Coordination compounds based on a phosphonic diamide-TEMPO diradical and CuII, NdIII, EuIII and TbIII ions: synthesis, magnetic properties and application in the aerobic oxidation of allylic and benzylic alcohols
Navarro, Yolanda; Soriano, Stéphane; de Castro Silva, Henrique; Iglesias, María José; Guedes, Guilherme P.; Ortiz, Fernando López; CrystEngComm 28 (2026) 1938–1953; doi:10.1039/D5CE01150G

data_7251647
_publ_section_title
;
 Coordination compounds based on a phosphonic diamide-TEMPO diradical and
 CuII, NdIII, EuIII and TbIII ions: synthesis, magnetic properties and
 application in the aerobic oxidation of allylic and benzylic alcohols
;
_journal_issue                   12
_journal_name_full               CrystEngComm
_journal_page_first              1938
_journal_page_last               1953
_journal_paper_doi               10.1039/D5CE01150G
_journal_volume                  28
_journal_year                    2026
_chemical_formula_moiety         'C63 H85 F18 N8 Nd O12 P2'
_chemical_formula_sum            'C63 H85 F18 N8 Nd O12 P2'
_chemical_formula_weight         1694.56
_space_group_crystal_system      orthorhombic
_space_group_IT_number           41
_space_group_name_Hall           'A 2 -2ab'
_space_group_name_H-M_alt        'A e a 2'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2026-02-08
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2026-02-11 deposited with the CCDC.	2026-02-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.4450(5)
_cell_length_b                   23.4941(4)
_cell_length_c                   17.6409(4)
_cell_measurement_reflns_used    9272
_cell_measurement_temperature    100
_cell_measurement_theta_max      72.22
_cell_measurement_theta_min      3.76
_cell_volume                     8059.1(3)
_computing_data_collection       'Bruker Smart (Bruker AXS, 2007)'
_computing_data_reduction        'Bruker Saint (Bruker AXS, 2007)'
_computing_molecular_graphics    'Mercury (Macrae et al., 2006)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS-1997  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0689
_diffrn_reflns_av_unetI/netI     0.0391
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            99067
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.373
_diffrn_reflns_theta_min         3.763
_exptl_absorpt_coefficient_mu    6.168
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.4457
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS, Bruker Analytical X-ray Systems,Inc., Madison WI, 1997.'
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.397
_exptl_crystal_description       block
_exptl_crystal_F_000             3468
_exptl_crystal_size_max          0.56
_exptl_crystal_size_mid          0.098
_exptl_crystal_size_min          0.075
_refine_diff_density_max         0.966
_refine_diff_density_min         -0.724
_refine_diff_density_rms         0.078
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.039(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     519
_refine_ls_number_reflns         7635
_refine_ls_number_restraints     237
_refine_ls_restrained_S_all      1.093
_refine_ls_R_factor_all          0.0479
_refine_ls_R_factor_gt           0.0403
_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^)+(0.0544P)^2^+17.7237P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0954
_refine_ls_wR_factor_ref         0.0998
_reflns_Friedel_coverage         0.932
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                6808
_reflns_number_total             7635
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce01150g2.cif
_cod_data_source_block           yn296_2
_cod_depositor_comments
'Adding full bibliography for 7251645--7251649.cif.'
_cod_original_sg_symbol_Hall     'A 2 -2ac'
_cod_database_code               7251647
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.655
_shelx_estimated_absorpt_t_min   0.130
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.961(5)
 0.039(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. Restrained distances
 N2-H2
 0.87 with sigma of 0.02
 C25A-C26A \\sim C25B-C26B \\sim C28A-C29A \\sim C28B-C29B
 with sigma of 0.02
 C26A-C27A \\sim C26B-C27B \\sim C27A-C28A \\sim C27B-C28B
 with sigma of 0.02
 C26A-O4A \\sim C26B-O4B \\sim C28A-O5A \\sim C28B-O5B
 with sigma of 0.02
 C25B-F1B \\sim C25B-F2B \\sim C25B-F3B \\sim C25A-F1A \\sim C25A-F2A \\sim
C25A-F3A
 with sigma of 0.01
 F1A-F2A \\sim F1A-F3A \\sim F2A-F3A \\sim F1B-F2B \\sim F1B-F3B \\sim F2B-F3B
 with sigma of 0.02
 C29A-F4A \\sim C29A-F5A \\sim C29A-F6A \\sim C29B-F4B \\sim C29B-F5B \\sim
C29B-F6B
 with sigma of 0.01
 F4A-F5A \\sim F4A-F6A \\sim F5A-F6A \\sim F4B-F5B \\sim F4B-F6B \\sim F5B-F6B
 with sigma of 0.02
 O5A-C27A \\sim O5B-C27B
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(F1A) \\sim Ueq, Uanis(F2A) \\sim Ueq, Uanis(F3A) \\sim Ueq, Uanis(F1B)
\\sim Ueq, Uanis(F2B) \\sim Ueq, Uanis(F3B) \\sim Ueq, Uanis(C25A) \\sim Ueq,
Uanis(C25B) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(F4A) \\sim Ueq, Uanis(F5A) \\sim Ueq, Uanis(F6A) \\sim Ueq, Uanis(F4B)
\\sim Ueq, Uanis(F5B) \\sim Ueq, Uanis(F6B) \\sim Ueq, Uanis(C29A) \\sim Ueq,
Uanis(C29B) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(C26A) \\sim Ueq, Uanis(C27A) \\sim Ueq, Uanis(C28A) \\sim Ueq,
Uanis(C29B) \\sim Ueq, Uanis(O4A) \\sim Ueq, Uanis(O5A) \\sim Ueq, Uanis(C26B)
\\sim Ueq, Uanis(C27B) \\sim Ueq, Uanis(C28B) \\sim Ueq, Uanis(C29B) \\sim Ueq,
Uanis(O4B) \\sim Ueq, Uanis(O5B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C26A) = Uanis(C26B)
Uanis(F4A) = Uanis(F4B)
Uanis(F5A) = Uanis(F5B)
Uanis(F6A) = Uanis(F6B)
Uanis(C28A) = Uanis(C28B)
Uanis(C25A) = Uanis(C25B)
Uanis(C29A) = Uanis(C29B)
Uanis(O5A) = Uanis(O5B)
Uanis(F1A) = Uanis(F1B)
Uanis(F2A) = Uanis(F2B)
Uanis(F3A) = Uanis(F3B)
Uanis(O4A) = Uanis(O4B)
Uanis(C27A) = Uanis(C27B)
5. Others
 Sof(O4B)=Sof(C25B)=Sof(C26B)=Sof(C27B)=Sof(H27B)=Sof(C28B)=Sof(C29B)=Sof(F1B)=
 Sof(F2B)=Sof(F3B)=Sof(O5B)=Sof(F4B)=Sof(F5B)=Sof(F6B)=1-FVAR(1)
 Sof(O4A)=Sof(C25A)=Sof(C26A)=Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(C29A)=Sof(F1A)=
 Sof(F2A)=Sof(F3A)=Sof(O5A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C10(H10), C1(H1)
6.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C18(H18A,H18B), C9(H9A,H9B), C11(H11A,H11B)
6.c Me refined with riding coordinates:
 C8(H8A,H8B,H8C), C14(H14A,H14B,H14C), C4(H4A,H4B,H4C), C16(H16A,H16B,H16C),
 C7(H7A,H7B,H7C), C17(H17A,H17B,H17C), C13(H13A,H13B,H13C), C5(H5A,H5B,H5C)
6.d Aromatic/amide H refined with riding coordinates:
 C24(H24), C20(H20), C22(H22), C23(H23), C21(H21), C32(H32), C27A(H27A),
 C27B(H27B)
;
_shelx_res_checksum              88821
_olex2_submission_special_instructions 'No special instructions were received'