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_4128958
_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         'C15 H21 F3 N2 Ni S2, C2 H3 N'
_chemical_formula_sum            'C17 H24 F3 N3 Ni S2'
_chemical_formula_weight         450.22
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-07-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.076(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.698(3)
_cell_length_b                   15.104(3)
_cell_length_c                   10.542(2)
_cell_measurement_reflns_used    9198
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      66.740
_cell_measurement_theta_min      4.591
_cell_volume                     1990.7(7)
_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      99.99
_diffrn_detector                 'Bruker CMOS area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker Micro-Source CMOS'
_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  0.0467
_diffrn_reflns_av_unetI/netI     0.0271
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            26307
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        66.734
_diffrn_reflns_theta_max         66.734
_diffrn_reflns_theta_min         4.591
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.668
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.3755
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1555 before and 0.0671 after correction. The Ratio of minimum to maximum transmission is 0.4988. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.502
_exptl_crystal_description       needle
_exptl_crystal_F_000             936
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.980
_refine_diff_density_min         -0.754
_refine_diff_density_rms         0.093
_refine_ls_extinction_coef       0.0018(5)
_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   1.091
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     265
_refine_ls_number_reflns         3479
_refine_ls_number_restraints     78
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0549
_refine_ls_R_factor_gt           0.0515
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0855P)^2^+3.9456P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1459
_refine_ls_wR_factor_ref         0.1521
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3244
_reflns_number_total             3479
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b07448_si_005.cif
_cod_data_source_block           niphcf3_jr
_cod_original_cell_volume        1990.8(7)
_cod_database_code               4128958
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.964
_shelx_estimated_absorpt_t_min   0.711
_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. Restrained distances
 N1B-C1B = N1A-C1A
 1.137 with sigma of 0.003
 N1B-C2B = N1A-C2A
 2.593 with sigma of 0.001
 C1B-C2B = C1A-C2A
 1.456 with sigma of 0.003
3. Rigid bond restraints
 N1A, C1A, C2A, N1B, C1B, C2B
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
N1A \\sim C1A \\sim C2A \\sim N1B \\sim C1B \\sim C2B: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01
5. Others
 Sof(N1B)=Sof(C1B)=Sof(C2B)=Sof(H2BA)=Sof(H2BB)=Sof(H2BC)=1-FVAR(1)
 Sof(N1A)=Sof(C1A)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=FVAR(1)
6.a Riding coordinates:
 C2A(H2AA,H2AB,H2AC), C2B(H2BA,H2BB,H2BC)
6.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B),
 C8(H8A,H8B)
6.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C13(H13), C00D(H00D)
6.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_shelx_res_checksum              64133
_shelx_hkl_checksum              42842
_olex2_submission_special_instructions 'No special instructions were received'