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_7134988
_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(C12 H42 N6)'
_chemical_formula_sum            'C13 H23 Fe3 N2 O18'
_chemical_formula_weight         662.88
_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     dual
_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                   8.2967(5)
_cell_length_b                   8.2967(5)
_cell_length_c                   62.793(6)
_cell_measurement_reflns_used    5418
_cell_measurement_temperature    393.00(10)
_cell_measurement_theta_max      29.8460
_cell_measurement_theta_min      3.8600
_cell_volume                     3743.3(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.63a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.63a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.63a (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    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      393.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.922
_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    -59.00  28.00   0.50    1.71    --    0.00 -57.00 -30.00  174
  2  \w    -89.00 -47.00   0.50    1.71    --    0.00 -77.00 120.00   84
;
_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      -0.0965936000
_diffrn_orient_matrix_UB_12      -0.0304282000
_diffrn_orient_matrix_UB_13      -0.0000285000
_diffrn_orient_matrix_UB_21      -0.0132409000
_diffrn_orient_matrix_UB_22      -0.0610265000
_diffrn_orient_matrix_UB_23      -0.0085721000
_diffrn_orient_matrix_UB_31      -0.0157069000
_diffrn_orient_matrix_UB_32      -0.0713140000
_diffrn_orient_matrix_UB_33      0.0073507000
_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  0.0734
_diffrn_reflns_av_unetI/netI     0.0534
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.922
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       81
_diffrn_reflns_limit_l_min       -83
_diffrn_reflns_number            5625
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.922
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.760
_diffrn_reflns_theta_min         3.845
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.805
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.20103
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.63a (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    1.764
_exptl_crystal_description       BLOCK
_exptl_crystal_F_000             2022
_refine_diff_density_max         0.750
_refine_diff_density_min         -0.575
_refine_diff_density_rms         0.087
_refine_ls_extinction_coef       0.0068(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     75
_refine_ls_number_reflns         1105
_refine_ls_number_restraints     48
_refine_ls_restrained_S_all      1.115
_refine_ls_R_factor_all          0.0489
_refine_ls_R_factor_gt           0.0378
_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^)+(0.0568P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1027
_refine_ls_wR_factor_ref         0.1083
_reflns_Friedel_coverage         0.000
_reflns_number_gt                814
_reflns_number_total             1105
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc03844h2.cif
_cod_data_source_block           2HTP
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_crystal_colour_primary' value 'BLACK' was changed
to 'black' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 7134983--7134988.cif.
;
_cod_original_cell_volume        3743.3(6)
_cod_original_sg_symbol_H-M      'R -3 c'
_cod_database_code               7134988
_shelx_shelxl_version_number     2019/3
_reflns_odcompleteness_completeness 99.43
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H) groups, All C(H,H,H) groups, All N(H,H) groups
2. Restrained distances
 N1_$1-C3_$1
 1.53 with sigma of 0.02
 N1_$2-C3_$2 = N1_$2-C4 = C3_$3-C3_$2 = N1_$3-C3_$3 = N1_$3-C4_$3
 1.53 with sigma of 0.02
3. Rigid bond restraints
 C3, N1, C4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C4 \\sim N1 \\sim C3: within 3.8A with sigma of 0.01 and sigma for terminal
atoms of 0.03 within 3.8A
Uanis(C4) \\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(C3) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.2
5. Rigid body (RIGU) restrains
 C4, N1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: N1(0.333333) H1a(0.333333) H1b(0.333333) C3(0.333333)
 H3b(0.333333) H3a(0.333333) C4(0.333333) H4a(0.333333) H4b(0.333333)
 H4c(0.333333)
7.a Riding coordinates:
 N1(H1a,H1b), C3(H3b,H3a), C4(H4a,H4b,H4c)
7.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C1(H1)
;
_shelx_res_checksum              73150
_shelx_hkl_checksum              10005
_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 2.842
_oxdiff_exptl_absorpt_empirical_full_min 0.539