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_7709490
_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         'C120 H90 N19 O70 Ti19, 0.5(C8 H24 N2)'
_chemical_formula_sum            'C124 H102 N20 O70 Ti19'
_chemical_formula_weight         3902.35
_space_group_crystal_system      orthorhombic
_space_group_IT_number           31
_space_group_name_Hall           'P 2ac -2'
_space_group_name_H-M_alt        'P m n 21'
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   22.0234(10)
_cell_length_b                   15.8771(5)
_cell_length_c                   28.8999(6)
_cell_measurement_reflns_used    7646
_cell_measurement_temperature    172.99(10)
_cell_measurement_theta_max      71.1900
_cell_measurement_theta_min      3.0230
_cell_volume                     10105.4(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 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 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 0.985
_diffrn_measured_fraction_theta_max 0.927
_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     38.00  83.00   1.00    9.30    --  106.49 -92.00  96.00   45
  2  \w     36.00 109.00   1.00    9.30    --  106.49-125.00  22.00   73
  3  \w     -3.00  23.00   1.00    0.55    --   48.45 -31.00-118.00   26
  4  \w     35.00  63.00   1.00    9.30    --  106.49 -57.00-120.00   28
  5  \w     98.00 160.00   1.00    9.30    --  106.49  31.00  41.00   62
  6  \w     98.00 176.00   1.00    9.30    --  106.49 125.00-120.00   78
  7  \w    -27.00  24.00   1.00    0.55    --  -48.45  19.00-150.00   51
  8  \w    -61.00 -23.00   1.00    9.30    --  -86.25  92.00-150.00   38
  9  \w    -41.00 -13.00   1.00    9.30    --  -86.25  38.00  30.00   28
 10  \w    -27.00  23.00   1.00    0.55    --  -48.45  19.00 150.00   50
 11  \w   -118.00 -74.00   1.00    0.55    --  -48.45-125.00  60.00   44
;
_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      -0.0166552000
_diffrn_orient_matrix_UB_12      -0.0339982000
_diffrn_orient_matrix_UB_13      0.0792882000
_diffrn_orient_matrix_UB_21      0.0131621000
_diffrn_orient_matrix_UB_22      -0.0609224000
_diffrn_orient_matrix_UB_23      -0.0411230000
_diffrn_orient_matrix_UB_31      0.0488877000
_diffrn_orient_matrix_UB_32      0.0049444000
_diffrn_orient_matrix_UB_33      0.0380000000
_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  0.0575
_diffrn_reflns_av_unetI/netI     0.0647
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.927
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            35091
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.927
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.491
_diffrn_reflns_theta_min         2.783
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.691
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71104
_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    1.282
_exptl_crystal_description       block
_exptl_crystal_F_000             3928
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.662
_refine_diff_density_min         -0.430
_refine_diff_density_rms         0.078
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.328(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1208
_refine_ls_number_reflns         13913
_refine_ls_number_restraints     518
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0965
_refine_ls_R_factor_gt           0.0704
_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^)+(0.1320P)^2^+0.0545P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1918
_refine_ls_wR_factor_ref         0.2147
_reflns_Friedel_coverage         0.960
_reflns_Friedel_fraction_full    0.986
_reflns_Friedel_fraction_max     0.927
_reflns_number_gt                9510
_reflns_number_total             13913
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt04170c2.cif
_cod_data_source_block           ti19pa19
_cod_database_code               7709490
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.878
_shelx_estimated_absorpt_t_min   0.825
_reflns_odcompleteness_completeness 98.58
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.672(14)
 0.328(14)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C66-C67
 1.45 with sigma of 0.02
 C45-C47
 2.35 with sigma of 0.02
 C47-C43
 2.35 with sigma of 0.02
 C44-C43 = C44-C45 = C46-C45 = C47-C46 = N1-C47 = N1-C43
 1.41 with sigma of 0.01
 O39B-C63A = O40A-C63A
 1.25 with sigma of 0.02
 O36-C54 = O37-C54
 1.25 with sigma of 0.02
 C44-C46
 2.35 with sigma of 0.02
 C47-C48
 1.45 with sigma of 0.02
 O39B-C63B
 1.25 with sigma of 0.02
 C46-N1
 2.35 with sigma of 0.02
 C42-C41
 1.53 with sigma of 0.02
 C43-C45
 2.35 with sigma of 0.02
 C55-C56 = C55-C57 = O38-C55
 1.45 with sigma of 0.01
 O38-C55
 1.45 with sigma of 0.02
 C57-C56
 2.35 with sigma of 0.01
 O38-C57
 2.35 with sigma of 0.01
 O38-C56
 2.35 with sigma of 0.02
 C2-C3 = C2-C1 = N7-C1 = N7-C5 = C5-C4 = C3-C4
 1.41 with sigma of 0.01
 C62B-C63B
 1.45 with sigma of 0.02
 C50-C51 = C50-C49 = N8-C49 = N8-C53 = C53-C52 = C52-C51
 1.41 with sigma of 0.02
 O40B-C63B = O39A-C63B
 1.25 with sigma of 0.02
 C62A-C63A
 1.45 with sigma of 0.02
 N9A-C62A = N9A-C58A = C59A-C58A = C60A-C59A = C61A-C60A = C62A-C61A
 1.41 with sigma of 0.02
 N9B-C62B = C62B-C61B = C61B-C60B = C60B-C59B = C59B-C58B = N9B-C58B
 1.41 with sigma of 0.02
 C65-C64
 1.45 with sigma of 0.02
 N11-C65
 1.45 with sigma of 0.02
 N11-C66
 1.45 with sigma of 0.02
 C67-C66
 1.45 with sigma of 0.02
 C4-C2
 2.35 with sigma of 0.02
 N7-C3
 2.8 with sigma of 0.02
 C5-C2
 2.8 with sigma of 0.02
 C4-C1
 2.8 with sigma of 0.02
4. Restrained planarity
 O24, O25, C43, C44, C45, C46, C47, C48
 with sigma of 0.01
 O39B, O40B, N9B, C58B, C59B, C60B, C61B, C62B, C63B
 with sigma of 0.01
 O36, O37, N8, C49, C50, C51, C52, C53, C54
 with sigma of 0.01
 O3, O4, N7, C1, C2, C3, C4, C5, C6
 with sigma of 0.01
 N9A, C58A, C59A, C60A, C61A, C62A
 with sigma of 0.01
 N2, C37, C38, C39, C40, C41
 with sigma of 0.01
5. Uiso/Uaniso restraints and constraints
O24 \\sim O25 \\sim N1 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim
C48: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O39B \\sim O40B \\sim N9B \\sim C58B \\sim C59B \\sim C60B \\sim C61B \\sim
C62B \\sim C63B: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
O36 \\sim O37 \\sim N8 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim
C54: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O38 \\sim C55 \\sim C56 \\sim C57: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
O3 \\sim O4 \\sim N7 \\sim C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O39A \\sim O40A \\sim N9A \\sim C58A \\sim C59A \\sim C60A \\sim C61A \\sim
C62A \\sim C63A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
O5 \\sim O6 \\sim N6 \\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
N2 \\sim 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
N11 \\sim C64 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C67: 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: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
6. Others
 Sof(O39B)=Sof(O40B)=Sof(N9B)=Sof(C58B)=Sof(H58B)=Sof(C59B)=Sof(H59B)=
 Sof(C60B)=Sof(H60B)=Sof(C61B)=Sof(H61B)=Sof(C62B)=Sof(C63B)=1-FVAR(1)
 Sof(O39A)=Sof(O40A)=Sof(N9A)=Sof(C58A)=Sof(H58A)=Sof(C59A)=Sof(H59A)=
 Sof(C60A)=Sof(H60A)=Sof(C61A)=Sof(H61A)=Sof(C62A)=Sof(C63A)=FVAR(1)
 Fixed Sof: O36(0.5) O37(0.5) N8(0.5) C49(0.5) H49(0.5) C50(0.5) H50(0.5)
 C51(0.5) H51(0.5) C52(0.5) H52(0.5) C53(0.5) C54(0.5) H11A(0.5) H11B(0.5)
 C64(0.5) H64A(0.5) H64B(0.5) H64C(0.5) C65(0.5) H65A(0.5) H65B(0.5) C66(0.5)
 H66A(0.5) H66B(0.5) C67(0.5) H67A(0.5) H67B(0.5) H67C(0.5)
7.a Ternary CH refined with riding coordinates:
 C55(H55)
7.b Secondary CH2 refined with riding coordinates:
 N11(H11A,H11B), C65(H65A,H65B), C66(H66A,H66B)
7.c Me refined with riding coordinates:
 C64(H64A,H64B,H64C), C67(H67A,H67B,H67C)
7.d Aromatic/amide H refined with riding coordinates:
 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),
  C49(H49), C50(H50), C51(H51), C52(H52), C58A(H58A), C58B(H58B), C59A(H59A),
 C59B(H59B), C60A(H60A), C60B(H60B), C61A(H61A), C61B(H61B)
7.e Idealised Me refined as rotating group:
 C56(H56A,H56B,H56C), C57(H57A,H57B,H57C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 566 electrons were 
found in a volume of 3379\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
26[CH3CN] per Unit Cell 
which account for 572 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              24028
_shelx_fab_checksum              60816
_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 1.407
_oxdiff_exptl_absorpt_empirical_full_min 0.866