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_7711107
_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         'C187 H271 K3 N4 O26 Ti4, 3(C7 H8)'
_chemical_formula_sum            'C208 H295 K3 N4 O26 Ti4'
_chemical_formula_weight         3576.36
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-03-30
_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                69.99(3)
_cell_angle_beta                 88.96(3)
_cell_angle_gamma                66.13(3)
_cell_formula_units_Z            2
_cell_length_a                   19.351(4)
_cell_length_b                   22.616(5)
_cell_length_c                   30.581(6)
_cell_measurement_reflns_used    127486
_cell_measurement_temperature    100
_cell_measurement_theta_max      72.47
_cell_measurement_theta_min      2.22
_cell_volume                     11387(6)
_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                 'Hybrid Pixel Counting Detector'
_diffrn_detector_area_resol_mean 5.81
_diffrn_detector_type            'Dectris Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.918
_diffrn_measurement_details
;
 6734 frames, detector distance = 55 mm
;
_diffrn_measurement_device       '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  0.1026
_diffrn_reflns_av_unetI/netI     0.0897
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.918
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            307544
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.918
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         77.195
_diffrn_reflns_theta_min         2.252
_diffrn_source                   'sealed x-ray tube'
_diffrn_source_current           0.600
_diffrn_source_power             0.030
_diffrn_source_target            Cu
_diffrn_source_type              'Xenocs Cu microfocus tube'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    2.095
_exptl_absorpt_correction_T_max  0.7001
_exptl_absorpt_correction_T_min  0.1272
_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    1.043
_exptl_crystal_description       Plate
_exptl_crystal_F_000             3848
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene'
_exptl_crystal_size_max          0.44
_exptl_crystal_size_mid          0.233
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.736
_refine_diff_density_min         -0.608
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.860
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2475
_refine_ls_number_reflns         44350
_refine_ls_number_restraints     1969
_refine_ls_restrained_S_all      0.854
_refine_ls_R_factor_all          0.0997
_refine_ls_R_factor_gt           0.0627
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0942P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1521
_refine_ls_wR_factor_ref         0.1642
_reflns_Friedel_coverage         0.000
_reflns_number_gt                24221
_reflns_number_total             44350
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01739c2.cif
_cod_data_source_block           3K
_cod_original_cell_volume        11387(5)
_cod_database_code               7711107
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.850
_shelx_estimated_absorpt_t_min   0.459
_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
 C215-C221 \\sim C222-C228
 with sigma of 0.02
 C215-C216 \\sim C215-C220 \\sim C222-C223 \\sim C222-C227
 with sigma of 0.02
 C216-C217 \\sim C219-C220 \\sim C223-C224 \\sim C226-C227
 with sigma of 0.02
 C217-C218 \\sim C218-C219 \\sim C224-C225 \\sim C225-C226
 with sigma of 0.02
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
4. Others
 Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(H48C)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=
 Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=Sof(C70)=Sof(C71)=Sof(H71A)=Sof(H71B)=
 Sof(H71C)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(H72C)=Sof(C73)=Sof(H73A)=Sof(H73B)=
 Sof(H73C)=Sof(C130)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C131)=Sof(H13D)=
 Sof(H13E)=Sof(H13F)=Sof(C132)=Sof(H13G)=Sof(H13H)=Sof(H13I)=Sof(C193)=
 Sof(H19M)=Sof(H19N)=Sof(H19O)=Sof(C194)=Sof(H19P)=Sof(H19Q)=Sof(H19R)=
 Sof(C195)=Sof(H19S)=Sof(H19T)=Sof(H19U)=Sof(C222)=Sof(C223)=Sof(H223)=
 Sof(C224)=Sof(H224)=Sof(C225)=Sof(H225)=Sof(C226)=Sof(H226)=Sof(C227)=
 Sof(H227)=Sof(C228)=Sof(H22F)=Sof(H22G)=Sof(H22H)=1-FVAR(1)
 Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=
 Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=Sof(C66)=Sof(C67)=Sof(H67A)=Sof(H67B)=
 Sof(H67C)=Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=Sof(C69)=Sof(H69A)=Sof(H69B)=
 Sof(H69C)=Sof(C127)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C128)=Sof(H12D)=
 Sof(H12E)=Sof(H12F)=Sof(C129)=Sof(H12G)=Sof(H12H)=Sof(H12I)=Sof(C190)=
 Sof(H19D)=Sof(H19E)=Sof(H19F)=Sof(C191)=Sof(H19G)=Sof(H19H)=Sof(H19I)=
 Sof(C192)=Sof(H19J)=Sof(H19K)=Sof(H19L)=Sof(C215)=Sof(C216)=Sof(H216)=
 Sof(C217)=Sof(H217)=Sof(C218)=Sof(H218)=Sof(C219)=Sof(H219)=Sof(C220)=
 Sof(H220)=Sof(C221)=Sof(H22C)=Sof(H22D)=Sof(H22E)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B), C37(H37A,H37B), C55(H55A,H55B), C74(H74A,H74B), C89(H89A,
 H89B), C104(H10J,H10K), C119(H11S,H11T), C137(H13S,H13T), C152(H15J,H15K),
 C167(H16V,H16W), C182(H18G,H18H), C200(H20D,H20E)
5.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C10(H10), C12(H12),
 C25(H25), C27(H27), C40(H40), C42(H42), C58(H58), C60(H60), C77(H77), C79(H79),
  C92(H92), C94(H94), C107(H107), C109(H109), C122(H122), C124(H124),
 C140(H140), C142(H142), C155(H155), C157(H157), C170(H170), C172(H172),
 C185(H185), C187(H187), C202(H202), C203(H203), C204(H204), C205(H205),
 C206(H206), C209(H209), C210(H210), C211(H211), C212(H212), C213(H213),
 C216(H216), C217(H217), C218(H218), C219(H219), C220(H220), C223(H223),
 C224(H224), C225(H225), C226(H226), C227(H227)
5.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,
 H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C30(H30A,H30B,H30C), C31(H31A,
 H31B,H31C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C),
 C36(H36A,H36B,H36C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C47(H47A,H47B,
 H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C52(H52A,
 H52B,H52C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C63(H63A,H63B,H63C),
 C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C67(H67A,H67B,H67C), C68(H68A,H68B,
 H68C), C69(H69A,H69B,H69C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C73(H73A,
 H73B,H73C), C82(H82A,H82B,H82C), C83(H83A,H83B,H83C), C84(H84A,H84B,H84C),
 C86(H86A,H86B,H86C), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C97(H97A,H97B,
 H97C), C98(H98A,H98B,H98C), C99(H99A,H99B,H99C), C101(H10A,H10B,H10C),
 C102(H10D,H10E,H10F), C103(H10G,H10H,H10I), C112(H11A,H11B,H11C), C113(H11D,
 H11E,H11F), C114(H11G,H11H,H11I), C116(H11J,H11K,H11L), C117(H11M,H11N,H11O),
 C118(H11P,H11Q,H11R), C127(H12A,H12B,H12C), C128(H12D,H12E,H12F), C129(H12G,
 H12H,H12I), C130(H13A,H13B,H13C), C131(H13D,H13E,H13F), C132(H13G,H13H,H13I),
 C134(H13J,H13K,H13L), C135(H13M,H13N,H13O), C136(H13P,H13Q,H13R), C145(H14A,
 H14B,H14C), C146(H14D,H14E,H14F), C147(H14G,H14H,H14I), C149(H14J,H14K,H14L),
 C150(H15D,H15E,H15F), C151(H15G,H15H,H15I), C160(H16D,H16E,H16F), C161(H16G,
 H16H,H16I), C162(H16J,H16K,H16L), C164(H16M,H16N,H16O), C165(H16P,H16Q,H16R),
 C166(H16S,H16T,H16U), C175(H17D,H17E,H17F), C176(H17G,H17H,H17I), C177(H17J,
 H17K,H17L), C179(H17M,H17N,H17O), C180(H18A,H18B,H18C), C181(H18D,H18E,H18F),
 C190(H19D,H19E,H19F), C191(H19G,H19H,H19I), C192(H19J,H19K,H19L), C193(H19M,
 H19N,H19O), C194(H19P,H19Q,H19R), C195(H19S,H19T,H19U), C197(H19V,H19W,H19X),
 C198(H19Y,H,HA), C199(H19Z,HB,HC), C207(H20F,H20G,H20H), C214(H21D,H21E,H21F),
 C221(H22C,H22D,H22E), C228(H22F,H22G,H22H)
;
_shelx_res_checksum              58217
_shelx_hkl_checksum              34658
_shelx_fab_checksum              91846
_olex2_submission_special_instructions 'No special instructions were received'