New Picolinate-Functionalized Titanium-Oxide Clusters: Syntheses, Structure and Photocatalytic H2 Evolution
Gao, Chang; Wang, Dexin; Liu, Yanshu; Zhang, Guanyun; Liu, Caiyun; Said, Amir; Niu, Huihui; Tung, Chen-Ho; Wang, Yifeng; Dalton Transactions  (2022) –; doi:10.1039/D2DT01882A

data_7711303
_publ_section_title
;
 New Picolinate-Functionalized Titanium-Oxide Clusters: Syntheses,
 Structure and Photocatalytic H2 Evolution
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT01882A
_journal_year                    2022
_chemical_formula_moiety
'C96 H64 N16 O50 Ti12, 2(C3 H8 O), C4 H11 N, 4(C2 H3 N), 4(C4 H12 N)'
_chemical_formula_sum            'C130 H151 N25 O52 Ti12'
_chemical_formula_weight         3470.55
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-03-20
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2022-04-04 deposited with the CCDC.	2022-09-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.617(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   17.8911(4)
_cell_length_b                   14.9531(4)
_cell_length_c                   28.9581(6)
_cell_measurement_reflns_used    13738
_cell_measurement_temperature    172.99
_cell_measurement_theta_max      75.6090
_cell_measurement_theta_min      3.0600
_cell_volume                     7659.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      172.99
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.938
_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     -3.00  22.00   1.00    0.31    --  -48.45 100.00 171.00   25
  2  \w    -79.00  -9.00   1.00    0.31    --  -48.45 100.00 171.00   70
  3  \w     14.00  69.00   1.00    0.31    --   48.45-100.00  66.00   55
  4  \w    -80.00 -54.00   1.00    2.70    --  -86.25 100.00 171.00   26
  5  \w     70.00 105.00   1.00    2.70    --  106.49-100.00  66.00   35
  6  \w    107.00 175.00   1.00    2.70    --  106.49 100.00 171.00   68
  7  \w   -120.00 -74.00   1.00    0.31    --  -48.45-125.00-180.00   46
  8  \w    -27.00  27.00   1.00    0.31    --  -48.45  19.00 -90.00   54
  9  \w   -120.00 -73.00   1.00    0.31    --  -48.45-125.00-120.00   47
 10  \w    -43.00 -14.00   1.00    2.70    --  -86.25  38.00 -90.00   29
 11  \w    -43.00 -17.00   1.00    2.70    --  -86.25  38.00  30.00   26
 12  \w    -40.00 -13.00   1.00    2.70    --  -86.25  38.00-120.00   27
 13  \w    -43.00 -16.00   1.00    2.70    --  -86.25  38.00   0.00   27
 14  \w   -141.00-115.00   1.00    2.70    --  -86.25-100.00  66.00   26
 15  \w     35.00  66.00   1.00    2.70    --  106.49 -57.00  90.00   31
 16  \w     34.00 105.00   1.00    2.70    --  106.49 -77.00  90.00   71
 17  \w     34.00  66.00   1.00    2.70    --  106.49 -57.00 -90.00   32
 18  \w     34.00  66.00   1.00    2.70    --  106.49 -57.00 -30.00   32
 19  \w     36.00  66.00   1.00    2.70    --  106.49 -57.00 120.00   30
 20  \w     34.00 106.00   1.00    2.70    --  106.49 -99.00  90.00   72
 21  \w     34.00  66.00   1.00    2.70    --  106.49 -57.00 -60.00   32
 22  \w     35.00  66.00   1.00    2.70    --  106.49 -57.00-180.00   31
 23  \w     34.00  66.00   1.00    2.70    --  106.49 -57.00-120.00   32
 24  \w     35.00  66.00   1.00    2.70    --  106.49 -57.00 150.00   31
 25  \w     34.00 105.00   1.00    2.70    --  106.49 -77.00-120.00   71
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0771761000
_diffrn_orient_matrix_UB_12      0.0476240000
_diffrn_orient_matrix_UB_13      0.0053056000
_diffrn_orient_matrix_UB_21      0.0361826000
_diffrn_orient_matrix_UB_22      -0.0852348000
_diffrn_orient_matrix_UB_23      -0.0168567000
_diffrn_orient_matrix_UB_31      -0.0177848000
_diffrn_orient_matrix_UB_32      0.0329619000
_diffrn_orient_matrix_UB_33      -0.0508232000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0795
_diffrn_reflns_av_unetI/netI     0.0790
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.938
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            50920
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.170
_diffrn_reflns_theta_min         3.087
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.815
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44056
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.505
_exptl_crystal_description       plate
_exptl_crystal_F_000             3572
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.074
_refine_diff_density_min         -0.707
_refine_diff_density_rms         0.121
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1020
_refine_ls_number_reflns         15222
_refine_ls_number_restraints     330
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.1122
_refine_ls_R_factor_gt           0.0782
_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^)+(0.1196P)^2^+15.6417P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2039
_refine_ls_wR_factor_ref         0.2230
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11647
_reflns_number_total             15222
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01882a2.cif
_cod_data_source_block           1
_cod_original_cell_volume        7659.7(3)
_cod_database_code               7711303
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_usercomment     'Ti O C N'
_shelx_estimated_absorpt_t_max   0.944
_shelx_estimated_absorpt_t_min   0.845
_reflns_odcompleteness_completeness 98.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H67A,H67B,H67C} of C67, All C(H,H) groups, All N(H)
  groups, All N(H,H) groups
 At 1.5 times of:
  All O(H) groups, {H53A,H53B,H53C} of C53, {H55A,H55B,H55C} of C55, {H51A,
  H51B,H51C} of C51, {H50A,H50B,H50C} of C50, {H59A,H59B,H59C} of C59, {H65A,
  H65B,H65C} of C65, {H63A,H63B,H63C} of C63, {H61A,H61B,H61C} of C61, {H57A,
  H57B,H57C} of C57
2. Restrained distances
 C66-C67
 1.45 with sigma of 0.01
 C64-C65
 1.45 with sigma of 0.01
 N9-C58 = N9-C56 = C57-C56 = C59-C58
 1.45 with sigma of 0.01
 C58-C56
 2.35 with sigma of 0.02
 N9-C57
 2.35 with sigma of 0.01
 N9-C59
 2.35 with sigma of 0.01
 C59-C57
 3.5 with sigma of 0.02
 C58-C57
 3 with sigma of 0.02
 N10-C66
 1.1 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
N10 \\sim C66 \\sim C67: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
N9 \\sim C56 \\sim C57 \\sim C58 \\sim C59: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
O1 \\sim O2 \\sim O3 \\sim O4 \\sim O5 \\sim O6 \\sim O7 \\sim O8 \\sim O9
\\sim O10 \\sim O11 \\sim O12 \\sim O13 \\sim O14 \\sim O15 \\sim O16 \\sim O17
\\sim O18 \\sim O19 \\sim O20 \\sim O21 \\sim O22 \\sim O23 \\sim O24 \\sim O25
\\sim O26: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 3.8A
4. Others
 Fixed Sof: N9(0.5) H9A(0.5) C56(0.5) H56A(0.5) H56B(0.5) C57(0.5) H57A(0.5)
 H57B(0.5) H57C(0.5) C58(0.5) H58A(0.5) H58B(0.5) C59(0.5) H59A(0.5) H59B(0.5)
 H59C(0.5)
5.a Ternary CH refined with riding coordinates:
 C49(H49)
5.b Secondary CH2 refined with riding coordinates:
 N12(H12A,H12B), N13(H13A,H13B), C52(H52A,H52B), C54(H54A,H54B), C56(H56A,
 H56B), C58(H58A,H58B), C60(H60A,H60B), C62(H62A,H62B)
5.c Aromatic/amide H refined with riding coordinates:
 N9(H9A), C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C10(H10),
 C13(H13), C14(H14), C15(H15), C16(H16), C19(H19), C20(H20), C21(H21), C22(H22),
  C25(H25), C26(H26), C27(H27), C28(H28), C31(H31), C32(H32), C33(H33),
 C34(H34), C37(H37), C38(H38), C39(H39), C40(H40), C43(H43), C44(H44), C45(H45),
  C46(H46)
5.d Idealised Me refined as rotating group:
 C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C53(H53A,H53B,H53C), C55(H55A,H55B,
 H55C), C57(H57A,H57B,H57C), C59(H59A,H59B,H59C), C61(H61A,H61B,H61C), C63(H63A,
 H63B,H63C), C65(H65A,H65B,H65C), C67(H67A,H67B,H67C)
5.e Idealised tetrahedral OH refined as rotating group:
 O26(H26A)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              42284
_shelx_hkl_checksum              29370
_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 1.700
_oxdiff_exptl_absorpt_empirical_full_min 0.488