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_7711304
_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
'C108 H72 N18 O54 Ti12, 1.5(H4 O2), 2(C4 H11 N)'
_chemical_formula_sum            'C116 H100 N20 O57 Ti12'
_chemical_formula_weight         3260.95
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-03-20
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-04-04 deposited with the CCDC.	2022-09-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.021(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   32.8178(7)
_cell_length_b                   15.2483(3)
_cell_length_c                   32.1138(8)
_cell_measurement_reflns_used    11844
_cell_measurement_temperature    173
_cell_measurement_theta_max      75.9610
_cell_measurement_theta_min      2.9650
_cell_volume                     14678.5(7)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      173
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.942
_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     30.00  88.00   1.00    0.29    --   48.45  67.00-157.00   58
  2  \w     88.00 161.00   1.00    1.13    --  106.49  67.00-157.00   73
  3  \w     93.00 173.00   1.00    1.13    --  106.49  57.00-120.00   80
  4  \w    102.00 177.00   1.00    1.13    --  106.49  19.00 150.00   75
  5  \w   -120.00 -30.00   1.00    0.29    --  -48.45 -67.00  69.00   90
  6  \w   -137.00-112.00   1.00    1.13    --  -86.25 -67.00  69.00   25
  7  \w    -61.00 -35.00   1.00    1.13    --  -86.25  67.00-157.00   26
  8  \w    -11.00  14.00   1.00    0.29    --  -48.45  67.00-157.00   25
  9  \w    -67.00 -31.00   1.00    0.29    --  -48.45  67.00-157.00   36
 10  \w    -42.00 -13.00   1.00    1.13    --  -86.25  38.00  30.00   29
 11  \w    -26.00  24.00   1.00    0.29    --  -48.45  19.00-150.00   50
 12  \w     39.00 105.00   1.00    1.13    --  106.49 -99.00 -60.00   66
 13  \w     35.00  64.00   1.00    1.13    --  106.49 -57.00 -60.00   29
 14  \w     40.00  81.00   1.00    1.13    --  106.49 -67.00  69.00   41
 15  \w     42.00 105.00   1.00    1.13    --  106.49 -77.00 120.00   63
 16  \w      3.00  55.00   1.00    0.29    --   48.45 -67.00  69.00   52
 17  \w     36.00  65.00   1.00    1.13    --  106.49 -57.00  30.00   29
 18  \w    140.00 178.00   1.00    1.13    --  106.49 125.00 120.00   38
 19  \w     96.00 130.00   1.00    1.13    --  106.49 125.00 120.00   34
;
_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      0.0203682000
_diffrn_orient_matrix_UB_12      -0.0559114000
_diffrn_orient_matrix_UB_13      0.0436424000
_diffrn_orient_matrix_UB_21      -0.0259668000
_diffrn_orient_matrix_UB_22      0.0540406000
_diffrn_orient_matrix_UB_23      0.0216855000
_diffrn_orient_matrix_UB_31      -0.0393777000
_diffrn_orient_matrix_UB_32      -0.0644947000
_diffrn_orient_matrix_UB_33      -0.0196682000
_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  0.0792
_diffrn_reflns_av_unetI/netI     0.0861
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.942
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -41
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            44649
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.544
_diffrn_reflns_theta_min         3.013
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.052
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75942
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.112a (Rigaku Oxford Diffraction, 2021)
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    1.476
_exptl_crystal_description       needle
_exptl_crystal_F_000             6624
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.352
_refine_diff_density_min         -1.224
_refine_diff_density_rms         0.131
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.908
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     933
_refine_ls_number_reflns         14543
_refine_ls_number_restraints     137
_refine_ls_restrained_S_all      0.922
_refine_ls_R_factor_all          0.1449
_refine_ls_R_factor_gt           0.1097
_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^)+(0.1880P)^2^+245.4452P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2974
_refine_ls_wR_factor_ref         0.3261
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10617
_reflns_number_total             14543
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01882a2.cif
_cod_data_source_block           2
_cod_original_cell_volume        14678.5(6)
_cod_database_code               7711304
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_usercomment     'Ti O C N'
_shelx_estimated_absorpt_t_max   0.942
_shelx_estimated_absorpt_t_min   0.713
_reflns_odcompleteness_completeness 98.68
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C40-C39
 1.42 with sigma of 0.02
 C58-C57
 1.45 with sigma of 0.02
 C57-N10
 1.45 with sigma of 0.02
 C58-N10
 2.35 with sigma of 0.02
 C39-C40
 1.42 with sigma of 0.02
 C41-C40
 1.42 with sigma of 0.02
 C41-N6
 1.42 with sigma of 0.02
 N6-C37
 1.42 with sigma of 0.02
 C37-C38
 1.42 with sigma of 0.02
 C39-C38
 1.42 with sigma of 0.02
 C42-C41
 1.42 with sigma of 0.02
 C39-C41
 2.35 with sigma of 0.02
 C39-C37
 2.35 with sigma of 0.02
 C37-C41
 2.35 with sigma of 0.02
 C40-C38
 2.35 with sigma of 0.02
 C38-N6
 2.35 with sigma of 0.02
 N6-C40
 2.35 with sigma of 0.02
 C37-C40
 2.8 with sigma of 0.02
 C39-N6
 2.8 with sigma of 0.02
 C38-C41
 2.8 with sigma of 0.02
 N10-C55
 1.45 with sigma of 0.02
 C56-N10
 2.35 with sigma of 0.02
 C56-C55
 1.45 with sigma of 0.02
3. Restrained planarity
 O26, O27, N9, C25, C26, C27, C28, C29, C30
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
N10 \\sim C55 \\sim C56 \\sim C57 \\sim C58: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C25 \\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(N10) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C55)
\\sim Ueq, Uanis(C56) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
5. Others
 Fixed Sof: H4A(0.5) H4B(0.5)
6.a Free rotating group:
 O4(H4A,H4B), O28(H28A,H28B)
6.b Secondary CH2 refined with riding coordinates:
 C55(H55A,H55B), C57(H57A,H57B)
6.c Aromatic/amide H refined with riding coordinates:
 N10(H10A), C1(H1), C2(H2), C3(H3), C4(H4), C9(H9), C10(H10), C11(H11),
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C19(H19), C20(H20), C21(H21),
  C22(H22), C27(H27), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32),
 C33(H33), C34(H34), C37(H37), C38(H38), C39(H39), C40(H40), C45(H45), C46(H46),
  C47(H47), C48(H48), C50(H50), C51(H51), C52(H52), C53(H53)
6.d Idealised Me refined as rotating group:
 C56(H56A,H56B,H56C), C58(H58A,H58B,H58C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 488 electrons were 
found in a volume of 1996\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
3[CH3CN] per Asymmetric Unit 
which account for 528 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              19880
_shelx_hkl_checksum              23606
_shelx_fab_checksum              42621
_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 1.290
_oxdiff_exptl_absorpt_empirical_full_min 0.392