Diiron Bridged-Thiolate Complexes That Bind N2 at the Fe(II)Fe(II), Fe(II)Fe(I), and Fe(I)Fe(I) Redox States.
Creutz, Sidney E.; Peters, Jonas C.; Journal of the American Chemical Society 137 (2015) 7310–7313; doi:10.1021/jacs.5b04738

data_4123807
_publ_section_title
;
 Diiron Bridged-Thiolate Complexes That Bind N2 at the Fe(II)Fe(II),
 Fe(II)Fe(I), and Fe(I)Fe(I) Redox States.
;
_journal_issue                   23
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7310
_journal_page_last               7313
_journal_paper_doi               10.1021/jacs.5b04738
_journal_volume                  137
_journal_year                    2015
_chemical_formula_moiety         'C54 H75 Fe2 N4 P4 S Si2, C16 Na O8'
_chemical_formula_sum            'C72 H75 Fe2 N4 Na O8.5 P4 S Si2'
_chemical_formula_weight         1479.17
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-04-02
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                80.8610(10)
_cell_angle_beta                 85.5850(10)
_cell_angle_gamma                61.5160(10)
_cell_formula_units_Z            2
_cell_length_a                   14.5315(5)
_cell_length_b                   14.5632(6)
_cell_length_c                   23.5306(9)
_cell_measurement_reflns_used    9995
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.95
_cell_measurement_theta_min      2.25
_cell_volume                     4321.3(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, 2008)'
_diffrn_ambient_temperature      99.97
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.914
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0452
_diffrn_reflns_av_unetI/netI     0.0586
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.914
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            147493
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.914
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.806
_diffrn_reflns_theta_min         2.207
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.515
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.6604
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0883 before and 0.0609 after correction.
The Ratio of minimum to maximum transmission is 0.8853.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_density_diffrn    1.137
_exptl_crystal_description       block
_exptl_crystal_F_000             1540
_refine_diff_density_max         1.711
_refine_diff_density_min         -0.920
_refine_diff_density_rms         0.149
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.152
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     902
_refine_ls_number_reflns         29312
_refine_ls_number_restraints     1043
_refine_ls_restrained_S_all      1.176
_refine_ls_R_factor_all          0.1256
_refine_ls_R_factor_gt           0.0806
_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^)+(0.1646P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2463
_refine_ls_wR_factor_ref         0.2716
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18308
_reflns_number_total             29312
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b04738_si_002.cif
_cod_data_source_block           compound12
_cod_depositor_comments
'Adding full bibliography for 4123801--4123807.cif.'
_cod_original_formula_sum        'C72 H75 Fe2 N4 Na O8.50 P4 S Si2'
_cod_database_code               4123807
_shelxl_version_number           2014/6
_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. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(C122) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C114) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C113) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C114) = Uanis(C111)
4. Same fragment restrains
{C313, C311, C312} sigma for 1-2: 0.02, 1-3: 0.04
{C315, C314, C316} sigma for 1-2: 0.02, 1-3: 0.04
{C316, C314, C315} sigma for 1-2: 0.02, 1-3: 0.04
as
{C312, C311, C313}
{C123, C121, C122} sigma for 1-2: 0.02, 1-3: 0.04
{C125, C124, C126} sigma for 1-2: 0.02, 1-3: 0.04
{C126, C124, C125} sigma for 1-2: 0.02, 1-3: 0.04
as
{C122, C121, C123}
{C113, C111, C112} sigma for 1-2: 0.02, 1-3: 0.04
{C115, C114, C116} sigma for 1-2: 0.02, 1-3: 0.04
{C116, C114, C115} sigma for 1-2: 0.02, 1-3: 0.04
as
{C112, C111, C113}
{C1C3, C2C3, O1C3, C3C3, C4C3, O2C3, C5C3, C6C3, O3C3, C7C3, C8C3, O4C3} sigma
for 1-2: 0.02, 1-3: 0.04
{C3C4, C4C4, O2C4, C5C4, C6C4, O3C4, C7C4, C8C4, O4C4, C1C4, C2C4, O1C4} sigma
for 1-2: 0.02, 1-3: 0.04
{C5C4, C6C4, O3C4, C7C4, C8C4, O4C4, C1C4, C2C4, O1C4, C3C4, C4C4, O2C4} sigma
for 1-2: 0.02, 1-3: 0.04
as
{C1C4, C2C4, O1C4, C3C4, C4C4, O2C4, C5C4, C6C4, O3C4, C7C4, C8C4, O4C4}
{C1C2, C2C2, O1C2, C3C2, C4C2, O2C2, C5C2, C6C2, O3C2, C7C2, C8C2, O4C2} sigma
for 1-2: 0.02, 1-3: 0.04
{C8C1, C7C1, O3C1, C6C1, C5C1, O2C1, C4C1, C3C1, O1C1, C2C1, C1C1, O4C1} sigma
for 1-2: 0.02, 1-3: 0.04
as
{C1C1, C2C1, O1C1, C3C1, C4C1, O2C1, C5C1, C6C1, O3C1, C7C1, C8C1, O4C1}
5. Others
 Sof(C116)=Sof(H11G)=Sof(H11H)=Sof(H11I)=Sof(C114)=Sof(H114)=Sof(C115)=
 Sof(H11J)=Sof(H11K)=Sof(H11L)=1-FVAR(1)
 Sof(C112)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C111)=Sof(H111)=Sof(C113)=
 Sof(H11D)=Sof(H11E)=Sof(H11F)=FVAR(1)
 Sof(C126)=Sof(H12G)=Sof(H12H)=Sof(H12I)=Sof(C124)=Sof(H124)=Sof(C125)=
 Sof(H12J)=Sof(H12K)=Sof(H12L)=1-FVAR(2)
 Sof(C122)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C121)=Sof(H121)=Sof(C123)=
 Sof(H12D)=Sof(H12E)=Sof(H12F)=FVAR(2)
 Sof(C316)=Sof(H31G)=Sof(H31H)=Sof(H31I)=Sof(C314)=Sof(H314)=Sof(C315)=
 Sof(H31J)=Sof(H31K)=Sof(H31L)=1-FVAR(3)
 Sof(C312)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C311)=Sof(H311)=Sof(C313)=
 Sof(H31D)=Sof(H31E)=Sof(H31F)=FVAR(3)
 Fixed Sof: Na2(0.5) C1C3(0.5) C2C3(0.5) O1C3(0.5) C3C3(0.5) C4C3(0.5)
 O2C3(0.5) C5C3(0.5) C6C3(0.5) O3C3(0.5) C7C3(0.5) C8C3(0.5) O4C3(0.5)
 C1C4(0.5) C2C4(0.5) O1C4(0.5) C3C4(0.5) C4C4(0.5) O2C4(0.5) C5C4(0.5)
 C6C4(0.5) O3C4(0.5) C7C4(0.5) C8C4(0.5) O4C4(0.5) Na1(0.5) C1C2(0.5) C2C2(0.5)
 O1C2(0.5) C3C2(0.5) C4C2(0.5) O2C2(0.5) C5C2(0.5) C6C2(0.5) O3C2(0.5)
 C7C2(0.5) C8C2(0.5) O4C2(0.5) C1C1(0.5) C2C1(0.5) O1C1(0.5) C3C1(0.5)
 C4C1(0.5) O2C1(0.5) C5C1(0.5) C6C1(0.5) O3C1(0.5) C7C1(0.5) C8C1(0.5) O4C1(0.5)
6.a Ternary CH refined with riding coordinates:
 C221(H221), C211(H211), C421(H421), C411(H411), C321(H321), C311(H311),
 C314(H314), C121(H121), C124(H124), C111(H111), C114(H114)
6.b Me refined with riding coordinates:
 C312(H31A,H31B,H31C), C313(H31D,H31E,H31F), C316(H31G,H31H,H31I), C315(H31J,
 H31K,H31L), C122(H12A,H12B,H12C), C123(H12D,H12E,H12F), C126(H12G,H12H,H12I),
 C125(H12J,H12K,H12L), C112(H11A,H11B,H11C), C113(H11D,H11E,H11F), C116(H11G,
 H11H,H11I), C115(H11J,H11K,H11L)
6.c Aromatic/amide H refined with riding coordinates:
 C05(H05), C04(H04), C03(H03), C15(H15), C45(H45), C14(H14), C42(H42),
 C25(H25), C22(H22), C44(H44), C43(H43), C35(H35), C12(H12), C24(H24), C23(H23),
  C13(H13), C32(H32), C34(H34), C33(H33)
6.d Idealised Me refined as rotating group:
 C223(H22A,H22B,H22C), C423(H42A,H42B,H42C), C213(H21A,H21B,H21C), C222(H22D,
 H22E,H22F), C422(H42D,H42E,H42F), C212(H21D,H21E,H21F), C413(H41A,H41B,H41C),
 C412(H41D,H41E,H41F), C323(H32A,H32B,H32C), C322(H32D,H32E,H32F)
;
_shelx_res_checksum              29603
_shelx_hkl_checksum              80499
_olex2_submission_special_instructions 'No special instructions were received'