A ferroelectric proton conductor with colossal polarization induced by in-plane symmetry breaking in a two-dimensional coordination polymer.
Song, Yanqing; Tsuji, Yuta; Sugimoto, Kunihisa; Kikuchi, Takashi; Shi, Yuxin; Murakami, Yusuke; Hiramatsu, Kotaro; Le Ouay, Benjamin; Ohba, Masaaki; Ohtani, Ryo; Chemical science 16 (2025) 13413–13421; doi:10.1039/d4sc08700c

data_1574940
_publ_section_title
;
 A ferroelectric proton conductor with colossal polarization induced by
 in-plane symmetry breaking in a two-dimensional coordination polymer.
;
_journal_issue                   29
_journal_name_full               'Chemical science'
_journal_page_first              13413
_journal_page_last               13421
_journal_paper_doi               10.1039/d4sc08700c
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C38 H28 Mn2 N10 O4 Re'
_chemical_formula_sum            'C38 H28 Mn2 N10 O4 Re'
_chemical_formula_weight         984.78
_space_group_crystal_system      tetragonal
_space_group_IT_number           85
_space_group_name_Hall           '-P 4a'
_space_group_name_H-M_alt        'P 4/n :2'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-11-19
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-16 deposited with the CCDC.	2025-06-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.3742(3)
_cell_length_b                   14.3742(3)
_cell_length_c                   18.1157(6)
_cell_measurement_reflns_used    11106
_cell_measurement_temperature    170
_cell_measurement_theta_max      30.1470
_cell_measurement_theta_min      2.6370
_cell_volume                     3743.02(17)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      170
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.876
_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    -69.00 -44.00   0.50    2.00    --  -10.20  45.00  30.00   50
  2  \w     20.00  60.00   0.50    2.00    --  -10.20  45.00  30.00   80
  3  \w    -99.00   7.00   0.50    2.00    --  -10.20  45.00  60.00  212
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC10 (RCD3): fixed-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0241
_diffrn_reflns_av_unetI/netI     0.0254
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.876
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            20197
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.876
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.980
_diffrn_reflns_theta_min         2.298
_exptl_absorpt_coefficient_mu    3.946
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71834
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_density_diffrn    1.748
_exptl_crystal_description       block
_exptl_crystal_F_000             1932
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         4.520
_refine_diff_density_min         -3.427
_refine_diff_density_rms         0.205
_refine_ls_extinction_coef       0.0040(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.138
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     349
_refine_ls_number_reflns         5240
_refine_ls_number_restraints     352
_refine_ls_restrained_S_all      1.145
_refine_ls_R_factor_all          0.0626
_refine_ls_R_factor_gt           0.0574
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0512P)^2^+33.8877P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1446
_refine_ls_wR_factor_ref         0.1469
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4727
_reflns_number_total             5240
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08700c2.cif
_cod_data_source_block           mnremecn_170_c_2
_cod_depositor_comments
'Adding full bibliography for 1574937--1574947.cif.'
_cod_original_cell_volume        3743.0(2)
_cod_original_sg_symbol_H-M      'P 4/n'
_cod_database_code               1574940
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.499(3)
 0.501(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
3. Restrained distances
 N8-C21
 1.14 with sigma of 0.02
 N7-C19
 1.14 with sigma of 0.02
 C21-N8
 1.137 with sigma of 0.01
 C22-N8
 2.593 with sigma of 0.02
 C19-N7
 1.137 with sigma of 0.01
 C19-C20
 1.456 with sigma of 0.01
 C20-N7
 2.593 with sigma of 0.02
 C21-C22
 1.456 with sigma of 0.01
 N8-C22
 2.59 with sigma of 0.04
 N7-C20
 2.59 with sigma of 0.04
 Re1-C17 \\sim Re1-C17A
 with sigma of 0.02
 Re2-C18 \\sim Re2-C18A
 with sigma of 0.02
 C17-N3 \\sim C17A-N3A
 with sigma of 0.02
 Mn1-C17 \\sim Mn1-C17A
 with sigma of 0.04
 Mn1-N4 \\sim Mn1-N4A
 with sigma of 0.02
 C18-N4 \\sim C18A-N4A
 with sigma of 0.02
 Mn1-N3 \\sim Mn1-N3A
 with sigma of 0.02
 Re2-N4 \\sim Re2-N4A
 with sigma of 0.04
 Mn1-C18 \\sim Mn1-C18A
 with sigma of 0.04
 N2-C9 \\sim N2A-C9A
 with sigma of 0.02
 Mn1-N2 \\sim Mn1-N2A
 with sigma of 0.02
 N2-C10 \\sim N2A-C10A
 with sigma of 0.02
 Mn1-C9 \\sim Mn1-C9A
 with sigma of 0.04
 N1-C9 \\sim N1-C9A
 with sigma of 0.04
 Re1-N3 \\sim Re1-N3A
 with sigma of 0.04
 C10-C9 \\sim C10A-C9A
 with sigma of 0.04
 N2-C11 \\sim N2A-C11A
 with sigma of 0.04
 C9A-C8 \\sim C9-C8
 with sigma of 0.02
 Re2-N8 \\sim Re1-N7
 with sigma of 0.02
 C16-C11 \\sim C16-C11A
 with sigma of 0.02
 C14-C13 \\sim C14-C13A
 with sigma of 0.02
 C11-C10 \\sim C11A-C10A
 with sigma of 0.02
 C11-C12 \\sim C11A-C12A
 with sigma of 0.02
 C13-C12 \\sim C13A-C12A
 with sigma of 0.02
 Mn1-C10 \\sim Mn1-C10A
 with sigma of 0.04
 C16-C10 \\sim C16-C10A
 with sigma of 0.04
 C16-C12 \\sim C16-C12A
 with sigma of 0.04
 C14-C12 \\sim C14-C12A
 with sigma of 0.04
 C11-C13 \\sim C11A-C13A
 with sigma of 0.04
 C10-C12 \\sim C10A-C12A
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
Re1 \\sim C17A \\sim N3A \\sim Mn1: within 2.5A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2.5A
C13 \\sim C14 \\sim C12 \\sim C11 \\sim C10 \\sim N2 \\sim C9 \\sim N1 \\sim
C8: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C14 \\sim C13A \\sim C12A \\sim C11A \\sim C10A \\sim N2A \\sim C9A \\sim C8
\\sim N1: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
Re2 \\sim N8 \\sim C21 \\sim C22: within 2.5A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2.5A
N7 \\sim C19 \\sim C20: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Re1 \\sim N7 \\sim C19 \\sim C20: within 2.5A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2.5A
N5 \\sim Re1: within 2.5A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2.5A
Re1 \\sim C17 \\sim N3 \\sim Mn1: within 2.5A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2.5A
Re2 \\sim C18 \\sim N4 \\sim Mn1: within 2.5A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2.5A
Re2 \\sim C18A \\sim N4A \\sim Mn1: within 2.5A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2.5A
Uanis(C17A) \\sim Ueq, Uanis(N3A) \\sim Ueq, Uanis(N3) \\sim Ueq, Uanis(C17)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C8) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 N2, C11, C12, C13, C9, C10
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N2A, C9A, C11A, C12A, C13A, C8, C10A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N8, C21, C22
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N7, C19, C20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H14A)=Sof(N2A)=Sof(C11A)=Sof(C13A)=Sof(H13A)=Sof(C10A)=Sof(H10A)=
 Sof(C12A)=Sof(H12A)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H8BC)=Sof(H8BD)=Sof(C17A)=
 Sof(N3A)=Sof(N4A)=Sof(C18A)=1-FVAR(1)
 Sof(N2)=Sof(H14)=Sof(C18)=Sof(N4)=Sof(C17)=Sof(C11)=Sof(N3)=Sof(C13)=Sof(H13)=
 Sof(C10)=Sof(H10)=Sof(C12)=Sof(H12)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H8AA)=
 Sof(H8AB)=FVAR(1)
7.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C9A(H9AA,H9AB), C8(H8AA,H8AB), C8(H8BC,H8BD)
7.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C14(H14A), C15(H15), C2(H2), C13(H13), C4(H4), C7(H7), C5(H5),
 C3(H3), C10(H10), C12(H12), C13A(H13A), C10A(H10A), C12A(H12A)
;
_shelx_res_checksum              99791
_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
;