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_7719371
_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         '2(C40 H58 Cl2 O2 P2 Ti), C6 H14, C4 H8 O'
_chemical_formula_sum            'C90 H138 Cl4 O5 P4 Ti2'
_chemical_formula_weight         1661.48
_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   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-09-08
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-09-08 deposited with the CCDC.	2025-07-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 111.060(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.5896(2)
_cell_length_b                   38.7640(5)
_cell_length_c                   11.9374(2)
_cell_measurement_reflns_used    18467
_cell_measurement_temperature    190(2)
_cell_measurement_theta_max      75.0950
_cell_measurement_theta_min      4.1180
_cell_volume                     4572.93(14)
_computing_cell_refinement       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_reduction        '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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      190(2)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.957
_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  0.0497
_diffrn_reflns_av_unetI/netI     0.0423
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -48
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            33534
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.621
_diffrn_reflns_theta_min         4.129
_exptl_absorpt_coefficient_mu    3.586
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.22143
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.207
_exptl_crystal_description       block
_exptl_crystal_F_000             1780
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.168
_refine_diff_density_min         -0.650
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.116
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     610
_refine_ls_number_reflns         9215
_refine_ls_number_restraints     359
_refine_ls_restrained_S_all      1.122
_refine_ls_R_factor_all          0.0711
_refine_ls_R_factor_gt           0.0671
_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^)+(0.0722P)^2^+7.2093P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1792
_refine_ls_wR_factor_ref         0.1818
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8456
_reflns_number_total             9215
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01492a1.cif
_cod_data_source_block           exp_22076_auto
_cod_depositor_comments
'Adding full bibliography for 7719368--7719372.cif.'
_cod_database_code               7719371
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.716
_shelx_estimated_absorpt_t_min   0.534
_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
 C49-C48 = C48-C47 = C47-C46 = C55-C54 = C54-C53 = C53-C52 = C51-C52 = C51-C50
 1.54 with sigma of 0.01
 O38-C46 = O38-C49
 1.43 with sigma of 0.01
 C46-C48 = C49-C47 = C50-C52 = C51-C53 = C53-C55 = C54-C52
 2.515 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C29 \\sim C30 \\sim C31 \\sim C32 \\sim C29A \\sim C30A \\sim C31A \\sim C32A
\\sim C11: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C24 \\sim C25 \\sim C26 \\sim C24A \\sim C25A \\sim C26A \\sim P21: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C53 \\sim C50 \\sim C51 \\sim C52 \\sim C54 \\sim C55 \\sim C47 \\sim O38 \\sim
C46 \\sim C49 \\sim C48: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
4. Same fragment restrains
{C11, C29A, C30A, C31A, C32A} sigma for 1-2: 0.01, 1-3: 0.02
as in
{C11, C29, C30, C31, C32}
{P21, C24A, C25A} sigma for 1-2: 0.01, 1-3: 0.02
as in
{P21, C24, C25}
5. Others
 Sof(C29A)=Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C31A)=Sof(H31D)=
 Sof(H31E)=Sof(H31F)=Sof(C32A)=Sof(H32D)=Sof(H32E)=Sof(H32F)=1-FVAR(1)
 Sof(C29)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C31)=Sof(H31A)=Sof(H31B)=
 Sof(H31C)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(1)
 Sof(C24A)=Sof(H24A)=Sof(C25A)=Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(C26A)=
 Sof(H26D)=Sof(H26E)=Sof(H26F)=1-FVAR(2)
 Sof(C24)=Sof(H24)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C26)=Sof(H26A)=
 Sof(H26B)=Sof(H26C)=FVAR(2)
 Fixed Sof: O38(0.5) C46(0.5) H46A(0.5) H46B(0.5) C49(0.5) H49A(0.5) H49B(0.5)
 C48(0.5) H48A(0.5) H48B(0.5) C47(0.5) H47A(0.5) H47B(0.5) C50(0.5) H50A(0.5)
 H50B(0.5) H50C(0.5) C51(0.5) H51A(0.5) H51B(0.5) C52(0.5) H52A(0.5) H52B(0.5)
 C53(0.5) H53A(0.5) H53B(0.5) C54(0.5) H54A(0.5) H54B(0.5) C55(0.5) H55A(0.5)
 H55B(0.5) H55C(0.5)
6.a Riding coordinates:
 C50(H50A,H50B,H50C)
6.b Ternary CH refined with riding coordinates:
 C22(H22), C24(H24), C24A(H24A)
6.c Secondary CH2 refined with riding coordinates:
 C46(H46A,H46B), C49(H49A,H49B), C48(H48A,H48B), C47(H47A,H47B), C51(H51A,
 H51B), C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B)
6.d Aromatic/amide H refined with riding coordinates:
 C5(H5), C7(H7), C10(H10), C12(H12), C16(H16), C17(H17), C18(H18), C19(H19)
6.e Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C23(H23A,H23B,
 H23C), C27(H27A,H27B,H27C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,
 H36B,H36C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C),
 C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C25(H25A,H25B,
 H25C), C26(H26A,H26B,H26C), C25A(H25D,H25E,H25F), C26A(H26D,H26E,H26F),
 C30A(H30D,H30E,H30F), C31A(H31D,H31E,H31F), C32A(H32D,H32E,H32F), C55(H55A,
 H55B,H55C)
;
_shelx_res_checksum              85458
_shelx_hkl_checksum              76785
_olex2_submission_special_instructions 'No special instructions were received'