Substituent effect in determining the total structure of an all-alkynyl-protected Ag<sub>98</sub> nanocluster for methanol tolerant oxygen reduction reaction.
Cui, Xiaoqin; Zhang, Xuehuan; Li, Ting; Zhu, Sheng; Han, Gaoyi; Li, Huan; Chemical science 15 (2024) 18161–18169; doi:10.1039/d4sc04318a

data_1572829
_publ_section_title
;
 Substituent effect in determining the total structure of an
 all-alkynyl-protected Ag<sub>98</sub> nanocluster for methanol tolerant
 oxygen reduction reaction.
;
_journal_issue                   43
_journal_name_full               'Chemical science'
_journal_page_first              18161
_journal_page_last               18169
_journal_paper_doi               10.1039/d4sc04318a
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C432 H192 Ag98 Cl4 F144'
_chemical_formula_sum            'C432 H192 Ag98 Cl4 F144'
_chemical_formula_weight         18830.90
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-06-13
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-06-13 deposited with the CCDC.	2024-10-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   32.4731(4)
_cell_length_b                   32.4731(4)
_cell_length_c                   96.4532(11)
_cell_measurement_reflns_used    39516
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      75.4820
_cell_measurement_theta_min      3.5280
_cell_volume                     88083.5(18)
_computing_cell_refinement       'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_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      150.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.956
_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    -11.00  16.00   0.25    1.91    --    0.00  78.00  -9.00  108
  2  \w     68.00  94.00   0.25    7.64    --  101.00 -82.00-154.00  104
  3  \w     78.00 189.00   0.25    7.64    --  101.00  78.00  -9.00  444
  4  \w    -28.00  33.00   0.25    1.91    --    0.00 -82.00  60.00  244
  5  \w     76.00 185.00   0.25    7.64    --  101.00  77.00 -30.00  436
  6  \w    122.00 190.00   0.25    7.64    --  101.00  82.00  60.00  272
  7  \w    105.00 130.00   0.25    7.64    --  101.00 -82.00-154.00  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0143416000
_diffrn_orient_matrix_UB_12      -0.0374505000
_diffrn_orient_matrix_UB_13      -0.0034798000
_diffrn_orient_matrix_UB_21      -0.0440699000
_diffrn_orient_matrix_UB_22      -0.0380328000
_diffrn_orient_matrix_UB_23      0.0078014000
_diffrn_orient_matrix_UB_31      -0.0291594000
_diffrn_orient_matrix_UB_32      -0.0123320000
_diffrn_orient_matrix_UB_33      -0.0135008000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0609
_diffrn_reflns_av_unetI/netI     0.0735
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       118
_diffrn_reflns_limit_l_min       -121
_diffrn_reflns_number            98151
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.541
_diffrn_reflns_theta_min         3.049
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    26.424
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.13769
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.108a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark black'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    2.130
_exptl_crystal_description       block
_exptl_crystal_F_000             52524
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.268
_refine_diff_density_max         1.531
_refine_diff_density_min         -1.876
_refine_diff_density_rms         0.192
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.946
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1908
_refine_ls_number_reflns         39365
_refine_ls_number_restraints     1700
_refine_ls_restrained_S_all      0.941
_refine_ls_R_factor_all          0.1170
_refine_ls_R_factor_gt           0.0778
_refine_ls_shift/su_max          0.050
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1672P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2263
_refine_ls_wR_factor_ref         0.2582
_reflns_Friedel_coverage         0.000
_reflns_number_gt                20863
_reflns_number_total             39365
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04318a2.cif
_cod_data_source_block           ag98
_cod_depositor_comments          'Adding full bibliography for 1572829.cif.'
_cod_original_cell_volume        88084(2)
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               1572829
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         Ag
_reflns_odcompleteness_completeness 99.63
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C40-C35
 1.54 with sigma of 0.01
 C9-C5
 1.54 with sigma of 0.01
 C02D-C01V
 1.2 with sigma of 0.01
 F196-C185
 1.35 with sigma of 0.01
 F104-C185
 1.35 with sigma of 0.01
 F372-C185
 1.35 with sigma of 0.01
 C206-C110
 1.54 with sigma of 0.01
 C357-C185
 1.54 with sigma of 0.001
 C80-C02U
 1.54 with sigma of 0.01
 F20-C102
 1.35 with sigma of 0.01
 C23-C02D
 1.54 with sigma of 0.001
 C42-C117
 1.54 with sigma of 0.01
 F2-C102
 1.35 with sigma of 0.01
 F32-C102
 1.35 with sigma of 0.01
 C14-C102
 1.54 with sigma of 0.001
 F45-C17 = F3-C17 = F22-C17
 1.35 with sigma of 0.01
 C42-C41
 1.2 with sigma of 0.0001
 C53-C128
 1.54 with sigma of 0.0001
 C17-C15
 1.54 with sigma of 0.001
 F144-C53
 1.35 with sigma of 0.01
 F12-C53
 1.35 with sigma of 0.01
 F43-C53
 1.35 with sigma of 0.01
 C43-C02Q
 1.2 with sigma of 0.01
 C49-C43
 1.54 with sigma of 0.01
 F50-C83
 1.35 with sigma of 0.01
 F15-C83
 1.35 with sigma of 0.01
 F26-C83
 1.35 with sigma of 0.01
 F117-C55
 1.35 with sigma of 0.01
 F27-C55
 1.35 with sigma of 0.01
 F23-C55
 1.35 with sigma of 0.01
 C55-C31
 1.54 with sigma of 0.01
 C030-C02J
 1.2 with sigma of 0.01
 C7-C02M
 1.54 with sigma of 0.01
 C02Y-C02T
 1.54 with sigma of 0.01
 C11-C02T
 1.2 with sigma of 0.01
 F30-C7
 1.35 with sigma of 0.01
 F021-C7
 1.35 with sigma of 0.01
 F01Z-C7
 1.35 with sigma of 0.01
 F021-F30
 2.2 with sigma of 0.01
 F021-F01Z
 2.2 with sigma of 0.01
 F30-F01Z
 2.2 with sigma of 0.01
 F41-C71
 1.35 with sigma of 0.01
 F61-C71
 1.35 with sigma of 0.01
 F28-C71
 1.35 with sigma of 0.01
 C020-C01U
 1.2 with sigma of 0.01
 F01A-C024
 1.35 with sigma of 0.01
 F02E-C024
 1.35 with sigma of 0.01
 F01E-C024
 1.35 with sigma of 0.01
 C16-C024
 1.54 with sigma of 0.01
 C02W-C020
 1.54 with sigma of 0.01
 C01Y-C01P
 1.54 with sigma of 0.01
 C01R-C01L
 1.54 with sigma of 0.01
 F018-C01Y
 1.35 with sigma of 0.01
 F019-C01Y
 1.35 with sigma of 0.01
 F025-C01Y
 1.35 with sigma of 0.01
 C01L-C01H
 1.2 with sigma of 0.01
 F02A-C80
 1.35 with sigma of 0.01
 F02N-C80
 1.35 with sigma of 0.01
 F01S-C80
 1.35 with sigma of 0.01
 C57-C5
 1.2 with sigma of 0.01
 C20-C031
 1.2 with sigma of 0.01
 C24-C20
 1.54 with sigma of 0.01
 C25-C22
 1.54 with sigma of 0.01
 F7-C25
 1.35 with sigma of 0.01
 F16-C25
 1.35 with sigma of 0.01
 F1-C25
 1.35 with sigma of 0.01
 C30-C10
 1.2 with sigma of 0.01
 C10-C02F
 1.54 with sigma of 0.01
 C01K-C01J
 1.2 with sigma of 0.01
 C01J-C01G
 1.54 with sigma of 0.01
 C34-C33
 1.2 with sigma of 0.01
 C33-C026
 1.54 with sigma of 0.01
 C71-C02Z
 1.54 with sigma of 0.01
 C35-C26
 1.2 with sigma of 0.01
 C265-C161
 1.54 with sigma of 0.001
 C39-C161
 1.2 with sigma of 0.01
 C8-C130
 1.54 with sigma of 0.01
 F53-C8 = F4-C8
 1.35 with sigma of 0.01
 F150-C8
 1.35 with sigma of 0.01
 C4-C110
 1.2 with sigma of 0.01
 C02L-C022
 1.54 with sigma of 0.01
 C83-C70A
 1.54 with sigma of 0.01
 C101-C030
 1.54 with sigma of 0.01
 C01V-C23
 2.74 with sigma of 0.01
 F02A-C02U
 2.36 with sigma of 0.01
 F20-C14
 2.36 with sigma of 0.01
 F196-C357
 2.36 with sigma of 0.01
 F01S-C02U
 2.36 with sigma of 0.01
 F104-C357
 2.36 with sigma of 0.01
 F2-C14
 2.36 with sigma of 0.01
 C357-F372
 2.36 with sigma of 0.01
 F02N-C02U
 2.36 with sigma of 0.01
 F32-C14
 2.36 with sigma of 0.01
 C105-C185
 4.32 with sigma of 0.01
 F45-C15
 2.36 with sigma of 0.01
 C4-C206
 2.74 with sigma of 0.01
 F144-C128
 2.36 with sigma of 0.01
 C57-C9
 2.74 with sigma of 0.01
 C102-C27
 4.32 with sigma of 0.001
 F22-C15
 2.36 with sigma of 0.01
 F3-C15
 2.36 with sigma of 0.01
 F43-C128
 2.36 with sigma of 0.01
 C17-C193
 4.32 with sigma of 0.01
 F12-C128
 2.36 with sigma of 0.01
 C35-C169
 4.32 with sigma of 0.01
 C41-C117
 2.74 with sigma of 0.001
 C346-C53
 4.32 with sigma of 0.001
 F45-F3
 2.2 with sigma of 0.01
 F45-F22
 2.2 with sigma of 0.01
 F22-F3
 2.2 with sigma of 0.01
 F50-F15
 2.2 with sigma of 0.01
 F15-F26
 2.2 with sigma of 0.01
 F26-F50
 2.2 with sigma of 0.01
 F117-C31
 2.36 with sigma of 0.01
 F27-C31
 2.36 with sigma of 0.01
 F23-C31
 2.36 with sigma of 0.01
 F117-F23
 2.2 with sigma of 0.01
 F27-F117
 2.2 with sigma of 0.01
 F27-F23
 2.2 with sigma of 0.01
 F021-C02M
 2.36 with sigma of 0.01
 F30-C02M
 2.36 with sigma of 0.01
 F01Z-C02M
 2.36 with sigma of 0.01
 F41-C02Z
 2.36 with sigma of 0.01
 C02Z-F61
 2.36 with sigma of 0.01
 F28-C02Z
 2.36 with sigma of 0.01
 F41-F61
 2.2 with sigma of 0.01
 F28-F61
 2.2 with sigma of 0.01
 F41-F28
 2.2 with sigma of 0.01
 F01A-F02E
 2.2 with sigma of 0.01
 F02E-F01E
 2.2 with sigma of 0.01
 F01E-F01A
 2.2 with sigma of 0.01
 F01A-C16
 2.36 with sigma of 0.01
 F02E-C16
 2.36 with sigma of 0.01
 F01E-C16
 2.36 with sigma of 0.01
 F019-F018
 2.2 with sigma of 0.01
 F018-F025
 2.2 with sigma of 0.01
 F025-F019
 2.2 with sigma of 0.01
 F018-C01P
 2.36 with sigma of 0.01
 F019-C01P
 2.36 with sigma of 0.01
 C01P-F025
 2.36 with sigma of 0.01
 F02A-F01S
 2.2 with sigma of 0.01
 F02A-F02N
 2.2 with sigma of 0.01
 F02N-F01S
 2.2 with sigma of 0.01
 F20-F32
 2.2 with sigma of 0.01
 F20-F2
 2.2 with sigma of 0.01
 F32-F2
 2.2 with sigma of 0.01
 F16-F7
 2.2 with sigma of 0.01
 F16-F1
 2.2 with sigma of 0.01
 F1-F7
 2.2 with sigma of 0.01
 F16-C22
 2.36 with sigma of 0.01
 F1-C22
 2.36 with sigma of 0.01
 F7-C22
 2.36 with sigma of 0.01
 C02F-C30
 2.74 with sigma of 0.01
 C20-C310
 4.32 with sigma of 0.04
 C031-C24
 2.74 with sigma of 0.01
 C25-C207
 4.32 with sigma of 0.01
 F43-F144
 2.2 with sigma of 0.01
 F43-F12
 2.2 with sigma of 0.01
 F12-F144
 2.2 with sigma of 0.01
 F150-F53
 2.2 with sigma of 0.01
 F53-F4
 2.2 with sigma of 0.01
 F4-F150
 2.2 with sigma of 0.01
 F4-C130
 2.36 with sigma of 0.01
 F150-C130
 2.36 with sigma of 0.01
 F53-C130
 2.36 with sigma of 0.01
 F104-F196
 2.36 with sigma of 0.01
 F196-F372
 2.36 with sigma of 0.01
 F372-F104
 2.36 with sigma of 0.01
 C161-C475
 4.32 with sigma of 0.01
 C8-C154
 4.32 with sigma of 0.01
 C02J-C101
 2.74 with sigma of 0.01
 C6-C030
 4.32 with sigma of 0.01
 C39-C265
 2.74 with sigma of 0.01
 Ag0G-C01V \\sim Ag7-C01V
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C57 \\sim C5 \\sim C9 \\sim C14 \\sim C19 \\sim C306 \\sim C27 \\sim C54 \\sim
F20 \\sim F2 \\sim F32 \\sim C102 \\sim C41 \\sim F12 \\sim C42 \\sim C53 \\sim
F43 \\sim C117 \\sim C48 \\sim C346 \\sim C51 \\sim C56 \\sim C128 \\sim F144
\\sim C142 \\sim C112 \\sim F50 \\sim F26 \\sim C83 \\sim C70A \\sim C49 \\sim
C48A \\sim C3 \\sim C17 \\sim C35 \\sim F3 \\sim C40 \\sim C15 \\sim C109 \\sim
C169 \\sim C193 \\sim C212 \\sim F45 \\sim F22 \\sim C26 \\sim F01Z \\sim F021
\\sim C02M \\sim C76 \\sim C91 \\sim F30 \\sim C7 \\sim F7 \\sim C25 \\sim F1
\\sim F16 \\sim C24 \\sim C22 \\sim C106 \\sim C310 \\sim C207 \\sim C39 \\sim
C206 \\sim C105 \\sim C192 \\sim C463 \\sim C357 \\sim F104 \\sim C161 \\sim
C185 \\sim F196 \\sim F372 \\sim C265 \\sim C90 \\sim C154 \\sim C475 \\sim
C395 \\sim C130 \\sim F4 \\sim C8 \\sim F53 \\sim F150 \\sim C69 \\sim C32
\\sim C02Y \\sim C02T \\sim C11 \\sim C20 \\sim C031 \\sim C99 \\sim C37 \\sim
C110 \\sim F01X \\sim C030 \\sim C55 \\sim F117 \\sim C101 \\sim C31 \\sim C65
\\sim C6 \\sim C164 \\sim C50 \\sim F27 \\sim F23 \\sim F15: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C110) \\sim Ueq, Uanis(C206) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C105)
\\sim Ueq, Uanis(C192) \\sim Ueq, Uanis(C463) \\sim Ueq, Uanis(C357) \\sim Ueq,
Uanis(F372) \\sim Ueq, Uanis(F104) \\sim Ueq, Uanis(F196) \\sim Ueq,
Uanis(C185) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C80) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C41, F12, C42, C53, F43, C117, C48, C346, C51, C56, C128, F144, C57, C5, C9,
 C14, C19, C306, C27, C54, F20, F2, F32, C102, F01Z, F021, C02M, C76, C91, F30,
 C7, F7, C25, F1, F16, C24, C22, C106, C310, C207, C20, C39, C192, C463, C161,
 C185, F196, C265, C90, C154, C475, C395, C130, F4, C8, F53, F150, Ag0Q, C02T,
 C02Y, C69, C32, C4, C110, C206, C37, C105, C357, F104, F372, C99, C11, Ag0X,
 C02Q, C43, C49, C70A, C112, C142, C3, C48A, F26, F50, C26, C17, C35, F3, C40,
 C15, C109, C169, C193, C212, F45, F15, C83, F22, F01X, C02J, C030, C71, F23,
 F27, C55, F117, F41, C101, C31, C65, C6, C164, C50, F61, F28
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
5. Others
 Sof(Ag3)=Sof(Ag1)=Sof(Ag6)=Sof(Ag2)=Sof(Ag5)=Sof(Ag4)=1-FVAR(1)
 Sof(Ag0T)=Sof(Ag0U)=Sof(Ag0V)=Sof(Ag0W)=Sof(Ag0X)=Sof(Ag0Y)=FVAR(1)
 Sof(Ag7)=1-FVAR(2)
 Sof(Ag0G)=FVAR(2)
6.a Aromatic/amide H refined with riding coordinates:
 C02G(H02G), C02V(H02V), C02O(H02O), C01N(H01N), C02B(H02B), C02K(H02K),
 C02P(H02P), C01W(H01W), C82(H82), C199(H199), C46(H46), C28(H28), C18(H18),
 C1(H1), C2(H2), C29(H29), C44(H44), C36(H36), C47(H47), C12(H12), C52(H52),
 C85(H85), C84(H84), C38(H38), C76(H76), C91(H91), C69(H69), C32(H32), C62(H62),
  C123(H123), C93(H93), C13(H13), C112(H112), C142(H142), C3(H3), C48A(H48A),
 C65(H65), C6(H6), C164(H164), C50(H50), C109(H109), C169(H169), C193(H193),
 C212(H212), C106(H106), C310(H310), C207(H207), C99(H99), C19(H19), C306(H306),
  C27(H27), C54(H54), C37(H37), C105(H105), C192(H192), C463(H463), C48(H48),
 C346(H346), C51(H51), C56(H56), C90(H90), C154(H154), C475(H475), C395(H395)
6.b Fitted hexagon refined as free rotating group:
 C01G(C01I,C02G,C02V,C02O,C01N), C01R(C01P,C02B,C02K,C02P,C01W), C026(C02Z,C82,
 C199,C46,C28), C02F(C022,C18,C1,C2,C29), C02H(C02R,C44,C36,C47,C12), C02W(C16,
 C52,C85,C84,C38), C02Y(C02M,C76,C91,C69,C32), C23(C02U,C62,C123,C93,C13),
 C49(C70A,C112,C142,C3,C48A), C101(C31,C65,C6,C164,C50), C40(C15,C109,C169,C193,
 C212), C24(C22,C106,C310,C207,C99), C9(C14,C19,C306,C27,C54), C206(C37,C105,
 C192,C463,C357), C117(C48,C346,C51,C56,C128), C265(C90,C154,C475,C395,C130)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              93776
_shelx_hkl_checksum              74554
_shelx_fab_checksum              23598
_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 4.998
_oxdiff_exptl_absorpt_empirical_full_min 0.535