Intramolecular Iron-Mediated C-H Bond Heterolysis with an Assist of Pendant Base in a [FeFe]-Hydrogenase Model.
Zheng, Dehua; Wang, Ning; Wang, Mei; Ding, Shengda; Ma, Chengbing; Darensbourg, Marcetta Y.; Hall, Michael B.; Sun, Licheng; Journal of the American Chemical Society  (2014) 141007112505006–; doi:10.1021/ja5078014

data_4122751
_publ_section_title
;
 Intramolecular Iron-Mediated C-H Bond Heterolysis with an Assist of
 Pendant Base in a [FeFe]-Hydrogenase Model.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              141007112505006
_journal_paper_doi               10.1021/ja5078014
_journal_year                    2014
_chemical_formula_moiety         'C39 H42 Fe2 N2 O4 P2 S2'
_chemical_formula_sum            'C39 H42 Fe2 N2 O4 P2 S2'
_chemical_formula_weight         840.50
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-04-07
_audit_creation_method
;
Olex2 1.2
(compiled 2014.02.17 svn.r2891 for OlexSys, GUI svn.r4777)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.1015(9)
_cell_length_b                   18.1158(9)
_cell_length_c                   23.9990(12)
_cell_measurement_reflns_used    9233
_cell_measurement_temperature    110
_cell_measurement_theta_max      26.749
_cell_measurement_theta_min      2.326
_cell_volume                     7869.8(7)
_computing_cell_refinement       'APEXII (Bruker, 2013)'
_computing_data_collection       'APEXII (Bruker, 2013)'
_computing_data_reduction        'SAINT (Bruker AXS Inc.)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2008)'
_diffrn_ambient_temperature      110
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker APEX2 area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_collimation    0.5
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0602
_diffrn_reflns_av_unetI/netI     0.0547
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            47239
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.351
_diffrn_reflns_theta_min         1.803
_diffrn_source                   'sealed X-ray tube'
_exptl_absorpt_coefficient_mu    0.967
_exptl_absorpt_correction_T_max  0.908
_exptl_absorpt_correction_T_min  0.890
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0479 before and 0.0321 after correction.
The Ratio of minimum to maximum transmission is 0.8615.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.419
_exptl_crystal_description       needle
_exptl_crystal_F_000             3488
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.585
_refine_diff_density_min         -0.308
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.991
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     574
_refine_ls_number_reflns         9800
_refine_ls_number_restraints     115
_refine_ls_restrained_S_all      0.987
_refine_ls_R_factor_all          0.1020
_refine_ls_R_factor_gt           0.0472
_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^)+(0.0506P)^2^+1.5901P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0937
_refine_ls_wR_factor_ref         0.1122
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5878
_reflns_number_total             9800
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5078014_si_002.cif
_cod_data_source_block           ok
_cod_database_code               4122751
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.910
_shelx_estimated_absorpt_t_min   0.830
_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
 C21_1, C22_1, C23_1, C24_1, C25_1, C26_1, C27_1
 C21_2, C22_2, C23_2, C24_2, C25_2, C26_2, C27_2
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
3. Same fragment restrains
{C5A, C6A, C7A, C8A, C9A}
as
{C5B, C6B, C7B, C8B, C9B}
4. Others
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(C22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24)=
 Sof(C25)=Sof(H25)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27)=1-FVAR(1)
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(C22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24)=
 Sof(C25)=Sof(H25)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27)=FVAR(1)
 Sof(C5B)=Sof(H5BA)=Sof(H5BB)=Sof(C6B)=Sof(C7B)=Sof(H7BA)=Sof(H7BB)=Sof(C8B)=
 Sof(H8BA)=Sof(H8BB)=Sof(H8BC)=Sof(C9B)=Sof(H9BA)=Sof(H9BB)=Sof(H9BC)=1-FVAR(2)
 Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(C6A)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(C8A)=
 Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C5A(H5AA,H5AB), C7A(H7AA,H7AB), C5B(H5BA,H5BB), C7B(H7BA,H7BB), C10(H10A,
 H10B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B),
 C21(H21A,H21B), C21(H21A,H21B)
5.b Aromatic/amide H refined with riding coordinates:
 C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C29(H29), C30(H30),
 C31(H31), C32(H32), C33(H33), C35(H35), C36(H36), C37(H37), C38(H38), C39(H39),
  C23(H23), C24(H24), C25(H25), C26(H26), C27(H27), C23(H23), C24(H24),
 C25(H25), C26(H26), C27(H27)
5.c Idealised Me refined as rotating group:
 C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,H9AC), C8B(H8BA,H8BB,H8BC), C9B(H9BA,H9BB,
 H9BC)
;
_shelx_res_checksum              70867
_shelx_hkl_checksum              74932
_olex2_computing_structure_refinement_long 'ShelXL (Sheldrick, 2008)'