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_4514702
_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         'C42 H65 Fe K N2 O6 P3'
_chemical_formula_sum            'C42 H65 Fe K N2 O6 P3'
_chemical_formula_weight         881.82
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-12-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.645(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.4864(6)
_cell_length_b                   23.9154(17)
_cell_length_c                   17.8619(10)
_cell_measurement_reflns_used    9960
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      39.16
_cell_measurement_theta_min      2.36
_cell_volume                     4470.5(5)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.982
_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  0.0480
_diffrn_reflns_av_unetI/netI     0.0334
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       42
_diffrn_reflns_limit_k_min       -42
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            220099
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         39.747
_diffrn_reflns_theta_min         2.124
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.584
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9517
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0705 before and 0.0550 after correction. The Ratio of minimum to maximum transmission is 0.9517. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'metallic brown'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.310
_exptl_crystal_description       chunk
_exptl_crystal_F_000             1876
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.23
_refine_diff_density_max         2.068
_refine_diff_density_min         -0.642
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     544
_refine_ls_number_reflns         26751
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0682
_refine_ls_R_factor_gt           0.0460
_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^)+(0.0391P)^2^+3.0025P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0998
_refine_ls_wR_factor_ref         0.1080
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21065
_reflns_number_total             26751
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b00523_si_002.cif
_cod_data_source_block           p17651
_cod_database_code               4514702
_shelx_shelxl_version_number     2018/1
_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. Others
 Sof(H34c)=Sof(H34d)=Sof(H36c)=Sof(H36d)=Sof(O1)=1-FVAR(1)
 Sof(O7)=Sof(H34a)=Sof(H34b)=Sof(H36a)=Sof(H36b)=FVAR(1)
 Sof(H41c)=Sof(H41d)=Sof(H39c)=Sof(H39d)=Sof(O4)=1-FVAR(2)
 Sof(O9)=Sof(H41a)=Sof(H41b)=Sof(H39a)=Sof(H39b)=FVAR(2)
 Sof(H33c)=Sof(H33d)=Sof(O10)=1-FVAR(3)
 Sof(O6)=Sof(H33a)=Sof(H33b)=FVAR(3)
 Sof(H40c)=Sof(H40d)=Sof(H38c)=Sof(H38d)=Sof(O8)=1-FVAR(4)
 Sof(O3)=Sof(H40a)=Sof(H40b)=Sof(H38a)=Sof(H38b)=FVAR(4)
3.a Ternary CH refined with riding coordinates:
 C20(H20), C23(H23), C17(H17), C14(H14)
3.b Secondary CH2 refined with riding coordinates:
 C37(H37a,H37b), C42(H42a,H42b), C31(H31a,H31b), C32(H32a,H32b), C40(H40a,
 H40b), C40(H40c,H40d), C41(H41a,H41b), C41(H41c,H41d), C38(H38a,H38b),
 C38(H38c,H38d), C34(H34a,H34b), C34(H34c,H34d), C35(H35a,H35b), C39(H39a,H39b),
  C39(H39c,H39d), C36(H36a,H36b), C36(H36c,H36d), C33(H33a,H33b), C33(H33c,H33d)
3.c Aromatic/amide H refined with riding coordinates:
 C30(H30), C27(H27), C8(H8), C29(H29), C2(H2), C28(H28), C6(H6), C11(H11),
 C9(H9), C10(H10), C5(H5), C4(H4), C3(H3)
3.d Idealised Me refined as rotating group:
 C19(H19a,H19b,H19c), C18(H18a,H18b,H18c), C21(H21a,H21b,H21c), C24(H24a,H24b,
 H24c), C16(H16a,H16b,H16c), C15(H15a,H15b,H15c), C13(H13a,H13b,H13c), C22(H22a,
 H22b,H22c)
;
_shelx_res_checksum              10350
_shelx_hkl_checksum              98902
_olex2_submission_special_instructions 'No special instructions were received'