Monocarboxylate-driven structural growth in Calix[n]arene-polyoxotitanate hybrid systems: utility in hydrogen production from water.
Yang, Xin-Xue; Yu, Wei-Dong; Yi, Xiao-Yi; Li, Lei-Jiao; Liu, Chao; Chemical communications (Cambridge, England) 56 (2020) 14035–14038; doi:10.1039/d0cc05336h

data_7127734
_publ_section_title
;
 Monocarboxylate-driven structural growth in Calix[n]arene-polyoxotitanate
 hybrid systems: utility in hydrogen production from water.
;
_journal_issue                   90
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              14035
_journal_page_last               14038
_journal_paper_doi               10.1039/d0cc05336h
_journal_volume                  56
_journal_year                    2020
_chemical_formula_moiety         'C130 H164 Br12 O46 Ti10'
_chemical_formula_sum            'C130 H164 Br12 O46 Ti10'
_chemical_formula_weight         3900.52
_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             2020-10-06
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2020-10-06 deposited with the CCDC.	2020-10-26 downloaded from the CCDC.
;
_cell_angle_alpha                98.6889(17)
_cell_angle_beta                 110.5977(17)
_cell_angle_gamma                100.0332(16)
_cell_formula_units_Z            1
_cell_length_a                   14.9660(3)
_cell_length_b                   15.4941(3)
_cell_length_c                   20.8678(4)
_cell_measurement_reflns_used    18020
_cell_measurement_temperature    150
_cell_measurement_theta_max      74.9120
_cell_measurement_theta_min      2.9490
_cell_volume                     4340.33(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.26a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.26a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.26a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.946
_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  23.00   0.50    0.77    --  -47.57  37.00 -30.00  104
  2  \w    -49.00 -24.00   0.50    3.50    --  -86.25 119.00 136.00   50
  3  \w    -84.00 -10.00   0.50    0.77    --  -47.57 119.00 136.00  148
  4  \w     26.00 118.00   0.50    0.77    --   47.57  77.00 -30.00  184
  5  \w     73.00  98.00   0.50    0.77    --   47.57 157.00 -69.00   50
  6  \w     93.00 118.00   0.50    3.50    --  106.49 157.00 -69.00   50
  7  \w     95.00 168.00   0.50    3.50    --  106.49 125.00   0.00  146
  8  \w    111.00 165.00   0.50    3.50    --  106.49 125.00  90.00  108
  9  \w    114.00 139.00   0.50    3.50    --  106.49 119.00 136.00   50
 10  \w     95.00 158.00   0.50    3.50    --  106.49  45.00  30.00  126
 11  \w     95.00 177.00   0.50    3.50    --  106.49  30.00 -60.00  164
 12  \w     95.00 158.00   0.50    3.50    --  106.49  45.00-180.00  126
 13  \w     69.00 118.00   0.50    3.50    --  106.49 -30.00  30.00   98
 14  \w     74.00 104.00   0.50    3.50    --  106.49 -94.00  90.00   60
 15  \w     60.00  85.00   0.50    0.77    --   47.57-119.00  50.00   50
 16  \w     37.00 109.00   0.50    3.50    --  106.49-119.00  50.00  144
 17  \w     43.00  68.00   0.50    3.50    --  106.49 -94.00  90.00   50
 18  \w     35.00 106.00   0.50    3.50    --  106.49-100.00  51.14  142
 19  \w     66.00 108.00   0.50    3.50    --  106.49-110.00 -73.59   84
 20  \w     77.00 134.00   0.50    3.50    --  106.49-157.00-103.00  114
 21  \w     71.00  97.00   0.50    3.50    --  106.49-125.00-180.00   52
 22  \w     67.00 105.00   0.50    3.50    --  106.49 -94.00-180.00   76
 23  \w     62.00 104.00   0.50    0.77    --   47.57-157.00-103.00   84
 24  \w     38.00 105.00   0.50    3.50    --  106.49 -94.00-150.00  134
 25  \w     36.00  89.00   0.50    3.50    --  106.49 -45.00-180.00  106
 26  \w     34.00 105.00   0.50    3.50    --  106.49 -30.00-180.00  142
 27  \w     37.00 109.00   0.50    3.50    --  106.49-125.00   0.00  144
 28  \w     38.00 117.00   0.50    3.50    --  106.49 -45.00   0.00  158
 29  \w    106.00 133.00   0.50    3.50    --  106.49  30.00 150.00   54
 30  \w    140.00 178.00   0.50    3.50    --  106.49  30.00 150.00   76
 31  \w     33.00  65.00   0.50    3.50    --  106.49 -30.00  30.00   64
 32  \w    -71.00 -45.00   0.50    0.77    --  -47.57 -77.00  60.00   52
 33  \w   -114.00 -33.00   0.50    0.77    --  -47.57 -77.00  30.00  162
 34  \w    -98.00 -73.00   0.50    3.50    --  -86.25-157.00-103.00   50
 35  \w   -109.00 -84.00   0.50    0.77    --  -47.57-157.00-103.00   50
 36  \w   -142.00-117.00   0.50    3.50    --  -86.25-119.00  50.00   50
 37  \w   -108.00 -83.00   0.50    0.77    --  -47.57 -77.00  60.00   50
 38  \w   -119.00 -75.00   0.50    0.77    --  -47.57-125.00  90.00   88
 39  \w   -120.00 -73.00   0.50    3.50    --  -86.25 -45.00  60.00   94
 40  \w   -158.00 -70.00   0.50    3.50    --  -86.25 -61.00 120.00  176
 41  \w   -105.00 -37.00   0.50    0.77    --  -47.57 157.00 -69.00  136
 42  \w    -92.00 -67.00   0.50    3.50    --  -86.25 157.00 -69.00   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      -0.1063766000
_diffrn_orient_matrix_UB_12      -0.0312989000
_diffrn_orient_matrix_UB_13      -0.0052684000
_diffrn_orient_matrix_UB_21      0.0353658000
_diffrn_orient_matrix_UB_22      0.0335595000
_diffrn_orient_matrix_UB_23      0.0802525000
_diffrn_orient_matrix_UB_31      -0.0174673000
_diffrn_orient_matrix_UB_32      0.0930563000
_diffrn_orient_matrix_UB_33      -0.0099023000
_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  0.0417
_diffrn_reflns_av_unetI/netI     0.0372
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.946
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            53345
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.575
_diffrn_reflns_theta_min         2.324
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.520
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.30130
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.26a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear reddish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.492
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1952
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.864
_refine_diff_density_min         -0.610
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1076
_refine_ls_number_reflns         17492
_refine_ls_number_restraints     186
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0833
_refine_ls_R_factor_gt           0.0655
_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^)+(0.1139P)^2^+2.8927P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1841
_refine_ls_wR_factor_ref         0.2014
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13085
_reflns_number_total             17492
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc05336h2.cif
_cod_data_source_block           Ti10-1
_cod_original_cell_volume        4340.31(15)
_cod_database_code               7127734
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.315
_shelx_estimated_absorpt_t_min   0.065
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C54-Br1 \\sim C54-Br2 \\sim C27-Br8 \\sim C27-Br9 \\sim C73-Br3 \\sim C73-Br4
 with sigma of 0.01
 C63-C64 \\sim C63-C65
 with sigma of 0.01
 C1-C2 \\sim C1-C3 \\sim C1-C4 \\sim C1-C5
 with sigma of 0.01
 C23-C20 \\sim C23-C21 \\sim C23-C22
 with sigma of 0.01
3. Rigid bond restraints
 C23
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C51, C58
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C68, C6A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C68, C7A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C68, C6
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C68, C28A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C58, C51A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C31
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C1, C5
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C1, C4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C1, C2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C30, C31
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C5A, C58
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
C68 \\sim C6A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C68 \\sim C7A: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C68 \\sim C6: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C68 \\sim C28A: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C1 \\sim C5: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C1 \\sim C4: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C1 \\sim C2: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C30 \\sim C31: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C5A \\sim C58: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
Uanis(C53) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C51)
\\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C51A) \\sim Ueq, Uanis(C6) \\sim Ueq,
Uanis(C7) \\sim Ueq, Uanis(C6A) \\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C28A)
\\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C20) \\sim Ueq,
Uanis(C48) \\sim Ueq, Uanis(C47A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
5. Others
 Sof(Br7)=Sof(H24C)=Sof(H24D)=1-FVAR(1)
 Sof(Br6)=Sof(H24A)=Sof(H24B)=FVAR(1)
 Sof(Br9)=Sof(H27C)=Sof(H27D)=1-FVAR(2)
 Sof(Br8)=Sof(H27A)=Sof(H27B)=FVAR(2)
 Sof(Br1)=Sof(H54C)=Sof(H54D)=1-FVAR(3)
 Sof(Br2)=Sof(H54A)=Sof(H54B)=FVAR(3)
 Sof(Br11)=1-FVAR(4)
 Sof(Br5)=FVAR(4)
 Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=1-FVAR(5)
 Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(H65C)=FVAR(5)
 Sof(H73C)=Sof(H73D)=Sof(Br3)=1-FVAR(6)
 Sof(Br4)=Sof(H73A)=Sof(H73B)=FVAR(6)
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=1-FVAR(7)
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=FVAR(7)
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=1-FVAR(8)
 Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=FVAR(8)
 Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=Sof(C51A)=Sof(H51A)=Sof(H51B)=
 Sof(H51C)=1-FVAR(9)
 Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=Sof(C51)=Sof(H51D)=Sof(H51E)=Sof(H51F)=
 FVAR(9)
 Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=
 Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=1-FVAR(10)
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=FVAR(10)
 Sof(C47A)=Sof(H47D)=Sof(H47E)=Sof(H47F)=1-FVAR(11)
 Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=FVAR(11)
 Sof(H49D)=Sof(H49E)=Sof(H49F)=Sof(C53A)=1-FVAR(12)
 Sof(C53)=Sof(H49A)=Sof(H49B)=Sof(H49C)=FVAR(12)
6.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C24(H24C,H24D), C24(H24A,H24B), C27(H27A,H27B), C27(H27C,
 H27D), C38(H38A,H38B), C39(H39A,H39B), C42(H42A,H42B), C54(H54C,H54D),
 C54(H54A,H54B), C61(H61A,H61B), C70(H70A,H70B), C73(H73A,H73B), C73(H73C,H73D)
6.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C15(H15), C17(H17), C33(H33), C37(H37), C44(H44), C45(H45)
6.c Idealised Me refined as rotating group:
 C62(H62A,H62B,H62C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C3(H3A,H3B,
 H3C), C4(H4A,H4B,H4C), C2(H2A,H2B,H2C), C5(H5A,H5B,H5C), C56(H56A,H56B,H56C),
 C30(H30A,H30B,H30C), C29(H29A,H29B,H29C), C1A(H1AA,H1AB,H1AC), C5A(H5AA,H5AB,
 H5AC), C51A(H51A,H51B,H51C), C59(H59A,H59B,H59C), C51(H51D,H51E,H51F), C7(H7A,
 H7B,H7C), C28(H28A,H28B,H28C), C6(H6A,H6B,H6C), C6A(H6AA,H6AB,H6AC), C7A(H7AA,
 H7AB,H7AC), C28A(H28D,H28E,H28F), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C),
 C22(H22A,H22B,H22C), C49(H49A,H49B,H49C), C49(H49D,H49E,H49F), C47(H47A,H47B,
 H47C), C48(H48A,H48B,H48C), C47A(H47D,H47E,H47F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              96476
_shelx_fab_checksum              82224
_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 2.949
_oxdiff_exptl_absorpt_empirical_full_min 0.670