Scaffold-based [Fe]-hydrogenase model: H<sub>2</sub> activation initiates Fe(0)-hydride extrusion and non-biomimetic hydride transfer.
Kerns, Spencer A.; Seo, Junhyeok; Lynch, Vincent M.; Shearer, Jason; Goralski, Sean T.; Sullivan, Eileen R.; Rose, Michael J.; Chemical science 12 (2021) 12838–12846; doi:10.1039/d0sc03154b

data_1564614
_publ_section_title
;
 Scaffold-based [Fe]-hydrogenase model: H<sub>2</sub> activation initiates
 Fe(0)-hydride extrusion and non-biomimetic hydride transfer.
;
_journal_issue                   38
_journal_name_full               'Chemical science'
_journal_page_first              12838
_journal_page_last               12846
_journal_paper_doi               10.1039/d0sc03154b
_journal_volume                  12
_journal_year                    2021
_chemical_formula_moiety         'C64 H44 Fe2 N4 O6 S2, 2(C2 H3 N), 1.005(O)'
_chemical_formula_sum            'C68 H50 Fe2 N6 O7 S2'
_chemical_formula_weight         1238.96
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-12-16
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_audit_update_record
;
2019-12-24 deposited with the CCDC.	2021-09-01 downloaded from the CCDC.
;
_cell_angle_alpha                85.196(8)
_cell_angle_beta                 78.200(8)
_cell_angle_gamma                68.001(9)
_cell_formula_units_Z            2
_cell_length_a                   12.1400(12)
_cell_length_b                   14.7031(14)
_cell_length_c                   18.3340(17)
_cell_measurement_reflns_used    4716
_cell_measurement_temperature    100.1(6)
_cell_measurement_theta_max      72.8580
_cell_measurement_theta_min      3.1970
_cell_volume                     2970.1(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT n/a (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.1(6)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2940
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.975
_diffrn_measured_fraction_theta_max 0.943
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -72.00  36.00   1.00   10.00    --  -39.84  77.00-120.00  108
  2  \w   -114.00 -15.00   1.00   10.00    --  -39.84 -38.00 -30.00   99
  3  \w    -64.00  34.00   1.00   10.00    --  -39.84  38.00 150.00   98
  4  \w     55.00 127.00   1.00   10.00    --   39.84-178.00 120.00   72
  5  \w     83.00 178.00   1.00   12.50    --  108.64  45.00 150.00   95
  6  \w     35.00 118.00   1.00   12.50    --  108.64-125.00 150.00   83
  7  \w     32.00 141.00   1.00   12.50    --  108.64 -77.00  60.00  109
  8  \w     35.00 118.00   1.00   12.50    --  108.64-125.00-120.00   83
  9  \w     36.00 138.00   1.00   12.50    --  108.64 -61.00-180.00  102
 10  \w     83.00 178.00   1.00   12.50    --  108.64  45.00 -30.00   95
 11  \w     36.00 134.00   1.00   12.50    --  108.64 -45.00 -30.00   98
 12  \w     35.00  93.00   1.00   12.50    --  108.64-125.00  30.00   58
 13  \w     56.00 178.00   1.00   12.50    --  108.64  15.00 -90.00  122
 14  \w   -112.00 -12.00   1.00   10.00    --  -39.84 -57.00 120.00  100
 15  \w   -116.00  -7.00   1.00   10.00    --  -39.84 -77.00  60.00  109
 16  \w   -116.00  -7.00   1.00   10.00    --  -39.84 -77.00 -30.00  109
 17  \w   -116.00 -63.00   1.00   10.00    --  -39.84 -77.00-120.00   53
 18  \w     80.00 178.00   1.00   12.50    --  108.64  61.00  90.00   98
 19  \w     76.00 178.00   1.00   12.50    --  108.64  77.00 -90.00  102
 20  \w     80.00 178.00   1.00   12.50    --  108.64  30.00  60.00   98
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0346991000
_diffrn_orient_matrix_UB_12      0.0665892000
_diffrn_orient_matrix_UB_13      -0.0624867000
_diffrn_orient_matrix_UB_21      0.0879965000
_diffrn_orient_matrix_UB_22      0.0131495000
_diffrn_orient_matrix_UB_23      0.0442622000
_diffrn_orient_matrix_UB_31      0.1023406000
_diffrn_orient_matrix_UB_32      -0.0903749000
_diffrn_orient_matrix_UB_33      -0.0388172000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0780
_diffrn_reflns_av_unetI/netI     0.0968
_diffrn_reflns_Laue_measured_fraction_full 0.975
_diffrn_reflns_Laue_measured_fraction_max 0.943
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            29922
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.943
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.154
_diffrn_reflns_theta_min         2.462
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.067
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.43990
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.39a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.385
_exptl_crystal_description       plate
_exptl_crystal_F_000             1280
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.051
_refine_diff_density_max         1.068
_refine_diff_density_min         -0.514
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     871
_refine_ls_number_reflns         11382
_refine_ls_number_restraints     152
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.1415
_refine_ls_R_factor_gt           0.0904
_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^)+(0.0906P)^2^+8.3422P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2078
_refine_ls_wR_factor_ref         0.2386
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7130
_reflns_number_total             11382
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc03154b2.cif
_cod_data_source_block           sak_feacyl_deprot
_cod_depositor_comments
'Adding full bibliography for 1564612--1564614.cif.'
_cod_original_cell_volume        2970.0(5)
_cod_database_code               1564614
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C25 H50 N2 S1 O3 Fe1'
_shelx_estimated_absorpt_t_max   0.782
_shelx_estimated_absorpt_t_min   0.402
_reflns_odcompleteness_completeness 98.77
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C68-C67
 1.45 with sigma of 0.02
 C67-N69
 1.15 with sigma of 0.02
 S2A-C69
 1.8 with sigma of 0.03
 C56-S2
 1.8 with sigma of 0.01
 C69-S2A
 1.8 with sigma of 0.01
 S2-C52 \\sim S2-C52A
 with sigma of 0.02
 C46-C50 \\sim C46-C50A
 with sigma of 0.02
 C50-C51 \\sim C50A-C51A
 with sigma of 0.02
 C50-C55 \\sim C50A-C55A
 with sigma of 0.02
 C51-C52 \\sim C51A-C52A
 with sigma of 0.02
 C52-C53 \\sim C52A-C53A
 with sigma of 0.02
 C52-S2A \\sim C52A-S2A
 with sigma of 0.02
 C53-C54 \\sim C53A-C54A
 with sigma of 0.02
 C54-C55 \\sim C54A-C55A
 with sigma of 0.02
 S2-C51 \\sim S2-C51A
 with sigma of 0.04
 S2-C53 \\sim S2-C53A
 with sigma of 0.04
 C46-C51 \\sim C46-C51A
 with sigma of 0.04
 C46-C55 \\sim C46-C55A
 with sigma of 0.04
 C50-C52 \\sim C50A-C52A
 with sigma of 0.04
 C50-C54 \\sim C50A-C54A
 with sigma of 0.04
 C51-C53 \\sim C51A-C53A
 with sigma of 0.04
 C51-C55 \\sim C51A-C55A
 with sigma of 0.04
 C51-S2A \\sim C51A-S2A
 with sigma of 0.04
 C52-C54 \\sim C52A-C54A
 with sigma of 0.04
 C53-C55 \\sim C53A-C55A
 with sigma of 0.04
 C53-S2A \\sim C53A-S2A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C51A \\sim C52A \\sim C53A
\\sim C54A \\sim C55A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C56 \\sim S2: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
Uanis(C50) = Uanis(C50A)
4. Others
 Sof(S2A)=Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(H69C)=Sof(C50A)=Sof(C51A)=Sof(H51A)=
 Sof(C52A)=Sof(C53A)=Sof(H53A)=Sof(C54A)=Sof(H54A)=Sof(C55A)=Sof(H55A)=1-FVAR(1)
 Sof(S2)=Sof(C50)=Sof(C51)=Sof(H51)=Sof(C52)=Sof(C53)=Sof(H53)=Sof(C54)=
 Sof(H54)=Sof(C55)=Sof(H55)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=FVAR(1)
 Sof(N69)=Sof(C67)=Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=1-FVAR(2)
 Sof(N6)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=Sof(C65)=FVAR(2)
 Uiso(O7)=Uiso(O8)=Uiso(O9)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C2(H2), C30(H30)
5.b Me refined with riding coordinates:
 C56(H56A,H56B,H56C), C69(H69A,H69B,H69C)
5.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C7(H7), C9(H9), C10(H10), C11(H11), C13(H13), C15(H15),
 C16(H16), C17(H17), C20(H20), C23(H23), C25(H25), C26(H26), C27(H27), C32(H32),
  C33(H33), C35(H35), C37(H37), C38(H38), C39(H39), C41(H41), C43(H43),
 C44(H44), C45(H45), C48(H48), C51(H51), C53(H53), C54(H54), C55(H55),
 C51A(H51A), C53A(H53A), C54A(H54A), C55A(H55A)
5.d Idealised Me refined as rotating group:
 C021(H02A,H02B,H02C), C28(H28A,H28B,H28C), C62(H62A,H62B,H62C), C64(H64A,H64B,
 H64C), C66(H66A,H66B,H66C), C68(H68A,H68B,H68C)
;
_shelx_res_checksum              78149
_olex2_date_sample_data_collection 2019-08-05
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.220
_oxdiff_exptl_absorpt_empirical_full_min 0.582