Formate Complexes of Tri- and Tetravalent Titanium Supported by a Tris(phenolato)amine Ligand
Okuda, Jun; Okumura, Akira; Ghana, Priyabrata; Fink, Fabian; Schmidt, Regina; Hoffmann, Alexander; Spaniol, Thomas Paul; Herres-Pawlis, Sonja; Dalton Transactions  (2022) –; doi:10.1039/D2DT01739C

data_7711105
_publ_section_title
;
 Formate Complexes of Tri- and Tetravalent Titanium Supported by a
 Tris(phenolato)amine Ligand
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT01739C
_journal_year                    2022
_chemical_formula_moiety         'C49 H76 N O4 Ti'
_chemical_formula_sum            'C49 H76 N O4 Ti'
_chemical_formula_weight         791.00
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-10-13
_audit_creation_method
;
Olex2 1.5
(compiled 2021.08.20 svn.r13c46975 for OlexSys, GUI svn.r6405)
;
_audit_update_record
;
2022-06-01 deposited with the CCDC.	2022-08-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.06(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.251(4)
_cell_length_b                   18.683(4)
_cell_length_c                   12.230(2)
_cell_measurement_reflns_used    44351
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      72.50
_cell_measurement_theta_min      3.22
_cell_volume                     4616.5(17)
_computing_cell_refinement
;
X-Area Recipe 1.36.0.0 (STOE, 2020)
;
_computing_data_collection
;
X-Area Pilatus3_SV 1.31.170.0 (STOE, 2020)
;
_computing_data_reduction
;
X-Area Integrate 1.78.3.0 (STOE, 2020)
X-Area LANA 1.83.8.0 (STOE, 2020)
;
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.00
_diffrn_detector                 Pilatus200K
_diffrn_detector_area_resol_mean 5.81
_diffrn_detector_type            'DECTRIS PILATUS 200K'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_details
;
 3785 frames, detector distance = 55 mm
;
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '0.5 mm diameter'
_diffrn_radiation_monochromator  'Graded multilayer mirror'
_diffrn_radiation_polarisn_norm  270
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0356
_diffrn_reflns_av_unetI/netI     0.0314
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            26594
_diffrn_reflns_point_group_measured_fraction_full 0.909
_diffrn_reflns_point_group_measured_fraction_max 0.885
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.163
_diffrn_reflns_theta_min         3.222
_diffrn_source                   'GeniX 3D HF Cu'
_diffrn_source_current           1.000
_diffrn_source_power             0.050
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.884
_exptl_absorpt_correction_T_max  0.3618
_exptl_absorpt_correction_T_min  0.0716
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE X-Red32, absorption correction by Gaussian integration, analogous to
P. Coppens in: F. R. Ahmed (Editor), "Crystallographic Computing", Munksgaard,
Copenhagen (1970), 255 - 270. Afterwards scaling of reflection intensities was
performed within STOE LANA. J. Koziskova, F. Hahn, J. Richter, J. Kozisek, Acta
Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
Finally a spherical absorption correction was done within STOE LANA.
;
_exptl_crystal_colour            'Pale blue'
_exptl_crystal_density_diffrn    1.138
_exptl_crystal_description       Block
_exptl_crystal_F_000             1724
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: diethyl ether'
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.32
_refine_diff_density_max         1.262
_refine_diff_density_min         -0.793
_refine_diff_density_rms         0.129
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.016(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     526
_refine_ls_number_reflns         8038
_refine_ls_number_restraints     362
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0748
_refine_ls_R_factor_gt           0.0692
_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^)+(0.1785P)^2^+1.7544P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1735
_refine_ls_wR_factor_ref         0.1988
_reflns_Friedel_coverage         0.787
_reflns_Friedel_fraction_full    0.819
_reflns_Friedel_fraction_max     0.780
_reflns_number_gt                7780
_reflns_number_total             8038
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01739c2.cif
_cod_data_source_block           4Et2O
_cod_original_cell_volume        4616.3(18)
_cod_database_code               7711105
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.584
_shelx_estimated_absorpt_t_min   0.505
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.01 within 2A
3. Others
 Fixed Sof: C15B(0.45) H15A(0.45) H15B(0.45) H15C(0.45) C15A(0.55) H15D(0.55)
 H15E(0.55) H15F(0.55)
4.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C16(H16A,H16B), C31(H31A,H31B), C46(H46A,H46B), C48(H48A,H48B)
4.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C7(H7), C20(H20), C22(H22), C35(H35), C37(H37)
4.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,
 H13C), C14(H14A,H14B,H14C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,
 H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C),
 C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C43(H43A,H43B,
 H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C47(H47A,H47B,H47C), C49(H49A,
 H49B,H49C), C15B(H15A,H15B,H15C), C15A(H15D,H15E,H15F)
;
_shelx_res_checksum              76486
_shelx_hkl_checksum              55297
_olex2_submission_special_instructions 'No special instructions were received'