Synthesis, structure anatomy, and catalytic properties of Ag14Cu2 nanoclusters co-protected by alkynyl and phosphine ligands
Shen, Quanli; Cong, Xuzi; Chen, Leyi; Wang, Lei; Liu, Yonggang; Wang, Likai; Tang, Zhenghua; Dalton Transactions  (2023) –; doi:10.1039/D3DT02838K

data_7714261
_publ_section_title
;
 Synthesis, structure anatomy, and catalytic properties of Ag14Cu2
 nanoclusters co-protected by alkynyl and phosphine ligands
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT02838K
_journal_year                    2023
_chemical_formula_moiety         'C212 H102 Ag14 Cu2 F84 P4'
_chemical_formula_sum            'C212 H102 Ag14 Cu2 F84 P4'
_chemical_formula_weight         6006.07
_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             2022-04-29
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-05-17 deposited with the CCDC.	2023-10-16 downloaded from the CCDC.
;
_cell_angle_alpha                105.4210(10)
_cell_angle_beta                 105.0070(10)
_cell_angle_gamma                116.9920(10)
_cell_formula_units_Z            1
_cell_length_a                   18.68860(10)
_cell_length_b                   19.6047(2)
_cell_length_c                   19.8873(2)
_cell_measurement_reflns_used    145426
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      31.2000
_cell_measurement_theta_min      2.2910
_cell_volume                     5614.54(14)
_computing_cell_refinement       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.122a (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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.855
_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     -9.00  38.00   0.50    1.20    --    4.52 -99.00 141.00   94
  2  \w     -6.00  75.00   0.50    1.20    --    4.52  57.00 -60.00  162
  3  \w    -20.00  23.00   0.50    1.20    --   -6.00  33.00  56.40   86
  4  \w    -19.00  69.00   0.50    1.20    --   -6.24  30.00 148.80  176
  5  \w    -20.00  52.00   0.50    1.20    --   -6.00  33.00   0.14  144
  6  \w    -19.00  59.00   0.50    1.20    --   -6.24  19.00  90.00  156
  7  \w    -19.00  68.00   0.50    1.20    --   -6.24  31.00 -61.48  174
  8  \w    -19.00  55.00   0.50    1.20    --   -6.24  30.00-129.72  148
  9  \w    -19.00  68.00   0.50    1.20    --   -6.24  28.00-166.20  174
 10  \w    -29.00  21.00   0.50    1.20    --    4.52  99.00-112.00  100
 11  \w     -9.00  22.00   0.50    1.20    --   -6.24  99.00-112.00   62
 12  \w    -40.00 -12.00   0.50    1.20    --   -6.24  99.00-112.00   56
 13  \w    -79.00  15.00   0.50    1.20    --   -6.24 -77.00  90.00  188
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0055255000
_diffrn_orient_matrix_UB_12      0.0208483000
_diffrn_orient_matrix_UB_13      0.0378920000
_diffrn_orient_matrix_UB_21      0.0037664000
_diffrn_orient_matrix_UB_22      -0.0309722000
_diffrn_orient_matrix_UB_23      0.0095640000
_diffrn_orient_matrix_UB_31      0.0470106000
_diffrn_orient_matrix_UB_32      0.0257501000
_diffrn_orient_matrix_UB_33      0.0131950000
_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  0.0255
_diffrn_reflns_av_unetI/netI     0.0188
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.855
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            170364
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.855
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.012
_diffrn_reflns_theta_min         2.251
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.522
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77284
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.122a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_density_diffrn    1.776
_exptl_crystal_description       block
_exptl_crystal_F_000             2906
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.247
_refine_diff_density_min         -3.782
_refine_diff_density_rms         0.119
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1547
_refine_ls_number_reflns         30605
_refine_ls_number_restraints     301
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0450
_refine_ls_R_factor_gt           0.0358
_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^)+(0.0487P)^2^+15.8362P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0931
_refine_ls_wR_factor_ref         0.1007
_reflns_Friedel_coverage         0.000
_reflns_number_gt                26169
_reflns_number_total             30605
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02838k2.cif
_cod_data_source_block           exp_1924_mgy3_auto
_cod_original_cell_volume        5614.53(10)
_cod_database_code               7714261
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Ag Cu CHFPCl'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C13-F37
 1.36 with sigma of 0.02
 C51-F15
 1.29 with sigma of 0.02
 C51-F31
 1.36 with sigma of 0.02
 C13-F19
 1.27 with sigma of 0.02
 C51-F2
 1.27 with sigma of 0.02
 C103-F33
 1.29 with sigma of 0.02
 C103-F17
 1.36 with sigma of 0.02
 C103-F35
 1.27 with sigma of 0.02
 C13-F9
 1.29 with sigma of 0.02
 C53-F25
 1.27 with sigma of 0.02
 C53-F3
 1.29 with sigma of 0.02
 C53-F49
 1.36 with sigma of 0.02
 C103-F33 \\sim C103-F17 \\sim C103-F35
 with sigma of 0.02
 C51-F15 \\sim C51-F31 \\sim C51-F2
 with sigma of 0.02
 C13-F9 \\sim C13-F37 \\sim C13-F19
 with sigma of 0.02
 F15-F31 \\sim F31-F2 \\sim F2-F15
 with sigma of 0.03
 F33-F17 \\sim F17-F35 \\sim F35-F33
 with sigma of 0.03
 F9-F37 \\sim F37-F19 \\sim F19-F9
 with sigma of 0.03
 C3-F2 \\sim C3-F47
 with sigma of 0.04
 C3-C51 \\sim C3-C105
 with sigma of 0.02
 F15-F2 \\sim F45-F47
 with sigma of 0.04
 C51-F31 \\sim C105-F23
 with sigma of 0.02
 F31-F2 \\sim F23-F47
 with sigma of 0.04
 C3-F15 \\sim C3-F45
 with sigma of 0.04
 C13-F19 \\sim C13-F11
 with sigma of 0.02
 C103-F17 \\sim C103-F5
 with sigma of 0.02
 C51-F15 \\sim C105-F45
 with sigma of 0.02
 C103-F35 \\sim C103-F41
 with sigma of 0.02
 C51-F2 \\sim C105-F47
 with sigma of 0.02
 C3-F31 \\sim C3-F23
 with sigma of 0.04
 C13-F9 \\sim C13-F21
 with sigma of 0.02
 C13-F37 \\sim C13-F43
 with sigma of 0.02
 F15-F31 \\sim F45-F23
 with sigma of 0.04
 C103-F33 \\sim C103-F39
 with sigma of 0.02
 F3-F49 \\sim F49-F25 \\sim F25-F3
 with sigma of 0.03
 C53-F3 \\sim C53-F49 \\sim C53-F25
 with sigma of 0.02
 F49-F25 \\sim F13-F53
 with sigma of 0.04
 C53-F49 \\sim C107-F13
 with sigma of 0.02
 C53-F3 \\sim C107-F51
 with sigma of 0.02
 C95-C53 \\sim C95-C107
 with sigma of 0.02
 F3-F25 \\sim F51-F53
 with sigma of 0.04
 C53-F25 \\sim C107-F53
 with sigma of 0.02
 C95-F49 \\sim C95-F13
 with sigma of 0.04
 C95-F3 \\sim C95-F51
 with sigma of 0.04
 C95-F25 \\sim C95-F53
 with sigma of 0.04
 F3-F49 \\sim F51-F13
 with sigma of 0.04
 C105-C3 \\sim C51-C3
 with sigma of 0.01
3. Rigid bond restraints
 C3, C51, F15, F31, F2
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C51 \\sim F15 \\sim F31 \\sim F2 \\sim C3: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 1.7A
Uanis(C51) = Uanis(C105)
5. Rigid body (RIGU) restrains
 C51, F15, F31, F2, C105, F45, F23, F47
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
 C103, F33, F17, F35, F39, F5, F41
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
 C13, F9, F37, F19, F21, F43, F11
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
 C53, F3, F49, F25, C107, F51, F13, F53, C95
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
6. Others
 Sof(F39)=Sof(F5)=Sof(F41)=1-FVAR(1)
 Sof(F33)=Sof(F17)=Sof(F35)=FVAR(1)
 Sof(F21)=Sof(F43)=Sof(F11)=1-FVAR(2)
 Sof(F9)=Sof(F37)=Sof(F19)=FVAR(2)
 Sof(C105)=Sof(F45)=Sof(F23)=Sof(F47)=1-FVAR(3)
 Sof(C51)=Sof(F15)=Sof(F31)=Sof(F2)=FVAR(3)
 Sof(C107)=Sof(F51)=Sof(F13)=Sof(F53)=1-FVAR(4)
 Sof(C53)=Sof(F3)=Sof(F49)=Sof(F25)=FVAR(4)
7.a Aromatic/amide H refined with riding coordinates:
 C24(H24), C28(H28), C30(H30), C32(H32), C38(H38), C42(H42), C48(H48),
 C52(H52), C62(H62), C64(H64), C70(H70), C72(H72), C84(H84), C86(H86), C88(H88),
  C100(H100), C102(H102), C104(H104), C106(H106), C108(H108), C27(H27),
 C55(H55), C7(H7), C57(H57), C29(H29), C61(H61), C31(H31), C63(H63), C2(H2),
 C65(H65), C67(H67), C69(H69), C35(H35), C71(H71), C9(H9), C73(H73), C37(H37),
 C75(H75), C77(H77), C39(H39), C5(H5), C83(H83), C85(H85), C43(H43), C45(H45),
 C91(H91), C97(H97), C49(H49), C99(H99), C25(H25), C101(H101)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              19403
_shelx_fab_checksum              70752
_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 1.296
_oxdiff_exptl_absorpt_empirical_full_min 0.821