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_7711102
_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         'C91 H133 N2 O8 Ti2, 11(C6 D6)'
_chemical_formula_sum            'C157 H133 D66 N2 O8 Ti2'
_chemical_formula_weight         2404.38
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      trigonal
_space_group_IT_number           144
_space_group_name_Hall           'P 31'
_space_group_name_H-M_alt        'P 31'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-03-10
_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                120
_cell_formula_units_Z            3
_cell_length_a                   17.598(3)
_cell_length_b                   17.598(3)
_cell_length_c                   39.046(8)
_cell_measurement_reflns_used    166358
_cell_measurement_temperature    100
_cell_measurement_theta_max      71.51
_cell_measurement_theta_min      2.90
_cell_volume                     10472(3)
_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)'
_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 1.000
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
 5558 frames, detector distance = 60 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           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0429
_diffrn_reflns_av_unetI/netI     0.0334
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            187957
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.925
_diffrn_reflns_theta_min         2.899
_diffrn_source                   'GeniX 3D HF Cu'
_diffrn_source_current           0.600
_diffrn_source_power             0.030
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.399
_exptl_absorpt_correction_T_max  0.4067
_exptl_absorpt_correction_T_min  0.2032
_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            'Dark Yellow'
_exptl_crystal_density_diffrn    1.144
_exptl_crystal_description       Block
_exptl_crystal_F_000             3789
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: benzene'
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.33
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.413
_refine_diff_density_min         -0.315
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.358(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.990
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1844
_refine_ls_number_reflns         25795
_refine_ls_number_restraints     626
_refine_ls_restrained_S_all      0.994
_refine_ls_R_factor_all          0.0485
_refine_ls_R_factor_gt           0.0419
_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^)+(0.0758P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1054
_refine_ls_wR_factor_ref         0.1080
_reflns_Friedel_coverage         1.000
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                22483
_reflns_number_total             25795
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01739c2.cif
_cod_data_source_block           7
_cod_original_cell_volume        10472(4)
_cod_database_code               7711102
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.730
_shelx_estimated_absorpt_t_min   0.612
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.642(4)
 0.358(4)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H15A,H15B,H15C} of C15, All C(H,H) groups
 At 1.5 times of:
  {H13A,H13B,H13C} of C13, {H11A,H11B,H11C} of C11, {H24A,H24B,H24C} of C24,
  {H26A,H26B,H26C} of C26, {H10A,H10B,H10C} of C10, {H9A,H9B,H9C} of C9, {H14A,
  H14B,H14C} of C14, {H25A,H25B,H25C} of C25, {H29A,H29B,H29C} of C29, {H28A,
  H28B,H28C} of C28, {H56A,H56B,H56C} of C56, {H39A,H39B,H39C} of C39, {H40A,
  H40B,H40C} of C40, {H44A,H44B,H44C} of C44, {H30A,H30B,H30C} of C30, {H41A,
  H41B,H41C} of C41, {H54A,H54B,H54C} of C54, {H55A,H55B,H55C} of C55, {H45A,
  H45B,H45C} of C45, {H43A,H43B,H43C} of C43, {H59A,H59B,H59C} of C59, {H69A,
  H69B,H69C} of C69, {H70A,H70B,H70C} of C70, {H60A,H60B,H60C} of C60, {H73A,
  H73B,H73C} of C73, {H58A,H58B,H58C} of C58, {H74A,H74B,H74C} of C74, {H75A,
  H75B,H75C} of C75, {H71A,H71B,H71C} of C71, {H89A,H89B,H89C} of C89, {H90A,
  H90B,H90C} of C90, {H88A,H88B,H88C} of C88, {H84A,H84B,H84C} of C84, {H86A,
  H86B,H86C} of C86, {H85A,H85B,H85C} of C85
3. Restrained distances
 C147-C149
 -2.2 with sigma of 0.02
 C146-C150
 -2.2 with sigma of 0.02
 C154-C155
 1.4 with sigma of 0.02
 C134-C135 \\sim C135-C136 \\sim C136-C137 \\sim C137-C138 \\sim C138-C139
\\sim C139-C134
 with sigma of 0.02
 C140-C141 \\sim C141-C142 \\sim C142-C143 \\sim C143-C144 \\sim C144-C145
\\sim C145-C140
 with sigma of 0.02
 C152-C153 \\sim C153-C154 \\sim C154-C155 \\sim C155-C156 \\sim C156-C157
\\sim C157-C152
 with sigma of 0.02
 C146-C147 \\sim C147-C148 \\sim C148-C149 \\sim C149-C150 \\sim C150-C151
\\sim C151-C146
 with sigma of 0.02
 C158-C159 \\sim C159-C160 \\sim C160-C161 \\sim C161-C162 \\sim C162-C163
\\sim C163-C158
 with sigma of 0.02
 C164-C165 \\sim C165-C166 \\sim C166-C167 \\sim C167-C168 \\sim C168-C169
\\sim C169-C164
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C146 \\sim C147 \\sim C148 \\sim C149 \\sim C150 \\sim C151 \\sim C152 \\sim
C153 \\sim C154 \\sim C155 \\sim C156 \\sim C157: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
C176 \\sim C177 \\sim C178 \\sim C179 \\sim C180 \\sim C181 \\sim C182 \\sim
C183 \\sim C184 \\sim C185 \\sim C186 \\sim C187: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
C122 \\sim C123 \\sim C124 \\sim C125 \\sim C126 \\sim C127 \\sim C128 \\sim
C129 \\sim C130 \\sim C131 \\sim C132 \\sim C133: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
5. Others
 Sof(C1B)=Sof(H1B)=1-FVAR(1)
 Sof(C1A)=Sof(H1A)=FVAR(1)
 Sof(C128)=Sof(D128)=Sof(C129)=Sof(D129)=Sof(C130)=Sof(D130)=Sof(C131)=
 Sof(D131)=Sof(C132)=Sof(D132)=Sof(C133)=Sof(D133)=1-FVAR(2)
 Sof(C122)=Sof(D122)=Sof(C123)=Sof(D123)=Sof(C124)=Sof(D124)=Sof(C125)=
 Sof(D125)=Sof(C126)=Sof(D126)=Sof(C127)=Sof(D127)=FVAR(2)
 Sof(C140)=Sof(D140)=Sof(C141)=Sof(D141)=Sof(C142)=Sof(D142)=Sof(C143)=
 Sof(D143)=Sof(C144)=Sof(D144)=Sof(C145)=Sof(D145)=1-FVAR(3)
 Sof(C134)=Sof(D134)=Sof(C135)=Sof(D135)=Sof(C136)=Sof(D136)=Sof(C137)=
 Sof(D137)=Sof(C138)=Sof(D138)=Sof(C139)=Sof(D139)=FVAR(3)
 Sof(C152)=Sof(D152)=Sof(C153)=Sof(D153)=Sof(C154)=Sof(D154)=Sof(C155)=
 Sof(D155)=Sof(C156)=Sof(D156)=Sof(C157)=Sof(D157)=1-FVAR(4)
 Sof(C146)=Sof(D146)=Sof(C147)=Sof(D147)=Sof(C148)=Sof(D148)=Sof(C149)=
 Sof(D149)=Sof(C150)=Sof(D150)=Sof(C151)=Sof(D151)=FVAR(4)
 Sof(C164)=Sof(D164)=Sof(C165)=Sof(D165)=Sof(C166)=Sof(D166)=Sof(C167)=
 Sof(D167)=Sof(C168)=Sof(D168)=Sof(C169)=Sof(D169)=1-FVAR(5)
 Sof(C158)=Sof(D158)=Sof(C159)=Sof(D159)=Sof(C160)=Sof(D160)=Sof(C161)=
 Sof(D161)=Sof(C162)=Sof(D162)=Sof(C163)=Sof(D163)=FVAR(5)
 Sof(C182)=Sof(D182)=Sof(C183)=Sof(D183)=Sof(C184)=Sof(D184)=Sof(C185)=
 Sof(D185)=Sof(C186)=Sof(D186)=Sof(C187)=Sof(D187)=1-FVAR(6)
 Sof(C176)=Sof(D176)=Sof(C177)=Sof(D177)=Sof(C178)=Sof(D178)=Sof(C179)=
 Sof(D179)=Sof(C180)=Sof(D180)=Sof(C181)=Sof(D181)=FVAR(6)
6.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C31(H31A,H31B), C46(H46A,H46B), C61(H61A,H61B), C76(H76A,
 H76B), C91(H91A,H91B)
6.b Aromatic/amide H refined with riding coordinates:
 C1A(H1A), C1B(H1B), C4(H4), C6(H6), C19(H19), C21(H21), C34(H34), C36(H36),
 C49(H49), C51(H51), C64(H64), C66(H66), C79(H79), C81(H81), C92(D92), C93(D93),
  C94(D94), C95(D95), C96(D96), C97(D97), C98(D98), C99(D99), C100(D100),
 C101(D101), C102(D102), C103(D103), C104(D104), C105(D105), C106(D106),
 C107(D107), C108(D108), C109(D109), C110(D110), C111(D111), C112(D112),
 C113(D113), C114(D114), C115(D115), C116(D116), C117(D117), C118(D118),
 C119(D119), C120(D120), C121(D121), C122(D122), C123(D123), C124(D124),
 C125(D125), C126(D126), C127(D127), C128(D128), C129(D129), C130(D130),
 C131(D131), C132(D132), C133(D133), C134(D134), C135(D135), C136(D136),
 C137(D137), C138(D138), C139(D139), C140(D140), C141(D141), C142(D142),
 C143(D143), C144(D144), C145(D145), C146(D146), C147(D147), C148(D148),
 C149(D149), C150(D150), C151(D151), C152(D152), C153(D153), C154(D154),
 C155(D155), C156(D156), C157(D157), C158(D158), C159(D159), C160(D160),
 C161(D161), C162(D162), C163(D163), C164(D164), C165(D165), C166(D166),
 C167(D167), C168(D168), C169(D169), C170(D170), C171(D171), C172(D172),
 C173(D173), C174(D174), C175(D175), C176(D176), C177(D177), C178(D178),
 C179(D179), C180(D180), C181(D181), C182(D182), C183(D183), C184(D184),
 C185(D185), C186(D186), C187(D187)
6.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)
;
_shelx_res_checksum              69781
_shelx_hkl_checksum              77500
_olex2_submission_special_instructions 'No special instructions were received'