Syntheses, structures and ligand binding modes of titanium-oxide complexes of 2-picolinate
Gao, Chang; Liu, Caiyun; Said, Amir; Niu, Huihui; Wang, Dexin; Wang, Guo; Tung, Chen-Ho; Wang, Yifeng; Dalton Transactions  (2022) –; doi:10.1039/D1DT04170C

data_7709491
_publ_section_title
;
 Syntheses, structures and ligand binding modes of titanium-oxide
 complexes of 2-picolinate
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D1DT04170C
_journal_year                    2022
_chemical_formula_moiety         'C66 H86 N8 O56 Ti18'
_chemical_formula_sum            'C66 H86 N8 O56 Ti18'
_chemical_formula_weight         2749.62
_space_group_crystal_system      cubic
_space_group_IT_number           211
_space_group_name_Hall           'I 4 2 3'
_space_group_name_H-M_alt        'I 4 3 2'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-11-29
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2021-12-06 deposited with the CCDC.	2022-01-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            6
_cell_length_a                   32.0910(3)
_cell_length_b                   32.0910(3)
_cell_length_c                   32.0910(4)
_cell_measurement_reflns_used    6261
_cell_measurement_temperature    172.99(10)
_cell_measurement_theta_max      69.0980
_cell_measurement_theta_min      3.8540
_cell_volume                     33048.3(6)
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      172.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.955
_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     93.00 165.00   1.00   33.00    --  106.49  38.00-120.00   72
  2  \w    -23.00  25.00   1.00    3.80    --  -48.45  19.00-120.00   48
  3  \w    -65.00 -39.00   1.00   33.00    --  -86.25  78.00 -85.00   26
  4  \w   -105.00 -75.00   1.00   33.00    --  -86.25  78.00 -85.00   30
;
_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      -0.0108223000
_diffrn_orient_matrix_UB_12      0.0020988000
_diffrn_orient_matrix_UB_13      -0.0466756000
_diffrn_orient_matrix_UB_21      -0.0468001000
_diffrn_orient_matrix_UB_22      0.0011151000
_diffrn_orient_matrix_UB_23      0.0109069000
_diffrn_orient_matrix_UB_31      0.0015434000
_diffrn_orient_matrix_UB_32      0.0479287000
_diffrn_orient_matrix_UB_33      0.0018551000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0857
_diffrn_reflns_av_unetI/netI     0.0489
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            18693
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         76.464
_diffrn_reflns_theta_min         2.754
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.639
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.43449
_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            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    0.829
_exptl_crystal_description       plate
_exptl_crystal_F_000             8292
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.605
_refine_diff_density_min         -0.493
_refine_diff_density_rms         0.087
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.50(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     255
_refine_ls_number_reflns         5244
_refine_ls_number_restraints     179
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.1433
_refine_ls_R_factor_gt           0.0904
_refine_ls_shift/su_max          0.018
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1830P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2498
_refine_ls_wR_factor_ref         0.3016
_reflns_Friedel_coverage         0.769
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.959
_reflns_number_gt                2831
_reflns_number_total             5244
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt04170c2.cif
_cod_data_source_block           ti18pa8
_cod_original_cell_volume        33048.3(9)
_cod_database_code               7709491
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'Ti O C'
_shelx_estimated_absorpt_t_max   0.896
_shelx_estimated_absorpt_t_min   0.728
_reflns_odcompleteness_completeness 99.04
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.50(3)
 0.50(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 N1B-C8B = C7B-C8B = C7B-C6B = C5B-C6B = C4B-C5B = N1B-C4B
 1.33 with sigma of 0.02
 O2-C2
 1.5 with sigma of 0.02
 C7A-N1A
 2.35 with sigma of 0.02
 N1A-C5A
 2.35 with sigma of 0.02
 O4-C3
 1.5 with sigma of 0.02
 N1A-C8A = C8A-C7A = C7A-C6A = C5A-C6A = C5A-C4A = N1A-C4A
 1.33 with sigma of 0.02
 N1A-C6A
 2.75 with sigma of 0.02
 C9B-C8B
 1.5 with sigma of 0.02
 N1B-C7B
 2.35 with sigma of 0.02
 C8A-C9A
 1.5 with sigma of 0.02
 C5B-N1B
 2.35 with sigma of 0.02
 C6B-N1B
 2.75 with sigma of 0.02
 C8B-C4B
 2.35 with sigma of 0.02
 C5A-C7A
 2.35 with sigma of 0.02
 C4A-C7A
 2.75 with sigma of 0.02
 C8B-C6B
 2.35 with sigma of 0.02
 C7B-C5B
 2.35 with sigma of 0.02
 C4A-C6A
 2.35 with sigma of 0.02
 C6B-C4B
 2.35 with sigma of 0.02
 C6A-C8A
 2.35 with sigma of 0.02
 C5A-C8A
 2.75 with sigma of 0.02
 C7B-C4B
 2.75 with sigma of 0.02
 C8B-C5B
 2.75 with sigma of 0.02
4. Rigid bond restraints
 O2, C2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 O4, C3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
5. Uiso/Uaniso restraints and constraints
O8A \\sim O9A \\sim N1A \\sim C4A \\sim C5A \\sim C6A \\sim C7A \\sim C8A \\sim
C9A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O2 \\sim C2: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
O4 \\sim C3: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
O8B \\sim O9B \\sim N1B \\sim C4B \\sim C5B \\sim C6B \\sim C7B \\sim C8B \\sim
C9B: within 2A with sigma of 0.004 and sigma for terminal atoms of 0.008 within
2A
O1 \\sim C1: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
Uanis(N1A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O8B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C7A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
6. Others
 Sof(O8B)=Sof(O9B)=Sof(N1B)=Sof(C4B)=Sof(H4B)=Sof(C5B)=Sof(H5B)=Sof(C6B)=
 Sof(H6B)=Sof(C7B)=Sof(H7B)=Sof(C8B)=Sof(C9B)=1-FVAR(1)
 Sof(O8A)=Sof(O9A)=Sof(N1A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=
 Sof(H6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(C9A)=FVAR(1)
 Fixed Sof: H1C(0.25) H1A(0.25) H1B(0.25)
7.a Me refined with riding coordinates:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C)
7.b Aromatic/amide H refined with riding coordinates:
 C4A(H4A), C4B(H4B), C5A(H5A), C5B(H5B), C6A(H6A), C6B(H6B), C7A(H7A), C7B(H7B)
7.c Idealised Me refined as rotating group:
 C1(H1C,H1A,H1B)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 3030 electrons were 
found in a volume of 19585\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
3.5[CH4O] per Asymmetric Unit 
which account for 3024 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              55924
_shelx_fab_checksum              17559
_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 2.013
_oxdiff_exptl_absorpt_empirical_full_min 0.535