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_7709489
_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         'C56 H96 N4 O48 Ti17'
_chemical_formula_sum            'C56 H96 N4 O48 Ti17'
_chemical_formula_weight         2407.66
_space_group_crystal_system      monoclinic
_space_group_IT_number           11
_space_group_name_Hall           '-P 2yb'
_space_group_name_H-M_alt        'P 1 21/m 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-01-11
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2022-01-27 deposited with the CCDC.	2022-01-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.466(15)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.1453(18)
_cell_length_b                   25.9558(14)
_cell_length_c                   14.178(2)
_cell_measurement_reflns_used    3589
_cell_measurement_temperature    172.99(10)
_cell_measurement_theta_max      72.2260
_cell_measurement_theta_min      3.3290
_cell_volume                     4810.4(11)
_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(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.824
_diffrn_measured_fraction_theta_max 0.738
_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     34.00  66.00   1.00   11.83    --  106.49 -57.00 -90.00   32
  2  \w     35.00  66.00   1.00   11.83    --  106.49 -57.00-120.00   31
  3  \w     37.00 106.00   1.00   11.83    --  106.49-125.00-150.00   69
  4  \w     39.00  85.00   1.00   11.83    --  106.49-134.00  29.00   46
  5  \w     37.00  66.00   1.00   11.83    --  106.49 -57.00  60.00   29
  6  \w    -27.00  27.00   1.00    4.05    --  -48.20  19.00-150.00   54
  7  \w    -78.00 -19.00   1.00   11.83    --  -86.25 103.00-155.00   59
  8  \w   -120.00 -37.00   1.00    4.05    --  -48.20 -21.00-111.00   83
  9  \w   -147.00 -74.00   1.00   11.83    --  -86.25 -21.00-111.00   73
;
_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      -0.0545305000
_diffrn_orient_matrix_UB_12      0.0148197000
_diffrn_orient_matrix_UB_13      -0.1132351000
_diffrn_orient_matrix_UB_21      0.1010175000
_diffrn_orient_matrix_UB_22      -0.0076137000
_diffrn_orient_matrix_UB_23      -0.0157585000
_diffrn_orient_matrix_UB_31      -0.0278238000
_diffrn_orient_matrix_UB_32      -0.0569380000
_diffrn_orient_matrix_UB_33      -0.0273316000
_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  0.0544
_diffrn_reflns_av_unetI/netI     0.0635
_diffrn_reflns_Laue_measured_fraction_full 0.824
_diffrn_reflns_Laue_measured_fraction_max 0.738
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            15616
_diffrn_reflns_point_group_measured_fraction_full 0.824
_diffrn_reflns_point_group_measured_fraction_max 0.738
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.110
_diffrn_reflns_theta_min         3.381
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.086
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60509
_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    1.662
_exptl_crystal_description       needle
_exptl_crystal_F_000             2436
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.476
_refine_diff_density_min         -1.113
_refine_diff_density_rms         0.156
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     641
_refine_ls_number_reflns         7758
_refine_ls_number_restraints     180
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.1319
_refine_ls_R_factor_gt           0.1015
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1802P)^2^+27.5065P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2870
_refine_ls_wR_factor_ref         0.3121
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5265
_reflns_number_total             7758
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt04170c2.cif
_cod_data_source_block           ti17pa4
_cod_original_cell_volume        4810.3(11)
_cod_database_code               7709489
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_usercomment     'Ti O C N'
_shelx_estimated_absorpt_t_max   0.889
_shelx_estimated_absorpt_t_min   0.531
_reflns_odcompleteness_completeness 83.01
_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 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
 O21-C23B = C23B-C24
 1.45 with sigma of 0.02
 C26_$1-C26
 2.35 with sigma of 0.02
 O27-C28
 2.35 with sigma of 0.001
 C26_$1-C25_$1 = O20-C25_$1
 1.45 with sigma of 0.02
 C28-C27
 1.45 with sigma of 0.01
 O20-C26_$1
 2.35 with sigma of 0.02
 O27-C27
 1.45 with sigma of 0.01
 O21-C23A = C23A-C24
 1.45 with sigma of 0.02
 O26-C30A
 2.35 with sigma of 0.02
 C14-O19
 2.35 with sigma of 0.02
 C14-C13
 1.45 with sigma of 0.02
 O23-C19
 1.45 with sigma of 0.02
 C20-C19
 1.45 with sigma of 0.02
 O24-C18
 2.35 with sigma of 0.02
 C17-C18
 1.45 with sigma of 0.02
 O24-C17
 1.45 with sigma of 0.02
 O26-C29
 1.45 with sigma of 0.02
 O26-C30B
 2.35 with sigma of 0.02
 C29-C30B
 1.45 with sigma of 0.02
 O21-C24
 2.35 with sigma of 0.02
 O21-C23A = C23A-C24 = C23B-C24 = O21-C23B
 1.45 with sigma of 0.02
 O22-C22A
 2.35 with sigma of 0.02
 C22A-C21
 1.45 with sigma of 0.02
 O22-C21
 1.45 with sigma of 0.02
 C31-C32
 1.45 with sigma of 0.02
 C18-C17
 1.45 with sigma of 0.02
 C30B-C29
 1.45 with sigma of 0.02
 C30A-C29
 1.45 with sigma of 0.02
 C16-C15 = O25-C15
 1.45 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O20 \\sim C25 \\sim C26: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O27 \\sim C27 \\sim C28: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O21 \\sim C23B \\sim C24: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O21 \\sim C23A \\sim C24: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O19 \\sim C13 \\sim C14: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O26 \\sim C29 \\sim C30A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O28 \\sim C31 \\sim C32: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O22 \\sim C21 \\sim C22B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O23 \\sim C19 \\sim C20: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O24 \\sim C17 \\sim C18: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O26 \\sim C29 \\sim C30B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O21 \\sim C24: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
O25 \\sim C15 \\sim C16: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O22 \\sim C21 \\sim C22A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
4. Others
 Sof(H29A)=Sof(H29B)=Sof(C30A)=Sof(H30A)=Sof(H30B)=Sof(H30C)=1-FVAR(1)
 Sof(H29C)=Sof(H29D)=Sof(C30B)=Sof(H30D)=Sof(H30E)=Sof(H30F)=FVAR(1)
 Fixed Sof: C13(0.5) H13A(0.5) H13B(0.5) C14(0.5) H14A(0.5) H14B(0.5)
 H14C(0.5) H15A(0.5) H15B(0.5) H16A(0.5) H16B(0.5) H16C(0.5) H17A(0.5)
 H17B(0.5) H18B(0.5) H18C(0.5) H21A(0.5) H21B(0.5) H21C(0.5) H21D(0.5)
 C22A(0.5) H22A(0.5) H22B(0.5) H22C(0.5) C22B(0.5) H22D(0.5) H22E(0.5)
 H22F(0.5) C23A(0.5) H23A(0.5) H23B(0.5) C23B(0.5) H23C(0.5) H23D(0.5)
 H24A(0.5) H24B(0.5) H24C(0.5) H24D(0.5) H24E(0.5) H24F(0.5) C26(0.5) H26A(0.5)
 H26B(0.5) H26C(0.5) C25(0.5) H25A(0.5) H25B(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C15(H15A,H15B), C17(H17A,H17B), C19(H19A,H19B), C21(H21A,
 H21B), C21(H21C,H21D), C23A(H23A,H23B), C23B(H23C,H23D), C27(H27A,H27B),
 C29(H29A,H29B), C29(H29C,H29D), C31(H31A,H31B), C25(H25A,H25B)
5.b Me refined with riding coordinates:
 C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C26(H26A,H26B,H26C)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C10(H10)
5.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C22A(H22A,H22B,H22C), C22B(H22D,
 H22E,H22F), C24(H24A,H24B,H24C), C24(H24D,H24E,H24F), C28(H28A,H28B,H28C),
 C30A(H30A,H30B,H30C), C30B(H30D,H30E,H30F), C32(H32A,H32B,H32C)
;
_shelx_res_checksum              59323
_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 1.363
_oxdiff_exptl_absorpt_empirical_full_min 0.667