A tetranuclear lanthanum-nickel hydrido complex supported by an arene-anchored bis(phosphinomethylamido) ligand.
He, Xiuyan; Wu, Changjiang; Hong, Dongjing; Fang, Huayi; Cui, Peng; Chemical communications (Cambridge, England) 62 (2026) 3807–3810; doi:10.1039/d5cc06726j

data_7135357
_publ_section_title
;
 A tetranuclear lanthanum-nickel hydrido complex supported by an
 arene-anchored bis(phosphinomethylamido) ligand.
;
_journal_issue                   12
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              3807
_journal_page_last               3810
_journal_paper_doi               10.1039/d5cc06726j
_journal_volume                  62
_journal_year                    2026
_chemical_formula_moiety         'C64 H88 I2 La2 N4 Ni2 P4, 2(C6 H6)'
_chemical_formula_sum            'C76 H100 I2 La2 N4 Ni2 P4'
_chemical_formula_weight         1842.51
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-12-23
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-09-03 deposited with the CCDC.	2026-01-07 downloaded from the CCDC.
;
_cell_angle_alpha                79.748(13)
_cell_angle_beta                 71.941(15)
_cell_angle_gamma                67.907(14)
_cell_formula_units_Z            1
_cell_length_a                   11.364(14)
_cell_length_b                   13.293(15)
_cell_length_c                   14.600(16)
_cell_measurement_reflns_used    7196
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      27.953
_cell_measurement_theta_min      2.155
_cell_volume                     1938(4)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker D8 Venture diffractometer'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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      296.15
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.942
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0376
_diffrn_reflns_av_unetI/netI     0.0563
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.942
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            17472
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.088
_diffrn_reflns_theta_min         1.471
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_target            Mo
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.479
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.3246
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1251 before and 0.0505 after correction.
The Ratio of minimum to maximum transmission is 0.4354.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.579
_exptl_crystal_description       block
_exptl_crystal_F_000             920
_exptl_crystal_recrystallization_method
'The crystals were growth by means of evaporation of a mixture of n-hexane and toluene at RT.'
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.929
_refine_diff_density_min         -1.172
_refine_diff_density_rms         0.122
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.969
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     597
_refine_ls_number_reflns         8900
_refine_ls_number_restraints     536
_refine_ls_restrained_S_all      0.957
_refine_ls_R_factor_all          0.0647
_refine_ls_R_factor_gt           0.0461
_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^)+(0.0795P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1192
_refine_ls_wR_factor_ref         0.1295
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6703
_reflns_number_total             8900
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc06726j2.cif
_cod_data_source_block           1_a
_cod_database_code               7135357
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.790
_shelx_estimated_absorpt_t_min   0.739
_exptl_crystal_mounting_method
'Crystals were removed from the crystallisation vial and immediately coated with polybutenes oil (CAS: 9003-29-6) on a glass slide. A suitable single crystal coated with polybutenes oil as less as possible was sealed in capillary tube filled with argon. The capillary tube with single crystal was mounted on copper pin with solid paraffin.'
_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
 C38-C37 = C37-C36 = C36-C35 = C35-C34 = C34-C33 = C38-C33
 1.39 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
P2 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C27A \\sim
C28A \\sim C29A \\sim C30A \\sim C31A \\sim C32A: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
P1 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C14A \\sim
C15A \\sim C16A \\sim C17A \\sim C18A \\sim C19A: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
C38 \\sim C33 \\sim C34 \\sim C35 \\sim C37 \\sim C36 \\sim C38A \\sim C33A
\\sim C34A \\sim C35A \\sim C37A \\sim C36A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
4. Same fragment restrains
{P1, C14A, C15A, C16A, C17A, C18A, C19A} sigma for 1-2: 0.01, 1-3: 0.04
as in
{P1, C14, C15, C16, C17, C18, C19}
{P2, C27A, C28A, C29A, C30A, C31A, C32A} sigma for 1-2: 0.01, 1-3: 0.04
as in
{P2, C27, C28, C29, C30, C31, C32}
{C33A, C34A, C35A, C36A, C37A, C38A} sigma for 1-2: 0.01, 1-3: 0.04
as in
{C33, C34, C35, C36, C37, C38}
5. Others
 Sof(I1A)=1-FVAR(1)
 Sof(I1)=FVAR(1)
 Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C16A)=
 Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18D)=
 Sof(H18E)=Sof(H18F)=Sof(C19A)=Sof(H19D)=Sof(H19E)=Sof(H19F)=1-FVAR(2)
 Sof(C14)=Sof(H14)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16)=Sof(H16A)=
 Sof(H16B)=Sof(H16C)=Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=FVAR(2)
 Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29A)=
 Sof(H29D)=Sof(H29E)=Sof(H29F)=Sof(C30A)=Sof(H30A)=Sof(C31A)=Sof(H31D)=
 Sof(H31E)=Sof(H31F)=Sof(C32A)=Sof(H32D)=Sof(H32E)=Sof(H32F)=1-FVAR(3)
 Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29)=Sof(H29A)=
 Sof(H29B)=Sof(H29C)=Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(3)
 Sof(C33A)=Sof(H33A)=Sof(C34A)=Sof(H34A)=Sof(C35A)=Sof(H35A)=Sof(C36A)=
 Sof(H36A)=Sof(C37A)=Sof(H37A)=Sof(C38A)=Sof(H38A)=1-FVAR(4)
 Sof(C33)=Sof(H33)=Sof(C34)=Sof(H34)=Sof(C35)=Sof(H35)=Sof(C36)=Sof(H36)=
 Sof(C37)=Sof(H37)=Sof(C38)=Sof(H38)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C14(H14), C17(H17), C27(H27), C30(H30), C14A(H14A), C17A(H17A), C27A(H27A),
 C30A(H30A)
6.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C26(H26A,H26B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11), C21(H21),
 C22(H22), C23(H23), C24(H24), C33(H33), C34(H34), C35(H35), C36(H36), C37(H37),
  C38(H38), C33A(H33A), C34A(H34A), C35A(H35A), C36A(H36A), C37A(H37A),
 C38A(H38A)
6.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C31(H31A,H31B,H31C), C32(H32A,
 H32B,H32C), C15A(H15D,H15E,H15F), C16A(H16D,H16E,H16F), C18A(H18D,H18E,H18F),
 C19A(H19D,H19E,H19F), C28A(H28D,H28E,H28F), C29A(H29D,H29E,H29F), C31A(H31D,
 H31E,H31F), C32A(H32D,H32E,H32F)
;
_shelx_res_checksum              97958
_olex2_submission_special_instructions 'No special instructions were received'