Redox-Innocent Metal-Assisted Cleavage of S-S Bond in a Disulfide-Containing Ligand.
Esmieu, Charlène; Orio, Maylis; Le Pape, Laurent; Lebrun, Colette; Pécaut, Jacques; Ménage, Stéphane; Torelli, Stéphane; Inorganic chemistry 55 (2016) 6208–6217; doi:10.1021/acs.inorgchem.6b00819

data_4347973
_publ_section_title
;
 Redox-Innocent Metal-Assisted Cleavage of S-S Bond in a
 Disulfide-Containing Ligand.
;
_journal_issue                   12
_journal_name_full               'Inorganic chemistry'
_journal_page_first              6208
_journal_page_last               6217
_journal_paper_doi               10.1021/acs.inorgchem.6b00819
_journal_volume                  55
_journal_year                    2016
_chemical_formula_moiety
'C80.12 H81 Cu4 F6.37 N18 O6.37 S4.12, 2.74(C2 H3 N), 5.88(C F3 O3 S)'
_chemical_formula_sum            'C91.49 H89.22 Cu4 F24 N20.74 O24 S10'
_chemical_formula_weight         2894.00
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2016-05-09
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                87.155(4)
_cell_angle_beta                 77.418(4)
_cell_angle_gamma                75.588(5)
_cell_formula_units_Z            2
_cell_length_a                   13.9189(6)
_cell_length_b                   17.8863(10)
_cell_length_c                   25.2254(13)
_cell_measurement_reflns_used    4137
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      29.0090
_cell_measurement_theta_min      3.3347
_cell_volume                     5936.3(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector_area_resol_mean 15.9653
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_details
;
  1 omega  -23.00   23.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.8738  -99.0000 -120.0000 46

  2 omega  -42.00   53.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.8738   37.0000 -120.0000 95

  3 omega  -87.00    4.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.8738  -37.0000   60.0000 91

  4 omega  -88.00    3.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.8738  -57.0000  -30.0000 91

  5 omega   -4.00   27.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       17.1550   57.0000 -120.0000 31

  6 omega  -95.00  -34.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.8738 -179.0000  -30.0000 61
;
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0190909000
_diffrn_orient_matrix_UB_12      -0.0397797000
_diffrn_orient_matrix_UB_13      0.0048647000
_diffrn_orient_matrix_UB_21      -0.0155784000
_diffrn_orient_matrix_UB_22      0.0069125000
_diffrn_orient_matrix_UB_23      0.0283962000
_diffrn_orient_matrix_UB_31      -0.0478775000
_diffrn_orient_matrix_UB_32      -0.0068691000
_diffrn_orient_matrix_UB_33      -0.0004104000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0702
_diffrn_reflns_av_unetI/netI     0.1602
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            48265
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         3.341
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.996
_exptl_absorpt_correction_T_max  0.972
_exptl_absorpt_correction_T_min  0.766
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.619
_exptl_crystal_description       plate
_exptl_crystal_F_000             2935
_exptl_crystal_size_max          0.581
_exptl_crystal_size_mid          0.222
_exptl_crystal_size_min          0.028
_refine_diff_density_max         1.945
_refine_diff_density_min         -1.262
_refine_diff_density_rms         0.127
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1609
_refine_ls_number_reflns         24071
_refine_ls_number_restraints     95
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.1898
_refine_ls_R_factor_gt           0.0959
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1211P)^2^+9.8075P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2205
_refine_ls_wR_factor_ref         0.2731
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12132
_reflns_number_total             24071
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic6b00819_si_002.cif
_cod_data_source_block           st447_2
_cod_database_code               4347973
_chemical_oxdiff_formula         'C90 H90 Cu4 F24 N20 O24 S10'
_shelx_estimated_absorpt_t_max   0.973
_shelx_estimated_absorpt_t_min   0.595
_reflns_odcompleteness_completeness 99.04
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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
 N92-C93 = N95-C99
 1.15 with sigma of 0.01
 C93-C94 = C99-C100
 1.45 with sigma of 0.01
 N92-C94 = N95-C100
 2.55 with sigma of 0.02
 S12-C2S
 1.8 with sigma of 0.002
3. Rigid bond restraints
 C92, C91
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(O5S3) \\sim Ueq, Uanis(O4S3) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(F3S2) \\sim Ueq, Uanis(F2S2) \\sim Ueq, Uanis(F1S2) \\sim Ueq,
Uanis(O3S2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(O2S3) \\sim Ueq, Uanis(N95) \\sim Ueq, Uanis(C92) \\sim Ueq, Uanis(C93)
\\sim Ueq, Uanis(C2S) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(O2S2) \\sim Ueq, Uanis(O1S2) \\sim Ueq, Uanis(O3S2) \\sim Ueq, Uanis(S12)
\\sim Ueq, Uanis(C2S) \\sim Ueq, Uanis(F3S2) \\sim Ueq, Uanis(F2S2) \\sim Ueq,
Uanis(F1S2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(S14) = Uanis(F1S4) = Uanis(F2S4) = Uanis(F3S4) = Uanis(O1S4) =
Uanis(O2S4) = Uanis(O3S4) = Uanis(C4S) = Uanis(S14B) = Uanis(F4S4) =
Uanis(F5S4) = Uanis(F6S4) = Uanis(O4S4) = Uanis(O5S4) = Uanis(O6S4) =
Uanis(C4SB)
5. Same fragment restrains
{N94, C97, C98} sigma for 1-2: 0.02, 1-3: 0.04
as
{N95, C99, C100}
6. Others
 Sof(S13B)=Sof(F4S3)=Sof(F5S3)=Sof(F6S3)=Sof(O4S3)=Sof(O5S3)=Sof(C3SB)=1-FVAR(1)
 Sof(N95)=Sof(C99)=Sof(C100)=Sof(H10C)=Sof(H10D)=Sof(H10E)=Sof(S13)=Sof(F1S3)=
 Sof(F2S3)=Sof(F3S3)=Sof(O2S3)=Sof(O3S3)=Sof(C3S)=FVAR(1)
 Sof(S14B)=Sof(F4S4)=Sof(F5S4)=Sof(F6S4)=Sof(O4S4)=Sof(O5S4)=Sof(O6S4)=
 Sof(C4SB)=1-FVAR(2)
 Sof(S14)=Sof(F1S4)=Sof(F2S4)=Sof(F3S4)=Sof(O1S4)=Sof(O2S4)=Sof(O3S4)=Sof(C4S)=
 FVAR(2)
7.a :
 S14(F1S4,F2S4,F3S4,O1S4,O2S4,O3S4,C4S), S14B(F4S4,F5S4,F6S4,O4S4,O5S4,O6S4,
 C4SB)
7.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C10(H10A,H10B), C16(H16A,H16B), C22(H22A,H22B), C28(H28A,H28B),
 C47(H47A,H47B), C48(H48A,H48B), C50(H50A,H50B), C56(H56A,H56B), C62(H62A,H62B),
  C68(H68A,H68B)
7.c Me refined with riding coordinates:
 C94(H94A,H94B,H94C), C100(H10C,H10D,H10E)
7.d Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C18(H18), C19(H19), C20(H20),
 C21(H21), C24(H24), C25(H25), C26(H26), C27(H27), C30(H30), C31(H31), C32(H32),
  C33(H33), C43(H43), C45(H45), C52(H52), C53(H53), C54(H54), C55(H55),
 C58(H58), C59(H59), C60(H60), C61(H61), C64(H64), C65(H65), C66(H66), C67(H67),
  C70(H70), C71(H71), C72(H72), C73(H73)
7.e Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C82(H82A,H82B,H82C), C84(H84A,H84B,H84C), C86(H86A,H86B,
 H86C), C88(H88A,H88B,H88C), C92(H92A,H92B,H92C), C96(H96A,H96B,H96C), C98(H98A,
 H98B,H98C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'