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_7719370
_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         'C43.626 H64.75 Cl O3 P2 Ti'
_chemical_formula_sum            'C43.63 H64.75 Cl O3 P2 Ti'
_chemical_formula_weight         782.52
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-09-03
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-09-04 deposited with the CCDC.	2025-07-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.7601(5)
_cell_length_b                   16.3399(3)
_cell_length_c                   10.4561(2)
_cell_measurement_reflns_used    10248
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      75.5860
_cell_measurement_theta_min      4.2210
_cell_volume                     4401.16(14)
_computing_cell_refinement       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.101a (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)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.956
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0528
_diffrn_reflns_av_unetI/netI     0.0553
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            17589
_diffrn_reflns_point_group_measured_fraction_full 0.908
_diffrn_reflns_point_group_measured_fraction_max 0.849
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.496
_diffrn_reflns_theta_min         3.203
_exptl_absorpt_coefficient_mu    3.161
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83440
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.101a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            purple-red
_exptl_crystal_density_diffrn    1.181
_exptl_crystal_description       block
_exptl_crystal_F_000             1678
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.454
_refine_diff_density_min         -0.427
_refine_diff_density_rms         0.087
_refine_ls_abs_structure_details
;
 Flack x determined using 2321 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.022(10)
_refine_ls_extinction_coef       0.00043(10)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.094
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     558
_refine_ls_number_reflns         7861
_refine_ls_number_restraints     134
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.0793
_refine_ls_R_factor_gt           0.0730
_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^)+(0.0439P)^2^+16.0306P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1680
_refine_ls_wR_factor_ref         0.1708
_reflns_Friedel_coverage         0.596
_reflns_Friedel_fraction_full    0.795
_reflns_Friedel_fraction_max     0.715
_reflns_number_gt                7201
_reflns_number_total             7861
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01492a1.cif
_cod_data_source_block           exp_20438_auto
_cod_depositor_comments
'Adding full bibliography for 7719368--7719372.cif.'
_cod_database_code               7719370
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C41-C43 \\sim C41A-C43A
 with sigma of 0.02
 C41-C44 \\sim C41A-C44A
 with sigma of 0.02
 C41-C42 \\sim C41A-C42A
 with sigma of 0.02
 C4-C43 \\sim C4-C43A
 with sigma of 0.04
 C4-C44 \\sim C4-C44A
 with sigma of 0.04
 C4-C42 \\sim C4-C42A
 with sigma of 0.04
 C43-C44 \\sim C43A-C44A
 with sigma of 0.04
 C43-C42 \\sim C43A-C42A
 with sigma of 0.04
 C44-C42 \\sim C44A-C42A
 with sigma of 0.04
 C41-C4 \\sim C41A-C4
 with sigma of 0.02
 C42A-C41A \\sim C42-C41 \\sim C44A-C41A \\sim C44-C41 \\sim C43-C41 \\sim
C43A-C41A
 with sigma of 0.02
 C44-C43 \\sim C44-C42 \\sim C43-C42
 with sigma of 0.02
 C44A-C42A \\sim C43A-C42A \\sim C44A-C43A
 with sigma of 0.02
 C44-C4 \\sim C43-C4 \\sim C42-C4
 with sigma of 0.02
 C43A-C4 \\sim C44A-C4 \\sim C42A-C4
 with sigma of 0.02
 C31-C8 \\sim C31-C1A
 with sigma of 0.02
 C48-C49 \\sim C48-C49A
 with sigma of 0.02
 C50-C49 \\sim C50-C49A
 with sigma of 0.02
 C49A-C48 \\sim C50-C49A \\sim C50-C49 \\sim C49-C48
 with sigma of 0.02
 P30-C30 \\sim P30-C30A
 with sigma of 0.02
 C30-C32 \\sim C30A-C32A
 with sigma of 0.02
 P30-C32 \\sim P30-C32A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C49: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C49 \\sim C49A: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
Uanis(C43A) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C42A) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C43A) \\sim Ueq, Uanis(C42A) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.006
Uanis(C30A) \\sim Ueq, Uanis(C32A) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C1)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C32A) \\sim Ueq, Uanis(C1) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C1) \\sim Ueq, Uanis(C32A) \\sim Ueq: with sigma of 0.0001 and sigma for
terminal atoms of 0.0002
Uanis(C30) \\sim Ueq: with sigma of 0.00001 and sigma for terminal atoms of
0.00002
4. Rigid body (RIGU) restrains
 C4, C41A, C43A, C44A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C4, C41, C42, C43, C44
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Others
 Sof(C44A)=Sof(H44D)=Sof(H44E)=Sof(H44F)=Sof(C43A)=Sof(H43D)=Sof(H43E)=
 Sof(H43F)=Sof(C41A)=Sof(C42A)=Sof(H42D)=Sof(H42E)=Sof(H42F)=1-FVAR(1)
 Sof(C41)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=Sof(C44)=Sof(H44A)=Sof(H44B)=
 Sof(H44C)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=FVAR(1)
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=1-FVAR(2)
 Sof(H31)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=FVAR(2)
 Sof(H48C)=Sof(H48D)=Sof(H50C)=Sof(H50D)=Sof(C49A)=Sof(H49C)=Sof(H49D)=1-FVAR(3)
 Sof(H48A)=Sof(H48B)=Sof(H50A)=Sof(H50B)=Sof(C49)=Sof(H49A)=Sof(H49B)=FVAR(3)
 Sof(C30A)=Sof(H30A)=Sof(H30B)=Sof(C32A)=Sof(H32D)=Sof(H32E)=Sof(H32F)=1-FVAR(4)
 Sof(C30)=Sof(H30)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C32)=Sof(H32A)=
 Sof(H32B)=Sof(H32C)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C31(H31), C30(H30)
6.b Secondary CH2 refined with riding coordinates:
 C51(H51A,H51B), C48(H48A,H48B), C48(H48C,H48D), C50(H50A,H50B), C50(H50C,
 H50D), C49(H49A,H49B), C49A(H49C,H49D), C30A(H30A,H30B)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C13(H13), C10(H10), C16(H16), C12(H12), C11(H11), C18(H18)
6.d Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C27(H27A,H27B,
 H27C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C43(H43A,H43B,H43C), C28(H28A,
 H28B,H28C), C24(H24A,H24B,H24C), C29(H29A,H29B,H29C), C36(H36A,H36B,H36C),
 C44(H44A,H44B,H44C), C42(H42A,H42B,H42C), C44A(H44D,H44E,H44F), C43A(H43D,H43E,
 H43F), C42A(H42D,H42E,H42F), C8(H8A,H8B,H8C), C1A(H1AA,H1AB,H1AC), C1(H1A,H1B,
 H1C), C32(H32A,H32B,H32C), C32A(H32D,H32E,H32F)
;
_shelx_res_checksum              77414
_shelx_hkl_checksum              61970
_olex2_submission_special_instructions 'No special instructions were received'