Cation Engineering in Two-Dimensional Ruddlesden-Popper Lead Iodide Perovskites with Mixed Large A-Site Cations in the Cages.
Fu, Yongping; Jiang, Xinyi; Li, Xiaotong; Traore, Boubacar; Spanopoulos, Ioannis; Katan, Claudine; Even, Jacky; Kanatzidis, Mercouri G.; Harel, Elad; Journal of the American Chemical Society 142 (2020) 4008–4021; doi:10.1021/jacs.9b13587

data_4134198
_publ_section_title
;
 Cation Engineering in Two-Dimensional Ruddlesden-Popper Lead Iodide
 Perovskites with Mixed Large A-Site Cations in the Cages.
;
_journal_issue                   8
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4008
_journal_page_last               4021
_journal_paper_doi               10.1021/jacs.9b13587
_journal_volume                  142
_journal_year                    2020
_chemical_formula_moiety
'0.5(I8 Pb2), I6 Pb2, 2(C2 H8 N), 2(C4 H12 N)'
_chemical_formula_sum            'C12 H40 I10 N4 Pb3'
_chemical_formula_weight         2131.05
_space_group_crystal_system      orthorhombic
_space_group_IT_number           36
_space_group_name_Hall           'C 2c -2'
_space_group_name_H-M_alt        'C m c 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-08-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   52.0158(16)
_cell_length_b                   8.9727(3)
_cell_length_c                   8.9745(3)
_cell_measurement_reflns_used    9793
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      30.06
_cell_measurement_theta_min      2.30
_cell_volume                     4188.6(2)
_computing_cell_refinement       APEX-2
_computing_data_collection       APEX-2
_computing_data_reduction        APEX-2
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      298.01
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0564
_diffrn_reflns_av_unetI/netI     0.0327
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       73
_diffrn_reflns_limit_h_min       -73
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            59074
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.176
_diffrn_reflns_theta_min         0.783
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    19.409
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.5007
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   APEX-2
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    3.379
_exptl_crystal_description       square
_exptl_crystal_F_000             3664
_exptl_crystal_size_max          0.244
_exptl_crystal_size_mid          0.224
_exptl_crystal_size_min          0.11
_refine_diff_density_max         2.088
_refine_diff_density_min         -1.696
_refine_diff_density_rms         0.368
_refine_ls_abs_structure_details
;
 The structure can converge (shift<0.05)before adding hydrogens. However, it cannot converge after adding hydrogen. Since discussion of hydrogen bonding is not involved in this paper, the shift caused by the hydrogen will not influence the structure.
 Flack x determined using 2124 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.003(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     95
_refine_ls_number_reflns         6246
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0599
_refine_ls_R_factor_gt           0.0444
_refine_ls_shift/su_max          1.543
_refine_ls_shift/su_mean         0.040
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0714P)^2^+76.1417P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1257
_refine_ls_wR_factor_ref         0.1425
_reflns_Friedel_coverage         0.884
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                5176
_reflns_number_total             6246
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13587_si_001.cif
_cod_data_source_block           ea1
_cod_depositor_comments
'Adding full bibliography for 4134198--4134201.cif.'
_cod_database_code               4134198
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.224
_shelx_estimated_absorpt_t_min   0.088
_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-C1 = C1-C2
 1.5 with sigma of 0.02
 N2-C3
 1.5 with sigma of 0.02
 N2-C3 = C3-C4
 1.5 with sigma of 0.02
 C3-C4
 1.5 with sigma of 0.02
 C3-C4 = C4-C5
 1.5 with sigma of 0.02
 C4-C5 = C5-C6
 1.5 with sigma of 0.02
 N1-C2
 2.592 with sigma of 0.04
 N2-C4
 2.592 with sigma of 0.04
 C3-C5
 2.592 with sigma of 0.04
 C4-C6
 2.592 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uiso(N1) = Uiso(C1) = Uiso(C2)
Uiso(N2) = Uiso(C3)
Uiso(N2) = Uiso(C3) = Uiso(C4)
Uiso(N2) = Uiso(C3) = Uiso(C4) = Uiso(C5) = Uiso(C6)
4.a Secondary CH2 refined with riding coordinates:
 C1(H1D,H1E), C3(H3A,H3B), C4(H4A,H4B), C5(H5B,H5A)
4.b Idealised Me refined as rotating group:
 N1(H1A,H1B,H1C), N2(H2A,H2B,H2C), C2(H2D,H2E,H2F), C6(H6B,H6A,H6C)
;
_olex2_submission_special_instructions 'No special instructions were received'