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_7130392
_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         'C106 H142 N2 O16 Ti4'
_chemical_formula_sum            'C106 H142 N2 O16 Ti4'
_chemical_formula_weight         1891.81
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_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                90.5700(10)
_cell_angle_beta                 105.9730(10)
_cell_angle_gamma                114.5140(10)
_cell_formula_units_Z            1
_cell_length_a                   12.37700(10)
_cell_length_b                   12.6781(2)
_cell_length_c                   19.3873(2)
_cell_measurement_reflns_used    17259
_cell_measurement_temperature    150
_cell_measurement_theta_max      76.4460
_cell_measurement_theta_min      2.3910
_cell_volume                     2634.17(6)
_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                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.960
_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    -42.00  25.00   0.50    0.54    --  -47.70  37.00   0.00  134
  2  \w    -24.00  28.00   0.50    0.54    --  -47.70  19.00 -60.00  104
  3  \w    -41.00  25.00   0.50    0.54    --  -47.70  37.00  60.00  132
  4  \w    -50.00 -25.00   0.50    2.14    --  -86.25  45.00  90.00   50
  5  \w    -79.00  25.00   0.50    0.54    --  -47.70 100.00  74.00  208
  6  \w    -13.00  23.00   0.50    0.54    --   47.70 -19.00  60.00   72
  7  \w      0.00  25.00   0.50    0.54    --   47.70-100.00 -31.00   50
  8  \w     28.00  54.00   0.50    0.54    --   47.70-100.00 -31.00   52
  9  \w     40.00  73.00   0.50    2.14    --  106.49-100.00 -31.00   66
 10  \w     44.00  71.00   0.50    2.14    --  106.49 -61.00 -30.00   54
 11  \w     83.00 108.00   0.50    2.14    --  106.49 -94.00  30.00   50
 12  \w     92.00 117.00   0.50    2.14    --  106.49-125.00 120.00   50
 13  \w     34.00 117.00   0.50    2.14    --  106.49-125.00 150.00  166
 14  \w     44.00  70.00   0.50    2.14    --  106.49 -61.00 120.00   52
 15  \w     40.00 103.00   0.50    2.14    --  106.49 -94.00 150.00  126
 16  \w     46.00 133.00   0.50    2.14    --  106.49-148.00  41.93  174
 17  \w     64.00 117.00   0.50    2.14    --  106.49-125.00-120.00  106
 18  \w     78.00 108.00   0.50    2.14    --  106.49 -94.00-150.00   60
 19  \w     37.00  69.00   0.50    2.14    --  106.49 -61.00-150.00   64
 20  \w     34.00 101.00   0.50    2.14    --  106.49 -77.00-150.00  134
 21  \w     34.00  92.00   0.50    2.14    --  106.49-125.00 -30.00  116
 22  \w     37.00 100.00   0.50    2.14    --  106.49-125.00  30.00  126
 23  \w     45.00 107.00   0.50    2.14    --  106.49-125.00  60.00  124
 24  \w     44.00  77.00   0.50    2.14    --  106.49-125.00 120.00   66
 25  \w     35.00  71.00   0.50    2.14    --  106.49 -61.00 150.00   72
 26  \w     93.00 173.00   0.50    2.14    --  106.49  15.00 150.00  160
 27  \w    115.00 178.00   0.50    2.14    --  106.49  15.00  60.00  126
 28  \w    116.00 165.00   0.50    2.14    --  106.49  30.00   0.00   98
 29  \w    105.00 131.00   0.50    2.14    --  106.49 100.00  74.00   52
 30  \w     86.00 173.00   0.50    2.14    --  106.49  77.00  30.00  174
 31  \w    108.00 177.00   0.50    2.14    --  106.49  30.00 -60.00  138
 32  \w    134.00 159.00   0.50    2.14    --  106.49  30.00-150.00   50
 33  \w    104.00 131.00   0.50    2.14    --  106.49  30.00-150.00   54
 34  \w    -69.00 -16.00   0.50    2.14    --  -86.25  61.00 120.00  106
 35  \w    -83.00 -58.00   0.50    2.14    --  -86.25 100.00  74.00   50
 36  \w    -71.00 -44.00   0.50    2.14    --  -86.25  61.00-180.00   54
 37  \w   -137.00-111.00   0.50    2.14    --  -86.25-100.00 -31.00   52
 38  \w   -156.00-113.00   0.50    2.14    --  -86.25 -94.00  60.00   86
 39  \w   -129.00-102.00   0.50    2.14    --  -86.25 -94.00 120.00   54
 40  \w   -106.00 -70.00   0.50    0.54    --  -47.70-125.00 120.00   72
 41  \w   -119.00 -72.00   0.50    0.54    --  -47.70-125.00  90.00   94
 42  \w   -114.00 -89.00   0.50    0.54    --  -47.70-125.00-150.00   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      -0.0002698000
_diffrn_orient_matrix_UB_12      0.0405818000
_diffrn_orient_matrix_UB_13      -0.0746578000
_diffrn_orient_matrix_UB_21      -0.1432004000
_diffrn_orient_matrix_UB_22      -0.0683917000
_diffrn_orient_matrix_UB_23      -0.0277683000
_diffrn_orient_matrix_UB_31      -0.0124560000
_diffrn_orient_matrix_UB_32      0.1089885000
_diffrn_orient_matrix_UB_33      0.0250412000
_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  0.0463
_diffrn_reflns_av_unetI/netI     0.0463
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            34723
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.902
_diffrn_reflns_theta_min         2.395
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.977
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72489
_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    1.193
_exptl_crystal_description       block
_exptl_crystal_F_000             1008
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.612
_refine_diff_density_min         -0.855
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     781
_refine_ls_number_reflns         10672
_refine_ls_number_restraints     167
_refine_ls_restrained_S_all      1.129
_refine_ls_R_factor_all          0.0665
_refine_ls_R_factor_gt           0.0537
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0867P)^2^+1.1367P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1498
_refine_ls_wR_factor_ref         0.1568
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9118
_reflns_number_total             10672
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc03131k2.cif
_cod_data_source_block           Ti4-DMF
_cod_database_code               7130392
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         CHONTi
_shelx_estimated_absorpt_t_max   0.469
_shelx_estimated_absorpt_t_min   0.318
_olex2_refinement_description
;
1. Restrained distances
 N58-C55
 1.45 with sigma of 0.01
 C19A-C17A
 2.2 with sigma of 0.01
2. Rigid bond restraints
 C24, C1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C55, O56
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C55, N58
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
3. Uiso/Uaniso restraints and constraints
C7 \\sim C14: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C7 \\sim C15: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C7 \\sim C16: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
N58 \\sim C60A: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
N58 \\sim C59A: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
N58 \\sim C60: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
N58 \\sim C59: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C8) \\sim
Ueq, Uanis(C57) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C23) \\sim Ueq,
Uanis(C10) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C58)
\\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C15) \\sim Ueq,
Uanis(C11) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C59)
\\sim Ueq, Uanis(C16A) \\sim Ueq, Uanis(C15A) \\sim Ueq, Uanis(C6A) \\sim Ueq,
Uanis(C59) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C17A) \\sim Ueq, Uanis(C17)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=1-FVAR(1)
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=FVAR(1)
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(H61C)=
 Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=1-FVAR(2)
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=FVAR(2)
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=1-FVAR(3)
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=FVAR(3)
 Sof(C55A)=Sof(H55A)=Sof(C59A)=Sof(H59D)=Sof(H59E)=Sof(H59F)=Sof(C60A)=
 Sof(H60D)=Sof(H60E)=Sof(H60F)=1-FVAR(4)
 Sof(C55)=Sof(H55)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=Sof(C59)=Sof(H59A)=
 Sof(H59B)=Sof(H59C)=FVAR(4)
 Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(C14A)=Sof(H14D)=Sof(H14E)=
 Sof(H14F)=Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=1-FVAR(5)
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=FVAR(5)
 Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=
 1-FVAR(6)
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=
 FVAR(6)
 Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(C19A)=Sof(H19D)=Sof(H19E)=
 Sof(H19F)=1-FVAR(7)
 Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=
 FVAR(7)
5.a Secondary CH2 refined with riding coordinates:
 C52(H52A,H52B), C32(H32A,H32B), C54(H54A,H54B), C40(H40A,H40B)
5.b Aromatic/amide H refined with riding coordinates:
 C49(H49), C25(H25), C47(H47), C29(H29), C44(H44), C37(H37), C35(H35),
 C41(H41), C55(H55), C55A(H55A)
5.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C3(H3A,H3B,H3C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C),
 C11(H11A,H11B,H11C), C16(H16A,H16B,H16C), C14(H14A,H14B,H14C), C13(H13A,H13B,
 H13C), C60(H60A,H60B,H60C), C19(H19A,H19B,H19C), C59(H59A,H59B,H59C), C10(H10A,
 H10B,H10C), C12(H12A,H12B,H12C), C8(H8A,H8B,H8C), C6(H6A,H6B,H6C), C5(H5A,H5B,
 H5C), C21(H21A,H21B,H21C), C57(H57A,H57B,H57C), C23(H23A,H23B,H23C), C22(H22A,
 H22B,H22C), C61(H61A,H61B,H61C), C20(H20A,H20B,H20C), C58(H58A,H58B,H58C),
 C4(H4A,H4B,H4C), C2(H2A,H2B,H2C), C1(H1A,H1B,H1C), C59A(H59D,H59E,H59F),
 C60A(H60D,H60E,H60F), C16A(H16D,H16E,H16F), C14A(H14D,H14E,H14F), C15A(H15D,
 H15E,H15F), C6A(H6AA,H6AB,H6AC), C5A(H5AA,H5AB,H5AC), C17A(H17D,H17E,H17F),
 C19A(H19D,H19E,H19F)
;
_shelx_res_checksum              37676
_shelx_hkl_checksum              13410
_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 1.515
_oxdiff_exptl_absorpt_empirical_full_min 0.587