Controlling the Reactivity of Bifunctional Ligands: Carboxylate-Bridged Nonheme Diiron(II) Complexes Bearing Free Thiol Groups.
Pal, Nabhendu; Majumdar, Amit; Inorganic chemistry 55 (2016) 3181–3191; doi:10.1021/acs.inorgchem.6b00316

data_4347538
_publ_section_title
;
 Controlling the Reactivity of Bifunctional Ligands: Carboxylate-Bridged
 Nonheme Diiron(II) Complexes Bearing Free Thiol Groups.
;
_journal_issue                   6
_journal_name_full               'Inorganic chemistry'
_journal_page_first              3181
_journal_page_last               3191
_journal_paper_doi               10.1021/acs.inorgchem.6b00316
_journal_volume                  55
_journal_year                    2016
_chemical_formula_moiety         'C50 H54 Fe2 N10 O3 S, 2(B F4)'
_chemical_formula_sum            'C50 H54 B2 F8 Fe2 N10 O3 S'
_chemical_formula_weight         1160.41
_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'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2015-09-14
_audit_creation_method
;
Olex2 1.2
(compiled 2014.08.28 svn.r2986 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                90
_cell_angle_beta                 111.377(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   28.622(4)
_cell_length_b                   15.157(2)
_cell_length_c                   29.712(4)
_cell_measurement_reflns_used    2762
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      17.49
_cell_measurement_theta_min      2.32
_cell_volume                     12003(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2014.7-1 (Bruker-Axs,2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      150(2)
_diffrn_measured_fraction_theta_full 0.953
_diffrn_measured_fraction_theta_max 0.912
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'phi and omega scan'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.2325
_diffrn_reflns_av_unetI/netI     0.2019
_diffrn_reflns_Laue_measured_fraction_full 0.953
_diffrn_reflns_Laue_measured_fraction_max 0.912
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            55600
_diffrn_reflns_point_group_measured_fraction_full 0.953
_diffrn_reflns_point_group_measured_fraction_max 0.912
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.754
_diffrn_reflns_theta_min         1.472
_diffrn_source_type              'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.589
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.4751
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/3 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.1637 before and 0.0736 after correction.
The Ratio of minimum to maximum transmission is 0.6375.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.284
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             4784
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.011
_refine_diff_density_min         -0.641
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.009
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     649
_refine_ls_number_reflns         10494
_refine_ls_number_restraints     127
_refine_ls_restrained_S_all      1.005
_refine_ls_R_factor_all          0.2172
_refine_ls_R_factor_gt           0.1072
_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^)+(0.1307P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2486
_refine_ls_wR_factor_ref         0.2854
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4466
_reflns_number_total             10494
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic6b00316_si_002.cif
_cod_data_source_block           4Mercapto
_cod_original_sg_symbol_H-M      C2/c
_cod_database_code               4347538
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.891
_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
 C43A-C42A \\sim C43B-C42B
 with sigma of 0.02
 N10B-C42B \\sim N10A-C42A
 with sigma of 0.02
 C35B-C34B \\sim C35A-C34A
 with sigma of 0.02
 N9-C35B \\sim N9-C35A \\sim N10B-C35B \\sim N10A-C35A
 with sigma of 0.02
 F2A-B1A \\sim F2B-B1B
 with sigma of 0.02
 F1B-B1B \\sim F1A-B1A
 with sigma of 0.02
 F4A-B1A \\sim F4B-B1B
 with sigma of 0.02
 F3A-B1A \\sim F3B-B1B
 with sigma of 0.02
 N1B-C13B \\sim N1A-C13A
 with sigma of 0.02
 C14-C13B \\sim C14-C13A
 with sigma of 0.02
 N1B-C2B \\sim N6B-C23B \\sim N1A-C2A \\sim N6A-C23A
 with sigma of 0.02
 C23B-C1B \\sim C2B-C1B \\sim C2A-C1A \\sim C23A-C1A
 with sigma of 0.02
 F6A-B2 \\sim F6B-B2 \\sim F8A-B2 \\sim F8B-B2 \\sim F7A-B2 \\sim F7B-B2 \\sim
F5B-B2 \\sim F5A-B2
 with sigma of 0.02
 N3B-C10B \\sim N3A-C10A \\sim N2B-C5B \\sim N2A-C5A
 with sigma of 0.02
 C9A-C10A \\sim C9B-C10B \\sim C9A-C8A \\sim C9B-C8B \\sim C8B-C7B \\sim
C8A-C7A \\sim C7B-C6B \\sim C7A-
 C6A \\sim C6B-C5B \\sim C6A-C5A \\sim C5A-C10A \\sim C5B-C10B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C4B) = Uanis(C4A)
Uanis(C2B) = Uanis(C2A) = Uanis(C1A) = Uanis(C1B) = Uanis(C3A) = Uanis(C3B)
Uanis(C34B) = Uanis(C34A)
Uanis(C12B) = Uanis(C12A) = Uanis(C11B) = Uanis(C11A)
Uanis(N7) = Uanis(N6A) = Uanis(N6B) = Uanis(N1A) = Uanis(N1B) = Uanis(N2A) =
Uanis(N2B) = Uanis(N3A) = Uanis(N3B) = Uanis(C5A) = Uanis(C5B) = Uanis(C10A) =
Uanis(C10B)
Uanis(C42A) = Uanis(C43A)
Uanis(N9) = Uanis(N10A) = Uanis(N10B) = Uanis(C42A) = Uanis(C42B) = Uanis(C43A)
= Uanis(C43B)
Uanis(C35B) = Uanis(C35A)
Uanis(C25) = Uanis(C24B) = Uanis(C24A)
Uanis(C33A) = Uanis(C32A)
Uanis(C25) = Uanis(C32A) = Uanis(C32B) = Uanis(C33B) = Uanis(C33A)
Uanis(C34A) = Uanis(C34B) = Uanis(C35A) = Uanis(C35B)
Uanis(C22B) = Uanis(C21A) = Uanis(C21B) = Uanis(C22A)
Uanis(F1A) = Uanis(F1B) = Uanis(F2A) = Uanis(F2B) = Uanis(F3A) = Uanis(F3B) =
Uanis(F4A) = Uanis(F4B) = Uanis(B1B) = Uanis(B1A)
Uanis(C14) = Uanis(C13B) = Uanis(C13A)
Uanis(C23B) = Uanis(C23A)
Uanis(F8B) = Uanis(F8A)
Uanis(F5B) = Uanis(F5A)
Uanis(F7B) = Uanis(F7A)
Uanis(B2) = Uanis(F8A) = Uanis(F6A) = Uanis(F6B)
Uanis(C8B) = Uanis(C7B) = Uanis(C6B) = Uanis(C9B) = Uanis(C8A) = Uanis(C7A) =
Uanis(C6A) = Uanis(C9A)
4. Others
 Sof(C1B)=Sof(H1B)=Sof(C2B)=Sof(H2BA)=Sof(H2BB)=Sof(C3B)=Sof(H3BA)=Sof(H3BB)=
 Sof(C4B)=Sof(C5B)=Sof(C6B)=Sof(H6B)=Sof(C7B)=Sof(H7B)=Sof(C8B)=Sof(H8B)=
 Sof(C9B)=Sof(H9B)=Sof(C10B)=Sof(C11B)=Sof(H11C)=Sof(H11D)=Sof(C12B)=Sof(H12D)=
 Sof(H12E)=Sof(H12F)=Sof(C13B)=Sof(H13C)=Sof(H13D)=Sof(C21B)=Sof(H21C)=
 Sof(H21D)=Sof(C22B)=Sof(H22D)=Sof(H22E)=Sof(H22F)=Sof(C23B)=Sof(H23C)=
 Sof(H23D)=Sof(C24B)=Sof(H24C)=Sof(H24D)=Sof(C32B)=Sof(H32C)=Sof(H32D)=
 Sof(C33B)=Sof(H33D)=Sof(H33E)=Sof(H33F)=Sof(C34B)=Sof(H34C)=Sof(H34D)=
 Sof(C35B)=Sof(C42B)=Sof(H42C)=Sof(H42D)=Sof(C43B)=Sof(H43D)=Sof(H43E)=
 Sof(H43F)=Sof(N1B)=Sof(N2B)=Sof(N3B)=Sof(N6B)=Sof(N10B)=1-FVAR(1)
 Sof(C1A)=Sof(H1A)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=
 Sof(C4A)=Sof(C5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8A)=
 Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(C11A)=Sof(H11A)=Sof(H11B)=Sof(C12A)=Sof(H12A)=
 Sof(H12B)=Sof(H12C)=Sof(C13A)=Sof(H13A)=Sof(H13B)=Sof(C21A)=Sof(H21A)=
 Sof(H21B)=Sof(C22A)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C23A)=Sof(H23A)=
 Sof(H23B)=Sof(C24A)=Sof(H24A)=Sof(H24B)=Sof(C32A)=Sof(H32A)=Sof(H32B)=
 Sof(C33A)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C34A)=Sof(H34A)=Sof(H34B)=
 Sof(C35A)=Sof(C42A)=Sof(H42A)=Sof(H42B)=Sof(C43A)=Sof(H43A)=Sof(H43B)=
 Sof(H43C)=Sof(N1A)=Sof(N2A)=Sof(N3A)=Sof(N6A)=Sof(N10A)=FVAR(1)
 Sof(B1B)=Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(F4B)=1-FVAR(2)
 Sof(B1A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=FVAR(2)
 Sof(F5B)=Sof(F6B)=Sof(F7B)=Sof(F8B)=1-FVAR(3)
 Sof(F5A)=Sof(F6A)=Sof(F7A)=Sof(F8A)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C1A(H1A), C1B(H1B)
5.b Secondary CH2 refined with riding coordinates:
 C2A(H2AA,H2AB), C2B(H2BA,H2BB), C3A(H3AA,H3AB), C3B(H3BA,H3BB), C11A(H11A,
 H11B), C11B(H11C,H11D), C13A(H13A,H13B), C13B(H13C,H13D), C21A(H21A,H21B),
 C21B(H21C,H21D), C23A(H23A,H23B), C23B(H23C,H23D), C24A(H24A,H24B), C24B(H24C,
 H24D), C32A(H32A,H32B), C32B(H32C,H32D), C34A(H34A,H34B), C34B(H34C,H34D),
 C42A(H42A,H42B), C42B(H42C,H42D)
5.c Aromatic/amide H refined with riding coordinates:
 C6A(H6A), C6B(H6B), C7A(H7A), C7B(H7B), C8A(H8A), C8B(H8B), C9A(H9A),
 C9B(H9B), C16(H16), C17(H17), C18(H18), C19(H19), C27(H27), C28(H28), C29(H29),
  C30(H30), C37(H37), C38(H38), C39(H39), C40(H40), C46(H46), C47(H47),
 C49(H49), C50(H50)
5.d Idealised Me refined as rotating group:
 C12A(H12A,H12B,H12C), C12B(H12D,H12E,H12F), C22A(H22A,H22B,H22C), C22B(H22D,
 H22E,H22F), C33A(H33A,H33B,H33C), C33B(H33D,H33E,H33F), C43A(H43A,H43B,H43C),
 C43B(H43D,H43E,H43F)
;
_shelx_res_checksum              80874
_shelx_hkl_checksum              15951
_olex2_submission_special_instructions 'No special instructions were received'