Structural insight into halide-coordinated [Fe4S4XnY4−n]2− clusters (X, Y = Cl, Br, I) by XRD and Mössbauer spectroscopy
Schüren, Andreas O.; Ridgway, Benjamin M.; Di Salvo, Florencia; Carella, Luca M.; Gramm, Verena K.; Metzger, Elisa; Doctorovich, Fabio; Rentschler, Eva; Schünemann, Volker; Ruschewitz, Uwe; Klein, Axel; Dalton Transactions 52 (2023) 1277–1290; doi:10.1039/D2DT03203A

data_7712073
_publ_section_title
;
 Structural insight into halide-coordinated [Fe4S4XnY4&#x2212;n]2&#x2212;
 clusters (X, Y = Cl, Br, I) by XRD and M\"ossbauer spectroscopy
;
_journal_issue                   5
_journal_name_full               'Dalton Transactions'
_journal_page_first              1277
_journal_page_last               1290
_journal_paper_doi               10.1039/D2DT03203A
_journal_volume                  52
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_compound_source
'slow diffusion of diethyl ether into MeCN solutions'
_chemical_formula_moiety         'Cl1.65 Fe4 I2.35 S4, 2(C10 H16 N)'
_chemical_formula_sum            'C20 H32 Cl1.65 Fe4 I2.35 N2 S4'
_chemical_formula_weight         1008.59
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Hygroscopic,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2020-12-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-12-08 deposited with the CCDC.	2022-12-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.3025(19)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.1754(3)
_cell_length_b                   14.7340(4)
_cell_length_c                   17.5672(4)
_cell_measurement_reflns_used    5845
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      23.1620
_cell_measurement_theta_min      4.0730
_cell_volume                     3389.65(14)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Fe4  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Fe4  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Fe4  1 2013,16:14:44)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1158
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.916
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0810
_diffrn_reflns_av_unetI/netI     0.0810
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.916
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            25715
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.864
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.491
_diffrn_reflns_theta_min         3.679
_exptl_absorpt_coefficient_mu    4.206
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88048
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Fe4  1 2013,16:14:44)
EmpirI3al absorption correction using spherI3al harmonI3s,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.976
_exptl_crystal_description       block
_exptl_crystal_F_000             1946
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_geom_special_details
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covarI1nce matrix.  The cell esds are taken
 into account indivI4ually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropI3)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
_refine_diff_density_max         0.544
_refine_diff_density_min         -0.720
_refine_diff_density_rms         0.110
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   -0.05(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     344
_refine_ls_number_reflns         8159
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.1003
_refine_ls_R_factor_gt           0.0493
_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^)+(0.0430P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0982
_refine_ls_wR_factor_ref         0.1275
_reflns_Friedel_coverage         0.883
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.811
_reflns_number_gt                5001
_reflns_number_total             8159
_reflns_special_details
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistI3s and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divI4ed by the number that would be
 possI2le theoretI3ally, ignoring centrI3 projections and
 systematI3 absences.
;
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt03203a2.cif
_cod_data_source_block           exp_3083
_cod_database_code               7712073
_shelx_shelxl_version_number     2018/3
_computing_molecular_graphi3s    'ShelXle C. B. Hubschle (Rev 749 ,2011)'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 1.05(4)
 -0.05(4)
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. Others
 Sof(Cl3)=1-FVAR(1)
 Sof(I3)=FVAR(1)
 Sof(Cl4)=1-FVAR(2)
 Sof(I4)=FVAR(2)
 Sof(Cl2)=1-FVAR(3)
 Sof(I2)=FVAR(3)
4.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C17(H17A,H17B)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C12(H12), C13(H13), C14(H14),
 C15(H15), C16(H16)
4.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C18(H18A,H18B,H18C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              6016
_shelx_hkl_checksum              11118
_olex2_submission_special_instructions 'No special instructions were received'