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_7712071
_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_compound_source
'slow diffusion of diethyl ether into MeCN solutions'
_chemical_formula_moiety         'Br2.13 Fe4 I1.87 S4, 2(C10 H16 N)'
_chemical_formula_sum            'C20 H32 Br2.13 Fe4 I1.87 N2 S4'
_chemical_formula_weight         1059.79
_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
_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
;
2021-01-13 deposited with the CCDC.	2022-12-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.118(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.210(1)
_cell_length_b                   14.957(1)
_cell_length_c                   17.513(2)
_cell_measurement_reflns_used    24299
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      54.20
_cell_measurement_theta_min      4.17
_cell_volume                     3440.5(5)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_device_type  'STOE-IPDS 2'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0355
_diffrn_reflns_av_unetI/netI     0.0225
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            26772
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.304
_diffrn_reflns_theta_min         2.063
_exptl_absorpt_coefficient_mu    6.030
_exptl_absorpt_correction_T_max  0.5084
_exptl_absorpt_correction_T_min  0.1818
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
Numeric absorption correction was performed 
using X-RED und X-SHAPE packages.
;
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    2.046
_exptl_crystal_description       plates
_exptl_crystal_F_000             2031
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_size_max          1.0
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.689
_refine_diff_density_min         -0.609
_refine_diff_density_rms         0.085
_refine_ls_abs_structure_details
;
 Flack x determined using 2821 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.017(12)
_refine_ls_extinction_coef       0.00058(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     312
_refine_ls_number_reflns         7401
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0439
_refine_ls_R_factor_gt           0.0365
_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^)+(0.0463P)^2^+8.9617P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0892
_refine_ls_wR_factor_ref         0.0960
_reflns_Friedel_coverage         0.934
_reflns_Friedel_fraction_full    0.956
_reflns_Friedel_fraction_max     0.926
_reflns_number_gt                6526
_reflns_number_total             7401
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt03203a2.cif
_cod_data_source_block           shelx
_cod_database_code               7712071
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. 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
2. Shared sites
{I3, Br3}
{I2, Br2}
{I4, Br4}
{I1, Br1}
3. Uiso/Uaniso restraints and constraints
Uanis(I3) = Uanis(Br3)
Uanis(I2) = Uanis(Br2)
Uanis(I4) = Uanis(Br4)
Uanis(I1) = Uanis(Br1)
4. Others
 Sof(Br3)=1-FVAR(1)
 Sof(I3)=FVAR(1)
 Sof(Br2)=1-FVAR(2)
 Sof(I2)=FVAR(2)
 Sof(I4)=1-FVAR(3)
 Sof(Br4)=FVAR(3)
 Sof(I1)=1-FVAR(4)
 Sof(Br1)=FVAR(4)
5.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C16(H16A,H16B)
5.b Me refined with riding coordinates:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C18(H18A,H18B,H18C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C11(H11), C12(H12), C13(H13),
 C14(H14), C15(H15)
;
_shelx_res_checksum              78043
_shelx_hkl_checksum              76583
_olex2_submission_special_instructions 'No special instructions were received'