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_7127733
_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         'C148 H217 O33 Ti6, C3 H8 O'
_chemical_formula_sum            'C151 H225 O34 Ti6'
_chemical_formula_weight         2871.70
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_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                90
_cell_angle_beta                 99.4230(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.3911(2)
_cell_length_b                   25.7936(3)
_cell_length_c                   33.0748(4)
_cell_measurement_reflns_used    19705
_cell_measurement_temperature    150
_cell_measurement_theta_max      70.8240
_cell_measurement_theta_min      6.3490
_cell_volume                     18002.9(3)
_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    'SHELXS  (Sheldrick, 2008)'
_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 0.964
_diffrn_measured_fraction_theta_max 0.941
_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    -60.00 -34.00   1.00    5.00    --    0.00 178.00 120.00   26
  2  \w     -6.00  39.00   1.00    5.00    --    0.00 -89.00-111.00   45
  3  \w    -73.00 -35.00   1.00    5.00    --    0.00 178.00   0.00   38
  4  \w     32.00 127.00   1.00   10.00    --   56.00  57.00 -60.00   95
  5  \w    -12.00  79.00   1.00   10.00    --   56.00 -57.00 150.00   91
  6  \w     85.00 111.00   1.00   10.00    --   56.00  38.00 120.00   26
  7  \w     33.00 126.00   1.00   10.00    --   56.00  57.00   0.00   93
  8  \w     33.00  58.00   1.00   10.00    --   56.00-125.00 -30.00   25
  9  \w     91.00 162.00   1.00   20.00    --  112.00  50.00-150.00   71
 10  \w     64.00 110.00   1.00   20.00    --  112.00-111.00   0.00   46
 11  \w     40.00 131.00   1.00   20.00    --  112.00 -50.00 120.00   91
 12  \w     70.00  96.00   1.00   20.00    --  112.00 -63.00-120.00   26
 13  \w     39.00 116.00   1.00   20.00    --  112.00-111.00  90.00   77
 14  \w     87.00 178.00   1.00   20.00    --  112.00  63.00 -90.00   91
 15  \w     99.00 136.00   1.00   20.00    --  112.00 -63.00-120.00   37
;
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0254739000
_diffrn_orient_matrix_UB_12      -0.0422499000
_diffrn_orient_matrix_UB_13      -0.0259113000
_diffrn_orient_matrix_UB_21      0.0572014000
_diffrn_orient_matrix_UB_22      -0.0083049000
_diffrn_orient_matrix_UB_23      0.0342789000
_diffrn_orient_matrix_UB_31      -0.0375776000
_diffrn_orient_matrix_UB_32      -0.0413418000
_diffrn_orient_matrix_UB_33      0.0195942000
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0392
_diffrn_reflns_av_unetI/netI     0.0658
_diffrn_reflns_Laue_measured_fraction_full 0.964
_diffrn_reflns_Laue_measured_fraction_max 0.941
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            58351
_diffrn_reflns_point_group_measured_fraction_full 0.964
_diffrn_reflns_point_group_measured_fraction_max 0.941
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.799
_diffrn_reflns_theta_min         3.578
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    2.654
_exptl_absorpt_correction_T_max  0.451
_exptl_absorpt_correction_T_min  0.322
_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    1.060
_exptl_crystal_description       block
_exptl_crystal_F_000             6140
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.702
_refine_diff_density_min         -0.879
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1947
_refine_ls_number_reflns         32628
_refine_ls_number_restraints     249
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0928
_refine_ls_R_factor_gt           0.0655
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1029P)^2^+7.7731P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1740
_refine_ls_wR_factor_ref         0.1915
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22947
_reflns_number_total             32628
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc05336h2.cif
_cod_data_source_block           Ti6-4
_cod_database_code               7127733
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.455
_shelx_estimated_absorpt_t_min   0.231
_reflns_odcompleteness_completeness 96.63
_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, All C(H,H,H,H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C107-C106 \\sim C107-C108 \\sim C119-C44 \\sim C119-C43
 with sigma of 0.01
 C161-C2 \\sim C161-C3 \\sim C161-C4 \\sim C161-C5 \\sim C161-C6 \\sim C161-C7
 with sigma of 0.01
 C8-C9 \\sim C8-C10 \\sim C8-C11 \\sim C8-C12 \\sim C8-C13 \\sim C8-C14
 with sigma of 0.01
 C15-C16 \\sim C15-C17 \\sim C15-C18 \\sim C15-C19 \\sim C15-C20 \\sim C15-C21
 with sigma of 0.01
 C22-C23 \\sim C22-C24 \\sim C22-C25 \\sim C22-C26 \\sim C22-C27 \\sim C22-C28
 with sigma of 0.01
 C98-C97 \\sim C98-C99 \\sim C98-C100
 with sigma of 0.01
3. Rigid bond restraints
 O33, C145
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.001
 C145, C29
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.001
 C145, C146
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.001
 C119, C43
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C43, C44
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C44, C119
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C108, C107
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
O33 \\sim C145: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C145 \\sim C29: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C145 \\sim C146: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C119 \\sim C43: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C108 \\sim C107: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Uanis(C35) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C21)
\\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C119) \\sim Ueq, Uanis(C143) \\sim Ueq,
Uanis(C9) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C17)
\\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C28) \\sim Ueq,
Uanis(C23) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C12)
\\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C107) \\sim Ueq, Uanis(C108) \\sim Ueq,
Uanis(C106) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C160) \\sim Ueq, Uanis(C1)
\\sim Ueq, Uanis(C34) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
5. Others
 Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=1-FVAR(1)
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=FVAR(1)
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C7)=
 Sof(H7A)=Sof(H7B)=Sof(H7C)=1-FVAR(2)
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C2)=
 Sof(H2A)=Sof(H2B)=Sof(H2C)=FVAR(2)
 Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C14)=Sof(H14J)=Sof(H14K)=Sof(H14L)=
 Sof(C10)=Sof(H10M)=Sof(H10N)=Sof(H10O)=1-FVAR(3)
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C11)=Sof(H11D)=Sof(H11E)=Sof(H11F)=
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=FVAR(3)
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=1-FVAR(4)
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=FVAR(4)
 Sof(C119)=Sof(H119)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=Sof(C44)=Sof(H44A)=
 Sof(H44B)=Sof(H44C)=1-FVAR(5)
 Sof(C107)=Sof(H107)=Sof(C108)=Sof(H10P)=Sof(H10Q)=Sof(H10R)=Sof(C106)=
 Sof(H10S)=Sof(H10T)=Sof(H10U)=FVAR(5)
 Sof(H16D)=Sof(H16H)=Sof(H16I)=Sof(H16J)=Sof(H1BD)=Sof(H1BE)=Sof(H1BF)=
 Sof(C163)=Sof(H163)=1-FVAR(6)
 Sof(H161)=Sof(H16E)=Sof(H16F)=Sof(H16G)=Sof(C160)=Sof(H160)=Sof(H1AA)=
 Sof(H1AB)=Sof(H1AC)=FVAR(6)
6.a Ternary CH refined with riding coordinates:
 C145(H145), C61(H61), C150(H150), C107(H107), C119(H119), C160(H160),
 C163(H163)
6.b Secondary CH2 refined with riding coordinates:
 C02C(H02A,H02B), C50(H50A,H50B), C81(H81A,H81B), C121(H12D,H12E), C125(H12F,
 H12G), C140(H14M,H14N), C86(H86A,H86B)
6.c Aromatic/amide H refined with riding coordinates:
 C37(H37), C41(H41), C47(H47), C48(H48), C66(H66), C68(H68), C80(H80),
 C85(H85), C90(H90), C92(H92), C117(H117), C123(H123), C131(H131), C133(H133),
 C136(H136), C138(H138)
6.d Tetrahedral OH refined with riding coordinates:
 O161(H161), O161(H16D)
6.e Idealised Me refined as rotating group:
 C154(H15A,H15B,H15C), C110(H11A,H11B,H11C), C153(H15D,H15E,H15F), C94(H94A,
 H94B,H94C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C7(H7A,H7B,H7C), C6(H6A,H6B,H6C),
  C4(H4A,H4B,H4C), C2(H2A,H2B,H2C), C152(H15G,H15H,H15I), C156(H15J,H15K,H15L),
 C142(H14A,H14B,H14C), C144(H14D,H14E,H14F), C146(H14G,H14H,H14I), C29(H29A,
 H29B,H29C), C159(H15M,H15N,H15O), C158(H15P,H15Q,H15R), C31(H31A,H31B,H31C),
 C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C57(H57A,H57B,
 H57C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C62(H62A,H62B,H62C), C63(H63A,
 H63B,H63C), C72(H72A,H72B,H72C), C73(H73A,H73B,H73C), C74(H74A,H74B,H74C),
 C75(H75A,H75B,H75C), C76(H76A,H76B,H76C), C77(H77A,H77B,H77C), C93(H93A,H93B,
 H93C), C95(H95A,H95B,H95C), C96(H96A,H96B,H96C), C97(H97A,H97B,H97C), C99(H99A,
 H99B,H99C), C100(H10A,H10B,H10C), C103(H10D,H10E,H10F), C104(H10G,H10H,H10I),
 C105(H10J,H10K,H10L), C9(H9A,H9B,H9C), C11(H11D,H11E,H11F), C13(H13A,H13B,
 H13C), C12(H12A,H12B,H12C), C14(H14J,H14K,H14L), C10(H10M,H10N,H10O),
 C113(H11G,H11H,H11I), C114(H11J,H11K,H11L), C115(H11M,H11N,H11O), C127(H12H,
 H12I,H12J), C128(H12K,H12L,H12M), C129(H12N,H12O,H12P), C17(H17A,H17B,H17C),
 C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C20(H20A,H20B,H20C), C18(H18A,H18B,
 H18C), C16(H16A,H16B,H16C), C149(H14O,H14P,H14Q), C151(H15S,H15T,H15U),
 C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C23(H23A,H23B,
 H23C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C24(H24A,
 H24B,H24C), C26(H26A,H26B,H26C), C108(H10P,H10Q,H10R), C106(H10S,H10T,H10U),
 C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C162(H16E,H16F,H16G), C162(H16H,H16I,
 H16J), C1(H1AA,H1AB,H1AC), C1(H1BD,H1BE,H1BF)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              38948
_shelx_fab_checksum              77545
_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 1.489
_oxdiff_exptl_absorpt_empirical_full_min 0.628