Tuning Reactivity of Bioinspired [NiFe]-Hydrogenase Models by Ligand Design and Modeling the CO Inhibition Process
Brazzolotto, Deborah; Wang, Lianke; Tang, Hao; Gennari, Marcello; Queyriaux, Nicolas; Philouze, Christian; Demeshko, Serhiy; Meyer, Franc; Orio, Maylis; Artero, Vincent; Hall, Michael B.; Duboc, Carole; ACS Catalysis 8 (2018) 10658–; doi:10.1021/acscatal.8b02830

data_4515757
_publ_section_title
;
 Tuning Reactivity of Bioinspired [NiFe]-Hydrogenase Models by Ligand
 Design and Modeling the CO Inhibition Process
;
_journal_issue                   11
_journal_name_full               'ACS Catalysis'
_journal_page_first              10658
_journal_paper_doi               10.1021/acscatal.8b02830
_journal_volume                  8
_journal_year                    2018
_chemical_formula_moiety
'C49 H45 Fe N2 Ni O S2, 0.69(C H2 Cl2), 2(B0.5 F2), 0.15(C4 H10 O), 0.15(H2 O)'
_chemical_formula_sum            'C50.31 H48.22 B Cl1.39 F4 Fe N2 Ni O1.31 S2'
_chemical_formula_weight         1016.42
_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             2017-06-23
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                90
_cell_angle_beta                 127.48(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   25.286(5)
_cell_length_b                   23.295(5)
_cell_length_c                   20.693(4)
_cell_measurement_reflns_used    63311
_cell_measurement_temperature    200
_cell_measurement_theta_max      27.537
_cell_measurement_theta_min      2.210
_cell_volume                     9673(5)
_computing_cell_refinement       EvalCCD
_computing_data_collection       Collect
_computing_data_reduction        EvalCCD
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_diffrn_ambient_temperature      200
_diffrn_detector                 'CCD area detector'
_diffrn_detector_type            'APEX II'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  'Bruker-AXS-enraf-nonius KappaAPEXII'
_diffrn_measurement_method       'Phi and omega scans'
_diffrn_radiation_collimation    'Montel optic'
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Multilayer mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0391
_diffrn_reflns_av_unetI/netI     0.0267
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            63311
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.537
_diffrn_reflns_theta_min         2.210
_diffrn_source                   'Incoatec ISG250'
_diffrn_source_target            Mo
_diffrn_source_type              'Microfocus sealed tube'
_exptl_absorpt_coefficient_mu    0.907
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.711926
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2004/1 (Bruker,2004) was used for absorption correction.
R(int) was 0.0603 before and 0.0366 after correction.
The Ratio of minimum to maximum transmission is 0.7119.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.396
_exptl_crystal_description       needle
_exptl_crystal_F_000             4201
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.44
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.941
_refine_diff_density_min         -0.606
_refine_diff_density_rms         0.091
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.241
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     621
_refine_ls_number_reflns         11046
_refine_ls_number_restraints     622
_refine_ls_restrained_S_all      1.216
_refine_ls_R_factor_all          0.0868
_refine_ls_R_factor_gt           0.0666
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+84.9581P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1507
_refine_ls_wR_factor_ref         0.1615
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9024
_reflns_number_total             11046
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b02830_si_001.cif
_cod_data_source_block           NiFeCpSTAR
_cod_database_code               4515757
_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 O(H,H) groups
2. Restrained distances
 C54-C53
 1.5 with sigma of 0.02
 C54-O2
 1.5 with sigma of 0.02
 O2-C55
 1.5 with sigma of 0.02
 C55-C56
 1.5 with sigma of 0.02
 C53-O2
 2.5 with sigma of 0.02
 C54-C55
 2.5 with sigma of 0.02
 O2-C56
 2.5 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(C53) = Uanis(C56) = Uanis(O3)
Uanis(C54) = Uanis(C55)
5. Others
 Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=Sof(O2)=Sof(C54)=Sof(H54A)=Sof(H54B)=
 Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=Sof(O3)=
 Sof(H3A)=Sof(H3B)=0.5*(1-FVAR(2))
 Sof(Cl1)=Sof(Cl2)=Sof(C52)=Sof(H52A)=Sof(H52B)=FVAR(1)
6.a Riding coordinates:
 O3(H3A,H3B)
6.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C11(H11A,H11B), C52(H52A,H52B), C54(H54A,H54B), C55(H55A,H55B)
6.c Aromatic/amide H refined with riding coordinates:
 C34(H34), C3(H3), C35(H35), C15(H15), C2(H2), C32(H32), C19(H19), C28(H28),
 C30(H30), C7(H7), C4(H4), C36(H36), C21(H21), C29(H29), C8(H8), C37(H37),
 C23(H23), C18(H18), C16(H16), C38(H38), C22(H22), C25(H25), C9(H9), C17(H17),
 C31(H31), C24(H24)
6.d Idealised Me refined with riding coordinates:
 C53(H53A,H53B,H53C)
6.e Idealised Me refined as rotating group:
 C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C47(H47A,H47B,H47C), C49(H49A,H49B,
 H49C), C48(H48A,H48B,H48C), C56(H56A,H56B,H56C)
;
_shelx_res_checksum              58886
_shelx_hkl_checksum              40876
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'