Stepwise assembly of thiacalix[4]arene-protected Ag/Ti bimetallic nanoclusters: accurate identification of catalytic Ag sites in CO<sub>2</sub> electroreduction.
Tian, Yi-Qi; Mu, Wen-Lei; Wu, Lin-Lin; Yi, Xiao-Yi; Yan, Jun; Liu, Chao; Chemical science 14 (2023) 10212–10218; doi:10.1039/d3sc02793g

data_1569792
_publ_section_title
;
 Stepwise assembly of thiacalix[4]arene-protected Ag/Ti bimetallic
 nanoclusters: accurate identification of catalytic Ag sites in
 CO<sub>2</sub> electroreduction.
;
_journal_issue                   37
_journal_name_full               'Chemical science'
_journal_page_first              10212
_journal_page_last               10218
_journal_paper_doi               10.1039/d3sc02793g
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C86 H100 Ag2.6 O11 S8 Ti2, 2[CH3CN]'
_chemical_formula_sum            'C86 H100 Ag2.6 O11 S8 Ti2'
_chemical_formula_weight         1942.40
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2023-04-10
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-05-13 deposited with the CCDC.	2023-09-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.461(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.4327(4)
_cell_length_b                   19.1408(5)
_cell_length_c                   19.9855(6)
_cell_measurement_reflns_used    16222
_cell_measurement_temperature    150
_cell_measurement_theta_max      32.4460
_cell_measurement_theta_min      2.2570
_cell_volume                     5053.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_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)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'Image Plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'Rigaku IP'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.994
_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    -34.00  45.00   0.50   25.00    --   13.79 -95.00  38.00  158
  2  \w    -25.00   0.00   0.50   25.00    --  -14.57 -99.00 -60.00   50
  3  \w    -17.00  20.00   0.50   25.00    --  -14.57 -99.00-120.00   74
  4  \w    -26.00  20.00   0.50   25.00    --  -14.57 -99.00-180.00   92
  5  \w    -58.00 -18.00   0.50   25.00    --   13.79 -19.00 -30.00   80
  6  \w    -34.00  15.00   0.50   25.00    --  -14.57 -95.00  38.00   98
  7  \w    -44.00 -15.00   0.50   25.00    --  -14.57  95.00 148.00   58
  8  \w     47.00  73.00   0.50   25.00    --   13.79 178.00   0.00   52
  9  \w     40.00  82.00   0.50   25.00    --   13.79 178.00 -30.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku R-AXIS SPIDER IP'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0214041000
_diffrn_orient_matrix_UB_12      0.0025714000
_diffrn_orient_matrix_UB_13      -0.0350705000
_diffrn_orient_matrix_UB_21      -0.0186194000
_diffrn_orient_matrix_UB_22      -0.0346422000
_diffrn_orient_matrix_UB_23      0.0005751000
_diffrn_orient_matrix_UB_31      -0.0455892000
_diffrn_orient_matrix_UB_32      0.0129329000
_diffrn_orient_matrix_UB_33      0.0084831000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0477
_diffrn_reflns_av_unetI/netI     0.0378
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            44577
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.999
_diffrn_reflns_theta_min         2.001
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.861
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64392
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.68a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.277
_exptl_crystal_description       block
_exptl_crystal_F_000             1996
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.489
_refine_diff_density_min         -0.357
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     631
_refine_ls_number_reflns         9875
_refine_ls_number_restraints     224
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0753
_refine_ls_R_factor_gt           0.0553
_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^)+(0.0507P)^2^+7.2026P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1332
_refine_ls_wR_factor_ref         0.1397
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7418
_reflns_number_total             9875
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02793g2.cif
_cod_data_source_block           Ti2Ag3
_cod_depositor_comments
'Adding full bibliography for 1569790--1569794.cif.'
_cod_original_formula_sum        'C86 H100 Ag2.60 O11 S8 Ti2'
_cod_database_code               1569792
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_usercomment     CHONTi
_shelx_estimated_absorpt_t_max   0.782
_shelx_estimated_absorpt_t_min   0.673
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C43-C41
 2.2 with sigma of 0.01
 C15-C11 \\sim C15-C11A
 with sigma of 0.02
 C15-C10 \\sim C15-C10A
 with sigma of 0.02
 C012-C3 \\sim C012-C51
 with sigma of 0.02
 C012-C5 \\sim C012-C4
 with sigma of 0.02
 C012-C50 \\sim C012-C6
 with sigma of 0.02
 C018-C7 \\sim C018-C47
 with sigma of 0.02
 C018-C8 \\sim C018-C48
 with sigma of 0.02
 C018-C9 \\sim C018-C49
 with sigma of 0.02
 C40-C45 \\sim C40-C41
 with sigma of 0.02
 C40-C44 \\sim C40-C43
 with sigma of 0.02
 C40-C46 \\sim C40-C42
 with sigma of 0.02
3. Rigid bond restraints
 C012, C51
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C015, C13
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C018, C49
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C018, C8
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C11, C15
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C40, C46
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C40, C41
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C11A, C15
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
C44 \\sim C43 \\sim C45 \\sim C41 \\sim C46 \\sim C42: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C9 \\sim C47 \\sim C7 \\sim C48 \\sim C8 \\sim C49: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C50 \\sim C51 \\sim C3 \\sim C4 \\sim C5 \\sim C6: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
Uanis(C44) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C45)
\\sim Ueq, Uanis(C11A) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C8) \\sim Ueq,
Uanis(C7) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C10A) \\sim Ueq, Uanis(C5)
\\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C47) \\sim Ueq,
Uanis(C49) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C43)
\\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C10) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C7, C8, C9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C45, C44, C46
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C41, C43, C42
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C11A)=Sof(H11D)=Sof(H11E)=
 Sof(H11F)=1-FVAR(1)
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=
 FVAR(1)
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=1-FVAR(2)
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=
 Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=FVAR(2)
 Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=
 Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(H48C)=1-FVAR(3)
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=
 Sof(H9A)=Sof(H9B)=Sof(H9C)=FVAR(3)
 Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=
 Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=1-FVAR(4)
 Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=
 Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=FVAR(4)
7.a Riding coordinates:
 C43(H43A,H43B,H43C)
7.b Aromatic/amide H refined with riding coordinates:
 C28(H28), C22(H22), C30(H30), C18(H18), C26(H26), C37(H37), C16(H16), C35(H35)
7.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C12(H12A,H12B,H12C), C3(H3A,H3B,H3C), C45(H45A,H45B,
 H45C), C5(H5A,H5B,H5C), C50(H50A,H50B,H50C), C44(H44A,H44B,H44C), C14(H14A,
 H14B,H14C), C46(H46A,H46B,H46C), C11(H11A,H11B,H11C), C10(H10A,H10B,H10C),
 C10A(H10D,H10E,H10F), C11A(H11D,H11E,H11F), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C),
 C9(H9A,H9B,H9C), C4(H4A,H4B,H4C), C51(H51A,H51B,H51C), C6(H6A,H6B,H6C),
 C47(H47A,H47B,H47C), C49(H49A,H49B,H49C), C48(H48A,H48B,H48C), C41(H41A,H41B,
 H41C), C42(H42A,H42B,H42C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              24929
_shelx_fab_checksum              88809
_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 2.418
_oxdiff_exptl_absorpt_empirical_full_min 0.795