Hemilabile Proton Relays and Redox Activity Lead to {FeNO} <sup>x</sup> and Significant Rate Enhancements in NO<sub>2</sub><sup>-</sup> Reduction.
Cheung, Pui Man; Burns, Kyle T.; Kwon, Yubin M.; Deshaye, Megan Y.; Aguayo, Kristopher J.; Oswald, Victoria F.; Seda, Takele; Zakharov, Lev N.; Kowalczyk, Tim; Gilbertson, John D.; Journal of the American Chemical Society 140 (2018) 17040–17050; doi:10.1021/jacs.8b08520

data_4133104
_publ_section_title
;
 Hemilabile Proton Relays and Redox Activity Lead to {FeNO} <sup>x</sup>
 and Significant Rate Enhancements in NO<sub>2</sub><sup>-</sup>
 Reduction.
;
_journal_issue                   49
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              17040
_journal_page_last               17050
_journal_paper_doi               10.1021/jacs.8b08520
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C29 H38 Fe N4 O2'
_chemical_formula_sum            'C29 H38 Fe N4 O2'
_chemical_formula_weight         530.48
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-12-19
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.03.02 svn.r3394 for Rigaku Oxford Diffraction, GUI svn.r5318)
;
_cell_angle_alpha                90
_cell_angle_beta                 108.215(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.7147(5)
_cell_length_b                   13.7514(5)
_cell_length_c                   16.3476(7)
_cell_measurement_reflns_used    13829
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.2510
_cell_measurement_theta_min      2.4350
_cell_volume                     2715.1(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.38b (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.38b (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.38b (Rigaku OD, 2017)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Pilatus P200K HPC detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -59.00  90.00   0.50    5.00    --    0.00   9.00 -72.00  298
  2  \w    -23.00  22.00   0.50    5.00    --    0.00  45.00-180.00   90
  3  \w    -90.00 -45.00   0.50    5.00    --    0.00 -10.00-108.00   90
;
_diffrn_measurement_device       'ROD XtaLABPRO'
_diffrn_measurement_device_type  'ROD XtaLABPRO'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0294792000
_diffrn_orient_matrix_UB_12      -0.0053058000
_diffrn_orient_matrix_UB_13      -0.0444255000
_diffrn_orient_matrix_UB_21      0.0292560000
_diffrn_orient_matrix_UB_22      0.0400835000
_diffrn_orient_matrix_UB_23      -0.0095582000
_diffrn_orient_matrix_UB_31      0.0415453000
_diffrn_orient_matrix_UB_32      -0.0320268000
_diffrn_orient_matrix_UB_33      -0.0045763000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0393
_diffrn_reflns_av_unetI/netI     0.0315
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            23324
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.102
_diffrn_reflns_theta_min         1.978
_diffrn_source                   '3.0 kW sealed X-ray tube'
_diffrn_source_type              'Fine-focus sealed X-ray Source (Mo)'
_diffrn_standards_decay_%        0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.588
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67550
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.38b (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.298
_exptl_crystal_description       prism
_exptl_crystal_F_000             1128
_exptl_crystal_preparation       Loop
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.31
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.415
_refine_diff_density_min         -0.378
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     344
_refine_ls_number_reflns         5963
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0426
_refine_ls_R_factor_gt           0.0336
_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^)+(0.0535P)^2^+1.1561P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0865
_refine_ls_wR_factor_ref         0.0946
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5060
_reflns_number_total             5963
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b08520_si_002.cif
_cod_data_source_block           gilb367
_cod_database_code               4133104
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C29 H39 Fe N4 O2'
_reflns_odcompleteness_completeness 99.62
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.04
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(H1BD)=Sof(H1BE)=Sof(H1BF)=1-FVAR(1)
 Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C22(H22), C25(H25)
3.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C15(H15A,H15B), C12(H12A,H12B), C13(H13A,
 H13B), C14(H14A,H14B)
3.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C18(H18), C6(H6), C5(H5), C20(H20), C19(H19)
3.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C1(H1AA,H1AB,H1AC), C23(H23A,H23B,H23C), C26(H26A,H26B,H26C),
  C27(H27A,H27B,H27C), C24(H24A,H24B,H24C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.391
_oxdiff_exptl_absorpt_empirical_full_min 0.741