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_4003963
_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
'0.5(Br14 Pb4), 2(C6 H16 N), 0.5(C2 N2), 2(H)'
_chemical_formula_sum            'C13 H34 Br7 N3 Pb2'
_chemical_formula_weight         1206.18
_chemical_name_common            'Hexylammonium Methylammonium Lead Bromide'
_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'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2021-03-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.05
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   48.559
_cell_length_b                   8.328
_cell_length_c                   8.325
_cell_measurement_reflns_used    3073
_cell_measurement_temperature    322.99(14)
_cell_measurement_theta_max      28.8570
_cell_measurement_theta_min      2.5060
_cell_volume                     3366.623
_computing_cell_refinement       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      322.99(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.971
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w     -9.00  76.00   0.50   50.00    --    4.87  57.00 -30.00  170
  2  \w     -4.00  54.00   0.50   50.00    --    4.87  57.00  90.00  116
  3  \w    -17.00  25.00   0.50   50.00    --    4.87 -99.00   0.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0108893000
_diffrn_orient_matrix_UB_12      -0.0520980000
_diffrn_orient_matrix_UB_13      0.0226085000
_diffrn_orient_matrix_UB_21      -0.0093354000
_diffrn_orient_matrix_UB_22      -0.0654711000
_diffrn_orient_matrix_UB_23      0.0019500000
_diffrn_orient_matrix_UB_31      0.0027630000
_diffrn_orient_matrix_UB_32      -0.0159042000
_diffrn_orient_matrix_UB_33      -0.0821277000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0884
_diffrn_reflns_av_unetI/netI     0.0433
_diffrn_reflns_Laue_measured_fraction_full 0.971
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_number            2945
_diffrn_reflns_point_group_measured_fraction_full 0.971
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        25.240
_diffrn_reflns_theta_max         25.240
_diffrn_reflns_theta_min         2.481
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    18.301
_exptl_absorpt_correction_T_max  0.01383
_exptl_absorpt_correction_T_min  0.00206
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.25a (Rigaku Oxford Diffraction, 2018)
Spherical absorption correction
 using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_density_diffrn    2.380
_exptl_crystal_description       'light yellow plate'
_exptl_crystal_F_000             2168
_exptl_crystal_size_max          0.155
_exptl_crystal_size_mid          0.144
_exptl_crystal_size_min          0.056
_refine_diff_density_max         2.296
_refine_diff_density_min         -0.870
_refine_diff_density_rms         0.357
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     78
_refine_ls_number_reflns         2945
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.1130
_refine_ls_R_factor_gt           0.0884
_refine_ls_shift/su_max          0.1594
_refine_ls_shift/su_mean         0.0043
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1721P)^2^+24.6685P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2669
_refine_ls_wR_factor_ref         0.2932
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1739
_reflns_number_total             2945
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm1c01129_si_002.cif
_cod_data_source_block           esv_2_129a_ht
_cod_original_cell_volume        3366.5
_cod_database_code               4003963
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C13 H38 N3 Pb2 Br7'
_reflns_odcompleteness_completeness 95.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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-C2 = C2-C3
 1.5 with sigma of 0.02
 C2-C3 = 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
 C5-C6 = C6-C7
 1.5 with sigma of 0.02
 C3-C7
 2 with sigma of 0.02
 C7-C3
 2.2 with sigma of 0.02
 C8-NA
 1.5 with sigma of 0.02
 N2-C3
 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
 C4-C6
 2.45 with sigma of 0.04
 C5-C7
 2.45 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uiso(N2) = Uiso(C2) = Uiso(C3) = Uiso(C5) = Uiso(C4) = Uiso(C7) = Uiso(C6)
4. Others
 Fixed Sof: C8(0.5) H8(0.5) NA(0.5) HA(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C2(H2D,H2E)
5.b Idealised Me refined as rotating group:
 N2(H2A,H2B,H2C), C7(H3C,H7A,H7B)
;
_shelx_res_checksum              12580
_shelx_hkl_checksum              86526
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.292
_oxdiff_exptl_absorpt_empirical_full_min 0.599