A 10(6)-Fold Enhancement in N2-Binding Affinity of an Fe2(μ-H)2 Core upon Reduction to a Mixed-Valence Fe(II)Fe(I) State.
Rittle, Jonathan; McCrory, Charles C. L.; Peters, Jonas C.; Journal of the American Chemical Society 136 (2014) 13853–13862; doi:10.1021/ja507217v

data_4122632
_publ_section_title
;
 A 10(6)-Fold Enhancement in N2-Binding Affinity of an Fe2(\m-H)2 Core
 upon Reduction to a Mixed-Valence Fe(II)Fe(I) State.
;
_journal_issue                   39
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13853
_journal_page_last               13862
_journal_paper_doi               10.1021/ja507217v
_journal_volume                  136
_journal_year                    2014
_chemical_formula_moiety
'C48 H74 Fe2 N4 O P4 Si2, 2(C8 H16 Na0.5 O4), 1.5(C4 H10 O)'
_chemical_formula_sum            'C70 H120.99 Fe2 N4 Na O10.5 P4 Si2'
_chemical_formula_weight         1501.40
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-05-28
_audit_creation_method
;
Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816),
 SHELXL-2014,
 and manual edit
;
_cell_angle_alpha                94.695(2)
_cell_angle_beta                 90.478(2)
_cell_angle_gamma                119.603(2)
_cell_formula_units_Z            2
_cell_length_a                   14.5593(10)
_cell_length_b                   14.5601(10)
_cell_length_c                   21.2237(14)
_cell_measurement_temperature    100
_cell_volume                     3892.5(5)
_computing_cell_refinement       'SAINT V8.34A (Bruker-AXS, 2007)'
_computing_data_collection       'APEX2 2014.1-1 (Bruker-AXS, 2007)'
_computing_data_reduction        'SAINT V8.34A (Bruker-AXS, 2007)'
_computing_molecular_graphics    'DIAMOND 3 (Crystal Impact, 1999)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/2 (Sheldrick, 2014)'
_computing_structure_solution    'XT-2014/1 (Sheldrick, 2012)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 8.33
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.929
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0472
_diffrn_reflns_av_unetI/netI     0.0424
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.929
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            144423
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.929
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         31.065
_diffrn_reflns_theta_min         1.616
_diffrn_source_current           30
_diffrn_source_power             1.5
_diffrn_source_target            Mo
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.548
_exptl_absorpt_correction_T_max  0.7462
_exptl_absorpt_correction_T_min  0.7003
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
;
_exptl_crystal_density_diffrn    1.281
_exptl_crystal_F_000             1608
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.21
_refine_diff_density_max         1.416
_refine_diff_density_min         -1.017
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1195
_refine_ls_number_reflns         23165
_refine_ls_number_restraints     103
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0813
_refine_ls_R_factor_gt           0.0487
_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^)+(0.0528P)^2^+3.3097P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1117
_refine_ls_wR_factor_ref         0.1279
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16445
_reflns_number_total             23165
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja507217v_si_003.cif
_cod_data_source_block           a14074
_cod_depositor_comments
'Adding full bibliography for 4122631--4122632.cif.'
_cod_original_formula_sum        'C70 H120.99 Fe2 N4 Na O10.50 P4 Si2'
_cod_database_code               4122632
_shelxl_version_number           2014-2
_shelx_estimated_absorpt_t_max   0.894
_shelx_estimated_absorpt_t_min   0.875
_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. Rigid body (RIGU) restrains
 C31A, C33A, C32A, C26A, C27A, C28A, C29A, C30A, C25A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C53A, C54A, O5A, C55A, C56A, O2A, C49A, C50A, O3A, C51A, C52A, O4A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Same fragment restrains
{O10, C65, C66, C67, C68}
as
{O11, C69, C70, C71, C72}
{O10, C65, C66, C67, C68}
as
{O11A, C69A, C70A, C71A, C72A}
4. Others
 1*[Sof(O11)+Sof(C69)+Sof(H69A)+Sof(H69B)+Sof(H69C)+Sof(C70)+Sof(H70A)+
 Sof(H70B)+Sof(C71)+Sof(H71A)+Sof(H71B)+Sof(C72)+Sof(H72A)+Sof(H72B)+Sof(H72C)]+
 1*[Sof(O11A)+Sof(C69A)+Sof(H69D)+Sof(H69E)+Sof(H69F)+Sof(C70A)+Sof(H70C)+
 Sof(H70D)+Sof(C71A)+Sof(H71C)+Sof(H71D)+Sof(C72A)+Sof(H72D)+Sof(H72E)+
 Sof(H72F)]=0.5 with esd of 0.001
 Sof(P3A)=Sof(C25A)=Sof(C26A)=Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(H28A)=
 Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(H30A)=Sof(C31A)=Sof(H31A)=Sof(C32A)=
 Sof(H32D)=Sof(H32E)=Sof(H32F)=Sof(C33A)=Sof(H33D)=Sof(H33E)=Sof(H33F)=
 Sof(C34A)=Sof(H34A)=Sof(C35A)=Sof(H35D)=Sof(H35E)=Sof(H35F)=Sof(C36A)=
 Sof(H36D)=Sof(H36E)=Sof(H36F)=1-FVAR(1)
 Sof(P3)=Sof(C25)=Sof(C26)=Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28)=Sof(C29)=
 Sof(H29)=Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31)=Sof(C32)=Sof(H32A)=Sof(H32B)=
 Sof(H32C)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C34)=Sof(H34)=Sof(C35)=
 Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=FVAR(1)
 Sof(O2A)=Sof(O3A)=Sof(O4A)=Sof(O5A)=Sof(C49A)=Sof(H49C)=Sof(H49D)=Sof(C50A)=
 Sof(H50C)=Sof(H50D)=Sof(C51A)=Sof(H51C)=Sof(H51D)=Sof(C52A)=Sof(H52C)=
 Sof(H52D)=Sof(C53A)=Sof(H53C)=Sof(H53D)=Sof(C54A)=Sof(H54C)=Sof(H54D)=
 Sof(C55A)=Sof(H55C)=Sof(H55D)=Sof(C56A)=Sof(H56C)=Sof(H56D)=1-FVAR(2)
 Sof(O2)=Sof(O3)=Sof(O4)=Sof(O5)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(C50)=
 Sof(H50A)=Sof(H50B)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(C52)=Sof(H52A)=Sof(H52B)=
 Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(C55)=Sof(H55A)=
 Sof(H55B)=Sof(C56)=Sof(H56A)=Sof(H56B)=FVAR(2)
 Sof(O6A)=Sof(O7A)=Sof(O8A)=Sof(O9A)=Sof(C57A)=Sof(H57C)=Sof(H57D)=Sof(C58A)=
 Sof(H58C)=Sof(H58D)=Sof(C59A)=Sof(H59C)=Sof(H59D)=Sof(C60A)=Sof(H60C)=
 Sof(H60D)=Sof(C61A)=Sof(H61C)=Sof(H61D)=Sof(C62A)=Sof(H62C)=Sof(H62D)=
 Sof(C63A)=Sof(H63C)=Sof(H63D)=Sof(C64A)=Sof(H64C)=Sof(H64D)=1-FVAR(3)
 Sof(O6)=Sof(O7)=Sof(O8)=Sof(O9)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(C58)=
 Sof(H58A)=Sof(H58B)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(C60)=Sof(H60A)=Sof(H60B)=
 Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(C63)=Sof(H63A)=
 Sof(H63B)=Sof(C64)=Sof(H64A)=Sof(H64B)=FVAR(3)
 Sof(O11)=Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(H69C)=Sof(C70)=Sof(H70A)=Sof(H70B)=
 Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(H72C)=FVAR(4)
 Sof(O11A)=Sof(C69A)=Sof(H69D)=Sof(H69E)=Sof(H69F)=Sof(C70A)=Sof(H70C)=
 Sof(H70D)=Sof(C71A)=Sof(H71C)=Sof(H71D)=Sof(C72A)=Sof(H72D)=Sof(H72E)=
 Sof(H72F)=FVAR(5)
 Uiso(O11)=Uiso(C69)=Uiso(C70)=Uiso(C71)=Uiso(C72)=FVAR(6)
 Uiso(O11A)=Uiso(C69A)=Uiso(C70A)=Uiso(C71A)=Uiso(C72A)=FVAR(7)
5.a Ternary CH refined with riding coordinates:
 C7(H7), C10(H10), C19(H19), C22(H22), C31(H31), C34(H34), C31A(H31A),
 C34A(H34A), C43(H43), C46(H46)
5.b Secondary CH2 refined with riding coordinates:
 C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B), C52(H52A,H52B), C53(H53A,
 H53B), C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B), C49A(H49C,H49D),
 C50A(H50C,H50D), C51A(H51C,H51D), C52A(H52C,H52D), C53A(H53C,H53D), C54A(H54C,
 H54D), C55A(H55C,H55D), C56A(H56C,H56D), C57(H57A,H57B), C58(H58A,H58B),
 C59(H59A,H59B), C60(H60A,H60B), C61(H61A,H61B), C62(H62A,H62B), C63(H63A,H63B),
  C64(H64A,H64B), C57A(H57C,H57D), C58A(H58C,H58D), C59A(H59C,H59D), C60A(H60C,
 H60D), C61A(H61C,H61D), C62A(H62C,H62D), C63A(H63C,H63D), C64A(H64C,H64D),
 C66(H66A,H66B), C67(H67A,H67B), C70(H70A,H70B), C71(H71A,H71B), C70A(H70C,
 H70D), C71A(H71C,H71D)
5.c Me refined with riding coordinates:
 C72(H72A,H72B,H72C), C72A(H72D,H72E,H72F)
5.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C15(H15), C16(H16), C17(H17), C18(H18),
 C27(H27), C28(H28), C29(H29), C30(H30), C27A(H27A), C28A(H28A), C29A(H29A),
 C30A(H30A), C39(H39), C40(H40), C41(H41), C42(H42)
5.e Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C),
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C), C36(H36A,
 H36B,H36C), C32A(H32D,H32E,H32F), C33A(H33D,H33E,H33F), C35A(H35D,H35E,H35F),
 C36A(H36D,H36E,H36F), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C47(H47A,H47B,
 H47C), C48(H48A,H48B,H48C), C65(H65A,H65B,H65C), C68(H68A,H68B,H68C), C69(H69A,
 H69B,H69C), C69A(H69D,H69E,H69F)
;