Organic Cation Alloying on Intralayer A and Interlayer A' sites in 2D Hybrid Dion-Jacobson Lead Bromide Perovskites (A')(A)Pb<sub>2</sub>Br<sub>7</sub>.
Mao, Lingling; Guo, Peijun; Kepenekian, Mikaël; Spanopoulos, Ioannis; He, Yihui; Katan, Claudine; Even, Jacky; Schaller, Richard D.; Seshadri, Ram; Stoumpos, Constantinos C.; Kanatzidis, Mercouri G.; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c01625

data_4134813
_publ_section_title
;
 Organic Cation Alloying on Intralayer A and Interlayer A' sites in 2D
 Hybrid Dion-Jacobson Lead Bromide Perovskites
 (A')(A)Pb<sub>2</sub>Br<sub>7</sub>.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c01625
_journal_year                    2020
_chemical_formula_moiety         '0.5(C2 H10 Br14 N4 Pb4), 0.5(C12 H32 N4)'
_chemical_formula_sum            'C7 H21 Br7 N4 Pb2'
_chemical_formula_weight         1135.03
_space_group_crystal_system      monoclinic
_space_group_IT_number           8
_space_group_name_Hall           'C -2y'
_space_group_name_H-M_alt        'C 1 m 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-01-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 89.99(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.4615(17)
_cell_length_b                   8.4650(17)
_cell_length_c                   16.004(3)
_cell_measurement_reflns_used    3564
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      29.62
_cell_measurement_theta_min      2.54
_cell_volume                     1146.3(4)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'image plate (34 cm diameter)'
_diffrn_detector_area_resol_mean 6.67
_diffrn_detector_type            STOE
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_details      ' 117 frames, detector distance = 100 mm'
_diffrn_measurement_device       '2-circle goniometer'
_diffrn_measurement_device_type  'STOE IPDS 2'
_diffrn_measurement_method       'rotation method'
_diffrn_radiation_collimation    '0.5 mm diameter, monocapillary'
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0308
_diffrn_reflns_av_unetI/netI     0.0275
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            5567
_diffrn_reflns_point_group_measured_fraction_full 0.935
_diffrn_reflns_point_group_measured_fraction_max 0.921
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.177
_diffrn_reflns_theta_min         2.545
_diffrn_source
'sealed X-ray tube, 12 x 0.4 mm long-fine focus'
_diffrn_source_current           40
_diffrn_source_power             2.00
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    26.864
_exptl_absorpt_correction_T_max  0.4733
_exptl_absorpt_correction_T_min  0.0415
_exptl_absorpt_correction_type   integration
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    3.288
_exptl_crystal_description       plate
_exptl_crystal_F_000             1000
_exptl_crystal_size_max          0.1069
_exptl_crystal_size_mid          0.0790
_exptl_crystal_size_min          0.0132
_refine_diff_density_max         1.309
_refine_diff_density_min         -1.878
_refine_diff_density_rms         0.289
_refine_ls_abs_structure_details
;
 Flack x determined using 1002 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.23(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     75
_refine_ls_number_reflns         3034
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0560
_refine_ls_R_factor_gt           0.0460
_refine_ls_shift/su_max          0.979
_refine_ls_shift/su_mean         0.161
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0641P)^2^+8.6979P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1138
_refine_ls_wR_factor_ref         0.1196
_reflns_Friedel_coverage         0.851
_reflns_Friedel_fraction_full    0.878
_reflns_Friedel_fraction_max     0.848
_reflns_number_gt                2564
_reflns_number_total             3034
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01625_si_002.cif
_cod_data_source_block           cm
_cod_database_code               4134813
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.465(15)
 0.535(15)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups, All N(H,H,H) groups
3. Restrained distances
 C1-N1 = N1-C5
 1.5 with sigma of 0.02
 N1-C5 = C5-C4
 1.5 with sigma of 0.02
 C5-C4 = C4-C3
 1.5 with sigma of 0.02
 C4-C3 = C3-C2
 1.5 with sigma of 0.02
 C2-C1 = C1-N1
 1.5 with sigma of 0.02
 N2-C6 = C6-C4
 1.5 with sigma of 0.02
 C3-C4 = C4-C6
 1.5 with sigma of 0.02
 N3-C7
 1.4 with sigma of 0.02
 N4-C7 = C7-N3
 1.4 with sigma of 0.02
 N3-C7 = C7-N4
 1.35 with sigma of 0.02
 C1-C5
 2.442 with sigma of 0.04
 N1-C4
 2.457 with sigma of 0.04
 C5-C3
 2.457 with sigma of 0.04
 C4-C2
 2.487 with sigma of 0.04
 C2-N1
 2.457 with sigma of 0.04
 N2-C4
 2.661 with sigma of 0.04
 C3-C6
 2.598 with sigma of 0.04
 N4-N3
 2.425 with sigma of 0.04
 N3-N4
 2.416 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
Uiso(C1) = Uiso(N1) = Uiso(C5) = Uiso(C4) = Uiso(C3) = Uiso(C2)
Uiso(C1) = Uiso(N1) = Uiso(C5) = Uiso(C4) = Uiso(C3) = Uiso(C2) = Uiso(N2)
Uiso(C1) = Uiso(N1) = Uiso(C5) = Uiso(C4) = Uiso(C3) = Uiso(C2) = Uiso(C6) =
Uiso(N2)
Uiso(C7) = Uiso(C7) = Uiso(C7) = Uiso(C7) = Uiso(C7)
Uiso(C7) = Uiso(N3)
Uiso(C7) = Uiso(N4) = Uiso(N3)
5. Others
 Fixed Sof: H1A(0.5) H1B(0.5) H2A(0.5) H2B(0.5) H2C(0.5) H1C(0.5) H1D(0.5)
 H2D(0.5) H2E(0.5) H3A(0.5) H3B(0.5) H4(0.5) H5A(0.5) H5B(0.5) H6A(0.5) H6B(0.5)
6.a Ternary CH refined with riding coordinates:
 C4(H4)
6.b Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), C1(H1C,H1D), C2(H2D,H2E), C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B)
6.c Aromatic/amide H refined with riding coordinates:
 C7(H7)
6.d X=CH2 refined with riding coordinates:
 N3(H3C,H3D), N4(H4A,H4B)
6.e Idealised Me refined as rotating group:
 N2(H2A,H2B,H2C)
;
_shelx_res_checksum              34731
_shelx_hkl_checksum              2942
_olex2_submission_special_instructions 'No special instructions were received'