Dinitrogen Reduction to Ammonium at Rhenium Utilizing Light and Proton-Coupled Electron Transfer.
Bruch, Quinton J.; Connor, Gannon P.; Chen, Chun-Hsing; Holland, Patrick L.; Mayer, James M.; Hasanayn, Faraj; Miller, Alexander J. M.; Journal of the American Chemical Society  (2019) –; doi:10.1021/jacs.9b10031

data_4133754
_publ_section_title
;
 Dinitrogen Reduction to Ammonium at Rhenium Utilizing Light and
 Proton-Coupled Electron Transfer.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b10031
_journal_year                    2019
_chemical_formula_moiety         '1(C17 H31 Cl3 N O2 P2 Re)'
_chemical_formula_sum            'C17 H31 Cl3 N O2 P2 Re'
_chemical_formula_weight         635.92
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-08-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.225(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.3376(4)
_cell_length_b                   22.9642(10)
_cell_length_c                   19.6707(8)
_cell_measurement_reflns_used    9987
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      72.378
_cell_measurement_theta_min      2.976
_cell_volume                     4621.7(3)
_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      100.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.989
_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  0.0575
_diffrn_reflns_av_unetI/netI     0.0379
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            48657
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.526
_diffrn_reflns_theta_min         2.976
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    14.888
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.5379
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1008 before and 0.0599 after correction. The Ratio of minimum to maximum transmission is 0.7138. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.828
_exptl_crystal_description       block
_exptl_crystal_F_000             2496
_exptl_crystal_size_max          0.221
_exptl_crystal_size_mid          0.131
_exptl_crystal_size_min          0.128
_refine_diff_density_max         1.887
_refine_diff_density_min         -0.814
_refine_diff_density_rms         0.139
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.122
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     515
_refine_ls_number_reflns         9077
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.122
_refine_ls_R_factor_all          0.0393
_refine_ls_R_factor_gt           0.0316
_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^)+(0.0244P)^2^+9.8195P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0685
_refine_ls_wR_factor_ref         0.0713
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7929
_reflns_number_total             9077
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b10031_si_002.cif
_cod_data_source_block           x1803003
_cod_database_code               4133754
_shelx_shelxl_version_number     2018/3
_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. Restrained distances
 P2-C15 = P2-C15A
 1.83 with sigma of 0.02
 C17A-C15A = C17-C15 = C16A-C15A = C16-C15
 1.53 with sigma of 0.02
 C17-C16
 2.54 with sigma of 0.04
 C17A-C16A
 2.54 with sigma of 0.04
 C16-P2
 2.74 with sigma of 0.04
 C16A-P2
 2.74 with sigma of 0.04
 C17-P2
 2.74 with sigma of 0.04
 C17A-P2
 2.74 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C15 \\sim C15A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
4. Others
 Sof(C17A)=Sof(H17d)=Sof(H17e)=Sof(H17f)=Sof(C15A)=Sof(H15A)=Sof(C16A)=
 Sof(H16d)=Sof(H16e)=Sof(H16f)=1-FVAR(1)
 Sof(C15)=Sof(H15)=Sof(C17)=Sof(H17a)=Sof(H17b)=Sof(H17c)=Sof(C16)=Sof(H16a)=
 Sof(H16b)=Sof(H16c)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C29(H29), C9(H9), C26(H26), C32(H32), C23(H23), C12(H12), C6(H6), C15(H15),
 C15A(H15A)
5.b Aromatic/amide H refined with riding coordinates:
 C20(H20), C19(H19), C2(H2), C21(H21), C3(H3), C4(H4)
5.c Idealised Me refined as rotating group:
 C33(H33a,H33b,H33c), C34(H34a,H34b,H34c), C27(H27a,H27b,H27c), C24(H24a,H24b,
 H24c), C7(H7a,H7b,H7c), C30(H30a,H30b,H30c), C8(H8a,H8b,H8c), C25(H25a,H25b,
 H25c), C31(H31a,H31b,H31c), C14(H14a,H14b,H14c), C13(H13a,H13b,H13c), C11(H11a,
 H11b,H11c), C28(H28a,H28b,H28c), C10(H10a,H10b,H10c), C17(H17a,H17b,H17c),
 C16(H16a,H16b,H16c), C17A(H17d,H17e,H17f), C16A(H16d,H16e,H16f)
;
_shelx_res_checksum              75874
_shelx_hkl_checksum              47802
_olex2_submission_special_instructions 'No special instructions were received'