Ni(I)/Ru(II) Model for the Ni-L State of the [NiFe]Hydrogenases: Synthesis, Spectroscopy, and Reactivity.
Chambers, Geoffrey M.; Mitra, Joyee; Rauchfuss, Thomas B.; Stein, Matthias; Inorganic chemistry 53 (2014) 4243–4249; doi:10.1021/ic500389p

data_4337899
_publ_section_title
;
 Ni(I)/Ru(II) Model for the Ni-L State of the [NiFe]Hydrogenases:
 Synthesis, Spectroscopy, and Reactivity.
;
_journal_issue                   8
_journal_name_full               'Inorganic chemistry'
_journal_page_first              4243
_journal_page_last               4249
_journal_paper_doi               10.1021/ic500389p
_journal_volume                  53
_journal_year                    2014
_chemical_formula_moiety         'C32 H12 B F24, C39 H43 Ni P2 Ru S2'
_chemical_formula_sum            'C71 H55 B F24 Ni P2 Ru S2'
_chemical_formula_weight         1660.80
_chemical_name_systematic
;
? 
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-01-13
_audit_creation_method           SHELXL-97
_audit_update_record
;
? 
;
_cell_angle_alpha                90.00
_cell_angle_beta                 96.940(3)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   11.9100(9)
_cell_length_b                   16.8607(11)
_cell_length_c                   34.616(3)
_cell_measurement_reflns_used    0
_cell_measurement_temperature    100
_cell_measurement_theta_max      0.000
_cell_measurement_theta_min      0.000
_cell_volume                     6900.3(9)
_computing_cell_refinement       'SAINT V7.68A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2013.2-0 (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.27A (Bruker, 2012)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'SHELXTL V6.12 (Bruker, 2005)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'Bruker Kappa/ApexII CCD'
_diffrn_measurement_method       'profile data from \f and \w scans'
_diffrn_radiation_monochromator  'multilayer optics''
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0794
_diffrn_reflns_av_unetI/netI     0.0476
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            102997
_diffrn_reflns_theta_full        25.74
_diffrn_reflns_theta_max         25.74
_diffrn_reflns_theta_min         2.10
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    0.706
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8402
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.0775 before and 0.0703 after correction. The Ratio of minimum to maximum transmission is 0.8402. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.599
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             3344
_exptl_crystal_size_max          0.146
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.052
_refine_diff_density_max         1.902
_refine_diff_density_min         -0.700
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1102
_refine_ls_number_reflns         13163
_refine_ls_number_restraints     1915
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0669
_refine_ls_R_factor_gt           0.0433
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0315P)^2^+12.9763P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0880
_refine_ls_wR_factor_ref         0.0966
_reflns_number_gt                10180
_reflns_number_total             13163
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic500389p_si_002.cif
_cod_data_source_block           mo_uiuc_b82x_0m
_cod_depositor_comments
'Adding full bibliography for 4337898--4337899.cif.'
_cod_database_code               4337899
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All S(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C5-C8B \\sim C5-C8A
 with sigma of 0.01
 C32-C27 \\sim C31-C29 \\sim C16-C13 \\sim C24-C21 \\sim C7-C3 \\sim C8A-C5
 \\sim C8B-C5 \\sim C15A-C11 \\sim C15B-C11 \\sim C23-C19
 with sigma of 0.01
 F13A-F14A \\sim F13A-F15A \\sim F14A-F15A \\sim F13B-F14B \\sim F13B-F15B
 \\sim F14B-F15B \\sim F19A-F20A \\sim F19A-F21A \\sim F20A-F21A 
 \\sim F19B-F20B \\sim F19B-F21B \\sim F20B-F21B \\sim F7A-F8A
 \\sim F7A-F9A \\sim F8A-F9A \\sim F1A-F2A \\sim F1A-F3A \\sim F2A-F3A 
 \\sim F1B-F2B \\sim F1B-F3B \\sim F2B-F3B
 \\sim F4-F5 \\sim F4-F6 \\sim F5-F6 \\sim F7A-F8A \\sim F7A-F9A \\sim F8A-F9A
 \\sim F7B-F8B \\sim F7B-F9B \\sim F8B-F9B \\sim F10-F11 \\sim F10-F12 
 \\sim F11-F12 \\sim F16-F17 \\sim F16-F18
 \\sim F17-F18 \\sim F22A-F24A \\sim F22A-F23A \\sim F23A-F24A \\sim F22B-F23B
 \\sim F22B-F24B \\sim F23B-F24B
 with sigma of 0.01
 F13A-C32 \\sim F13B-C32 \\sim F15A-C32 \\sim F15B-C32 \\sim F14A-C32 
 \\sim F14B-C32 \\sim F8A-C15A \\sim F9A-C15A \\sim F7A-C15A \\sim F8B-C15B
 \\sim F9B-C15B \\sim F7B-C15B \\sim F12-C16 \\sim F11-C16 \\sim F10-C16 
 \\sim F3A-C8A \\sim F1A-C8A \\sim F2A-C8A \\sim F3B-C8B \\sim F1B-C8B
 \\sim F2B-C8B \\sim F19A-C24 \\sim F19B-C24 \\sim F20A-C24 \\sim F20B-C24 
 \\sim F21A-C24 \\sim F21B-C24 \\sim F22A-C23 \\sim F24A-C23 \\sim F23B-C23
 \\sim F18-C31 \\sim F17-C31 \\sim F16-C31 \\sim F6-C7 \\sim F5-C7
 \\sim F4-C7 \\sim F22B-C23 \\sim F23B-C23 \\sim F24B-C23
 with sigma of 0.01
 C43B-C44B \\sim C43A-C44A
 with sigma of 0.01
 Ru1-C43B \\sim Ru1-C43A
 with sigma of 0.01
 S1-C43B \\sim S2-C43A
 with sigma of 0.01
 S2-C43A \\sim S1-C43B
 with sigma of 0.01
 C45A-C44A \\sim C45B-C44B
 with sigma of 0.01
 S1-C45A \\sim S2-C45B
 with sigma of 0.01
3. Rigid bond restraints
 C43A, C44A, C44B, C43B, C45A, C45B, C44A, C44B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
F1A \\sim F1B \\sim F2A \\sim F2B \\sim F3A \\sim F3B \\sim F4 \\sim F5 \\sim
F6 \\sim F7A \\sim F7B \\sim F8A \\sim F8B \\sim F9A \\sim F9B \\sim F10 \\sim
F11 \\sim F12 \\sim F13A \\sim F13B \\sim F14A \\sim F14B \\sim F15A \\sim F15B
\\sim F16 \\sim F17 \\sim F18 \\sim F19A \\sim F19B \\sim F20A \\sim F20B \\sim
F21A \\sim F21B \\sim F22A \\sim F24A \\sim F23B \\sim F24B \\sim F23A \\sim
F22B: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.01
C44B \\sim C44A \\sim C43B \\sim C43A \\sim C44A \\sim C44B \\sim C45A \\sim
C45B: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F1A) \\sim Ueq, Uanis(F1B) \\sim Ueq, Uanis(F2A) \\sim Ueq, Uanis(F2B)
\\sim Ueq, Uanis(F3A) \\sim Ueq, Uanis(F3B) \\sim Ueq, Uanis(F4) \\sim Ueq,
Uanis(F5) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(F7A) \\sim Ueq, Uanis(F7B)
\\sim Ueq, Uanis(F8A) \\sim Ueq, Uanis(F8B) \\sim Ueq, Uanis(F9A) \\sim Ueq,
Uanis(F9B) \\sim Ueq, Uanis(F10) \\sim Ueq, Uanis(F11) \\sim Ueq, Uanis(F12)
\\sim Ueq, Uanis(F13A) \\sim Ueq, Uanis(F13B) \\sim Ueq, Uanis(F14A) \\sim Ueq,
Uanis(F14B) \\sim Ueq, Uanis(F15A) \\sim Ueq, Uanis(F15B) \\sim Ueq, Uanis(F16)
\\sim Ueq, Uanis(F17) \\sim Ueq, Uanis(F18) \\sim Ueq, Uanis(F19A) \\sim Ueq,
Uanis(F19B) \\sim Ueq, Uanis(F20A) \\sim Ueq, Uanis(F20B) \\sim Ueq,
Uanis(F21A) \\sim Ueq, Uanis(F21B) \\sim Ueq, Uanis(F22A) \\sim Ueq,
Uanis(F24A) \\sim Ueq, Uanis(F23B) \\sim Ueq, Uanis(F24B) \\sim Ueq,
Uanis(F23A) \\sim Ueq, Uanis(F22B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.01
Uanis(C8A) = Uanis(C8B)
Uanis(C15A) = Uanis(C15B)
5. Others
 1*[Sof(F13A)+Sof(F14A)+Sof(F15A)]+1*[Sof(F13B)+Sof(F14B)+Sof(F15B)]=1 with
 esd of 0.0001
 Sof(F13A)=Sof(F14A)=Sof(F15A)=FVAR(1)
 Sof(F19B)=Sof(F20B)=Sof(F21B)=1-FVAR(2)
 Sof(F19A)=Sof(F20A)=Sof(F21A)=FVAR(2)
 Sof(C43B)=Sof(C44B)=Sof(H44C)=Sof(H44D)=Sof(C45B)=Sof(H45C)=Sof(H45D)=
 Sof(H43B)=1-FVAR(3)
 Sof(C43A)=Sof(H43A)=Sof(C44A)=Sof(H44A)=Sof(H44B)=Sof(C45A)=Sof(H45A)=
 Sof(H45B)=FVAR(3)
 Sof(F13B)=Sof(F14B)=Sof(F15B)=FVAR(4)
 Sof(C8B)=Sof(F1B)=Sof(F2B)=Sof(F3B)=1-FVAR(5)
 Sof(C8A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=FVAR(5)
 Sof(C15B)=Sof(F7B)=Sof(F8B)=Sof(F9B)=Sof(F23B)=Sof(F24B)=Sof(F22B)=1-FVAR(6)
 Sof(C15A)=Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(F22A)=Sof(F24A)=Sof(F23A)=FVAR(6)
6.a Ternary CH refined with riding coordinates:
 C39(H39)
6.b Secondary CH2 refined with riding coordinates:
 C44A(H44A,H44B), C44B(H44C,H44D), C45A(H45A,H45B), C45B(H45C,H45D), C70(H70A,
 H70B), C71(H71A,H71B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C6(H6), C10(H10), C12(H12), C14(H14), C18(H18), C20(H20),
 C22(H22), C26(H26), C28(H28), C30(H30), C34(H34), C35(H35), C37(H37), C38(H38),
  C47(H47), C48(H48), C49(H49), C50(H50), C51(H51), C53(H53), C54(H54),
 C55(H55), C56(H56), C57(H57), C59(H59), C60(H60), C61(H61), C62(H62), C63(H63),
  C65(H65), C66(H66), C67(H67), C68(H68), C69(H69)
6.d Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C)
;