A low-dimensional ferrocenium lead-iodide perovskite ferroelastic with a narrow band gap.
Xu, Zhe-Kun; Wang, Zhong-Xia; Chemical communications (Cambridge, England) 61 (2025) 15810–15813; doi:10.1039/d5cc03384e

data_7135189
_publ_section_title
;
 A low-dimensional ferrocenium lead-iodide perovskite ferroelastic with a
 narrow band gap.
;
_journal_issue                   81
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              15810
_journal_page_last               15813
_journal_paper_doi               10.1039/d5cc03384e
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'I3 Pb, 0.5(C20 H20 Fe2)'
_chemical_formula_sum            'C10 H10 Fe I3 Pb'
_chemical_formula_weight         773.92
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-09-06
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2025-10-15 deposited with the CCDC.	2025-10-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.820(2)
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   19.1013(4)
_cell_length_b                   18.1903(4)
_cell_length_c                   13.8623(3)
_cell_measurement_reflns_used    10306
_cell_measurement_temperature    221(3)
_cell_measurement_theta_max      31.1960
_cell_measurement_theta_min      2.1640
_cell_volume                     4810.74(18)
_computing_cell_refinement       'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      221(3)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.792
_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    -63.00 -37.00   0.50    2.00    --    5.05 -77.00  90.00   52
  2  \w    -65.00   7.00   0.50    2.00    --   -5.21 -37.00 150.00  144
  3  \w      1.00  28.00   0.50    2.00    --    5.05 -77.00  90.00   54
  4  \w    -65.00   8.00   0.50    2.00    --    5.05 -57.00 -90.00  146
  5  \w    -17.00  16.00   0.50    2.00    --   -5.21 -99.00-120.00   66
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0117711000
_diffrn_orient_matrix_UB_12      -0.0356469000
_diffrn_orient_matrix_UB_13      -0.0137441000
_diffrn_orient_matrix_UB_21      0.0297731000
_diffrn_orient_matrix_UB_22      -0.0156138000
_diffrn_orient_matrix_UB_23      0.0247916000
_diffrn_orient_matrix_UB_31      -0.0188931000
_diffrn_orient_matrix_UB_32      -0.0024104000
_diffrn_orient_matrix_UB_33      0.0426822000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0243
_diffrn_reflns_av_unetI/netI     0.0269
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.792
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            19294
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.792
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.965
_diffrn_reflns_theta_min         2.098
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    17.137
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.35630
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.108a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dull dark black'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    3.206
_exptl_crystal_description       plate
_exptl_crystal_F_000             4044
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.789
_refine_diff_density_min         -0.877
_refine_diff_density_rms         0.149
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     237
_refine_ls_number_reflns         6056
_refine_ls_number_restraints     474
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.0325
_refine_ls_R_factor_gt           0.0248
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0228P)^2^+13.3807P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0519
_refine_ls_wR_factor_ref         0.0534
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5174
_reflns_number_total             6056
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc03384e3.cif
_cod_data_source_block           Fc_PbI3_220K
_cod_database_code               7135189
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C H Fe I Pb'
_chemical_oxdiff_usercomment     \
_shelx_estimated_absorpt_t_max   0.279
_shelx_estimated_absorpt_t_min   0.279
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C1A-C13 = C1A-C16 = C15-C13 = C15-C11 = C16-C11
 1.42 with sigma of 0.02
 Fe2-C17 = Fe2-C12 = Fe2-C19 = Fe2-C13 = Fe2-C1A = Fe2-C11
 2.05 with sigma of 0.02
 C18-C17 = C17-C12 = C19-C18 = C19-C14 = C14-C12
 1.42 with sigma of 0.02
 C2-C1 = C3-C2 = C4-C3 = C5-C4 = C5-C1
 1.42 with sigma of 0.02
 C2A-C1A = C3A-C2A = C4A-C3A = C5A-C4A = C5A-C1A
 1.42 with sigma of 0.02
 C9-C8 = C9-C10 = C6-C10 = C7-C6 = C8-C7
 1.42 with sigma of 0.02
 C9A-C8A = C9A-C10A = C6A-C10A = C7A-C6A = C8A-C7A
 1.42 with sigma of 0.02
 C7-C10 \\sim C7A-C10A
 with sigma of 0.04
 C7-C8 \\sim C7A-C8A
 with sigma of 0.02
 C6-C8 \\sim C6A-C8A
 with sigma of 0.04
 C10-C6 \\sim C10A-C6A
 with sigma of 0.02
 C10-C9 \\sim C10A-C9A
 with sigma of 0.02
 C7-C6 \\sim C7A-C6A
 with sigma of 0.02
 Fe1-C8 \\sim Fe1-C8A
 with sigma of 0.04
 C7-C9 \\sim C7A-C9A
 with sigma of 0.04
 C10-C8 \\sim C10A-C8A
 with sigma of 0.04
 C9-C8 \\sim C9A-C8A
 with sigma of 0.02
 C6-C9 \\sim C6A-C9A
 with sigma of 0.04
 Fe1-C7 \\sim Fe1-C7A
 with sigma of 0.04
 Fe1-C10 \\sim Fe1-C10A
 with sigma of 0.04
 Fe1-C6 \\sim Fe1-C6A
 with sigma of 0.04
 Fe1-C9 \\sim Fe1-C9A
 with sigma of 0.04
 C4-C5 \\sim C4A-C5A
 with sigma of 0.02
 C4-C1 \\sim C4A-C20
 with sigma of 0.04
 C3-C2 \\sim C3A-C2A
 with sigma of 0.02
 Fe1-C5 \\sim Fe1-C5A
 with sigma of 0.04
 C3-C1 \\sim C3A-C20
 with sigma of 0.04
 C4-C2 \\sim C4A-C2A
 with sigma of 0.04
 C3-C5 \\sim C3A-C5A
 with sigma of 0.04
 Fe1-C4 \\sim Fe1-C4A
 with sigma of 0.02
 C4-C3 \\sim C4A-C3A
 with sigma of 0.02
 C2-C5 \\sim C2A-C5A
 with sigma of 0.04
 C2-C1 \\sim C2A-C20
 with sigma of 0.02
 C1-C5 \\sim C20-C5A
 with sigma of 0.02
 Fe1-C3 \\sim Fe1-C3A
 with sigma of 0.02
 Fe1-C2 \\sim Fe1-C2A
 with sigma of 0.02
 Fe1-C1 \\sim Fe1-C20
 with sigma of 0.02
3. Rigid bond restraints
 C7, C10, C6, C9, C8, C10A, C6A, C7A, C8A, C9A
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
C7 \\sim C10 \\sim C6 \\sim C9 \\sim C8 \\sim C10A \\sim C6A \\sim C7A \\sim
C8A \\sim C9A: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 2A
Uanis(C13) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C16)
\\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(Fe2) \\sim Ueq, Uanis(C14) \\sim Ueq,
Uanis(C12) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C19)
\\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C7) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C9) \\sim
Ueq, Uanis(C8) \\sim Ueq, Uanis(C10A) \\sim Ueq, Uanis(C6A) \\sim Ueq,
Uanis(C7A) \\sim Ueq, Uanis(C8A) \\sim Ueq, Uanis(C9A) \\sim Ueq: with sigma of
0.02 and sigma for terminal atoms of 0.04
Uanis(C7) = Uanis(C10) = Uanis(C6) = Uanis(C9) = Uanis(C8) = Uanis(C10A) =
Uanis(C6A) = Uanis(C7A) = Uanis(C8A) = Uanis(C9A)
Uanis(C4) = Uanis(C3) = Uanis(C2) = Uanis(C1) = Uanis(C5) = Uanis(C4A) =
Uanis(C3A) = Uanis(C2A) = Uanis(C20) = Uanis(C5A)
5. Rigid body (RIGU) restrains
 C17, C12, C14, C19, C18, C1A, C13, C16, C15, C11
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C7, C10, C6, C9, C8, C10A, C6A, C7A, C8A, C9A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: C4(0.5) H4(0.5) C7(0.5) H7(0.5) C3(0.5) H3(0.5) C14(0.5) H14(0.5)
 C13(0.5) H13(0.5) C15(0.5) H15(0.5) C2(0.5) H2(0.5) C11(0.5) H11(0.5) C10(0.5)
 H10(0.5) C12(0.5) H12(0.5) C1(0.5) H1(0.5) C6(0.5) H6(0.5) C5(0.5) H5(0.5)
 C9(0.5) H9(0.5) C8(0.5) H8(0.5) C16(0.5) H16(0.5) C17(0.5) H17(0.5) C18(0.5)
 H18(0.5) C19(0.5) H19(0.5) C1A(0.5) H1A(0.5) C10A(0.5) H10A(0.5) C6A(0.5)
 H6A(0.5) C7A(0.5) H7A(0.5) C8A(0.5) H8A(0.5) C9A(0.5) H9A(0.5) C4A(0.5)
 H4A(0.5) C3A(0.5) H3A(0.5) C2A(0.5) H2A(0.5) C20(0.5) H20(0.5) C5A(0.5)
 H5A(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C7(H7), C3(H3), C14(H14), C13(H13), C15(H15), C2(H2), C11(H11),
 C10(H10), C12(H12), C1(H1), C6(H6), C5(H5), C9(H9), C8(H8), C16(H16), C17(H17),
  C18(H18), C19(H19), C1A(H1A), C10A(H10A), C6A(H6A), C7A(H7A), C8A(H8A),
 C9A(H9A), C4A(H4A), C3A(H3A), C2A(H2A), C20(H20), C5A(H5A)
;
_shelx_res_checksum              69821
_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 2.523
_oxdiff_exptl_absorpt_empirical_full_min 0.653