Ag<sub>10</sub>Cu<sub>16</sub> nanoclusters with triple-ligand protection: total structure and electronic structure analysis.
Sun, Xueli; Li, Simin; Tian, Guolong; Gao, Yanli; Wei, Jianyu; Shen, Hui; Physical chemistry chemical physics : PCCP 25 (2023) 17901–17906; doi:10.1039/d3cp02227g

data_7246973
_publ_section_title
;
 Ag<sub>10</sub>Cu<sub>16</sub> nanoclusters with triple-ligand
 protection: total structure and electronic structure analysis.
;
_journal_issue                   27
_journal_name_full               'Physical chemistry chemical physics : PCCP'
_journal_page_first              17901
_journal_page_last               17906
_journal_paper_doi               10.1039/d3cp02227g
_journal_volume                  25
_journal_year                    2023
_chemical_formula_moiety
'C216 H204 Ag10 Cu16 F24 O16 P4 S16, 2[CH3CH2OCH2CH3], 1[CH3CH2OCH2CH3]'
_chemical_formula_sum            'C228 H234 Ag10 Cu16 F24 O19 P4 S16'
_chemical_formula_weight         6466.32
_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
_audit_creation_date             2023-02-10
_audit_creation_method
;
Olex2 1.3
(compiled 2020.06.28 svn.raecde09e for OlexSys, GUI svn.r6132)
;
_audit_update_record
;
2023-04-21 deposited with the CCDC.	2023-06-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.2820(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   18.3848(2)
_cell_length_b                   34.2944(4)
_cell_length_c                   18.6956(2)
_cell_measurement_reflns_used    47243
_cell_measurement_temperature    100(1)
_cell_measurement_theta_max      65.8560
_cell_measurement_theta_min      2.5560
_cell_volume                     11716.7(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_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)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(1)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -24.00  38.00   0.50    1.00    --  -43.22  19.00 150.00  124
  2  \w   -122.00  -4.00   0.50    1.00    --  -43.22 -19.00 -30.00  236
  3  \w    -42.00  35.00   0.50    1.00    --  -43.22  37.00 -90.00  154
  4  \w    -74.00  32.00   0.50    1.00    --  -43.22  77.00-180.00  212
  5  \w     70.00 120.00   0.50    1.00    --   45.10   0.00 -90.00  100
  6  \w     72.00  97.00   0.50    1.00    --   45.10-125.00 -90.00   50
  7  \w    -89.00 -15.00   0.50    2.00    --  -88.32 125.00  30.00  148
  8  \w    -35.00  -9.00   0.50    2.00    --  -88.32  30.00-180.00   52
  9  \w    -50.00 -25.00   0.50    2.00    --  -88.32  45.00  30.00   50
 10  \w    -35.00  -9.00   0.50    2.00    --  -88.32  30.00 -30.00   52
 11  \w    -35.00  -8.00   0.50    2.00    --  -88.32  30.00 -60.00   54
 12  \w    -34.00  -9.00   0.50    2.00    --  -88.32  30.00   0.00   50
 13  \w    -34.00  -8.00   0.50    2.00    --  -88.32  30.00-120.00   52
 14  \w    -47.00 -12.00   0.50    2.00    --  -88.32  45.00   0.00   70
 15  \w   -138.00 -92.00   0.50    2.00    --  -88.32 -94.00-120.00   92
 16  \w    -34.00  -8.00   0.50    2.00    --  -88.32  30.00 150.00   52
 17  \w    -44.00 -11.00   0.50    2.00    --  -88.32  45.00 -60.00   66
 18  \w    -50.00 -13.00   0.50    2.00    --  -88.32  45.00-180.00   74
 19  \w    -35.00  -8.00   0.50    2.00    --  -88.32  30.00  30.00   54
 20  \w    -50.00 -19.00   0.50    2.00    --  -88.32  45.00-120.00   62
 21  \w    -46.00 -16.00   0.50    2.00    --  -88.32  45.00-150.00   60
 22  \w    -34.00  -8.00   0.50    2.00    --  -88.32  30.00 -90.00   52
 23  \w    -51.00 -11.00   0.50    2.00    --  -88.32  45.00 -30.00   80
 24  \w    -35.00 -10.00   0.50    2.00    --  -88.32  30.00-150.00   50
 25  \w     30.00  97.00   0.50    2.00    --   90.19 -77.00   0.00  134
 26  \w    138.00 165.00   0.50    2.00    --   90.19 125.00  60.00   54
 27  \w     88.00 113.00   0.50    2.00    --   90.19-125.00  90.00   50
 28  \w     40.00  81.00   0.50    2.00    --   90.19-125.00  90.00   82
 29  \w     50.00 104.00   0.50    2.00    --   90.19 -77.00 120.00  108
 30  \w    132.00 163.00   0.50    2.00    --   90.19 125.00   0.00   62
 31  \w     93.00 121.00   0.50    2.00    --   90.19 125.00   0.00   56
 32  \w     64.00 115.00   0.50    2.00    --   90.19-125.00   0.00  102
 33  \w     93.00 118.00   0.50    2.00    --   90.19 125.00 -90.00   50
 34  \w     64.00 108.00   0.50    2.00    --   90.19 -94.00 120.00   88
 35  \w    132.00 162.00   0.50    2.00    --   90.19 125.00-120.00   60
 36  \w     97.00 123.00   0.50    2.00    --   90.19 125.00-120.00   52
 37  \w     13.00  38.00   0.50    2.00    --   90.19 -45.00  60.00   50
 38  \w     68.00 156.00   0.50    2.00    --   90.19  61.00  30.00  176
 39  \w     69.00 111.00   0.50    2.00    --   90.19-125.00 -90.00   84
 40  \w     19.00  59.00   0.50    2.00    --   90.19 -94.00 120.00   80
 41  \w     51.00 110.00   0.50    2.00    --   90.19-125.00 -60.00  118
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0496208000
_diffrn_orient_matrix_UB_12      -0.0136511000
_diffrn_orient_matrix_UB_13      0.0564411000
_diffrn_orient_matrix_UB_21      -0.0579971000
_diffrn_orient_matrix_UB_22      0.0303107000
_diffrn_orient_matrix_UB_23      -0.0281084000
_diffrn_orient_matrix_UB_31      -0.0358501000
_diffrn_orient_matrix_UB_32      -0.0302007000
_diffrn_orient_matrix_UB_33      -0.0537977000
_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  0.0479
_diffrn_reflns_av_unetI/netI     0.0296
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            121132
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        64.000
_diffrn_reflns_theta_max         64.000
_diffrn_reflns_theta_min         2.577
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.292
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62688
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.110a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.833
_exptl_crystal_description       block
_exptl_crystal_F_000             6440
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.480
_refine_diff_density_min         -1.965
_refine_diff_density_rms         0.174
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1325
_refine_ls_number_reflns         19433
_refine_ls_number_restraints     565
_refine_ls_restrained_S_all      1.110
_refine_ls_R_factor_all          0.0986
_refine_ls_R_factor_gt           0.0825
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1517P)^2^+73.6936P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2456
_refine_ls_wR_factor_ref         0.2587
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15810
_reflns_number_total             19433
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cp02227g2.cif
_cod_data_source_block           xl-4-0425-d13_auto
_cod_depositor_comments          'Adding full bibliography for 7246973.cif.'
_cod_database_code               7246973
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHONYbNi
_shelx_estimated_absorpt_t_max   0.426
_shelx_estimated_absorpt_t_min   0.307
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     61.08
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C102-C88
 1.55 with sigma of 0.02
 C101-C88 = C97-C88
 2.55 with sigma of 0.02
 C90-C89
 1.45 with sigma of 0.02
 C92-C90 = C93-C90
 3.2 with sigma of 0.02
 C93-C89 = C92-C89
 2.5 with sigma of 0.02
 C92-C89 = C93-C89
 2.5 with sigma of 0.02
 S7-C90
 1.72 with sigma of 0.02
 C87-C63
 1.54 with sigma of 0.02
 C68-C66
 1.54 with sigma of 0.02
 F9-F7 \\sim F7-F10
 with sigma of 0.02
 F10-C77 \\sim F9-C77 \\sim F7-C77
 with sigma of 0.02
 Cu6A-O8 \\sim Cu6-O8
 with sigma of 0.02
 Ag3-S3 \\sim Ag3A-S3
 with sigma of 0.02
 Ag5-P2 \\sim Ag5A-P2
 with sigma of 0.02
 Ag5A-S6 \\sim Ag5-S6
 with sigma of 0.02
 Cu7-S3 \\sim Cu7A-S3
 with sigma of 0.02
 Cu7-O3 \\sim Cu7A-O3
 with sigma of 0.02
3. Restrained planarity
 C89, C91, C92, C93, C94, C215, C397
 with sigma of 0.1
 C88, C97, C98, C99, C100, C101, C102
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
F7 \\sim F9 \\sim F10 \\sim O6 \\sim O8 \\sim C35 \\sim C77: within 3.8A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 3.8A
C81 \\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86 \\sim C87: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C79 \\sim C88 \\sim C97 \\sim C98 \\sim C99 \\sim C100 \\sim C101 \\sim C102:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C10 \\sim C58 \\sim C67 \\sim C69 \\sim C78 \\sim C80: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C71 \\sim C72 \\sim C73 \\sim C74 \\sim C75 \\sim C76: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C32 \\sim C40 \\sim C57 \\sim C62 \\sim C65 \\sim C70: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C103 \\sim C104 \\sim C105 \\sim C106 \\sim C107 \\sim C108: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C25 \\sim C64 \\sim C103 \\sim C104 \\sim C105 \\sim C106 \\sim C107 \\sim
C108: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
F8 \\sim F11 \\sim F12 \\sim C55: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
F8 \\sim F11 \\sim F12 \\sim O5 \\sim O7 \\sim C46 \\sim C55: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
S8 \\sim C79 \\sim C88 \\sim C97 \\sim C98 \\sim C99 \\sim C100 \\sim C101
\\sim C102: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
S7 \\sim C89 \\sim C90 \\sim C91 \\sim C92 \\sim C93 \\sim C94 \\sim C215 \\sim
C397: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
Ag3 \\sim Ag3A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Ag5 \\sim Ag5A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Cu7 \\sim Cu7A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Uanis(C79) \\sim Ueq, Uanis(C88) \\sim Ueq, Uanis(C102) \\sim Ueq, Uanis(C101)
\\sim Ueq, Uanis(C100) \\sim Ueq, Uanis(C99) \\sim Ueq, Uanis(C98) \\sim Ueq,
Uanis(C97) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(Cu6A)=Sof(Ag3A)=Sof(Ag5A)=Sof(Cu7A)=1-FVAR(1)
 Sof(Ag3)=Sof(Ag5)=Sof(Cu6)=Sof(Cu7)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C11(H11A,H11B), C13(H13A,H13B), C14(H14A,H14B), C25(H25A,H25B),
 C54(H54A,H54B), C60(H60B,H60A), C63(H63A,H63B), C64(H64A,H64B), C66(H66A,H66B),
  C68(H68A,H68B), C79(H79A,H79B), C87(H87A,H87B), C88(H88A,H88B), C89(H89A,
 H89B), C90(H90A,H90B)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C12(H12), C15(H15), C20(H20), C21(H21), C22(H22), C23(H23),
 C24(H24), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30), C31(H31), C33(H33),
  C34(H34), C36(H36), C37(H37), C38(H38), C39(H39), C40(H40), C41(H41),
 C42(H42), C43(H43), C44(H44), C45(H45), C47(H47), C48(H48), C50(H50), C51(H51),
  C52(H52), C53(H53), C56(H56), C57(H57), C58(H58), C59(H59), C61(H61),
 C62(H62), C65(H65), C67(H67), C69(H69), C70(H70), C71(H71), C72(H72), C73(H73),
  C75(H75), C76(H76), C78(H78), C80(H80), C81(H81), C83(H83), C84(H84),
 C85(H85), C86(H86), C97(H97), C98(H98), C99(H99), C100(H100), C101(H101),
 C103(H103), C105(H105), C106(H106), C107(H107), C108(H108), C94(H94), C92(H92),
  C93(H93), C215(H215), C397(H397)
6.c Fitted hexagon refined as free rotating group:
 C48(C49,C50,C51,C52,C53), C71(C72,C73,C74,C75,C76), C81(C82,C83,C84,C85,C86),
 C97(C98,C99,C100,C101,C102), C103(C104,C105,C106,C107,C108), C94(C92,C91,C93,
 C215,C397)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              99904
_shelx_fab_checksum              66945
_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 1.864
_oxdiff_exptl_absorpt_empirical_full_min 0.622