#------------------------------------------------------------------------------
#$Date: 2019-11-22 22:36:26 +0200 (Fri, 22 Nov 2019) $
#$Revision: 231452 $
#$URL: file:///home/coder/svn-repositories/cod/cif/4/00/32/4003236.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_4003236
loop_
_publ_author_name
'Stoumpos, Constantinos C.'
'Cao, Duyen H.'
'Clark, Daniel J.'
'Young, Joshua'
'Rondinelli, James M.'
'Jang, Joon I.'
'Hupp, Joseph T.'
'Kanatzidis, Mercouri G.'
_publ_section_title
;
 Ruddlesden--Popper Hybrid Lead Iodide Perovskite 2D Homologous
 Semiconductors
;
_journal_issue                   8
_journal_name_full               'Chemistry of Materials'
_journal_page_first              2852
_journal_paper_doi               10.1021/acs.chemmater.6b00847
_journal_volume                  28
_journal_year                    2016
_chemical_formula_moiety         2(C4H9NH3),3(CH3NH3),Pb4I13
_chemical_formula_sum            'C11 H42 I13 N5 Pb4'
_chemical_formula_weight         2722.95
_chemical_name_common            'Bytulammonium Methylammonium Lead iodide'
_space_group_IT_number           40
_space_group_name_Hall           'C -2c -2c'
_space_group_name_H-M_alt        'C c 2 m'
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      40
_symmetry_space_group_name_H-M   'C c 2 m'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2013
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.9274(4)
_cell_length_b                   64.383(3)
_cell_length_c                   8.8816(4)
_cell_measurement_reflns_used    7976
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      26.88
_cell_measurement_theta_min      2.47
_cell_volume                     5104.9(4)
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'image plate (34 cm diameter)'
_diffrn_detector_area_resol_mean 6.67
_diffrn_detector_type            STOE
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       '2-circle goniometer'
_diffrn_measurement_device_type  'STOE IPDS 2T'
_diffrn_measurement_method       'rotation method'
_diffrn_radiation_collimation    '0.5 mm diameter, monocapillary'
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_polarisn_norm  0
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0506
_diffrn_reflns_av_unetI/netI     0.0439
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       76
_diffrn_reflns_limit_k_min       -76
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            13717
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.471
_diffrn_source
'sealed X-ray tube, 12 x 0.4 mm long-fine focus'
_diffrn_source_current           30
_diffrn_source_power             1.20
_diffrn_source_voltage           40
_exptl_absorpt_coefficient_mu    21.026
_exptl_absorpt_correction_T_max  0.6753
_exptl_absorpt_correction_T_min  0.0740
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details   X-SHAPE
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    3.543
_exptl_crystal_description       'rectangular plate'
_exptl_crystal_F_000             4640
_exptl_crystal_size_max          0.079
_exptl_crystal_size_mid          0.073
_exptl_crystal_size_min          0.009
_refine_diff_density_max         1.746
_refine_diff_density_min         -1.470
_refine_diff_density_rms         0.234
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.435(35)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.986
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           fullcycle
_refine_ls_number_parameters     135
_refine_ls_number_reflns         4671
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      0.986
_refine_ls_R_factor_all          0.0864
_refine_ls_R_factor_gt           0.0431
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[σ²(Fo²)+(0.0736P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1123
_refine_ls_wR_factor_ref         0.1387
_reflns_Friedel_coverage         0.982
_reflns_Friedel_fraction_full    0.970
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                2625
_reflns_number_total             4671
_reflns_threshold_expression     'I > 2σ(I)'
_cod_data_source_file            cm6b00847_si_002.cif
_cod_data_source_block           BA2MA3Pb4I13_Cc2m
_cod_original_sg_symbol_Hall     C-2c-2c
_cod_database_code               4003236
_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.
;
_shelxl_version_number           2013-4
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y, -z'
'-x, y, z+1/2'
'x, y, -z+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z'
'-x+1/2, y+1/2, z+1/2'
'x+1/2, y+1/2, -z+1/2'
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
Pb1 Pb 0.2502(3) 0.1997(3) 0.2500 0.0421(7) Uani 1 2 d S T P
Pb2 Pb 0.2502(2) 0.2983(3) 0.2500 0.0413(7) Uani 1 2 d S T P
Pb3 Pb 0.2497(2) 0.1007(3) 0.2500 0.0483(9) Uani 1 2 d S T P
Pb4 Pb 0.2485(2) 0.3976(3) 0.2500 0.0450(8) Uani 1 2 d S T P
I1 I 0.5000 0.2923(3) 0.5000 0.101(2) Uani 1 2 d S T P
I2 I 0.0000 0.1949(3) 0.5000 0.105(3) Uani 1 2 d S T P
I3 I 0.2886(9) 0.1513(3) 0.2500 0.114(3) Uani 1 2 d S T P
I4 I 0.2104(4) 0.2479(3) 0.2500 0.1040(13) Uani 1 2 d S T P
I5 I 0.2965(7) 0.3463(3) 0.2500 0.095(2) Uani 1 2 d S T P
I6 I 0.5000 0.2030(3) 0.5000 0.124(3) Uani 1 2 d S T P
I7 I 0.0000 0.3902(3) 0.5000 0.100(2) Uani 1 2 d S T P
I8 I 0.5000 0.0966(3) 0.5000 0.100(2) Uani 1 2 d S T P
I9 I 0.5000 0.4007(3) 0.5000 0.090(2) Uani 1 2 d S T P
I10 I 0.1905(8) 0.0538(3) 0.2500 0.121(3) Uani 1 2 d S T P
I11 I 0.1898(10) 0.4437(3) 0.2500 0.139(4) Uani 1 2 d S T P
I12 I 0.0000 0.1069(3) 0.5000 0.088(2) Uani 1 2 d S T P
I13 I 0.0000 0.3014(3) 0.5000 0.119(3) Uani 1 2 d S T P
N1 N 0.326(9) 0.1476(14) 0.7500 0.20(3) Uiso 1 2 d DS . P
H1A H 0.3694 0.1527 0.6678 0.301 Uiso 0.5 1 calc R U P
H1B H 0.3364 0.1338 0.7508 0.301 Uiso 0.5 2 calc R U P
H1C H 0.3698 0.1529 0.8314 0.301 Uiso 0.5 1 calc R U P
C1 C 0.141(11) 0.1538(16) 0.7500 0.20(3) Uiso 1 2 d DS . P
H1D H 0.1168 0.1611 0.8411 0.301 Uiso 0.5 1 calc R U P
H1E H 0.0823 0.1413 0.7440 0.301 Uiso 0.5 2 calc R U P
H1F H 0.1193 0.1625 0.6649 0.301 Uiso 0.5 1 calc R U P
N2 N 0.199(6) 0.2569(10) 0.7500 0.16(2) Uiso 1 2 d DS . P
H2A H 0.1714 0.2594 0.8445 0.236 Uiso 0.5 1 calc R U P
H2B H 0.1267 0.2500 0.7026 0.236 Uiso 0.5 1 calc R U P
H2C H 0.2162 0.2688 0.7029 0.236 Uiso 0.5 1 calc R U P
C2 C 0.330(6) 0.2449(15) 0.7500 0.16(2) Uiso 1 2 d DS . P
H2D H 0.4156 0.2540 0.7499 0.236 Uiso 1 2 calc R U P
H2E H 0.3320 0.2363 0.6618 0.236 Uiso 0.5 1 calc R U P
H2F H 0.3321 0.2363 0.8383 0.236 Uiso 0.5 1 calc R U P
N3 N 0.217(6) 0.3529(8) 0.7500 0.102(13) Uiso 1 2 d DS . P
H3A H 0.2445 0.3607 0.8283 0.153 Uiso 0.5 1 calc R U P
H3B H 0.1196 0.3501 0.7566 0.153 Uiso 0.5 2 calc R U P
H3C H 0.2348 0.3598 0.6651 0.153 Uiso 0.5 1 calc R U P
C3 C 0.300(7) 0.3341(9) 0.7500 0.102(13) Uiso 1 2 d DS . P
H3D H 0.3554 0.3329 0.8423 0.153 Uiso 0.5 1 calc R U P
H3E H 0.3684 0.3340 0.6665 0.153 Uiso 0.5 1 calc R U P
H3F H 0.2326 0.3225 0.7411 0.153 Uiso 0.5 2 calc R U P
N4 N 0.2486 0.4279 0.7500 0.119(17) Uiso 1 2 d DS . P
H4A H 0.1639 0.4207 0.7500 0.178 Uiso 1 2 calc R U P
H4B H 0.3016 0.4248 0.8318 0.178 Uiso 0.5 1 calc R U P
H4C H 0.3016 0.4248 0.6682 0.178 Uiso 0.5 1 calc R U P
C4 C 0.2129 0.4507 0.7500 0.1(12) Uiso 1 2 d DS . P
H4D H 0.1526 0.4538 0.6619 0.143 Uiso 0.5 1 calc R U P
H4E H 0.1526 0.4538 0.8381 0.143 Uiso 0.5 1 calc R U P
C5 C 0.3428 0.4645 0.7500 0.1(12) Uiso 1 2 d DS . P
H5A H 0.4039 0.4623 0.6611 0.143 Uiso 0.5 1 calc R U P
H5B H 0.4039 0.4623 0.8389 0.143 Uiso 0.5 1 calc R U P
C6 C 0.2730 0.4870 0.7500 0.1(12) Uiso 1 2 d DS . P
H6A H 0.2100 0.4886 0.6618 0.143 Uiso 0.5 1 calc R U P
H6B H 0.2100 0.4886 0.8382 0.143 Uiso 0.5 1 calc R U P
C7 C 0.3901 0.5039 0.7500 0.1(12) Uiso 1 2 d DS . P
H7A H 0.3420 0.5172 0.7500 0.178 Uiso 1 2 calc R U P
H7B H 0.4515 0.5026 0.6617 0.178 Uiso 0.5 1 calc R U P
H7C H 0.4515 0.5026 0.8383 0.178 Uiso 0.5 1 calc R U P
N5 N 0.2558 0.0777 0.7500 0.9(3) Uiso 1 2 d DS . P
H5C H 0.1701 0.0847 0.7500 1.361 Uiso 1 2 calc R U P
H5D H 0.3084 0.0809 0.6682 1.361 Uiso 0.5 1 calc R U P
H5E H 0.3084 0.0809 0.8318 1.361 Uiso 0.5 1 calc R U P
C8 C 0.2229 0.0548 0.7500 0.9(12) Uiso 1 2 d DS . P
H8A H 0.1612 0.0520 0.8376 1.089 Uiso 0.5 1 calc R U P
H8B H 0.1612 0.0520 0.6624 1.089 Uiso 0.5 1 calc R U P
C9 C 0.3449 0.0391 0.7500 0.9(12) Uiso 1 2 d DS . P
H9A H 0.4073 0.0407 0.8388 1.089 Uiso 0.5 1 calc R U P
H9B H 0.4073 0.0407 0.6612 1.089 Uiso 0.5 1 calc R U P
C10 C 0.2691 0.0183 0.7500 0.9(12) Uiso 1 2 d DS . P
H10A H 0.2051 0.0175 0.6619 1.089 Uiso 0.5 1 calc R U P
H10B H 0.2051 0.0175 0.8381 1.089 Uiso 0.5 1 calc R U P
C11 C 0.3753 -0.0007 0.7500 0.9(12) Uiso 1 2 d DS . P
H11A H 0.3170 -0.0132 0.7500 1.361 Uiso 1 2 calc R U P
H11B H 0.4373 -0.0003 0.8383 1.361 Uiso 0.5 1 calc R U P
H11C H 0.4373 -0.0003 0.6617 1.361 Uiso 0.5 1 calc R U P
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'
I I -0.4742 1.8119 '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
I4 Pb1 I3 179.8(8) . .
I4 Pb1 I6 90.8(7) . .
I3 Pb1 I6 89.4(7) . .
I4 Pb1 I6 90.8(7) . 3_654
I3 Pb1 I6 89.4(7) . 3_654
I6 Pb1 I6 89.5(3) . 3_654
I4 Pb1 I2 90.9(7) . .
I3 Pb1 I2 88.9(8) . .
I6 Pb1 I2 90.66(8) . .
I6 Pb1 I2 178.2(9) 3_654 .
I4 Pb1 I2 90.9(7) . 3_554
I3 Pb1 I2 88.9(8) . 3_554
I6 Pb1 I2 178.2(9) . 3_554
I6 Pb1 I2 90.66(8) 3_654 3_554
I2 Pb1 I2 89.1(3) . 3_554
I5 Pb2 I13 91.7(8) . 3_554
I5 Pb2 I13 91.7(8) . .
I13 Pb2 I13 89.4(3) 3_554 .
I5 Pb2 I1 91.5(7) . 3_654
I13 Pb2 I1 90.73(10) 3_554 3_654
I13 Pb2 I1 176.7(9) . 3_654
I5 Pb2 I1 91.5(7) . .
I13 Pb2 I1 176.7(9) 3_554 .
I13 Pb2 I1 90.73(10) . .
I1 Pb2 I1 88.9(3) 3_654 .
I5 Pb2 I4 178.6(6) . .
I13 Pb2 I4 89.2(7) 3_554 .
I13 Pb2 I4 89.2(7) . .
I1 Pb2 I4 87.5(6) 3_654 .
I1 Pb2 I4 87.5(6) . .
I10 Pb3 I8 92.3(8) . .
I10 Pb3 I8 92.3(8) . 3_654
I8 Pb3 I8 89.2(3) . 3_654
I10 Pb3 I12 90.2(8) . 3_554
I8 Pb3 I12 177.5(10) . 3_554
I8 Pb3 I12 90.90(10) 3_654 3_554
I10 Pb3 I12 90.2(8) . .
I8 Pb3 I12 90.90(10) . .
I8 Pb3 I12 177.5(10) 3_654 .
I12 Pb3 I12 88.9(3) 3_554 .
I10 Pb3 I3 176.2(8) . .
I8 Pb3 I3 90.4(9) . .
I8 Pb3 I3 90.4(9) 3_654 .
I12 Pb3 I3 87.1(8) 3_554 .
I12 Pb3 I3 87.1(8) . .
I11 Pb4 I9 93.6(8) . .
I11 Pb4 I9 93.6(8) . 3_654
I9 Pb4 I9 89.1(3) . 3_654
I11 Pb4 I7 91.6(8) . 3_554
I9 Pb4 I7 174.9(11) . 3_554
I9 Pb4 I7 90.83(10) 3_654 3_554
I11 Pb4 I7 91.6(8) . .
I9 Pb4 I7 90.83(10) . .
I9 Pb4 I7 174.9(11) 3_654 .
I7 Pb4 I7 88.7(3) 3_554 .
I11 Pb4 I5 177.4(9) . .
I9 Pb4 I5 88.3(8) . .
I9 Pb4 I5 88.3(8) 3_654 .
I7 Pb4 I5 86.5(8) 3_554 .
I7 Pb4 I5 86.5(8) . .
Pb2 I1 Pb2 166.1(12) 2_656 .
Pb1 I2 Pb1 168.8(14) . 2_556
Pb1 I3 Pb3 167.6(12) . .
Pb1 I4 Pb2 167.2(6) . .
Pb2 I5 Pb4 165.0(9) . .
Pb1 I6 Pb1 172.4(12) . 2_656
Pb4 I7 Pb4 162.6(14) . 2_556
Pb3 I8 Pb3 170.4(14) 2_656 .
Pb4 I9 Pb4 172.9(14) 2_656 .
Pb3 I12 Pb3 165.5(13) . 2_556
Pb2 I13 Pb2 172.7(14) . 2_556
C5 C4 N4 115.2 . .
C4 C5 C6 104.2 . .
C7 C6 C5 112.8 . .
C9 C8 N5 121.5 . .
C8 C9 C10 105.9 . .
C9 C10 C11 115.4 . .
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
Pb1 I4 3.12(2) .
Pb1 I3 3.14(2) .
Pb1 I6 3.154(8) .
Pb1 I6 3.154(8) 3_654
Pb1 I2 3.164(8) .
Pb1 I2 3.164(8) 3_554
Pb2 I5 3.122(17) .
Pb2 I13 3.156(8) 3_554
Pb2 I13 3.156(8) .
Pb2 I1 3.170(8) 3_654
Pb2 I1 3.170(8) .
Pb2 I4 3.26(2) .
Pb3 I10 3.06(2) .
Pb3 I8 3.161(8) .
Pb3 I8 3.161(8) 3_654
Pb3 I12 3.172(9) 3_554
Pb3 I12 3.172(9) .
Pb3 I3 3.27(2) .
Pb4 I11 3.01(2) .
Pb4 I9 3.164(8) .
Pb4 I9 3.164(8) 3_654
Pb4 I7 3.175(9) 3_554
Pb4 I7 3.175(9) .
Pb4 I5 3.330(15) .
I1 Pb2 3.170(8) 2_656
I2 Pb1 3.164(8) 2_556
I6 Pb1 3.154(8) 2_656
I7 Pb4 3.175(10) 2_556
I8 Pb3 3.161(8) 2_656
I9 Pb4 3.164(8) 2_656
I12 Pb3 3.172(9) 2_556
I13 Pb2 3.156(8) 2_556
N1 C1 1.7(9) .
N2 C2 1.40(7) .
N3 C3 1.42(12) .
N4 C4 1.4997 .
C4 C5 1.4612 .
C5 C6 1.5798 .
C6 C7 1.5073 .
N5 C8 1.5034 .
C8 C9 1.4848 .
C9 C10 1.4984 .
C10 C11 1.5503 .
