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_7709492
_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         'C95 H65 N15 O61 Ti15, C4 H11 N'
_chemical_formula_sum            'C99 H76 N16 O61 Ti15'
_chemical_formula_weight         3184.25
_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   mixed
_audit_creation_date             2021-11-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-12-06 deposited with the CCDC.	2022-01-31 downloaded from the CCDC.
;
_cell_angle_alpha                89.709(3)
_cell_angle_beta                 80.240(3)
_cell_angle_gamma                81.263(4)
_cell_formula_units_Z            2
_cell_length_a                   15.9539(6)
_cell_length_b                   17.4707(9)
_cell_length_c                   29.0128(9)
_cell_measurement_reflns_used    12118
_cell_measurement_temperature    172.99(10)
_cell_measurement_theta_max      76.3440
_cell_measurement_theta_min      2.9420
_cell_volume                     7875.3(6)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_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 0.957
_diffrn_measured_fraction_theta_max 0.901
_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   -107.00 -72.00   1.00    6.60    --  -86.25  86.00  16.00   35
  2  \w   -158.00-113.00   1.00    6.60    --  -86.25 -86.00-101.00   45
  3  \w   -106.00 -79.00   1.00    6.60    --  -86.25 -86.00-101.00   27
  4  \w    -65.00 -23.00   1.00    6.60    --  -86.25  86.00  16.00   42
  5  \w    135.00 172.00   1.00    6.60    --  106.49  86.00  16.00   37
  6  \w    101.00 131.00   1.00    6.60    --  106.49  86.00  16.00   30
  7  \w    -26.00  27.00   1.00    1.40    --  -48.45  19.00 -90.00   53
  8  \w    -75.00  24.00   1.00    1.40    --  -48.45  86.00  16.00   99
  9  \w   -120.00 -73.00   1.00    1.40    --  -48.45-125.00  60.00   47
 10  \w    -21.00  75.00   1.00    1.40    --   48.45 -86.00-101.00   96
 11  \w   -159.00 -73.00   1.00    6.60    --  -86.25 -38.00 -60.00   86
 12  \w    -66.00 -14.00   1.00    6.60    --  -86.25  57.00  30.00   52
 13  \w     35.00 106.00   1.00    6.60    --  106.49 -99.00 120.00   71
 14  \w     34.00 106.00   1.00    6.60    --  106.49 -99.00 150.00   72
 15  \w     37.00 112.00   1.00    6.60    --  106.49 -86.00-101.00   75
 16  \w     36.00 111.00   1.00    6.60    --  106.49-125.00 120.00   75
 17  \w     94.00 120.00   1.00    6.60    --  106.49  19.00-150.00   26
 18  \w    123.00 177.00   1.00    6.60    --  106.49  19.00-150.00   54
 19  \w     34.00 105.00   1.00    6.60    --  106.49 -99.00  30.00   71
 20  \w     37.00 175.00   1.00    6.60    --  106.49   0.00-180.00  138
 21  \w     34.00 106.00   1.00    6.60    --  106.49 -99.00 -30.00   72
 22  \w     34.00 106.00   1.00    6.60    --  106.49 -99.00-150.00   72
;
_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      -0.0604998000
_diffrn_orient_matrix_UB_12      -0.0052046000
_diffrn_orient_matrix_UB_13      -0.0356149000
_diffrn_orient_matrix_UB_21      -0.0479786000
_diffrn_orient_matrix_UB_22      -0.0555062000
_diffrn_orient_matrix_UB_23      0.0322090000
_diffrn_orient_matrix_UB_31      -0.0622017000
_diffrn_orient_matrix_UB_32      0.0696771000
_diffrn_orient_matrix_UB_33      0.0244631000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1059
_diffrn_reflns_av_unetI/netI     0.1111
_diffrn_reflns_Laue_measured_fraction_full 0.957
_diffrn_reflns_Laue_measured_fraction_max 0.901
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            73602
_diffrn_reflns_point_group_measured_fraction_full 0.957
_diffrn_reflns_point_group_measured_fraction_max 0.901
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.593
_diffrn_reflns_theta_min         2.962
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.825
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78205
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.343
_exptl_crystal_description       block
_exptl_crystal_F_000             3200
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.574
_refine_diff_density_min         -0.554
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.944
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1725
_refine_ls_number_reflns         29824
_refine_ls_number_restraints     2097
_refine_ls_restrained_S_all      0.989
_refine_ls_R_factor_all          0.1590
_refine_ls_R_factor_gt           0.0831
_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^)+(0.1465P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2232
_refine_ls_wR_factor_ref         0.2729
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12485
_reflns_number_total             29824
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt04170c2.cif
_cod_data_source_block           ti15pa15
_cod_database_code               7709492
_shelxl_version_number           2013-4
_chemical_oxdiff_usercomment     'Ti O C'
_shelx_estimated_absorpt_t_max   0.821
_shelx_estimated_absorpt_t_min   0.772
_diffrn_oxdiff_digest_frames
;
0127c494afdb3da2e0ebfc1b1324270fff01375d122
;
_diffrn_oxdiff_digest_hkl
;
01b88409bd41435dd56a9ec9edb127edc0d6a7
;
_reflns_odcompleteness_completeness 96.10
_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
2. Restrained distances
 N13-C81 = N13-C77 = C78-C77 = C78-C79 = C80-C79 = C80-C81
 1.42 with sigma of 0.02
 C80-N13
 2.35 with sigma of 0.02
 C77-C79
 2.35 with sigma of 0.02
 C81-C77
 2.35 with sigma of 0.02
 C78-C80
 2.35 with sigma of 0.02
 C79-C81
 2.35 with sigma of 0.02
 C45-C47
 2.35 with sigma of 0.02
 C48-N8
 2.35 with sigma of 0.02
 C46-C48
 2.35 with sigma of 0.02
 C47-C49
 2.35 with sigma of 0.02
 C45-C46 = C47-C46 = C47-C48 = C48-C49 = N8-C49 = N8-C45
 1.42 with sigma of 0.02
 C49-C45
 2.35 with sigma of 0.02
 N8-C46
 2.35 with sigma of 0.02
 C22-C21
 1.42 with sigma of 0.02
 C24-C23
 1.42 with sigma of 0.02
 C21-C23
 2.35 with sigma of 0.02
 C22-C23
 1.42 with sigma of 0.02
 C20-C22
 2.35 with sigma of 0.02
 N16-H16A
 0.98 with sigma of 0.02
3. Restrained planarity
 O51, O52, N13, C76, C77, C78, C79, C80, C81
 with sigma of 0.01
4. Rigid bond restraints
 C70, C71
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.01
 C35, C36
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.01
 O37, C44
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.01
 C73, C74
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
O51 \\sim O52 \\sim N13 \\sim C76 \\sim C77 \\sim C78 \\sim C79 \\sim C80 \\sim
C81: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O41 \\sim O42 \\sim N9 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim
C56: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O39 \\sim O40 \\sim N8 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim
C50: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O27 \\sim O28 \\sim N4 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim
C25: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33
\\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41
\\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49
\\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57
\\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65
\\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73
\\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81
\\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86 \\sim C87 \\sim C88 \\sim C89
\\sim C90 \\sim C91 \\sim C92 \\sim C93 \\sim C94 \\sim C95 \\sim C96 \\sim C97
\\sim C98 \\sim C99: within 3.8A with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C10) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(N2) \\sim
Ueq, Uanis(C12) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C13) \\sim Ueq,
Uanis(O24) \\sim Ueq, Uanis(O23) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(N1) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(O36) \\sim Ueq, Uanis(O35)
\\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C3) \\sim Ueq,
Uanis(C2) \\sim Ueq, Uanis(C1) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O21) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(O22) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(O52) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(O51) \\sim Ueq, Uanis(C77)
\\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(N13) \\sim Ueq, Uanis(C81) \\sim Ueq,
Uanis(C80) \\sim Ueq, Uanis(C79) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C92) \\sim Ueq, Uanis(N15) \\sim Ueq, Uanis(C88) \\sim Ueq, Uanis(C89)
\\sim Ueq, Uanis(C90) \\sim Ueq, Uanis(C91) \\sim Ueq, Uanis(C93) \\sim Ueq,
Uanis(O55) \\sim Ueq, Uanis(O56) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(N3) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C16)
\\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C19) \\sim Ueq,
Uanis(O25) \\sim Ueq, Uanis(O26) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O54) \\sim Ueq, Uanis(C87) \\sim Ueq, Uanis(O53) \\sim Ueq, Uanis(C86)
\\sim Ueq, Uanis(C85) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C83) \\sim Ueq,
Uanis(C82) \\sim Ueq, Uanis(N14) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C45) \\sim Ueq, Uanis(N8) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C50)
\\sim Ueq, Uanis(O39) \\sim Ueq, Uanis(O40) \\sim Ueq, Uanis(C48) \\sim Ueq,
Uanis(C47) \\sim Ueq, Uanis(C46) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
6.a Secondary CH2 refined with riding coordinates:
 C97(H97A,H97B), C98(H98A,H98B)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11),
 C14(H14), C15(H15), C16(H16), C17(H17), C20(H20), C21(H21), C22(H22), C23(H23),
  C26(H26), C27(H27), C28(H28), C29(H29), C32(H32), C33(H33), C34(H34),
 C35(H35), C38(H38), C39(H39), C40(H40), C41(H41), C44(H44), C45(H45), C46(H46),
  C47(H47), C48(H48), C51(H51), C52(H52), C53(H53), C54(H54), C57(H57),
 C58(H58), C59(H59), C60(H60), C61(H61), C64(H64), C65(H65), C66(H66), C67(H67),
  C70(H70), C71(H71), C72(H72), C73(H73), C78(H78), C79(H79), C80(H80),
 C81(H81), C82(H82), C83(H83), C84(H84), C85(H85), C88(H88), C89(H89), C90(H90),
  C91(H91), C94(H94), C95(H95)
6.c Idealised Me refined as rotating group:
 C96(H96A,H96B,H96C), C99(H99A,H99B,H99C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 483 electrons were 
found in a volume of 2531\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
11[CH3CN] per Asymmetric Unit 
which account for 484 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              66420
_shelx_fab_checksum              37276
_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 1.619
_oxdiff_exptl_absorpt_empirical_full_min 0.498