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_7127729
_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         'C116 H160 N4 O22 Ti4, 4(C3 H7 N O)'
_chemical_formula_sum            'C128 H188 N8 O26 Ti4'
_chemical_formula_weight         2446.45
_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             2020-10-06
_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                82.875(3)
_cell_angle_beta                 72.447(4)
_cell_angle_gamma                75.012(4)
_cell_formula_units_Z            1
_cell_length_a                   14.4277(6)
_cell_length_b                   14.6080(5)
_cell_length_c                   17.6599(7)
_cell_measurement_reflns_used    13428
_cell_measurement_temperature    150
_cell_measurement_theta_max      29.8440
_cell_measurement_theta_min      2.1860
_cell_volume                     3423.7(2)
_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_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_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    -65.00  28.00   0.50   15.00    --    5.62 -73.00  71.00  186
  2  \w    -28.00  21.00   0.50   15.00    --    5.62 -37.00  90.00   98
  3  \w    -23.00  29.00   0.50   15.00    --   -6.01 -99.00  30.00  104
  4  \w    -19.00   6.00   0.50   15.00    --   -6.01 -19.00 -60.00   50
  5  \w    -16.00  40.00   0.50   15.00    --    5.62 -99.00-150.00  112
  6  \w    -15.00  25.00   0.50   15.00    --   -6.01 -99.00 -90.00   80
  7  \w    -54.00  22.00   0.50   15.00    --    5.62 -57.00 -60.00  152
  8  \w     18.00  57.00   0.50   15.00    --    5.62  73.00-159.00   78
  9  \w    -68.00 -42.00   0.50   15.00    --    5.62 -37.00  90.00   52
 10  \w    -64.00  12.00   0.50   15.00    --    5.62 -37.00   0.00  152
;
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0398100000
_diffrn_orient_matrix_UB_12      0.0328152000
_diffrn_orient_matrix_UB_13      0.0242384000
_diffrn_orient_matrix_UB_21      -0.0312421000
_diffrn_orient_matrix_UB_22      -0.0025051000
_diffrn_orient_matrix_UB_23      -0.0235625000
_diffrn_orient_matrix_UB_31      -0.0158625000
_diffrn_orient_matrix_UB_32      -0.0380772000
_diffrn_orient_matrix_UB_33      0.0252256000
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0544
_diffrn_reflns_av_unetI/netI     0.0470
_diffrn_reflns_Laue_measured_fraction_full 0.998
_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       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            55130
_diffrn_reflns_point_group_measured_fraction_full 0.998
_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         1.931
_exptl_absorpt_coefficient_mu    0.293
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82271
_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    1.187
_exptl_crystal_description       block
_exptl_crystal_F_000             1308
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.6
_exptl_crystal_size_min          0.5
_refine_diff_density_max         0.652
_refine_diff_density_min         -0.818
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     862
_refine_ls_number_reflns         13423
_refine_ls_number_restraints     129
_refine_ls_restrained_S_all      1.115
_refine_ls_R_factor_all          0.0969
_refine_ls_R_factor_gt           0.0649
_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^)+(0.1366P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1933
_refine_ls_wR_factor_ref         0.2115
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9012
_reflns_number_total             13423
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc05336h2.cif
_cod_data_source_block           Ti4-4
_cod_database_code               7127729
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.867
_shelx_estimated_absorpt_t_min   0.799
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C29-C30
 1.45 with sigma of 0.01
 C48-C42
 1.45 with sigma of 0.001
 C29-C30 \\sim C29-C31 \\sim C29-C32 \\sim C29-C33 \\sim C29-C34 \\sim C29-C35
 with sigma of 0.01
 C42-C43 \\sim C42-C44 \\sim C42-C45 \\sim C42-C46 \\sim C42-C47 \\sim C42-C48
 with sigma of 0.01
 C52-C53 \\sim C52A-C53A
 with sigma of 0.01
3. Rigid bond restraints
 C51
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C63, C64
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C64, C65
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C18, C21
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C44, C42
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 N3, C60
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C53A, C52A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
C65 \\sim C64A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
N3 \\sim C60: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
Uanis(C48) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C31)
\\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C65) \\sim Ueq,
Uanis(C69) \\sim Ueq, Uanis(C64A) \\sim Ueq, Uanis(C53A) \\sim Ueq, Uanis(C52)
\\sim Ueq, Uanis(C52A) \\sim Ueq, Uanis(C33) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
5. Others
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=1-FVAR(1)
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=FVAR(1)
 Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(H48C)=
 Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=1-FVAR(2)
 Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=
 Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=FVAR(2)
 Sof(H63C)=Sof(H63D)=Sof(H65D)=Sof(H65E)=Sof(H65F)=Sof(C64A)=Sof(H64C)=
 Sof(H64D)=1-FVAR(3)
 Sof(H63A)=Sof(H63B)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H65A)=Sof(H65B)=
 Sof(H65C)=FVAR(3)
 Sof(H51C)=Sof(H51D)=Sof(C52A)=Sof(H52C)=Sof(H52D)=Sof(C53A)=Sof(H53D)=
 Sof(H53E)=Sof(H53F)=1-FVAR(4)
 Sof(H51A)=Sof(H51B)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(C53)=Sof(H53A)=Sof(H53B)=
 Sof(H53C)=FVAR(4)
6.a Secondary CH2 refined with riding coordinates:
 C49(H49A,H49B), C00T(H00A,H00B), C22(H22A,H22B), C11(H11A,H11B), C63(H63A,
 H63B), C63(H63C,H63D), C51(H51A,H51B), C51(H51C,H51D), C64(H64A,H64B),
 C64A(H64C,H64D), C52(H52A,H52B), C52A(H52C,H52D)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C17(H17), C39(H39), C26(H26), C37(H37), C28(H28), C15(H15),
 C59(H59), C56(H56), C67(H67), C69(H69)
6.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C58(H58A,H58B,H58C), C10(H10A,H10B,H10C), C20(H20A,H20B,
 H20C), C61(H61A,H61B,H61C), C19(H19A,H19B,H19C), C8(H8A,H8B,H8C), C21(H21A,
 H21B,H21C), C57(H57A,H57B,H57C), C60(H60A,H60B,H60C), C31(H31A,H31B,H31C),
 C33(H33A,H33B,H33C), C35(H35A,H35B,H35C), C32(H32A,H32B,H32C), C34(H34A,H34B,
 H34C), C30(H30A,H30B,H30C), C47(H47A,H47B,H47C), C45(H45A,H45B,H45C), C43(H43A,
 H43B,H43C), C44(H44A,H44B,H44C), C48(H48A,H48B,H48C), C46(H46A,H46B,H46C),
 C65(H65A,H65B,H65C), C65(H65D,H65E,H65F), C55(H55A,H55B,H55C), C70(H70A,H70B,
 H70C), C68(H68A,H68B,H68C), C71(H71A,H71B,H71C), C53(H53A,H53B,H53C),
 C53A(H53D,H53E,H53F)
;
_shelx_res_checksum              6524
_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 1.648
_oxdiff_exptl_absorpt_empirical_full_min 0.722