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_7711101
_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         'C190 H276 N6 Na2 O24 Ti4, 6(C2 H3 N)'
_chemical_formula_sum            'C202 H294 N12 Na2 O24 Ti4'
_chemical_formula_weight         3512.05
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-03-16
_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                 93.3425(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.1034(3)
_cell_length_b                   34.4125(3)
_cell_length_c                   24.7529(3)
_cell_measurement_reflns_used    162176
_cell_measurement_temperature    100
_cell_measurement_theta_max      72.61
_cell_measurement_theta_min      2.57
_cell_volume                     20496.6(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 (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 0.997
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_details
;
 3589 frames, detector distance = 55 mm
;
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_collimation    '0.5 mm diameter'
_diffrn_radiation_monochromator  graphite
_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  0.0650
_diffrn_reflns_av_unetI/netI     0.0395
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       39
_diffrn_reflns_limit_k_min       -42
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            273898
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.683
_diffrn_reflns_theta_min         2.568
_diffrn_source                   'GeniX 3D HF Cu'
_diffrn_source_current           0.600
_diffrn_source_power             0.030
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.827
_exptl_absorpt_correction_T_max  0.1660
_exptl_absorpt_correction_T_min  0.0477
_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 orange'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.138
_exptl_crystal_description       block
_exptl_crystal_F_000             7568
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetonitrile'
_exptl_crystal_size_max          0.66
_exptl_crystal_size_mid          0.547
_exptl_crystal_size_min          0.42
_refine_diff_density_max         0.899
_refine_diff_density_min         -0.651
_refine_diff_density_rms         0.143
_refine_ls_extinction_coef       0.00061(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/1 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2331
_refine_ls_number_reflns         40090
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.1055
_refine_ls_R_factor_gt           0.0845
_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^)+(0.1800P)^2^+2.4290P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2397
_refine_ls_wR_factor_ref         0.2674
_reflns_Friedel_coverage         0.000
_reflns_number_gt                28559
_reflns_number_total             40090
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01739c2.cif
_cod_data_source_block           3Na
_cod_database_code               7711101
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.514
_shelx_estimated_absorpt_t_min   0.379
_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. Others
 Sof(C45B)=Sof(H45D)=Sof(H45E)=Sof(H45F)=Sof(C46B)=Sof(H46D)=Sof(H46E)=
 Sof(H46F)=1-FVAR(1)
 Sof(C45A)=Sof(H45A)=Sof(H45B)=Sof(H45C)=Sof(C46A)=Sof(H46A)=Sof(H46B)=
 Sof(H46C)=FVAR(1)
 Sof(C19B)=Sof(H19D)=Sof(H19E)=Sof(H19F)=Sof(C20B)=Sof(H20D)=Sof(H20E)=
 Sof(H20F)=Sof(C21B)=Sof(H21C)=Sof(H21D)=Sof(H21E)=1-FVAR(2)
 Sof(C119)=Sof(H11F)=Sof(H11G)=Sof(H11H)=Sof(C120)=Sof(H12A)=Sof(H12B)=
 Sof(H12C)=Sof(C121)=Sof(H12D)=Sof(H12E)=Sof(H12F)=FVAR(2)
3.a Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C36(H36A,H36B), C51(H51A,H51B), C66(H66A,H66B), C81(H81A,
 H81B), C96(H96A,H96B), C111(H11D,H11E), C126(H12P,H12Q), C141(H14G,H14H),
 C156(H15S,H15T), C171(H17D,H17E), C186(H18S,H18T)
3.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C11(H11), C24(H24),
 C26(H26), C39(H39), C41(H41), C54(H54), C56(H56), C69(H69), C71(H71), C84(H84),
  C86(H86), C99(H99), C101(H101), C114(H114), C116(H116), C129(H129),
 C131(H131), C144(H144), C146(H146), C159(H159), C161(H161), C174(H174),
 C176(H176)
3.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C), C31(H31A,H31B,H31C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C),
 C35(H35A,H35B,H35C), C44(H44A,H44B,H44C), C45A(H45A,H45B,H45C), C46A(H46A,H46B,
 H46C), C45B(H45D,H45E,H45F), C46B(H46D,H46E,H46F), C48(H48A,H48B,H48C),
 C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C59(H59A,H59B,H59C), C60(H60A,H60B,
 H60C), C61(H61A,H61B,H61C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C65(H65A,
 H65B,H65C), C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C76(H76A,H76B,H76C),
 C78(H78A,H78B,H78C), C79(H79A,H79B,H79C), C80(H80A,H80B,H80C), C89(H89A,H89B,
 H89C), C90(H90A,H90B,H90C), C91(H91A,H91B,H91C), C93(H93A,H93B,H93C), C94(H94A,
 H94B,H94C), C95(H95A,H95B,H95C), C104(H10A,H10B,H10C), C105(H10D,H10E,H10F),
 C106(H10G,H10H,H10I), C108(H10J,H10K,H10L), C109(H10M,H10N,H10O), C110(H11A,
 H11B,H11C), C119(H11F,H11G,H11H), C120(H12A,H12B,H12C), C121(H12D,H12E,H12F),
 C19B(H19D,H19E,H19F), C20B(H20D,H20E,H20F), C21B(H21C,H21D,H21E), C123(H12G,
 H12H,H12I), C124(H12J,H12K,H12L), C125(H12M,H12N,H12O), C134(H13A,H13B,H13C),
 C135(H13D,H13E,H13F), C136(H13G,H13H,H13I), C138(H13J,H13K,H13L), C139(H13M,
 H13N,H13O), C140(H14D,H14E,H14F), C149(H14I,H14J,H14K), C150(H15D,H15E,H15F),
 C151(H15G,H15H,H15I), C153(H15J,H15K,H15L), C154(H15M,H15N,H15O), C155(H15P,
 H15Q,H15R), C164(H16D,H16E,H16F), C165(H16G,H16H,H16I), C166(H16J,H16K,H16L),
 C168(H16M,H16N,H16O), C169(H16P,H16Q,H16R), C170(H17A,H17B,H17C), C179(H17F,
 H17G,H17H), C180(H18D,H18E,H18F), C181(H18G,H18H,H18I), C183(H18J,H18K,H18L),
 C184(H18M,H18N,H18O), C185(H18P,H18Q,H18R), C188(H18U,H18V,H18W), C190(H19G,
 H19H,H19I), C192(H19J,H19K,H19L), C194(H19M,H19N,H19O), C196(H19P,H19Q,H19R),
 C198(H19S,H19T,H19U), C200(H20G,H20H,H20I), C202(H20J,H20K,H20L)
;
_shelx_res_checksum              81538
_shelx_hkl_checksum              62803
_olex2_submission_special_instructions 'No special instructions were received'