#------------------------------------------------------------------------------
#$Date: 2020-04-22 22:24:56 +0300 (Wed, 22 Apr 2020) $
#$Revision: 251025 $
#$URL: file:///home/coder/svn-repositories/cod/cif/4/00/35/4003535.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_4003535
loop_
_publ_author_name
'Ma̧czka, Mirosław'
'Gagor, Anna'
'Zarȩba, Jan K.'
'Stefanska, Dagmara'
'Drozd, Marek'
'Balciunas, Sergejus'
'Šimėnas, Mantas'
'Banys, Juras'
'Sieradzki, Adam'
_publ_section_title
;
 Three-Dimensional Perovskite Methylhydrazinium Lead Chloride with Two
 Polar Phases and Unusual Second-Harmonic Generation Bistability above
 Room Temperature
;
_journal_name_full               'Chemistry of Materials'
_journal_paper_doi               10.1021/acs.chemmater.0c00973
_journal_year                    2020
_chemical_formula_sum            'C H7 Cl3 N2 Pb'
_chemical_formula_weight         360.63
_space_group_crystal_system      orthorhombic
_space_group_IT_number           26
_space_group_name_Hall           'P -2 -2b'
_space_group_name_H-M_alt        'P b 21 m'
_atom_sites_solution_hydrogens   mixed
_audit_creation_method           SHELXL-2018/3
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.7416(4)
_cell_length_b                   11.4227(2)
_cell_length_c                   11.4054(3)
_cell_measurement_reflns_used    13962
_cell_measurement_temperature    360.1(1)
_cell_measurement_theta_max      32.2630
_cell_measurement_theta_min      3.4130
_cell_volume                     748.02(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      360.1(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6249
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.951
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0413
_diffrn_reflns_av_unetI/netI     0.0339
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.951
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            7752
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.905
_diffrn_reflns_theta_full        28.000
_diffrn_reflns_theta_max         29.360
_diffrn_reflns_theta_min         3.548
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    23.523
_exptl_absorpt_correction_T_max  0.640
_exptl_absorpt_correction_T_min  0.032
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    3.202
_exptl_crystal_description       plate
_exptl_crystal_F_000             640
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.617
_refine_diff_density_min         -1.313
_refine_diff_density_rms         0.256
_refine_ls_abs_structure_details
;
 Flack x determined using 796 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.023(13)
_refine_ls_extinction_coef       0.0062(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     75
_refine_ls_number_reflns         1954
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0329
_refine_ls_R_factor_gt           0.0310
_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/[σ²(Fo²)+(0.0447P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0728
_refine_ls_wR_factor_ref         0.0748
_reflns_Friedel_coverage         0.811
_reflns_Friedel_fraction_full    0.955
_reflns_Friedel_fraction_max     0.853
_reflns_number_gt                1868
_reflns_number_total             1954
_reflns_threshold_expression     'I > 2σ(I)'
_cod_data_source_file            cm0c00973_si_003.cif
_cod_data_source_block           PhaseI
_cod_database_code               4003535
_shelx_shelxl_version_number     2018/3
_shelx_space_group_comment
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_oxdiff_exptl_absorpt_empirical_full_min 0.421
_oxdiff_exptl_absorpt_empirical_full_max 2.317
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z'
'x, y, -z'
'-x, y+1/2, z'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Pb1 Pb 0.48433(8) 0.48361(5) 0.000000 0.02598(18) Uani 1 2 d S T P . .
Pb2 Pb 0.59541(9) 0.49641(5) 0.500000 0.03009(19) Uani 1 2 d S T P . .
Cl1 Cl 0.0983(7) 0.4128(4) 0.500000 0.0489(12) Uani 1 2 d S T P . .
Cl2 Cl 0.4688(6) 0.4806(10) 0.2503(2) 0.0637(11) Uani 1 1 d . . . . .
Cl3 Cl 0.5225(15) 0.7307(6) 0.000000 0.074(2) Uani 1 2 d S T P . .
Cl4 Cl 0.9793(7) 0.5047(5) 0.000000 0.0625(17) Uani 1 2 d S T P . .
Cl5 Cl 0.3934(9) 0.7190(5) 0.500000 0.0571(16) Uani 1 2 d S T P . .
N2 N 0.837(3) 0.7174(17) 0.7171(14) 0.071(4) Uani 1 1 d . . . . .
H2A H 0.716206 0.693128 0.759669 0.085 Uiso 1 1 calc R U . . .
H2B H 0.787237 0.776051 0.672221 0.085 Uiso 1 1 calc R U . . .
C2 C 1.024(4) 0.7651(19) 0.8010(18) 0.067(6) Uani 1 1 d . . . . .
H2C H 1.149196 0.709747 0.806814 0.100 Uiso 1 1 calc R U . . .
H2D H 0.956753 0.777235 0.877090 0.100 Uiso 1 1 calc R U . . .
H2E H 1.082469 0.838031 0.771355 0.100 Uiso 1 1 calc R U . . .
N1 N 0.903(3) 0.6305(14) 0.6481(12) 0.081(5) Uani 1 1 d . . . . .
H1A H 1.011672 0.655744 0.598352 0.121 Uiso 1 1 d R U . . .
H1C H 0.961203 0.572844 0.691812 0.121 Uiso 1 1 d R U . . .
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Pb Pb -3.3944 10.1111 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
Cl3 Pb1 Cl4 80.7(2) . . ?
Cl3 Pb1 Cl2 90.8(2) . . ?
Cl4 Pb1 Cl2 91.84(7) . . ?
Cl3 Pb1 Cl2 90.8(2) . 3 ?
Cl4 Pb1 Cl2 91.84(7) . 3 ?
Cl2 Pb1 Cl2 176.2(2) . 3 ?
Cl3 Pb1 Cl3 176.34(2) . 2_645 ?
Cl4 Pb1 Cl3 95.6(2) . 2_645 ?
Cl2 Pb1 Cl3 89.3(2) . 2_645 ?
Cl2 Pb1 Cl3 89.3(2) 3 2_645 ?
Cl3 Pb1 Cl4 89.7(2) . 1_455 ?
Cl4 Pb1 Cl4 170.4(2) . 1_455 ?
Cl2 Pb1 Cl4 88.27(6) . 1_455 ?
Cl2 Pb1 Cl4 88.27(6) 3 1_455 ?
Cl3 Pb1 Cl4 94.0(2) 2_645 1_455 ?
Cl5 Pb2 Cl2 87.3(2) . . ?
Cl5 Pb2 Cl2 87.3(2) . 3_556 ?
Cl2 Pb2 Cl2 150.52(18) . 3_556 ?
Cl5 Pb2 Cl1 83.98(15) . . ?
Cl2 Pb2 Cl1 75.31(10) . . ?
Cl2 Pb2 Cl1 75.31(11) 3_556 . ?
Cl5 Pb2 Cl1 132.82(15) . 1_655 ?
Cl2 Pb2 Cl1 102.43(9) . 1_655 ?
Cl2 Pb2 Cl1 102.43(9) 3_556 1_655 ?
Cl1 Pb2 Cl1 143.20(18) . 1_655 ?
Cl5 Pb2 Cl5 156.64(6) . 2_646 ?
Cl2 Pb2 Cl5 86.8(2) . 2_646 ?
Cl2 Pb2 Cl5 86.8(2) 3_556 2_646 ?
Cl1 Pb2 Cl5 72.66(13) . 2_646 ?
Cl1 Pb2 Cl5 70.54(13) 1_655 2_646 ?
Pb2 Cl1 Pb2 143.20(18) . 1_455 ?
Pb1 Cl2 Pb2 163.36(19) . . ?
Pb1 Cl3 Pb1 174.8(4) . 2_655 ?
Pb1 Cl4 Pb1 170.4(2) . 1_655 ?
N1 N2 C2 115.9(16) . . ?
N1 N2 H2A 108.3 . . ?
C2 N2 H2A 108.3 . . ?
N1 N2 H2B 108.3 . . ?
C2 N2 H2B 108.3 . . ?
H2A N2 H2B 107.4 . . ?
N2 C2 H2C 109.5 . . ?
N2 C2 H2D 109.5 . . ?
H2C C2 H2D 109.5 . . ?
N2 C2 H2E 109.5 . . ?
H2C C2 H2E 109.5 . . ?
H2D C2 H2E 109.5 . . ?
N2 N1 H1A 109.7 . . ?
N2 N1 H1C 109.2 . . ?
H1A N1 H1C 109.3 . . ?
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Pb1 Cl3 2.831(7) . ?
Pb1 Cl4 2.852(4) . ?
Pb1 Cl2 2.857(3) . ?
Pb1 Cl2 2.857(3) 3 ?
Pb1 Cl3 2.890(7) 2_645 ?
Pb1 Cl4 2.910(4) 1_455 ?
Pb2 Cl5 2.794(6) . ?
Pb2 Cl2 2.944(3) . ?
Pb2 Cl2 2.944(3) 3_556 ?
Pb2 Cl1 3.010(4) . ?
Pb2 Cl1 3.041(4) 1_655 ?
Pb2 Cl5 3.170(6) 2_646 ?
N2 N1 1.32(2) . ?
N2 C2 1.54(3) . ?
N2 H2A 0.8900 . ?
N2 H2B 0.8900 . ?
C2 H2C 0.9600 . ?
C2 H2D 0.9600 . ?
C2 H2E 0.9600 . ?
N1 H1A 0.8918 . ?
N1 H1C 0.8920 . ?
loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
_geom_hbond_publ_flag
N2 H2A Cl2 0.89 2.81 3.45(2) 129.7 3_556 yes
N2 H2B Cl1 0.89 2.59 3.355(18) 143.9 2_656 yes
N1 H1A Cl5 0.89 2.57 3.436(17) 165.4 1_655 yes
