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_7130389
_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         'C47 H59 O5 Ti, C6 H16 N, 2[C3H8O]'
_chemical_formula_sum            'C60 H91 N O7 Ti'
_chemical_formula_weight         986.23
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 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                 96.7860(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.6310(2)
_cell_length_b                   12.8546(2)
_cell_length_c                   25.6170(3)
_cell_measurement_reflns_used    23732
_cell_measurement_temperature    150
_cell_measurement_theta_max      77.0200
_cell_measurement_theta_min      2.3780
_cell_volume                     6092.14(14)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 5.6
_diffrn_detector_type            'Bruker SMART CCD 6000 area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.982
_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     48.00  73.00   0.50    0.30    --   47.45  78.00 -52.00   50
  2  \w    131.00 176.00   0.50    0.50    --  107.75  78.00 -52.00   90
  3  \w    148.00 178.00   0.50    0.50    --  107.75  45.00 -60.00   60
  4  \w    111.00 173.00   0.50    0.50    --  107.75  30.00 -90.00  124
  5  \w     96.00 136.00   0.50    0.50    --  107.75  45.00 -60.00   80
  6  \w    103.00 129.00   0.50    0.50    --  107.75  77.00 -90.00   52
  7  \w     85.00 124.00   0.50    0.50    --  107.75  78.00 -52.00   78
  8  \w     94.00 137.00   0.50    0.50    --  107.75  15.00  30.00   86
  9  \w    145.00 175.00   0.50    0.50    --  107.75  15.00  30.00   60
 10  \w     95.00 178.00   0.50    0.50    --  107.75  15.00-120.00  166
 11  \w     41.00 108.00   0.50    0.50    --  107.75 -94.00   0.00  134
 12  \w    -71.00  25.00   0.50    0.30    --  -47.45  78.00 -52.00  192
 13  \w    -38.00 -13.00   0.50    0.50    --  -86.25  78.00 -52.00   50
 14  \w    -46.00 -21.00   0.50    0.50    --  -86.25  45.00  90.00   50
 15  \w    -50.00 -17.00   0.50    0.50    --  -86.25  45.00 150.00   66
 16  \w   -120.00 -72.00   0.50    0.30    --  -47.45-125.00  30.00   96
 17  \w   -118.00 -71.00   0.50    0.30    --  -47.45-125.00 -30.00   94
 18  \w   -102.00 -24.00   0.50    0.30    --  -47.45 -78.00-177.00  156
 19  \w   -135.00-110.00   0.50    0.50    --  -86.25 -78.00-177.00   50
 20  \w     36.00  70.00   0.50    0.50    --  107.75 -61.00   0.00   68
 21  \w     21.00  70.00   0.50    0.30    --   47.45 -78.00-177.00   98
 22  \w     51.00 104.00   0.50    0.50    --  107.75 -78.00-177.00  106
 23  \w     76.00 102.00   0.50    0.50    --  107.75 -77.00-150.00   52
 24  \w     37.00  91.00   0.50    0.50    --  107.75 -77.00-120.00  108
 25  \w     42.00  67.00   0.50    0.50    --  107.75 -77.00-150.00   50
 26  \w     38.00  79.00   0.50    0.50    --  107.75 -77.00 -90.00   82
 27  \w     39.00  65.00   0.50    0.50    --  107.75 -61.00-180.00   52
 28  \w     37.00  84.00   0.50    0.50    --  107.75 -77.00   0.00   94
 29  \w     47.00  98.00   0.50    0.50    --  107.75 -77.00  30.00  102
 30  \w     45.00  84.00   0.50    0.50    --  107.75 -77.00  90.00   78
 31  \w     40.00  66.00   0.50    0.50    --  107.75 -61.00 120.00   52
 32  \w     44.00  69.00   0.50    0.50    --  107.75 -61.00  90.00   50
 33  \w     37.00  62.00   0.50    0.50    --  107.75 -61.00-120.00   50
 34  \w     35.00  62.00   0.50    0.50    --  107.75 -61.00-150.00   54
 35  \w    145.00 171.00   0.50    0.50    --  107.75 125.00-150.00   52
;
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART CCD 6000 area detector'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0147950000
_diffrn_orient_matrix_UB_12      -0.0426133000
_diffrn_orient_matrix_UB_13      -0.0538902000
_diffrn_orient_matrix_UB_21      0.0419371000
_diffrn_orient_matrix_UB_22      -0.0920073000
_diffrn_orient_matrix_UB_23      0.0274075000
_diffrn_orient_matrix_UB_31      -0.0704270000
_diffrn_orient_matrix_UB_32      -0.0638585000
_diffrn_orient_matrix_UB_33      -0.0035368000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0439
_diffrn_reflns_av_unetI/netI     0.0417
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            58299
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.749
_diffrn_reflns_theta_min         2.388
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.471
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61337
_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 orangish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.075
_exptl_crystal_description       block
_exptl_crystal_F_000             1848
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.922
_refine_diff_density_min         -0.568
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     699
_refine_ls_number_reflns         12766
_refine_ls_number_restraints     324
_refine_ls_restrained_S_all      1.142
_refine_ls_R_factor_all          0.0876
_refine_ls_R_factor_gt           0.0764
_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^)+(0.1998P)^2^+0.0290P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2378
_refine_ls_wR_factor_ref         0.2561
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10043
_reflns_number_total             12766
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc03131k2.cif
_cod_data_source_block           Ti-iPrOH
_cod_database_code               7130389
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         CHONTi
_shelx_estimated_absorpt_t_max   0.667
_shelx_estimated_absorpt_t_min   0.527
_olex2_refinement_description
;
1. Restrained distances
 C50-C49
 1.55 with sigma of 0.01
 H52B-H53A
 2 with sigma of 0.01
 H44A-H49B
 2 with sigma of 0.01
 C31-C63
 1.55 with sigma of 0.01
 C41-C37
 2.2 with sigma of 0.01
 C41-C40
 2.2 with sigma of 0.01
 C14-C60 \\sim C14-C54
 with sigma of 0.02
 C14-C57 \\sim C14-C58
 with sigma of 0.02
 C14-C48 \\sim C14-C59
 with sigma of 0.02
 C31-C62 \\sim C31-C35
 with sigma of 0.02
 C31-C43 \\sim C31-C63
 with sigma of 0.02
 C31-C33 \\sim C31-C34
 with sigma of 0.02
 C15-C32 \\sim C15-C47
 with sigma of 0.02
 C15-C65 \\sim C15-C45
 with sigma of 0.02
 C15-C66 \\sim C15-C46
 with sigma of 0.02
 C16-C36 \\sim C16-C37
 with sigma of 0.02
 C16-C38 \\sim C16-C41
 with sigma of 0.02
 C16-C39 \\sim C16-C40
 with sigma of 0.02
2. Uiso/Uaniso restraints and constraints
C50 \\sim C49 \\sim C51 \\sim C52 \\sim C44 \\sim C53 \\sim N7: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C33 \\sim C34 \\sim C62 \\sim C35 \\sim C43 \\sim C63: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C58) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C48)
\\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C54) \\sim Ueq,
Uanis(C61) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C51)
\\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C44) \\sim Ueq,
Uanis(N7) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C61)
\\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C38) \\sim Ueq,
Uanis(C36) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C63)
\\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C65) \\sim Ueq,
Uanis(C66) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C36)
\\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C41) \\sim Ueq,
Uanis(C39) \\sim Ueq, Uanis(C40) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
3. Others
 Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=
 Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=1-FVAR(1)
 Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(H48C)=
 Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=FVAR(1)
 Sof(H64A)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=Sof(C61)=Sof(H61A)=Sof(H61B)=
 Sof(H61C)=1-FVAR(2)
 Sof(H64)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=Sof(C42)=Sof(H42A)=Sof(H42B)=
 Sof(H42C)=FVAR(2)
 Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(H63C)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=1-FVAR(3)
 Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=FVAR(3)
 Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=
 Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=1-FVAR(4)
 Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(H65C)=
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(4)
 Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=1-FVAR(5)
 Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=FVAR(5)
4.a Riding coordinates:
 C63(H63A,H63B,H63C), C34(H34A,H34B,H34C), C45(H45A,H45B,H45C), C37(H37A,H37B,
 H37C)
4.b Ternary CH refined with riding coordinates:
 N7(H7), C64(H64), C64(H64A)
4.c Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C00Q(H00A,H00B), C20(H20A,H20B), C67(H67A,H67B), C53(H53A,
 H53B), C51(H51A,H51B), C49(H49A,H49B)
4.d Aromatic/amide H refined with riding coordinates:
 C30(H30), C11(H11), C18(H18), C23(H23), C9(H9), C3(H3), C2(H2), C28(H28)
4.e Idealised Me refined as rotating group:
 C62(H62A,H62B,H62C), C43(H43A,H43B,H43C), C33(H33A,H33B,H33C), C57(H57A,H57B,
 H57C), C48(H48A,H48B,H48C), C60(H60A,H60B,H60C), C44(H44A,H44B,H44C), C50(H50A,
 H50B,H50C), C52(H52A,H52B,H52C), C59(H59A,H59B,H59C), C58(H58A,H58B,H58C),
 C54(H54A,H54B,H54C), C56(H56A,H56B,H56C), C42(H42A,H42B,H42C), C55(H55A,H55B,
 H55C), C61(H61A,H61B,H61C), C66(H66A,H66B,H66C), C65(H65A,H65B,H65C), C32(H32A,
 H32B,H32C), C39(H39A,H39B,H39C), C36(H36A,H36B,H36C), C38(H38A,H38B,H38C),
 C35(H35A,H35B,H35C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C41(H41A,H41B,
 H41C), C40(H40A,H40B,H40C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 302 electrons were 
found in a volume of 1462\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 9[C3H8O] per Formula Unit 
which account for 306 electrons per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              52905
_shelx_hkl_checksum              12045
_shelx_fab_checksum              33724
_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 1.349
_oxdiff_exptl_absorpt_empirical_full_min 0.701