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_4333590
_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), 4(C2 H3 N)'
_chemical_formula_sum            'C62 H57 F12 Fe2 N15 O12 S4'
_chemical_formula_weight         1672.17
_chemical_name_systematic
;
 ? 
;
_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     direct
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                106.9800(10)
_cell_angle_beta                 109.4480(10)
_cell_angle_gamma                97.5000(10)
_cell_formula_units_Z            1
_cell_length_a                   10.6568(2)
_cell_length_b                   12.9150(2)
_cell_length_c                   15.0100(3)
_cell_measurement_reflns_used    9892
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      67.23
_cell_measurement_theta_min      3.35
_cell_volume                     1802.68(6)
_computing_cell_refinement       'SAINT v8.18C (Bruker, 2012)'
_computing_data_collection       'Proteum2 (Bruker, 2010)'
_computing_data_reduction        'SAINT v8.18C (Bruker, 2012)'
_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    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'CCD area detector'
_diffrn_detector_type            'Bruker Pt 135 CCD area detector'
_diffrn_measured_fraction_theta_full 0.899
_diffrn_measured_fraction_theta_max 0.899
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker Pt 135 CCD area detector'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_collimation    'focused optics'
_diffrn_radiation_monochromator  'Bruker Helios multilayer optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54188
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0393
_diffrn_reflns_av_unetI/netI     0.0437
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            16924
_diffrn_reflns_theta_full        67.53
_diffrn_reflns_theta_max         67.53
_diffrn_reflns_theta_min         3.35
_diffrn_source                   'Microstar rotating anode'
_diffrn_source_target            Cu
_diffrn_source_type              'rotating anode'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.198
_exptl_absorpt_correction_T_max  0.7530
_exptl_absorpt_correction_T_min  0.5882
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0907 before and 0.0575 after correction.
The Ratio of minimum to maximum transmission is 0.7811.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear pinkish pink'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   pinkish
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.540
_exptl_crystal_description       block
_exptl_crystal_F_000             854
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.591
_refine_diff_density_min         -0.742
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     523
_refine_ls_number_reflns         5831
_refine_ls_number_restraints     23
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0555
_refine_ls_R_factor_gt           0.0526
_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^)+(0.1040P)^2^+1.3733P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1550
_refine_ls_wR_factor_ref         0.1591
_reflns_number_gt                5463
_reflns_number_total             5831
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic302087f_si_002_3.cif
_cod_data_source_block           compound_2*4MeCN
_cod_database_code               4333590
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H24 of C24, H11 of C11, H6 of C6, H4 of C4, H16A of C16A, H21 of C21, H1 of
  C1, H17A of C17A, H8 of C8, H18 of C18, H17 of C17, H18A of C18A, H12 of C12,
  H10 of C10, H23 of C23, H3 of C3, H16 of C16, H22 of C22, {H19A,H19B} of C19,
  H15A of C15A, H15 of C15, H2 of C2, {H13A,H13B,H13C,H13D} of C13
 At 1.5 times of:
  {H1CA,H1CB,H1CC} of C1C, {H3AA,H3AB,H3AC} of C3AA, {H3AD,H3AE,H3AF} of C3A
2. Restrained distances
 C14A-C13 ~ C14-C13
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C18) = Uanis(C18A)
Uanis(C16) = Uanis(C16A)
Uanis(C15) = Uanis(C15A)
Uanis(C14) = Uanis(C14A)
Uanis(C2T) = Uanis(C2TA)
Uanis(F6T) = Uanis(F6TA)
Uanis(F5T) = Uanis(F5TA)
Uanis(F4T) = Uanis(F4TA)
Uanis(S2T) = Uanis(S2TA)
Uanis(O4T) = Uanis(O4TA)
Uanis(O6T) = Uanis(O6TA)
Uanis(O5T) = Uanis(O5TA)
Uanis(F1T) = Uanis(F1TA)
Uanis(F2T) = Uanis(F2TA)
Uanis(F3T) = Uanis(F3TA)
Uanis(C1T) = Uanis(C1TA)
Uanis(O3T) = Uanis(O3TA)
Uanis(O2T) = Uanis(O2TA)
Uanis(C17) = Uanis(C17A)
Uiso(N2A) = Uiso(N2AA) = Uiso(C3A) = Uiso(C3AA) = Uiso(C4A) = Uiso(C4AA)
4. Same fragment restrains
{S2TA, O6TA, O4TA, O5TA, C2TA, F6TA, F5TA, F4TA}
as
{S2T, O5T, O6T, O4T, C2T, F5T, F4T, F6T}
{N2A, C4A, C3A}
as
{N2AA, C4AA, C3AA}
5. others
 Sof(S2T)=Sof(O5T)=Sof(O6T)=Sof(O4T)=Sof(C2T)=Sof(F5T)=Sof(F4T)=Sof(F6T)=
 Sof(H13A)=Sof(H13B)=1-Sof(O5T)=1-Sof(O5T)=Sof(C18)=Sof(H18)=Sof(C14)=Sof(C17)=
 Sof(H17)=Sof(C15)=Sof(H15)=Sof(C16)=Sof(H16)=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)=1-Sof(O5T)=1-Sof(O5T)=1-Sof(O5T)=
 Sof(N2A)=Sof(C4A)=Sof(C3A)=Sof(H3AD)=Sof(H3AE)=Sof(H3AF)=1-Sof(O5T)=1-Sof(O5T)=
 1-Sof(O5T)=1-Sof(O5T)=1-Sof(O5T)=1-Sof(O5T)
 Sof(O2T)=Sof(O3T)=Sof(F1T)=Sof(F2T)=Sof(F3T)=Sof(C1T)=1-Sof(O3T)=1-Sof(O3T)=1-
 Sof(O3T)=1-Sof(O3T)=1-Sof(O3T)=1-Sof(O3T)
6.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C13(H13C,H13D), C19(H19A,H19B)
6.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C6(H6), C24(H24), C1(H1), C18(H18), C12(H12), C11(H11), C10(H10),
 C23(H23), C2(H2), C3(H3), C22(H22), C21(H21), C4(H4), C17(H17), C15(H15),
 C16(H16), C18A(H18A), C17A(H17A), C16A(H16A), C15A(H15A)
6.c Idealised Me refined as rotating group:
 C1C(H1CA,H1CB,H1CC), C3A(H3AD,H3AE,H3AF), C3AA(H3AA,H3AB,H3AC)
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