# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2005 data_global _journal_coden_Cambridge 182 loop_ _publ_author_name 'Arnold Guloy' 'Jun Guan' 'Zhongjia Tang' _publ_contact_author_name 'Prof Arnold Guloy' _publ_contact_author_address ; Department of Chemistry University of Houston 136 Fleming Building University of Houston Houston Texas 77204-5003 UNITED STATES OF AMERICA ; _publ_contact_author_email AGULOY@UH.EDU _publ_requested_journal 'Chemical Communications' _publ_section_title ; [H3N(CH2)7NH3]8(CH3NH3)2 Sn(IV)Sn(II)12I46 - A Mixed-valent Hybrid Compound with a Uniquely Templated Defect-Perovskite Structure ; data_good _database_code_depnum_ccdc_archive 'CCDC 246164' _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C58 H172 I46 N18 Sn13' _chemical_formula_weight 8502.51 _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' Sn Sn -0.6537 1.4246 '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' _symmetry_cell_setting Tetragonal _symmetry_space_group_name_H-M P4(2)/mnm loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-y+1/2, x+1/2, z+1/2' 'y+1/2, -x+1/2, z+1/2' '-x+1/2, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z+1/2' 'y, x, -z' '-y, -x, -z' '-x, -y, -z' 'x, y, -z' 'y-1/2, -x-1/2, -z-1/2' '-y-1/2, x-1/2, -z-1/2' 'x-1/2, -y-1/2, z-1/2' '-x-1/2, y-1/2, z-1/2' '-y, -x, z' 'y, x, z' _cell_length_a 26.9174(13) _cell_length_b 26.9174(13) _cell_length_c 12.7329(9) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 9225.6(9) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min 1.07 _cell_measurement_theta_max 25.04 _exptl_crystal_description block _exptl_crystal_colour 'dark red' _exptl_crystal_size_max 0.36 _exptl_crystal_size_mid 0.32 _exptl_crystal_size_min 0.30 _exptl_crystal_density_diffrn 3.061 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 7468 _exptl_absorpt_coefficient_mu 9.455 _exptl_absorpt_correction_type SADABS _exptl_absorpt_correction_T_min 0.53925 _exptl_absorpt_correction_T_max 1.0000 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 'Siemens SMART CCD' _diffrn_measurement_method CCD _diffrn_detector_area_resol_mean 1K _diffrn_standards_decay_% 0.0 _diffrn_reflns_number 47031 _diffrn_reflns_av_R_equivalents 0.0393 _diffrn_reflns_av_sigmaI/netI 0.0144 _diffrn_reflns_limit_h_min -25 _diffrn_reflns_limit_h_max 32 _diffrn_reflns_limit_k_min -32 _diffrn_reflns_limit_k_max 32 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 1.07 _diffrn_reflns_theta_max 25.04 _reflns_number_total 4411 _reflns_number_observed 3523 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens SMART software (Siemens, 1996)' _computing_cell_refinement 'Siemens SMART software (Siemens, 1996)' _computing_data_reduction 'Siemens SMART software (Siemens, 1996)' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'SHELXS-97 (Sheldrick, 1990)' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 12 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^)+(0.0200P)^2^+156.2772P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary diffmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment noref _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.000376(9) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 4399 _refine_ls_number_parameters 139 _refine_ls_number_restraints 15 _refine_ls_R_factor_all 0.0689 _refine_ls_R_factor_obs 0.0527 _refine_ls_wR_factor_all 0.1320 _refine_ls_wR_factor_obs 0.1102 _refine_ls_goodness_of_fit_all 1.223 _refine_ls_goodness_of_fit_obs 1.242 _refine_ls_restrained_S_all 1.330 _refine_ls_restrained_S_obs 1.246 _refine_ls_shift/esd_max 0.004 _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 Sn1 Sn 0.34760(5) 0.34760(5) 0.5000 0.0512(4) Uani 1 d S . Sn2 Sn 0.32812(4) 0.32812(4) 0.0000 0.0394(3) Uani 1 d S . Sn3 Sn 0.0000 0.0000 -0.5000 0.0450(5) Uani 1 d S . Sn4 Sn 0.00791(4) 0.33003(4) -0.5000 0.0375(3) Uani 1 d S . Sn5 Sn 0.00407(4) 0.33285(4) 0.0000 0.0385(3) Uani 1 d S . I1 I 0.34394(5) 0.34394(5) 0.24728(11) 0.0847(5) Uani 1 d S . I2 I 0.25389(5) 0.25389(5) 0.0000 0.0769(6) Uani 1 d S . I3 I 0.42685(5) 0.25991(5) 0.5000 0.0755(4) Uani 1 d S . I4 I 0.41017(5) 0.24427(6) 0.0000 0.0757(4) Uani 1 d S . I5 I 0.07469(5) 0.07469(5) -0.5000 0.0737(6) Uani 1 d S . I6 I 0.0000 0.0000 -0.2783(2) 0.0993(8) Uani 1 d S . I7 I 0.00091(4) 0.33522(4) -0.25037(6) 0.0678(3) Uani 1 d . . I8 I 0.09520(5) 0.27400(5) 0.0000 0.0717(4) Uani 1 d S . I9 I 0.06852(5) 0.42864(5) 0.0000 0.0672(4) Uani 1 d S . I10 I 0.09274(5) 0.40191(5) -0.5000 0.0722(4) Uani 1 d S . I11 I 0.06740(5) 0.23913(5) -0.5000 0.0708(4) Uani 1 d S . I12 I 0.42177(6) 0.42177(6) 0.5000 0.0881(7) Uani 1 d S . I13 I -0.07632(5) 0.07632(5) -0.5000 0.1120(10) Uani 1 d S . N1 N 0.1413(6) 0.3634(6) 0.2097(14) 0.137(6) Uiso 1 d D . H11A H 0.1481(6) 0.3944(6) 0.1897(14) 0.205 Uiso 1 calc R . H11B H 0.1158(6) 0.3637(6) 0.2541(14) 0.205 Uiso 1 calc R . H11C H 0.1335(6) 0.3453(6) 0.1536(14) 0.205 Uiso 1 calc R . C1 C 0.1854(8) 0.3416(8) 0.2623(18) 0.139(8) Uiso 1 d D . H1A H 0.1942(8) 0.3610(8) 0.3237(18) 0.167 Uiso 1 calc R . H1B H 0.2135(8) 0.3411(8) 0.2148(18) 0.167 Uiso 1 calc R . C2 C 0.1716(10) 0.2899(9) 0.2937(28) 0.230(16) Uiso 1 d D . H2A H 0.1420(10) 0.2907(9) 0.3371(28) 0.276 Uiso 1 calc R . H2B H 0.1644(10) 0.2704(9) 0.2315(28) 0.276 Uiso 1 calc R . C3 C 0.2118(13) 0.2675(11) 0.3511(28) 0.282(21) Uiso 1 d D . H3A H 0.2057(13) 0.2702(11) 0.4259(28) 0.338 Uiso 1 calc R . H3B H 0.2427(13) 0.2846(11) 0.3353(28) 0.338 Uiso 1 calc R . C4 C 0.2159(14) 0.2159(14) 0.3217(51) 0.309(34) Uiso 1 d SD . H4A H 0.2104(14) 0.2104(14) 0.2473(51) 0.371 Uiso 1 calc SR . H4B H 0.1944(14) 0.1944(14) 0.3628(51) 0.371 Uiso 1 calc SR . N2 N 0.1921(9) -0.0230(9) -0.2824(21) 0.228(12) Uiso 1 d D . H22A H 0.1842(9) -0.0480(9) -0.3250(21) 0.342 Uiso 1 calc R . H22B H 0.2101(9) -0.0345(9) -0.2291(21) 0.342 Uiso 1 calc R . H22C H 0.2096(9) -0.0005(9) -0.3178(21) 0.342 Uiso 1 calc R . C5 C 0.1497(11) -0.0016(11) -0.2446(28) 0.236(17) Uiso 1 d D . H5A H 0.1180(11) -0.0125(11) -0.2626(28) 0.283 Uiso 1 calc R . C6 C 0.1586(13) 0.0398(11) -0.1731(26) 0.257(18) Uiso 1 d D . H6A H 0.1689(13) 0.0345(11) -0.1043(26) 0.308 Uiso 1 calc R . C7 C 0.1515(13) 0.0861(10) -0.2106(26) 0.232(16) Uiso 1 d D . H7A H 0.1377(13) 0.0835(10) -0.2807(26) 0.279 Uiso 1 calc R . H7B H 0.1836(13) 0.1022(10) -0.2167(26) 0.279 Uiso 1 calc R . C8 C 0.1186(15) 0.1186(15) -0.1473(44) 0.294(31) Uiso 1 d SD . H8A H 0.0978(15) 0.0978(15) -0.1030(44) 0.353 Uiso 1 calc SR . H8B H 0.1390(15) 0.1390(15) -0.1016(44) 0.353 Uiso 1 calc SR . N3 N 0.0000 0.5000 0.2500 0.203(21) Uiso 1 d SD . C9 C -0.0333(24) 0.5336(24) 0.3033(57) 0.111(24) Uiso 0.25 d PD . 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 Sn1 0.0577(6) 0.0577(6) 0.0382(9) 0.000 0.000 0.0146(8) Sn2 0.0419(5) 0.0419(5) 0.0342(8) 0.000 0.000 0.0083(6) Sn3 0.0447(7) 0.0447(7) 0.0456(13) 0.000 0.000 0.0093(10) Sn4 0.0375(5) 0.0425(6) 0.0325(5) 0.000 0.000 -0.0050(4) Sn5 0.0417(6) 0.0407(6) 0.0329(5) 0.000 0.000 -0.0012(5) I1 0.1011(7) 0.1011(7) 0.0520(8) 0.0043(6) 0.0043(6) 0.0134(9) I2 0.0651(7) 0.0651(7) 0.100(2) 0.000 0.000 -0.0154(9) I3 0.0741(9) 0.0578(8) 0.0947(11) 0.000 0.000 0.0248(7) I4 0.0558(8) 0.0847(10) 0.0865(10) 0.000 0.000 0.0365(7) I5 0.0781(8) 0.0781(8) 0.0650(12) 0.000 0.000 -0.0249(10) I6 0.1274(13) 0.1274(13) 0.0430(11) 0.000 0.000 -0.049(2) I7 0.0836(6) 0.0904(7) 0.0293(4) 0.0017(4) 0.0022(4) 0.0013(5) I8 0.0596(8) 0.0679(8) 0.0877(10) 0.000 0.000 0.0231(6) I9 0.0666(8) 0.0544(7) 0.0807(9) 0.000 0.000 -0.0217(6) I10 0.0581(8) 0.0634(8) 0.0952(10) 0.000 0.000 -0.0278(6) I11 0.0635(8) 0.0562(7) 0.0928(10) 0.000 0.000 0.0161(6) I12 0.0783(9) 0.0783(9) 0.108(2) 0.000 0.000 -0.0005(11) I13 0.0807(11) 0.0807(11) 0.175(3) 0.000 0.000 0.0454(13) _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 Sn1 I12 2.823(3) . ? Sn1 I3 3.1815(12) 7_556 ? Sn1 I3 3.1815(12) . ? Sn1 I1 3.2208(14) 10_556 ? Sn1 I1 3.2208(14) . ? Sn2 I2 2.826(2) . ? Sn2 I4 3.1577(12) 7 ? Sn2 I4 3.1577(12) . ? Sn2 I1 3.2058(15) . ? Sn2 I1 3.2058(15) 10 ? Sn3 I6 2.823(2) 9_554 ? Sn3 I6 2.823(2) . ? Sn3 I5 2.843(2) 9_554 ? Sn3 I5 2.843(2) . ? Sn3 I13 2.905(2) . ? Sn3 I13 2.905(2) 9_554 ? Sn4 I11 2.924(2) . ? Sn4 I10 2.993(2) . ? Sn4 I7 3.1871(8) . ? Sn4 I7 3.1871(8) 10_554 ? Sn5 I8 2.920(2) . ? Sn5 I9 3.108(2) . ? Sn5 I7 3.1897(8) 10 ? Sn5 I7 3.1897(8) . ? N1 C1 1.48(2) . ? C1 C2 1.49(2) . ? C2 C3 1.44(2) . ? C3 C4 1.44(3) . ? C4 C3 1.44(3) 16 ? N2 C5 1.37(2) . ? C5 C6 1.46(2) . ? C6 C7 1.35(2) . ? C7 C8 1.48(2) . ? C8 C7 1.48(2) 16 ? N3 C9 1.44(3) 12_666 ? N3 C9 1.44(3) . ? N3 C9 1.44(3) 2_565 ? N3 C9 1.44(3) 11_566 ? 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 I12 Sn1 I3 92.90(5) . 7_556 ? I12 Sn1 I3 92.90(5) . . ? I3 Sn1 I3 174.21(9) 7_556 . ? I12 Sn1 I1 92.48(5) . 10_556 ? I3 Sn1 I1 89.875(4) 7_556 10_556 ? I3 Sn1 I1 89.875(4) . 10_556 ? I12 Sn1 I1 92.48(5) . . ? I3 Sn1 I1 89.875(4) 7_556 . ? I3 Sn1 I1 89.875(4) . . ? I1 Sn1 I1 175.04(10) 10_556 . ? I2 Sn2 I4 89.38(4) . 7 ? I2 Sn2 I4 89.38(4) . . ? I4 Sn2 I4 178.76(8) 7 . ? I2 Sn2 I1 100.83(4) . . ? I4 Sn2 I1 90.117(8) 7 . ? I4 Sn2 I1 90.117(8) . . ? I2 Sn2 I1 100.83(4) . 10 ? I4 Sn2 I1 90.117(8) 7 10 ? I4 Sn2 I1 90.117(8) . 10 ? I1 Sn2 I1 158.34(8) . 10 ? I6 Sn3 I6 180.0 9_554 . ? I6 Sn3 I5 90.0 9_554 9_554 ? I6 Sn3 I5 90.0 . 9_554 ? I6 Sn3 I5 90.0 9_554 . ? I6 Sn3 I5 90.0 . . ? I5 Sn3 I5 180.0 9_554 . ? I6 Sn3 I13 90.0 9_554 . ? I6 Sn3 I13 90.0 . . ? I5 Sn3 I13 90.0 9_554 . ? I5 Sn3 I13 90.0 . . ? I6 Sn3 I13 90.0 9_554 9_554 ? I6 Sn3 I13 90.0 . 9_554 ? I5 Sn3 I13 90.0 9_554 9_554 ? I5 Sn3 I13 90.0 . 9_554 ? I13 Sn3 I13 180.0 . 9_554 ? I11 Sn4 I10 97.07(5) . . ? I11 Sn4 I7 93.96(3) . . ? I10 Sn4 I7 90.96(3) . . ? I11 Sn4 I7 93.96(3) . 10_554 ? I10 Sn4 I7 90.96(3) . 10_554 ? I7 Sn4 I7 171.56(5) . 10_554 ? I8 Sn5 I9 88.92(5) . . ? I8 Sn5 I7 91.90(3) . 10 ? I9 Sn5 I7 89.90(3) . 10 ? I8 Sn5 I7 91.90(3) . . ? I9 Sn5 I7 89.90(3) . . ? I7 Sn5 I7 176.19(5) 10 . ? Sn2 I1 Sn1 171.65(8) . . ? Sn4 I7 Sn5 173.87(5) . . ? N1 C1 C2 106.9(17) . . ? C3 C2 C1 109.8(22) . . ? C2 C3 C4 109.1(24) . . ? C3 C4 C3 94.4(40) . 16 ? N2 C5 C6 113.8(25) . . ? C7 C6 C5 117.6(28) . . ? C6 C7 C8 116.0(27) . . ? C7 C8 C7 114.1(47) 16 . ? C9 N3 C9 102.8(27) 12_666 . ? C9 N3 C9 102.8(27) 12_666 2_565 ? C9 N3 C9 123.9(64) . 2_565 ? C9 N3 C9 123.9(64) 12_666 11_566 ? C9 N3 C9 102.8(27) . 11_566 ? C9 N3 C9 102.8(27) 2_565 11_566 ? _refine_diff_density_max 1.892 _refine_diff_density_min -1.445 _refine_diff_density_rms 0.185