(4NPEA)<sub>2</sub>PbI<sub>4</sub> (4NPEA = 4-Nitrophenylethylammonium): Structural, NMR, and Optical Properties of a 3 ×3 Corrugated 2D Hybrid Perovskite.
Tremblay, Marie-Hélène; Thouin, Félix; Leisen, Johannes; Bacsa, John; Srimath Kandada, Ajay Ram; Hoffman, Justin M.; Kanatzidis, Mercouri G.; Mohite, Aditya D.; Silva, Carlos; Barlow, Stephen; Marder, Seth R.; Journal of the American Chemical Society 141 (2019) 4521–4525; doi:10.1021/jacs.8b13207

data_4128939
_publ_section_title
;
 (4NPEA)<sub>2</sub>PbI<sub>4</sub> (4NPEA = 4-Nitrophenylethylammonium):
 Structural, NMR, and Optical Properties of a 3 \\times 3 Corrugated 2D
 Hybrid Perovskite.
;
_journal_issue                   11
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4521
_journal_page_last               4525
_journal_paper_doi               10.1021/jacs.8b13207
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         '(I4 Pb), 2(C8 H11 N2 O2)'
_chemical_formula_sum            'C16 H22 I4 N4 O4 Pb'
_chemical_formula_weight         1049.16
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-10-20
_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                 98.2252(17)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.0976(4)
_cell_length_b                   19.8255(3)
_cell_length_c                   12.6149(2)
_cell_measurement_reflns_used    32454
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      33.7420
_cell_measurement_theta_min      1.9140
_cell_volume                     5222.16(15)
_computing_cell_refinement       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.43c (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      100(2)
_diffrn_detector                 HyPix
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 1.000
_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     -2.00  80.00   0.50   25.00    --   15.69  38.00 -60.00  164
  2  \w     57.00  85.00   0.50   25.00    --   15.69   0.00 -30.00   56
  3  \w      4.00  34.00   0.50   25.00    --   15.69  57.00-150.00   60
  4  \w    -34.00  -1.00   0.50   25.00    --   15.69   0.00 -30.00   66
  5  \w    -24.00   5.00   0.50   25.00    --   15.69 -57.00-120.00   58
  6  \w    -56.00  34.00   0.50   25.00    --   15.69 -57.00-150.00  180
  7  \w    -24.00  59.00   0.50   25.00    --  -15.84  38.00-180.00  166
  8  \w    -59.00  34.00   0.50   25.00    --   15.69 -38.00 -60.00  186
  9  \w    -86.00 -32.00   0.50   25.00    --  -15.84 -57.00  60.00  108
 10  \w    -89.00 -21.00   0.50   25.00    --  -15.84 -57.00-180.00  136
;
_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      0.0144901000
_diffrn_orient_matrix_UB_12      -0.0293935000
_diffrn_orient_matrix_UB_13      0.0248131000
_diffrn_orient_matrix_UB_21      -0.0307133000
_diffrn_orient_matrix_UB_22      -0.0134875000
_diffrn_orient_matrix_UB_23      0.0038903000
_diffrn_orient_matrix_UB_31      -0.0007337000
_diffrn_orient_matrix_UB_32      -0.0153028000
_diffrn_orient_matrix_UB_33      -0.0509651000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0476
_diffrn_reflns_av_unetI/netI     0.0348
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            90640
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.575
_diffrn_reflns_theta_min         1.928
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    11.218
_exptl_absorpt_correction_T_max  0.908
_exptl_absorpt_correction_T_min  0.408
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.43c (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    2.669
_exptl_crystal_description       plate
_exptl_crystal_F_000             3776
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.099
_exptl_crystal_size_mid          0.088
_exptl_crystal_size_min          0.019
_refine_diff_density_max         3.260
_refine_diff_density_min         -2.533
_refine_diff_density_rms         0.238
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     555
_refine_ls_number_reflns         14658
_refine_ls_number_restraints     603
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0704
_refine_ls_R_factor_gt           0.0521
_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^)+(0.0421P)^2^+85.4699P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1129
_refine_ls_wR_factor_ref         0.1208
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11561
_reflns_number_total             14658
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b13207_si_002.cif
_cod_data_source_block           mht-iii-53
_cod_original_cell_volume        5222.17(16)
_cod_database_code               4128939
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C180  I32  N12  O8  Pb8  '
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_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. Restrained distances
 N2_4-C8_4
 1.48 with sigma of 0.005
 C8_1-C7_1
 1.52 with sigma of 0.005
 N1_3-C1_3
 1.47 with sigma of 0.005
 Pb1-I2B \\sim Pb1-I2A
 with sigma of 0.005
 Pb2-I4A \\sim Pb2-I4B
 with sigma of 0.002
 O2_4-N1_4 \\sim O1_4-N1_4
 with sigma of 0.002
 C6_2-C1_2 \\sim C2_2-C1_2
 with sigma of 0.002
 C3_2-C2_2 \\sim C6_2-C5_2
 with sigma of 0.002
 C5_2-C4_2 \\sim C4_2-C3_2
 with sigma of 0.002
3. Restrained planarity
 C2_3, C1_3, C6_3, C5_3, C4_3, C3_3, N1_3
 with sigma of 0.002
4. Uiso/Uaniso restraints and constraints
I4A \\sim I4B: within 2A with sigma of 0.004 and sigma for terminal atoms of
0.008
I7B \\sim I7A: within 2A with sigma of 0.004 and sigma for terminal atoms of
0.008
Uanis(I7B) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C6_4) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C1_2) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C1_1) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C1_3) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(I8A) = Uanis(I8B)
Uanis(I2A) = Uanis(I2B)
5. Rigid body (RIGU) restrains
 Pb2, I4A
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 O1_4, N1_4, O2_4, C1_4, C2_4, C6_4, C3_4, C5_4, C4_4, C7_4, C8_4, N2_4
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 C7_2, O1_2, N1_2, O2_2, C1_2, C2_2, C6_2, C3_2, C5_2, C4_2, C8_2, N2_2
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 C7_1, O1_1, N1_1, O2_1, C1_1, C2_1, C6_1, C3_1, C5_1, C4_1, C8_1, N2_1
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 C1_3, O1_3, N1_3, O2_3, C2_3, C6_3, C3_3, C5_3, C4_3, C7_3, C8_3, N2_3
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
6. Same fragment restrains
{O1_2, O2_2, N1_2, N2_2, C1_2, C2_2, C3_2, C4_2, C5_2, C6_2, C7_2, C8_2}
{O1_3, O2_3, N1_3, N2_3, C1_3, C2_3, C3_3, C4_3, C5_3, C6_3, C7_3, C8_3}
{O1_4, O2_4, N1_4, N2_4, C1_4, C2_4, C3_4, C4_4, C5_4, C6_4, C7_4, C8_4}
as
{O1_1, O2_1, N1_1, N2_1, C1_1, C2_1, C3_1, C4_1, C5_1, C6_1, C7_1, C8_1} sigma
for 1-2: 0.002 1-3: 0.004
7. Others
 Sof(I8B)=Sof(I4A)=Sof(I7B)=Sof(I2B)=1-FVAR(1)
 Sof(I2A)=Sof(I8A)=Sof(I7A)=Sof(I4B)=FVAR(1)
8.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C7(H7A,H7B), C8(H8A,H8B), C7(H7A,H7B), C8(H8A,H8B),
 C7(H7A,H7B), C8(H8A,H8B)
8.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C2(H2), C3(H3), C5(H5), C6(H6), C2(H2),
 C3(H3), C5(H5), C6(H6), C2(H2), C3(H3), C5(H5), C6(H6)
8.c Idealised Me refined as rotating group:
 N2(H2A,H2B,H2C), N2(H2A,H2B,H2C), N2(H2A,H2B,H2C), N2(H2A,H2B,H2C)
;
_shelx_res_checksum              90688
_shelx_hkl_checksum              18132
_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-III-53
_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 1.235
_oxdiff_exptl_absorpt_empirical_full_min 0.860