Probing the surface-active sites of metal nanoclusters with atomic precision: a case study of Au<sub>5</sub>Ag<sub>11</sub>.
Cao, Yaoyao; Xu, Ying; Shen, Honglei; Pan, Peiyao; Zou, Xuejuan; Kang, Xi; Zhu, Manzhou; Nanoscale 15 (2023) 13784–13789; doi:10.1039/d3nr03288d

data_1569669
_publ_section_title
;
 Probing the surface-active sites of metal nanoclusters with atomic
 precision: a case study of Au<sub>5</sub>Ag<sub>11</sub>.
;
_journal_issue                   33
_journal_name_full               Nanoscale
_journal_page_first              13784
_journal_page_last               13789
_journal_paper_doi               10.1039/d3nr03288d
_journal_volume                  15
_journal_year                    2023
_chemical_formula_moiety         'C136 H128 Ag9 Au5 Cu2 O2 P4 S8'
_chemical_formula_sum            'C136 H128 Ag9 Au5 Cu2 O2 P4 S8'
_chemical_formula_weight         4257.48
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-05-10
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-05-10 deposited with the CCDC.	2023-08-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.5410(10)
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   28.0881(3)
_cell_length_b                   18.3857(2)
_cell_length_c                   82.4807(10)
_cell_measurement_reflns_used    59041
_cell_measurement_temperature    120
_cell_measurement_theta_max      69.71
_cell_measurement_theta_min      4.81
_cell_volume                     42579.2(8)
_computing_cell_refinement       'X-Area Recipe 1.33.0.0 (STOE, 2015)'
_computing_data_collection       'X-Area Pilatus3_SV 1.31.153.0 (STOE, 2018)'
_computing_data_reduction
;
X-Area Integrate 1.74.2.0 (STOE, 2018)
X-Area LANA 1.75.3.0 (STOE, 2018)
;
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      120
_diffrn_detector                 Pilatus300K
_diffrn_detector_area_resol_mean 5.81
_diffrn_detector_type            'DECTRIS PILATUS 300K'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measurement_details      '2201 frames, detector distance = 60 mm'
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '1.2 mm, 0.6 diameter'
_diffrn_radiation_monochromator  'Graded multilayer mirror'
_diffrn_radiation_polarisn_norm  270
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54186
_diffrn_reflns_av_R_equivalents  0.0905
_diffrn_reflns_av_unetI/netI     0.1024
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       64
_diffrn_reflns_limit_l_min       -100
_diffrn_reflns_number            196619
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.686
_diffrn_reflns_theta_max         69.641
_diffrn_reflns_theta_min         4.009
_diffrn_source                   'GeniX 3D HF Cu'
_diffrn_source_current           0.600
_diffrn_source_power             0.030
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    21.347
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.4354
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE LANA, absorption correction by scaling of reflection intensities.
J. Koziskova, F. Hahn, J. Richter, J. Kozisek, "Comparison of different
absorption corrections on the model structure of tetrakis(\m~2~-acetato)-
diaqua-di-copper(II)", Acta Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
;
_exptl_crystal_density_diffrn    1.992
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             24288
_refine_diff_density_max         1.663
_refine_diff_density_min         -1.082
_refine_diff_density_rms         0.182
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.821
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2183
_refine_ls_number_reflns         39370
_refine_ls_number_restraints     2448
_refine_ls_restrained_S_all      0.807
_refine_ls_R_factor_all          0.0753
_refine_ls_R_factor_gt           0.0423
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0394P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0892
_refine_ls_wR_factor_ref         0.0952
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23449
_reflns_number_total             39370
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3nr03288d2.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 1569669--1569671.cif.'
_cod_database_code               1569669
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
C01J \\sim C02E \\sim C05M \\sim C05G \\sim C039 \\sim C01W \\sim C01K \\sim
C01L \\sim C01N \\sim C01O \\sim C01P \\sim C01U \\sim C01V \\sim C01X \\sim
C01Y \\sim C01Z \\sim C020 \\sim C022 \\sim C023 \\sim C024 \\sim C025 \\sim
C026 \\sim C027 \\sim C028 \\sim C029 \\sim C02A \\sim C02B \\sim C02D \\sim
C02F \\sim C02H \\sim C02I \\sim C02J \\sim C02K \\sim C02L \\sim C02O \\sim
C02P \\sim C02Q \\sim C02S \\sim C044 \\sim C02M \\sim C02R \\sim C021 \\sim
C01T \\sim C02T \\sim C02U \\sim C02V \\sim C02W \\sim C02X \\sim C02Y \\sim
C02Z \\sim C030 \\sim C031 \\sim C036 \\sim C052 \\sim C05H \\sim C070 \\sim
C05Y \\sim C032 \\sim C033 \\sim C034 \\sim C035 \\sim C037 \\sim C038 \\sim
C03A \\sim C03B \\sim C04C \\sim C06H \\sim C06S \\sim C072 \\sim C06Q \\sim
C03C \\sim C03D \\sim C03E \\sim C03F \\sim C03G \\sim C03H \\sim C03I \\sim
C03J \\sim C03K \\sim C03L \\sim C03M \\sim C03N \\sim C03O \\sim C03P \\sim
C03Q \\sim C03R \\sim C03S \\sim C03T \\sim C03U \\sim C03V \\sim C03W \\sim
C03X \\sim C03Y \\sim C03Z \\sim C040 \\sim C041 \\sim C042 \\sim C045 \\sim
C046 \\sim C047 \\sim C048 \\sim C049 \\sim C04A \\sim C04B \\sim C04D \\sim
C04E \\sim C04F \\sim C04G \\sim C04H \\sim C04I \\sim C053 \\sim C05R \\sim
C06U \\sim C06W \\sim C06A \\sim C04J \\sim C04L \\sim C04M \\sim C04N \\sim
C04O \\sim C04P \\sim C04Q \\sim C02N \\sim C02C \\sim C04K \\sim C02G \\sim
C043 \\sim C04R \\sim C04S \\sim C04T \\sim C04U \\sim C04V \\sim C04W \\sim
C04X \\sim C04Y \\sim C04Z \\sim C050 \\sim C051 \\sim C054 \\sim C055 \\sim
C056 \\sim C057 \\sim C058 \\sim C059 \\sim C05A \\sim C05B \\sim C05C \\sim
C05D \\sim C05E \\sim C05F \\sim C078 \\sim C07H \\sim C07E \\sim C077 \\sim
C06T \\sim C05I \\sim C05J \\sim C05K \\sim C05L \\sim C05N \\sim C05O \\sim
C05P \\sim C05Q \\sim C05S \\sim C05T \\sim C05U \\sim C05V \\sim C05W \\sim
C05Z \\sim C060 \\sim C061 \\sim C062 \\sim C063 \\sim C064 \\sim C065 \\sim
C066 \\sim C067 \\sim C068 \\sim C069 \\sim C06B \\sim C06C \\sim C06D \\sim
C06E \\sim C06F \\sim C06G \\sim C06I \\sim C06J \\sim C06K \\sim C06L \\sim
C06N \\sim C06O \\sim C06P \\sim C06R \\sim C06V \\sim C06X \\sim C06Y \\sim
C071 \\sim C073 \\sim C074 \\sim C075 \\sim C076 \\sim C07A \\sim C07C \\sim
C13: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C01J) \\sim Ueq, Uanis(C02E) \\sim Ueq, Uanis(C05M) \\sim Ueq,
Uanis(C05G) \\sim Ueq, Uanis(C039) \\sim Ueq, Uanis(C01W) \\sim Ueq,
Uanis(C01K) \\sim Ueq, Uanis(C01L) \\sim Ueq, Uanis(C01N) \\sim Ueq,
Uanis(C01O) \\sim Ueq, Uanis(C01P) \\sim Ueq, Uanis(C01U) \\sim Ueq,
Uanis(C01V) \\sim Ueq, Uanis(C01X) \\sim Ueq, Uanis(C01Y) \\sim Ueq,
Uanis(C01Z) \\sim Ueq, Uanis(C020) \\sim Ueq, Uanis(C022) \\sim Ueq,
Uanis(C023) \\sim Ueq, Uanis(C024) \\sim Ueq, Uanis(C025) \\sim Ueq,
Uanis(C026) \\sim Ueq, Uanis(C027) \\sim Ueq, Uanis(C028) \\sim Ueq,
Uanis(C029) \\sim Ueq, Uanis(C02A) \\sim Ueq, Uanis(C02B) \\sim Ueq,
Uanis(C02D) \\sim Ueq, Uanis(C02F) \\sim Ueq, Uanis(C02H) \\sim Ueq,
Uanis(C02I) \\sim Ueq, Uanis(C02J) \\sim Ueq, Uanis(C02K) \\sim Ueq,
Uanis(C02L) \\sim Ueq, Uanis(C02O) \\sim Ueq, Uanis(C02P) \\sim Ueq,
Uanis(C02Q) \\sim Ueq, Uanis(C02S) \\sim Ueq, Uanis(C044) \\sim Ueq,
Uanis(C02M) \\sim Ueq, Uanis(C02R) \\sim Ueq, Uanis(C021) \\sim Ueq,
Uanis(C01T) \\sim Ueq, Uanis(C02T) \\sim Ueq, Uanis(C02U) \\sim Ueq,
Uanis(C02V) \\sim Ueq, Uanis(C02W) \\sim Ueq, Uanis(C02X) \\sim Ueq,
Uanis(C02Y) \\sim Ueq, Uanis(C02Z) \\sim Ueq, Uanis(C030) \\sim Ueq,
Uanis(C031) \\sim Ueq, Uanis(C036) \\sim Ueq, Uanis(C052) \\sim Ueq,
Uanis(C05H) \\sim Ueq, Uanis(C070) \\sim Ueq, Uanis(C05Y) \\sim Ueq,
Uanis(C032) \\sim Ueq, Uanis(C033) \\sim Ueq, Uanis(C034) \\sim Ueq,
Uanis(C035) \\sim Ueq, Uanis(C037) \\sim Ueq, Uanis(C038) \\sim Ueq,
Uanis(C03A) \\sim Ueq, Uanis(C03B) \\sim Ueq, Uanis(C04C) \\sim Ueq,
Uanis(C06H) \\sim Ueq, Uanis(C06S) \\sim Ueq, Uanis(C072) \\sim Ueq,
Uanis(C06Q) \\sim Ueq, Uanis(C03C) \\sim Ueq, Uanis(C03D) \\sim Ueq,
Uanis(C03E) \\sim Ueq, Uanis(C03F) \\sim Ueq, Uanis(C03G) \\sim Ueq,
Uanis(C03H) \\sim Ueq, Uanis(C03I) \\sim Ueq, Uanis(C03J) \\sim Ueq,
Uanis(C03K) \\sim Ueq, Uanis(C03L) \\sim Ueq, Uanis(C03M) \\sim Ueq,
Uanis(C03N) \\sim Ueq, Uanis(C03O) \\sim Ueq, Uanis(C03P) \\sim Ueq,
Uanis(C03Q) \\sim Ueq, Uanis(C03R) \\sim Ueq, Uanis(C03S) \\sim Ueq,
Uanis(C03T) \\sim Ueq, Uanis(C03U) \\sim Ueq, Uanis(C03V) \\sim Ueq,
Uanis(C03W) \\sim Ueq, Uanis(C03X) \\sim Ueq, Uanis(C03Y) \\sim Ueq,
Uanis(C03Z) \\sim Ueq, Uanis(C040) \\sim Ueq, Uanis(C041) \\sim Ueq,
Uanis(C042) \\sim Ueq, Uanis(C045) \\sim Ueq, Uanis(C046) \\sim Ueq,
Uanis(C047) \\sim Ueq, Uanis(C048) \\sim Ueq, Uanis(C049) \\sim Ueq,
Uanis(C04A) \\sim Ueq, Uanis(C04B) \\sim Ueq, Uanis(C04D) \\sim Ueq,
Uanis(C04E) \\sim Ueq, Uanis(C04F) \\sim Ueq, Uanis(C04G) \\sim Ueq,
Uanis(C04H) \\sim Ueq, Uanis(C04I) \\sim Ueq, Uanis(C053) \\sim Ueq,
Uanis(C05R) \\sim Ueq, Uanis(C06U) \\sim Ueq, Uanis(C06W) \\sim Ueq,
Uanis(C06A) \\sim Ueq, Uanis(C04J) \\sim Ueq, Uanis(C04L) \\sim Ueq,
Uanis(C04M) \\sim Ueq, Uanis(C04N) \\sim Ueq, Uanis(C04O) \\sim Ueq,
Uanis(C04P) \\sim Ueq, Uanis(C04Q) \\sim Ueq, Uanis(C02N) \\sim Ueq,
Uanis(C02C) \\sim Ueq, Uanis(C04K) \\sim Ueq, Uanis(C02G) \\sim Ueq,
Uanis(C043) \\sim Ueq, Uanis(C04R) \\sim Ueq, Uanis(C04S) \\sim Ueq,
Uanis(C04T) \\sim Ueq, Uanis(C04U) \\sim Ueq, Uanis(C04V) \\sim Ueq,
Uanis(C04W) \\sim Ueq, Uanis(C04X) \\sim Ueq, Uanis(C04Y) \\sim Ueq,
Uanis(C04Z) \\sim Ueq, Uanis(C050) \\sim Ueq, Uanis(C051) \\sim Ueq,
Uanis(C054) \\sim Ueq, Uanis(C055) \\sim Ueq, Uanis(C056) \\sim Ueq,
Uanis(C057) \\sim Ueq, Uanis(C058) \\sim Ueq, Uanis(C059) \\sim Ueq,
Uanis(C05A) \\sim Ueq, Uanis(C05B) \\sim Ueq, Uanis(C05C) \\sim Ueq,
Uanis(C05D) \\sim Ueq, Uanis(C05E) \\sim Ueq, Uanis(C05F) \\sim Ueq,
Uanis(C078) \\sim Ueq, Uanis(C07H) \\sim Ueq, Uanis(C07E) \\sim Ueq,
Uanis(C077) \\sim Ueq, Uanis(C06T) \\sim Ueq, Uanis(C05I) \\sim Ueq,
Uanis(C05J) \\sim Ueq, Uanis(C05K) \\sim Ueq, Uanis(C05L) \\sim Ueq,
Uanis(C05N) \\sim Ueq, Uanis(C05O) \\sim Ueq, Uanis(C05P) \\sim Ueq,
Uanis(C05Q) \\sim Ueq, Uanis(C05S) \\sim Ueq, Uanis(C05T) \\sim Ueq,
Uanis(C05U) \\sim Ueq, Uanis(C05V) \\sim Ueq, Uanis(C05W) \\sim Ueq,
Uanis(C05Z) \\sim Ueq, Uanis(C060) \\sim Ueq, Uanis(C061) \\sim Ueq,
Uanis(C062) \\sim Ueq, Uanis(C063) \\sim Ueq, Uanis(C064) \\sim Ueq,
Uanis(C065) \\sim Ueq, Uanis(C066) \\sim Ueq, Uanis(C067) \\sim Ueq,
Uanis(C068) \\sim Ueq, Uanis(C069) \\sim Ueq, Uanis(C06B) \\sim Ueq,
Uanis(C06C) \\sim Ueq, Uanis(C06D) \\sim Ueq, Uanis(C06E) \\sim Ueq,
Uanis(C06F) \\sim Ueq, Uanis(C06G) \\sim Ueq, Uanis(C06I) \\sim Ueq,
Uanis(C06J) \\sim Ueq, Uanis(C06K) \\sim Ueq, Uanis(C06L) \\sim Ueq,
Uanis(C06N) \\sim Ueq, Uanis(C06O) \\sim Ueq, Uanis(C06P) \\sim Ueq,
Uanis(C06R) \\sim Ueq, Uanis(C06V) \\sim Ueq, Uanis(C06X) \\sim Ueq,
Uanis(C06Y) \\sim Ueq, Uanis(C071) \\sim Ueq, Uanis(C073) \\sim Ueq,
Uanis(C074) \\sim Ueq, Uanis(C075) \\sim Ueq, Uanis(C076) \\sim Ueq,
Uanis(C07A) \\sim Ueq, Uanis(C07C) \\sim Ueq, Uanis(C13) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
2.a Aromatic/amide H refined with riding coordinates:
 C02E(H02E), C05M(H5), C05G(H6), C039(H039), C01W(H01W), C01K(H01K),
 C01P(H01P), C01U(H01U), C023(H023), C029(H029), C02F(H02F), C02H(H02H),
 C02I(H02I), C02J(H02J), C02K(H02K), C02L(H02L), C02P(H02P), C02S(H02S),
 C044(H044), C02M(H02M), C02R(H02R), C021(H021), C02T(H02T), C02U(H02U),
 C02W(H02W), C02X(H02X), C02Y(H02Y), C036(H036), C052(H052), C05H(H05H),
 C070(H070), C05Y(H05Y), C032(H032), C033(H033), C034(H034), C035(H035),
 C03A(H03A), C06H(H06U), C06S(H06V), C072(H072), C03C(H03I), C03F(H03F),
 C03G(H03J), C03H(H03N), C03K(H03K), C03L(H03L), C03M(H03M), C03P(H03P),
 C03Q(H03Q), C03R(H03R), C03U(H03U), C03V(H03V), C03W(H03W), C03Z(H03Z),
 C040(H040), C041(H041), C042(H042), C045(H045), C046(H046), C04A(H04A),
 C04B(H04B), C04D(H04D), C04G(H04G), C04H(H04H), C05R(H7), C06U(H06W),
 C06W(H06X), C04L(H04L), C04M(H04M), C04N(H04W), C04O(H04O), C04P(H04P),
 C02C(H02C), C04K(H04), C02G(H02G), C043(H043), C04R(H04R), C04S(H04S),
 C04U(H04U), C04V(H04V), C04X(H04X), C04Y(H04Y), C04Z(H04Z), C050(H050),
 C054(H054), C055(H055), C059(H059), C05A(H05G), C05C(H05L), C05D(H05M),
 C05E(H05N), C07H(H07H), C07E(H07G), C077(H077), C05I(H05O), C05K(H05S),
 C05L(H05T), C05N(H8), C05O(H05U), C05Q(H05Z), C05S(H05), C05T(H1), C05W(H3),
 C05Z(H4), C060(H060), C062(H062), C064(H064), C065(H065), C068(H068),
 C069(H069), C06B(H06D), C06D(H06H), C06F(H06I), C06G(H06J), C06O(H06Q),
 C06R(H10), C06Y(H06Y), C071(H071), C074(H074), C076(H076)
2.b Fitted hexagon refined as free rotating group:
 C01J(C02E,C05M,C05G,C039,C01W), C02S(C044,C02M,C02R,C021,C01T), C031(C036,
 C052,C05H,C070,C05Y), C03B(C04C,C06H,C06S,C072,C06Q), C04I(C053,C05R,C06U,C06W,
 C06A), C04Q(C02N,C02C,C04K,C02G,C043), C05F(C078,C07H,C07E,C077,C06T)
2.c Idealised Me refined as rotating group:
 C03I(H03B,H03C,H03D), C03T(H03E,H03G,H03H), C048(H04I,H04J,H04K), C04F(H04N,
 H04Q,H04T), C04T(H04C,H04E,H04F), C051(H05A,H05B,H05C), C056(H05D,H05E,H05F),
 C05B(H05I,H05J,H05K), C05J(H05P,H05Q,H05R), C05P(H05V,H05W,H05X), C05V(H2,H,
 HA), C067(H06A,H06B,H06C), C06C(H06E,H06F,H06G), C06E(H06Z,HB,HC), C06I(H06,HD,
 HE), C06J(H9,HF,HG), C06K(H06K,H06L,H06M), C06N(H06N,H06O,H06P), C06V(H06R,
 H06S,H06T), C06X(H11,HH,HI), C073(H07A,H07B,H07C), C075(H07I,H07J,H07K),
 C07A(H07D,H07E,H07F), C13(H13A,H13B,H13C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              59549
_shelx_fab_checksum              21571
_olex2_submission_special_instructions 'No special instructions were received'