#------------------------------------------------------------------------------
#$Date: 2019-10-28 12:44:41 +0200 (Mon, 28 Oct 2019) $
#$Revision: 220085 $
#$URL: file:///home/coder/svn-repositories/cod/cif/4/51/49/4514923.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_4514923
loop_
_publ_author_name
'Fu, Yongping'
'Hautzinger, Matthew P.'
'Luo, Ziyu'
'Wang, Feifan'
'Pan, Dongxu'
'Aristov, Michael M.'
'Guzei, Ilia A.'
'Pan, Anlian'
'Zhu, Xiaoyang'
'Jin, Song'
_publ_section_title
;
 Incorporating Large A Cations into Lead Iodide Perovskite Cages: Relaxed
 Goldschmidt Tolerance Factor and Impact on Exciton-Phonon Interaction.
;
_journal_issue                   8
_journal_name_full               'ACS central science'
_journal_page_first              1377
_journal_page_last               1386
_journal_paper_doi               10.1021/acscentsci.9b00367
_journal_volume                  5
_journal_year                    2019
_chemical_formula_moiety         '0.5(I14 Pb4), 2(C6 H16 N), C H6 N'
_chemical_formula_sum            'C13 H38 I7 N3 Pb2'
_chemical_formula_weight         1539.14
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-04-30
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.030(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   45.146(16)
_cell_length_b                   8.814(3)
_cell_length_c                   8.695(3)
_cell_measurement_reflns_used    9941
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.57
_cell_measurement_theta_min      3.29
_cell_volume                     3407(2)
_computing_cell_refinement       'SAINT+ Ver. 8.34A (Bruker-AXS, 2014)'
_computing_data_collection       'APEX2 Ver. 2014.11-0 (Bruker-AXS, 2014)'
_computing_data_reduction        'SAINT+ Ver. 8.34A (Bruker-AXS, 2014)'
_computing_molecular_graphics    'OLEX2 (Dolomanov et al., 2009)'
_computing_publication_material  'OLEX2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2015b)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      99.99
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '0.5\ ω and 0.5\ φ scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0456
_diffrn_reflns_av_unetI/netI     0.0170
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       58
_diffrn_reflns_limit_h_min       -58
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            61721
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         27.574
_diffrn_reflns_theta_min         1.832
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    16.217
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5430
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Krause et al., 2015) was used for absorption correction.'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    3.000
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             2688
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.003
_refine_diff_density_max         2.357
_refine_diff_density_min         -1.316
_refine_diff_density_rms         0.171
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     125
_refine_ls_number_reflns         3931
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0241
_refine_ls_R_factor_gt           0.0211
_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/[σ²(Fo²)+(0.0248P)²+22.1354P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0496
_refine_ls_wR_factor_ref         0.0509
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3641
_reflns_number_total             3931
_reflns_threshold_expression     'I > 2σ(I)'
_cod_data_source_file            oc9b00367_si_002.cif
_cod_data_source_block           (HA)2(MA)Pb2I7
_cod_database_code               4514923
_shelx_shelxl_version_number     2018/1
_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_max   0.953
_shelx_estimated_absorpt_t_min   0.563
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N2-C7 = N3_$1-C8_$1
 1.47 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uiso(C8) = Uiso(C7) = Uiso(N3) = Uiso(N2)
4. Others
 Sof(N3)=Sof(H3C)=Sof(H3D)=Sof(H3E)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=0.5*(1-
 FVAR(2))
 Sof(N2)=Sof(H2C)=Sof(H2D)=Sof(H2E)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=0.5*
 FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B)
5.b Idealised Me refined as rotating group:
 N1(H1A,H1B,H1C), C1(H1D,H1E,H1F), N2(H2C,H2D,H2E), C7(H7A,H7B,H7C), N3(H3C,
 H3D,H3E), C8(H8A,H8B,H8C)
;
_olex2_submission_special_instructions 'No special instructions were received'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y, -z+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y, z-1/2'
'-x+1/2, -y+1/2, -z'
'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
_atom_site_disorder_assembly
_atom_site_disorder_group
Pb1 Pb 0.42673(2) 0.75058(2) 0.18607(2) 0.01095(5) Uani 1 1 d . . . . .
I1 I 0.35633(2) 0.71510(3) 0.14140(3) 0.01658(7) Uani 1 1 d . . . . .
I2 I 0.42898(2) 1.05290(3) -0.00873(3) 0.02040(7) Uani 1 1 d . . . . .
I3 I 0.500000 0.75307(4) 0.250000 0.01635(9) Uani 1 2 d S T P . .
I4 I 0.43021(2) 0.44742(3) 0.38541(3) 0.01647(7) Uani 1 1 d . . . . .
N1 N 0.37319(9) 0.3201(4) 0.0623(4) 0.0191(8) Uani 1 1 d . . . . .
H1A H 0.365810 0.312023 -0.041692 0.023 Uiso 1 1 calc GR . . . .
H1B H 0.393443 0.305352 0.079222 0.023 Uiso 1 1 calc GR . . . .
H1C H 0.369083 0.414209 0.096163 0.023 Uiso 1 1 calc GR . . . .
C1 C 0.23083(12) 0.0924(6) 0.3437(7) 0.0320(12) Uani 1 1 d . . . . .
H1D H 0.218762 0.086865 0.238614 0.048 Uiso 1 1 calc GR . . . .
H1E H 0.230047 0.195682 0.384378 0.048 Uiso 1 1 calc GR . . . .
H1F H 0.222783 0.021204 0.412604 0.048 Uiso 1 1 calc GR . . . .
C2 C 0.26327(11) 0.0509(6) 0.3366(6) 0.0266(11) Uani 1 1 d . . . . .
H2A H 0.274821 0.045681 0.444229 0.032 Uiso 1 1 calc R . . . .
H2B H 0.263740 -0.050951 0.289165 0.032 Uiso 1 1 calc R . . . .
C3 C 0.27839(11) 0.1637(5) 0.2429(5) 0.0212(9) Uani 1 1 d . . . . .
H3A H 0.266544 0.170583 0.136034 0.025 Uiso 1 1 calc R . . . .
H3B H 0.278269 0.265059 0.291727 0.025 Uiso 1 1 calc R . . . .
C4 C 0.31061(10) 0.1216(5) 0.2321(5) 0.0185(9) Uani 1 1 d . . . . .
H4A H 0.310687 0.022415 0.178810 0.022 Uiso 1 1 calc R . . . .
H4B H 0.322291 0.110358 0.338911 0.022 Uiso 1 1 calc R . . . .
C5 C 0.32591(11) 0.2391(5) 0.1440(6) 0.0216(10) Uani 1 1 d . . . . .
H5A H 0.315624 0.242460 0.033752 0.026 Uiso 1 1 calc R . . . .
H5B H 0.324042 0.340434 0.190342 0.026 Uiso 1 1 calc R . . . .
C6 C 0.35876(11) 0.2031(6) 0.1495(5) 0.0218(10) Uani 1 1 d . . . . .
H6A H 0.369155 0.199933 0.259514 0.026 Uiso 1 1 calc R . . . .
H6B H 0.360731 0.101973 0.102695 0.026 Uiso 1 1 calc R . . . .
N2 N 0.5111(3) 0.8414(15) 0.6694(15) 0.022(2) Uiso 0.302(6) 1 d D . . A -1
H2C H 0.530978 0.838787 0.712660 0.027 Uiso 0.302(6) 1 calc GR . . A -1
H2D H 0.503723 0.936091 0.680289 0.027 Uiso 0.302(6) 1 calc GR . . A -1
H2E H 0.508912 0.817834 0.566102 0.027 Uiso 0.302(6) 1 calc GR . . A -1
C7 C 0.4946(4) 0.7311(16) 0.748(2) 0.022(2) Uiso 0.302(6) 1 d D . . A -1
H7A H 0.503168 0.629746 0.740577 0.033 Uiso 0.302(6) 1 calc GR . . A -1
H7B H 0.473393 0.730720 0.698786 0.033 Uiso 0.302(6) 1 calc GR . . A -1
H7C H 0.496268 0.759020 0.858656 0.033 Uiso 0.302(6) 1 calc GR . . A -1
N3 N 0.5098(5) 0.345(2) 0.346(2) 0.022(2) Uiso 0.198(6) 1 d D . . A -2
H3C H 0.515608 0.327026 0.449976 0.027 Uiso 0.198(6) 1 calc GR . . A -2
H3D H 0.496040 0.421077 0.331742 0.027 Uiso 0.198(6) 1 calc GR . . A -2
H3E H 0.526116 0.371663 0.303677 0.027 Uiso 0.198(6) 1 calc GR . . A -2
C8 C 0.4964(6) 0.207(2) 0.270(3) 0.022(2) Uiso 0.198(6) 1 d D . . A -2
H8A H 0.477932 0.182061 0.309321 0.033 Uiso 0.198(6) 1 calc GR . . A -2
H8B H 0.510654 0.122477 0.291621 0.033 Uiso 0.198(6) 1 calc GR . . A -2
H8C H 0.491549 0.223249 0.156458 0.033 Uiso 0.198(6) 1 calc GR . . A -2
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'
I I -0.4742 1.8119 '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'
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
I1 Pb1 I2 92.417(10) . 6_576
I1 Pb1 I2 98.231(9) . .
I1 Pb1 I3 174.061(10) . .
I1 Pb1 I4 92.144(10) . 6_565
I1 Pb1 I4 86.366(9) . .
I2 Pb1 I2 89.35(3) 6_576 .
I2 Pb1 I3 87.673(10) . .
I2 Pb1 I3 88.270(9) 6_576 .
I2 Pb1 I4 175.398(9) . .
I2 Pb1 I4 90.67(3) 6_576 .
I2 Pb1 I4 90.65(3) . 6_565
I2 Pb1 I4 175.392(10) 6_576 6_565
I4 Pb1 I3 87.126(10) 6_565 .
I4 Pb1 I3 87.727(9) . .
I4 Pb1 I4 88.97(3) 6_565 .
Pb1 I2 Pb1 155.753(11) 6_575 .
Pb1 I3 Pb1 179.227(14) . 2_655
Pb1 I4 Pb1 155.372(11) 6_566 .
H1A N1 H1B 109.5 . .
H1A N1 H1C 109.5 . .
H1B N1 H1C 109.5 . .
C6 N1 H1A 109.5 . .
C6 N1 H1B 109.5 . .
C6 N1 H1C 109.5 . .
H1D C1 H1E 109.5 . .
H1D C1 H1F 109.5 . .
H1E C1 H1F 109.5 . .
C2 C1 H1D 109.5 . .
C2 C1 H1E 109.5 . .
C2 C1 H1F 109.5 . .
C1 C2 H2A 109.0 . .
C1 C2 H2B 109.0 . .
H2A C2 H2B 107.8 . .
C3 C2 C1 113.0(4) . .
C3 C2 H2A 109.0 . .
C3 C2 H2B 109.0 . .
C2 C3 H3A 108.9 . .
C2 C3 H3B 108.9 . .
H3A C3 H3B 107.7 . .
C4 C3 C2 113.4(4) . .
C4 C3 H3A 108.9 . .
C4 C3 H3B 108.9 . .
C3 C4 H4A 109.0 . .
C3 C4 H4B 109.0 . .
C3 C4 C5 112.9(4) . .
H4A C4 H4B 107.8 . .
C5 C4 H4A 109.0 . .
C5 C4 H4B 109.0 . .
C4 C5 H5A 109.3 . .
C4 C5 H5B 109.3 . .
H5A C5 H5B 107.9 . .
C6 C5 C4 111.8(4) . .
C6 C5 H5A 109.3 . .
C6 C5 H5B 109.3 . .
N1 C6 C5 110.6(4) . .
N1 C6 H6A 109.5 . .
N1 C6 H6B 109.5 . .
C5 C6 H6A 109.5 . .
C5 C6 H6B 109.5 . .
H6A C6 H6B 108.1 . .
H2C N2 H2D 109.5 . .
H2C N2 H2E 109.5 . .
H2D N2 H2E 109.5 . .
C7 N2 H2C 109.5 . .
C7 N2 H2D 109.5 . .
C7 N2 H2E 109.5 . .
N2 C7 H7A 109.5 . .
N2 C7 H7B 109.5 . .
N2 C7 H7C 109.5 . .
H7A C7 H7B 109.5 . .
H7A C7 H7C 109.5 . .
H7B C7 H7C 109.5 . .
H3C N3 H3D 109.5 . .
H3C N3 H3E 109.5 . .
H3D N3 H3E 109.5 . .
C8 N3 H3C 109.5 . .
C8 N3 H3D 109.5 . .
C8 N3 H3E 109.5 . .
N3 C8 H8A 109.5 . .
N3 C8 H8B 109.5 . .
N3 C8 H8C 109.5 . .
H8A C8 H8B 109.5 . .
H8A C8 H8C 109.5 . .
H8B C8 H8C 109.5 . .
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
Pb1 I1 3.1499(12) .
Pb1 I2 3.1558(10) 6_576
Pb1 I2 3.1688(8) .
Pb1 I3 3.2573(12) .
Pb1 I4 3.1699(9) 6_565
Pb1 I4 3.1740(8) .
N1 H1A 0.9100 .
N1 H1B 0.9100 .
N1 H1C 0.9100 .
N1 C6 1.495(6) .
C1 H1D 0.9800 .
C1 H1E 0.9800 .
C1 H1F 0.9800 .
C1 C2 1.521(7) .
C2 H2A 0.9900 .
C2 H2B 0.9900 .
C2 C3 1.520(7) .
C3 H3A 0.9900 .
C3 H3B 0.9900 .
C3 C4 1.519(6) .
C4 H4A 0.9900 .
C4 H4B 0.9900 .
C4 C5 1.523(6) .
C5 H5A 0.9900 .
C5 H5B 0.9900 .
C5 C6 1.509(7) .
C6 H6A 0.9900 .
C6 H6B 0.9900 .
N2 H2C 0.9100 .
N2 H2D 0.9100 .
N2 H2E 0.9100 .
N2 C7 1.467(5) .
C7 H7A 0.9800 .
C7 H7B 0.9800 .
C7 H7C 0.9800 .
N3 H3C 0.9100 .
N3 H3D 0.9100 .
N3 H3E 0.9100 .
N3 C8 1.466(5) .
C8 H8A 0.9800 .
C8 H8B 0.9800 .
C8 H8C 0.9800 .
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
N1 H1A I1 0.91 2.72 3.619(4) 167.8 6_565 yes
N1 H1B I2 0.91 2.92 3.580(4) 130.4 1_545 yes
N1 H1C I1 0.91 2.76 3.655(4) 169.2 . yes
N2 H2C I2 0.91 3.03 3.756(14) 137.9 5_676 yes
N2 H2D I3 0.91 2.82 3.694(14) 162.0 5_676 yes
N2 H2E I3 0.91 2.77 3.677(13) 177.6 . yes
N3 H3C I3 0.91 2.91 3.72(2) 149.4 5_666 yes
N3 H3D I3 0.91 3.02 3.704(19) 132.9 . yes
N3 H3D I4 0.91 3.10 3.78(2) 133.3 . yes
N3 H3E I4 0.91 2.86 3.75(2) 168.9 2_655 yes
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
C1 C2 C3 C4 -178.8(4)
C2 C3 C4 C5 -177.5(4)
C3 C4 C5 C6 174.0(4)
C4 C5 C6 N1 -180.0(4)
