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_1573945
_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         '2(C42 H30 Au2 Cu P), 0.5[]'
_chemical_formula_sum            'C84 H60 Au4 Cu2 P2'
_chemical_formula_weight         2046.20
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-09-12
_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                88.962(4)
_cell_angle_beta                 76.498(4)
_cell_angle_gamma                69.963(4)
_cell_formula_units_Z            2
_cell_length_a                   12.6398(6)
_cell_length_b                   16.7456(9)
_cell_length_c                   18.5200(9)
_cell_measurement_reflns_used    16075
_cell_measurement_temperature    170.00(10)
_cell_measurement_theta_max      28.9650
_cell_measurement_theta_min      1.7670
_cell_volume                     3572.7(3)
_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 1.000
_diffrn_measured_fraction_theta_max 0.842
_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    -40.00 -14.00   0.50    2.81    --    5.00  45.00 174.50   52
  2  \w    -21.00  33.00   0.50    2.81    --  -10.70  45.00  30.00  108
  3  \w     -6.00  78.00   0.50    2.81    --  -10.70  45.00 177.41  168
  4  \w      8.00  69.00   0.50    2.81    --  -10.70  45.00 -14.02  122
  5  \w    -99.00  19.00   0.50    2.81    --  -10.70  45.00 150.00  236
  6  \w     29.00  55.00   0.50    2.81    --  -10.70  45.00 150.00   52
  7  \w    -62.00 -35.00   0.50    2.81    --  -10.70  45.00  30.00   54
  8  \w   -100.00  78.00   0.50    2.81    --  -10.70  45.00  90.00  356
;
_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      -0.0007437000
_diffrn_orient_matrix_UB_12      -0.0315317000
_diffrn_orient_matrix_UB_13      -0.0247458000
_diffrn_orient_matrix_UB_21      -0.0525447000
_diffrn_orient_matrix_UB_22      -0.0008734000
_diffrn_orient_matrix_UB_23      0.0235892000
_diffrn_orient_matrix_UB_31      -0.0320667000
_diffrn_orient_matrix_UB_32      0.0323595000
_diffrn_orient_matrix_UB_33      -0.0197417000
_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  0.0594
_diffrn_reflns_av_unetI/netI     0.0724
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.842
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            59738
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.842
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.034
_diffrn_reflns_theta_min         1.767
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    8.855
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49116
_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 yellow'
_exptl_crystal_density_diffrn    1.902
_exptl_crystal_description       block
_exptl_crystal_F_000             1936
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.03
_refine_diff_density_max         5.658
_refine_diff_density_min         -1.912
_refine_diff_density_rms         0.213
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     829
_refine_ls_number_reflns         19237
_refine_ls_number_restraints     127
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0851
_refine_ls_R_factor_gt           0.0517
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0601P)^2^+4.8149P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1200
_refine_ls_wR_factor_ref         0.1306
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13577
_reflns_number_total             19237
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nr05341a2.cif
_cod_data_source_block           mx10980_sq
_cod_depositor_comments
'Adding full bibliography for 1573943--1573945.cif.'
_cod_database_code               1573945
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         AuCuCHPCl
_chemical_oxdiff_usercomment     CHNO
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C55-C54 = C56-C55 = C57-C56 = C58-C57 = C58-C53 = C54-C53
 1.39 with sigma of 0.01
 C16-C15 = C15-C14 = C14-C13 = C13-C12 = C12-C11 = C16-C11
 1.39 with sigma of 0.01
 C5-C4 = C6-C5 = C7-C6 = C8-C3 = C8-C7 = C4-C3
 1.39 with sigma of 0.01
3. Rigid bond restraints
 C5, C6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58: within 1.7A with sigma
of 0.02 and sigma for terminal atoms of 0.04 within 1.7A
C16 \\sim C15 \\sim C14 \\sim C13 \\sim C12 \\sim C11: within 1.7A with sigma
of 0.02 and sigma for terminal atoms of 0.04 within 1.7A
C3 \\sim C8 \\sim C7 \\sim C6 \\sim C4 \\sim C5: within 1.7A with sigma of 0.02
and sigma for terminal atoms of 0.04 within 1.7A
5.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C12(H12), C13(H13), C14(H14),
 C15(H15), C16(H16), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C26(H26),
  C27(H27), C28(H28), C29(H29), C30(H30), C32(H32), C33(H33), C34(H34),
 C35(H35), C36(H36), C38(H38), C39(H39), C40(H40), C41(H41), C42(H42), C46(H46),
  C47(H47), C48(H48), C49(H49), C50(H50), C54(H54), C55(H55), C56(H56),
 C57(H57), C58(H58), C62(H62), C63(H63), C64(H64), C65(H65), C66(H66), C68(H68),
  C69(H69), C70(H70), C71(H71), C72(H72), C74(H74), C75(H75), C76(H76),
 C77(H77), C78(H78), C80(H80), C81(H81), C82(H82), C83(H83), C84(H84)
;
_shelx_res_checksum              55963
_shelx_hkl_checksum              14454
_shelx_fab_checksum              11696
_platon_squeeze_void_probe_radius 1.20
_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 2.238
_oxdiff_exptl_absorpt_empirical_full_min 0.332