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_7127727
_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         'C132 H168 N4 O26 Ti6, 2(C2 H3 N)'
_chemical_formula_sum            'C136 H174 N6 O26 Ti6'
_chemical_formula_weight         2596.20
_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     iterative
_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                 106.320(7)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   18.742(2)
_cell_length_b                   15.6878(19)
_cell_length_c                   24.515(3)
_cell_measurement_reflns_used    9897
_cell_measurement_temperature    150
_cell_measurement_theta_max      26.244
_cell_measurement_theta_min      2.205
_cell_volume                     6917.5(14)
_computing_cell_refinement       'SAINT v8.27A (Bruker, 2012)'
_computing_data_reduction        'SAINT v8.27A (Bruker, 2012)'
_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 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_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  0.0390
_diffrn_reflns_av_unetI/netI     0.0527
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            42708
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.510
_diffrn_reflns_theta_min         1.560
_diffrn_source                   'microfocus sealed X-ray 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    0.399
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6118
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0943 before and 0.0486 after correction.
The Ratio of minimum to maximum transmission is 0.8208.
The \l/2 correction factor is 0.0015.
;
_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    1.246
_exptl_crystal_description       block
_exptl_crystal_F_000             2744
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.4
_refine_diff_density_max         0.424
_refine_diff_density_min         -0.409
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     918
_refine_ls_number_reflns         14055
_refine_ls_number_restraints     154
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.1102
_refine_ls_R_factor_gt           0.0551
_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^)+(0.0797P)^2^+4.1049P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1394
_refine_ls_wR_factor_ref         0.1762
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8359
_reflns_number_total             14055
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc05336h2.cif
_cod_data_source_block           Ti6-2
_cod_original_cell_volume        6917.6(15)
_cod_database_code               7127727
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.857
_shelx_estimated_absorpt_t_min   0.796
_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
 C13-C72 \\sim C13-C16 \\sim C13-C73 \\sim C13-C22 \\sim C13-C74 \\sim C13-C69
 with sigma of 0.01
 C21-C20 \\sim C21-C75 \\sim C75-C19 \\sim C21-C76 \\sim C21-C18 \\sim C21-C77
 with sigma of 0.01
 C14-C17 \\sim C14-C71 \\sim C14-C70 \\sim C14-C9 \\sim C14-C6 \\sim C14-C7
 with sigma of 0.01
 C8-C78 \\sim C8-C15 \\sim C8-C79
 with sigma of 0.01
 C1-C2 \\sim C1-C3 \\sim C1-C4 \\sim C1-C5
 with sigma of 0.01
3. Rigid bond restraints
 C1, C2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C1, C4
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C13, C74
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
C1 \\sim C4: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C13 \\sim C74: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
Uanis(C3) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C71)
\\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C2) \\sim Ueq,
Uanis(C4) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C75)
\\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C12) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C74) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=1-FVAR(1)
 Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(H77C)=
 Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(H75C)=FVAR(1)
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=1-FVAR(2)
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H70C)=
 Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=FVAR(2)
 Sof(H1B)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C2)=Sof(H2A)=Sof(H2B)=
 Sof(H2C)=1-FVAR(3)
 Sof(H1A)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C3)=Sof(H3A)=Sof(H3B)=
 Sof(H3C)=FVAR(3)
 Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(H73C)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=
 Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(H72C)=1-FVAR(4)
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(H69C)=
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C1(H1A), C1(H1B), C12(H12), C29(H29)
6.b Secondary CH2 refined with riding coordinates:
 C38(H38A,H38B), C45(H45A,H45B), C52(H52A,H52B), C56(H56A,H56B)
6.c Aromatic/amide H refined with riding coordinates:
 C23(H23), C24(H24), C26(H26), C27(H27), C33(H33), C37(H37), C40(H40),
 C44(H44), C47(H47), C49(H49), C57(H57), C59(H59), C63(H63), C64(H64), C65(H65),
  C66(H66)
6.d Idealised Me refined as rotating group:
 C79(H79A,H79B,H79C), C78(H78A,H78B,H78C), C15(H15A,H15B,H15C), C10(H10A,H10B,
 H10C), C11(H11A,H11B,H11C), C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C31(H31A,
 H31B,H31C), C76(H76A,H76B,H76C), C77(H77A,H77B,H77C), C75(H75A,H75B,H75C),
 C19(H19A,H19B,H19C), C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C9(H9A,H9B,H9C),
  C71(H71A,H71B,H71C), C7(H7A,H7B,H7C), C6(H6A,H6B,H6C), C70(H70A,H70B,H70C),
 C17(H17A,H17B,H17C), C60(H60A,H60B,H60C), C5(H5A,H5B,H5C), C3(H3A,H3B,H3C),
 C4(H4A,H4B,H4C), C2(H2A,H2B,H2C), C22(H22A,H22B,H22C), C69(H69A,H69B,H69C),
 C16(H16A,H16B,H16C), C73(H73A,H73B,H73C), C74(H74A,H74B,H74C), C72(H72A,H72B,
 H72C)
;
_shelx_res_checksum              7078
_olex2_submission_special_instructions 'No special instructions were received'