Functional Models for the Mono- and Di-nitrosyl Intermediates of FNORs: Semireduction versus Superreduction of NO.
Jana, Manish; White, Corey J.; Pal, Nabhendu; Demeshko, Serhiy; Kupper, Claudia; Meyer, Franc; Lehnert, Nicolai; Majumdar, Amit; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.9b13795

data_4134569
_publ_section_title
;
 Functional Models for the Mono- and Di-nitrosyl Intermediates of FNORs:
 Semireduction versus Superreduction of NO.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b13795
_journal_year                    2020
_chemical_formula_moiety         'C86 H100 Fe4 N20 O5, 4(B F4)'
_chemical_formula_sum            'C86 H100 B4 F16 Fe4 N20 O5'
_chemical_formula_weight         2064.49
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-21
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                113.567(7)
_cell_angle_beta                 90.687(8)
_cell_angle_gamma                116.641(8)
_cell_formula_units_Z            2
_cell_length_a                   18.424(6)
_cell_length_b                   18.600(6)
_cell_length_c                   21.629(6)
_cell_measurement_reflns_used    7971
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      22.78
_cell_measurement_theta_min      2.20
_cell_volume                     5905(3)
_computing_cell_refinement       'SAINT v8.38A (Bruker, 2016)'
_computing_data_collection       'APEX2 v2017.3-0 (Bruker-Axs,2016)'
_computing_data_reduction        'SAINT v8.38A (Bruker, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXD (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.938
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'phi and omega scan'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1240
_diffrn_reflns_av_unetI/netI     0.1962
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.938
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            52982
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.774
_diffrn_reflns_theta_min         2.099
_diffrn_source_type              'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.556
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6071
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1215 before and 0.0872 after correction.
The Ratio of minimum to maximum transmission is 0.8147.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            brown
_exptl_crystal_density_diffrn    1.161
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2128
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.16
_refine_diff_density_max         2.480
_refine_diff_density_min         -0.935
_refine_diff_density_rms         0.175
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.317
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1148
_refine_ls_number_reflns         21259
_refine_ls_number_restraints     47
_refine_ls_restrained_S_all      1.318
_refine_ls_R_factor_all          0.2657
_refine_ls_R_factor_gt           0.1606
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4090
_refine_ls_wR_factor_ref         0.4750
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8673
_reflns_number_total             21259
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13795_si_002.cif
_cod_data_source_block           Dimermixedvalence
_cod_original_sg_symbol_H-M      P-1
_cod_database_code               4134569
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.916
_shelx_estimated_absorpt_t_min   0.887
_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
 N10-C43A
 2.5 with sigma of 0.02
 O4-H4 = O2-H2
 0.84 with sigma of 0.02
 C76-C75 \\sim C55A-C54 \\sim C55B-C54
 with sigma of 0.02
 F1-B1 \\sim F4B-B1 \\sim F4A-B1 \\sim F3B-B1 \\sim F3A-B1
 with sigma of 0.02
 F6-B2 \\sim F8B-B2 \\sim F8A-B2
 with sigma of 0.02
 F13-B4 \\sim F14-B4 \\sim F16B-B4 \\sim F16A-B4 \\sim F15B-B4 \\sim F15A-B4
 with sigma of 0.02
 C12B-C11 \\sim C12A-C11
 with sigma of 0.02
 N10-C42B \\sim N10-C42A
 with sigma of 0.02
 C42B-C43B \\sim C42A-C43A
 with sigma of 0.02
 N13-C54 \\sim N5-C21 \\sim N18-C75 \\sim N10-C42A \\sim N10-C42B
 with sigma of 0.02
 F9B-B3 \\sim F9A-B3
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(Fe1) = Uanis(Fe2) = Uanis(O1)
Uanis(Fe3) = Uanis(Fe4) = Uanis(O5)
Uanis(C53) = Uanis(C48)
Uanis(C20) = Uanis(C19) = Uanis(C18)
Uanis(C54) = Uanis(C55B) = Uanis(C55A)
Uanis(F1) = Uanis(F4B) = Uanis(F4A)
Uanis(B1) = Uanis(F3A) = Uanis(F3B)
Uanis(F6) = Uanis(F8B) = Uanis(F8A)
Uanis(B2) = Uanis(B4)
Uanis(F14) = Uanis(F15A) = Uanis(F15B) = Uanis(F13) = Uanis(F16A) = Uanis(F16B)
Uanis(F11) = Uanis(F12B) = Uanis(F12A)
Uanis(C85) = Uanis(C86)
Uanis(C11) = Uanis(C12A) = Uanis(C12B)
Uanis(C43B) = Uanis(C42B) = Uanis(C43A) = Uanis(C42A)
Uanis(F11) = Uanis(F9A) = Uanis(F9B)
4. Others
 Sof(H11C)=Sof(H11D)=Sof(C12B)=Sof(H12D)=Sof(H12E)=Sof(H12F)=Sof(C42B)=
 Sof(H42C)=Sof(H42D)=Sof(C43B)=Sof(H43D)=Sof(H43E)=Sof(H43F)=Sof(H54C)=
 Sof(H54D)=Sof(C55B)=Sof(H55D)=Sof(H55E)=Sof(H55F)=1-FVAR(1)
 Sof(H11A)=Sof(H11B)=Sof(C12A)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C42A)=
 Sof(H42A)=Sof(H42B)=Sof(C43A)=Sof(H43A)=Sof(H43B)=Sof(H43C)=Sof(H54A)=
 Sof(H54B)=Sof(C55A)=Sof(H55A)=Sof(H55B)=Sof(H55C)=FVAR(1)
 Sof(F3B)=Sof(F4B)=Sof(F8B)=Sof(F9B)=Sof(F12B)=Sof(F15B)=Sof(F16B)=1-FVAR(2)
 Sof(F3A)=Sof(F4A)=Sof(F8A)=Sof(F9A)=Sof(F12A)=Sof(F15A)=Sof(F16A)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C1(H1), C44(H44)
5.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C11(H11A,H11B), C11(H11C,H11D), C13(H13A,H13B),
 C21(H21A,H21B), C23(H23A,H23B), C24(H24A,H24B), C32(H32A,H32B), C34(H34A,H34B),
  C42A(H42A,H42B), C42B(H42C,H42D), C45(H45A,H45B), C46(H46A,H46B), C54(H54A,
 H54B), C54(H54C,H54D), C56(H56A,H56B), C64(H64A,H64B), C66(H66A,H66B),
 C67(H67A,H67B), C75(H75A,H75B), C77(H77A,H77B), C85(H85A,H85B)
5.c Me refined with riding coordinates:
 C12A(H12A,H12B,H12C), C12B(H12D,H12E,H12F)
5.d Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C16(H16), C17(H17), C18(H18), C19(H19),
 C27(H27), C28(H28), C29(H29), C30(H30), C37(H37), C38(H38), C39(H39), C40(H40),
  C49(H49), C50(H50), C51(H51), C52(H52), C59(H59), C60(H60), C61(H61),
 C62(H62), C70(H70), C71(H71), C72(H72), C73(H73), C80(H80), C81(H81), C82(H82),
  C83(H83)
5.e Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C33(H33A,H33B,H33C), C43A(H43A,H43B,H43C), C43B(H43D,
 H43E,H43F), C55A(H55A,H55B,H55C), C55B(H55D,H55E,H55F), C65(H65A,H65B,H65C),
 C76(H76A,H76B,H76C), C86(H86A,H86B,H86C)
;
_shelx_res_checksum              38689
_shelx_hkl_checksum              69360
_shelx_fab_checksum              85871
_olex2_submission_special_instructions 'No special instructions were received'