A DFT-Elucidated Comparison of the Solution-Phase and SAM Electrochemical Properties of Short-Chain Mercaptoalkylferrocenes: Synthetic and Spectroscopic Aspects, and the Structure of Fc-CH2CH2-S-S-CH2CH2-Fc.
Lewtak, Jan P.; Landman, Marilé; Fernández, Israel; Swarts, Jannie C.; Inorganic chemistry 55 (2016) 2584–2596; doi:10.1021/acs.inorgchem.5b02936

data_4347246
_publ_section_title
;
 A DFT-Elucidated Comparison of the Solution-Phase and SAM Electrochemical
 Properties of Short-Chain Mercaptoalkylferrocenes: Synthetic and
 Spectroscopic Aspects, and the Structure of Fc-CH2CH2-S-S-CH2CH2-Fc.
;
_journal_issue                   5
_journal_name_full               'Inorganic chemistry'
_journal_page_first              2584
_journal_page_last               2596
_journal_paper_doi               10.1021/acs.inorgchem.5b02936
_journal_volume                  55
_journal_year                    2016
_chemical_formula_moiety         'C24 H26 Fe2 S2'
_chemical_formula_sum            'C24 H26 Fe2 S2'
_chemical_formula_weight         490.27
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2014
_cell_angle_alpha                111.24(12)
_cell_angle_beta                 92.08(9)
_cell_angle_gamma                93.43(11)
_cell_formula_units_Z            2
_cell_length_a                   5.794(13)
_cell_length_b                   12.06(3)
_cell_length_c                   16.07(4)
_cell_measurement_reflns_used    9836
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      30.47
_cell_measurement_theta_min      2.63
_cell_volume                     1043(4)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics
; <i>ORTEP-3 for Windows</i> (Farrugia, 1997), 
 <i>Mercury</i> (Macrae <i>et al</i>., 2008) 
_computing_publication_material   'SHELXL-2013' 

_refine_special_details
Only one of the four five-membered (Cp) rings in the asymmetric unit displayed larger 
thermal motion for three of its five carbon atoms (C20, C21, C24). This five-membered 
ring had to be refined using the EADP instruction to model the anisotropic thermal 
parameters of these three atoms (C20, C21, C24) and also C22 in this ring, 
on that of C23. As a result of this model, the Hirshfeld test flagged these warnings.  
Unrestricted refinement (without EADP instruction) of this Cp ring resulted 
in large librations for these three atoms. This seemed chemically and physically 
unsatisfactory as there is no apparent reason for three out of five carbon ring 
atoms of this Cp ring to behave as such. Hence the EADP instruction and subsequent 
Hirshfeld test alerts. Alerts related to the high difference electron density peak 
refer to the peak directly related to the modelling of the thermal motion of 
these atoms in this five membered ring. This peak appears close to C20 and C24. 
;
_computing_structure_refinement  'SHELXTL-2013, SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_solution    'SHELXTS-2013 (Sheldrick, 2013)'
_diffrn_ambient_temperature      150(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker kappa Proton CMOS'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'Quazar multi-layer optics'
_diffrn_radiation_source         'I\ms micro focus'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0427
_diffrn_reflns_av_unetI/netI     0.0186
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            41547
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.681
_diffrn_reflns_theta_min         2.640
_exptl_absorpt_coefficient_mu    1.599
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6383
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.562
_exptl_crystal_description       plate
_exptl_crystal_F_000             508
_exptl_crystal_size_max          0.628
_exptl_crystal_size_mid          0.319
_exptl_crystal_size_min          0.122
_refine_diff_density_max         2.873
_refine_diff_density_min         -1.197
_refine_diff_density_rms         0.142
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     229
_refine_ls_number_reflns         3946
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0588
_refine_ls_R_factor_gt           0.0553
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0897P)^2^+4.4155P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1464
_refine_ls_wR_factor_ref         0.1497
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3626
_reflns_number_total             3946
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b02936_si_002.cif
_cod_data_source_block           shelx
_cod_original_cell_volume        1043(5)
_cod_database_code               4347246
_shelx_estimated_absorpt_t_min   0.433
_shelx_estimated_absorpt_t_max   0.829
_shelxl_version_number           2014-3
_shelx_res_checksum              52723
_shelx_hkl_checksum              95040