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_7130391
_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         'C100 H136 O16 Ti4'
_chemical_formula_sum            'C100 H136 O16 Ti4'
_chemical_formula_weight         1785.68
_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   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                80.451(3)
_cell_angle_beta                 76.371(3)
_cell_angle_gamma                65.491(3)
_cell_formula_units_Z            1
_cell_length_a                   12.0088(4)
_cell_length_b                   12.1232(4)
_cell_length_c                   18.4541(5)
_cell_measurement_reflns_used    7801
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      75.0670
_cell_measurement_theta_min      2.4780
_cell_volume                     2368.67(14)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_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_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.969
_diffrn_measured_fraction_theta_max 0.910
_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    -29.00  18.00   1.00    3.00    --  -47.45  19.00  60.00   47
  2  \w    -63.00 -29.00   1.00   10.00    -- -100.00  57.00  90.00   34
  3  \w    -69.00 -35.00   1.00   10.00    -- -100.00  57.00 150.00   34
  4  \w    -91.00 -63.00   1.00    3.00    --  -47.45 141.00  22.00   28
  5  \w    -69.00 -43.00   1.00   10.00    -- -100.00 151.00 -20.82   26
  6  \w    -97.00 -35.00   1.00    3.00    --  -47.45 128.00-149.00   62
  7  \w    -69.00 -27.00   1.00   10.00    -- -100.00  57.00 -60.00   42
  8  \w    -28.00  -3.00   1.00    3.00    --  -47.45  19.00-120.00   25
  9  \w     74.00 103.00   1.00    3.00    --   47.45 128.00-149.00   29
 10  \w     76.00 128.00   1.00   10.00    --  107.75 128.00-149.00   52
 11  \w     68.00 107.00   1.00    3.00    --   47.45 141.00  22.00   39
 12  \w     95.00 120.00   1.00   10.00    --  107.75 141.00  22.00   25
 13  \w     29.00 120.00   1.00    3.00    --   47.45  77.00-180.00   91
 14  \w     37.00  63.00   1.00   10.00    --  107.75 -57.00  30.00   26
 15  \w     38.00  63.00   1.00   10.00    --  107.75 -57.00   0.00   25
 16  \w     35.00 101.00   1.00   10.00    --  107.75 -99.00 -60.00   66
 17  \w     86.00 123.00   1.00   10.00    --  107.75-141.00 -35.00   37
 18  \w     57.00  95.00   1.00    3.00    --   47.45-141.00 -35.00   38
 19  \w     37.00  62.00   1.00   10.00    --  107.75 -57.00 -60.00   25
 20  \w     40.00  96.00   1.00   10.00    --  107.75 -99.00 -30.00   56
 21  \w     38.00  92.00   1.00   10.00    --  107.75 -99.00   0.00   54
 22  \w     37.00  62.00   1.00   10.00    --  107.75 -57.00 -30.00   25
 23  \w     36.00  62.00   1.00   10.00    --  107.75 -57.00 -90.00   26
 24  \w     43.00 104.00   1.00   10.00    --  107.75-125.00-180.00   61
 25  \w     75.00 101.00   1.00   10.00    --  107.75 -99.00-180.00   26
 26  \w     35.00  63.00   1.00   10.00    --  107.75 -57.00-180.00   28
 27  \w    -19.00  20.00   1.00    3.00    --   47.45 -19.00-120.00   39
 28  \w    -27.00  16.00   1.00    3.00    --   47.45 -19.00-150.00   43
 29  \w   -119.00 -83.00   1.00    3.00    --  -47.45-141.00 -35.00   36
 30  \w     37.00  64.00   1.00    3.00    --   47.45-128.00 136.00   27
 31  \w     50.00  75.00   1.00   10.00    --  107.75-128.00 136.00   25
 32  \w     35.00 112.00   1.00   10.00    --  107.75-125.00 150.00   77
 33  \w     41.00 101.00   1.00   10.00    --  107.75 -77.00 150.00   60
 34  \w   -120.00 -79.00   1.00   10.00    -- -100.00-141.00 -35.00   41
 35  \w   -125.00 -92.00   1.00   10.00    -- -100.00 -99.00 -90.00   33
 36  \w   -114.00 -87.00   1.00   10.00    -- -100.00 -37.00-150.00   27
 37  \w   -148.00-118.00   1.00   10.00    -- -100.00 -99.00-180.00   30
 38  \w   -169.00-144.00   1.00   10.00    -- -100.00 -99.00 -90.00   25
 39  \w   -168.00-136.00   1.00   10.00    -- -100.00 -37.00-150.00   32
 40  \w   -169.00 -92.00   1.00   10.00    -- -100.00 -37.00-180.00   77
 41  \w   -164.00-119.00   1.00   10.00    -- -100.00 -19.00   0.00   45
 42  \w   -151.00-126.00   1.00   10.00    -- -100.00-128.00 136.00   25
 43  \w   -122.00 -83.00   1.00   10.00    -- -100.00-125.00  90.00   39
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0209398000
_diffrn_orient_matrix_UB_12      -0.0266682000
_diffrn_orient_matrix_UB_13      0.0855889000
_diffrn_orient_matrix_UB_21      0.0909356000
_diffrn_orient_matrix_UB_22      -0.1332961000
_diffrn_orient_matrix_UB_23      -0.0093472000
_diffrn_orient_matrix_UB_31      0.1090035000
_diffrn_orient_matrix_UB_32      0.0337845000
_diffrn_orient_matrix_UB_33      0.0031543000
_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  0.0458
_diffrn_reflns_av_unetI/netI     0.0504
_diffrn_reflns_Laue_measured_fraction_full 0.969
_diffrn_reflns_Laue_measured_fraction_max 0.910
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            26973
_diffrn_reflns_point_group_measured_fraction_full 0.969
_diffrn_reflns_point_group_measured_fraction_max 0.910
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.552
_diffrn_reflns_theta_min         2.471
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.274
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85024
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
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    1.252
_exptl_crystal_description       block
_exptl_crystal_F_000             952
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.600
_refine_diff_density_min         -0.846
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     725
_refine_ls_number_reflns         9191
_refine_ls_number_restraints     136
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0765
_refine_ls_R_factor_gt           0.0541
_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^)+(0.0712P)^2^+1.2747P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1381
_refine_ls_wR_factor_ref         0.1519
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6821
_reflns_number_total             9191
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc03131k2.cif
_cod_data_source_block           Ti4-EtOH
_cod_original_cell_volume        2368.67(15)
_cod_database_code               7130391
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.440
_shelx_estimated_absorpt_t_min   0.291
_olex2_refinement_description
;
1. Restrained distances
 O1-H1B
 0.85 with sigma of 0.01
 O1-H1A
 0.85 with sigma of 0.01
 Ti1-H1B
 2.39302 with sigma of 0.02
 Ti1-H1A
 2.437614 with sigma of 0.02
 C4-H1B
 1.883275 with sigma of 0.02
 C2-H1A
 1.853119 with sigma of 0.02
 C00S-C52 \\sim C00S-C8A
 with sigma of 0.02
 C00S-C46 \\sim C00S-C3A
 with sigma of 0.02
 C00S-C48 \\sim C00S-C7A
 with sigma of 0.02
2. Rigid bond restraints
 C00S, C3A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C47) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C45)
\\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C41) \\sim Ueq,
Uanis(C33) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C35)
\\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C3A) \\sim Ueq, Uanis(C48) \\sim Ueq,
Uanis(C7A) \\sim Ueq, Uanis(C30) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C29) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C42A)
\\sim Ueq, Uanis(C38A) \\sim Ueq, Uanis(C48) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
4. Others
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C32)=Sof(H32A)=Sof(H32B)=1-FVAR(1)
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=FVAR(1)
 Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=
 Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=1-FVAR(2)
 Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=
 Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(H48C)=FVAR(2)
 Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C43)=1-FVAR(3)
 Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=Sof(C53)=Sof(C47)=Sof(H47A)=Sof(H47B)=
 Sof(H47C)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=FVAR(3)
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=1-FVAR(4)
 Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=
 Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=FVAR(4)
 Sof(H1B)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=Sof(C4)=Sof(H4A)=Sof(H4B)=1-
 FVAR(5)
 Sof(H1A)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=Sof(C2)=Sof(H2A)=Sof(H2B)=
 FVAR(5)
 Sof(C42A)=Sof(H42D)=Sof(H42E)=Sof(H42F)=Sof(C38A)=Sof(H38D)=Sof(H38E)=
 Sof(H38F)=1-FVAR(6)
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=
 FVAR(6)
5.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C22(H22A,H22B), C15(H15A,H15B), C1(H1C,H1D), C011(H01A,H01B),
 C31(H31A,H31B), C2(H2A,H2B), C4(H4A,H4B), C32(H32A,H32B)
5.b Aromatic/amide H refined with riding coordinates:
 C19(H19), C28(H28), C26(H26), C12(H12), C17(H17), C9(H9), C44(H44), C54(H54)
5.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C56(H56A,H56B,H56C), C36(H36A,H36B,H36C), C37(H37A,H37B,
 H37C), C45(H45A,H45B,H45C), C47(H47A,H47B,H47C), C55(H55A,H55B,H55C), C29(H29A,
 H29B,H29C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C41(H41A,H41B,H41C),
 C59(H59A,H59B,H59C), C57(H57A,H57B,H57C), C35(H35A,H35B,H35C), C33(H33A,H33B,
 H33C), C34(H34A,H34B,H34C), C30(H30A,H30B,H30C), C52(H52A,H52B,H52C), C46(H46A,
 H46B,H46C), C48(H48A,H48B,H48C), C8A(H8AA,H8AB,H8AC), C7A(H7AA,H7AB,H7AC),
 C3A(H3AA,H3AB,H3AC), C39(H39A,H39B,H39C), C38(H38A,H38B,H38C), C42(H42A,H42B,
 H42C), C42A(H42D,H42E,H42F), C38A(H38D,H38E,H38F)
;
_shelx_res_checksum              5317
_shelx_hkl_checksum              92338
_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 1.975
_oxdiff_exptl_absorpt_empirical_full_min 0.535