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_4333588
_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         'C48 H42 Cu2 N10, 4(C F3 O3 S)'
_chemical_formula_sum            'C52 H42 Cu2 F12 N10 O12 S4'
_chemical_formula_weight         1482.28
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                90.00
_cell_angle_beta                 97.1390(10)
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   42.0617(8)
_cell_length_b                   10.7977(2)
_cell_length_c                   28.7341(5)
_cell_measurement_reflns_used    9812
_cell_measurement_temperature    100
_cell_measurement_theta_max      63.13
_cell_measurement_theta_min      3.10
_cell_volume                     12949.0(4)
_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
;
XS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD area detector'
_diffrn_detector_type            'Bruker Pt 135 CCD area detector'
_diffrn_measured_fraction_theta_full 0.956
_diffrn_measured_fraction_theta_max 0.956
_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  0.0523
_diffrn_reflns_av_unetI/netI     0.0411
_diffrn_reflns_limit_h_max       45
_diffrn_reflns_limit_h_min       -45
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            51265
_diffrn_reflns_theta_full        63.43
_diffrn_reflns_theta_max         63.43
_diffrn_reflns_theta_min         1.55
_diffrn_source                   'Microstar rotating anode'
_diffrn_source_target            Cu
_diffrn_source_type              'rotating anode'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.896
_exptl_absorpt_correction_T_max  0.7523
_exptl_absorpt_correction_T_min  0.5776
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0954 before and 0.0702 after correction.
The Ratio of minimum to maximum transmission is 0.7678.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear light blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.521
_exptl_crystal_description       block
_exptl_crystal_F_000             6000
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.424
_refine_diff_density_min         -0.919
_refine_diff_density_rms         0.100
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     849
_refine_ls_number_reflns         10140
_refine_ls_number_restraints     22
_refine_ls_restrained_S_all      1.100
_refine_ls_R_factor_all          0.0686
_refine_ls_R_factor_gt           0.0591
_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^)+(0.1098P)^2^+38.9880P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1730
_refine_ls_wR_factor_ref         0.1797
_reflns_number_gt                8486
_reflns_number_total             10140
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic302087f_si_002_1.cif
_cod_data_source_block           compound_3
_cod_database_code               4333588
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H22 of C22, H24A of C24A, H15 of C15, H6 of C6, H8 of C8, {H19A,H19B} of
  C19, H2 of C2, {H13A,H13B} of C13, H24 of C24, H18A of C18A, H1A of C1A, H17A
  of C17A, H4 of C4, H10A of C10A, {H19C,H19D} of C19A, H16A of C16A, H9 of C9,
  H18 of C18, H6A of C6A, H2A of C2A, H21A of C21A, H23B of C23B, {H13C,H13D}
  of C13A, H9A of C9A, H3 of C3, H4A of C4A, H22A of C22A, H23A of C23A, H24B
  of C24B, H22B of C22B, H10 of C10, H21B of C21B, H15A of C15A, H1 of C1, H17
  of C17, H12A of C12A, H21 of C21, H16 of C16, H8A of C8A, H12 of C12, {H19E,
  H19F} of C19B, H3A of C3A, H23 of C23
2. Shared sites
{C19A, C19B}
3. Restrained distances
 F4S-C2S ~ F5S-C2S
 with sigma of 0.02
 C20A-C19A ~ C20B-C19B
 with sigma of 0.02
 N3A-C19B ~ N3A-C19A
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(N5A) = Uanis(N5B)
Uanis(C20A) = Uanis(C20B)
Uanis(C21A) = Uanis(C21B)
Uanis(C22A) = Uanis(C22B)
Uanis(C23A) = Uanis(C23B)
Uanis(C24A) = Uanis(C24B)
Uanis(S4S) = Uanis(S5S)
Uanis(C4S) = Uanis(C5S)
Uanis(F10S) = Uanis(F14S)
Uanis(F11S) = Uanis(F15S)
Uanis(F12S) = Uanis(F13S)
Uanis(O10S) = Uanis(O14S)
Uanis(O11S) = Uanis(O15S)
Uanis(O12S) = Uanis(O13S)
Uanis(C19A) = Uanis(C19B)
5. Same fragment restrains
{O12S, O10S, O11S, S4S, C4S, F12S, F11S, F10S}
as
{O13S, O14S, O15S, S5S, C5S, F15S, F14S, F13S}
6. others
 Sof(O12S)=Sof(O10S)=Sof(O11S)=Sof(S4S)=Sof(C4S)=Sof(F12S)=Sof(F11S)=Sof(F10S)=
 1-Sof(O10S)=1-Sof(O10S)=1-Sof(O10S)=1-Sof(O10S)=1-Sof(O10S)=1-Sof(O10S)=1-
 Sof(O10S)=1-Sof(O10S)
 Sof(N5A)=Sof(C20A)=Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(H22A)=Sof(C23A)=
 Sof(H23A)=Sof(C24A)=Sof(H24A)=Sof(C19A)=Sof(H19C)=Sof(H19D)=1-Sof(C20A)=1-
 Sof(C20A)=1-Sof(C20A)=1-Sof(C20A)=1-Sof(C20A)=1-Sof(C20A)=1-Sof(C20A)=1-
 Sof(C20A)=1-Sof(C20A)=1-Sof(C20A)=1-Sof(C20A)=1-Sof(C20A)=1-Sof(C20A)
7.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C13(H13A,H13B), C19A(H19C,H19D), C13A(H13C,H13D), C19B(H19E,
 H19F)
7.b Aromatic/amide H refined with riding coordinates:
 C12A(H12A), C12(H12), C1(H1), C18(H18), C8(H8), C22(H22), C6A(H6A), C6(H6),
 C15(H15), C24(H24), C21A(H21A), C22A(H22A), C23A(H23A), C24A(H24A), C3A(H3A),
 C10(H10), C10A(H10A), C3(H3), C9(H9), C17(H17), C16A(H16A), C1A(H1A), C16(H16),
  C9A(H9A), C2(H2), C21(H21), C8A(H8A), C15A(H15A), C18A(H18A), C4(H4),
 C23(H23), C4A(H4A), C17A(H17A), C2A(H2A), C24B(H24B), C23B(H23B), C22B(H22B),
 C21B(H21B)
7.c Fitted hexagon refined as free rotating group:
 N5A(C20A,C21A,C22A,C23A,C24A), N5B(C24B,C23B,C22B,C21B,C20B)
;