A Thermodynamic Model for Redox-Dependent Binding of Carbon Monoxide at Site-Differentiated, High Spin Iron Clusters.
Arnett, Charles H.; Chalkley, Matthew J.; Agapie, Theodor; Journal of the American Chemical Society 140 (2018) 5569–5578; doi:10.1021/jacs.8b01825

data_4132141
_publ_section_title
;
 A Thermodynamic Model for Redox-Dependent Binding of Carbon Monoxide at
 Site-Differentiated, High Spin Iron Clusters.
;
_journal_issue                   16
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5569
_journal_page_last               5578
_journal_paper_doi               10.1021/jacs.8b01825
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety
'C84 H60 Fe4 N12 O4, 2(C F3 O3 S), C H2 Cl2, 1.13(C Cl2), 0.62(C4 H10 O)'
_chemical_formula_sum            'C90.6 H68.17 Cl4.26 F6 Fe4 N12 O10.62 S2'
_chemical_formula_weight         2047.49
_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     direct
_audit_creation_date             2017-06-22
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_cell_angle_alpha                100.128(2)
_cell_angle_beta                 93.878(4)
_cell_angle_gamma                93.078(3)
_cell_formula_units_Z            2
_cell_length_a                   15.486(2)
_cell_length_b                   15.4964(18)
_cell_length_c                   19.448(2)
_cell_measurement_reflns_used    9699
_cell_measurement_temperature    100
_cell_measurement_theta_max      32.767
_cell_measurement_theta_min      2.308
_cell_volume                     4573.6(9)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.997
_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           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0614
_diffrn_reflns_av_unetI/netI     0.0524
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            200849
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         34.933
_diffrn_reflns_theta_min         1.067
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.870
_exptl_absorpt_correction_T_max  0.7475
_exptl_absorpt_correction_T_min  0.6628
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0601 before and 0.0461 after correction. The Ratio of minimum to maximum transmission is 0.8867. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.487
_exptl_crystal_description       block
_exptl_crystal_F_000             2086
_exptl_crystal_size_max          0.44
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.13
_refine_diff_density_max         2.984
_refine_diff_density_min         -2.087
_refine_diff_density_rms         0.157
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1231
_refine_ls_number_reflns         39977
_refine_ls_number_restraints     294
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.1245
_refine_ls_R_factor_gt           0.0807
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1265P)^2^+11.5723P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2239
_refine_ls_wR_factor_ref         0.2577
_reflns_Friedel_coverage         0.000
_reflns_number_gt                26400
_reflns_number_total             39977
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b01825_si_001.cif
_cod_data_source_block           a16144
_cod_original_cell_volume        4573.6(10)
_cod_original_formula_sum        'C90.60 H68.17 Cl4.26 F6 Fe4 N12 O10.62 S2'
_cod_database_code               4132141
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O14-C93 = O14-C92
 1.411 with sigma of 0.01
 C92-C93
 2.743 with sigma of 0.01
 O14-C94 = O14-C91
 2.376 with sigma of 0.01
 C94-C93 = C92-C91
 1.517 with sigma of 0.01
 C91-C94
 4.743 with sigma of 0.01
 C90-Cl5 = C90-Cl6 = C89-Cl8 = C89-Cl7
 1.67 with sigma of 0.05
 Cl5-Cl6 = Cl8-Cl7
 2.85 with sigma of 0.05
 S1-O5 \\sim S1-O7 \\sim S1-O6 \\sim S3-O11 \\sim S3-O13 \\sim S3-O12 \\sim
S2_$1-O9_$1 \\sim S2_$1-O10_$1
 \\sim S2_$1-O8_$1
 with sigma of 0.02
 S2-C86 \\sim S1_$2-C85_$2 \\sim S3_$2-C87_$2
 with sigma of 0.02
 F1-C85 \\sim F2-C85 \\sim F3-C85 \\sim F9-C87 \\sim F7-C87 \\sim F8-C87 \\sim
F6_$1-C86_$1 \\sim F5_$1-
 C86_$1 \\sim F4_$1-C86_$1
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
S2 \\sim C91 \\sim C92 \\sim O14 \\sim C86 \\sim F5 \\sim F4 \\sim F6 \\sim C93
\\sim C94 \\sim O8 \\sim O10 \\sim O9 \\sim Cl6 \\sim Cl5 \\sim C90 \\sim F3
\\sim S1 \\sim O5 \\sim C85 \\sim O6 \\sim O7 \\sim F1 \\sim F2 \\sim F9 \\sim
S3 \\sim C87 \\sim O11 \\sim O12 \\sim O13 \\sim F7 \\sim F8 \\sim Cl8 \\sim
C89 \\sim Cl7 \\sim C88 \\sim Cl1 \\sim Cl4 \\sim H88A \\sim H88B \\sim H88C
\\sim H88D \\sim Cl3 \\sim Cl2: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08
4. Others
 Sof(H88C)=Sof(H88D)=Sof(Cl3)=Sof(Cl2)=1-FVAR(1)
 Sof(Cl1)=Sof(Cl4)=Sof(H88A)=Sof(H88B)=FVAR(1)
 Sof(Cl8)=Sof(S2)=Sof(C86)=Sof(O8)=Sof(F5)=Sof(O10)=Sof(F4)=Sof(F6)=Sof(O9)=
 Sof(C89)=Sof(Cl7)=1-FVAR(2)
 Sof(S3)=Sof(F9)=Sof(C87)=Sof(F7)=Sof(F8)=Sof(O11)=Sof(O12)=Sof(C91)=Sof(H91A)=
 Sof(H91B)=Sof(H91C)=Sof(C94)=Sof(H94A)=Sof(H94B)=Sof(H94C)=Sof(O14)=Sof(C92)=
 Sof(H92A)=Sof(H92B)=Sof(C93)=Sof(H93A)=Sof(H93B)=Sof(O13)=FVAR(2)
 Fixed Sof: Cl5(0.75) Cl6(0.75) C90(0.75)
5.a Secondary CH2 refined with riding coordinates:
 C88(H88A,H88B), C88(H88C,H88D), C92(H92A,H92B), C93(H93A,H93B)
5.b Aromatic/amide H refined with riding coordinates:
 C54(H54), C24(H24), C6(H6), C55(H55), C57(H57), C68(H68), C76(H76),
 C0AA(H0AA), C67(H67), C39(H39), C49(H49), C18(H18), C38(H38), C50(H50), C2(H2),
  C41(H41), C21(H21), C81(H81), C40(H40), C77(H77), C64(H64), C66(H66),
 C52(H52), C56(H56), C71(H71), C80(H80), C32(H32), C15(H15), C73(H73), C12(H12),
  C58(H58), C72(H72), C51(H51), C44(H44), C46(H46), C75(H75), C83(H83),
 C43(H43), C9(H9), C84(H84), C59(H59), C17(H17), C35(H35), C34(H34), C65(H65),
 C62(H62), C23(H23), C11(H11), C22(H22), C63(H63), C82(H82), C45(H45), C16(H16),
  C33(H33), C30(H30), C74(H74), C27(H27), C10(H10), C29(H29), C28(H28)
5.c Idealised Me refined as rotating group:
 C91(H91A,H91B,H91C), C94(H94A,H94B,H94C)
;
_olex2_submission_original_sample_id p16144
_olex2_submission_special_instructions 'No special instructions were received'