Organic ammonium modulated mixed-valence multiferroics exhibiting large spontaneous strain and exchange bias.
Yan, Qin-Yuan; Han, Song-De; Xu, Ting; Ji, Cui-Xian; Lv, Lin-Lin; Yao, Zhao-Quan; Zhao, Jiong-Peng; Liu, Fu-Chen; Chemical communications (Cambridge, England) 61 (2025) 16412–16415; doi:10.1039/d5cc03844h

data_7134986
_publ_section_title
;
 Organic ammonium modulated mixed-valence multiferroics exhibiting large
 spontaneous strain and exchange bias.
;
_journal_issue                   84
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              16412
_journal_page_last               16415
_journal_paper_doi               10.1039/d5cc03844h
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C9 H9 Fe3 O18, C3 H12 N2, H2 O'
_chemical_formula_sum            'C12 H23 Fe3 N2 O19'
_chemical_formula_weight         666.87
_space_group_crystal_system      trigonal
_space_group_IT_number           167
_space_group_name_Hall           '-R 3 2"c'
_space_group_name_H-M_alt        'R -3 c :H'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2025-06-02
_audit_creation_method
;
Olex2 1.5-ac6-020
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6966)
;
_audit_update_record
;
2025-07-07 deposited with the CCDC.	2025-09-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   8.2548(6)
_cell_length_b                   8.2548(6)
_cell_length_c                   63.391(5)
_cell_measurement_reflns_used    1932
_cell_measurement_temperature    403.00(10)
_cell_measurement_theta_max      29.8670
_cell_measurement_theta_min      5.2770
_cell_volume                     3740.9(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-ac6-020 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-020 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution
'olex2.solve 1.5-ac6-020 (Bourhis et al., 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      403.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.930
_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    -26.00  28.00   0.50    4.16    --    0.00 -57.00 150.00  108
  2  \w    -87.00 -20.00   0.50    4.16    --    0.00 -77.00 -60.00  134
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual offset/far'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0325806000
_diffrn_orient_matrix_UB_12      0.0715563000
_diffrn_orient_matrix_UB_13      -0.0077322000
_diffrn_orient_matrix_UB_21      -0.0548312000
_diffrn_orient_matrix_UB_22      0.0348394000
_diffrn_orient_matrix_UB_23      0.0046094000
_diffrn_orient_matrix_UB_31      0.0760214000
_diffrn_orient_matrix_UB_32      0.0591646000
_diffrn_orient_matrix_UB_33      0.0066493000
_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  0.0778
_diffrn_reflns_av_unetI/netI     0.0587
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.930
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       84
_diffrn_reflns_limit_l_min       -78
_diffrn_reflns_number            5423
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.930
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.822
_diffrn_reflns_theta_min         3.839
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.809
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.50862
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.776
_exptl_crystal_description       block
_exptl_crystal_F_000             2034
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.301
_refine_diff_density_min         -0.393
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     101
_refine_ls_number_reflns         1124
_refine_ls_number_restraints     112
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0458
_refine_ls_R_factor_gt           0.0346
_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/[\s^2^(Fo^2^)+(0.0401P)^2^+4.4057P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0947
_refine_ls_wR_factor_ref         0.1023
_reflns_Friedel_coverage         0.000
_reflns_number_gt                848
_reflns_number_total             1124
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc03844h2.cif
_cod_data_source_block           1HTP
_cod_depositor_comments
'Adding full bibliography for 7134983--7134988.cif.'
_cod_original_cell_volume        3740.9(6)
_cod_original_sg_symbol_H-M      'R -3 c'
_cod_database_code               7134986
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.840
_shelx_estimated_absorpt_t_min   0.714
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups, All N(H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 N1-C1 = N2-C3 = N2-C2 = C1-C2
 1.48 with sigma of 0.02
 N2-C1
 2.5 with sigma of 0.02
 N2-C3 = N2-C2 = C1-C2 = N1-C1
 1.48 with sigma of 0.02
3. Rigid bond restraints
 N1, C3, O1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1, N1, C2, N2, C3, O1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C3 \\sim N1 \\sim O1: within 3.8A with sigma of 0.01 and sigma for terminal
atoms of 0.03 within 3.8A
N1 \\sim C1 \\sim C2 \\sim N2 \\sim C3 \\sim O1: within 3.8A with sigma of 0.01
and sigma for terminal atoms of 0.03 within 3.8A
Uanis(N1) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(N2) \\sim
Ueq, Uanis(C3) \\sim Ueq, Uanis(O1) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.2
5. Others
 Fixed Sof: N1(0.166667) H1A(0.166667) H1C(0.166667) H1B(0.166667)
 C3(0.166667) H3A(0.166667) H3B(0.166667) H3C(0.166667) O1(0.166667)
 H1F(0.166667) H1G(0.166667) C2(0.166667) H2A(0.166667) H2B(0.166667)
 N2(0.166667) H2D(0.166667) H2C(0.166667) C1(0.166667) H1D(0.166667)
 H1E(0.166667)
6.a Riding coordinates:
 N1(H1A,H1C,H1B), C3(H3A,H3B,H3C), O1(H1F,H1G), N2(H2D,H2C), C1(H1D,H1E)
6.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B)
6.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5)
;
_shelx_res_checksum              8932
_shelx_hkl_checksum              12634
_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 1.340
_oxdiff_exptl_absorpt_empirical_full_min 0.734