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_4128961
_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
'C20 H26 Cl Fe N2 Ni O S2, 1.5(C H2 Cl2), B F4'
_chemical_formula_sum            'C21.5 H29 B Cl4 F4 Fe N2 Ni O S2'
_chemical_formula_weight         738.76
_space_group_crystal_system      orthorhombic
_space_group_IT_number           56
_space_group_name_Hall           '-P 2ab 2ac'
_space_group_name_H-M_alt        'P c c n'
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.3768(4)
_cell_length_b                   22.6888(6)
_cell_length_c                   24.5582(7)
_cell_measurement_reflns_used    9758
_cell_measurement_temperature    100
_cell_measurement_theta_max      78.736
_cell_measurement_theta_min      3.599
_cell_volume                     6339.1(3)
_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 0.968
_diffrn_measured_fraction_theta_max 0.968
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker CMOS area detector'
_diffrn_measurement_method       '\f and \w 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  0.0645
_diffrn_reflns_av_unetI/netI     0.0400
_diffrn_reflns_Laue_measured_fraction_full 0.968
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            31259
_diffrn_reflns_point_group_measured_fraction_full 0.968
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        62.666
_diffrn_reflns_theta_max         62.666
_diffrn_reflns_theta_min         3.599
_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    9.124
_exptl_absorpt_correction_T_max  0.1579
_exptl_absorpt_correction_T_min  0.0251
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1649 before and 0.1044 after correction. The Ratio of minimum to maximum transmission is 0.1590. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.548
_exptl_crystal_description       plate
_exptl_crystal_F_000             3000
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.835
_refine_diff_density_min         -0.985
_refine_diff_density_rms         0.164
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.127
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     386
_refine_ls_number_reflns         4926
_refine_ls_number_restraints     124
_refine_ls_restrained_S_all      1.127
_refine_ls_R_factor_all          0.1039
_refine_ls_R_factor_gt           0.0953
_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^)+(0.1036P)^2^+73.6076P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2362
_refine_ls_wR_factor_ref         0.2442
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4437
_reflns_number_total             4926
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b07448_si_004.cif
_cod_data_source_block           nicl
_cod_original_formula_sum        'C21.50 H29 B Cl4 F4 Fe N2 Ni O S2'
_cod_database_code               4128961
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.462
_shelx_estimated_absorpt_t_min   0.263
_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
 B1_1, F1_1, F2_1, F3_1, F4_1
 B1_2, F1_2, F2_2, F3_2, F4_2
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C17, C18, C19, C20, C21
 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: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21: within 2A with sigma of 0.005 and
sigma for terminal atoms of 0.01
4. Same fragment restrains
{B1_2, F1_2, F2_2, F3_2, F4_2}
as
{B1_1, F1_1, F2_1, F3_1, F4_1} sigma for 1-2: 0.005 1-3: 0.04
5. 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)
 Fixed Sof: H1BA(0.5) H1BB(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C8(H8A,H8B), C9(H9A,H9B),
 C10(H10A,H10B), C1A(H1AA,H1AB), C1B(H1BA,H1BB)
6.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C15(H15), C16(H16), C17(H17), C18(H18), C19(H19),
 C20(H20), C21(H21)
6.c Idealised Me refined as rotating group:
 C0AA(H0AA,H0AB,H0AC)
;
_shelx_res_checksum              97896
_shelx_hkl_checksum              4449
_shelx_fab_checksum              95736
_olex2_submission_special_instructions 'No special instructions were received'