Characterization of the Earliest Intermediate of Fe-N<sub>2</sub> Protonation: CW and Pulse EPR Detection of an Fe-NNH Species and Its Evolution to Fe-NNH<sub>2</sub><sup/>.
Nesbit, Mark A.; Oyala, Paul H.; Peters, Jonas C.; Journal of the American Chemical Society 141 (2019) 8116–8127; doi:10.1021/jacs.8b12082

data_4127262
_publ_section_title
;
 Characterization of the Earliest Intermediate of Fe-N<sub>2</sub>
 Protonation: CW and Pulse EPR Detection of an Fe-NNH Species and Its
 Evolution to Fe-NNH<sub>2</sub><sup/>.
;
_journal_issue                   20
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8116
_journal_page_last               8127
_journal_paper_doi               10.1021/jacs.8b12082
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C96 H126 B Br Fe O6 P3'
_chemical_formula_sum            'C96 H126 B Br Fe O6 P3'
_chemical_formula_weight         1615.44
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-10-19
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                93.843(5)
_cell_angle_beta                 90.086(5)
_cell_angle_gamma                109.902(5)
_cell_formula_units_Z            2
_cell_length_a                   13.3439(11)
_cell_length_b                   13.9184(11)
_cell_length_c                   25.1806(19)
_cell_measurement_reflns_used    9312
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      79.6
_cell_measurement_theta_min      3.39
_cell_volume                     4386.0(6)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      99.99
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.937
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1587
_diffrn_reflns_av_unetI/netI     0.0976
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.937
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            95174
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.937
_diffrn_reflns_theta_full        67.000
_diffrn_reflns_theta_max         86.680
_diffrn_reflns_theta_min         3.386
_exptl_absorpt_coefficient_mu    2.828
_exptl_absorpt_correction_T_max  0.7543
_exptl_absorpt_correction_T_min  0.5540
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1736 before and 0.1182 after correction.
The Ratio of minimum to maximum transmission is 0.7345.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            brown
_exptl_crystal_density_diffrn    1.223
_exptl_crystal_description       block
_exptl_crystal_F_000             1722
_refine_diff_density_max         1.696
_refine_diff_density_min         -1.968
_refine_diff_density_rms         0.162
_refine_ls_extinction_coef       0.00039(10)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1004
_refine_ls_number_reflns         18705
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.1526
_refine_ls_R_factor_gt           0.1122
_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^)+(0.1128P)^2^+45.2958P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2578
_refine_ls_wR_factor_ref         0.2874
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13592
_reflns_number_total             18705
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b12082_si_002.cif
_cod_data_source_block           ArP3BFeBr
_cod_depositor_comments
'Adding full bibliography for 4127262--4127263.cif.'
_cod_database_code               4127262
_shelxl_version_number           2013-2
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C49(H49), C77(H77), C58(H58), C90(H90), C17(H17), C81(H81), C45(H45),
 C94(H94), C13(H13), C62(H62), C26(H26), C30(H30)
2.b Aromatic/amide H refined with riding coordinates:
 C85(H85), C8(H8), C76(H76), C57(H57), C72(H72), C53(H53), C5(H5), C21(H21),
 C25(H25), C40(H40), C4(H4), C12(H12), C67(H67), C70(H70), C3(H3), C44(H44),
 C89(H89), C69(H69), C68(H68), C34(H34), C37(H37), C2(H2), C36(H36), C35(H35)
2.c Idealised Me refined as rotating group:
 C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C83(H83A,H83B,H83C), C19(H19A,H19B,
 H19C), C18(H18A,H18B,H18C), C78(H78A,H78B,H78C), C93(H93A,H93B,H93C), C80(H80A,
 H80B,H80C), C96(H96A,H96B,H96C), C46(H46A,H46B,H46C), C79(H79A,H79B,H79C),
 C60(H60A,H60B,H60C), C82(H82A,H82B,H82C), C48(H48A,H48B,H48C), C95(H95A,H95B,
 H95C), C15(H15A,H15B,H15C), C91(H91A,H91B,H91C), C47(H47A,H47B,H47C), C59(H59A,
 H59B,H59C), C61(H61A,H61B,H61C), C92(H92A,H92B,H92C), C31(H31A,H31B,H31C),
 C29(H29A,H29B,H29C), C16(H16A,H16B,H16C), C14(H14A,H14B,H14C), C63(H63A,H63B,
 H63C), C32(H32A,H32B,H32C), C27(H27A,H27B,H27C), C64(H64A,H64B,H64C), C28(H28A,
 H28B,H28C)
;
_olex2_submission_special_instructions 'No special instructions were received'