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_4002997
_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         '0.5(I8 Pb2), 2(C7 H9 I N)'
_chemical_formula_sum            'C14 H18 I6 N2 Pb'
_chemical_formula_weight         1182.89
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-24
_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                 103.3561(14)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   16.9722(2)
_cell_length_b                   8.87790(12)
_cell_length_c                   8.67966(11)
_cell_measurement_reflns_used    30547
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      38.1740
_cell_measurement_theta_min      2.3350
_cell_volume                     1272.46(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.876
_diffrn_measured_fraction_theta_max 0.935
_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    -55.00 -11.00   0.50    2.00    --  -25.84 -41.00  -2.00   88
  2  \w    -21.00   4.00   0.50    2.00    --  -25.84  41.00 150.00   50
  3  \w     31.00  56.00   0.50    2.00    --   25.84  41.00 150.00   50
  4  \w    -28.00  -3.00   0.50    2.00    --   25.84 -41.00  -2.00   50
  5  \w    -47.00  31.00   0.50    2.00    --   25.84 -57.00 -90.00  156
  6  \w     10.00  99.00   0.50    2.00    --   25.84  57.00  30.00  178
  7  \w    -39.00 -13.00   0.50    2.00    --   25.84 -57.00 -60.00   52
  8  \w      2.00  98.00   0.50    2.00    --   25.84  77.00 120.00  192
  9  \w     27.00  98.00   0.50    2.00    --   25.84  57.00 -60.00  142
 10  \w    -32.00  38.00   0.50    2.00    --   25.84 -57.00-150.00  140
 11  \w    -46.00  46.00   0.50    2.00    --   25.84 -77.00-150.00  184
 12  \w     14.00  86.00   0.50    2.00    --   25.84  57.00-180.00  144
 13  \w     19.00  95.00   0.50    2.00    --   25.84  57.00-120.00  152
;
_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      0.0372622000
_diffrn_orient_matrix_UB_12      -0.0119531000
_diffrn_orient_matrix_UB_13      0.0555960000
_diffrn_orient_matrix_UB_21      0.0149313000
_diffrn_orient_matrix_UB_22      -0.0400659000
_diffrn_orient_matrix_UB_23      -0.0579957000
_diffrn_orient_matrix_UB_31      0.0153071000
_diffrn_orient_matrix_UB_32      0.0680828000
_diffrn_orient_matrix_UB_33      -0.0244113000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0526
_diffrn_reflns_av_unetI/netI     0.0289
_diffrn_reflns_Laue_measured_fraction_full 0.876
_diffrn_reflns_Laue_measured_fraction_max 0.935
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            35845
_diffrn_reflns_point_group_measured_fraction_full 0.876
_diffrn_reflns_point_group_measured_fraction_max 0.935
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         36.307
_diffrn_reflns_theta_min         2.467
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    13.909
_exptl_absorpt_correction_T_max  0.264
_exptl_absorpt_correction_T_min  0.043
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.37a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Spherical absorption correction
 using equivalent radius and absorption coefficient.
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    3.087
_exptl_crystal_description       prism
_exptl_crystal_F_000             1032
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.353
_exptl_crystal_size_mid          0.297
_exptl_crystal_size_min          0.13
_refine_diff_density_max         1.989
_refine_diff_density_min         -2.477
_refine_diff_density_rms         0.195
_refine_ls_extinction_coef       0.00426(14)
_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   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     108
_refine_ls_number_reflns         5770
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0265
_refine_ls_R_factor_gt           0.0237
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0286P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0517
_refine_ls_wR_factor_ref         0.0526
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5437
_reflns_number_total             5770
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm9b01564_si_005.cif
_cod_data_source_block           mht-iv-63-e
_cod_database_code               4002997
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C28  H36  I12  N4  Pb2  '
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     36.23
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All N(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C6(H6), C5(H5), C9(H9)
2.c Idealised Me refined as rotating group:
 N12(H12A,H12B,H12C)
;
_shelx_res_checksum              47211
_shelx_hkl_checksum              24663
_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-63-E
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.866
_oxdiff_exptl_absorpt_empirical_full_min 0.689
_oxdiff_exptl_absorpt_spherical_max 0.134
_oxdiff_exptl_absorpt_spherical_min 0.092