Syntheses and Electronic Structure of Bimetallic Complexes Containing a Flexible Redox-Active Bridging Ligand
Stacey Lindsay; Siu K. Lo; Oliver R. Maguire; Eckhard Bill; Michael R. Probert; Stephen Sproules; Corinna R. Hess; Inorganic Chemistry 52 (2013) 898–909; doi:10.1021/ic302087f

data_4333591
_publ_section_title
;
 Syntheses and Electronic Structure of Bimetallic Complexes Containing a
 Flexible Redox-Active Bridging Ligand
;
_journal_name_full               'Inorganic Chemistry'
_journal_page_first              898
_journal_page_last               909
_journal_paper_doi               10.1021/ic302087f
_journal_volume                  52
_journal_year                    2013
_chemical_formula_moiety
'C50 H42 F6 Fe2 N10 O6 S2, 2(C F3 O3 S), 2(C2 H3 N)'
_chemical_formula_sum            'C56 H48 F12 Fe2 N12 O12 S4'
_chemical_formula_weight         1549.00
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                69.606(4)
_cell_angle_beta                 86.687(5)
_cell_angle_gamma                76.892(4)
_cell_formula_units_Z            1
_cell_length_a                   8.9929(11)
_cell_length_b                   12.9736(18)
_cell_length_c                   14.7541(16)
_cell_measurement_reflns_used    9940
_cell_measurement_temperature    120
_cell_measurement_theta_max      30.61
_cell_measurement_theta_min      2.57
_cell_volume                     1571.0(3)
_computing_cell_refinement       'SAINT V8.27B (Bruker, 2011)'
_computing_data_collection       'SMART v5.625 (Bruker, 2001)'
_computing_data_reduction        'SAINT V8.27B (Bruker, 2011)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
XL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
XM, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      120
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 5.6
_diffrn_detector_type            'Bruker SMART CCD 6000 area detector'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART CCD 6000 area detector'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0228
_diffrn_reflns_av_unetI/netI     0.0307
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            21754
_diffrn_reflns_theta_full        30.58
_diffrn_reflns_theta_max         30.58
_diffrn_reflns_theta_min         1.47
_diffrn_source                   'sealed x-ray tube'
_diffrn_source_current           35.0
_diffrn_source_power             1.75
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.702
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.5782
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS was used for absorption correction.
wR2(int) was 0.0614 before and 0.0376 after correction.
The Ratio of minimum to maximum transmission is 0.7750.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear reddish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.637
_exptl_crystal_description       block
_exptl_crystal_F_000             788
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.18
_refine_diff_density_max         1.023
_refine_diff_density_min         -0.634
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     483
_refine_ls_number_reflns         9589
_refine_ls_number_restraints     22
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0451
_refine_ls_R_factor_gt           0.0388
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0560P)^2^+0.7339P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1012
_refine_ls_wR_factor_ref         0.1061
_reflns_number_gt                8260
_reflns_number_total             9589
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic302087f_si_002_4.cif
_cod_data_source_block           compound_2*2MeCN
_cod_database_code               4333591
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H15 of C15, H17 of C17, H24 of C24, H18 of C18, H10 of C10, H12 of C12, H11
  of C11, H23 of C23, H21 of C21, H16 of C16, H1 of C1, H3 of C3, H6 of C6,
  {H13A,H13B} of C13, H22 of C22, {H19A,H19B} of C19, H8 of C8, H2 of C2, H4 of
  C4
 At 1.5 times of:
  {H3AD,H3AE,H3AF} of C3AA, {H3AA,H3AB,H3AC} of C3A
2. Uiso/Uaniso restraints and constraints
Uanis(O5T) = Uanis(O6TA)
Uanis(O6T) = Uanis(O4TA)
Uanis(O4T) = Uanis(O5TA)
Uanis(C2T) = Uanis(C2TA)
Uanis(F4T) = Uanis(F6TA)
Uanis(F6T) = Uanis(F5TA)
Uanis(F5T) = Uanis(F4TA)
Uanis(C3A) = Uanis(C3AA)
Uanis(C2A) = Uanis(C2AA)
Uanis(N1A) = Uanis(N1AA)
3. Same fragment restrains
{S2T, O5T, O4T, O6T, C2T, F6T, F5T, F4T}
as
{S2TA, O6TA, O4TA, O5TA, C2TA, F6TA, F4TA, F5TA}
{C2A, C3A, N1A}
as
{C2AA, C3AA, N1AA}
4. others
 Sof(S2T)=Sof(O5T)=Sof(O4T)=Sof(O6T)=Sof(C2T)=Sof(F6T)=Sof(F5T)=Sof(F4T)=1-
 Sof(O5T)=1-Sof(O5T)=1-Sof(O5T)=1-Sof(O5T)=1-Sof(O5T)=1-Sof(O5T)=1-Sof(O5T)=1-
 Sof(O5T)=1-Sof(O5T)=1-Sof(O5T)=1-Sof(O5T)=1-Sof(O5T)=1-Sof(O5T)=1-Sof(O5T)=
 Sof(C2A)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=Sof(N1A)
5.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C19(H19A,H19B)
5.b Me refined with riding coordinates:
 C3AA(H3AD,H3AE,H3AF)
5.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C2(H2), C21(H21), C12(H12), C1(H1), C4(H4), C3(H3), C6(H6), C17(H17),
 C22(H22), C18(H18), C23(H23), C15(H15), C10(H10), C11(H11), C24(H24), C16(H16)
5.d Idealised Me refined as rotating group:
 C3A(H3AA,H3AB,H3AC)
;