An Ultrastable Ti-based Metallocalixarene Nanocage Cluster with Photocatalytic Amines Oxidation Activity
Tian, Yi-Qi; Cui, Yun-Shu; Yu, Wei-Dong; Xu, Cong-Qiao; Yi, Xiao-Yi; Yan, Jun; Li, Jun; Liu, Chao; Chemical Communications  (2022) –; doi:10.1039/D2CC01740G

data_7130009
_publ_section_title
;
 An Ultrastable Ti-based Metallocalixarene Nanocage Cluster with
 Photocatalytic Amines Oxidation Activity
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC01740G
_journal_year                    2022
_chemical_formula_moiety         'C264 H312 O38 Ti12.987'
_chemical_formula_sum            'C264 H312 O38 Ti13'
_chemical_formula_weight         4715.82
_space_group_crystal_system      tetragonal
_space_group_IT_number           87
_space_group_name_Hall           '-I 4'
_space_group_name_H-M_alt        'I 4/m'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-07-30
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-08-05 deposited with the CCDC.	2022-04-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   23.2672(11)
_cell_length_b                   23.2672(11)
_cell_length_c                   25.827(2)
_cell_measurement_reflns_used    9756
_cell_measurement_temperature    90.0
_cell_measurement_theta_max      54.88
_cell_measurement_theta_min      3.79
_cell_volume                     13981.8(14)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2013/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      90.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.974
_diffrn_measured_fraction_theta_max 0.971
_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  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0513
_diffrn_reflns_av_unetI/netI     0.0376
_diffrn_reflns_Laue_measured_fraction_full 0.974
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            52593
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         55.003
_diffrn_reflns_theta_min         3.305
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    2.223
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.5607
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1459 before and 0.0761 after correction.
The Ratio of minimum to maximum transmission is 0.7468.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.120
_exptl_crystal_description       block
_exptl_crystal_F_000             4972
_refine_diff_density_max         0.999
_refine_diff_density_min         -2.080
_refine_diff_density_rms         0.090
_refine_ls_extinction_coef       0.00021(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     501
_refine_ls_number_reflns         6664
_refine_ls_number_restraints     174
_refine_ls_restrained_S_all      1.115
_refine_ls_R_factor_all          0.1096
_refine_ls_R_factor_gt           0.1035
_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^)+(0.0100P)^2^+120.0000P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2083
_refine_ls_wR_factor_ref         0.2104
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5922
_reflns_number_total             6664
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc01740g2.cif
_cod_data_source_block           Ti13L6
_cod_original_cell_volume        13981.7(17)
_cod_database_code               7130009
_shelxl_version_number           2013-2
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C37-C34
 1.5 with sigma of 0.01
 C33-C32
 2.3 with sigma of 0.01
 C24-C25A
 1.5 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C33 \\sim C38: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Uanis(C13) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C31)
\\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C37) \\sim Ueq,
Uanis(C34) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C45)
\\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq,
Uanis(C12) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C22)
\\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C26) \\sim Ueq,
Uanis(C26A) \\sim Ueq, Uanis(C23A) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C25A)
\\sim Ueq, Uanis(C24A) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C20, C21, C22
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8A)=Sof(C12)=Sof(C34)=Sof(C35)=Sof(H35A)=
 Sof(H35B)=Sof(H35C)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C37)=Sof(H37A)=
 Sof(H37B)=Sof(H37C)=1-FVAR(1)
 Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=Sof(C13)=Sof(C31)=Sof(H31A)=Sof(H31B)=
 Sof(H31C)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C33)=Sof(H33A)=Sof(H33B)=
 Sof(H33C)=Sof(C38)=FVAR(1)
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C25)=Sof(C26)=Sof(H26A)=Sof(H26B)=
 Sof(H26C)=Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=1-FVAR(2)
 Sof(C23A)=Sof(H23D)=Sof(H23E)=Sof(H23F)=Sof(C24)=Sof(H24A)=Sof(H24B)=
 Sof(H24C)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C25A)=FVAR(2)
 Fixed Sof: H21C(0.5) H21A(0.5) H21B(0.5) H45A(0.5) H45B(0.5) H45C(0.5)
6.a Riding coordinates:
 C23A(H23D,H23E,H23F)
6.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C43(H43A,H43B), C49(H49A,H49B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C7(H7), C7A(H7A), C8(H8), C8A(H8A), C18(H18), C47(H47)
6.d Idealised Me refined as rotating group:
 C21(H21C,H21A,H21B), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C24A(H24D,H24E,H24F), C26(H26A,H26B,H26C), C26A(H26D,H26E,H26F),
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C35(H35A,H35B,
 H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C44(H44A,H44B,H44C), C45(H45A,
 H45B,H45C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              22039
_shelx_hkl_checksum              81374
_shelx_fab_checksum              84195
_olex2_submission_special_instructions 'No special instructions were received'