Complexes of MN2S2·Fe(η(5)-C5R5)(CO) as platform for exploring cooperative heterobimetallic effects in HER electrocatalysis.
Ghosh, Pokhraj; Quiroz, Manuel; Wang, Ning; Bhuvanesh, Nattamai; Darensbourg, Marcetta Y.; Dalton transactions (Cambridge, England : 2003) 46 (2017) 5617–5624; doi:10.1039/c6dt04666e

data_7041978
_publ_section_title
;
 Complexes of MN2S2&#x00B7;Fe(\h(5)-C5R5)(CO) as platform for exploring
 cooperative heterobimetallic effects in HER electrocatalysis.
;
_journal_issue                   17
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              5617
_journal_page_last               5624
_journal_paper_doi               10.1039/c6dt04666e
_journal_volume                  46
_journal_year                    2017
_chemical_formula_moiety         'C20 H33 Fe N2 Ni O S2, F6 P'
_chemical_formula_sum            'C20 H33 F6 Fe N2 Ni O P S2'
_chemical_formula_weight         641.13
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-11-29
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2016-12-06 deposited with the CCDC.
2017-02-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   12.6068(4)
_cell_length_b                   14.4727(4)
_cell_length_c                   27.5824(8)
_cell_measurement_reflns_used    9106
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      70.010
_cell_measurement_theta_min      3.204
_cell_volume                     5032.5(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0846
_diffrn_reflns_av_unetI/netI     0.0293
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            64827
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.215
_diffrn_reflns_theta_min         3.204
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    8.272
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.5155
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1229 before and 0.0751 after correction.
The Ratio of minimum to maximum transmission is 0.6843.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.692
_exptl_crystal_description       block
_exptl_crystal_F_000             2640
_exptl_crystal_size_max          0.221
_exptl_crystal_size_mid          0.056
_exptl_crystal_size_min          0.019
_refine_diff_density_max         1.237
_refine_diff_density_min         -0.810
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     488
_refine_ls_number_reflns         4777
_refine_ls_number_restraints     1231
_refine_ls_restrained_S_all      1.513
_refine_ls_R_factor_all          0.0738
_refine_ls_R_factor_gt           0.0638
_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^)+(0.0657P)^2^+21.7290P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1507
_refine_ls_wR_factor_ref         0.1583
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4062
_reflns_number_total             4777
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6dt04666e2.cif
_cod_data_source_block           nifecpstar
_cod_depositor_comments
'Adding full bibliography for 7041975--7041978.cif.'
_cod_database_code               7041978
_shelx_estimated_absorpt_t_max   0.859
_shelx_estimated_absorpt_t_min   0.262
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F1-F6
 3.13 with sigma of 0.02
 Fe1-S1A \\sim Fe1-S2A \\sim Fe1-S1 \\sim Fe1-S2
 with sigma of 0.02
 Ni1A-S1A \\sim Ni1-S2 \\sim Ni1A-S2A \\sim Ni1-S1
 with sigma of 0.02
 S1A-C9A \\sim S2-C1 \\sim S2A-C1A \\sim S1-C9
 with sigma of 0.02
 P1-F1 \\sim P1-F5 \\sim P1-F2A \\sim P1-F2 \\sim P1-F3A \\sim P1-F6 \\sim
P1-F3 \\sim P1-F4A \\sim P1-F4 \\sim P1-
 F5A
 with sigma of 0.02
 F1-F2 \\sim F1-F3 \\sim F1-F4 \\sim F1-F5 \\sim F6-F2 \\sim F6-F3 \\sim F6-F4
\\sim F6-F5 \\sim F1-F2A \\sim F1-
 F3A \\sim F1-F4A \\sim F1-F5A \\sim F6-F2A \\sim F6-F3A \\sim F6-F4A \\sim
F6-F5A
 with sigma of 0.02
 F2-F3 \\sim F3-F4 \\sim F4-F5 \\sim F2A-F3A \\sim F3A-F4A \\sim F4A-F5A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Ni1 \\sim S1 \\sim S2 \\sim N1 \\sim N2 \\sim C1 \\sim C2 \\sim C3 \\sim C4
\\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim O1 \\sim Ni1A
\\sim S1A \\sim S2A \\sim N1A \\sim N2A \\sim C1A \\sim C2A \\sim C3A \\sim C4A
\\sim C5A \\sim C6A \\sim C7A \\sim C8A \\sim C9A \\sim C10A \\sim O1A: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08
P1 \\sim F1 \\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim F6 \\sim F2A \\sim F3A
\\sim F4A \\sim F5A: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08
Uanis(C10) = Uanis(C10A)
4. Rigid body (RIGU) restrains
 Ni1, S1, S2, N1, N2, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, O1, Ni1A, S1A,
 S2A, N1A, N2A, C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A, C10A, O1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 P1, F1, F2, F3, F4, F5, F6, F2A, F3A, F4A, F5A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{Ni1, S1, S2, N1, N2, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, O1} sigma for
1-2: 0.02, 1-3: 0.04
as
{Ni1A, S1A, S2A, N1A, N2A, C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A, C10A,
O1A}
6. Others
 Sof(Ni1A)=Sof(S1A)=Sof(S2A)=Sof(N1A)=Sof(N2A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=
 Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(C4A)=Sof(H4AA)=
 Sof(H4AB)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(C7A)=
 Sof(H7AA)=Sof(H7AB)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=
 Sof(C10A)=Sof(O1A)=1-FVAR(1)
 Sof(Ni1)=Sof(S1)=Sof(S2)=Sof(N1)=Sof(N2)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=
 Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C5)=
 Sof(H5A)=Sof(H5B)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(C8)=
 Sof(H8A)=Sof(H8B)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(C10)=Sof(O1)=FVAR(1)
 Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(F5A)=1-FVAR(2)
 Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=FVAR(2)
7.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B),
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C1A(H1AA,H1AB), C2A(H2AA,H2AB),
 C3A(H3AA,H3AB), C4A(H4AA,H4AB), C5A(H5AA,H5AB), C6A(H6AA,H6AB), C7A(H7AA,H7AB),
  C8A(H8AA,H8AB), C9A(H9AA,H9AB)
7.b Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C)
;
_shelx_res_checksum              92184
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'