 1.174 _refine_ls_goodness_of_fit_obs 1.179 _refine_ls_restrained_S_all 1.174 _refine_ls_restrained_S_obs 1.179 _refine_ls_shift/esd_max 0.001 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Pb Pb 0.0000 0.0000 0.0000 0.0322(2) Uani 1 d S . I1 I -0.27320(4) 0.08049(6) -0.07685(6) 0.0453(2) Uani 1 d . . I2 I -0.04948(5) -0.19265(6) -0.32000(6) 0.0445(2) Uani 1 d . . N1 N -0.2394(7) 0.0102(8) -0.6630(10) 0.051(2) Uani 1 d . . HN1A H -0.2061(30) 0.0229(50) -0.7386(24) 0.044(14) Uiso 1 calc R . HN1B H -0.1867(23) -0.0295(31) -0.5802(38) 0.044(14) Uiso 1 calc R . HN1C H -0.2645(10) 0.1030(21) -0.6391(59) 0.044(14) Uiso 1 calc R . C1 C -0.3407(9) -0.0994(12) -0.7146(11) 0.056(2) Uani 1 d . . H1A H -0.3131(9) -0.1998(12) -0.7420(11) 0.071(23) Uiso 1 calc R . H1B H -0.3969(9) -0.0569(12) -0.8063(11) 0.071(23) Uiso 1 calc R . C2 C -0.4013(8) -0.1254(10) -0.5918(11) 0.049(2) Uani 1 d . . H2A H -0.3435(8) -0.1634(10) -0.4992(11) 0.070(22) Uiso 1 calc R . H2B H -0.4600(8) -0.2075(10) -0.6266(11) 0.070(22) Uiso 1 calc R . C3 C -0.4611(8) 0.0194(10) -0.5502(11) 0.044(2) Uani 1 d . . H3A H -0.4013(8) 0.0941(10) -0.4965(11) 0.077(24) Uiso 1 calc R . H3B H -0.5083(8) 0.0692(10) -0.6444(11) 0.077(24) Uiso 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 Pb 0.0376(3) 0.0301(3) 0.0316(3) -0.00030(13) 0.0146(2) 0.00087(13) I1 0.0393(3) 0.0431(3) 0.0534(4) 0.0063(2) 0.0132(2) 0.0038(2) I2 0.0523(3) 0.0408(3) 0.0423(3) -0.0157(2) 0.0168(2) -0.0012(2) N1 0.055(4) 0.047(4) 0.063(5) 0.005(3) 0.033(4) 0.003(3) C1 0.063(6) 0.055(5) 0.060(5) -0.012(4) 0.034(5) -0.006(4) C2 0.055(5) 0.039(4) 0.062(5) 0.001(4) 0.034(4) -0.003(4) C3 0.042(4) 0.046(4) 0.048(5) -0.001(4) 0.021(4) -0.005(3) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Pb I1 3.1832(15) 3 ? Pb I1 3.1832(15) . ? Pb I2 3.2174(12) 4_565 ? Pb I2 3.2174(12) 2_545 ? Pb I2 3.2255(12) 3 ? Pb I2 3.2255(12) . ? I2 Pb 3.2174(12) 2_544 ? N1 C1 1.483(12) . ? C1 C2 1.504(12) . ? C2 C3 1.520(12) . ? C3 C3 1.51(2) 3_454 ? 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 I1 Pb I1 180.0 3 . ? I1 Pb I2 87.76(2) 3 4_565 ? I1 Pb I2 92.25(2) . 4_565 ? I1 Pb I2 92.25(2) 3 2_545 ? I1 Pb I2 87.75(2) . 2_545 ? I2 Pb I2 180.0 4_565 2_545 ? I1 Pb I2 90.27(2) 3 3 ? I1 Pb I2 89.73(2) . 3 ? I2 Pb I2 91.75(3) 4_565 3 ? I2 Pb I2 88.25(3) 2_545 3 ? I1 Pb I2 89.73(2) 3 . ? I1 Pb I2 90.27(2) . . ? I2 Pb I2 88.25(3) 4_565 . ? I2 Pb I2 91.75(3) 2_545 . ? I2 Pb I2 180.0 3 . ? Pb I2 Pb 148.47(2) 2_544 . ? N1 C1 C2 112.1(8) . . ? C1 C2 C3 114.9(8) . . ? C3 C3 C2 112.6(9) 3_454 . ? _refine_diff_density_max 1.267 _refine_diff_density_min -1.555 _refine_diff_density_rms 0.205 #===END # COMPOUND 2 data_2 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical '[H3N-(CH2)6-NH3]PbBr4' _chemical_formula_sum 'C6 H18 Br4 N2 Pb' _chemical_formula_weight 645.06 _chemical_melting_point ? _chemical_compound_source ? 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' 'Br' 'Br' -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Pb' 'Pb' -3.3944 10.1111 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting 'monoclinic' _symmetry_space_group_name_H-M P21/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 12.02(1) _cell_length_b 8.045(8) _cell_length_c 8.342(9) _cell_angle_alpha 90.00 _cell_angle_beta 105.66(3) _cell_angle_gamma 90.00 _cell_volume 777(2) _cell_formula_units_Z 2 _cell_measurement_temperature 298 _cell_measurement_reflns_used 25 _cell_measurement_theta_min 5.3 _cell_measurement_theta_max 11.7 _exptl_crystal_description 'parallelipiped' _exptl_crystal_colour 'colorless' _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.758 _exptl_crystal_density_method ? _exptl_crystal_F_000 580 _exptl_absorpt_coefficient_mu 21.122 _exptl_absorpt_correction_type 'psi-scan empirical' _exptl_absorpt_correction_T_min 0.31 _exptl_absorpt_correction_T_max 1.00 _exptl_special_details ; ? ; _diffrn_ambient_temperature 298 _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Crystal Logic Dual Goniometer diffractometer' _diffrn_measurement_method 'theta-2theta scans' _diffrn_standards_number 3 _diffrn_standards_interval_count 97 _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0.3 _diffrn_reflns_number 702 _diffrn_reflns_av_R_equivalents 0.0402 _diffrn_reflns_av_sigmaI/netI 0.0441 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -7 _diffrn_reflns_limit_k_max 0 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 7 _diffrn_reflns_theta_min 3.08 _diffrn_reflns_theta_max 19.50 _reflns_number_total 651 _reflns_number_observed 556 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Program COLLECT (UCLA Crystallographic package, C.E.Strouse, 1994)' _computing_cell_refinement 'Program LEAST (UCLA Crystallographic package, C.E.Strouse, 1994)' _computing_data_reduction 'Program REDUCE (UCLA Crystallographic package, C.E.Strouse, 1994)' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'ORTEP' _computing_publication_material ? _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[\s^2^(Fo^2^)+(0.0108P)^2^+7.8735P] 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 ? _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.012(1) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 651 _refine_ls_number_parameters 62 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0427 _refine_ls_R_factor_obs 0.0333 _refine_ls_wR_factor_all 0.0887 _refine_ls_wR_factor_obs 0.0828 _refine_ls_goodness_of_fit_all 1.093 _refine_ls_goodness_of_fit_obs 1.113 _refine_ls_restrained_S_all 1.093 _refine_ls_restrained_S_obs 1.113 _refine_ls_shift/esd_max 0.001 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Pb1 Pb 0.0000 0.0000 0.0000 0.0858(6) Uani 1 d S . Br1 Br -0.2519(2) 0.0738(2) -0.0654(3) 0.1243(10) Uani 1 d . . Br2 Br -0.0434(2) -0.1948(2) -0.3182(2) 0.1030(9) Uani 1 d . . N1 N -0.2184(17) 0.0251(18) -0.6460(22) 0.117(6) Uani 1 d . . C1 C -0.3345(41) -0.0922(36) -0.6981(51) 0.210(16) Uani 1 d . . C2 C -0.3858(48) -0.1129(49) -0.5729(56) 0.242(19) Uani 1 d . . C3 C -0.4640(37) 0.0339(46) -0.5669(54) 0.226(23) Uani 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 Pb1 0.1851(12) 0.0376(7) 0.0370(7) 0.0003(3) 0.0338(5) 0.0063(5) Br1 0.194(2) 0.0611(12) 0.0979(15) 0.0028(10) 0.0053(14) 0.0004(13) Br2 0.203(2) 0.0560(11) 0.0580(11) -0.0225(8) 0.0491(11) -0.0091(11) N1 0.163(16) 0.071(10) 0.133(14) -0.003(9) 0.067(12) -0.014(10) C1 0.314(50) 0.100(20) 0.235(39) 0.017(23) 0.107(35) -0.042(26) C2 0.338(60) 0.162(32) 0.233(43) 0.025(31) 0.091(38) 0.070(35) C3 0.212(42) 0.131(28) 0.264(55) 0.028(27) -0.060(33) 0.017(25) _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 Pb1 Br1 2.987(4) . ? Pb1 Br1 2.987(4) 3 ? Pb1 Br2 3.004(3) 3 ? Pb1 Br2 3.004(3) . ? Pb1 Br2 3.005(3) 4_565 ? Pb1 Br2 3.005(3) 2_545 ? Br2 Pb1 3.005(3) 2_544 ? N1 C1 1.64(4) . ? C1 C2 1.36(4) . ? C2 C3 1.52(6) . ? C3 C3 1.68(9) 3_454 ? 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 Br1 Pb1 Br1 180.0 . 3 ? Br1 Pb1 Br2 89.04(7) . 3 ? Br1 Pb1 Br2 90.96(7) 3 3 ? Br1 Pb1 Br2 90.96(7) . . ? Br1 Pb1 Br2 89.04(7) 3 . ? Br2 Pb1 Br2 180.0 3 . ? Br1 Pb1 Br2 92.92(7) . 4_565 ? Br1 Pb1 Br2 87.08(7) 3 4_565 ? Br2 Pb1 Br2 90.42(8) 3 4_565 ? Br2 Pb1 Br2 89.58(8) . 4_565 ? Br1 Pb1 Br2 87.08(7) . 2_545 ? Br1 Pb1 Br2 92.92(7) 3 2_545 ? Br2 Pb1 Br2 89.58(8) 3 2_545 ? Br2 Pb1 Br2 90.42(8) . 2_545 ? Br2 Pb1 Br2 180.0 4_565 2_545 ? Pb1 Br2 Pb1 149.31(8) . 2_544 ? C2 C1 N1 113.3(37) . . ? C1 C2 C3 110.1(36) . . ? C2 C3 C3 101.8(35) . 3_454 ? _refine_diff_density_max 0.531 _refine_diff_density_min -1.389 _refine_diff_density_rms 0.130 #===END