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_7712069
_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_formula_moiety         'Cl1.763 Fe4 I2.237 S4, 2(C10 H16 N)'
_chemical_formula_sum            'C20 H32 Cl1.76 Fe4 I2.24 N2 S4'
_chemical_formula_weight         998.53
_chemical_properties_physical    Air-sensitive,Moisture-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             2020-11-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-09-15 deposited with the CCDC.	2022-12-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.225(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.0899(4)
_cell_length_b                   14.6471(4)
_cell_length_c                   17.4361(5)
_cell_measurement_reflns_used    24431
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      28.1220
_cell_measurement_theta_min      4.2380
_cell_volume                     3323.30(17)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      173.15
_diffrn_detector_area_resol_mean 16.1158
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.900
_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  0.0428
_diffrn_reflns_av_unetI/netI     0.0491
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.900
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            23842
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.854
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.483
_diffrn_reflns_theta_min         3.953
_exptl_absorpt_coefficient_mu    4.197
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60207
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark black'
_exptl_crystal_density_diffrn    1.996
_exptl_crystal_description       block
_exptl_crystal_F_000             1930
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.439
_refine_diff_density_min         -0.361
_refine_diff_density_rms         0.086
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   -0.020(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.003
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     373
_refine_ls_number_reflns         7917
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.003
_refine_ls_R_factor_all          0.0390
_refine_ls_R_factor_gt           0.0302
_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^)+(0.0150P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0488
_refine_ls_wR_factor_ref         0.0528
_reflns_Friedel_coverage         0.896
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.808
_reflns_number_gt                7018
_reflns_number_total             7917
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt03203a2.cif
_cod_data_source_block           exp_3512
_cod_database_code               7712069
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.850
_shelx_estimated_absorpt_t_min   0.591
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 1.020(18)
 -0.020(18)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Shared sites
{I1, Cl1}
4. Uiso/Uaniso restraints and constraints
Uanis(I1) = Uanis(Cl1)
5. Others
 1*[Sof(Cl3)]+1*[Sof(I1)]+1*[Sof(I4)]+1*[Sof(Cl4)]=2 with esd of 0
 1*[Sof(Cl2)]+1*[Sof(I3)]+1*[Sof(I2)]+1*[Sof(Cl1)]=2 with esd of 0
6.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C17(H17A,H17B)
6.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)
6.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              25577
_shelx_hkl_checksum              7673
_olex2_submission_special_instructions 'No special instructions were received'