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_1569793
_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 H102 Ag2 N2 O11 S8 Ti2, C3 H7 N O'
_chemical_formula_sum            'C89 H109 Ag2 N3 O12 S8 Ti2'
_chemical_formula_weight         1980.81
_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   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2022-10-13
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-05-13 deposited with the CCDC.	2023-09-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.010(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.9703(13)
_cell_length_b                   15.9803(10)
_cell_length_c                   36.153(3)
_cell_measurement_reflns_used    4378
_cell_measurement_temperature    150
_cell_measurement_theta_max      24.3260
_cell_measurement_theta_min      2.1900
_cell_volume                     13220.1(16)
_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 2013/2 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.870
_diffrn_measured_fraction_theta_max 0.920
_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    -68.00  -5.00   0.25    1.25    --   -0.31 -19.00 -60.00  252
  2  \w     -4.00  39.75   0.25    1.25    --   -0.31  37.00 120.00  175
;
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1326
_diffrn_reflns_av_unetI/netI     0.1783
_diffrn_reflns_Laue_measured_fraction_full 0.870
_diffrn_reflns_Laue_measured_fraction_max 0.920
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            40452
_diffrn_reflns_point_group_measured_fraction_full 0.870
_diffrn_reflns_point_group_measured_fraction_max 0.920
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         24.750
_diffrn_reflns_theta_min         1.983
_diffrn_source_target            Mo
_exptl_absorpt_coefficient_mu    0.576
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87311
_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 orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    0.995
_exptl_crystal_description       block
_exptl_crystal_F_000             4104
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.642
_refine_diff_density_min         -0.800
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.860
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1194
_refine_ls_number_reflns         20834
_refine_ls_number_restraints     1020
_refine_ls_restrained_S_all      7.155
_refine_ls_R_factor_all          0.1518
_refine_ls_R_factor_gt           0.0804
_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^)+(0.0781P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1950
_refine_ls_wR_factor_ref         0.2211
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8828
_reflns_number_total             20834
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02793g2.cif
_cod_data_source_block           Ti2Ag2
_cod_depositor_comments
'Adding full bibliography for 1569790--1569794.cif.'
_cod_original_cell_volume        13220.2(16)
_cod_database_code               1569793
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.846
_shelx_estimated_absorpt_t_min   0.762
_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
 C26-C20
 2.5 with sigma of 0.01
 C26-C29
 2.5 with sigma of 0.01
 C37-C31
 1.5 with sigma of 0.01
 C14-C12
 2.2 with sigma of 0.01
 C25-C28
 1.45 with sigma of 0.01
 C61-C59
 2.5 with sigma of 0.01
 C61-C60
 2.5 with sigma of 0.01
 C60-C37
 1.45 with sigma of 0.01
 C60-C59
 2.5 with sigma of 0.01
 C61-C37
 1.45 with sigma of 0.01
 C59-C37
 1.45 with sigma of 0.01
 C21-N4
 1.45 with sigma of 0.01
 C21-C31
 1.45 with sigma of 0.01
 C28-C29 \\sim C28-C12
 with sigma of 0.02
 C28-C26 \\sim C28-C14
 with sigma of 0.02
 C28-C20 \\sim C28-C25
 with sigma of 0.02
 C30-C15 \\sim C30-C56
 with sigma of 0.02
 C30-C27 \\sim C30-C36
 with sigma of 0.02
 C30-C57 \\sim C30-C58
 with sigma of 0.02
 C37-C59 \\sim C37-C40
 with sigma of 0.02
 C37-C61 \\sim C37-C39
 with sigma of 0.02
 C37-C60 \\sim C37-C38
 with sigma of 0.02
 C7-C4 \\sim C7-C3
 with sigma of 0.02
 C7-C6 \\sim C7-C2
 with sigma of 0.02
 C7-C5 \\sim C7-C1
 with sigma of 0.02
3. Rigid bond restraints
 C37, C31
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 O00M, C19
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 O00N, C23
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C30, C27
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C6, C7
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
C28 \\sim C14 \\sim C29 \\sim C12 \\sim C20 \\sim C25 \\sim C26: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C37 \\sim C59 \\sim C60 \\sim C61 \\sim C38 \\sim C39 \\sim C40: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C7 \\sim C4 \\sim C5 \\sim C6 \\sim C1 \\sim C2 \\sim C3: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C22 \\sim C60 \\sim N1 \\sim C23: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
C27 \\sim C36 \\sim C15 \\sim C56 \\sim C57 \\sim C58 \\sim C30: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C19 \\sim C13 \\sim C13 \\sim N4: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
C41 \\sim C42 \\sim C43 \\sim C44: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C16 \\sim C17 \\sim C18 \\sim C45: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C50 \\sim C51 \\sim N3 \\sim C49: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C46 \\sim C47 \\sim C52 \\sim C48: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(C8) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C00Q) \\sim Ueq, Uanis(C00S)
\\sim Ueq, Uanis(C00T) \\sim Ueq, Uanis(C00V) \\sim Ueq, Uanis(C00W) \\sim Ueq,
Uanis(C00X) \\sim Ueq, Uanis(C00Y) \\sim Ueq, Uanis(C00Z) \\sim Ueq,
Uanis(C010) \\sim Ueq, Uanis(C011) \\sim Ueq, Uanis(C012) \\sim Ueq,
Uanis(C013) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C015) \\sim Ueq, Uanis(C016)
\\sim Ueq, Uanis(C017) \\sim Ueq, Uanis(C018) \\sim Ueq, Uanis(C019) \\sim Ueq,
Uanis(C01B) \\sim Ueq, Uanis(C01C) \\sim Ueq, Uanis(C01D) \\sim Ueq,
Uanis(C01E) \\sim Ueq, Uanis(C01F) \\sim Ueq, Uanis(C01G) \\sim Ueq,
Uanis(C01H) \\sim Ueq, Uanis(C01I) \\sim Ueq, Uanis(C01J) \\sim Ueq, Uanis(C34)
\\sim Ueq, Uanis(C01L) \\sim Ueq, Uanis(C01M) \\sim Ueq, Uanis(C01N) \\sim Ueq,
Uanis(C55) \\sim Ueq, Uanis(C01Q) \\sim Ueq, Uanis(C01R) \\sim Ueq, Uanis(C01S)
\\sim Ueq, Uanis(C01T) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C01V) \\sim Ueq,
Uanis(C33) \\sim Ueq, Uanis(C01X) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C48)
\\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C021) \\sim Ueq, Uanis(C10) \\sim Ueq,
Uanis(C023) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C54)
\\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C53) \\sim Ueq,
Uanis(C7) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C02D) \\sim Ueq, Uanis(C52)
\\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C50) \\sim Ueq,
Uanis(C23) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C02M)
\\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C57) \\sim Ueq,
Uanis(C44) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C02T) \\sim Ueq, Uanis(C51)
\\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C27) \\sim Ueq,
Uanis(C42) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C24)
\\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C37) \\sim Ueq,
Uanis(C61) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C5)
\\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C20) \\sim Ueq,
Uanis(C14) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C36)
\\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C38) \\sim Ueq,
Uanis(C40) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C1)
\\sim Ueq, Uanis(C3) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms
of 0.02
5. Others
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=
 Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=1-FVAR(1)
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=FVAR(1)
 Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=
 Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=1-FVAR(2)
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=FVAR(2)
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=
 Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=1-FVAR(3)
 Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(H61C)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=
 Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=FVAR(3)
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C3)=
 Sof(H3A)=Sof(H3B)=Sof(H3C)=1-FVAR(4)
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C6)=
 Sof(H6A)=Sof(H6B)=Sof(H6C)=FVAR(4)
6.a Riding coordinates:
 C13(H13A,H13B,H13C), C12(H12A,H12B,H12C), C25(H25A,H25B,H25C), C2(H2A,H2B,
 H2C), C3(H3A,H3B,H3C)
6.b Aromatic/amide H refined with riding coordinates:
 C00Z(H00Z), C9(H9), C015(H015), C016(H016), C019(H019), C01D(H01D),
 C01G(H01G), C01H(H01H), C01I(H01I), C01J(H01J), C01Q(H01Q), C01R(H01R),
 C01V(H01V), C32(H32), C54(H54), C49(H49), C53(H53), C19(H19), C23(H23)
6.c Idealised Me refined as rotating group:
 C02D(H02A,H02B,H02C), C52(H52A,H52B,H52C), C47(H47A,H47B,H47C), C50(H50A,H50B,
 H50C), C21(H21A,H21B,H21C), C16(H16A,H16B,H16C), C02M(H02D,H02E,H02F),
 C43(H43A,H43B,H43C), C15(H15A,H15B,H15C), C57(H57A,H57B,H57C), C44(H44A,H44B,
 H44C), C18(H18A,H18B,H18C), C02T(H02G,H02H,H02I), C51(H51A,H51B,H51C),
 C45(H45A,H45B,H45C), C27(H27A,H27B,H27C), C42(H42A,H42B,H42C), C22(H22A,H22B,
 H22C), C46(H46A,H46B,H46C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C29(H29A,
 H29B,H29C), C61(H61A,H61B,H61C), C60(H60A,H60B,H60C), C59(H59A,H59B,H59C),
 C5(H5A,H5B,H5C), C4(H4A,H4B,H4C), C6(H6A,H6B,H6C), C20(H20A,H20B,H20C),
 C14(H14A,H14B,H14C), C36(H36A,H36B,H36C), C56(H56A,H56B,H56C), C58(H58A,H58B,
 H58C), C38(H38A,H38B,H38C), C40(H40A,H40B,H40C), C39(H39A,H39B,H39C), C1(H1A,
 H1B,H1C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              73694
_shelx_fab_checksum              1907
_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
;