#------------------------------------------------------------------------------ #$Date: 2018-11-10 01:21:05 +0200 (Sat, 10 Nov 2018) $ #$Revision: 211871 $ #$URL: file:///home/coder/svn-repositories/cod/cif/1/55/02/1550207.cif $ #------------------------------------------------------------------------------ # # This file is available in the Crystallography Open Database (COD), # http://www.crystallography.net/ # # All data on this site have been placed in the public domain by the # contributors. # data_1550207 loop_ _publ_author_name 'Li, Tianyang' 'Dunlap-Shohl, Wiley' 'Reinheimer, Eric W.' 'LeMagueres, Pierre' 'Mitzi, David B.' _publ_section_title ; Melting Temperature Suppression of Layered Hybrid Lead Halide Perovskites via Organic Ammonium Cation Branching ; _journal_name_full 'Chemical Science' _journal_paper_doi 10.1039/C8SC03863E _journal_year 2019 _chemical_formula_moiety '0.5(I8 Pb2), C8 H26 N2' _chemical_formula_sum 'C8 H26 I4 N2 Pb' _chemical_formula_weight 865.10 _space_group_crystal_system tetragonal _space_group_IT_number 138 _space_group_name_Hall '-P 4ac 2ac' _space_group_name_H-M_alt 'P 42/n c m' _symmetry_space_group_name_Hall '-P 4ac 2ac' _symmetry_space_group_name_H-M 'P 42/n c m :2' _atom_sites_solution_hydrogens geom _atom_sites_solution_primary direct _audit_creation_date 2018-03-08 _audit_creation_method ; Olex2 1.2 (compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381) ; _audit_update_record ; 2018-08-24 deposited with the CCDC. 2018-11-09 downloaded from the CCDC. ; _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_formula_units_Z 4 _cell_length_a 8.9353(2) _cell_length_b 8.9353(2) _cell_length_c 24.9636(13) _cell_measurement_reflns_used 6263 _cell_measurement_temperature 293(2) _cell_measurement_theta_max 30.2310 _cell_measurement_theta_min 2.7640 _cell_volume 1993.08(12) _computing_cell_refinement 'CrysAlisPro 1.171.40.3a (Rigaku OD, 2018)' _computing_data_collection 'CrysAlisPro 1.171.40.3a (Rigaku OD, 2018)' _computing_data_reduction 'CrysAlisPro 1.171.40.3a (Rigaku OD, 2018)' _computing_molecular_graphics 'Olex2 (Dolomanov et al., 2009)' _computing_publication_material 'Olex2 (Dolomanov et al., 2009)' _computing_structure_refinement 'ShelXL (Sheldrick, 2015)' _computing_structure_solution 'ShelXT (Sheldrick, 2015)' _diffrn_ambient_temperature 293(2) _diffrn_measured_fraction_theta_full 0.999 _diffrn_measured_fraction_theta_max 0.999 _diffrn_measurement_device_type 'XtaLAB Synergy, Dualflex, HyPix' _diffrn_measurement_method '\w scans' _diffrn_radiation_type MoK\a _diffrn_radiation_wavelength 0.71073 _diffrn_reflns_av_R_equivalents 0.0251 _diffrn_reflns_av_unetI/netI 0.0144 _diffrn_reflns_Laue_measured_fraction_full 0.999 _diffrn_reflns_Laue_measured_fraction_max 0.999 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_l_max 29 _diffrn_reflns_limit_l_min -29 _diffrn_reflns_number 11096 _diffrn_reflns_point_group_measured_fraction_full 0.999 _diffrn_reflns_point_group_measured_fraction_max 0.999 _diffrn_reflns_theta_full 25.025 _diffrn_reflns_theta_max 25.025 _diffrn_reflns_theta_min 2.804 _diffrn_source 'microfocused sealed tube' _diffrn_standards_decay_% 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_number 0 _exptl_absorpt_coefficient_mu 14.644 _exptl_absorpt_correction_T_max 1.000 _exptl_absorpt_correction_T_min 0.576 _exptl_absorpt_correction_type gaussian _exptl_crystal_colour 'metallic orange' _exptl_crystal_colour_lustre metallic _exptl_crystal_colour_primary orange _exptl_crystal_density_diffrn 2.883 _exptl_crystal_description block _exptl_crystal_F_000 1528 _exptl_crystal_size_max 0.321 _exptl_crystal_size_mid 0.173 _exptl_crystal_size_min 0.025 _refine_diff_density_max 2.749 _refine_diff_density_min -2.003 _refine_diff_density_rms 0.300 _refine_ls_extinction_method none _refine_ls_goodness_of_fit_ref 1.145 _refine_ls_hydrogen_treatment constr _refine_ls_matrix_type full _refine_ls_number_parameters 38 _refine_ls_number_reflns 972 _refine_ls_number_restraints 29 _refine_ls_restrained_S_all 1.129 _refine_ls_R_factor_all 0.0627 _refine_ls_R_factor_gt 0.0609 _refine_ls_shift/su_max 1.026 _refine_ls_shift/su_mean 0.087 _refine_ls_structure_factor_coef Fsqd _refine_ls_weighting_details 'w=1/[\s^2^(Fo^2^)+(0.1568P)^2^+7.2173P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_weighting_scheme calc _refine_ls_wR_factor_gt 0.2229 _refine_ls_wR_factor_ref 0.2263 _reflns_Friedel_coverage 0.000 _reflns_number_gt 905 _reflns_number_total 972 _reflns_threshold_expression 'I > 2\s(I)' _cod_data_source_file c8sc03863e2.cif _cod_data_source_block 1me-pa_roomt_feb _cod_original_cell_volume 1993.10(15) _cod_database_code 1550207 _shelx_shelxl_version_number 2014/7 _shelx_space_group_comment ; The symmetry employed for this shelxl refinement is uniquely defined by the following loop, which should always be used as a source of symmetry information in preference to the above space-group names. They are only intended as comments. ; _olex2_refinement_description ; 1. Fixed Uiso At 1.2 times of: All C(H,H) groups, All N(H,H,H) groups At 1.5 times of: All C(H,H,H) groups 2. Restrained distances N1-C3 1.47 with sigma of 0.02 C4-C8 1.54 with sigma of 0.02 C8-C4 \\sim C4-C3 with sigma of 0.001 C5-C3 \\sim C4-C3 with sigma of 0.001 C8-C4 \\sim C4-C3 \\sim C5-C3 with sigma of 0.005 3. Uiso/Uaniso restraints and constraints Uanis(C8) = Uanis(C4) = Uanis(C3) = Uanis(N1) Uanis(C8) = Uanis(C4) = Uanis(C5) = Uanis(C3) = Uanis(N1) Uanis(C3) = Uanis(C8) 4. Rigid body (RIGU) restrains N1, C3, C4, C5, C8 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001 C8 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001 5. Others Fixed Sof: H1A(0.5) H1B(0.5) H1C(0.5) C4(0.5) H4A(0.5) H4B(0.5) C8(0.5) H8A(0.5) H8B(0.5) H8C(0.5) C5(0.5) H5A(0.5) H5B(0.5) H5C(0.5) 6.a Ternary CH refined with riding coordinates: C3(H3B), C3(H3A) 6.b Secondary CH2 refined with riding coordinates: C4(H4A,H4B) 6.c Idealised Me refined as rotating group: N1(H1A,H1B,H1C), C8(H8A,H8B,H8C), C5(H5A,H5B,H5C) ; _shelx_res_file ; 1me-pa_roomt_feb.res created by SHELXL-2014/7 TITL Me-PA_RoomT in P4(2)/ncm CELL 0.71073 8.935346 8.935346 24.963554 90 90 90 ZERR 4 0.000237 0.000237 0.001316 0 0 0 LATT 1 SYMM 0.5-Y,+X,0.5+Z SYMM 0.5-X,0.5-Y,+Z SYMM +Y,0.5-X,0.5+Z SYMM 0.5+X,-Y,0.5-Z SYMM -X,0.5+Y,0.5-Z SYMM 0.5+Y,0.5+X,-Z SYMM -Y,-X,-Z SFAC C H I N Pb UNIT 32 104 16 8 4 DFIX 1.47 N1 C3 DFIX 1.54 C4 C8 SADI 0.001 C8 C4 C4 C3 SADI 0.001 C5 C3 C4 C3 SADI 0.005 C8 C4 C4 C3 C5 C3 RIGU 0.001 0.001 N1 C3 C4 C5 C8 RIGU 0.001 0.001 C8 EADP C8 C4 C3 N1 EADP C8 C4 C5 C3 N1 EADP C3 C8 L.S. 20 PLAN 1 FREE C8 C5 MORE -1 BOND $H CONF fmap 2 53 acta 52 SHEL 10 0.84 REM REM REM WGHT 0.156800 7.217300 FVAR 0.46041 PB1 5 0.500000 0.500000 0.500000 10.25000 0.07478 0.07478 = 0.09416 -0.00478 -0.00478 -0.01633 I2 3 0.750000 0.750000 0.475582 10.25000 0.06654 0.06654 = 0.09329 0.00000 0.00000 -0.02807 I3 3 0.250000 0.750000 0.500000 10.25000 0.06774 0.06774 = 0.11914 0.00000 0.00000 0.01157 I4 3 0.441380 0.441380 0.375841 10.50000 0.13748 0.13748 = 0.08881 -0.00158 -0.00158 -0.01636 N1 4 0.464837 0.035163 0.410282 10.50000 0.14873 0.14873 = 0.15435 -0.02918 0.02918 0.00077 PART -1 AFIX 137 H1A 2 0.507711 0.121778 0.418907 10.50000 -1.20000 H1B 2 0.496868 -0.036070 0.432408 10.50000 -1.20000 H1C 2 0.365909 0.043803 0.413045 10.50000 -1.20000 AFIX 0 PART 0 C3 1 0.504901 -0.004901 0.354392 10.50000 0.14873 0.14873 = 0.15435 -0.02918 0.02918 0.00077 PART 2 AFIX 13 H3B 2 0.443867 0.056138 0.330173 10.50000 -1.20000 AFIX 13 PART 0 PART 1 H3A 2 0.437320 0.062683 0.335136 10.50000 -1.20000 AFIX 0 PART 0 PART 2 C4 1 0.667069 0.005272 0.336099 10.50000 0.14873 0.14873 = 0.15435 -0.02918 0.02918 0.00077 AFIX 23 H4A 2 0.702693 0.102012 0.348274 10.50000 -1.20000 H4B 2 0.720993 -0.068934 0.356879 10.50000 -1.20000 AFIX 0 C8 1 0.723442 -0.011188 0.278850 10.50000 0.14873 0.14873 = 0.15435 -0.02918 0.02918 0.00077 AFIX 137 H8A 2 0.826422 0.019038 0.277073 10.50000 -1.50000 H8B 2 0.664739 0.050805 0.255505 10.50000 -1.50000 H8C 2 0.714713 -0.113785 0.267873 10.50000 -1.50000 AFIX 0 PART 0 PART 1 C5 1 0.432613 -0.153975 0.340230 10.50000 0.14873 0.14873 = 0.15435 -0.02918 0.02918 0.00077 AFIX 137 H5A 2 0.329371 -0.138151 0.331220 10.50000 -1.50000 H5B 2 0.439174 -0.220418 0.370359 10.50000 -1.50000 H5C 2 0.483698 -0.197384 0.310179 10.50000 -1.50000 AFIX 0 HKLF 4 REM Me-PA_RoomT in P4(2)/ncm REM R1 = 0.0609 for 905 Fo > 4sig(Fo) and 0.0627 for all 972 data REM 38 parameters refined using 29 restraints END WGHT 0.1570 7.0093 REM Highest difference peak 2.749, deepest hole -2.003, 1-sigma level 0.300 Q1 1 0.2500 0.7500 0.4862 10.50000 0.05 2.33 ; _shelx_res_checksum 47431 _olex2_submission_special_instructions 'No special instructions were received' loop_ _space_group_symop_operation_xyz 'x, y, z' '-y+1/2, x, z+1/2' '-x+1/2, -y+1/2, z' 'y, -x+1/2, z+1/2' 'x+1/2, -y, -z+1/2' '-x, y+1/2, -z+1/2' 'y+1/2, x+1/2, -z' '-y, -x, -z' '-x, -y, -z' 'y-1/2, -x, -z-1/2' 'x-1/2, y-1/2, -z' '-y, x-1/2, -z-1/2' '-x-1/2, y, z-1/2' 'x, -y-1/2, z-1/2' '-y-1/2, -x-1/2, z' 'y, x, z' 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_site_symmetry_order _atom_site_calc_flag _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group Pb1 Pb 0.5000 0.5000 0.5000 0.0812(6) Uani 1 4 d S T P . . I2 I 0.7500 0.7500 0.47558(8) 0.0755(6) Uani 1 4 d S T P . . I3 I 0.2500 0.7500 0.5000 0.0849(7) Uani 1 4 d S T P . . I4 I 0.44138(17) 0.44138(17) 0.37584(7) 0.1213(8) Uani 1 2 d S T P . . N1 N 0.465(3) 0.035(3) 0.4103(14) 0.151(7) Uani 1 2 d DS TU P D . H1A H 0.5077 0.1218 0.4189 0.181 Uiso 0.5 1 calc GR . . A -1 H1B H 0.4969 -0.0361 0.4324 0.181 Uiso 0.5 1 calc GR . . A -1 H1C H 0.3659 0.0438 0.4130 0.181 Uiso 0.5 1 calc GR . . A -1 C3 C 0.505(3) -0.005(3) 0.3544(14) 0.151(7) Uani 1 2 d DS TU P . . H3B H 0.4439 0.0561 0.3302 0.181 Uiso 1 2 calc RS T P B 2 H3A H 0.4373 0.0627 0.3351 0.181 Uiso 1 2 calc RS T P C 1 C4 C 0.667(2) 0.005(5) 0.3361(9) 0.151(7) Uani 0.5 1 d D U . D 2 H4A H 0.7027 0.1020 0.3483 0.181 Uiso 0.5 1 calc R . . D 2 H4B H 0.7210 -0.0689 0.3569 0.181 Uiso 0.5 1 calc R . . D 2 C8 C 0.723(6) -0.011(4) 0.2789(10) 0.151(7) Uani 0.5 1 d D U . D 2 H8A H 0.8264 0.0190 0.2771 0.226 Uiso 0.5 1 calc GR . . D 2 H8B H 0.6647 0.0508 0.2555 0.226 Uiso 0.5 1 calc GR . . D 2 H8C H 0.7147 -0.1138 0.2679 0.226 Uiso 0.5 1 calc GR . . D 2 C5 C 0.433(4) -0.154(3) 0.340(2) 0.151(7) Uani 0.5 1 d D U . D 1 H5A H 0.3294 -0.1382 0.3312 0.226 Uiso 0.5 1 calc GR . . D 1 H5B H 0.4392 -0.2204 0.3704 0.226 Uiso 0.5 1 calc GR . . D 1 H5C H 0.4837 -0.1974 0.3102 0.226 Uiso 0.5 1 calc GR . . D 1 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 0.0748(7) 0.0748(7) 0.0942(9) -0.0048(3) -0.0048(3) -0.0163(4) I2 0.0665(7) 0.0665(7) 0.0933(12) 0.000 0.000 -0.0281(6) I3 0.0677(7) 0.0677(7) 0.1191(17) 0.000 0.000 0.0116(7) I4 0.1375(11) 0.1375(11) 0.0888(10) -0.0016(7) -0.0016(7) -0.0164(12) N1 0.149(11) 0.149(11) 0.154(16) -0.029(9) 0.029(9) 0.001(11) C3 0.149(11) 0.149(11) 0.154(16) -0.029(9) 0.029(9) 0.001(11) C4 0.149(11) 0.149(11) 0.154(16) -0.029(9) 0.029(9) 0.001(11) C8 0.149(11) 0.149(11) 0.154(16) -0.029(9) 0.029(9) 0.001(11) C5 0.149(11) 0.149(11) 0.154(16) -0.029(9) 0.029(9) 0.001(11) 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' I I -0.4742 1.8119 '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' Pb Pb -3.3944 10.1111 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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 I2 Pb1 I2 180.0 . 9_666 I3 Pb1 I2 90.0 9_666 9_666 I3 Pb1 I2 90.0 . 9_666 I3 Pb1 I2 90.0 9_666 . I3 Pb1 I2 90.0 . . I3 Pb1 I3 180.0 9_666 . I3 Pb1 I4 90.0 9_666 9_666 I3 Pb1 I4 90.0 . . I3 Pb1 I4 90.0 . 9_666 I3 Pb1 I4 90.0 9_666 . I4 Pb1 I2 87.48(5) . 9_666 I4 Pb1 I2 87.48(5) 9_666 . I4 Pb1 I2 92.52(5) 9_666 9_666 I4 Pb1 I2 92.52(5) . . I4 Pb1 I4 180.0 . 9_666 Pb1 I2 Pb1 158.16(7) 3_665 . Pb1 I3 Pb1 180.0 3_565 . H1A N1 H1B 109.4 . . H1A N1 H1C 109.4 . . H1B N1 H1C 109.4 . . C3 N1 H1A 109.5 . . C3 N1 H1B 109.5 . . C3 N1 H1C 109.6 . . N1 C3 H3B 108.3 . . N1 C3 H3A 99.5 . . N1 C3 C4 120(2) . 15_665 N1 C3 C4 120(2) . . N1 C3 C5 109(2) . 15_665 N1 C3 C5 109(2) . . C4 C3 H3B 108.1 15_665 . C4 C3 H3B 108.1 . . C4 C3 C4 91(4) 15_665 . C5 C3 H3A 99.4 15_665 . C5 C3 H3A 99.4 . . C5 C3 C5 134(4) . 15_665 C3 C4 H4A 106.0 . . C3 C4 H4B 105.5 . . H4A C4 H4B 106.2 . . C8 C4 C3 126(3) . . C8 C4 H4A 106.1 . . C8 C4 H4B 105.4 . . C4 C8 H8A 109.5 . . C4 C8 H8B 109.4 . . C4 C8 H8C 110.1 . . H8A C8 H8B 109.3 . . H8A C8 H8C 109.3 . . H8B C8 H8C 109.2 . . C3 C5 H5A 111.2 . . C3 C5 H5B 111.0 . . C3 C5 H5C 111.4 . . H5A C5 H5B 107.7 . . H5A C5 H5C 107.7 . . H5B C5 H5C 107.6 . . loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 Pb1 I2 3.2174(4) 9_666 Pb1 I2 3.2174(4) . Pb1 I3 3.15912(9) 9_666 Pb1 I3 3.15912(9) . Pb1 I4 3.1867(19) . Pb1 I4 3.1868(19) 9_666 I2 Pb1 3.2174(4) 3_665 I3 Pb1 3.15912(9) 3_565 N1 H1A 0.8904 . N1 H1B 0.8904 . N1 H1C 0.8904 . N1 C3 1.484(19) . C3 H3B 0.9800 . C3 H3A 0.9800 . C3 C4 1.522(15) 15_665 C3 C4 1.522(14) . C3 C5 1.522(15) . C3 C5 1.522(15) 15_665 C4 H4A 0.9700 . C4 H4B 0.9700 . C4 C8 1.522(15) . C8 H8A 0.9621 . C8 H8B 0.9620 . C8 H8C 0.9622 . C5 H5A 0.9775 . C5 H5B 0.9773 . C5 H5C 0.9778 . 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 N1 C3 C4 C8 -171(4) . C4 C3 C4 C8 63(6) 15_665