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#$Date: 2020-03-07 01:43:25 +0200 (Sat, 07 Mar 2020) $
#$Revision: 249142 $
#$URL: file:///home/coder/svn-repositories/cod/cif/4/13/43/4134351.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_4134351
loop_
_publ_author_name
'Schmitt, Tanja'
'Bourelle, Sean'
'Tye, Nathaniel'
'Soavi, Giancarlo'
'Bond, Andrew D.'
'Feldmann, Sascha'
'Traore, Boubacar'
'Katan, Claudine'
'Even, Jacky'
'Dutton, Siân E'
'Deschler, Felix'
_publ_section_title
;
 Control of crystal symmetry breaking with halogen substituted
 benzylammonium in layered hybrid metal-halide perovskites.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b11809
_journal_year                    2020
_chemical_absolute_configuration unk
_chemical_formula_moiety         '2(C7 H9 Br N +), I4 Pb 2-'
_chemical_formula_sum            'C14 H18 Br2 I4 N2 Pb'
_chemical_formula_weight         1088.91
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2018/1
_cell_angle_alpha                90
_cell_angle_beta                 95.5588(12)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.6328(2)
_cell_length_b                   8.9483(2)
_cell_length_c                   15.9326(4)
_cell_measurement_reflns_used    9892
_cell_measurement_temperature    180(2)
_cell_measurement_theta_max      70.09
_cell_measurement_theta_min      2.79
_cell_volume                     1224.99(5)
_computing_cell_refinement       'SAINT (Bruker, 2016)'
_computing_data_collection       'APEX3 (Bruker, 2016)'
_computing_data_reduction        SAINT
_computing_molecular_graphics    'Mercury (Macrae et al., 2008)'
_computing_publication_material  SHELXL
_computing_structure_refinement  'SHELXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      180(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker D8-QUEST PHOTON-100'
_diffrn_measurement_method       'ω and φ-scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0675
_diffrn_reflns_av_unetI/netI     0.0653
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            14915
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.087
_diffrn_reflns_theta_min         2.786
_diffrn_source                   'Incoatec I\mS Cu microsource'
_exptl_absorpt_coefficient_mu    56.787
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.3016
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Bruker, 2014)'
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    2.952
_exptl_crystal_description       lath
_exptl_crystal_F_000             960
_exptl_crystal_size_max          0.100
_exptl_crystal_size_mid          0.050
_exptl_crystal_size_min          0.020
_refine_diff_density_max         5.602
_refine_diff_density_min         -2.586
_refine_diff_density_rms         0.374
_refine_ls_abs_structure_details 'Refined as an inversion twin.'
_refine_ls_abs_structure_Flack   0.32(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     211
_refine_ls_number_reflns         4626
_refine_ls_number_restraints     85
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0631
_refine_ls_R_factor_gt           0.0583
_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)+(0.1206P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1523
_refine_ls_wR_factor_ref         0.1576
_reflns_Friedel_coverage         0.872
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                4291
_reflns_number_total             4626
_reflns_threshold_expression     'I > 2σ(I)'
_cod_data_source_file            ja9b11809_si_005.cif
_cod_data_source_block           bromobenzylammonium_180K
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               4134351
_cambridge_user_name             'Tanja Schmitt'
_cambridge_user_crsid            trs49
_cambridge_supervisor_name       'Sian Dutton'
_cambridge_supervisor_crsid      sed33
_cambridge_crystallographer_name 'Andrew Bond'
_cambridge_crystallographer_crsid adb29
_cambridge_data_id               AB_B1_0020
_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.
;
_shelx_estimated_absorpt_t_min   0.070
_shelx_estimated_absorpt_t_max   0.396
loop_
_space_group_symop_operation_xyz
'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 0.24572(10) -0.05602(14) -0.00046(5) 0.0164(2) Uani 1 1 d . . . . .
I1 I 0.25972(17) -0.0960(2) 0.20192(8) 0.0245(4) Uani 1 1 d . . . . .
I2 I 0.21945(18) -0.02387(19) -0.19813(8) 0.0264(4) Uani 1 1 d . . . . .
I3 I 0.44522(16) 0.24601(16) 0.00667(9) 0.0249(4) Uani 1 1 d . . . . .
I4 I -0.05650(17) 0.13737(17) 0.01447(10) 0.0267(4) Uani 1 1 d . . . . .
Br1 Br 0.9774(3) 0.0221(4) 0.58885(16) 0.0375(6) Uani 1 1 d . . . . .
N1 N 0.841(2) -0.133(3) 0.1699(12) 0.029(5) Uani 1 1 d . . . . .
H1A H 0.941031 -0.099672 0.176877 0.044 Uiso 1 1 calc R U . . .
H1B H 0.809214 -0.139417 0.113856 0.044 Uiso 1 1 calc R U . . .
H1C H 0.834826 -0.224248 0.194184 0.044 Uiso 1 1 calc R U . . .
C1 C 0.792(3) -0.013(3) 0.3051(15) 0.025(5) Uani 1 1 d . U . . .
C2 C 0.732(3) -0.113(4) 0.3635(16) 0.035(6) Uani 1 1 d . U . . .
H2A H 0.656366 -0.185298 0.344398 0.042 Uiso 1 1 calc R U . . .
C3 C 0.785(3) -0.103(3) 0.4498(15) 0.030(5) Uani 1 1 d . U . . .
H3A H 0.745627 -0.168281 0.489684 0.036 Uiso 1 1 calc R U . . .
C4 C 0.896(3) 0.005(3) 0.4750(13) 0.024(5) Uani 1 1 d . U . . .
C5 C 0.947(3) 0.106(3) 0.4164(16) 0.032(5) Uani 1 1 d . U . . .
H5A H 1.017267 0.183610 0.434983 0.038 Uiso 1 1 calc R U . . .
C6 C 0.897(3) 0.093(3) 0.3317(16) 0.029(5) Uani 1 1 d . U . . .
H6A H 0.937619 0.157665 0.291964 0.035 Uiso 1 1 calc R U . . .
C7 C 0.736(3) -0.023(4) 0.2114(18) 0.042(7) Uani 1 1 d . U . . .
H7A H 0.741334 0.076570 0.184809 0.050 Uiso 1 1 calc R U . . .
H7B H 0.627070 -0.058137 0.203926 0.050 Uiso 1 1 calc R U . . .
Br2 Br 0.6992(3) 0.3942(4) 0.55075(15) 0.0368(6) Uani 1 1 d . . . . .
N2 N 0.350(2) 0.521(3) 0.1562(12) 0.028(5) Uani 1 1 d . . . . .
H2B H 0.357222 0.614559 0.177937 0.043 Uiso 1 1 calc R U . . .
H2C H 0.290113 0.521887 0.106001 0.043 Uiso 1 1 calc R U . . .
H2D H 0.447127 0.486799 0.148020 0.043 Uiso 1 1 calc R U . . .
C8 C 0.383(3) 0.411(3) 0.2975(13) 0.023(5) Uani 1 1 d . U . . .
C9 C 0.453(3) 0.274(3) 0.3255(14) 0.027(5) Uani 1 1 d . U . . .
H9A H 0.433019 0.185984 0.292705 0.032 Uiso 1 1 calc R U . . .
C10 C 0.550(3) 0.266(3) 0.3986(15) 0.027(5) Uani 1 1 d . U . . .
H10A H 0.596381 0.174400 0.417525 0.032 Uiso 1 1 calc R U . . .
C11 C 0.577(3) 0.402(3) 0.4460(13) 0.025(5) Uani 1 1 d . U . . .
C12 C 0.506(3) 0.528(3) 0.4190(14) 0.026(5) Uani 1 1 d . U . . .
H12A H 0.521690 0.614505 0.452980 0.032 Uiso 1 1 calc R U . . .
C13 C 0.409(3) 0.540(3) 0.3451(15) 0.026(5) Uani 1 1 d . U . . .
H13A H 0.363452 0.632329 0.327589 0.031 Uiso 1 1 calc R U . . .
C14 C 0.279(3) 0.420(4) 0.2158(16) 0.035(6) Uani 1 1 d . U . . .
H14A H 0.265245 0.318650 0.190931 0.042 Uiso 1 1 calc R U . . .
H14B H 0.175179 0.458170 0.226682 0.042 Uiso 1 1 calc 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 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
I I -0.3257 6.8362 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Pb Pb -4.0753 8.5060 '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
I2 Pb1 I4 92.59(5) . . ?
I2 Pb1 I4 91.25(5) . 2_545 ?
I4 Pb1 I4 93.17(3) . 2_545 ?
I2 Pb1 I3 86.83(5) . . ?
I4 Pb1 I3 88.87(5) . . ?
I4 Pb1 I3 177.26(5) 2_545 . ?
I2 Pb1 I3 89.95(5) . 2_645 ?
I4 Pb1 I3 177.46(5) . 2_645 ?
I4 Pb1 I3 86.83(5) 2_545 2_645 ?
I3 Pb1 I3 91.21(2) . 2_645 ?
I2 Pb1 I1 177.73(6) . . ?
I4 Pb1 I1 86.39(5) . . ?
I4 Pb1 I1 86.79(5) 2_545 . ?
I3 Pb1 I1 95.17(5) . . ?
I3 Pb1 I1 91.07(4) 2_645 . ?
Pb1 I3 Pb1 155.54(6) . 2_655 ?
Pb1 I4 Pb1 152.50(6) . 2 ?
C7 N1 H1A 109.5 . . ?
C7 N1 H1B 109.5 . . ?
H1A N1 H1B 109.5 . . ?
C7 N1 H1C 109.5 . . ?
H1A N1 H1C 109.5 . . ?
H1B N1 H1C 109.5 . . ?
C6 C1 C2 121(2) . . ?
C6 C1 C7 119(2) . . ?
C2 C1 C7 120(2) . . ?
C3 C2 C1 120(3) . . ?
C3 C2 H2A 120.1 . . ?
C1 C2 H2A 120.1 . . ?
C4 C3 C2 118(2) . . ?
C4 C3 H3A 120.9 . . ?
C2 C3 H3A 120.9 . . ?
C3 C4 C5 121(2) . . ?
C3 C4 Br1 121.1(16) . . ?
C5 C4 Br1 118.4(18) . . ?
C6 C5 C4 120(2) . . ?
C6 C5 H5A 119.8 . . ?
C4 C5 H5A 119.8 . . ?
C1 C6 C5 120(2) . . ?
C1 C6 H6A 119.9 . . ?
C5 C6 H6A 119.9 . . ?
C1 C7 N1 109(2) . . ?
C1 C7 H7A 110.0 . . ?
N1 C7 H7A 110.0 . . ?
C1 C7 H7B 110.0 . . ?
N1 C7 H7B 110.0 . . ?
H7A C7 H7B 108.3 . . ?
C14 N2 H2B 109.5 . . ?
C14 N2 H2C 109.5 . . ?
H2B N2 H2C 109.5 . . ?
C14 N2 H2D 109.5 . . ?
H2B N2 H2D 109.5 . . ?
H2C N2 H2D 109.5 . . ?
C13 C8 C9 120(2) . . ?
C13 C8 C14 119(2) . . ?
C9 C8 C14 121(2) . . ?
C10 C9 C8 121(2) . . ?
C10 C9 H9A 119.4 . . ?
C8 C9 H9A 119.4 . . ?
C9 C10 C11 117(2) . . ?
C9 C10 H10A 121.3 . . ?
C11 C10 H10A 121.3 . . ?
C12 C11 C10 120(2) . . ?
C12 C11 Br2 121.4(19) . . ?
C10 C11 Br2 118.7(19) . . ?
C11 C12 C13 124(2) . . ?
C11 C12 H12A 117.8 . . ?
C13 C12 H12A 117.8 . . ?
C12 C13 C8 117(2) . . ?
C12 C13 H13A 121.3 . . ?
C8 C13 H13A 121.3 . . ?
N2 C14 C8 110(2) . . ?
N2 C14 H14A 109.8 . . ?
C8 C14 H14A 109.8 . . ?
N2 C14 H14B 109.8 . . ?
C8 C14 H14B 109.8 . . ?
H14A C14 H14B 108.2 . . ?
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 I2 3.1489(15) . ?
Pb1 I4 3.1589(17) . ?
Pb1 I4 3.1898(18) 2_545 ?
Pb1 I3 3.2009(18) . ?
Pb1 I3 3.2121(17) 2_645 ?
Pb1 I1 3.2348(16) . ?
Br1 C4 1.89(2) . ?
N1 C7 1.53(4) . ?
N1 H1A 0.9100 . ?
N1 H1B 0.9100 . ?
N1 H1C 0.9100 . ?
C1 C6 1.35(4) . ?
C1 C2 1.42(4) . ?
C1 C7 1.53(4) . ?
C2 C3 1.41(3) . ?
C2 H2A 0.9500 . ?
C3 C4 1.39(4) . ?
C3 H3A 0.9500 . ?
C4 C5 1.40(3) . ?
C5 C6 1.38(4) . ?
C5 H5A 0.9500 . ?
C6 H6A 0.9500 . ?
C7 H7A 0.9900 . ?
C7 H7B 0.9900 . ?
Br2 C11 1.89(2) . ?
N2 C14 1.49(4) . ?
N2 H2B 0.9100 . ?
N2 H2C 0.9100 . ?
N2 H2D 0.9100 . ?
C8 C13 1.38(3) . ?
C8 C9 1.43(4) . ?
C8 C14 1.51(3) . ?
C9 C10 1.37(3) . ?
C9 H9A 0.9500 . ?
C10 C11 1.44(3) . ?
C10 H10A 0.9500 . ?
C11 C12 1.33(4) . ?
C12 C13 1.38(3) . ?
C12 H12A 0.9500 . ?
C13 H13A 0.9500 . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C6 C1 C2 C3 -1(4) . . . . ?
C7 C1 C2 C3 179(2) . . . . ?
C1 C2 C3 C4 0(4) . . . . ?
C2 C3 C4 C5 3(4) . . . . ?
C2 C3 C4 Br1 -178.3(19) . . . . ?
C3 C4 C5 C6 -5(4) . . . . ?
Br1 C4 C5 C6 176(2) . . . . ?
C2 C1 C6 C5 -1(4) . . . . ?
C7 C1 C6 C5 179(2) . . . . ?
C4 C5 C6 C1 4(4) . . . . ?
C6 C1 C7 N1 91(3) . . . . ?
C2 C1 C7 N1 -89(3) . . . . ?
C13 C8 C9 C10 -1(4) . . . . ?
C14 C8 C9 C10 179(2) . . . . ?
C8 C9 C10 C11 0(4) . . . . ?
C9 C10 C11 C12 2(3) . . . . ?
C9 C10 C11 Br2 176.2(18) . . . . ?
C10 C11 C12 C13 -3(4) . . . . ?
Br2 C11 C12 C13 -177.0(19) . . . . ?
C11 C12 C13 C8 2(4) . . . . ?
C9 C8 C13 C12 0(3) . . . . ?
C14 C8 C13 C12 -180(2) . . . . ?
C13 C8 C14 N2 63(3) . . . . ?
C9 C8 C14 N2 -117(3) . . . . ?
