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_4134568
_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 O4, 4(B F4), 6(C3 H7 N O)'
_chemical_formula_sum            'C104 H142 B4 F16 Fe4 N26 O10'
_chemical_formula_weight         2487.07
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-11-23
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   29.597(3)
_cell_length_b                   14.1253(12)
_cell_length_c                   29.688(3)
_cell_measurement_reflns_used    9469
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.16
_cell_measurement_theta_min      2.42
_cell_volume                     12412(2)
_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 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker D8VENTURE with PHOTON II Detector'
_diffrn_measurement_method       'phi, omega and kappa scan'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0897
_diffrn_reflns_av_unetI/netI     0.0653
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            133860
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.714
_diffrn_reflns_theta_min         2.106
_diffrn_source_type              Micro-focus
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.546
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.6714
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0968 before and 0.0861 after correction.
The Ratio of minimum to maximum transmission is 0.9008.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            green-yellow
_exptl_crystal_density_diffrn    1.331
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             5184
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.888
_refine_diff_density_min         -0.867
_refine_diff_density_rms         0.077
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.34(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1471
_refine_ls_number_reflns         23091
_refine_ls_number_restraints     103
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0850
_refine_ls_R_factor_gt           0.0596
_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^)+(0.0778P)^2^+20.2137P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1446
_refine_ls_wR_factor_ref         0.1645
_reflns_Friedel_coverage         0.960
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                18240
_reflns_number_total             23091
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13795_si_002.cif
_cod_data_source_block           tetranuclear
_cod_original_cell_volume        12411.6(18)
_cod_database_code               4134568
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.918
_shelx_estimated_absorpt_t_min   0.889
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.66(2)
 0.34(2)
2. 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
3. Restrained distances
 O4-H4
 0.84 with sigma of 0.02
 F12B-B3B = F12A-B3A = F11-B3B = F11-B3A = F10B-B3B = F10A-B3A = F9-B3A = F9-B3B
 1.38 with sigma of 0.02
 O3-H3
 0.84 with sigma of 0.02
 C33A-C32A \\sim N8-C32A \\sim C33B-C32B \\sim N8-C32B
 with sigma of 0.02
 N21-C88 \\sim N21-C89A \\sim N21-C89B
 with sigma of 0.02
 C55A-C54 \\sim C55B-C54
 with sigma of 0.02
 F9-B3B \\sim F11-B3B \\sim F10B-B3B \\sim F12B-B3B \\sim F12A-B3A \\sim
F10A-B3A \\sim F9-B3A \\sim F11-B3A
 with sigma of 0.02
 F10A-B3A \\sim F10B-B3B \\sim F11-B3A \\sim F11-B3B \\sim F12B-B3B \\sim
F9-B3B \\sim F12A-B3A \\sim F9-B3A
 with sigma of 0.02
 F7-B2 \\sim F5-B2 \\sim F6-B2 \\sim F8B-B2 \\sim F8A-B2
 with sigma of 0.02
 F16B-B4B \\sim F14B-B4B \\sim F15B-B4B \\sim F15A-B4A \\sim F14A-B4A \\sim
F13-B4B \\sim F16A-B4A ~
 F13-B4A
 with sigma of 0.02
 O9B-C99B \\sim O9A-C99A
 with sigma of 0.02
 N25-C99B \\sim N25-C99A
 with sigma of 0.02
 N25-C1A \\sim N25-C100 \\sim N25-C1B \\sim N25-C101
 with sigma of 0.02
 F2-B1 \\sim F10B-B3B \\sim F10A-B3A \\sim F12A-B3A \\sim F12B-B3B \\sim
F11-B3B \\sim F11-B3A \\sim F9-
 B3A \\sim F9-B3B
 with sigma of 0.02
 F12A-B3A \\sim F10A-B3A \\sim F10B-B3B \\sim F11-B3A \\sim F12B-B3B \\sim
F9-B3B \\sim F9-B3A \\sim F11-B3B
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C42) = Uanis(C32A) = Uanis(C32B) = Uanis(C33A) = Uanis(C33B)
Uanis(C54) = Uanis(C55B) = Uanis(C55A)
Uanis(C88) = Uanis(C89A) = Uanis(C89B)
Uanis(F9) = Uanis(F11) = Uanis(F10B) = Uanis(F10A) = Uanis(F12A) = Uanis(F12B)
= Uanis(B3B) = Uanis(B3A)
Uanis(F6) = Uanis(F8A) = Uanis(F8B)
Uanis(F13) = Uanis(B4B) = Uanis(B4A) = Uanis(F14A) = Uanis(F14B) = Uanis(F16A)
= Uanis(F15A) = Uanis(F15B)
Uanis(F14B) = Uanis(F14A)
Uanis(O9B) = Uanis(O9A)
Uanis(C99A) = Uanis(C99B)
Uanis(C100) = Uanis(C1A) = Uanis(C1B) = Uanis(C101)
Uanis(C104) = Uanis(C103) = Uanis(C1C) = Uanis(C102) = Uanis(O10B) = Uanis(O10A)
5. Others
 Sof(C32B)=Sof(H32C)=Sof(H32D)=Sof(C33B)=Sof(H33D)=Sof(H33E)=Sof(H33F)=
 Sof(H54C)=Sof(H54D)=Sof(C55B)=Sof(H55D)=Sof(H55E)=Sof(H55F)=Sof(C89B)=
 Sof(H89D)=Sof(H89E)=Sof(H89F)=Sof(O9B)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=
 Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=Sof(C99B)=Sof(H99B)=Sof(O10B)=Sof(C1C)=
 Sof(H1C)=1-FVAR(1)
 Sof(C32A)=Sof(H32A)=Sof(H32B)=Sof(C33A)=Sof(H33A)=Sof(H33B)=Sof(H33C)=
 Sof(H54A)=Sof(H54B)=Sof(C55A)=Sof(H55A)=Sof(H55B)=Sof(H55C)=Sof(C89A)=
 Sof(H89A)=Sof(H89B)=Sof(H89C)=Sof(O9A)=Sof(C99A)=Sof(H99A)=Sof(C100)=Sof(H10A)=
 Sof(H10B)=Sof(H10C)=Sof(C101)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(O10A)=
 Sof(C102)=Sof(H102)=FVAR(1)
 Sof(F8B)=Sof(F10B)=Sof(F12B)=Sof(B3B)=Sof(F14B)=Sof(F15B)=Sof(F16B)=Sof(B4B)=
 1-FVAR(2)
 Sof(F8A)=Sof(F10A)=Sof(F12A)=Sof(B3A)=Sof(F14A)=Sof(F15A)=Sof(F16A)=Sof(B4A)=
 FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C44(H44)
6.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C11(H11A,H11B), C13(H13A,H13B), C21(H21A,H21B),
 C23(H23A,H23B), C24(H24A,H24B), C32A(H32A,H32B), C32B(H32C,H32D), C34(H34A,
 H34B), C42(H42A,H42B), 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)
6.c 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), C87(H87), C90(H90), C93(H93), C96(H96), C99A(H99A), C99B(H99B),
 C1C(H1C), C102(H102)
6.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C22(H22A,H22B,H22C), C33A(H33A,H33B,H33C), C33B(H33D,
 H33E,H33F), C43(H43A,H43B,H43C), C55A(H55A,H55B,H55C), C55B(H55D,H55E,H55F),
 C65(H65A,H65B,H65C), C76(H76A,H76B,H76C), C86(H86A,H86B,H86C), C88(H88A,H88B,
 H88C), C89A(H89A,H89B,H89C), C89B(H89D,H89E,H89F), C91(H91A,H91B,H91C),
 C92(H92A,H92B,H92C), C94(H94A,H94B,H94C), C95(H95A,H95B,H95C), C97(H97A,H97B,
 H97C), C98(H98A,H98B,H98C), C1A(H1AA,H1AB,H1AC), C1B(H1BA,H1BB,H1BC),
 C100(H10A,H10B,H10C), C101(H10D,H10E,H10F), C103(H10G,H10H,H10I), C104(H10J,
 H10K,H10L)
;
_shelx_res_checksum              79398
_shelx_hkl_checksum              56685
_shelx_fab_checksum              92621
_olex2_submission_special_instructions 'No special instructions were received'