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_7127735
_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
'C194.837 H156.893 F59.645 O46 Ti10, [+ solvents]'
_chemical_formula_sum            'C196 H158 F60 O46 Ti10'
_chemical_formula_weight         4868.21
_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             2020-10-12
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2020-10-12 deposited with the CCDC.	2020-10-26 downloaded from the CCDC.
;
_cell_angle_alpha                68.017(3)
_cell_angle_beta                 69.349(5)
_cell_angle_gamma                61.753(4)
_cell_formula_units_Z            1
_cell_length_a                   17.6619(9)
_cell_length_b                   18.0164(5)
_cell_length_c                   21.2467(9)
_cell_measurement_reflns_used    7957
_cell_measurement_temperature    150
_cell_measurement_theta_max      69.4990
_cell_measurement_theta_min      5.7500
_cell_volume                     5393.7(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_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     86.00 178.00   1.00   10.00    --  108.00  50.00  90.00   92
  2  \w     92.00 126.00   1.00   10.00    --  108.00 -50.00 -60.00   34
  3  \w     83.00 114.00   1.00   10.00    --  108.00-111.00 -90.00   31
  4  \w     44.00  85.00   1.00    5.00    --   54.00-125.00   0.00   41
  5  \w     49.00  76.00   1.00    5.00    --   54.00-125.00  90.00   27
  6  \w     31.00  81.00   1.00    5.00    --   54.00 -99.00 150.00   50
  7  \w     74.00 111.00   1.00   10.00    --  108.00-111.00  60.00   37
  8  \w     65.00 116.00   1.00   10.00    --  108.00-111.00 150.00   51
  9  \w     52.00 133.00   1.00   10.00    --  108.00 -77.00 150.00   81
 10  \w     48.00 175.00   1.00   10.00    --  108.00  12.00  60.00  127
 11  \w     99.00 127.00   1.00    5.00    --   54.00  19.00 -90.00   28
 12  \w    126.00 153.00   1.00   10.00    --  108.00  12.00-150.00   27
 13  \w    100.00 126.00   1.00   10.00    --  108.00 111.00-180.00   26
 14  \w     43.00 125.00   1.00   10.00    --  108.00  12.00-150.00   82
 15  \w     39.00  87.00   1.00   10.00    --  108.00 -50.00 -60.00   48
 16  \w     37.00  86.00   1.00   10.00    --  108.00-111.00 -30.00   49
 17  \w     42.00 129.00   1.00   10.00    --  108.00 -50.00  60.00   87
 18  \w     38.00 142.00   1.00   10.00    --  108.00 -91.00 -30.00  104
 19  \w     32.00  69.00   1.00    3.00    --    0.00  57.00 -30.00   37
 20  \w     34.00 115.00   1.00    5.00    --   54.00  57.00  60.00   81
 21  \w     36.00 129.00   1.00   10.00    --  108.00 -38.00 150.00   93
 22  \w     31.00 122.00   1.00    5.00    --   54.00  38.00 150.00   91
 23  \w     36.00  66.00   1.00   10.00    --  108.00-111.00  60.00   30
 24  \w    -15.00  71.00   1.00    5.00    --   54.00 -38.00 -90.00   86
 25  \w     24.00  72.00   1.00    5.00    --   54.00 -57.00-180.00   48
 26  \w     13.00  69.00   1.00    5.00    --   54.00  19.00 -90.00   56
 27  \w    -19.00  21.00   1.00    3.00    --    0.00 -57.00-180.00   40
 28  \w    -21.00  25.00   1.00    3.00    --    0.00  57.00 -30.00   46
 29  \w    -34.00  -9.00   1.00    3.00    --    0.00 124.00  23.00   25
 30  \w    -51.00 -26.00   1.00    3.00    --    0.00 148.00-172.00   25
 31  \w    -68.00 -24.00   1.00    3.00    --    0.00 -57.00-180.00   44
;
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0036026000
_diffrn_orient_matrix_UB_12      0.0493363000
_diffrn_orient_matrix_UB_13      -0.0764922000
_diffrn_orient_matrix_UB_21      -0.0976326000
_diffrn_orient_matrix_UB_22      0.0573970000
_diffrn_orient_matrix_UB_23      0.0226075000
_diffrn_orient_matrix_UB_31      0.0270870000
_diffrn_orient_matrix_UB_32      0.0658075000
_diffrn_orient_matrix_UB_33      0.0069250000
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0576
_diffrn_reflns_av_unetI/netI     0.0994
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            36375
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        64.991
_diffrn_reflns_theta_max         64.991
_diffrn_reflns_theta_min         4.076
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    0.473
_exptl_absorpt_correction_T_max  0.664
_exptl_absorpt_correction_T_min  0.431
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
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    1.499
_exptl_crystal_description       block
_exptl_crystal_F_000             2462
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.683
_refine_diff_density_min         -0.663
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1534
_refine_ls_number_reflns         18236
_refine_ls_number_restraints     2747
_refine_ls_restrained_S_all      0.988
_refine_ls_R_factor_all          0.1507
_refine_ls_R_factor_gt           0.0953
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1670P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2603
_refine_ls_wR_factor_ref         0.3050
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9847
_reflns_number_total             18236
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc05336h2.cif
_cod_data_source_block           Ti10-2
_cod_database_code               7127735
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.685
_shelx_estimated_absorpt_t_min   0.138
_reflns_odcompleteness_completeness 99.63
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C29-C30 \\sim C29-C32 \\sim C29-C28 \\sim C29-C26 \\sim C29-C21 \\sim C29-C31
 with sigma of 0.01
 C52-C2 \\sim C52-C50 \\sim C52-C53
 with sigma of 0.01
 C51-C6 \\sim C51-C7 \\sim C51-C8
 with sigma of 0.01
 C1-C3 \\sim C1-C4 \\sim C1-C5
 with sigma of 0.01
 C39-C40 \\sim C39-C41 \\sim C39-C42
 with sigma of 0.01
 C72-C73 \\sim C72-C74
 with sigma of 0.01
3. Rigid bond restraints
 C78
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C29, C28
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
C1 \\sim C01L \\sim C01V \\sim C02C \\sim C02Q \\sim C03T \\sim C03Y \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C27 \\sim C29 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37
\\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45
\\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim C54 \\sim C55 \\sim C56 \\sim C57
\\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65
\\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73
\\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79 \\sim C81 \\sim C3
\\sim C4 \\sim C5 \\sim C83 \\sim C84 \\sim C85 \\sim C86 \\sim C87 \\sim C88
\\sim C89 \\sim C90 \\sim C91 \\sim C92 \\sim C93 \\sim C95 \\sim C107 \\sim
C108 \\sim C109 \\sim C110 \\sim C111 \\sim C112 \\sim C113 \\sim C03D \\sim C6
\\sim C7 \\sim C8 \\sim C19 \\sim C20 \\sim C22 \\sim C26 \\sim C31 \\sim C32
\\sim C51 \\sim C2 \\sim C21 \\sim C23 \\sim C24 \\sim C25 \\sim C28 \\sim C30
\\sim C50 \\sim C52 \\sim C53 \\sim C114 \\sim C80 \\sim C82: within 3.8A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 3.8A
C78: within 0.001A with sigma of 2 and sigma for terminal atoms of 0.002 within
0.001A
C29 \\sim C28: within 0.001A with sigma of 2 and sigma for terminal atoms of
0.002 within 0.001A
5. Others
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=1-FVAR(1)
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(1)
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C8)=
 Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(C22)=Sof(H22)=
 Sof(C51)=1-FVAR(2)
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(C25)=
 Sof(H25)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=Sof(C52)=Sof(C53)=Sof(H53A)=
 Sof(H53B)=Sof(H53C)=FVAR(2)
 Sof(C114)=Sof(H11A)=Sof(H11B)=Sof(H11C)=1-FVAR(3)
 Sof(C03D)=Sof(H03D)=Sof(H03E)=Sof(H03F)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C72(H72), C76(H76), C78(H78)
6.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B), C43(H43A,H43B), C57(H57A,H57B)
6.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C13(H13), C35(H35), C37(H37), C47(H47), C49(H49), C19(H19), C22(H22),
 C23(H23), C25(H25)
6.d Idealised Me refined as rotating group:
 C03Y(H03A,H03B,H03C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,
 H42C), C73(H73A,H73B,H73C), C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C77(H77A,
 H77B,H77C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C03D(H03D,H03E,
 H03F), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C26(H26A,H26B,H26C),
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C2(H2A,H2B,H2C), C21(H21A,H21B,H21C),
  C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C50(H50A,H50B,H50C), C53(H53A,H53B,
 H53C), C114(H11A,H11B,H11C), C80(H80A,H80B,H80C), C82(H82A,H82B,H82C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              47959
_shelx_fab_checksum              96776
_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 2.855
_oxdiff_exptl_absorpt_empirical_full_min 0.472