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_4134566
_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         'C49 H63 Fe2 N14 O5, 3(B F4), C3 H7 N O'
_chemical_formula_sum            'C52 H70 B3 F12 Fe2 N15 O6'
_chemical_formula_weight         1373.36
_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
_audit_creation_date             2018-04-20
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.03 svn.r3497 for OlexSys, GUI svn.r5486)
;
_cell_angle_alpha                79.228(4)
_cell_angle_beta                 80.542(4)
_cell_angle_gamma                66.249(4)
_cell_formula_units_Z            2
_cell_length_a                   13.0940(19)
_cell_length_b                   13.229(2)
_cell_length_c                   21.320(3)
_cell_measurement_reflns_used    1938
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      16.36
_cell_measurement_theta_min      2.30
_cell_volume                     3304.4(8)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2014.7-1 (Bruker-Axs,2014)'
_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)'
_computing_structure_solution    'ShelXD (Sheldrick, 2008)'
_diffrn_ambient_temperature      150(2)
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.994
_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  0.1256
_diffrn_reflns_av_unetI/netI     0.1699
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            34519
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         25.882
_diffrn_reflns_theta_min         0.977
_diffrn_source_type              'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.530
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.6608
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/3 (Bruker,2014/3) was used for absorption correction.
wR2(int) was 0.0775 before and 0.0578 after correction.
The Ratio of minimum to maximum transmission is 0.8866.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            green
_exptl_crystal_density_diffrn    1.380
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1420
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.665
_refine_diff_density_min         -0.701
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     762
_refine_ls_number_reflns         12744
_refine_ls_number_restraints     184
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.2176
_refine_ls_R_factor_gt           0.0967
_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^)+(0.1432P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2368
_refine_ls_wR_factor_ref         0.3057
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5112
_reflns_number_total             12744
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13795_si_002.cif
_cod_data_source_block           dinitrosyl_tetrafluoroborate
_cod_original_cell_volume        3304.4(9)
_cod_database_code               4134566
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.939
_shelx_estimated_absorpt_t_min   0.901
_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
 C20-C18B
 2.44 with sigma of 0.02
 N10A-C42A \\sim N10B-C42B
 with sigma of 0.02
 C43B-C42B \\sim C43A-C42A
 with sigma of 0.02
 C40A-C39A \\sim C41A-C40A \\sim C41A-C36A \\sim C37A-C36A \\sim C38A-C37A
\\sim C39A-C38A
 with sigma of 0.02
 C41B-C36B \\sim C37B-C36B \\sim C38B-C37B \\sim C39B-C38B \\sim C40B-C39B
\\sim C41B-C40B
 with sigma of 0.02
 N9-C36A \\sim N9-C36B \\sim N10A-C41A \\sim N10B-C41B
 with sigma of 0.02
 N10A-C35A \\sim N9-C35A
 with sigma of 0.02
 N10B-C35B \\sim N9-C35B
 with sigma of 0.02
 N8-C31 \\sim N10B-C35B \\sim N9-C35B
 with sigma of 0.02
 N5-C21B \\sim N5-C21A \\sim C22A-C21A \\sim C22B-C21B
 with sigma of 0.02
 N14A-C47 \\sim N14B-C47
 with sigma of 0.02
 N8-C32A \\sim N8-C32B \\sim C33A-C32A \\sim C33B-C32B
 with sigma of 0.02
 C20-C15 \\sim C16A-C15 \\sim C17A-C16A \\sim C18A-C17A \\sim C19A-C18A \\sim
C20-C19A \\sim C16B-C15
 \\sim C17B-C16B \\sim C18B-C17B \\sim C19B-C18B \\sim C20-C19B
 with sigma of 0.02
 F5-B2 \\sim F6B-B2 \\sim F6A-B2 \\sim F7B-B2 \\sim F7A-B2 \\sim F8A-B2 \\sim
F8B-B2
 with sigma of 0.02
 F11B-B3B \\sim F10B-B3B \\sim F9B-B3B \\sim F12B-B3B
 with sigma of 0.02
 F9A-B3A \\sim F12A-B3A \\sim F11A-B3A \\sim F10A-B3A
 with sigma of 0.02
 F2-B1 \\sim F3A-B1 \\sim F4A-B1 \\sim F4B-B1 \\sim F1A-B1 \\sim F1A-B1
 with sigma of 0.02
 F2-B1 \\sim F1A-B1 \\sim F1B-B1 \\sim F4A-B1 \\sim F4B-B1 \\sim F3A-B1 \\sim
F3B-B1
 with sigma of 0.02
 F12A-B3A \\sim F12B-B3B \\sim F9A-B3A \\sim F9B-B3B \\sim F10A-B3A \\sim
F10B-B3B \\sim F11B-B3B ~
 F11A-B3A
 with sigma of 0.02
3. Restrained planarity
 C36B, C37B, C38B, C39B, C40B, C41B
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(N9) = Uanis(N10B) = Uanis(N10A)
Uanis(N6) = Uanis(C35B) = Uanis(C35A)
Uanis(C43A) = Uanis(C43B) = Uanis(C42A) = Uanis(C42B)
Uanis(C40A) = Uanis(C39A) = Uanis(C38A) = Uanis(C37A) = Uanis(C36A) =
Uanis(C36B) = Uanis(C41B) = Uanis(C40B) = Uanis(C39B) = Uanis(C45) =
Uanis(C38B) = Uanis(C41A) = Uanis(C37B)
Uanis(C13) = Uanis(C21A) = Uanis(C21B) = Uanis(C22B) = Uanis(C22A)
Uanis(N8) = Uanis(C32A) = Uanis(C32B) = Uanis(C33A) = Uanis(C33B)
Uanis(C15) = Uanis(C16A) = Uanis(C16B) = Uanis(C17A) = Uanis(C17B) =
Uanis(C18A) = Uanis(C18B) = Uanis(C19A) = Uanis(C19B) = Uanis(C20)
Uanis(F5) = Uanis(F6A) = Uanis(F6B) = Uanis(F7A) = Uanis(F7B) = Uanis(F8B) =
Uanis(F8A)
Uanis(O2) = Uanis(O4)
Uanis(F1A) = Uanis(F1B)
Uanis(C47) = Uanis(N14A) = Uanis(N14B) = Uanis(C49B) = Uanis(C49A) =
Uanis(C48B) = Uanis(C48A)
Uanis(F4B) = Uanis(F4A)
Uanis(F3B) = Uanis(F3A)
Uanis(B3B) = Uanis(B3A)
Uanis(F9B) = Uanis(F9A) = Uanis(F10A) = Uanis(F10B) = Uanis(F12B) = Uanis(F12A)
Uanis(F11B) = Uanis(F11A)
5. Others
 Sof(N10B)=Sof(N14B)=Sof(C16B)=Sof(H16B)=Sof(C17B)=Sof(H17B)=Sof(C18B)=
 Sof(H18B)=Sof(C19B)=Sof(H19B)=Sof(C21B)=Sof(H21C)=Sof(H21D)=Sof(C22B)=
 Sof(H22D)=Sof(H22E)=Sof(H22F)=Sof(C32B)=Sof(H32C)=Sof(H32D)=Sof(C33B)=
 Sof(H33D)=Sof(H33E)=Sof(H33F)=Sof(H34C)=Sof(H34D)=Sof(C35B)=Sof(C36B)=
 Sof(C37B)=Sof(H37B)=Sof(C38B)=Sof(H38B)=Sof(C39B)=Sof(H39B)=Sof(C40B)=
 Sof(H40B)=Sof(C41B)=Sof(C42B)=Sof(H42C)=Sof(H42D)=Sof(C43B)=Sof(H43D)=
 Sof(H43E)=Sof(H43F)=Sof(H47A)=Sof(C48B)=Sof(H48D)=Sof(H48E)=Sof(H48F)=
 Sof(C49B)=Sof(H49D)=Sof(H49E)=Sof(H49F)=1-FVAR(1)
 Sof(N10A)=Sof(N14A)=Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(H17A)=Sof(C18A)=
 Sof(H18A)=Sof(C19A)=Sof(H19A)=Sof(C21A)=Sof(H21A)=Sof(H21B)=Sof(C22A)=
 Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C32A)=Sof(H32A)=Sof(H32B)=Sof(C33A)=
 Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(H34A)=Sof(H34B)=Sof(C35A)=Sof(C36A)=
 Sof(C37A)=Sof(H37A)=Sof(C38A)=Sof(H38A)=Sof(C39A)=Sof(H39A)=Sof(C40A)=
 Sof(H40A)=Sof(C41A)=Sof(C42A)=Sof(H42A)=Sof(H42B)=Sof(C43A)=Sof(H43A)=
 Sof(H43B)=Sof(H43C)=Sof(H47)=Sof(C48A)=Sof(H48A)=Sof(H48B)=Sof(H48C)=Sof(C49A)=
 Sof(H49A)=Sof(H49B)=Sof(H49C)=FVAR(1)
 Sof(F1B)=Sof(F3B)=Sof(F4B)=Sof(F6B)=Sof(F7B)=Sof(F8B)=Sof(F9B)=Sof(F10B)=
 Sof(F11B)=Sof(F12B)=Sof(B3B)=1-FVAR(2)
 Sof(F1A)=Sof(F3A)=Sof(F4A)=Sof(F6A)=Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(F10A)=
 Sof(F11A)=Sof(F12A)=Sof(B3A)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C1(H1)
6.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C11(H11A,H11B), C13(H13A,H13B), C21A(H21A,H21B),
 C21B(H21C,H21D), C23(H23A,H23B), C24(H24A,H24B), C32A(H32A,H32B), C32B(H32C,
 H32D), C34(H34A,H34B), C34(H34C,H34D), C42A(H42A,H42B), C42B(H42C,H42D)
6.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C16A(H16A), C16B(H16B), C17A(H17A),
 C17B(H17B), C18A(H18A), C18B(H18B), C19A(H19A), C19B(H19B), C27(H27), C28(H28),
  C29(H29), C30(H30), C37A(H37A), C37B(H37B), C38A(H38A), C38B(H38B),
 C39A(H39A), C39B(H39B), C40A(H40A), C40B(H40B), C44(H44), C47(H47), C47(H47A),
 C52(H52)
6.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C22A(H22A,H22B,H22C), C22B(H22D,H22E,H22F), C33A(H33A,
 H33B,H33C), C33B(H33D,H33E,H33F), C43A(H43A,H43B,H43C), C43B(H43D,H43E,H43F),
 C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C48A(H48A,H48B,H48C), C48B(H48D,H48E,
 H48F), C49A(H49A,H49B,H49C), C49B(H49D,H49E,H49F), C50(H50A,H50B,H50C),
 C51(H51A,H51B,H51C)
;
_shelx_res_checksum              82867
_shelx_hkl_checksum              7186
_shelx_fab_checksum              99299
_olex2_submission_special_instructions 'No special instructions were received'