An atomically precise alloy AgCu cuboid nanocluster with a cubic core: gram scale synthesis, total structure, electronic structure, and catalytic performance.
Nag, Abhijit; Butt, Abdul Mannan; Yang, Moon Young; Managutti, Praveen B.; Pirzada, Bilal Masood; H Mohideen, M Infas; Abdelhady, Ahmed L.; Abu Haija, Mohamed; Mohamed, Sharmarke; Merinov, Boris V.; GoddardIII, William A; Qurashi, Ahsanulhaq; Materials horizons 12 (2025) 5252–5258; doi:10.1039/d4mh01324g

data_1574420
_publ_section_title
;
 An atomically precise alloy AgCu cuboid nanocluster with a cubic core:
 gram scale synthesis, total structure, electronic structure, and
 catalytic performance.
;
_journal_issue                   14
_journal_name_full               'Materials horizons'
_journal_page_first              5252
_journal_page_last               5258
_journal_paper_doi               10.1039/d4mh01324g
_journal_volume                  12
_journal_year                    2025
_chemical_formula_moiety
'C272 H264 Ag4 Cl8 Cu28 P8 S16, 8(C H Cl3), 7.5[C6H14]'
_chemical_formula_sum            'C325 H377 Ag4 Cl32 Cu28 P8 S16'
_chemical_formula_weight         8388.96
_space_group_crystal_system      tetragonal
_space_group_IT_number           87
_space_group_name_Hall           '-I 4'
_space_group_name_H-M_alt        'I 4/m'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-20
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-03-21 deposited with the CCDC.	2025-04-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   26.5679(3)
_cell_length_b                   26.5679(3)
_cell_length_c                   23.7512(5)
_cell_measurement_reflns_used    11164
_cell_measurement_temperature    99.99(11)
_cell_measurement_theta_max      71.4860
_cell_measurement_theta_min      2.3770
_cell_volume                     16764.9(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.68a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.68a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.68a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.966
_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   -118.00 -16.00   0.50    3.97    --  -41.23 -46.00-135.00  204
  2  \w   -177.00 -80.00   0.50   15.89    -- -105.75 -46.00-135.00  194
  3  \w   -108.00 -31.00   0.50   15.89    -- -105.75 109.00-121.00  154
  4  \w    -40.00 -12.00   0.50    3.97    --   41.23 -19.00 150.00   56
  5  \w    -40.00 -12.00   0.50    3.97    --   41.23 -19.00-120.00   56
  6  \w   -111.00 -33.00   0.50   15.89    -- -105.75 125.00 150.00  156
  7  \w     31.00  89.00   0.50   15.89    --  105.75 -61.00  30.00  116
  8  \w    -40.00 -12.00   0.50    3.97    --   41.23 -19.00-150.00   56
  9  \w    -40.00 -12.00   0.50    3.97    --   41.23 -19.00 -90.00   56
 10  \w     47.00 141.00   0.50   15.89    --  105.75  15.00   0.00  188
 11  \w     31.00  89.00   0.50   15.89    --  105.75 -61.00 -60.00  116
 12  \w     47.00 128.00   0.50   15.89    --  105.75  15.00  90.00  162
 13  \w     47.00 141.00   0.50   15.89    --  105.75  15.00 150.00  188
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0510
_diffrn_reflns_av_unetI/netI     0.0345
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            40133
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.059
_diffrn_reflns_theta_min         2.352
_exptl_absorpt_coefficient_mu    7.703
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.38781
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.68a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light brown'
_exptl_crystal_density_diffrn    1.662
_exptl_crystal_description       block
_exptl_crystal_F_000             8494
_exptl_crystal_size_max          0.178
_exptl_crystal_size_mid          0.173
_exptl_crystal_size_min          0.031
_refine_diff_density_max         0.740
_refine_diff_density_min         -0.630
_refine_diff_density_rms         0.104
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.094
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     708
_refine_ls_number_reflns         8565
_refine_ls_number_restraints     1104
_refine_ls_restrained_S_all      2.329
_refine_ls_R_factor_all          0.1003
_refine_ls_R_factor_gt           0.0806
_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^)+(0.1868P)^2^+15.9619P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2607
_refine_ls_wR_factor_ref         0.2919
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5979
_reflns_number_total             8565
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4mh01324g2.cif
_cod_data_source_block           agcu2507
_cod_depositor_comments          'Adding full bibliography for 1574420.cif.'
_cod_original_cell_volume        16764.9(5)
_cod_database_code               1574420
_shelx_shelxl_version_number     2019/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C34-C10
 1.563 with sigma of 0.0001
 C13-C28
 1.52 with sigma of 0.0001
 C9-C28
 1.543 with sigma of 0.0001
 C28-C13
 1.5435 with sigma of 0.0001
 Cl2-C25 = Cl4-C25 = Cl1-C25 = Cl1A-C25A = Cl2A-C25A = Cl4A-C25A
 1.74 with sigma of 0.01
 Cl1A-Cl2A
 2.85 with sigma of 0.02
 Cl2A-Cl4A
 2.85 with sigma of 0.02
 Cl4A-Cl1A
 2.85 with sigma of 0.02
 Cl1-Cl2
 2.85 with sigma of 0.02
 Cl2-Cl4
 2.85 with sigma of 0.02
 Cl4-Cl1
 2.85 with sigma of 0.02
 S4-C34 \\sim S4A-C34
 with sigma of 0.04
 C34-C40 \\sim C34A-C40A
 with sigma of 0.02
 S4-C34A \\sim S4A-C34A
 with sigma of 0.04
 C34-C3 \\sim C34A-C3A
 with sigma of 0.02
 S4A-C10A \\sim S4-C10
 with sigma of 0.01
 C40A-C34A \\sim C40-C34
 with sigma of 0.01
 C34A-C10A \\sim C34-C10
 with sigma of 0.01
 Cu7-P0B \\sim Cu5-P0B
 with sigma of 0.01
 P0B-C30A \\sim P0B-C30 \\sim P0B-C1A \\sim P0B-C1 \\sim P0B-C18 \\sim P0B-C18A
 with sigma of 0.01
 Cu5-S2 \\sim Cu7-S2A
 with sigma of 0.01
 S2-C9 \\sim S2A-C9A
 with sigma of 0.01
 C9-C28 \\sim C9A-C28A
 with sigma of 0.01
 C28-C13 \\sim C28A-C13A
 with sigma of 0.01
 Cl1-C25 \\sim Cl4-C25 \\sim Cl2-C25 \\sim Cl4-C25A \\sim Cl2-C25A \\sim
Cl1-C25A
 with sigma of 0.01
3. Restrained planarity
 C28, C13, C27, C7, C29, C15, C31
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C20 \\sim C37 \\sim C19 \\sim C39 \\sim C5 \\sim C41 \\sim C21 \\sim C46:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C3 \\sim C40 \\sim C42 \\sim C44 \\sim C11 \\sim C23 \\sim C40A \\sim C42A
\\sim C44A \\sim C11A \\sim C23A \\sim C3A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C30 \\sim C22 \\sim C24 \\sim C4 \\sim C17 \\sim C33 \\sim C30A \\sim C22A
\\sim C24A \\sim C33A \\sim C17A \\sim C4A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C1 \\sim C8 \\sim C6 \\sim C12 \\sim C26 \\sim C14 \\sim C1A \\sim C8A \\sim
C6A \\sim C12A \\sim C26A \\sim C14A: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C18 \\sim C16 \\sim C36 \\sim C2 \\sim C38 \\sim C32 \\sim C18A \\sim C16A
\\sim C36A \\sim C2A \\sim C38A \\sim C32A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C27 \\sim C7 \\sim C29 \\sim C15 \\sim C31 \\sim C27A \\sim C7A \\sim C29A
\\sim C15A \\sim C31A \\sim C13A \\sim C13: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
Uanis(C13) \\sim Ueq, Uanis(C13) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C30) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C33)
\\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C4) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(Cl1) \\sim Ueq, Uanis(Cl1A) \\sim Ueq, Uanis(Cl2) \\sim Ueq, Uanis(Cl2A)
\\sim Ueq, Uanis(Cl4) \\sim Ueq, Uanis(Cl4A) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(Cl1) \\sim Ueq, Uanis(Cl4) \\sim Ueq, Uanis(Cl2) \\sim Ueq, Uanis(C25)
\\sim Ueq, Uanis(C25A) \\sim Ueq, Uanis(Cl2A) \\sim Ueq, Uanis(Cl4A) \\sim Ueq,
Uanis(Cl1A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(S4) = Uanis(S4A)
Uanis(C10) = Uanis(C10A)
Uanis(C9) = Uanis(C9A)
Uanis(C28A) = Uanis(C28)
Uanis(S2) = Uanis(S2A)
Uanis(Cl2A) = Uanis(Cl2)
Uanis(Cl1) = Uanis(Cl1A)
Uanis(Cl4) = Uanis(Cl4A)
Uanis(C25) = Uanis(C25A)
Uanis(Cu7) = Uanis(Cu5)
5. Others
 Sof(Cu4)=Sof(S4)=Sof(Cu1)=1-FVAR(1)
 Sof(Cu6)=Sof(Cu3)=Sof(S4A)=FVAR(1)
 Sof(Cu7)=1-FVAR(2)
 Sof(Cu5)=FVAR(2)
 Fixed Sof: Ag2(0.5) Cu8(0.5) Cl5(0.5) C1(0.5) C8(0.5) H8(0.5) C6(0.5) H6(0.5)
 C12(0.5) H12(0.5) C26(0.5) H26(0.5) C14(0.5) H14(0.5) C10(0.5) H10A(0.5)
 H10B(0.5) C18(0.5) C16(0.5) H16(0.5) C36(0.5) H36(0.5) C2(0.5) H2(0.5)
 C38(0.5) H38(0.5) C32(0.5) H32(0.5) C20(0.5) H20A(0.5) H20B(0.5) C28(0.25)
 H28A(0.25) H28B(0.25) C30(0.5) C22(0.5) H22(0.5) C24(0.5) H24(0.5) C4(0.5)
 H4(0.5) C17(0.5) H17(0.5) C33(0.5) H33(0.5) C34(0.5) H34A(0.5) H34B(0.5)
 C40(0.5) C3(0.5) H3(0.5) C23(0.5) H23(0.5) C11(0.5) H11(0.5) C44(0.5) H44(0.5)
 C42(0.5) H42(0.5) C13(0.25) C27(0.25) H27(0.25) C7(0.25) H7(0.25) C29(0.25)
 H29(0.25) C15(0.25) H15(0.25) C31(0.25) H31(0.25) C9(0.25) H9A(0.25) H9B(0.25)
 C41(0.5) C5(0.5) H5(0.5) C39(0.5) H39(0.5) C19(0.5) H19(0.5) C37(0.5) H37(0.5)
 C21(0.5) H21(0.5) Cl3(0.5) C46(0.5) H46A(0.5) H46B(0.5) S2(0.25) C34A(0.5)
 H34C(0.5) H34D(0.5) C40A(0.5) C42A(0.5) H42A(0.5) C44A(0.5) H44A(0.5)
 C11A(0.5) H11A(0.5) C23A(0.5) H23A(0.5) C3A(0.5) H3A(0.5) C10A(0.5) H10C(0.5)
 H10D(0.5) C1A(0.5) C8A(0.5) H8A(0.5) C6A(0.5) H6A(0.5) C12A(0.5) H12A(0.5)
 C26A(0.5) H26A(0.5) C14A(0.5) H14A(0.5) C18A(0.5) C16A(0.5) H16A(0.5)
 C36A(0.5) H36A(0.5) C2A(0.5) H2A(0.5) C38A(0.5) H38A(0.5) C32A(0.5) H32A(0.5)
 C30A(0.5) C22A(0.5) H22A(0.5) C24A(0.5) H24A(0.5) C4A(0.5) H4A(0.5) C17A(0.5)
 H17A(0.5) C33A(0.5) H33A(0.5) S2A(0.25) C9A(0.25) H9AA(0.25) H9AB(0.25)
 C28A(0.25) H28C(0.25) H28D(0.25) C13A(0.25) C27A(0.25) H27A(0.25) C7A(0.25)
 H7A(0.25) C29A(0.25) H29A(0.25) C15A(0.25) H15A(0.25) C31A(0.25) H31A(0.25)
 Cl1(0.5) Cl4(0.5) Cl2(0.5) C25(0.5) H25(0.5) C25A(0.5) H25A(0.5) Cl2A(0.5)
 Cl4A(0.5) Cl1A(0.5)
6.a Ternary CH refined with riding coordinates:
 C25(H25), C25A(H25A)
6.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C20(H20A,H20B), C28(H28A,H28B), C34(H34A,H34B), C9(H9A,H9B),
 C46(H46A,H46B), C34A(H34C,H34D), C10A(H10C,H10D), C9A(H9AA,H9AB), C28A(H28C,
 H28D)
6.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C6(H6), C12(H12), C26(H26), C14(H14), C16(H16), C36(H36), C2(H2),
 C38(H38), C32(H32), C22(H22), C24(H24), C4(H4), C17(H17), C33(H33), C3(H3),
 C23(H23), C11(H11), C44(H44), C42(H42), C27(H27), C7(H7), C29(H29), C15(H15),
 C31(H31), C5(H5), C39(H39), C19(H19), C37(H37), C21(H21), C42A(H42A),
 C44A(H44A), C11A(H11A), C23A(H23A), C3A(H3A), C8A(H8A), C6A(H6A), C12A(H12A),
 C26A(H26A), C14A(H14A), C16A(H16A), C36A(H36A), C2A(H2A), C38A(H38A),
 C32A(H32A), C22A(H22A), C24A(H24A), C4A(H4A), C17A(H17A), C33A(H33A),
 C27A(H27A), C7A(H7A), C29A(H29A), C15A(H15A), C31A(H31A)
6.d Fitted hexagon refined as free rotating group:
 C1(C8,C6,C12,C26,C14), C18(C16,C36,C2,C38,C32), C30(C22,C24,C4,C17,C33),
 C40(C3,C23,C11,C44,C42), C13(C27,C7,C29,C15,C31), C41(C5,C39,C19,C37,C21),
 C40A(C42A,C44A,C11A,C23A,C3A), C1A(C8A,C6A,C12A,C26A,C14A), C18A(C16A,C36A,C2A,
 C38A,C32A), C30A(C22A,C24A,C4A,C17A,C33A), C13A(C27A,C7A,C29A,C15A,C31A)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 748 electrons were 
found in a volume of 2422\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
7.5[C6H14] per formula unit 
which account for 750 electrons 
per unit cell.
;
_shelx_res_checksum              562
_shelx_fab_checksum              91815
_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
;