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_7711106
_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         'C50 H76 N O4 Ti, C5 H12'
_chemical_formula_sum            'C55 H88 N O4 Ti'
_chemical_formula_weight         875.16
_chemical_properties_physical    Air-sensitive,Moisture-sensitive,Heat-sensitive
_space_group_crystal_system      tetragonal
_space_group_IT_number           76
_space_group_name_Hall           'P 4w'
_space_group_name_H-M_alt        'P 41'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-04-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-06-01 deposited with the CCDC.	2022-08-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.476(2)
_cell_length_b                   14.476(2)
_cell_length_c                   25.385(5)
_cell_measurement_reflns_used    30927
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.44
_cell_measurement_theta_min      2.13
_cell_volume                     5319.5(15)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_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 0.999
_diffrn_measurement_details
;
 523 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    '0.6 mm diameter'
_diffrn_radiation_monochromator  'Graded multilayer mirror'
_diffrn_radiation_polarisn_norm  270
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0494
_diffrn_reflns_av_unetI/netI     0.0620
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            41253
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.482
_diffrn_reflns_theta_min         2.134
_diffrn_source                   'Genix Mo'
_diffrn_source_current           1.000
_diffrn_source_power             0.050
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.203
_exptl_absorpt_correction_T_max  0.8705
_exptl_absorpt_correction_T_min  0.4765
_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            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.093
_exptl_crystal_description       block
_exptl_crystal_F_000             1916
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: THP, pentane'
_exptl_crystal_size_max          0.58
_exptl_crystal_size_mid          0.457
_exptl_crystal_size_min          0.31
_refine_diff_density_max         0.673
_refine_diff_density_min         -0.350
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details
;
 Flack x determined using 3209 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.14(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     929
_refine_ls_number_reflns         11956
_refine_ls_number_restraints     1333
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0885
_refine_ls_R_factor_gt           0.0589
_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^)+(0.0995P)^2^+0.5073P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1473
_refine_ls_wR_factor_ref         0.1628
_reflns_Friedel_coverage         0.918
_reflns_Friedel_fraction_full    0.963
_reflns_Friedel_fraction_max     0.960
_reflns_number_gt                8852
_reflns_number_total             11956
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01739c2.cif
_cod_data_source_block           4THP
_cod_original_cell_volume        5320.0(18)
_cod_database_code               7711106
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.940
_shelx_estimated_absorpt_t_min   0.891
_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
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
3. Others
 Sof(O1B)=Sof(O2B)=Sof(O3B)=Sof(C1B)=Sof(C2B)=Sof(C3B)=Sof(H3B)=Sof(C4B)=
 Sof(C5B)=Sof(H5B)=Sof(C6B)=Sof(C7B)=Sof(C8B)=Sof(H8D)=Sof(H8E)=Sof(H8F)=
 Sof(C9B)=Sof(H9D)=Sof(H9E)=Sof(H9F)=Sof(C10B)=Sof(H10D)=Sof(H10E)=Sof(H10F)=
 Sof(C15B)=Sof(H15C)=Sof(H15D)=Sof(C16B)=Sof(C17B)=Sof(C18B)=Sof(H18B)=
 Sof(C19B)=Sof(C20B)=Sof(H20B)=Sof(C21B)=Sof(C30B)=Sof(H30C)=Sof(H30D)=
 Sof(C31B)=Sof(C32B)=Sof(C33B)=Sof(H33B)=Sof(C34B)=Sof(C35B)=Sof(H35B)=
 Sof(C36B)=Sof(C37B)=Sof(C38B)=Sof(H38D)=Sof(H38E)=Sof(H38F)=Sof(C39B)=
 Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C40B)=Sof(H40D)=Sof(H40E)=Sof(H40F)=
 Sof(C45B)=Sof(H45C)=Sof(H45D)=Sof(C46B)=Sof(H46C)=Sof(H46D)=Sof(C47B)=
 Sof(H47C)=Sof(H47D)=Sof(H48C)=Sof(H48D)=Sof(C49B)=Sof(H49C)=Sof(H49D)=
 Sof(C50B)=Sof(H50C)=Sof(H50D)=Sof(H52C)=Sof(H52D)=Sof(C53B)=Sof(H53C)=
 Sof(H53D)=Sof(C54B)=Sof(H54C)=Sof(H54D)=Sof(C55B)=Sof(H55D)=Sof(H55E)=
 Sof(H55F)=1-FVAR(1)
 Sof(O1A)=Sof(O2A)=Sof(O3A)=Sof(C1A)=Sof(C2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=
 Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(C7A)=Sof(C8A)=Sof(H8A)=Sof(H8B)=Sof(H8C)=
 Sof(C9A)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10A)=Sof(H10A)=Sof(H10B)=Sof(H10C)=
 Sof(C15A)=Sof(H15A)=Sof(H15B)=Sof(C16A)=Sof(C17A)=Sof(C18A)=Sof(H18A)=
 Sof(C19A)=Sof(C20A)=Sof(H20A)=Sof(C21A)=Sof(C30A)=Sof(H30A)=Sof(H30B)=
 Sof(C31A)=Sof(C32A)=Sof(C33A)=Sof(H33A)=Sof(C34A)=Sof(C35A)=Sof(H35A)=
 Sof(C36A)=Sof(C37A)=Sof(C38A)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C39A)=
 Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C40A)=Sof(H40A)=Sof(H40B)=Sof(H40C)=
 Sof(C45A)=Sof(H45A)=Sof(H45B)=Sof(C46A)=Sof(H46A)=Sof(H46B)=Sof(C47A)=
 Sof(H47A)=Sof(H47B)=Sof(H48A)=Sof(H48B)=Sof(C49A)=Sof(H49A)=Sof(H49B)=
 Sof(C50A)=Sof(H50A)=Sof(H50B)=Sof(H52A)=Sof(H52B)=Sof(C53A)=Sof(H53A)=
 Sof(H53B)=Sof(C54A)=Sof(H54A)=Sof(H54B)=Sof(C55A)=Sof(H55A)=Sof(H55B)=
 Sof(H55C)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C15A(H15A,H15B), C15B(H15C,H15D), C30A(H30A,H30B), C30B(H30C,H30D), C45A(H45A,
 H45B), C46A(H46A,H46B), C47A(H47A,H47B), C45B(H45C,H45D), C46B(H46C,H46D),
 C47B(H47C,H47D), C48(H48A,H48B), C48(H48C,H48D), C49A(H49A,H49B), C50A(H50A,
 H50B), C49B(H49C,H49D), C50B(H50C,H50D), C52(H52A,H52B), C52(H52C,H52D),
 C53A(H53A,H53B), C54A(H54A,H54B), C53B(H53C,H53D), C54B(H54C,H54D)
4.b Aromatic/amide H refined with riding coordinates:
 C3A(H3A), C5A(H5A), C3B(H3B), C5B(H5B), C18A(H18A), C20A(H20A), C18B(H18B),
 C20B(H20B), C33A(H33A), C35A(H35A), C33B(H33B), C35B(H35B)
4.c Idealised Me refined as rotating group:
 C8A(H8A,H8B,H8C), C9A(H9A,H9B,H9C), C10A(H10A,H10B,H10C), C8B(H8D,H8E,H8F),
 C9B(H9D,H9E,H9F), C10B(H10D,H10E,H10F), C12(H12A,H12B,H12C), C13(H13A,H13B,
 H13C), C14(H14A,H14B,H14C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,
 H25B,H25C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C),
 C38A(H38A,H38B,H38C), C39A(H39A,H39B,H39C), C40A(H40A,H40B,H40C), C38B(H38D,
 H38E,H38F), C39B(H39D,H39E,H39F), C40B(H40D,H40E,H40F), C42(H42A,H42B,H42C),
 C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C51(H51A,H51B,H51C), C55A(H55A,H55B,
 H55C), C55B(H55D,H55E,H55F)
;
_shelx_res_checksum              83888
_shelx_hkl_checksum              68938
_olex2_submission_special_instructions 'No special instructions were received'