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_4133755
_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         'C17 H31 Cl3 N O2 P2 Re, C20 H30 Co'
_chemical_formula_sum            'C37 H61 Cl3 Co N O2 P2 Re'
_chemical_formula_weight         965.28
_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                 90.2480(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.30170(10)
_cell_length_b                   18.1366(3)
_cell_length_c                   22.0765(3)
_cell_measurement_reflns_used    9922
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      72.09
_cell_measurement_theta_min      3.15
_cell_volume                     4124.69(10)
_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 0.996
_diffrn_measured_fraction_theta_max 0.993
_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  0.0466
_diffrn_reflns_av_unetI/netI     0.0289
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            48339
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.162
_diffrn_reflns_theta_min         3.153
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    11.562
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.3901
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1074 before and 0.0518 after correction. The Ratio of minimum to maximum transmission is 0.5176. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.554
_exptl_crystal_description       Needle
_exptl_crystal_F_000             1956
_exptl_crystal_size_max          0.224
_exptl_crystal_size_mid          0.123
_exptl_crystal_size_min          0.116
_refine_diff_density_max         1.158
_refine_diff_density_min         -0.574
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     518
_refine_ls_number_reflns         8083
_refine_ls_number_restraints     107
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0332
_refine_ls_R_factor_gt           0.0280
_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^)+(0.0317P)^2^+4.6568P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0636
_refine_ls_wR_factor_ref         0.0658
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7258
_reflns_number_total             8083
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b10031_si_002.cif
_cod_data_source_block           x1803004
_cod_database_code               4133755
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.347
_shelx_estimated_absorpt_t_min   0.182
_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
 C8-C6 = C8A-C6A = C7-C6 = C7A-C6A
 1.53 with sigma of 0.02
 C9A-C10A = C9A-C11A
 1.52 with sigma of 0.02
 C32-C27
 1.495 with sigma of 0.02
 O1A-C1 \\sim O1-C1
 with sigma of 0.02
 P1A-O1A \\sim P1-O1
 with sigma of 0.02
 C17-C15 \\sim C16-C15 \\sim C14A-C12A \\sim C13A-C12A
 with sigma of 0.02
3. Restrained planarity
 C35, C30, C29, C34, C28, C33, C27, C32, C31, C36
 with sigma of 0.1
 C23, C18, C22, C26, C21, C25, C013, C20, C19, C24
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C11A \\sim C11: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
C9A \\sim C9: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
C10 \\sim C10A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
P1A \\sim P1: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
O1A \\sim O1: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
C6A \\sim C6: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
C7 \\sim C7A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
C8A \\sim C8: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
C32 \\sim C33 \\sim C28 \\sim C27 \\sim C31 \\sim C36: within 1.7A with sigma
of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Fixed Sof: P1(0.68) O1(0.68) C9(0.68) H9(0.68) C6(0.68) H6(0.68) C7(0.68)
 H7a(0.68) H7b(0.68) H7c(0.68) C8(0.68) H8a(0.68) H8b(0.68) H8c(0.68) C11(0.68)
 H11a(0.68) H11b(0.68) H11c(0.68) C10(0.68) H10a(0.68) H10b(0.68) H10c(0.68)
 P1A(0.32) C6A(0.32) H6A(0.32) C7A(0.32) H7Aa(0.32) H7Ab(0.32) H7Ac(0.32)
 C8A(0.32) H8Aa(0.32) H8Ab(0.32) H8Ac(0.32) C9A(0.32) H9A(0.32) C11A(0.32)
 H11d(0.32) H11e(0.32) H11f(0.32) C10A(0.32) H10d(0.32) H10e(0.32) H10f(0.32)
 O1A(0.32)
6.a Ternary CH refined with riding coordinates:
 C15(H15), C9(H9), C6(H6), C6A(H6A), C9A(H9A), C12A(H12A)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C3(H3)
6.c Idealised Me refined as rotating group:
 C26(H26a,H26b,H26c), C35(H35a,H35b,H35c), C34(H34a,H34b,H34c), C23(H23a,H23b,
 H23c), C17(H17a,H17b,H17c), C25(H25a,H25b,H25c), C24(H24a,H24b,H24c), C33(H33a,
 H33b,H33c), C013(H01a,H01b,H01c), C16(H16a,H16b,H16c), C7(H7a,H7b,H7c), C8(H8a,
 H8b,H8c), C32(H32a,H32b,H32c), C11(H11a,H11b,H11c), C36(H36a,H36b,H36c),
 C10(H10a,H10b,H10c), C7A(H7Aa,H7Ab,H7Ac), C8A(H8Aa,H8Ab,H8Ac), C11A(H11d,H11e,
 H11f), C10A(H10d,H10e,H10f), C13A(H13a,H13b,H13c), C14A(H14a,H14b,H14c)
;
_shelx_res_checksum              87414
_shelx_hkl_checksum              44054
_olex2_submission_special_instructions 'No special instructions were received'