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_7127726
_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         'C104 H136 N4 O22 Ti4'
_chemical_formula_sum            'C104 H136 N4 O22 Ti4'
_chemical_formula_weight         1985.76
_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     iterative
_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                103.020(6)
_cell_angle_beta                 102.821(6)
_cell_angle_gamma                107.509(5)
_cell_formula_units_Z            1
_cell_length_a                   14.2318(11)
_cell_length_b                   14.6532(12)
_cell_length_c                   18.0810(15)
_cell_measurement_reflns_used    2856
_cell_measurement_temperature    150
_cell_measurement_theta_max      28.56
_cell_measurement_theta_min      1.86
_cell_volume                     3328.9(5)
_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    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0770
_diffrn_reflns_av_unetI/netI     0.1302
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            34683
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.999
_diffrn_reflns_theta_min         1.666
_diffrn_source                   'sealed tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.286
_exptl_absorpt_correction_T_max  1.2
_exptl_absorpt_correction_T_min  0.7
_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 yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    0.991
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1052
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.524
_refine_diff_density_min         -0.471
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.883
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     730
_refine_ls_number_reflns         13068
_refine_ls_number_restraints     166
_refine_ls_restrained_S_all      0.896
_refine_ls_R_factor_all          0.1552
_refine_ls_R_factor_gt           0.0666
_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^)+(0.0898P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1571
_refine_ls_wR_factor_ref         0.1774
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5766
_reflns_number_total             13068
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc05336h2.cif
_cod_data_source_block           Ti4-3
_cod_database_code               7127726
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.919
_shelx_estimated_absorpt_t_min   0.847
_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
 N42-C43
 1.45 with sigma of 0.01
 N42A-C43A
 1.45 with sigma of 0.01
 C33-C26 \\sim C33-C34 \\sim C33-C27 \\sim C33-C35 \\sim C33-C28 \\sim C33-C36
 with sigma of 0.01
 C37-C8 \\sim C37-C9 \\sim C37-C32 \\sim C37-C5 \\sim C37-C6 \\sim C37-C7
 with sigma of 0.01
 C38-C11 \\sim C38-C12 \\sim C38-C10
 with sigma of 0.01
 C1-C2 \\sim C1-C3 \\sim C1-C4
 with sigma of 0.01
 N42-C20 \\sim N42A-C20
 with sigma of 0.01
 N42-C42 \\sim N42-C43
 with sigma of 0.01
 N42A-C42A \\sim N42A-C43A
 with sigma of 0.01
3. Rigid bond restraints
 C36, C33
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C7, C37
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C5, C37
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 O00F, C20
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C34, C33
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
C36 \\sim C33: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.001 within 2A
C7 \\sim C37: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.001 within 2A
C5 \\sim C37: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.001 within 2A
Uanis(C36) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C27)
\\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C8) \\sim Ueq,
Uanis(C32) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C9) \\sim
Ueq, Uanis(C5) \\sim Ueq, Uanis(N42) \\sim Ueq, Uanis(C43) \\sim Ueq,
Uanis(N42A) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(O6) \\sim Ueq, Uanis(C36)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=1-FVAR(1)
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=FVAR(1)
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C7)=
 Sof(H7A)=Sof(H7B)=Sof(H7C)=1-FVAR(2)
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=FVAR(2)
 Sof(H20A)=Sof(N42A)=Sof(C42A)=Sof(H42D)=Sof(H42E)=Sof(H42F)=Sof(C43A)=
 Sof(H43D)=Sof(H43E)=Sof(H43F)=1-FVAR(3)
 Sof(H20)=Sof(N42)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(C43)=Sof(H43A)=
 Sof(H43B)=Sof(H43C)=FVAR(3)
 Fixed Sof: H40(0.5) H40A(0.5) O1(0.5) O2(0.5) O3(0.5) O6(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C00D(H00A,H00B), C00J(H00C,H00D), C00N(H00E,H00F), C19(H19A,H19B)
6.b Aromatic/amide H refined with riding coordinates:
 C15(H15), C00O(H00O), C00R(H00R), C00T(H00T), C13(H13), C30(H30), C010(H010),
 C21(H21), C23(H23), C01D(H01D), C40(H40), C40(H40A), C20(H20), C20(H20A)
6.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C12(H12A,H12B,H12C), C4(H4A,H4B,H4C), C3(H3A,H3B,H3C),
 C11(H11A,H11B,H11C), C10(H10A,H10B,H10C), C01V(H01A,H01B,H01C), C01W(H01E,H01F,
 H01G), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C26(H26A,H26B,H26C), C36(H36A,
 H36B,H36C), C35(H35A,H35B,H35C), C34(H34A,H34B,H34C), C5(H5A,H5B,H5C), C9(H9A,
 H9B,H9C), C7(H7A,H7B,H7C), C6(H6A,H6B,H6C), C32(H32A,H32B,H32C), C8(H8A,H8B,
 H8C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C42A(H42D,H42E,H42F),
 C43A(H43D,H43E,H43F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              14752
_shelx_fab_checksum              46780
_olex2_submission_special_instructions 'No special instructions were received'