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_4002996
_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         'I4 Pb, 2(C7 H9 F N)'
_chemical_formula_sum            'C14 H18 F2 I4 N2 Pb'
_chemical_formula_weight         967.09
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-09-06
_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                 97.6029(19)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.69555(15)
_cell_length_b                   9.24417(16)
_cell_length_c                   27.5255(6)
_cell_measurement_reflns_used    24984
_cell_measurement_temperature    106(6)
_cell_measurement_theta_max      38.1200
_cell_measurement_theta_min      2.3730
_cell_volume                     2193.13(7)
_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      106(6)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.957
_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    -68.00 -43.00   0.50    4.44    --  -27.43 -60.00 -41.00   50
  2  \w    -85.00 -22.00   0.50    4.44    --  -27.43 -19.00 -30.00  126
  3  \w      2.00  28.00   0.50   10.00    --   27.43 -60.00 -41.00   52
  4  \w    -26.00  54.00   0.50   10.00    --   27.43 -99.00   0.00  160
  5  \w    -42.00  -7.00   0.50   10.00    --   27.43 -60.00 -41.00   70
  6  \w    -43.00  46.00   0.50   10.00    --   27.43 -57.00 -90.00  178
  7  \w     10.00 101.00   0.50   10.00    --   27.43  60.00  97.00  182
  8  \w     51.00  99.00   0.50   10.00    --   27.43  77.00  30.00   96
  9  \w     41.00  66.00   0.50   10.00    --   27.43 178.00-120.00   50
 10  \w      2.00  28.00   0.50   10.00    --   27.43  77.00  30.00   52
 11  \w    -30.00  -5.00   0.50   10.00    --  -27.43  60.00  97.00   50
 12  \w    -97.00 -59.00   0.50   10.00    --  -27.43 178.00  60.00   76
 13  \w    -89.00 -60.00   0.50   10.00    --  -27.43 178.00  90.00   58
 14  \w    -91.00 -60.00   0.50   10.00    --  -27.43 178.00 -90.00   62
 15  \w    -99.00  -9.00   0.50   10.00    --  -27.43 -57.00-150.00  180
 16  \w    -99.00 -81.00   0.50   10.00    --  -27.43 -57.00-180.00   36
;
_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      -0.0259803000
_diffrn_orient_matrix_UB_12      0.0480934000
_diffrn_orient_matrix_UB_13      -0.0194323000
_diffrn_orient_matrix_UB_21      0.0769768000
_diffrn_orient_matrix_UB_22      0.0254023000
_diffrn_orient_matrix_UB_23      0.0000088000
_diffrn_orient_matrix_UB_31      0.0129995000
_diffrn_orient_matrix_UB_32      -0.0541789000
_diffrn_orient_matrix_UB_33      -0.0172537000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0430
_diffrn_reflns_av_unetI/netI     0.0304
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.957
_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       46
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            60876
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         38.067
_diffrn_reflns_theta_min         2.326
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    13.339
_exptl_absorpt_correction_T_max  0.963
_exptl_absorpt_correction_T_min  0.065
_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    2.929
_exptl_crystal_description       plate
_exptl_crystal_F_000             1712
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by ---'
_exptl_crystal_size_max          0.261
_exptl_crystal_size_mid          0.168
_exptl_crystal_size_min          0.033
_refine_diff_density_max         2.574
_refine_diff_density_min         -2.163
_refine_diff_density_rms         0.252
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     210
_refine_ls_number_reflns         11438
_refine_ls_number_restraints     80
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0413
_refine_ls_R_factor_gt           0.0313
_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^)+(0.0215P)^2^+7.1154P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0602
_refine_ls_wR_factor_ref         0.0626
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9751
_reflns_number_total             11438
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm9b01564_si_001.cif
_cod_data_source_block           bz-i-79c
_cod_database_code               4002996
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C56  H72  F8  I16  N8  Pb4  '
_reflns_odcompleteness_completeness 99.96
_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, All N(H,H,H) groups
2. Rigid body (RIGU) restrains
 F1, N1, C1, C2, C3, C4, C5, C6, C7
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Same fragment restrains
{F1, N1, C1, C2, C3, C4, C5, C6, C7} sigma for 1-2: 0.001, 1-3: 0.001
as
{F2, N2, C8, C9, C10, C11, C12, C13, C14}
4.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C14(H14A,H14B)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C9(H9), C10(H10), C12(H12), C13(H13)
4.c Idealised Me refined as rotating group:
 N1(H1A,H1B,H1C), N2(H2A,H2B,H2C)
;
_shelx_res_checksum              19032
_shelx_hkl_checksum              23485
_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 BZ-I-79C
_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 1.635
_oxdiff_exptl_absorpt_empirical_full_min 0.528