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_4122748
_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, 2(B F4)'
_chemical_formula_sum            'C39 H42 B2 F8 Fe2 N2 O4 P2 S2'
_chemical_formula_weight         1014.12
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2014-04-17
_audit_creation_method
;
Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.474(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.135(4)
_cell_length_b                   19.904(8)
_cell_length_c                   28.122(12)
_cell_measurement_temperature    296(2)
_cell_volume                     5611(4)
_computing_cell_refinement       'SAINT (Bruker AXS Inc.)'
_computing_data_collection       'APEX2 (Bruker AXS Inc.)'
_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)'
_diffrn_ambient_temperature      296
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker APEX2 area detector'
_diffrn_measured_fraction_theta_full 0.948
_diffrn_measured_fraction_theta_max 0.975
_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  0.1533
_diffrn_reflns_av_unetI/netI     0.2507
_diffrn_reflns_Laue_measured_fraction_full 0.948
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            21191
_diffrn_reflns_point_group_measured_fraction_full 0.948
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.046
_diffrn_source                   'sealed X-ray tube'
_exptl_absorpt_coefficient_mu    0.708
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.201
_exptl_crystal_description       needle
_exptl_crystal_F_000             2072
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_exptl_transmission_factor_max   0.965
_exptl_transmission_factor_min   0.950
_platon_squeeze_details
;
A disordered included molecule of CH2Cl2 was present in the asymetric
unit.  After several attempts to model the disorder, it was decided
to subract the contribution of the included molecule from the refinement
by employing the SQUEEZE/PLATON program.
;
_refine_diff_density_max         0.362
_refine_diff_density_min         -0.385
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.996
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     647
_refine_ls_number_reflns         9630
_refine_ls_number_restraints     196
_refine_ls_restrained_S_all      0.997
_refine_ls_R_factor_all          0.2360
_refine_ls_R_factor_gt           0.0904
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0600P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1660
_refine_ls_wR_factor_ref         0.2199
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3307
_reflns_number_total             9630
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5078014_si_004.cif
_cod_data_source_block           dim_pnp
_cod_database_code               4122748
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.933
_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, All N(H) groups
2. Rigid bond restraints
 B1_1, F1_1, F2_1, F3_1, F4_1
 B1_2, F1_2, F2_2, F3_2, F4_2
 B1_3, F1_3, F2_3, F3_3, F4_3
 B1_4, F1_4, F2_4, F3_4, F4_4
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
3. Uiso/Uaniso restraints and constraints
B1_1 \\sim F1_1 \\sim F2_1 \\sim F3_1 \\sim F4_1 \\sim B1_2 \\sim F1_2 \\sim
F2_2 \\sim F3_2 \\sim F4_2 \\sim B1_3 \\sim F1_3 \\sim F2_3 \\sim F3_3 \\sim
F4_3 \\sim B1_4 \\sim F1_4 \\sim F2_4 \\sim F3_4 \\sim F4_4: within 1.7A with
sigma of 0.005 and sigma for terminal atoms of 0.01
4. Others
 Sof(B1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=1-FVAR(1)
 Sof(B1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=FVAR(1)
 Sof(B1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=1-FVAR(2)
 Sof(B1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C5(H5)
5.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B),
 C20(H20A,H20B), C27(H27A,H27B)
5.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C22(H22), C23(H23),
 C24(H24), C25(H25), C26(H26), C29(H29), C30(H30), C31(H31), C32(H32), C33(H33),
  C35(H35), C36(H36), C37(H37), C38(H38), C39(H39)
5.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C)
;
_shelx_res_checksum              93328
_shelx_hkl_checksum              89976
_shelx_fab_checksum              48403