Tripodal bisphenolate-bisphosphine ligands with hybrid hard/soft donors: titanium complexes and dinitrogen activation.
Xiong, Chunyan; Zhang, Jinwei; An, Jingyi; Yuan, Zhiqiang; Li, Zhaoxin; Liu, Yanhong; Hu, Shaowei; Dalton transactions (Cambridge, England : 2003) 54 (2025) 14142–14149; doi:10.1039/d5dt01492a

data_7719372
_publ_section_title
;
 Tripodal bisphenolate-bisphosphine ligands with hybrid hard/soft donors:
 titanium complexes and dinitrogen activation.
;
_journal_issue                   37
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              14142
_journal_page_last               14149
_journal_paper_doi               10.1039/d5dt01492a
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         '0.034(C87.707 H128.236 N2 O6 P4 Ti2)'
_chemical_formula_sum            'C2.97 H4.35 N0.07 O0.2 P0.14 Ti0.07'
_chemical_formula_weight         51.74
_chemical_properties_physical    Air-sensitive,Moisture-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             2024-03-13
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-03-28 deposited with the CCDC.	2025-07-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.9130(10)
_cell_angle_gamma                90
_cell_formula_units_Z            118
_cell_length_a                   24.5600(2)
_cell_length_b                   11.23810(10)
_cell_length_c                   40.0482(3)
_cell_measurement_reflns_used    43084
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.0250
_cell_measurement_theta_min      3.7520
_cell_volume                     10575.52(16)
_computing_cell_refinement       'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.950
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -23.00  27.00   0.50    0.38    --  -46.80  19.00 150.00  100
  2  \w    -29.00  17.00   0.50    0.38    --  -46.80  26.00  23.00   92
  3  \w    -40.00  22.00   0.50    0.38    --  -46.80  37.00-180.00  124
  4  \w     32.00 100.00   0.50    0.84    --  104.75 -94.00 -30.00  136
  5  \w     36.00 107.00   0.50    0.84    --  104.75 -94.00 120.00  142
  6  \w     77.00 103.00   0.50    0.84    --  104.75 -77.00  60.00   52
  7  \w     39.00  69.00   0.50    0.84    --  104.75 -61.00 150.00   60
  8  \w     42.00  71.00   0.50    0.84    --  104.75 -77.00  60.00   58
  9  \w     36.00  61.00   0.50    0.84    --  104.75 -61.00 -60.00   50
 10  \w     34.00  73.00   0.50    0.84    --  104.75 -61.00 -90.00   78
 11  \w     36.00  73.00   0.50    0.84    --  104.75 -61.00-120.00   74
 12  \w     41.00  73.00   0.50    0.84    --  104.75 -61.00-150.00   64
 13  \w     -6.00  19.00   0.50    0.38    --   46.80 -26.00-139.00   50
 14  \w     38.00 122.00   0.50    0.38    --   46.80  19.00-120.00  168
 15  \w     99.00 143.00   0.50    0.84    --  104.75  26.00  23.00   88
 16  \w     39.00 117.00   0.50    0.38    --   46.80  26.00  23.00  156
 17  \w    -58.00 -32.00   0.50    0.84    -- -102.00  61.00 150.00   52
 18  \w    -69.00 -44.00   0.50    0.84    -- -102.00  61.00  90.00   50
 19  \w   -103.00 -29.00   0.50    0.84    -- -102.00  77.00 -90.00  148
 20  \w    -65.00 -36.00   0.50    0.84    -- -102.00  61.00-180.00   58
 21  \w   -110.00 -35.00   0.50    0.84    -- -102.00 125.00-120.00  150
 22  \w   -158.00 -92.00   0.50    0.84    -- -102.00 -26.00-139.00  132
 23  \w   -173.00 -90.00   0.50    0.84    -- -102.00 -30.00-180.00  166
 24  \w   -102.00 -77.00   0.50    0.38    --  -46.80 -26.00-139.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0464832000
_diffrn_orient_matrix_UB_12      -0.0248370000
_diffrn_orient_matrix_UB_13      0.0345053000
_diffrn_orient_matrix_UB_21      0.0459127000
_diffrn_orient_matrix_UB_22      0.0407907000
_diffrn_orient_matrix_UB_23      -0.0167853000
_diffrn_orient_matrix_UB_31      -0.0055458000
_diffrn_orient_matrix_UB_32      0.1284902000
_diffrn_orient_matrix_UB_33      0.0119967000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0359
_diffrn_reflns_av_unetI/netI     0.0329
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.950
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       50
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            79076
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.950
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.372
_diffrn_reflns_theta_min         3.762
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.173
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83097
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.85a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    0.959
_exptl_crystal_description       plate
_exptl_crystal_F_000             3282
_refine_diff_density_max         0.874
_refine_diff_density_min         -0.503
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1071
_refine_ls_number_reflns         21044
_refine_ls_number_restraints     185
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0645
_refine_ls_R_factor_gt           0.0559
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0757P)^2^+12.9050P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1487
_refine_ls_wR_factor_ref         0.1541
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18001
_reflns_number_total             21044
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01492a1.cif
_cod_data_source_block           exp_18559_auto_sq
_cod_depositor_comments
'Adding full bibliography for 7719368--7719372.cif.'
_cod_original_cell_volume        10575.51(16)
_cod_original_formula_sum        'C2.97 H4.35 N0.07 O0.20 P0.14 Ti0.07'
_cod_database_code               7719372
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H O P Ti N'
_chemical_oxdiff_usercomment     'C H N Sb In Cl'
_reflns_odcompleteness_completeness 99.53
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 C87A-C85 \\sim C86-C85 \\sim C87-C85
 with sigma of 0.02
 C38-C33 \\sim C35-C33 \\sim C37-C33 \\sim C38A-C33 \\sim C37A-C33
 with sigma of 0.02
 C91-C92 \\sim C91A-C92
 with sigma of 0.02
 C91-C90 \\sim C91A-C90A
 with sigma of 0.02
 C70-C72 \\sim C70-C71 \\sim C73-C70 \\sim C7A-C72A \\sim C7A-C71A \\sim
C73A-C7A
 with sigma of 0.02
 C44A-C43 \\sim C13-C43
 with sigma of 0.02
 C44A-C45A \\sim C13-C45
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C37) \\sim Ueq, Uanis(C37A) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C13) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C45A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C87) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
4. Rigid body (RIGU) restrains
 C38A, C35, C38, C37, C37A, C33
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C86A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C86A, C69
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C90, C91, C91A, C90A, C89
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C71A, C73, C73A, C72A, C7A, C71, C72, C70, C69
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C45A, C44A, C45, C13, C43
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Others
 Sof(C87)=Sof(H87D)=Sof(H87E)=Sof(H87F)=Sof(C86)=Sof(H86D)=Sof(H86E)=Sof(H86F)=
 1-FVAR(1)
 Sof(C86A)=Sof(H86A)=Sof(H86B)=Sof(H86C)=Sof(C87A)=Sof(H87A)=Sof(H87B)=
 Sof(H87C)=FVAR(1)
 Sof(C38)=Sof(H38D)=Sof(H38E)=Sof(H38F)=Sof(C37)=Sof(H37D)=Sof(H37E)=Sof(H37F)=
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=1-FVAR(2)
 Sof(H33)=Sof(C38A)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C37A)=Sof(H37A)=
 Sof(H37B)=Sof(H37C)=FVAR(2)
 Sof(C91A)=Sof(H91C)=Sof(H91D)=Sof(C90A)=Sof(H90C)=Sof(H90D)=1-FVAR(3)
 Sof(H89A)=Sof(H89B)=Sof(H92A)=Sof(H92B)=Sof(C90)=Sof(H90A)=Sof(H90B)=Sof(C91)=
 Sof(H91A)=Sof(H91B)=FVAR(3)
 Sof(C7A)=Sof(C72A)=Sof(H72D)=Sof(H72E)=Sof(H72F)=Sof(C71A)=Sof(H71D)=
 Sof(H71E)=Sof(H71F)=Sof(C73A)=Sof(H73D)=Sof(H73E)=Sof(H73F)=1-FVAR(4)
 Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(H72C)=Sof(C70)=Sof(C71)=Sof(H71A)=Sof(H71B)=
 Sof(H71C)=Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(H73C)=FVAR(4)
 Sof(H43A)=Sof(H43B)=Sof(C45A)=Sof(H45C)=Sof(H45D)=Sof(C44A)=Sof(H44A)=
 Sof(H44B)=1-FVAR(5)
 Sof(H46A)=Sof(H46B)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(C13)=Sof(H13A)=Sof(H13B)=
 FVAR(5)
6.a Ternary CH refined with riding coordinates:
 C50(H50), C47(H47), C4(H4), C1(H1), C33(H33)
6.b Secondary CH2 refined with riding coordinates:
 C46(H46A,H46B), C89(H89A,H89B), C43(H43A,H43B), C92(H92A,H92B), C90(H90A,
 H90B), C45(H45A,H45B), C13(H13A,H13B), C91(H91A,H91B), C91A(H91C,H91D),
 C90A(H90C,H90D), C45A(H45C,H45D), C44A(H44A,H44B)
6.c Aromatic/amide H refined with riding coordinates:
 C32(H32), C9(H9), C55(H55), C15(H15), C17(H17), C76(H76), C12(H12), C10(H10),
 C79(H79), C30(H30), C11(H11), C58(H58), C56(H56), C57(H57), C63(H63), C61(H61)
6.d Idealised Me refined as rotating group:
 C67(H67A,H67B,H67C), C83(H83A,H83B,H83C), C68(H68A,H68B,H68C), C25(H25A,H25B,
 H25C), C49(H49A,H49B,H49C), C41(H41A,H41B,H41C), C82(H82A,H82B,H82C), C26(H26A,
 H26B,H26C), C52(H52A,H52B,H52C), C84(H84A,H84B,H84C), C40(H40A,H40B,H40C),
 C48(H48A,H48B,H48C), C51(H51A,H51B,H51C), C42(H42A,H42B,H42C), C66(H66A,H66B,
 H66C), C24(H24A,H24B,H24C), C2(H2A,H2B,H2C), C6(H6A,H6B,H6C), C5(H5A,H5B,H5C),
 C23(H23A,H23B,H23C), C3(H3A,H3B,H3C), C22(H22A,H22B,H22C), C21(H21A,H21B,H21C),
  C88(H88A,H88B,H88C), C86A(H86A,H86B,H86C), C87A(H87A,H87B,H87C), C87(H87D,
 H87E,H87F), C86(H86D,H86E,H86F), C38A(H38A,H38B,H38C), C37A(H37A,H37B,H37C),
 C38(H38D,H38E,H38F), C37(H37D,H37E,H37F), C35(H35A,H35B,H35C), C72(H72A,H72B,
 H72C), C71(H71A,H71B,H71C), C73(H73A,H73B,H73C), C72A(H72D,H72E,H72F),
 C71A(H71D,H71E,H71F), C73A(H73D,H73E,H73F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              12671
_shelx_hkl_checksum              77731
_shelx_fab_checksum              11561
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.268
_oxdiff_exptl_absorpt_empirical_full_min 0.458