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_4134812
_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         '0.25(Br28 Pb8), C6 H16 N2, C H5 N2'
_chemical_formula_sum            'C7 H21 Br7 N4 Pb2'
_chemical_formula_weight         1135.03
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yc'
_space_group_name_H-M_alt        'P 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2020-01-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.00(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.138(3)
_cell_length_b                   11.909(2)
_cell_length_c                   11.905(2)
_cell_measurement_reflns_used    2355
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      24.95
_cell_measurement_theta_min      3.42
_cell_volume                     2288.0(7)
_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      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 0.999
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       '2-circle goniometer'
_diffrn_measurement_device_type  'STOE IPDS 2T'
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1541
_diffrn_reflns_av_unetI/netI     0.2378
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            22064
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.174
_diffrn_reflns_theta_min         2.729
_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
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    26.918
_exptl_absorpt_correction_T_max  0.5940
_exptl_absorpt_correction_T_min  0.0540
_exptl_absorpt_correction_type   integration
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    3.295
_exptl_crystal_description       plate
_exptl_crystal_F_000             2000
_exptl_crystal_size_max          0.0850
_exptl_crystal_size_mid          0.0569
_exptl_crystal_size_min          0.0092
_refine_diff_density_max         2.067
_refine_diff_density_min         -1.492
_refine_diff_density_rms         0.337
_refine_ls_abs_structure_details
;
 Flack x determined using 883 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(8)
_refine_ls_extinction_coef       0.00057(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   0.771
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     237
_refine_ls_number_reflns         11594
_refine_ls_number_restraints     55
_refine_ls_restrained_S_all      0.770
_refine_ls_R_factor_all          0.2444
_refine_ls_R_factor_gt           0.0633
_refine_ls_shift/su_max          1.182
_refine_ls_shift/su_mean         0.018
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0684P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1319
_refine_ls_wR_factor_ref         0.1907
_reflns_Friedel_coverage         0.998
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                3080
_reflns_number_total             11594
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01625_si_004.cif
_cod_data_source_block           pc
_cod_original_cell_volume        2288.0(8)
_cod_database_code               4134812
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.55(5)
 0.45(5)
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
 C3-C2 = C2-C1
 1.5 with sigma of 0.02
 C3-C4
 1.5 with sigma of 0.02
 C12-N3 = N3-C8
 1.5 with sigma of 0.02
 N3-C8 = C8-C9
 1.5 with sigma of 0.02
 C8-C9 = C9-C10
 1.5 with sigma of 0.02
 C9-C10 = C10-C11
 1.5 with sigma of 0.02
 C10-C11 = C11-C12
 1.5 with sigma of 0.02
 C11-C12 = C12-N3
 1.5 with sigma of 0.02
 C9-C10 = C10-C13
 1.5 with sigma of 0.02
 C10-C13 = C13-N4
 1.5 with sigma of 0.02
 C2-C3 = C3-C7
 1.5 with sigma of 0.02
 C3-C7 = C7-N2
 1.5 with sigma of 0.02
 N7-C14 = C14-N8
 1.3 with sigma of 0.02
 N6-C6 = C6-N5
 1.3 with sigma of 0.02
 C2-N1
 2.53 with sigma of 0.04
 C1-C5
 2.558 with sigma of 0.04
 N1-C4
 2.598 with sigma of 0.04
 C5-C3
 2.572 with sigma of 0.04
 C4-C2
 2.572 with sigma of 0.04
 C3-C1
 2.53 with sigma of 0.04
 C12-C8
 2.598 with sigma of 0.04
 N3-C9
 2.572 with sigma of 0.04
 C8-C10
 2.558 with sigma of 0.04
 C9-C11
 2.598 with sigma of 0.04
 C10-C12
 2.598 with sigma of 0.04
 C11-N3
 2.558 with sigma of 0.04
 C9-C13
 2.442 with sigma of 0.04
 C10-N4
 2.661 with sigma of 0.04
 C2-C7
 2.442 with sigma of 0.04
 C3-N2
 2.661 with sigma of 0.04
 N7-N8
 2.337 with sigma of 0.04
 N6-N5
 2.337 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
Uiso(C4) = Uiso(C5) = Uiso(N1) = Uiso(C2) = Uiso(C3) = Uiso(C1)
Uiso(C8) = Uiso(C9) = Uiso(C10) = Uiso(C11) = Uiso(C12) = Uiso(C13) = Uiso(N3)
= Uiso(N4)
Uiso(C1) = Uiso(N2) = Uiso(C4) = Uiso(C5) = Uiso(N1) = Uiso(C2) = Uiso(C3) =
Uiso(C7)
Uiso(N5) = Uiso(C6) = Uiso(N6)
Uiso(N7) = Uiso(C14) = Uiso(N8)
5.a Ternary CH refined with riding coordinates:
 C3(H3), C10(H10)
5.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C4(H4A,H4B), C2(H2A,H2B), N1(H1C,H1D), C5(H5A,H5B), N3(H3A,H3B),
 C8(H8A,H8B), C13(H13A,H13B), C11(H11A,H11B), C9(H9A,H9B), C12(H12A,H12B),
 C7(H7A,H7B)
5.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C6(H6)
5.d X=CH2 refined with riding coordinates:
 N7(H7C,H7D), N5(H5C,H5D), N6(H6A,H6B), N8(H8C,H8D)
5.e Idealised Me refined as rotating group:
 N4(H4C,H4D,H4E), N2(H2C,H2D,H2E)
;
_shelx_res_checksum              75095
_shelx_hkl_checksum              25366
_olex2_submission_special_instructions 'No special instructions were received'