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_7127731
_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         'C68 H97 O15 Ti3, C27 H53 O12.518 Ti3'
_chemical_formula_sum            'C95 H150 O27.52 Ti6'
_chemical_formula_weight         2019.86
_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                84.214(19)
_cell_angle_beta                 70.821(18)
_cell_angle_gamma                86.94(2)
_cell_formula_units_Z            2
_cell_length_a                   15.419(5)
_cell_length_b                   19.356(6)
_cell_length_c                   20.165(7)
_cell_measurement_reflns_used    2856
_cell_measurement_temperature    150
_cell_measurement_theta_max      28.56
_cell_measurement_theta_min      1.86
_cell_volume                     5654(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    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1387
_diffrn_reflns_av_unetI/netI     0.2109
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            27554
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        21.000
_diffrn_reflns_theta_max         21.000
_diffrn_reflns_theta_min         2.021
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           0.0
_diffrn_source_power             0.0
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           0.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.468
_exptl_absorpt_correction_T_max  0.869
_exptl_absorpt_correction_T_min  0.799
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            'clear reddish black'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.186
_exptl_crystal_description       block
_exptl_crystal_F_000             2144
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.784
_refine_diff_density_min         -0.485
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.950
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1313
_refine_ls_number_reflns         12006
_refine_ls_number_restraints     338
_refine_ls_restrained_S_all      0.973
_refine_ls_R_factor_all          0.2360
_refine_ls_R_factor_gt           0.1047
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1583P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2495
_refine_ls_wR_factor_ref         0.2953
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4976
_reflns_number_total             12006
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc05336h2.cif
_cod_data_source_block           Ti6-5
_cod_database_code               7127731
_shelx_shelxl_version_number     2018/3
_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
 C84-C86
 1.45 with sigma of 0.01
 C84-C85
 1.45 with sigma of 0.01
 C63-C88
 1.45 with sigma of 0.01
 C20-C18 \\sim C20-C19 \\sim C20-C17
 with sigma of 0.01
 C52-C49 \\sim C52-C51 \\sim C52-C50
 with sigma of 0.01
 C47-C44 \\sim C47-C46 \\sim C47-C45
 with sigma of 0.01
 C55-C54 \\sim C55-C6 \\sim C55-C56
 with sigma of 0.01
 C77-C80 \\sim C77-C79 \\sim C77-C78
 with sigma of 0.01
 C1-C2 \\sim C1-C3 \\sim C1-C4
 with sigma of 0.01
3. Rigid bond restraints
 C72, C71
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.01
 C59, C61A
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.01
 C86, C84
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.001
 C61, C59
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.01
 C88, C63
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C72 \\sim C71: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C59 \\sim C61A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C86 \\sim C84: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C61 \\sim C59: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C88 \\sim C63: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Uanis(O24) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C74)
\\sim Ueq, Uanis(C88) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C76) \\sim Ueq,
Uanis(C81) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C83)
\\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C68) \\sim Ueq,
Uanis(C65) \\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C79) \\sim Ueq, Uanis(C80)
\\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(C87) \\sim Ueq, Uanis(C54) \\sim Ueq,
Uanis(C77) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C51)
\\sim Ueq, Uanis(O23) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C64) \\sim Ueq,
Uanis(C66) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(O16) \\sim Ueq, Uanis(C18)
\\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C02R) \\sim Ueq, Uanis(C1) \\sim Ueq,
Uanis(O20) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(O25) \\sim Ueq, Uanis(C72)
\\sim Ueq, Uanis(O19) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(O23A) \\sim Ueq,
Uanis(O17) \\sim Ueq, Uanis(C83A) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C82)
\\sim Ueq, Uanis(C90) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
5. Others
 Sof(Ti1)=Sof(Ti4)=Sof(O20)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(O18)=
 Sof(O17)=Sof(O23A)=Sof(O12A)=Sof(O24)=1-FVAR(1)
 Sof(Ti2)=Sof(O21)=Sof(Ti5)=Sof(O16)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=
 Sof(O19)=Sof(O23)=Sof(O25)=FVAR(1)
 Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=1-FVAR(2)
 Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(H65C)=FVAR(2)
 Sof(C83A)=Sof(H83D)=Sof(H83E)=Sof(H83F)=1-FVAR(3)
 Sof(C83)=Sof(H83A)=Sof(H83B)=Sof(H83C)=FVAR(3)
 Sof(C61A)=Sof(H61D)=Sof(H61E)=Sof(H61F)=1-FVAR(4)
 Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(H61C)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C71(H71), C75(H75)
6.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C21(H21A,H21B), C28(H28A,H28B), C33(H33A,H33B)
6.c Aromatic/amide H refined with riding coordinates:
 C57(H57), C9(H9), C12(H12), C14(H14), C23(H23), C25(H25), C35(H35), C37(H37)
6.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C01Z(H01A,H01B,H01C), C19(H19A,H19B,H19C), C02R(H02A,
 H02B,H02C), C02M(H02D,H02E,H02F), C17(H17A,H17B,H17C), C50(H50A,H50B,H50C),
 C49(H49A,H49B,H49C), C51(H51A,H51B,H51C), C30(H30A,H30B,H30C), C31(H31A,H31B,
 H31C), C32(H32A,H32B,H32C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C43(H43A,
 H43B,H43C), C54(H54A,H54B,H54C), C56(H56A,H56B,H56C), C6(H6A,H6B,H6C),
 C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C80(H80A,H80B,
 H80C), C79(H79A,H79B,H79C), C78(H78A,H78B,H78C), C89(H89A,H89B,H89C), C2(H2A,
 H2B,H2C), C4(H4A,H4B,H4C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C64(H64A,
 H64B,H64C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C68(H68A,H68B,H68C),
 C69(H69A,H69B,H69C), C72(H72A,H72B,H72C), C73(H73A,H73B,H73C), C74(H74A,H74B,
 H74C), C76(H76A,H76B,H76C), C3(H3A,H3B,H3C), C85(H85A,H85B,H85C), C86(H86A,
 H86B,H86C), C87(H87A,H87B,H87C), C82(H82A,H82B,H82C), C83(H83A,H83B,H83C),
 C83A(H83D,H83E,H83F), C60(H60A,H60B,H60C), C61(H61A,H61B,H61C), C61A(H61D,H61E,
 H61F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              71390
_shelx_fab_checksum              98646
_olex2_submission_special_instructions 'No special instructions were received'