Controlling O<sub>2</sub> Reactivity in Synthetic Analogues of [NiFeS]- and [NiFeSe]-Hydrogenase Active Sites.
Yang, Xuemei; Elrod, Lindy C.; Le, Trung; Vega, Valeria S.; Naumann, Haley; Rezenom, Yohannes; Reibenspies, Joseph H.; Hall, Michael B.; Darensbourg, Marcetta Y.; Journal of the American Chemical Society 141 (2019) 15338–15347; doi:10.1021/jacs.9b07448

data_4128960
_publ_section_title
;
 Controlling O<sub>2</sub> Reactivity in Synthetic Analogues of [NiFeS]-
 and [NiFeSe]-Hydrogenase Active Sites.
;
_journal_issue                   38
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              15338
_journal_page_last               15347
_journal_paper_doi               10.1021/jacs.9b07448
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C21 H26 F3 Fe N2 Ni O S2, B F4, C H2 Cl2'
_chemical_formula_sum            'C22 H28 B Cl2 F7 Fe N2 Ni O S2'
_chemical_formula_weight         729.85
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-12-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 107.146(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.0122(4)
_cell_length_b                   31.7923(14)
_cell_length_c                   11.9134(6)
_cell_measurement_reflns_used    9901
_cell_measurement_temperature    100
_cell_measurement_theta_max      67.71
_cell_measurement_theta_min      4.78
_cell_volume                     2899.8(2)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker CMOS area detector'
_diffrn_detector_area_resol_mean 10.5
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker CMOS area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0653
_diffrn_reflns_av_unetI/netI     0.0476
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            31845
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.543
_diffrn_reflns_theta_min         2.780
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    8.463
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.4483
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1423 before and 0.0840 after correction. The Ratio of minimum to maximum transmission is 0.5953. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.672
_exptl_crystal_description       needle
_exptl_crystal_F_000             1480
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.250
_refine_diff_density_min         -0.455
_refine_diff_density_rms         0.105
_refine_ls_extinction_coef       0.00056(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     382
_refine_ls_number_reflns         5275
_refine_ls_number_restraints     33
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.1110
_refine_ls_R_factor_gt           0.0835
_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^)+(0.0003P)^2^+25.8502P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1652
_refine_ls_wR_factor_ref         0.1789
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4021
_reflns_number_total             5275
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b07448_si_003.cif
_cod_data_source_block           nicf3fe
_cod_database_code               4128960
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.485
_shelx_estimated_absorpt_t_min   0.282
_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 bond restraints
 Cl1_1, Cl2_1, C1_1
 Cl1_2, Cl2_2, C1_2
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
3. Uiso/Uaniso restraints and constraints
Cl1_1 \\sim Cl2_1 \\sim C1_1 \\sim Cl1_2 \\sim Cl2_2 \\sim C1_2: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01
4. Same fragment restrains
{Cl1_2, Cl2_2, C1_2}
as
{Cl1_1, Cl2_1, C1_1} sigma for 1-2: 0.005 1-3: 0.04
5. Others
 Sof(Cl1)=Sof(Cl2)=Sof(C1)=Sof(H1A)=Sof(H1B)=1-FVAR(1)
 Sof(Cl1)=Sof(Cl2)=Sof(C1)=Sof(H1A)=Sof(H1B)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B),
 C9(H9A,H9B), C1(H1A,H1B), C1(H1A,H1B)
6.b Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C14(H14), C15(H15), C17(H17), C18(H18), C19(H19),
 C20(H20), C21(H21)
6.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C)
;
_shelx_res_checksum              50580
_shelx_hkl_checksum              39848
_olex2_submission_special_instructions 'No special instructions were received'