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_7719368
_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         'C40 H60 O2 P2'
_chemical_formula_sum            'C40 H60 O2 P2'
_chemical_formula_weight         634.82
_chemical_name_systematic
6,6'-((2-(diisopropylphosphaneyl)phenyl)phosphanediyl)bis(2,4-di-tert-butylphenol)
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-09-04
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-09-04 deposited with the CCDC.	2025-07-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.256(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.1606(3)
_cell_length_b                   24.9127(7)
_cell_length_c                   13.6600(3)
_cell_measurement_reflns_used    12302
_cell_measurement_temperature    197.15
_cell_measurement_theta_max      75.5460
_cell_measurement_theta_min      3.5560
_cell_volume                     4095.45(18)
_computing_cell_refinement       'CrysAlisPro 1.171.42.102a (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 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_temperature      197.15
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.941
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0505
_diffrn_reflns_av_unetI/netI     0.0402
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.941
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            30404
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.941
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.692
_diffrn_reflns_theta_min         3.548
_diffrn_source                   'Rotating-anode X-ray tube'
_exptl_absorpt_coefficient_mu    1.172
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66982
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.102a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            white
_exptl_crystal_density_diffrn    1.030
_exptl_crystal_description       block
_exptl_crystal_F_000             1384
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.509
_refine_diff_density_min         -0.366
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     507
_refine_ls_number_reflns         8211
_refine_ls_number_restraints     118
_refine_ls_restrained_S_all      1.202
_refine_ls_R_factor_all          0.0840
_refine_ls_R_factor_gt           0.0631
_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^)+(0.1100P)^2^+0.7129P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1744
_refine_ls_wR_factor_ref         0.1989
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5905
_reflns_number_total             8211
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01492a1.cif
_cod_data_source_block           exp_22003_auto
_cod_depositor_comments
'Adding full bibliography for 7719368--7719372.cif.'
_cod_original_cell_volume        4095.48(19)
_cod_database_code               7719368
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 C26-C27 \\sim C24-C25A \\sim C25-C26A
 with sigma of 0.02
 C36-C34A \\sim C34-C37A \\sim C37-C36A
 with sigma of 0.02
 C32A-C32 \\sim C33A-C33
 with sigma of 0.02
3. Rigid bond restraints
 C16, C20
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C20, C21
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C20, C22
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C20, C23
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
Uanis(C23) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C20) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
5. Rigid body (RIGU) restrains
 C5
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C27, C26A, C25, C25A, C24, C26, C7
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C34, C34A, C36, C36A, C37, C37A, C35
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C28
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C33, C33A, C32, C32A, C28A, C28, P28
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
6. Others
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C26A)=Sof(H26D)=Sof(H26E)=
 Sof(H26F)=Sof(C25A)=Sof(H25D)=Sof(H25E)=Sof(H25F)=1-FVAR(1)
 Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=FVAR(1)
 Sof(C37A)=Sof(H37D)=Sof(H37E)=Sof(H37F)=Sof(C34A)=Sof(H34D)=Sof(H34E)=
 Sof(H34F)=Sof(C36A)=Sof(H36D)=Sof(H36E)=Sof(H36F)=1-FVAR(2)
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=FVAR(2)
 Sof(C33A)=Sof(H33D)=Sof(H33E)=Sof(H33F)=Sof(C32A)=Sof(H32D)=Sof(H32E)=
 Sof(H32F)=Sof(C28A)=Sof(H28A)=1-FVAR(3)
 Sof(C28)=Sof(H28)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C33)=Sof(H33A)=
 Sof(H33B)=Sof(H33C)=FVAR(3)
7.a Ternary CH refined with riding coordinates:
 C29(H29), C28(H28), C28A(H28A)
7.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C9(H9), C19(H19), C12(H12), C10(H10), C4(H4), C11(H11), C17(H17)
7.c Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C30(H30A,H30B,H30C), C23(H23A,H23B,H23C), C31(H31A,H31B,H31C), C39(H39A,
 H39B,H39C), C25(H25A,H25B,H25C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C),
 C27(H27A,H27B,H27C), C26A(H26D,H26E,H26F), C25A(H25D,H25E,H25F), C37(H37A,H37B,
 H37C), C36(H36A,H36B,H36C), C34(H34A,H34B,H34C), C37A(H37D,H37E,H37F),
 C34A(H34D,H34E,H34F), C36A(H36D,H36E,H36F), C32(H32A,H32B,H32C), C33(H33A,H33B,
 H33C), C33A(H33D,H33E,H33F), C32A(H32D,H32E,H32F)
7.d Idealised tetrahedral OH refined as rotating group:
 O42(H42), O24(H24)
;
_shelx_res_checksum              68277
_shelx_hkl_checksum              76250
_olex2_submission_special_instructions 'No special instructions were received'