57Fe Mössbauer Spectroscopy and High-Pressure Structural Analysis for Mechanism of Pressure-Induced Unique Magnetic Behaviour in (cation)[FeIIFeIII(dto)3] (cation = Ph4P and nPrPh3P; dto = 1,2-dithiooxalato)
Taniai, Ryosuke; Endo, Tsubasa; KANETOMO, Takuya; Okazawa, Atsushi; Kadobayashi, Hirokazu; Kawaguchi, Saori I.; Enomoto, Masaya; Dalton Transactions  (2023) –; doi:10.1039/D3DT00858D

data_7713114
_publ_section_title
;
 57Fe M\"ossbauer Spectroscopy and High-Pressure Structural Analysis for
 Mechanism of Pressure-Induced Unique Magnetic Behaviour in
 (cation)[FeIIFeIII(dto)3] (cation = Ph4P and nPrPh3P; dto =
 1,2-dithiooxalato)
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00858D
_journal_year                    2023
_chemical_formula_moiety         'C6 Fe2 O6 S6, 2(C10.5 H11 P0.5)'
_chemical_formula_sum            'C27 H22 Fe2 O6 P S6'
_chemical_formula_weight         777.47
_chemical_melting_point          450
_chemical_properties_physical    Heat-sensitive
_space_group_crystal_system      hexagonal
_space_group_IT_number           173
_space_group_name_Hall           'P 6c'
_space_group_name_H-M_alt        'P 63'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-03-18
_audit_creation_method
;
Olex2 1.5
(compiled 2023.02.24 svn.rf166f9f3 for OlexSys, GUI svn.r6725)
;
_audit_update_record
;
2023-03-20 deposited with the CCDC.	2023-03-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            2
_cell_length_a                   10.0805(4)
_cell_length_b                   10.0805(4)
_cell_length_c                   17.8516(10)
_cell_measurement_reflns_used    3923
_cell_measurement_temperature    93.00
_cell_measurement_theta_max      25.4880
_cell_measurement_theta_min      2.5860
_cell_volume                     1570.98(12)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_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      93.0
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_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    -93.00 -15.00   0.50    5.87    --   -4.70   9.00 157.00  156
  2  \w     40.00  67.00   0.50    5.87    --    4.70  28.00   0.00   54
  3  \w    -84.00   6.00   0.50    5.87    --    4.70  28.00   0.00  180
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC10 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0299
_diffrn_reflns_av_unetI/netI     0.0267
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            9321
_diffrn_reflns_point_group_measured_fraction_full 0.961
_diffrn_reflns_point_group_measured_fraction_max 0.921
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.098
_diffrn_reflns_theta_min         2.282
_exptl_absorpt_coefficient_mu    1.413
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72248
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dull dark black'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.644
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             790
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method 'a liquid--liquid diffusion method'
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.932
_refine_diff_density_min         -0.371
_refine_diff_density_rms         0.142
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.47(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.150
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     232
_refine_ls_number_reflns         2131
_refine_ls_number_restraints     207
_refine_ls_restrained_S_all      1.106
_refine_ls_R_factor_all          0.0784
_refine_ls_R_factor_gt           0.0679
_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^)+(0.0903P)^2^+3.3248P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1738
_refine_ls_wR_factor_ref         0.1804
_reflns_Friedel_coverage         0.792
_reflns_Friedel_fraction_full    0.920
_reflns_Friedel_fraction_max     0.842
_reflns_number_gt                1819
_reflns_number_total             2131
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00858d2.cif
_cod_data_source_block           exp_2364
_cod_original_cell_volume        1570.98(15)
_cod_database_code               7713114
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.946
_shelx_estimated_absorpt_t_min   0.849
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.53(10)
 0.47(10)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C3-C4
 1.38 with sigma of 0.02
 C4-C5
 1.38 with sigma of 0.02
 C5-C6
 1.38 with sigma of 0.02
 C6-C7
 1.38 with sigma of 0.02
 C7-C8
 1.38 with sigma of 0.02
 C3-C8
 1.38 with sigma of 0.02
 C3A-C4A
 1.38 with sigma of 0.02
 C4A-C5A
 1.38 with sigma of 0.02
 C5A-C6A
 1.38 with sigma of 0.02
 C6A-C7A
 1.38 with sigma of 0.02
 C7A-C8A
 1.38 with sigma of 0.02
 C3A-C8A
 1.38 with sigma of 0.02
 C9-P1
 1.86 with sigma of 0.01
 C9-C10
 1.52 with sigma of 0.01
 C10-C11
 1.52 with sigma of 0.01
 C9A-P1A
 1.86 with sigma of 0.01
 C9A-C10A
 1.52 with sigma of 0.01
 C10A-C11A
 1.52 with sigma of 0.01
 C3-C5
 2.39 with sigma of 0.04
 C4-C6
 2.39 with sigma of 0.04
 C5-C7
 2.39 with sigma of 0.04
 C6-C8
 2.39 with sigma of 0.04
 C7-C3
 2.39 with sigma of 0.04
 C8-C4
 2.39 with sigma of 0.04
 C3A-C5A
 2.39 with sigma of 0.04
 C4A-C6A
 2.39 with sigma of 0.04
 C5A-C7A
 2.39 with sigma of 0.04
 C6A-C8A
 2.39 with sigma of 0.04
 C7A-C3A
 2.39 with sigma of 0.04
 C8A-C4A
 2.39 with sigma of 0.04
 C9-C11
 2.51 with sigma of 0.02
 C9A-C11A
 2.51 with sigma of 0.02
4. Restrained planarity
 C3, C4, C5, C6, C7, C8
 with sigma of 0.1
 C3A, C4A, C5A, C6A, C7A, C8A
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim O1 \\sim O2 \\sim S1 \\sim S2: within 2A with sigma of 0.02
and sigma for terminal atoms of 0.04 within 2A
C9 \\sim C10 \\sim C11 \\sim C9A \\sim C10A \\sim C11A \\sim P1 \\sim P1A:
within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C3A \\sim C4A \\sim C5A
\\sim C6A \\sim C7A \\sim C8A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
6. Others
 Fixed Sof: P1(0.16667) C3(0.5) C6(0.5) H6(0.5) C5(0.5) H5(0.5) C7(0.5)
 H7(0.5) C8(0.5) H8(0.5) C4(0.5) H4(0.5) C5A(0.5) H5A(0.5) C4A(0.5) H4A(0.5)
 C3A(0.5) C8A(0.5) H8A(0.5) P1A(0.16667) C7A(0.5) H7A(0.5) C6A(0.5) H6A(0.5)
 C9(0.16667) H9A(0.16667) H9B(0.16667) C10(0.16667) H10A(0.16667) H10B(0.16667)
 C11(0.16667) H11A(0.16667) H11B(0.16667) H11C(0.16667) C9A(0.16667)
 H9AA(0.16667) H9AB(0.16667) C10A(0.16667) H10C(0.16667) H10D(0.16667)
 C11A(0.16667) H11D(0.16667) H11E(0.16667) H11F(0.16667)
7.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C9A(H9AA,H9AB), C10A(H10C,H10D)
7.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C5(H5), C7(H7), C8(H8), C4(H4), C5A(H5A), C4A(H4A), C8A(H8A),
 C7A(H7A), C6A(H6A)
7.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C11A(H11D,H11E,H11F)
;
_shelx_res_checksum              89180
_shelx_hkl_checksum              13629
_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
;