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_4002994
_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_absolute_configuration ad
_chemical_formula_moiety         'I4 Pb, 2(C7 H9 Cl N)'
_chemical_formula_sum            'C14 H18 Cl2 I4 N2 Pb'
_chemical_formula_weight         999.99
_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             2019-01-20
_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                 95.9401(13)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.63101(11)
_cell_length_b                   8.95452(10)
_cell_length_c                   15.8648(2)
_cell_measurement_reflns_used    20639
_cell_measurement_temperature    225.00(10)
_cell_measurement_theta_max      37.7530
_cell_measurement_theta_min      2.5750
_cell_volume                     1219.55(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.24a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.24a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.24a (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      225.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.960
_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     14.00  40.00   0.50    3.00    --   25.84 -41.00  27.00   52
  2  \w     14.00  39.00   0.50   12.00    --   25.84 -57.00 -30.00   50
  3  \w    -28.00  -3.00   0.50   12.00    --   25.84 -41.00  27.00   50
  4  \w    -47.00   5.00   0.50   12.00    --   25.84 -57.00 -30.00  104
  5  \w    -44.00  40.00   0.50   12.00    --   25.84 -19.00 -90.00  168
  6  \w     13.00  40.00   0.50   12.00    --   25.84  41.00-179.00   54
  7  \w    -17.00  24.00   0.50   12.00    --  -25.84  41.00-179.00   82
  8  \w     18.00 100.00   0.50   12.00    --   25.84  38.00 -60.00  164
  9  \w     28.00  99.00   0.50   12.00    --   25.84  57.00 -30.00  142
 10  \w     41.00  90.00   0.50   12.00    --   25.84 178.00 120.00   98
 11  \w     51.00  97.00   0.50   12.00    --   25.84 178.00 150.00   92
 12  \w     41.00  94.00   0.50   12.00    --   25.84 178.00  30.00  106
 13  \w     43.00  97.00   0.50   12.00    --   25.84 178.00   0.00  108
 14  \w     40.00  87.00   0.50   12.00    --   25.84 178.00-120.00   94
 15  \w    -60.00 -14.00   0.50   12.00    --  -25.84 -41.00  27.00   92
 16  \w    -99.00  -3.00   0.50   12.00    --  -25.84 -77.00   0.00  192
;
_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      -0.0708020000
_diffrn_orient_matrix_UB_12      -0.0102401000
_diffrn_orient_matrix_UB_13      -0.0262807000
_diffrn_orient_matrix_UB_21      0.0313025000
_diffrn_orient_matrix_UB_22      0.0394873000
_diffrn_orient_matrix_UB_23      -0.0330733000
_diffrn_orient_matrix_UB_31      0.0288541000
_diffrn_orient_matrix_UB_32      -0.0679283000
_diffrn_orient_matrix_UB_33      -0.0153319000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0349
_diffrn_reflns_av_unetI/netI     0.0401
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            39072
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.940
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         37.864
_diffrn_reflns_theta_min         2.372
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    12.199
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.055
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.24a (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    2.723
_exptl_crystal_description       plate
_exptl_crystal_F_000             888
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.364
_exptl_crystal_size_mid          0.165
_exptl_crystal_size_min          0.04
_refine_diff_density_max         2.211
_refine_diff_density_min         -1.241
_refine_diff_density_rms         0.166
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.136(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.984
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     211
_refine_ls_number_reflns         12381
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.984
_refine_ls_R_factor_all          0.0538
_refine_ls_R_factor_gt           0.0396
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0541P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0873
_refine_ls_wR_factor_ref         0.0919
_reflns_Friedel_coverage         0.867
_reflns_Friedel_fraction_full    0.990
_reflns_Friedel_fraction_max     0.917
_reflns_number_gt                9925
_reflns_number_total             12381
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm9b01564_si_002.cif
_cod_data_source_block           mht-iv-61-c
_cod_database_code               4002994
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C28  H36  Cl4  I8  N4  Pb2  '
_reflns_odcompleteness_completeness 99.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     36.23
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.864(5)
 0.136(5)
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:
 C5(H5A,H5B), C12(H12A,H12B)
3.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C3(H3), C2(H2), C7(H7), C13(H13), C9(H9), C14(H14), C10(H10)
3.c Idealised Me refined as rotating group:
 N1(H1A,H1B,H1C), N2(H2A,H2B,H2C)
;
_shelx_res_checksum              16665
_shelx_hkl_checksum              26368
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_original_sample_id MHT-IV-61-C
_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 1.805
_oxdiff_exptl_absorpt_empirical_full_min 0.527