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_4514701
_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
'2(C30 H41 Fe N4 P3), 2(C32 H12 B F24), 0.5(C10)'
_chemical_formula_sum            'C129 H106 B2 F48 Fe2 N8 P6'
_chemical_formula_weight         2999.35
_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                 101.904(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   22.4451(18)
_cell_length_b                   12.1053(6)
_cell_length_c                   25.482(2)
_cell_measurement_reflns_used    9677
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      0.974
_cell_measurement_theta_min      0.595
_cell_volume                     6774.7(8)
_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      100.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0840
_diffrn_reflns_av_unetI/netI     0.0509
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            86754
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         79.656
_diffrn_reflns_theta_min         2.943
_exptl_absorpt_coefficient_mu    3.434
_exptl_absorpt_correction_T_max  0.974
_exptl_absorpt_correction_T_min  0.595
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1244 before'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.470
_exptl_crystal_description       block
_exptl_crystal_F_000             3040
_exptl_crystal_size_max          0.284
_exptl_crystal_size_mid          0.142
_exptl_crystal_size_min          0.06
_refine_diff_density_max         2.192
_refine_diff_density_min         -0.843
_refine_diff_density_rms         0.118
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/1 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     907
_refine_ls_number_reflns         14524
_refine_ls_number_restraints     800
_refine_ls_restrained_S_all      1.009
_refine_ls_R_factor_all          0.1178
_refine_ls_R_factor_gt           0.0967
_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^)+(0.1468P)^2^+26.6461P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2546
_refine_ls_wR_factor_ref         0.2736
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11713
_reflns_number_total             14524
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b00523_si_002.cif
_cod_data_source_block           mkt_a
_cod_original_cell_volume        6774.6(9)
_cod_database_code               4514701
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.820
_shelx_estimated_absorpt_t_min   0.442
_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. 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
3. Others
 Fixed Sof: C1(0.5) C2(0.5) C4(0.5) C7(0.5)
4.a Ternary CH refined with riding coordinates:
 C01P(H01P), C01Z(H01Z), C02A(H02J), C02J(H02S)
4.b Aromatic/amide H refined with riding coordinates:
 C00K(H00K), C00N(H00N), C00Q(H00Q), C00X(H00X), C00Y(H00Y), C013(H013),
 C014(H014), C019(H019), C01E(H01E), C01I(H01I), C01K(H01K), C01N(H01N),
 C01O(H01O), C01Q(H01Q), C01S(H01S), C01T(H01T), C01U(H01U), C01V(H01V),
 C01W(H01W), C020(H020), C023(H023), C026(H026), C028(H028), C02B(H02K),
 C02I(H02R)
4.c Idealised Me refined as rotating group:
 C01C(H01A,H01B,H01C), C01X(H01D,H01F,H01G), C021(H02A,H02B,H02C), C025(H02D,
 H02E,H02F), C029(H02G,H02H,H02I), C02D(H02L,H02M,H02N), C02G(H02O,H02P,H02Q),
 C02K(H02T,H02U,H02V)
;
_shelx_res_checksum              5298
_shelx_hkl_checksum              66225
_olex2_submission_special_instructions 'No special instructions were received'