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_7134987
_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, 0.333(C18 H54 N6)'
_chemical_formula_sum            'C15 H27 Fe3 N2 O18'
_chemical_formula_weight         690.93
_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                   8.4183(6)
_cell_length_b                   8.4183(6)
_cell_length_c                   63.025(5)
_cell_measurement_reflns_used    928
_cell_measurement_temperature    422.98(10)
_cell_measurement_theta_max      25.9720
_cell_measurement_theta_min      2.8830
_cell_volume                     3868.1(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.9f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.9f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.9f (Rigaku OD, 2015)'
_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      422.98(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -53.00  30.00   0.50    2.00    --   12.90 -57.00 -60.00  166
  2  \w    -71.00   5.00   0.50    2.00    --  -13.20 -77.00 -90.00  152
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro: 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      0.0773598000
_diffrn_orient_matrix_UB_12      0.0681447000
_diffrn_orient_matrix_UB_13      -0.0055669000
_diffrn_orient_matrix_UB_21      0.0227733000
_diffrn_orient_matrix_UB_22      0.0598354000
_diffrn_orient_matrix_UB_23      0.0088234000
_diffrn_orient_matrix_UB_31      0.0543229000
_diffrn_orient_matrix_UB_32      -0.0351813000
_diffrn_orient_matrix_UB_33      0.0042329000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0360
_diffrn_reflns_av_unetI/netI     0.0299
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       67
_diffrn_reflns_limit_l_min       -74
_diffrn_reflns_number            3540
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.868
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.750
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82249
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.9f (Rigaku Oxford Diffraction, 2015)
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    1.780
_exptl_crystal_description       block
_exptl_crystal_F_000             2118
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.422
_refine_diff_density_min         -0.347
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     84
_refine_ls_number_reflns         768
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.143
_refine_ls_R_factor_all          0.0464
_refine_ls_R_factor_gt           0.0342
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0422P)^2^+6.8628P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0855
_refine_ls_wR_factor_ref         0.0942
_reflns_Friedel_coverage         0.000
_reflns_number_gt                567
_reflns_number_total             768
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc03844h2.cif
_cod_data_source_block           3HTP
_cod_depositor_comments
'Adding full bibliography for 7134983--7134988.cif.'
_cod_original_cell_volume        3868.0(7)
_cod_original_sg_symbol_H-M      'R -3 c'
_cod_database_code               7134987
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.844
_shelx_estimated_absorpt_t_min   0.622
_reflns_odcompleteness_completeness 99.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C5-C4
 1.54 with sigma of 0.02
 N1-C4
 1.52 with sigma of 0.02
 N1-C3
 1.52 with sigma of 0.02
 C3-C3_$1
 1.52 with sigma of 0.02
 C4-C3
 2.45 with sigma of 0.02
3. Restrained planarity
 C3, C5, C4, N1
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C5) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(C3) \\sim
Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Fixed Sof: C3(0.333333) H3B(0.333333) H3A(0.333333) N1(0.333333)
 H1A(0.333333) H1B(0.333333) C4(0.333333) H4A(0.333333) H4B(0.333333)
 C5(0.333333) H5A(0.333333) H5B(0.333333) H5C(0.333333)
6.a Riding coordinates:
 C3(H3B,H3A), N1(H1A,H1B)
6.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C1(H1)
6.d Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C)
;
_shelx_res_checksum              42981
_shelx_hkl_checksum              45501
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.109
_oxdiff_exptl_absorpt_empirical_full_min 0.894