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_7130390
_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         'C90 H110 O10 Ti2, 4[CH4O]'
_chemical_formula_sum            'C94 H126 O14 Ti2'
_chemical_formula_weight         1575.74
_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             2022-06-28
_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                 102.0212(17)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.8135(4)
_cell_length_b                   22.9853(4)
_cell_length_c                   23.1531(4)
_cell_measurement_reflns_used    30285
_cell_measurement_temperature    150
_cell_measurement_theta_max      76.7450
_cell_measurement_theta_min      2.7140
_cell_volume                     10313.1(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 2013/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.965
_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      4.00  30.00   0.50    5.22    --   47.45 -44.00 -21.00   52
  2  \w     38.00  85.00   0.50   16.00    --  107.75 -77.00  60.00   94
  3  \w     75.00 102.00   0.50   16.00    --  107.75-125.00   0.00   54
  4  \w     45.00  71.00   0.50   16.00    --  107.75 -61.00 -90.00   52
  5  \w     59.00  98.00   0.50   16.00    --  107.75 -77.00-120.00   78
  6  \w     81.00 106.00   0.50   16.00    --  107.75 -77.00-180.00   50
  7  \w     43.00 103.00   0.50   16.00    --  107.75 -77.00-150.00  120
  8  \w     67.00 128.00   0.50   16.00    --  107.75   0.00 -60.00  122
  9  \w    113.00 176.00   0.50   16.00    --  107.75  45.00-120.00  126
 10  \w    130.00 163.00   0.50   16.00    --  107.75 125.00 -60.00   66
 11  \w     93.00 146.00   0.50   16.00    --  107.75  61.00  30.00  106
 12  \w    143.00 168.00   0.50   16.00    --  107.75  15.00  60.00   50
 13  \w     98.00 126.00   0.50   16.00    --  107.75  15.00  60.00   56
 14  \w     98.00 175.00   0.50   16.00    --  107.75  44.00 128.00  154
 15  \w     92.00 125.00   0.50   16.00    --  107.75 125.00 -60.00   66
 16  \w     52.00 112.00   0.50    5.22    --   47.45  44.00 128.00  120
 17  \w     40.00  67.00   0.50   16.00    --  107.75 -61.00 120.00   54
 18  \w     50.00 103.00   0.50   16.00    --  107.75 -77.00 120.00  106
 19  \w     40.00  99.00   0.50   16.00    --  107.75 -77.00  90.00  118
 20  \w     43.00  69.00   0.50   16.00    --  107.75 -61.00  30.00   52
 21  \w     40.00 105.00   0.50   16.00    --  107.75 -77.00 -30.00  130
 22  \w     35.00  92.00   0.50   16.00    --  107.75 -94.00 -30.00  114
 23  \w     35.00  71.00   0.50   16.00    --  107.75 -61.00-150.00   72
 24  \w     38.00  64.00   0.50   16.00    --  107.75 -61.00-120.00   52
 25  \w     46.00  71.00   0.50   16.00    --  107.75 -61.00-180.00   50
 26  \w     37.00  62.00   0.50   16.00    --  107.75 -61.00 -30.00   50
 27  \w     35.00  64.00   0.50   16.00    --  107.75 -77.00  30.00   58
 28  \w     35.00  61.00   0.50   16.00    --  107.75-125.00   0.00   52
 29  \w    -31.00  20.00   0.50    5.22    --  -47.45  44.00 128.00  102
 30  \w    -49.00 -18.00   0.50   16.00    --  -86.25  44.00 128.00   62
 31  \w    -89.00 -48.00   0.50    5.22    --  -47.45 125.00 -30.00   82
 32  \w    -50.00 -16.00   0.50   16.00    --  -86.25  45.00 -60.00   68
 33  \w    -26.00  26.00   0.50    5.22    --  -47.45  19.00 -60.00  104
 34  \w   -117.00 -34.00   0.50    5.22    --  -47.45 -44.00 -21.00  166
 35  \w   -116.00 -71.00   0.50    5.22    --  -47.45-125.00 -60.00   90
 36  \w   -140.00-115.00   0.50   16.00    --  -86.25 -44.00 -21.00   50
;
_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      -0.0747373000
_diffrn_orient_matrix_UB_12      0.0223129000
_diffrn_orient_matrix_UB_13      -0.0174656000
_diffrn_orient_matrix_UB_21      0.0171919000
_diffrn_orient_matrix_UB_22      0.0300832000
_diffrn_orient_matrix_UB_23      -0.0546551000
_diffrn_orient_matrix_UB_31      -0.0206880000
_diffrn_orient_matrix_UB_32      -0.0556299000
_diffrn_orient_matrix_UB_33      -0.0365612000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0707
_diffrn_reflns_av_unetI/netI     0.0570
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            102523
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.435
_diffrn_reflns_theta_min         2.675
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.668
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81457
_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    1.015
_exptl_crystal_description       block
_exptl_crystal_F_000             3096
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.5
_refine_diff_density_max         0.682
_refine_diff_density_min         -0.400
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1190
_refine_ls_number_reflns         21636
_refine_ls_number_restraints     314
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0842
_refine_ls_R_factor_gt           0.0648
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.1236P)^2^+0.7802P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1852
_refine_ls_wR_factor_ref         0.2004
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15750
_reflns_number_total             21636
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc03131k2.cif
_cod_data_source_block           Ti2-MeOH
_cod_database_code               7130390
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         CHONTi
_shelx_estimated_absorpt_t_max   0.489
_shelx_estimated_absorpt_t_min   0.489
_olex2_refinement_description
;
1. Restrained distances
 C1-C2
 1.55 with sigma of 0.01
 C4-C2
 1.45 with sigma of 0.01
 C5-C2
 1.45 with sigma of 0.01
 C4-C1
 2.2 with sigma of 0.01
2. Rigid bond restraints
 C9, C91
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C79, C95A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O13, C40
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C33, C91
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C41, C81
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C54, C67
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C56, C57
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C56, C69
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C58, C75
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C60, C77
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C68, C69
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C33, C32
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C36, C32
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C83, C84
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C89, C78A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C70, C74A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
3. Uiso/Uaniso restraints and constraints
C79 \\sim C95A: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C89 \\sim C78A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C70 \\sim C74A: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
Uanis(C86) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C80) \\sim Ueq, Uanis(C10)
\\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C5) \\sim Ueq,
Uanis(C7) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4A) \\sim Ueq, Uanis(C5A)
\\sim Ueq, Uanis(C6A) \\sim Ueq, Uanis(C6B) \\sim Ueq, Uanis(C4B) \\sim Ueq,
Uanis(C8) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C12A) \\sim Ueq, Uanis(C16A)
\\sim Ueq, Uanis(C90A) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C4) \\sim Ueq,
Uanis(C6) \\sim Ueq, Uanis(C88A) \\sim Ueq, Uanis(C15A) \\sim Ueq, Uanis(C80A)
\\sim Ueq, Uanis(C86A) \\sim Ueq, Uanis(C24A) \\sim Ueq, Uanis(C22) \\sim Ueq,
Uanis(C94A) \\sim Ueq, Uanis(C95A) \\sim Ueq, Uanis(C96A) \\sim Ueq,
Uanis(C14A) \\sim Ueq, Uanis(C18A) \\sim Ueq, Uanis(C74A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C4B)=Sof(H4BA)=Sof(H4BB)=Sof(H4BC)=Sof(C5B)=Sof(H5BA)=Sof(H5BB)=Sof(H5BC)=
 Sof(C6B)=Sof(H6BA)=Sof(H6BB)=Sof(H6BC)=1-FVAR(1)
 Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=
 Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=FVAR(1)
 Sof(C12A)=Sof(H12D)=Sof(H12E)=Sof(H12F)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=1-FVAR(2)
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=
 Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(2)
 Sof(C90A)=Sof(H90D)=Sof(H90E)=Sof(H90F)=Sof(C22A)=Sof(H22D)=Sof(H22E)=
 Sof(H22F)=Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(3)
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=
 Sof(C90)=Sof(H90A)=Sof(H90B)=Sof(H90C)=FVAR(3)
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C1)=
 Sof(H1A)=Sof(H1B)=Sof(H1C)=1-FVAR(4)
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C5)=
 Sof(H5A)=Sof(H5B)=Sof(H5C)=FVAR(4)
 Sof(C88A)=Sof(H88D)=Sof(H88E)=Sof(H88F)=Sof(C78A)=Sof(H78D)=Sof(H78E)=
 Sof(H78F)=Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=1-FVAR(5)
 Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(H78C)=Sof(C88)=Sof(H88A)=Sof(H88B)=Sof(H88C)=
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(5)
 Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C80A)=Sof(H80D)=Sof(H80E)=
 Sof(H80F)=Sof(C86A)=Sof(H86D)=Sof(H86E)=Sof(H86F)=1-FVAR(6)
 Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(H80C)=Sof(C86)=Sof(H86A)=Sof(H86B)=Sof(H86C)=
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(6)
 Sof(C96A)=Sof(H96D)=Sof(H96E)=Sof(H96F)=Sof(C94A)=Sof(H94D)=Sof(H94E)=
 Sof(H94F)=Sof(C95A)=Sof(H95D)=Sof(H95E)=Sof(H95F)=1-FVAR(7)
 Sof(C94)=Sof(H94A)=Sof(H94B)=Sof(H94C)=Sof(C96)=Sof(H96A)=Sof(H96B)=Sof(H96C)=
 Sof(C95)=Sof(H95A)=Sof(H95B)=Sof(H95C)=FVAR(7)
 Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C74A)=Sof(H74D)=Sof(H74E)=
 Sof(H74F)=Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=1-FVAR(8)
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=
 Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=FVAR(8)
5.a Riding coordinates:
 C47(H47A,H47B,H47C), C4A(H4AA,H4AB,H4AC), C74A(H74D,H74E,H74F)
5.b Secondary CH2 refined with riding coordinates:
 C53(H53A,H53B), C28(H28A,H28B), C42(H42A,H42B), C35(H35A,H35B), C61(H61A,
 H61B), C49(H49A,H49B), C57(H57A,H57B), C73(H73A,H73B)
5.c Aromatic/amide H refined with riding coordinates:
 C26(H26), C65(H65), C83(H83), C69(H69), C63(H63), C85(H85), C82(H82),
 C37(H37), C67(H67), C81(H81), C75(H75), C77(H77), C39(H39), C20(H20), C32(H32),
  C34(H34)
5.d Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C14(H14A,H14B,H14C), C18(H18A,H18B,H18C), C22(H22A,H22B,
 H22C), C74(H74A,H74B,H74C), C16(H16A,H16B,H16C), C78(H78A,H78B,H78C), C88(H88A,
 H88B,H88C), C90(H90A,H90B,H90C), C3(H3A,H3B,H3C), C15(H15A,H15B,H15C), C7(H7A,
 H7B,H7C), C94(H94A,H94B,H94C), C96(H96A,H96B,H96C), C95(H95A,H95B,H95C),
 C80(H80A,H80B,H80C), C86(H86A,H86B,H86C), C24(H24A,H24B,H24C), C5(H5A,H5B,H5C),
  C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C6A(H6AA,H6AB,
 H6AC), C5A(H5AA,H5AB,H5AC), C4B(H4BA,H4BB,H4BC), C5B(H5BA,H5BB,H5BC), C6B(H6BA,
 H6BB,H6BC), C12A(H12D,H12E,H12F), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C90A(H90D,
 H90E,H90F), C22A(H22D,H22E,H22F), C16A(H16D,H16E,H16F), C4(H4A,H4B,H4C),
 C6(H6A,H6B,H6C), C1(H1A,H1B,H1C), C88A(H88D,H88E,H88F), C78A(H78D,H78E,H78F),
 C15A(H15D,H15E,H15F), C24A(H24D,H24E,H24F), C80A(H80D,H80E,H80F), C86A(H86D,
 H86E,H86F), C96A(H96D,H96E,H96F), C94A(H94D,H94E,H94F), C95A(H95D,H95E,H95F),
 C18A(H18D,H18E,H18F), C14A(H14D,H14E,H14F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 296 electrons were 
found in a volume of 3069\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 4[CH4O] per Formula Unit 
which account for 288 electrons per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              24819
_shelx_hkl_checksum              8136
_shelx_fab_checksum              35876
_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 1.583
_oxdiff_exptl_absorpt_empirical_full_min 0.566