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_4128959
_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         'C22 H32 Fe N3 Ni O3 S2, B F4'
_chemical_formula_sum            'C22 H32 B F4 Fe N3 Ni O3 S2'
_chemical_formula_weight         651.99
_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                 100.622(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.8354(7)
_cell_length_b                   9.9750(4)
_cell_length_c                   13.3013(5)
_cell_measurement_reflns_used    9933
_cell_measurement_temperature    100
_cell_measurement_theta_max      67.251
_cell_measurement_theta_min      5.579
_cell_volume                     2586.67(17)
_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      100.0
_diffrn_detector                 'Bruker CMOS area detector'
_diffrn_detector_area_resol_mean 10.5
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_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  0.0652
_diffrn_reflns_av_unetI/netI     0.0391
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            30203
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.284
_diffrn_reflns_theta_max         67.284
_diffrn_reflns_theta_min         2.266
_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    7.448
_exptl_absorpt_correction_T_max  0.7529
_exptl_absorpt_correction_T_min  0.3285
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1617 before and 0.0944 after correction. The Ratio of minimum to maximum transmission is 0.4363. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.674
_exptl_crystal_description       plate
_exptl_crystal_F_000             1344
_exptl_crystal_size_max          0.288
_exptl_crystal_size_mid          0.208
_exptl_crystal_size_min          0.038
_refine_diff_density_max         1.164
_refine_diff_density_min         -0.850
_refine_diff_density_rms         0.107
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     423
_refine_ls_number_reflns         4592
_refine_ls_number_restraints     173
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0664
_refine_ls_R_factor_gt           0.0607
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0783P)^2^+10.8049P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1529
_refine_ls_wR_factor_ref         0.1580
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4176
_reflns_number_total             4592
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b07448_si_006.cif
_cod_data_source_block           ninme2
_cod_database_code               4128959
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.765
_shelx_estimated_absorpt_t_min   0.223
_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
 C1A_1, C2A_1, C3A_1, C4A_1, C5A_1
 C1A_2, C2A_2, C3A_2, C4A_2, C5A_2
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 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 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
C1A_1 \\sim C2A_1 \\sim C3A_1 \\sim C4A_1 \\sim C5A_1 \\sim C1A_2 \\sim C2A_2
\\sim C3A_2 \\sim C4A_2 \\sim C5A_2: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01
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 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(B1_3) = Uanis(B1_4)
4. Same fragment restrains
{C1A_2, C2A_2, C3A_2, C4A_2, C5A_2}
as
{C1A_1, C2A_1, C3A_1, C4A_1, C5A_1} sigma for 1-2: 0.005 1-3: 0.04
{B1_4, F1_4, F2_4, F3_4, F4_4}
as
{B1_3, F1_3, F2_3, F3_3, F4_3} sigma for 1-2: 0.001 1-3: 0.04
5. Others
 Sof(C1A)=Sof(H1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=
 Sof(C5A)=Sof(H5A)=1-FVAR(1)
 Sof(C1A)=Sof(H1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=
 Sof(C5A)=Sof(H5A)=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)
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)
6.b Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C14(H14), C15(H15), C1A(H1A), C2A(H2A), C3A(H3A),
 C4A(H4A), C5A(H5A), C1A(H1A), C2A(H2A), C3A(H3A), C4A(H4A), C5A(H5A)
6.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C)
;
_shelx_res_checksum              1559
_shelx_hkl_checksum              70359
_olex2_submission_special_instructions 'No special instructions were received'