Ancillary ligand-regulated Ti(iv)-based metallocalixarene coordination cages for photocatalytic H2 evolution
Tian, Yi-Qi; Cui, Yun-Shu; Zhu, Jia-Hui; Xu, Cong-Qiao; Yi, Xiao-Yi; Li, Jun; Liu, Chao; Chemical Communications  (2022) –; doi:10.1039/D2CC03131K

data_7130394
_publ_section_title
;
 Ancillary ligand-regulated Ti(iv)-based metallocalixarene coordination
 cages for photocatalytic H2 evolution
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC03131K
_journal_year                    2022
_chemical_formula_moiety
'C342 H414 N6 O60 Ti12, 2.667(C6 H9 N3), 2[C2H3N], 4[C2H3N]'
_chemical_formula_sum            'C370 H456 N20 O60 Ti12'
_chemical_formula_weight         6718.32
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-06-24
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-06-28 deposited with the CCDC.	2022-07-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   33.1580(13)
_cell_length_b                   33.1580(13)
_cell_length_c                   31.9101(17)
_cell_measurement_reflns_used    10989
_cell_measurement_temperature    150
_cell_measurement_theta_max      27.5170
_cell_measurement_theta_min      2.2600
_cell_volume                     30383(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.26a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.26a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.26a (Rigaku OD, 2018)'
_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                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.992
_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    -58.00  28.00   0.50  150.00    --   14.02 -53.00-105.00  172
  2  \w     17.00  43.00   0.50  150.00    --   14.02-125.00   5.00   52
  3  \w    -69.00 -31.50   0.50  150.00    --  -14.41 -69.00-156.00   75
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0002104000
_diffrn_orient_matrix_UB_12      -0.0177635000
_diffrn_orient_matrix_UB_13      0.0125655000
_diffrn_orient_matrix_UB_21      0.0196144000
_diffrn_orient_matrix_UB_22      0.0023441000
_diffrn_orient_matrix_UB_23      -0.0110379000
_diffrn_orient_matrix_UB_31      0.0150254000
_diffrn_orient_matrix_UB_32      0.0170186000
_diffrn_orient_matrix_UB_33      0.0146281000
_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  0.0702
_diffrn_reflns_av_unetI/netI     0.0718
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_k_min       -40
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            37423
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.991
_diffrn_reflns_theta_min         1.982
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.286
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76595
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.26a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear reddish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.061
_exptl_crystal_description       cube
_exptl_crystal_F_000             10284
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.559
_refine_diff_density_min         -0.269
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.977
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     756
_refine_ls_number_reflns         13149
_refine_ls_number_restraints     105
_refine_ls_restrained_S_all      1.004
_refine_ls_R_factor_all          0.1211
_refine_ls_R_factor_gt           0.0733
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.1240P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1856
_refine_ls_wR_factor_ref         0.2075
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7609
_reflns_number_total             13149
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc03131k2.cif
_cod_data_source_block           Ti12L6-1
_cod_original_cell_volume        30383(3)
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               7130394
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         CHONTi
_shelx_estimated_absorpt_t_max   0.919
_shelx_estimated_absorpt_t_min   0.870
_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
 C9A-C8
 1.45 with sigma of 0.01
 C56-C53
 1.45 with sigma of 0.01
3. Rigid bond restraints
 C56A, C53
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
C20 \\sim C21: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C20 \\sim C22: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C20 \\sim C23: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Uanis(C55) \\sim Ueq, Uanis(C54A) \\sim Ueq, Uanis(C55A) \\sim Ueq, Uanis(C9)
\\sim Ueq, Uanis(C9A) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C54A) \\sim Ueq,
Uanis(C56) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C56A) \\sim Ueq, Uanis(C21)
\\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C34) \\sim Ueq,
Uanis(C34A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=Sof(C34A)=Sof(H34D)=Sof(H34E)=
 Sof(H34F)=Sof(C33A)=Sof(H33D)=Sof(H33E)=Sof(H33F)=1-FVAR(1)
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=FVAR(1)
 Sof(H8B)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=1-FVAR(2)
 Sof(H8A)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=FVAR(2)
 Sof(C55A)=Sof(H55D)=Sof(H55E)=Sof(H55F)=Sof(C54A)=Sof(H54D)=Sof(H54E)=
 Sof(H54F)=Sof(C56A)=Sof(H56D)=Sof(H56E)=Sof(H56F)=1-FVAR(3)
 Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=
 Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=FVAR(3)
 Fixed Sof: H60A(0.33333) H60B(0.33333) H60C(0.33333)
6.a Riding coordinates:
 C33A(H33D,H33E,H33F), C56A(H56D,H56E,H56F)
6.b Ternary CH refined with riding coordinates:
 C11(H11), C8(H8A), C8(H8B)
6.c Secondary CH2 refined with riding coordinates:
 C35(H35A,H35B), C24(H24A,H24B), C46(H46A,H46B), C018(H01A,H01B)
6.d Aromatic/amide H refined with riding coordinates:
 C4(H4), C1(H1), C6(H6), C28(H28), C26(H26), C37(H37), C39(H39), C16(H16),
 C18(H18), C48(H48), C50(H50)
6.e Idealised Me refined as rotating group:
 C45(H45A,H45B,H45C), C44(H44A,H44B,H44C), C12(H12A,H12B,H12C), C43(H43A,H43B,
 H43C), C10(H10A,H10B,H10C), C13(H13A,H13B,H13C), C21(H21A,H21B,H21C), C22(H22A,
 H22B,H22C), C23(H23A,H23B,H23C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C),
 C33(H33A,H33B,H33C), C5A(H5AA,H5AB,H5AC), C34A(H34D,H34E,H34F), C9(H9A,H9B,
 H9C), C56(H56A,H56B,H56C), C55(H55A,H55B,H55C), C54(H54A,H54B,H54C), C55A(H55D,
 H55E,H55F), C54A(H54D,H54E,H54F), C9A(H9AA,H9AB,H9AC), C57(H57A,H57B,H57C),
 C60(H60A,H60B,H60C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 390 electrons were 
found in a volume of 6825\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 2[C2H3N], 4[C2H3N] per Formula Unit 
which account for 396 electrons per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              23939
_shelx_hkl_checksum              9926
_shelx_fab_checksum              6772
_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 2.510
_oxdiff_exptl_absorpt_empirical_full_min 0.813