Anchored Ag+ sites on a thiacalix[4]arene-stabilized Ti-oxo cluster enable efficient CO2-to-CO electroreduction
Han, Qian; Wang, Xiao-Wei; Zhu, Hong-Yan; Li, Lan-Yan; Yu, Wei-Dong; Liu, Chao; CrystEngComm 28 (2026) 806–811; doi:10.1039/D5CE01062D

data_7251449
_publ_section_title
;
 Anchored Ag+ sites on a thiacalix[4]arene-stabilized Ti-oxo cluster
 enable efficient CO2-to-CO electroreduction
;
_journal_issue                   4
_journal_name_full               CrystEngComm
_journal_page_first              806
_journal_page_last               811
_journal_paper_doi               10.1039/D5CE01062D
_journal_volume                  28
_journal_year                    2026
_chemical_formula_moiety         'C60 H66 O12 S4 Ti2, 2(C2 H3 N), 2(C6 H16 N)'
_chemical_formula_sum            'C76 H104 N4 O12 S4 Ti2'
_chemical_formula_weight         1489.67
_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     dual
_audit_creation_date             2025-10-04
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-10-04 deposited with the CCDC.	2025-12-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.259(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.8614(5)
_cell_length_b                   13.3481(5)
_cell_length_c                   23.7581(9)
_cell_measurement_reflns_used    16051
_cell_measurement_temperature    150
_cell_measurement_theta_max      34.0080
_cell_measurement_theta_min      2.2770
_cell_volume                     4077.7(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 2013/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_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    -47.00  20.00   0.50   20.00    --   13.79 -37.00 -60.00  134
  2  \w    -24.00  20.00   0.50   20.00    --  -14.57 -99.00 -60.00   88
  3  \w     36.00  69.00   0.50   20.00    --   13.79-136.00-121.00   66
  4  \w     35.00  66.00   0.50   20.00    --   13.79-178.00-150.00   62
  5  \w     14.00  40.00   0.50   20.00    --   13.79-133.00  56.00   52
  6  \w    -24.00  17.00   0.50   20.00    --  -14.57 -99.00  60.00   82
  7  \w    -35.00   0.00   0.50   20.00    --  -14.57 -37.00  90.00   70
  8  \w    -88.00 -50.00   0.50   20.00    --  -14.57 -37.00  90.00   76
  9  \w     44.00  74.00   0.50   20.00    --   13.79 178.00-120.00   60
 10  \w     59.00  84.00   0.50   20.00    --   13.79 178.00  30.00   50
;
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0551247000
_diffrn_orient_matrix_UB_12      -0.0010719000
_diffrn_orient_matrix_UB_13      -0.0002609000
_diffrn_orient_matrix_UB_21      0.0011326000
_diffrn_orient_matrix_UB_22      0.0531193000
_diffrn_orient_matrix_UB_23      0.0006689000
_diffrn_orient_matrix_UB_31      0.0016726000
_diffrn_orient_matrix_UB_32      -0.0011846000
_diffrn_orient_matrix_UB_33      0.0298517000
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0413
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            7973
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.000
_diffrn_reflns_theta_min         2.199
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    0.356
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78029
_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    1.213
_exptl_crystal_description       block
_exptl_crystal_F_000             1584
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.791
_refine_diff_density_min         -0.647
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.985
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     471
_refine_ls_number_reflns         7973
_refine_ls_number_restraints     211
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.1018
_refine_ls_R_factor_gt           0.0915
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.1828P)^2^+4.9615P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2731
_refine_ls_wR_factor_ref         0.2852
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6616
_reflns_number_total             7973
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce01062d2.cif
_cod_data_source_block           Ti2-Sal
_cod_database_code               7251449
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         CHONTiS
_shelx_estimated_absorpt_t_max   0.901
_shelx_estimated_absorpt_t_min   0.842
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.786(3)
 0.214(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
3. Restrained distances
 C32-C4
 1.45 with sigma of 0.01
 C2-C3
 1.45 with sigma of 0.01
 C3-C1
 1.45 with sigma of 0.01
 C7-C33
 1.45 with sigma of 0.01
 C17-C14
 1.45 with sigma of 0.01
 C3-C32
 2.2 with sigma of 0.01
 C3-C2 \\sim C3-C1
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
C3 \\sim C32 \\sim C4 \\sim C5 \\sim C6 \\sim N7 \\sim C2 \\sim C1 \\sim C3:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C7) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(N5) \\sim Ueq, Uanis(C27)
\\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(N4) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C3) \\sim Ueq, Uanis(N7) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C5) \\sim
Ueq, Uanis(C4) \\sim Ueq, Uanis(C6) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C26) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C16)
\\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C3, N7, C32, C5, C4, C6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C14, C17, C15, C16, C24, C25, C27, C26
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H3BC)=Sof(H3BD)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=1-FVAR(1)
 Sof(H3AA)=Sof(H3AB)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=FVAR(1)
 Fixed Sof: N4(0.5) N5(0.5) H33A(0.5) H33B(0.5) H33C(0.5) H33D(0.5) H33E(0.5)
 H33F(0.5) C31(0.5) C7(0.5)
7.a Riding coordinates:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C25(H25A,H25B,
 H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C), C33(H33A,H33B,H33C), C33(H33D,H33E,H33F), C4(H4A,H4B,H4C), C6(H6A,
 H6B,H6C), C2(H2A,H2B,H2C), C1(H1A,H1B,H1C)
7.b Ternary CH refined with riding coordinates:
 C28(H28), N7(H7)
7.c Secondary CH2 refined with riding coordinates:
 C3(H3AA,H3AB), C3(H3BC,H3BD), C32(H32A,H32B), C5(H5A,H5B)
7.d Aromatic/amide H refined with riding coordinates:
 C35(H35), C36(H36), C37(H37), C38(H38), C11(H11), C13(H13), C19(H19), C21(H21)
;
_shelx_res_checksum              90539
_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 1.354
_oxdiff_exptl_absorpt_empirical_full_min 0.735