Incorporating Large A Cations into Lead Iodide Perovskite Cages: Relaxed Goldschmidt Tolerance Factor and Impact on Exciton-Phonon Interaction.
Fu, Yongping; Hautzinger, Matthew P.; Luo, Ziyu; Wang, Feifan; Pan, Dongxu; Aristov, Michael M.; Guzei, Ilia A.; Pan, Anlian; Zhu, Xiaoyang; Jin, Song; ACS central science 5 (2019) 1377–1386; doi:10.1021/acscentsci.9b00367

data_4514923
_publ_section_title
;
 Incorporating Large A Cations into Lead Iodide Perovskite Cages: Relaxed
 Goldschmidt Tolerance Factor and Impact on Exciton-Phonon Interaction.
;
_journal_issue                   8
_journal_name_full               'ACS central science'
_journal_page_first              1377
_journal_page_last               1386
_journal_paper_doi               10.1021/acscentsci.9b00367
_journal_volume                  5
_journal_year                    2019
_chemical_formula_moiety         '0.5(I14 Pb4), 2(C6 H16 N), C H6 N'
_chemical_formula_sum            'C13 H38 I7 N3 Pb2'
_chemical_formula_weight         1539.14
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-04-30
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.030(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   45.146(16)
_cell_length_b                   8.814(3)
_cell_length_c                   8.695(3)
_cell_measurement_reflns_used    9941
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.57
_cell_measurement_theta_min      3.29
_cell_volume                     3407(2)
_computing_cell_refinement       'SAINT+ Ver. 8.34A (Bruker-AXS, 2014)'
_computing_data_collection       'APEX2 Ver. 2014.11-0 (Bruker-AXS, 2014)'
_computing_data_reduction        'SAINT+ Ver. 8.34A (Bruker-AXS, 2014)'
_computing_molecular_graphics    'OLEX2 (Dolomanov et al., 2009)'
_computing_publication_material  'OLEX2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2015b)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      99.99
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '0.5\ \w and 0.5\ \f scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0456
_diffrn_reflns_av_unetI/netI     0.0170
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       58
_diffrn_reflns_limit_h_min       -58
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            61721
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         27.574
_diffrn_reflns_theta_min         1.832
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    16.217
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5430
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Krause et al., 2015) was used for absorption correction.'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    3.000
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             2688
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.003
_refine_diff_density_max         2.357
_refine_diff_density_min         -1.316
_refine_diff_density_rms         0.171
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     125
_refine_ls_number_reflns         3931
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0241
_refine_ls_R_factor_gt           0.0211
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0248P)^2^+22.1354P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0496
_refine_ls_wR_factor_ref         0.0509
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3641
_reflns_number_total             3931
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            oc9b00367_si_002.cif
_cod_data_source_block           (HA)2(MA)Pb2I7
_cod_database_code               4514923
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.953
_shelx_estimated_absorpt_t_min   0.563
_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
 N2-C7 = N3_$1-C8_$1
 1.47 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uiso(C8) = Uiso(C7) = Uiso(N3) = Uiso(N2)
4. Others
 Sof(N3)=Sof(H3C)=Sof(H3D)=Sof(H3E)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=0.5*(1-
 FVAR(2))
 Sof(N2)=Sof(H2C)=Sof(H2D)=Sof(H2E)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=0.5*
 FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B)
5.b Idealised Me refined as rotating group:
 N1(H1A,H1B,H1C), C1(H1D,H1E,H1F), N2(H2C,H2D,H2E), C7(H7A,H7B,H7C), N3(H3C,
 H3D,H3E), C8(H8A,H8B,H8C)
;
_shelx_res_checksum              55604
_shelx_hkl_checksum              32985
_olex2_submission_special_instructions 'No special instructions were received'