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_7127730
_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 H154 Br4 N2 O20 Ti4, 6(C2 H3 N)'
_chemical_formula_sum            'C144 H172 Br4 N8 O20 Ti4'
_chemical_formula_weight         2846.13
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 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                90
_cell_angle_beta                 94.280(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.9642(7)
_cell_length_b                   24.0870(7)
_cell_length_c                   23.8190(7)
_cell_measurement_reflns_used    2956
_cell_measurement_temperature    150
_cell_measurement_theta_max      28.56
_cell_measurement_theta_min      1.86
_cell_volume                     15427.0(8)
_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 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_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  0.0330
_diffrn_reflns_av_unetI/netI     0.0477
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            46513
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.000
_diffrn_reflns_theta_min         1.715
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    1.297
_exptl_absorpt_correction_T_max  0.595
_exptl_absorpt_correction_T_min  0.542
_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    1.225
_exptl_crystal_description       block
_exptl_crystal_F_000             5920
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.4
_refine_diff_density_max         1.358
_refine_diff_density_min         -1.114
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.122
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1016
_refine_ls_number_reflns         15071
_refine_ls_number_restraints     188
_refine_ls_restrained_S_all      1.140
_refine_ls_R_factor_all          0.1042
_refine_ls_R_factor_gt           0.0696
_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^)+(0.1437P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2038
_refine_ls_wR_factor_ref         0.2236
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10367
_reflns_number_total             15071
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc05336h2.cif
_cod_data_source_block           Ti4-5
_cod_database_code               7127730
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.625
_shelx_estimated_absorpt_t_min   0.563
_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
 C81-C75
 1.45 with sigma of 0.01
 C59-C56A \\sim C59-C55 \\sim C59-C55A \\sim C59-C57 \\sim C59-C57A \\sim
C59-C56A
 with sigma of 0.01
 C82-C49 \\sim C82-C50 \\sim C82-C51 \\sim C82-C52 \\sim C82-C53 \\sim C82-C54
 with sigma of 0.01
 C83-C60 \\sim C83-C61 \\sim C83-C62 \\sim C83-C63 \\sim C83-C64 \\sim C83-C65
 with sigma of 0.01
 C1-C44 \\sim C1-C45 \\sim C1-C46
 with sigma of 0.01
3. Rigid bond restraints
 C59
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
C59: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.2 within 2A
Uanis(C53) \\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C60)
\\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C69) \\sim Ueq,
Uanis(C73) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C78A)
\\sim Ueq, Uanis(C81) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C68) \\sim Ueq,
Uanis(C39) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C54)
\\sim Ueq, Uanis(C57A) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C45) \\sim Ueq,
Uanis(C25A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C55A) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C56A) \\sim Ueq: with sigma
of 0.001 and sigma for terminal atoms of 0.002
5. Others
 Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=
 Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=1-FVAR(1)
 Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(H63C)=Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(H61C)=
 Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(H65C)=FVAR(1)
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=
 Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=1-FVAR(2)
 Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=
 Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=FVAR(2)
 Sof(C69)=Sof(H69)=Sof(C73)=Sof(H73)=Sof(C72)=Sof(H72)=Sof(C70)=Sof(H70)=
 Sof(C78A)=Sof(Br4)=Sof(C25A)=1-FVAR(3)
 Sof(Br3)=Sof(C80)=Sof(H80)=Sof(C79)=Sof(H79)=Sof(C77)=Sof(H77)=Sof(C78)=
 Sof(C76)=Sof(H76)=Sof(C25)=FVAR(3)
 Sof(C55A)=Sof(H55A)=Sof(H55B)=Sof(H55C)=Sof(C57A)=Sof(H57A)=Sof(H57B)=
 Sof(H57C)=Sof(C56A)=Sof(H56A)=Sof(H56B)=Sof(H56C)=1-FVAR(4)
 Sof(C56)=Sof(H56D)=Sof(H56E)=Sof(H56F)=Sof(C57)=Sof(H57D)=Sof(H57E)=Sof(H57F)=
 Sof(C55)=Sof(H55D)=Sof(H55E)=Sof(H55F)=FVAR(4)
 Fixed Sof: N3(0.5) C9(0.5) C68(0.5) H68A(0.5) H68B(0.5) H68C(0.5) N82(0.5)
 C81(0.5) H81A(0.5) H81B(0.5) H81C(0.5) C75(0.5)
6.a Ternary CH refined with riding coordinates:
 C42(H42), C39(H39)
6.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C00Y(H00A,H00B), C22(H22A,H22B), C29(H29A,H29B)
6.c Aromatic/amide H refined with riding coordinates:
 C18(H18), C20(H20), C24(H24), C26(H26), C31(H31), C3(H3), C2(H2), C5(H5),
 C6(H6), C33(H33), C13(H13), C11(H11), C80(H80), C79(H79), C77(H77), C76(H76),
 C69(H69), C73(H73), C72(H72), C70(H70)
6.d Idealised Me refined as rotating group:
 C37(H37A,H37B,H37C), C41(H41A,H41B,H41C), C38(H38A,H38B,H38C), C40(H40A,H40B,
 H40C), C43(H43A,H43B,H43C), C68(H68A,H68B,H68C), C50(H50A,H50B,H50C), C52(H52A,
 H52B,H52C), C54(H54A,H54B,H54C), C51(H51A,H51B,H51C), C53(H53A,H53B,H53C),
 C49(H49A,H49B,H49C), C63(H63A,H63B,H63C), C61(H61A,H61B,H61C), C65(H65A,H65B,
 H65C), C62(H62A,H62B,H62C), C60(H60A,H60B,H60C), C64(H64A,H64B,H64C), C47(H47A,
 H47B,H47C), C66(H66A,H66B,H66C), C81(H81A,H81B,H81C), C55A(H55A,H55B,H55C),
 C57A(H57A,H57B,H57C), C56A(H56A,H56B,H56C), C56(H56D,H56E,H56F), C57(H57D,H57E,
 H57F), C55(H55D,H55E,H55F), C44(H44A,H44B,H44C), C46(H46A,H46B,H46C), C45(H45A,
 H45B,H45C)
;
_shelx_res_checksum              87707
_olex2_submission_special_instructions 'No special instructions were received'