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_7719369
_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         'C50 H62 Cl O3 P2 Ti'
_chemical_formula_sum            'C50 H62 Cl O3 P2 Ti'
_chemical_formula_weight         856.28
_chemical_properties_physical    Air-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
_atom_sites_solution_primary     dual
_audit_creation_date             2025-02-05
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-02-05 deposited with the CCDC.	2025-07-31 downloaded from the CCDC.
;
_cell_angle_alpha                68.257(5)
_cell_angle_beta                 89.943(4)
_cell_angle_gamma                77.107(4)
_cell_formula_units_Z            2
_cell_length_a                   10.4694(5)
_cell_length_b                   14.6704(9)
_cell_length_c                   16.5469(8)
_cell_measurement_reflns_used    11172
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      76.2530
_cell_measurement_theta_min      3.3450
_cell_volume                     2291.7(2)
_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 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.942
_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     49.00  74.00   0.50    0.60    --  104.75-125.00 -90.00   50
  2  \w     58.00 113.00   0.50    0.60    --  104.75-125.00 -60.00  110
  3  \w     79.00 117.00   0.50    0.60    --  104.75-125.00  30.00   76
  4  \w     35.00  74.00   0.50    0.60    --  104.75-125.00  30.00   78
  5  \w     51.00  87.00   0.50    0.60    --  104.75 -94.00 -30.00   72
  6  \w     83.00 109.00   0.50    0.60    --  104.75-125.00 -90.00   52
  7  \w    -18.00  74.00   0.50    0.20    --   46.38 -88.00  48.00  184
  8  \w     41.00  98.00   0.50    0.60    --  104.75 -94.00 150.00  114
  9  \w     46.00 110.00   0.50    0.60    --  104.75-125.00 120.00  128
 10  \w     52.00 122.00   0.50    0.60    --  104.75 -88.00  48.00  140
 11  \w     33.00 104.00   0.50    0.60    --  104.75 -77.00   0.00  142
 12  \w     47.00  72.00   0.50    0.60    --  104.75 -61.00  60.00   50
 13  \w    -23.00  44.00   0.50    0.20    --   46.38 -37.00 -60.00  134
 14  \w    151.00 176.00   0.50    0.60    --  104.75  45.00-180.00   50
 15  \w     84.00 173.00   0.50    0.60    --  104.75 125.00  90.00  178
 16  \w     81.00 157.00   0.50    0.60    --  104.75  88.00 165.00  152
 17  \w     92.00 145.00   0.50    0.60    --  104.75  45.00  90.00  106
 18  \w     94.00 128.00   0.50    0.60    --  104.75  15.00  90.00   68
 19  \w    -39.00  24.00   0.50    0.20    --  -46.38  37.00 120.00  126
 20  \w    -22.00  20.00   0.50    0.20    --  -46.38  19.00  60.00   84
 21  \w     -7.00  29.00   0.50    0.20    --  -46.38  19.00-120.00   72
 22  \w    -24.00  24.00   0.50    0.20    --  -46.38  19.00-180.00   96
 23  \w    -66.00 -33.00   0.50    0.60    -- -102.00 125.00-180.00   66
 24  \w   -116.00 -76.00   0.50    0.60    -- -102.00 125.00-180.00   80
 25  \w    -68.00  20.00   0.50    0.20    --  -46.38  88.00 165.00  176
 26  \w   -104.00 -79.00   0.50    0.60    -- -102.00  88.00 165.00   50
 27  \w    -63.00 -38.00   0.50    0.60    -- -102.00  61.00-120.00   50
 28  \w    -57.00 -29.00   0.50    0.60    -- -102.00  61.00 -90.00   56
 29  \w    -75.00 -35.00   0.50    0.60    -- -102.00  77.00-180.00   80
 30  \w    -69.00 -32.00   0.50    0.60    -- -102.00  61.00-180.00   74
 31  \w   -168.00-142.00   0.50    0.60    -- -102.00 -15.00-180.00   52
 32  \w   -139.00 -88.00   0.50    0.60    -- -102.00 -15.00-180.00  102
 33  \w   -174.00-113.00   0.50    0.60    -- -102.00 -30.00 -90.00  122
 34  \w   -170.00-124.00   0.50    0.60    -- -102.00 -45.00  30.00   92
 35  \w   -104.00 -78.00   0.50    0.60    -- -102.00 -88.00  48.00   52
 36  \w   -135.00 -82.00   0.50    0.60    -- -102.00 -94.00 150.00  106
 37  \w   -172.00-146.00   0.50    0.60    -- -102.00 -94.00 150.00   52
 38  \w   -116.00 -71.00   0.50    0.20    --  -46.38-125.00 120.00   90
 39  \w   -172.00-147.00   0.50    0.60    -- -102.00 -88.00  48.00   50
 40  \w   -106.00 -81.00   0.50    0.20    --  -46.38-125.00-150.00   50
 41  \w   -164.00 -73.00   0.50    0.60    -- -102.00-125.00-180.00  182
;
_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      0.0646012000
_diffrn_orient_matrix_UB_12      -0.1133635000
_diffrn_orient_matrix_UB_13      0.0266040000
_diffrn_orient_matrix_UB_21      0.0642144000
_diffrn_orient_matrix_UB_22      0.0231122000
_diffrn_orient_matrix_UB_23      -0.0869043000
_diffrn_orient_matrix_UB_31      0.1211496000
_diffrn_orient_matrix_UB_32      0.0132587000
_diffrn_orient_matrix_UB_33      0.0432320000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0684
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.942
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            9109
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.745
_diffrn_reflns_theta_min         3.341
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.085
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66609
_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            'purple red colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.241
_exptl_crystal_description       block
_exptl_crystal_F_000             910
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.223
_refine_diff_density_min         -0.996
_refine_diff_density_rms         0.117
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     564
_refine_ls_number_reflns         9109
_refine_ls_number_restraints     130
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.1093
_refine_ls_R_factor_gt           0.0995
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1247P)^2^+9.1526P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2720
_refine_ls_wR_factor_ref         0.2786
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7758
_reflns_number_total             9109
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01492a1.cif
_cod_data_source_block           exp_16253_auto_tw
_cod_depositor_comments
'Adding full bibliography for 7719368--7719372.cif.'
_cod_database_code               7719369
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H O P Ti Cl'
_shelx_estimated_absorpt_t_max   0.748
_shelx_estimated_absorpt_t_min   0.690
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.744(5)
 0.256(5)
2. 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
3. Uiso/Uaniso restraints and constraints
O3 \\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim C47A \\sim C48A \\sim C49A
\\sim C50A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
4. Same fragment restrains
{O3, C47A, C48A, C49A, C50A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{O3, C47, C48, C49, C50}
5. Others
 Sof(C47A)=Sof(H47C)=Sof(H47D)=Sof(C48A)=Sof(H48C)=Sof(H48D)=Sof(C49A)=
 Sof(H49C)=Sof(H49D)=Sof(C50A)=Sof(H50C)=Sof(H50D)=1-FVAR(1)
 Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(C49)=Sof(H49A)=
 Sof(H49B)=Sof(C50)=Sof(H50A)=Sof(H50B)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C47(H47A,H47B), C48(H48A,H48B), C49(H49A,H49B), C50(H50A,H50B), C47A(H47C,
 H47D), C48A(H48C,H48D), C49A(H49C,H49D), C50A(H50C,H50D)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C15(H15), C16(H16), C17(H17), C18(H18), C22(H22), C24(H24), C36(H36),
  C38(H38)
6.c Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,
 H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C40(H40A,H40B,H40C), C41(H41A,
 H41B,H41C), C42(H42A,H42B,H42C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C),
 C46(H46A,H46B,H46C)
;
_shelx_res_checksum              44206
_shelx_hkl_checksum              72966
_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 2.504
_oxdiff_exptl_absorpt_empirical_full_min 0.451