Light Enhanced Fe-Mediated Nitrogen Fixation: Mechanistic Insights Regarding H<sub>2</sub> Elimination, HER, and NH<sub>3</sub> Generation.
Schild, Dirk J.; Peters, Jonas C.; ACS catalysis 9 (2019) 4286–4295; doi:10.1021/acscatal.9b00523

data_4514703
_publ_section_title
;
 Light Enhanced Fe-Mediated Nitrogen Fixation: Mechanistic Insights
 Regarding H<sub>2</sub> Elimination, HER, and NH<sub>3</sub> Generation.
;
_journal_issue                   5
_journal_name_full               'ACS catalysis'
_journal_page_first              4286
_journal_page_last               4295
_journal_paper_doi               10.1021/acscatal.9b00523
_journal_volume                  9
_journal_year                    2019
_chemical_formula_moiety         'C40 H61 Fe K N2 O4 P3'
_chemical_formula_sum            'C40 H61 Fe K N2 O4 P3'
_chemical_formula_weight         816.72
_chemical_name_systematic        P2PFeanion
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_symmetry_space_group_name_Hall  '-P 2ac 2n'
_symmetry_space_group_name_H-M   'P n m a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-06
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.9569(13)
_cell_length_b                   17.0296(9)
_cell_length_c                   12.1851(6)
_cell_measurement_reflns_used    9390
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.48
_cell_measurement_theta_min      2.59
_cell_volume                     5386.2(5)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0545
_diffrn_reflns_av_unetI/netI     0.0235
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            73356
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.506
_diffrn_reflns_theta_min         2.293
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.478
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6723
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1363 before and 0.0568 after correction. The Ratio of minimum to maximum transmission is 0.9017. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.007
_exptl_crystal_description       block
_exptl_crystal_F_000             1728
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.12
_refine_diff_density_max         3.977
_refine_diff_density_min         -1.496
_refine_diff_density_rms         0.242
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.123
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     287
_refine_ls_number_reflns         6368
_refine_ls_number_restraints     303
_refine_ls_restrained_S_all      1.114
_refine_ls_R_factor_all          0.1162
_refine_ls_R_factor_gt           0.1026
_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^)+(0.1969P)^2^+18.6631P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3059
_refine_ls_wR_factor_ref         0.3201
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5334
_reflns_number_total             6368
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b00523_si_002.cif
_cod_data_source_block           p17634pnma
_cod_database_code               4514703
_shelx_shelxl_version_number     2016/6
_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. Uiso/Uaniso restraints and constraints
Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C24) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.001
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Fixed Sof: O2(0.5) O1(0.5) O3(0.5) C20(0.5) H20A(0.5) H20B(0.5) C21(0.5)
 H21A(0.5) H21B(0.5) C18(0.5) H18A(0.5) H18B(0.5) C19(0.5) H19A(0.5) H19B(0.5)
 C17(0.5) H17A(0.5) H17B(0.5) C22(0.5) H22A(0.5) H22B(0.5)
5.a Ternary CH refined with riding coordinates:
 C5(H5), C2(H2)
5.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C21(H21A,H21B), C18(H18A,H18B), C19(H19A,H19B), C17(H17A,
 H17B), C23(H23A,H23B), C24(H24A,H24B), C22(H22A,H22B)
5.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C10(H10), C8(H8), C14(H14), C15(H15), C9(H9), C16(H16)
5.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C4(H4A,H4B,H4C), C3(H3A,H3B,H3C), C1(H1A,H1B,H1C)
;
_olex2_submission_special_instructions 'No special instructions were received'