Shedding Light on the Stability and Structure‒Property Relationships of Two-Dimensional Hybrid Lead Bromide Perovskites
Vasileiadou, Eugenia S.; Hadar, Ido; Kepenekian, Mikaël; Even, Jacky; Tu, Qing; Malliakas, Christos D.; Friedrich, Daniel; Spanopoulos, Ioannis; Hoffman, Justin M.; Dravid, Vinayak P.; Kanatzidis, Mercouri G.; Chemistry of Materials  (2021) –; doi:10.1021/acs.chemmater.1c01129

data_4003961
_publ_section_title
;
 Shedding Light on the Stability and Structure--Property Relationships of
 Two-Dimensional Hybrid Lead Bromide Perovskites
;
_journal_name_full               'Chemistry of Materials'
_journal_paper_doi               10.1021/acs.chemmater.1c01129
_journal_year                    2021
_chemical_formula_moiety         'Br7 Pb2, C16 H40 N2, C H6 N'
_chemical_formula_sum            'C17 H46 Br7 N3 Pb2'
_chemical_formula_weight         1266.32
_chemical_name_common            'Octylammonium Methylammonium Lead Bromide'
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     heavy
_audit_creation_date             2019-11-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.010(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   52.952(5)
_cell_length_b                   8.3232(7)
_cell_length_c                   8.3225(7)
_cell_measurement_reflns_used    7818
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      29.38
_cell_measurement_theta_min      2.31
_cell_volume                     3668.0(6)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.864
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0769
_diffrn_reflns_av_unetI/netI     0.0847
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.864
_diffrn_reflns_limit_h_max       76
_diffrn_reflns_limit_h_min       -80
_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            40438
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.830
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.749
_diffrn_reflns_theta_min         0.769
_exptl_absorpt_coefficient_mu    16.803
_exptl_absorpt_correction_type   none
_exptl_crystal_density_diffrn    2.293
_exptl_crystal_description       'light yellow plate'
_exptl_crystal_F_000             2312
_refine_diff_density_max         2.262
_refine_diff_density_min         -2.067
_refine_diff_density_rms         0.441
_refine_ls_abs_structure_details
;
 Flack x determined using 2304 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.500(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.001
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     152
_refine_ls_number_reflns         12154
_refine_ls_number_restraints     52
_refine_ls_restrained_S_all      1.001
_refine_ls_R_factor_all          0.1490
_refine_ls_R_factor_gt           0.0717
_refine_ls_shift/su_max          0.1583
_refine_ls_shift/su_mean         0.0056
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1268P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1936
_refine_ls_wR_factor_ref         0.2333
_reflns_Friedel_coverage         0.920
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.795
_reflns_number_gt                5885
_reflns_number_total             12154
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm1c01129_si_004.cif
_cod_data_source_block           43c
_cod_original_cell_volume        3668.0(5)
_cod_database_code               4003961
_shelx_shelxl_version_number     2017/1
_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
 1.5 with sigma of 0.02
 C5-C6 = C6-C7
 1.5 with sigma of 0.02
 C6-C7 = C7-C8
 1.5 with sigma of 0.02
 C3-C4 = C4-C5
 1.5 with sigma of 0.02
 C2-C3 = C3-C4
 1.5 with sigma of 0.02
 N2-C2 = C2-C3
 1.5 with sigma of 0.02
 C4-C5 = C5-C6
 1.5 with sigma of 0.02
 C16-C15 = C15-C14
 1.5 with sigma of 0.02
 C13-C14
 1.5 with sigma of 0.02
 C15-C14 = C14-C13
 1.5 with sigma of 0.02
 C12-C13 = C13-C14
 1.5 with sigma of 0.02
 C11-C12 = C12-C13
 1.5 with sigma of 0.02
 C10-C11 = C11-C12
 1.5 with sigma of 0.02
 C16-C15
 1.5 with sigma of 0.02
 C15-C16
 1.5 with sigma of 0.02
 C7-C8 = C8-C9
 1.5 with sigma of 0.02
 C9-C8 = C8-C7
 1.5 with sigma of 0.02
 N3-C10 = C10-C11
 1.5 with sigma of 0.02
 N3-C10
 1.5 with sigma of 0.02
 C15-C16 = C16-C0AA
 1.5 with sigma of 0.02
 C5-C7
 2.45 with sigma of 0.04
 C6-C8
 2.45 with sigma of 0.04
 C2-C4
 2.45 with sigma of 0.04
 C3-C5
 2.45 with sigma of 0.04
 N2-C3
 2.45 with sigma of 0.04
 C4-C6
 2.45 with sigma of 0.04
 C16-C14
 2.45 with sigma of 0.04
 C15-C13
 2.45 with sigma of 0.04
 C12-C14
 2.45 with sigma of 0.04
 C11-C13
 2.45 with sigma of 0.04
 C10-C12
 2.45 with sigma of 0.04
 C7-C9
 2.45 with sigma of 0.04
 C9-C7
 2.45 with sigma of 0.04
 N3-C11
 2.45 with sigma of 0.04
 C15-C0AA
 2.45 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uiso(C1) = Uiso(N1)
Uiso(C3) = Uiso(C4) = Uiso(C5)
Uiso(C2) = Uiso(N2)
Uiso(N2) = Uiso(C2) = Uiso(C3) = Uiso(C4)
Uiso(C16) = Uiso(C15) = Uiso(C14)
Uiso(C13) = Uiso(C14) = Uiso(C15) = Uiso(C16)
Uiso(N2) = Uiso(C2) = Uiso(C3) = Uiso(C4) = Uiso(C5) = Uiso(C6) = Uiso(C7) =
Uiso(C8) = Uiso(C9)
Uiso(N3) = Uiso(C10) = Uiso(C11) = Uiso(C12) = Uiso(C13) = Uiso(C14) =
Uiso(C15) = Uiso(C16)
4.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B),
 C8(H8A,H8B), C14(H14A,H14B), C16(H16A,H16B), C15(H15A,H15B), C13(H13A,H13B),
 C12(H12A,H12B), C11(H11A,H11B), C10(H10A,H10B)
4.b Idealised Me refined as rotating group:
 N2(H2C,H2D,H2E), C1(H1A,H1B,H1C), N1(H1D,H1E,H1F), C9(H9A,H9B,H9C), N3(H3C,
 H3D,H3E), C0AA(H0AA,H0AB,H0AC)
;
_shelx_res_checksum              7743
_shelx_hkl_checksum              7052
_olex2_submission_special_instructions 'No special instructions were received'