Binuclear Ruthenium Complexes of a Neutral Radical Bridging Ligand. A New "Spin" on Mixed Valency
Stephen D. J. McKinnon; Brian O. Patrick; A. B. P. Lever; Robin G. Hicks; Inorganic Chemistry 52 (2013) 8053–8066; doi:10.1021/ic400704j

data_4335469
_publ_section_title
;
 Binuclear Ruthenium Complexes of a Neutral Radical Bridging Ligand. A New
 "Spin" on Mixed Valency
;
_journal_name_full               'Inorganic Chemistry'
_journal_page_first              8053
_journal_page_last               8066
_journal_paper_doi               10.1021/ic400704j
_journal_volume                  52
_journal_year                    2013
_chemical_formula_moiety         'C34 H25 F24 N6 O9 Ru2, F6 P, C1 H2 Cl2'
_chemical_formula_sum            'C35 H27 Cl2 F30 N6 O9 P Ru2'
_chemical_formula_weight         1549.63
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_symmetry_space_group_name_Hall  'P 2c -2n'
_symmetry_space_group_name_H-M   'P n a 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2013-06-03
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.0533(13)
_cell_length_b                   9.9881(5)
_cell_length_c                   26.4832(17)
_cell_measurement_reflns_used    8923
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      22.571
_cell_measurement_theta_min      2.186
_cell_volume                     5304.4(6)
_computing_data_reduction        'SAINT v7.53A (Bruker, 2008)'
_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
;
_diffrn_ambient_temperature      173.15
_diffrn_measured_fraction_theta_full 0.751
_diffrn_measured_fraction_theta_max 0.996
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0651
_diffrn_reflns_av_unetI/netI     0.0582
_diffrn_reflns_Laue_measured_fraction_full 0.751
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            30270
_diffrn_reflns_point_group_measured_fraction_full 0.681
_diffrn_reflns_point_group_measured_fraction_max 0.905
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         22.789
_diffrn_reflns_theta_min         2.031
_exptl_absorpt_coefficient_mu    0.861
_exptl_absorpt_correction_T_max  0.975
_exptl_absorpt_correction_T_min  0.691
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0901 before and 0.0634 after correction.
The Ratio of minimum to maximum transmission is 0.7092.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            green
_exptl_crystal_density_diffrn    1.940
_exptl_crystal_F_000             3032
_exptl_crystal_size_max          0.60
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.591
_refine_diff_density_min         -0.575
_refine_diff_density_rms         0.088
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.43(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     853
_refine_ls_number_reflns         6507
_refine_ls_number_restraints     1445
_refine_ls_restrained_S_all      1.002
_refine_ls_R_factor_all          0.0634
_refine_ls_R_factor_gt           0.0431
_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^)+(0.0365P)^2^+9.7117P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0835
_refine_ls_wR_factor_ref         0.0941
_reflns_Friedel_coverage         0.772
_reflns_Friedel_fraction_full    0.608
_reflns_Friedel_fraction_max     0.810
_reflns_number_gt                5406
_reflns_number_total             6507
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic400704j_si_006.cif
_cod_data_source_block           rh068
_cod_database_code               4335469
_cod_database_fobs_code          4335469
_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. Restrained distances
 F5B-F5
 -0.6 with sigma of 0.02
 F6B-F6
 -0.6 with sigma of 0.02
 F4B-F4
 -0.6 with sigma of 0.02
 F7-F7B
 -0.6 with sigma of 0.02
 F8B-F8
 -0.6 with sigma of 0.02
 F9B-F9
 -0.6 with sigma of 0.02
 Cl1-C56 = Cl2-C56
 1.7602 with sigma of 0.002
 Cl1-Cl2
 2.9338 with sigma of 0.004
 Cl1B-C56B = Cl2B-C56B
 1.7602 with sigma of 0.002
 Cl1B-Cl2B
 2.9338 with sigma of 0.004
 F7-F8 \\sim F8-F9 \\sim F9-F7
 with sigma of 0.02
 F7B-F8B \\sim F8B-F9B \\sim F9B-F7B
 with sigma of 0.02
 C31-F7 \\sim C31-F8 \\sim C31-F9 \\sim C31-F7B \\sim C31-F8B \\sim C31-F9B
 with sigma of 0.02
C41-F13 \\sim C41-F14 \\sim C41-F15 \\sim C41-F13B \\sim C41-F14B \\sim C41-F15B
 with sigma of 0.02
F13-F14 \\sim F14-F15 \\sim F15-F13 \\sim F13B-F14B \\sim F14B-F15B 
\\sim F15B-F13B with sigma of 0.02
C55-F22 \\sim C55-F23 \\sim C55-F24 \\sim C55-F22B \\sim C55-F23B \\sim C55-F24B
 with sigma of 0.02
 F22-F23 \\sim F23-F24 \\sim F24-F22 \\sim F22B-F23B \\sim F23B-F24B 
\\sim F24B-F22B with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.1 and sigma
for terminal atoms of 0.2
Uanis(F4B) = Uanis(F4)
Uanis(F6B) = Uanis(F6)
Uanis(F5B) = Uanis(F5)
Uanis(F22) = Uanis(F23) = Uanis(F24)
Uanis(F23B) = Uanis(F22B) = Uanis(F24B)
Uanis(Cl2) = Uanis(Cl2B)
Uanis(C56) = Uanis(C56B)
Uanis(Cl1) = Uanis(Cl1B)
4. others
 Sof(F6B)=Sof(F4B)=Sof(F5B)=1-FVAR(1)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(1)
 Sof(F7B)=Sof(F8B)=Sof(F9B)=1-FVAR(2)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(2)
 Sof(F13B)=Sof(F14B)=Sof(F15B)=1-FVAR(3)
 Sof(F13)=Sof(F14)=Sof(F15)=FVAR(3)
 Sof(F22)=Sof(F23)=Sof(F24)=1-FVAR(4)
 Sof(F22B)=Sof(F23B)=Sof(F24B)=FVAR(4)
 Sof(Cl1B)=Sof(C56B)=Sof(H56C)=Sof(H56D)=Sof(Cl2B)=1-FVAR(5)
 Sof(Cl1)=Sof(Cl2)=Sof(C56)=Sof(H56A)=Sof(H56B)=FVAR(5)
5.a Ternary CH refined with riding coordinates:
 C3(H3), C6(H6)
5.b Secondary CH2 refined with riding coordinates:
 C56(H56A,H56B), C56B(H56C,H56D)
5.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C23(H23), C33(H33), C43(H43), C53(H53)
5.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C15(H15A,
 H15B,H15C), C16(H16A,H16B,H16C)
;
_shelxl_version_number           2012-9