Structures of (4-Y-C6H4CH2NH3)2PbI4 {Y = H, F, Cl, Br, I}: Tuning of Hybrid Organic Inorganic Perovskite Structures from Ruddlesden‒Popper to Dion‒Jacobson Limits
Tremblay, Marie-Hélène; Bacsa, John; Zhao, Boqin; Pulvirenti, Federico; Barlow, Stephen; Marder, Seth R.; Chemistry of Materials 31 (2019) 6145–; doi:10.1021/acs.chemmater.9b01564

data_4002995
_publ_section_title
;
 Structures of (4-Y-C6H4CH2NH3)2PbI4 {Y = H, F, Cl, Br, I}: Tuning of
 Hybrid Organic Inorganic Perovskite Structures from Ruddlesden--Popper to
 Dion--Jacobson Limits
;
_journal_issue                   16
_journal_name_full               'Chemistry of Materials'
_journal_page_first              6145
_journal_paper_doi               10.1021/acs.chemmater.9b01564
_journal_volume                  31
_journal_year                    2019
_chemical_formula_moiety         '2(C7 H9 Br N), I4 Pb'
_chemical_formula_sum            'C14 H18 Br2 I4 N2 Pb'
_chemical_formula_weight         1088.91
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-09-07
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.07.26 svn.r3523 for OlexSys, GUI svn.r5532)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.1410(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.60610(10)
_cell_length_b                   8.91160(10)
_cell_length_c                   15.8703(2)
_cell_measurement_reflns_used    24746
_cell_measurement_temperature    104.0(8)
_cell_measurement_theta_max      38.0940
_cell_measurement_theta_min      2.2850
_cell_volume                     1212.26(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.15a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.15a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.15a (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)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      104.0(8)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.952
_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    -92.00 -67.00   0.50    2.00    --  -27.43 150.00  15.00   50
  2  \w    -74.00 -30.00   0.50    2.00    --  -27.43 123.00-147.00   88
  3  \w     53.00  78.00   0.50    2.00    --   27.43 150.00  15.00   50
  4  \w     19.00  44.00   0.50    2.00    --   27.43-123.00 132.00   50
  5  \w     64.00  94.00   0.50    2.00    --   27.43-150.00 -30.00   60
  6  \w   -100.00  -1.00   0.50    2.00    --  -27.43 -77.00 120.00  198
  7  \w     39.00 101.00   0.50    2.00    --   27.43  57.00-120.00  124
  8  \w    -39.00   7.00   0.50    2.00    --   27.43 -57.00 -90.00   92
  9  \w     38.00  64.00   0.50    2.00    --   27.43 -99.00-180.00   52
 10  \w     11.00  49.00   0.50    2.00    --   27.43  77.00-180.00   76
 11  \w     62.00 101.00   0.50    2.00    --   27.43  77.00-180.00   78
 12  \w    -36.00  46.00   0.50    9.67    --   27.43 -57.00-180.00  164
 13  \w     16.00  42.00   0.50    9.67    --   27.43 -57.00 -90.00   52
 14  \w      5.00 101.00   0.50    9.67    --   27.43  77.00  30.00  192
 15  \w    -35.00  27.00   0.50    9.67    --   27.43 -57.00  90.00  124
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0092473000
_diffrn_orient_matrix_UB_12      -0.0784361000
_diffrn_orient_matrix_UB_13      0.0061354000
_diffrn_orient_matrix_UB_21      0.0070577000
_diffrn_orient_matrix_UB_22      0.0109277000
_diffrn_orient_matrix_UB_23      0.0444537000
_diffrn_orient_matrix_UB_31      -0.0819289000
_diffrn_orient_matrix_UB_32      -0.0079038000
_diffrn_orient_matrix_UB_33      0.0004637000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0325
_diffrn_reflns_av_unetI/netI     0.0347
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            34298
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.929
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         37.982
_diffrn_reflns_theta_min         2.376
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    15.348
_exptl_absorpt_correction_T_max  0.906
_exptl_absorpt_correction_T_min  0.049
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.15a (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    2.983
_exptl_crystal_description       plate
_exptl_crystal_F_000             960
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by ---'
_exptl_crystal_size_max          0.299
_exptl_crystal_size_mid          0.211
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.142
_refine_diff_density_min         -1.309
_refine_diff_density_rms         0.191
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.314(3)
_refine_ls_extinction_coef       0.00050(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     212
_refine_ls_number_reflns         12266
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.0267
_refine_ls_R_factor_gt           0.0242
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0262P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0514
_refine_ls_wR_factor_ref         0.0519
_reflns_Friedel_coverage         0.861
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.903
_reflns_number_gt                11554
_reflns_number_total             12266
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm9b01564_si_003.cif
_cod_data_source_block           bz-i-21c
_cod_database_code               4002995
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C28  H36  Br4  I8  N4  Pb2  '
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     36.23
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.686(3)
 0.314(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H,H) groups
3.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C14(H14A,H14B)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C9(H9), C10(H10), C12(H12), C13(H13)
3.c Idealised Me refined as rotating group:
 N1(H1A,H1B,H1C), N2(H2A,H2B,H2C)
;
_shelx_res_checksum              32654
_shelx_hkl_checksum              81125
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method 'The crystal was mounted on a None'
_olex2_submission_original_sample_id BZ-I-21C
_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 1.373
_oxdiff_exptl_absorpt_empirical_full_min 0.690