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_1574946
_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 H26 Mn2 N10 O4 Re'
_chemical_formula_sum            'C38 H26 Mn2 N10 O4 Re'
_chemical_formula_weight         982.77
_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
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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                   14.3992(3)
_cell_length_b                   14.3992(3)
_cell_length_c                   18.2847(7)
_cell_measurement_reflns_used    9019
_cell_measurement_temperature    270
_cell_measurement_theta_max      29.9610
_cell_measurement_theta_min      2.5810
_cell_volume                     3791.09(18)
_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      270
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.850
_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     35.00  61.00   0.50    2.00    --    5.00  45.00  30.00   52
  2  \w      3.00  29.00   0.50    2.00    --    5.00  45.00  30.00   52
  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  0.0234
_diffrn_reflns_av_unetI/netI     0.0260
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.850
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            18827
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.850
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.044
_diffrn_reflns_theta_min         2.289
_exptl_absorpt_coefficient_mu    3.895
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65492
_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    1.722
_exptl_crystal_description       block
_exptl_crystal_F_000             1924
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.844
_refine_diff_density_min         -1.804
_refine_diff_density_rms         0.122
_refine_ls_extinction_coef       0.00095(13)
_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   1.183
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     349
_refine_ls_number_reflns         5174
_refine_ls_number_restraints     258
_refine_ls_restrained_S_all      1.207
_refine_ls_R_factor_all          0.0538
_refine_ls_R_factor_gt           0.0422
_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^)+(0.0280P)^2^+12.2064P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0967
_refine_ls_wR_factor_ref         0.1008
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4312
_reflns_number_total             5174
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08700c2.cif
_cod_data_source_block           mnremecn_270_c_2
_cod_depositor_comments
'Adding full bibliography for 1574937--1574947.cif.'
_cod_original_cell_volume        3791.1(2)
_cod_original_sg_symbol_H-M      'P 4/n'
_cod_database_code               1574946
_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
 N7-C19
 1.14 with sigma of 0.02
 N8-C21
 1.14 with sigma of 0.02
 C19-C20
 1.456 with sigma of 0.01
 C21-N8
 1.137 with sigma of 0.01
 C19-N7
 1.137 with sigma of 0.01
 C21-C22
 1.456 with sigma of 0.01
 C22-N8
 2.593 with sigma of 0.02
 C20-N7
 2.593 with sigma of 0.02
 N8-C22
 2.59 with sigma of 0.04
 N7-C20
 2.59 with sigma of 0.04
 Re2-C9AA \\sim Re2-C9AB
 with sigma of 0.02
 Mn1-N18 \\sim Mn1-N18A
 with sigma of 0.02
 N18-C9AA \\sim N18A-C9AB
 with sigma of 0.02
 Re2-N18 \\sim Re2-N18A
 with sigma of 0.04
 Mn1-C9AA \\sim Mn1-C9AB
 with sigma of 0.04
 Mn1-N2 \\sim Mn1-N2A
 with sigma of 0.02
 N2-C10 \\sim N2A-C10A
 with sigma of 0.02
 N2-C9 \\sim N2A-C9A
 with sigma of 0.02
 C16-C11 \\sim C16-C11A
 with sigma of 0.02
 C10-C11 \\sim C10A-C11A
 with sigma of 0.02
 C8-C9 \\sim C8-C9A
 with sigma of 0.02
 C11-C12 \\sim C11A-C12A
 with sigma of 0.02
 C14-C13 \\sim C14-C13A
 with sigma of 0.02
 C13-C12 \\sim C13A-C12A
 with sigma of 0.02
 Re1-C17 \\sim Re1-C17A
 with sigma of 0.02
 Mn1-C10 \\sim Mn1-C10A
 with sigma of 0.04
 Mn1-C9 \\sim Mn1-C9A
 with sigma of 0.04
 Mn1-N3 \\sim Mn1-N3A
 with sigma of 0.02
 N2-C8 \\sim N2A-C8
 with sigma of 0.04
 C17-N3 \\sim C17A-N3A
 with sigma of 0.02
 N2-C11 \\sim N2A-C11A
 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
 C10-C9 \\sim C10A-C9A
 with sigma of 0.04
 C10-C12 \\sim C10A-C12A
 with sigma of 0.04
 C11-C13 \\sim C11A-C13A
 with sigma of 0.04
 C14-C12 \\sim C14-C12A
 with sigma of 0.04
 Re1-N3 \\sim Re1-N3A
 with sigma of 0.04
 Mn1-C17 \\sim Mn1-C17A
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
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
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
N2 \\sim C12 \\sim C10 \\sim C9 \\sim C13 \\sim C11 \\sim C8 \\sim C14: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C13A \\sim C9A \\sim C12A \\sim N2A \\sim C10A \\sim C11A \\sim C8 \\sim C14:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Re2 \\sim C9AB \\sim N18A \\sim Mn1: within 2.5A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2.5A
Re2 \\sim C9AA \\sim N18 \\sim Mn1: 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
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
5. Rigid body (RIGU) restrains
 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
 C8, C9A, N2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H8BC)=Sof(H8BD)=Sof(H14A)=Sof(C13A)=Sof(H13A)=Sof(C12A)=Sof(H12A)=
 Sof(C11A)=Sof(C10A)=Sof(H10A)=Sof(N2A)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(N18A)=
 Sof(C9AB)=Sof(N3A)=Sof(C17A)=1-FVAR(1)
 Sof(N2)=Sof(N18)=Sof(C17)=Sof(N3)=Sof(C9AA)=Sof(C10)=Sof(H10)=Sof(H8AA)=
 Sof(H8AB)=Sof(C11)=Sof(H14)=Sof(C13)=Sof(H13)=Sof(C9)=Sof(H9A)=Sof(H9B)=
 Sof(C12)=Sof(H12)=FVAR(1)
7.a Secondary CH2 refined with riding coordinates:
 C8(H8AA,H8AB), C8(H8BC,H8BD), C9(H9A,H9B), C9A(H9AA,H9AB)
7.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C10(H10), C4(H4), C7(H7), C15(H15), C14(H14), C14(H14A), C13(H13),
 C5(H5), C12(H12), C13A(H13A), C12A(H12A), C10A(H10A)
;
_shelx_res_checksum              18620
_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
;