Electrocatalytic nitrogen reduction to ammonia by graphene-supported Au<sub>4</sub>Cu<sub>2</sub> and Au<sub>2</sub>Ag<sub>2</sub> nanoclusters.
Shehzad, Aamir; Yi, Qiuhao; Cui, Chaonan; Luo, Zhixun; Nanoscale 17 (2025) 7453–7459; doi:10.1039/d4nr05341a

data_1573944
_publ_section_title
;
 Electrocatalytic nitrogen reduction to ammonia by graphene-supported
 Au<sub>4</sub>Cu<sub>2</sub> and Au<sub>2</sub>Ag<sub>2</sub>
 nanoclusters.
;
_journal_issue                   12
_journal_name_full               Nanoscale
_journal_page_first              7453
_journal_page_last               7459
_journal_paper_doi               10.1039/d4nr05341a
_journal_volume                  17
_journal_year                    2025
_chemical_formula_moiety         'C26 H20 Au P, 1/3(C H2 Cl2)'
_chemical_formula_sum            'C26.33333 H20.66667 Au Cl0.66667 P'
_chemical_formula_weight         788.66
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-10-11
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-10-14 deposited with the CCDC.	2025-02-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.670(7)
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   13.1746(8)
_cell_length_b                   12.7141(8)
_cell_length_c                   39.686(4)
_cell_measurement_reflns_used    5379
_cell_measurement_temperature    170.00(10)
_cell_measurement_theta_max      27.7380
_cell_measurement_theta_min      1.9080
_cell_volume                     6625.5(9)
_computing_cell_refinement       'CrysAlisPro 1.171.39.45i (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.45i (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.45i (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      170.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.833
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -68.00  56.00   0.50    5.32    --  -10.70  45.00  90.00  248
  2  \w    -74.00  66.00   0.50    5.32    --  -10.70  45.00 176.94  280
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC10 (RCD3): fixed-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0375897000
_diffrn_orient_matrix_UB_12      0.0381777000
_diffrn_orient_matrix_UB_13      -0.0029730000
_diffrn_orient_matrix_UB_21      -0.0035256000
_diffrn_orient_matrix_UB_22      0.0207730000
_diffrn_orient_matrix_UB_23      0.0164904000
_diffrn_orient_matrix_UB_31      0.0387242000
_diffrn_orient_matrix_UB_32      -0.0348583000
_diffrn_orient_matrix_UB_33      0.0063878000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1156
_diffrn_reflns_av_unetI/netI     0.1321
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.833
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       55
_diffrn_reflns_limit_l_min       -56
_diffrn_reflns_number            49079
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.833
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.094
_diffrn_reflns_theta_min         1.673
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    6.824
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47711
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.45i (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_density_diffrn    1.770
_exptl_crystal_description       block
_exptl_crystal_F_000             3408
_exptl_crystal_size_max          0.02
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         5.536
_refine_diff_density_min         -7.314
_refine_diff_density_rms         0.370
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     784
_refine_ls_number_reflns         17752
_refine_ls_number_restraints     474
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.2070
_refine_ls_R_factor_gt           0.1560
_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^)+(0.1134P)^2^+438.5848P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3465
_refine_ls_wR_factor_ref         0.3686
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10736
_reflns_number_total             17752
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nr05341a2.cif
_cod_data_source_block           mx11069
_cod_depositor_comments
;
Adding full bibliography for 1573943--1573945.cif.

2025-05-14
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C79 H62 Au3 Cl2 P3'
_cod_original_formula_weight         1765.99
_cod_original_formula_moiety         '3(C26 H20 Au P), C H2 Cl2'
_cod_original_formula_units_Z            4
_cod_database_code               1573944
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         AuCuPCHOCl
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim
Ueq, Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C8)
\\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C11) \\sim Ueq,
Uanis(C12) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15)
\\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq,
Uanis(C19) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22)
\\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C25) \\sim Ueq,
Uanis(C26) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C2A) \\sim Ueq, Uanis(C3A)
\\sim Ueq, Uanis(C4A) \\sim Ueq, Uanis(C5A) \\sim Ueq, Uanis(C6A) \\sim Ueq,
Uanis(C7A) \\sim Ueq, Uanis(C8A) \\sim Ueq, Uanis(C9A) \\sim Ueq, Uanis(C10A)
\\sim Ueq, Uanis(C11A) \\sim Ueq, Uanis(C12A) \\sim Ueq, Uanis(C13A) \\sim Ueq,
Uanis(C14A) \\sim Ueq, Uanis(C15A) \\sim Ueq, Uanis(C16A) \\sim Ueq,
Uanis(C17A) \\sim Ueq, Uanis(C18A) \\sim Ueq, Uanis(C19A) \\sim Ueq,
Uanis(C20A) \\sim Ueq, Uanis(C21A) \\sim Ueq, Uanis(C22A) \\sim Ueq,
Uanis(C23A) \\sim Ueq, Uanis(C24A) \\sim Ueq, Uanis(C25A) \\sim Ueq,
Uanis(C26A) \\sim Ueq, Uanis(C1B) \\sim Ueq, Uanis(C2B) \\sim Ueq, Uanis(C3B)
\\sim Ueq, Uanis(C4B) \\sim Ueq, Uanis(C5B) \\sim Ueq, Uanis(C6B) \\sim Ueq,
Uanis(C7B) \\sim Ueq, Uanis(C8B) \\sim Ueq, Uanis(C9B) \\sim Ueq, Uanis(C10B)
\\sim Ueq, Uanis(C11B) \\sim Ueq, Uanis(C12B) \\sim Ueq, Uanis(C13B) \\sim Ueq,
Uanis(C14B) \\sim Ueq, Uanis(C15B) \\sim Ueq, Uanis(C16B) \\sim Ueq,
Uanis(C17B) \\sim Ueq, Uanis(C18B) \\sim Ueq, Uanis(C19B) \\sim Ueq,
Uanis(C20B) \\sim Ueq, Uanis(C21B) \\sim Ueq, Uanis(C22B) \\sim Ueq,
Uanis(C23B) \\sim Ueq, Uanis(C24B) \\sim Ueq, Uanis(C25B) \\sim Ueq,
Uanis(C26B) \\sim Ueq, Uanis(C27) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C22(H22), C23(H23),
  C24(H24), C25(H25), C26(H26), C2A(H2A), C3A(H3A), C4A(H4A), C5A(H5A),
 C6A(H6A), C8A(H8A), C9A(H9A), C10A(H10A), C11A(H11A), C12A(H12A), C14A(H14A),
 C15A(H15A), C16A(H16A), C17A(H17A), C18A(H18A), C22A(H22A), C23A(H23A),
 C24A(H24A), C25A(H25A), C26A(H26A), C2B(H2B), C3B(H3B), C4B(H4B), C5B(H5B),
 C6B(H6B), C8B(H8B), C9B(H9B), C10B(H10B), C11B(H11B), C12B(H12B), C14B(H14B),
 C15B(H15B), C16B(H16B), C17B(H17B), C18B(H18B), C22B(H22B), C23B(H23B),
 C24B(H24B), C25B(H25B), C26B(H26B)
;
_shelx_res_checksum              59057
_shelx_hkl_checksum              43147
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.661
_oxdiff_exptl_absorpt_empirical_full_min 0.616