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_7130393
_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         '2(C50 H66 O7 Ti2)'
_chemical_formula_sum            'C100 H132 O14 Ti4'
_chemical_formula_weight         1749.65
_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                98.670(3)
_cell_angle_beta                 102.662(4)
_cell_angle_gamma                101.765(4)
_cell_formula_units_Z            2
_cell_length_a                   15.0667(7)
_cell_length_b                   16.2142(8)
_cell_length_c                   21.1278(5)
_cell_measurement_reflns_used    9180
_cell_measurement_temperature    149.98(11)
_cell_measurement_theta_max      72.6350
_cell_measurement_theta_min      2.8170
_cell_volume                     4825.8(4)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.98(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.939
_diffrn_measured_fraction_theta_max 0.998
_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    -65.00 -23.00   0.75    6.00    --  -43.05  88.00  63.00   56
  2  \w      4.00  30.25   0.75    6.00    --  -43.05  88.00  63.00   35
  3  \w    -37.00  23.00   0.75    6.00    --   43.05 -19.00  30.00   80
  4  \w    -15.00  74.25   0.75    6.00    --   43.05 -88.00 -53.00  119
  5  \w      6.00  39.00   0.75    6.00    --   43.05 -37.00-150.00   44
  6  \w    -30.00  39.00   0.75    6.00    --   43.05 -37.00 -30.00   92
  7  \w    -29.00  -0.50   0.75    6.00    --   43.05 -37.00-150.00   38
  8  \w    -37.00  22.25   0.75    6.00    --   43.05 -19.00 -90.00   79
  9  \w    -35.00  -8.75   0.75    6.00    --   43.05 -19.00 -60.00   35
 10  \w     58.00  96.25   0.75   16.00    --  109.26 -94.00 -90.00   51
 11  \w     75.00 101.25   0.75   16.00    --  109.26 -77.00-180.00   35
 12  \w     36.00  66.00   0.75   16.00    --  109.26 -61.00 -60.00   40
 13  \w     35.00  90.50   0.75   16.00    --  109.26 -88.00 -53.00   74
 14  \w     48.00 103.50   0.75   16.00    --  109.26 -94.00  30.00   74
 15  \w     36.00  95.25   0.75   16.00    --  109.26-125.00 150.00   79
 16  \w     80.00 169.25   0.75   16.00    --  109.26  77.00 120.00  119
 17  \w    143.00 168.50   0.75   16.00    --  109.26  88.00  63.00   34
 18  \w     78.00 121.50   0.75   16.00    --  109.26  88.00  63.00   58
 19  \w     52.00  98.50   0.75    6.00    --   43.05 179.00 -90.00   62
 20  \w    -54.00 -28.50   0.75   16.00    -- -100.00  45.00  30.00   34
 21  \w    -54.00 -27.00   0.75   16.00    -- -100.00  45.00  60.00   36
 22  \w    -80.00 -53.75   0.75   16.00    -- -100.00  88.00  63.00   35
 23  \w    -59.00 -29.75   0.75   16.00    -- -100.00 125.00 120.00   39
 24  \w    -69.00 -42.75   0.75   16.00    -- -100.00 125.00   0.00   35
 25  \w    -55.00 -25.75   0.75   16.00    -- -100.00  61.00 -90.00   39
 26  \w    -80.00 -32.00   0.75   16.00    -- -100.00 142.00-126.60   64
 27  \w    -89.00 -26.75   0.75   16.00    -- -100.00 125.00-180.00   83
 28  \w   -107.00 -74.75   0.75   16.00    -- -100.00  77.00-180.00   43
 29  \w   -123.00 -90.75   0.75   16.00    -- -100.00 142.00-126.60   43
 30  \w   -112.00 -26.50   0.75   16.00    -- -100.00 125.00 -30.00  114
 31  \w   -110.00 -53.75   0.75   16.00    -- -100.00 125.00  30.00   75
 32  \w   -112.00 -79.00   0.75   16.00    -- -100.00 125.00   0.00   44
 33  \w   -126.00 -33.75   0.75   16.00    -- -100.00 145.00 109.40  123
 34  \w   -112.00 -62.50   0.75   16.00    -- -100.00 125.00 120.00   66
 35  \w   -174.00-106.50   0.75   16.00    -- -100.00 -45.00  60.00   90
 36  \w   -135.00-108.75   0.75   16.00    -- -100.00 -94.00  60.00   35
 37  \w   -139.00 -82.00   0.75   16.00    -- -100.00-125.00 120.00   76
 38  \w   -120.00 -48.75   0.75    6.00    --  -43.05-179.00  30.00   95
 39  \w   -156.00-130.50   0.75   16.00    -- -100.00 -94.00   0.00   34
 40  \w   -159.00 -77.25   0.75   16.00    -- -100.00 -61.00 -30.00  109
 41  \w   -118.00 -76.75   0.75   16.00    -- -100.00 -30.00-150.00   55
 42  \w   -171.00-120.75   0.75   16.00    -- -100.00 -30.00-150.00   67
 43  \w   -172.00 -92.50   0.75   16.00    -- -100.00 -88.00 -53.00  106
 44  \w   -169.00-143.50   0.75   16.00    -- -100.00 -94.00  60.00   34
 45  \w   -168.00-142.50   0.75   16.00    -- -100.00-125.00 120.00   34
 46  \w     40.00 110.50   0.75   16.00    --  109.26-125.00-120.00   94
;
_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      0.0178257000
_diffrn_orient_matrix_UB_12      -0.0244766000
_diffrn_orient_matrix_UB_13      -0.0686379000
_diffrn_orient_matrix_UB_21      0.0197581000
_diffrn_orient_matrix_UB_22      0.0954139000
_diffrn_orient_matrix_UB_23      -0.0052860000
_diffrn_orient_matrix_UB_31      0.1047849000
_diffrn_orient_matrix_UB_32      0.0113027000
_diffrn_orient_matrix_UB_33      0.0330159000
_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  0.1313
_diffrn_reflns_av_unetI/netI     0.1203
_diffrn_reflns_Laue_measured_fraction_full 0.939
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            59740
_diffrn_reflns_point_group_measured_fraction_full 0.939
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         64.999
_diffrn_reflns_theta_min         2.190
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.188
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82115
_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    1.204
_exptl_crystal_description       block
_exptl_crystal_F_000             1864
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.851
_refine_diff_density_min         -0.504
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.957
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1158
_refine_ls_number_reflns         16415
_refine_ls_number_restraints     73
_refine_ls_restrained_S_all      0.966
_refine_ls_R_factor_all          0.1302
_refine_ls_R_factor_gt           0.0707
_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^)+(0.0971P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1706
_refine_ls_wR_factor_ref         0.1950
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9391
_reflns_number_total             16415
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc03131k2.cif
_cod_data_source_block           Ti4-iPrOH
_cod_database_code               7130393
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.448
_shelx_estimated_absorpt_t_min   0.299
_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
 C81-C82A
 1.55 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C37) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C51)
\\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C39A) \\sim Ueq, Uanis(C38A) \\sim Ueq,
Uanis(C37A) \\sim Ueq, Uanis(C82A) \\sim Ueq, Uanis(C80A) \\sim Ueq, Uanis(C1)
\\sim Ueq, Uanis(C3A) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
4. Others
 Sof(C39A)=Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C38A)=Sof(H38D)=Sof(H38E)=
 Sof(H38F)=Sof(C37A)=Sof(H37D)=Sof(H37E)=Sof(H37F)=1-FVAR(1)
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=FVAR(1)
 Sof(H81A)=Sof(C80A)=Sof(H80D)=Sof(H80E)=Sof(H80F)=Sof(C82A)=Sof(H82D)=
 Sof(H82E)=Sof(H82F)=1-FVAR(2)
 Sof(H81)=Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(H80C)=Sof(C82)=Sof(H82A)=Sof(H82B)=
 Sof(H82C)=FVAR(2)
 Sof(H1B)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=1-FVAR(3)
 Sof(H1A)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=FVAR(3)
5.a Riding coordinates:
 C1(H1A), C1(H1B)
5.b Ternary CH refined with riding coordinates:
 C4(H4), C86(H86), C81(H81), C81(H81A)
5.c Secondary CH2 refined with riding coordinates:
 C58(H58A,H58B), C011(H01A,H01B), C26(H26A,H26B), C46(H46A,H46B), C78(H78A,
 H78B), C19(H19A,H19B), C59(H59A,H59B), C79(H79A,H79B)
5.d Aromatic/amide H refined with riding coordinates:
 C14(H14), C56(H56), C12(H12), C8(H8), C18(H18), C40(H40), C01C(H01C),
 C21(H21), C23(H23), C73(H73), C36(H36), C71(H71), C77(H77), C42(H42), C61(H61),
  C65(H65)
5.e Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C5(H5A,H5B,H5C), C30(H30A,H30B,H30C), C53(H53A,H53B,H53C),
 C55(H55A,H55B,H55C), C29(H29A,H29B,H29C), C02J(H02A,H02B,H02C), C28(H28A,H28B,
 H28C), C87(H87A,H87B,H87C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C31(H31A,
 H31B,H31C), C02Q(H02D,H02E,H02F), C85(H85A,H85B,H85C), C52(H52A,H52B,H52C),
 C7(H7A,H7B,H7C), C88(H88A,H88B,H88C), C02V(H02G,H02H,H02I), C64(H64A,H64B,
 H64C), C02X(H02J,H02K,H02L), C32(H32A,H32B,H32C), C83(H83A,H83B,H83C),
 C69(H69A,H69B,H69C), C51(H51A,H51B,H51C), C49(H49A,H49B,H49C), C37(H37A,H37B,
 H37C), C39(H39A,H39B,H39C), C38(H38A,H38B,H38C), C39A(H39D,H39E,H39F),
 C38A(H38D,H38E,H38F), C37A(H37D,H37E,H37F), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C),
 C80(H80A,H80B,H80C), C82(H82A,H82B,H82C), C80A(H80D,H80E,H80F), C82A(H82D,H82E,
 H82F), C3A(H3AA,H3AB,H3AC)
;
_shelx_res_checksum              6228
_shelx_hkl_checksum              23219
_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 3.184
_oxdiff_exptl_absorpt_empirical_full_min 0.490