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_7711104
_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         'C90 H132 N2 O6 Ti2, 4(C6 H14)'
_chemical_formula_sum            'C114 H188 N2 O6 Ti2'
_chemical_formula_weight         1778.45
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 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                 107.21(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.488(4)
_cell_length_b                   23.772(5)
_cell_length_c                   25.128(5)
_cell_measurement_reflns_used    37976
_cell_measurement_temperature    100
_cell_measurement_theta_max      72.40
_cell_measurement_theta_min      2.54
_cell_volume                     11120(4)
_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
_diffrn_detector                 Pilatus200K
_diffrn_detector_area_resol_mean 5.81
_diffrn_detector_type            'DECTRIS PILATUS 200K'
_diffrn_measured_fraction_theta_full 0.974
_diffrn_measured_fraction_theta_max 0.951
_diffrn_measurement_details
;
 2034 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  0.0578
_diffrn_reflns_av_unetI/netI     0.0605
_diffrn_reflns_Laue_measured_fraction_full 0.974
_diffrn_reflns_Laue_measured_fraction_max 0.951
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            69768
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.951
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.120
_diffrn_reflns_theta_min         2.537
_diffrn_source                   'GeniX 3D HF Cu'
_diffrn_source_current           0.600
_diffrn_source_power             0.030
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.595
_exptl_absorpt_correction_T_max  0.9497
_exptl_absorpt_correction_T_min  0.3374
_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            Orange
_exptl_crystal_density_diffrn    1.062
_exptl_crystal_description       Rod
_exptl_crystal_F_000             3912
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane'
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.391
_refine_diff_density_min         -0.399
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1218
_refine_ls_number_reflns         20847
_refine_ls_number_restraints     885
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.1174
_refine_ls_R_factor_gt           0.0731
_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^)+(0.0741P)^2^+18.3285P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1669
_refine_ls_wR_factor_ref         0.1986
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14251
_reflns_number_total             20847
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01739c2.cif
_cod_data_source_block           5
_cod_original_cell_volume        11119(4)
_cod_database_code               7711104
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.924
_shelx_estimated_absorpt_t_min   0.515
_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. Restrained distances
 C106-C105 \\sim C1D-C1C
 with sigma of 0.02
 C106-C107 \\sim C1D-C1E
 with sigma of 0.02
 C105-C104 \\sim C1C-C1B
 with sigma of 0.02
 C108-C107 \\sim C1F-C1E
 with sigma of 0.02
 C105-C107 \\sim C1C-C1E
 with sigma of 0.04
 C105-C103 \\sim C1C-C1A
 with sigma of 0.04
 C104-C103 \\sim C1B-C1A
 with sigma of 0.02
 C106-C108 \\sim C1D-C1F
 with sigma of 0.04
 C106-C104 \\sim C1D-C1B
 with sigma of 0.04
3. 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 0.02 within 2A
4. Others
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(C1C)=
 Sof(H1CA)=Sof(H1CB)=Sof(C1D)=Sof(H1DA)=Sof(H1DB)=Sof(C1E)=Sof(H1EA)=Sof(H1EB)=
 Sof(C1F)=Sof(H1FA)=Sof(H1FB)=Sof(H1FC)=1-FVAR(1)
 Sof(C103)=Sof(H10K)=Sof(H10L)=Sof(H10M)=Sof(C104)=Sof(H10N)=Sof(H10O)=
 Sof(C105)=Sof(H10P)=Sof(H10Q)=Sof(C106)=Sof(H10R)=Sof(H10S)=Sof(C107)=
 Sof(H10T)=Sof(H10U)=Sof(C108)=Sof(H10V)=Sof(H10W)=Sof(H10X)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C16(H16A,H16B), C31(H31A,H31B), C46(H46A,H46B), C61(H61A,H61B),
 C76(H76A,H76B), C02T(H02A,H02B), C02X(H02C,H02D), C032(H03G,H03H), C037(H03I,
 H03J), C92(H92A,H92B), C93(H93A,H93B), C94(H94A,H94B), C95(H95A,H95B),
 C98(H98A,H98B), C99(H99A,H99B), C100(H10D,H10E), C101(H10F,H10G), C104(H10N,
 H10O), C105(H10P,H10Q), C106(H10R,H10S), C107(H10T,H10U), C1B(H1BA,H1BB),
 C1C(H1CA,H1CB), C1D(H1DA,H1DB), C1E(H1EA,H1EB)
5.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C7(H7), C20(H20), C22(H22), C35(H35), C37(H37), C50(H50), C52(H52),
 C65(H65), C67(H67), C80(H80), C82(H82)
5.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), C15(H15A,H15B,H15C), 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), C54(H54A,
 H54B,H54C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C58(H58A,H58B,H58C),
 C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C69(H69A,H69B,H69C), C70(H70A,H70B,
 H70C), C71(H71A,H71B,H71C), C73(H73A,H73B,H73C), C74(H74A,H74B,H74C), C75(H75A,
 H75B,H75C), C84(H84A,H84B,H84C), C85(H85A,H85B,H85C), C86(H86A,H86B,H86C),
 C88(H88A,H88B,H88C), C89(H89A,H89B,H89C), C90(H90A,H90B,H90C), C03A(H03A,H03B,
 H03C), C031(H03D,H03E,H03F), C91(H91A,H91B,H91C), C96(H96A,H96B,H96C),
 C97(H97A,H97B,H97C), C102(H10H,H10I,H10J), C103(H10K,H10L,H10M), C108(H10V,
 H10W,H10X), C1A(H1AA,H1AB,H1AC), C1F(H1FA,H1FB,H1FC)
;
_shelx_res_checksum              95664
_shelx_hkl_checksum              97175
_olex2_submission_special_instructions 'No special instructions were received'