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_7251648
_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_absolute_configuration unk
_chemical_formula_moiety         'C63 H85 Eu F18 N8 O12 P2'
_chemical_formula_sum            'C63 H85 Eu F18 N8 O12 P2'
_chemical_formula_weight         1702.28
_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     iterative
_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                   19.5128(4)
_cell_length_b                   23.4721(5)
_cell_length_c                   17.5090(5)
_cell_measurement_reflns_used    9695
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      38.594
_cell_measurement_theta_min      2.025
_cell_volume                     8019.2(3)
_computing_cell_refinement       'SAINT V8.40A (Bruker Nano, Inc., 2019)'
_computing_data_collection       'Bruker Instrument Service vV6.2.12'
_computing_data_reduction        'SAINT V8.40A (Bruker Nano, Inc., 2019)'
_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 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0816
_diffrn_reflns_av_unetI/netI     0.0399
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            148932
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.507
_diffrn_reflns_theta_min         2.025
_exptl_absorpt_coefficient_mu    0.921
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6926
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0828 before and 0.0576 after correction. The Ratio of minimum to maximum transmission is 0.9294. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.410
_exptl_crystal_description       block
_exptl_crystal_F_000             3480
_exptl_crystal_size_max          0.137
_exptl_crystal_size_mid          0.123
_exptl_crystal_size_min          0.058
_refine_diff_density_max         0.619
_refine_diff_density_min         -0.490
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.185(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     545
_refine_ls_number_reflns         12229
_refine_ls_number_restraints     308
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0419
_refine_ls_R_factor_gt           0.0320
_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^)+(0.0208P)^2^+7.9834P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0621
_refine_ls_wR_factor_ref         0.0655
_reflns_Friedel_coverage         0.941
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                10554
_reflns_number_total             12229
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce01150g2.cif
_cod_data_source_block           yn999_amended
_cod_depositor_comments
'Adding full bibliography for 7251645--7251649.cif.'
_cod_original_sg_symbol_Hall     'A 2 -2ac'
_cod_database_code               7251648
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.949
_shelx_estimated_absorpt_t_min   0.884
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.815(9)
 0.185(9)
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 0.01
 N4-H4
 0.87 with sigma of 0.01
 O5-C27 \\sim O5A-C27A
 with sigma of 0.04
 O5-C29 \\sim O5A-C29A
 with sigma of 0.04
 O4-C25A \\sim O4A-C25B
 with sigma of 0.04
 C27-C29 \\sim C27A-C29A
 with sigma of 0.04
 C26-C25A \\sim C26A-C25B \\sim C28-C29 \\sim C28A-C29A
 with sigma of 0.01
 O4-C27 \\sim O4A-C27A
 with sigma of 0.04
 F6-C29 \\sim F6A-C29A \\sim F4-C29 \\sim F4A-C29A \\sim F5-C29 \\sim F5A-C29A
\\sim C25A-F1A \\sim C25B-
 F1B \\sim C25A-F2A \\sim C25B-F2B \\sim C25A-F3A \\sim C25B-F3B
 with sigma of 0.01
 C27-C25A \\sim C27A-C25B
 with sigma of 0.04
 O5-C28 \\sim O5A-C28A
 with sigma of 0.01
 F6-F4 \\sim F6A-F4A \\sim F6-F5 \\sim F6A-F5A \\sim F4-F5 \\sim F4A-F5A \\sim
F1A-F2A \\sim F1B-F2B \\sim F1A-
 F3A \\sim F1B-F3B \\sim F2A-F3A \\sim F2B-F3B
 with sigma of 0.04
 C28-C27 \\sim C28A-C27A
 with sigma of 0.01
 C26-C27 \\sim C26A-C27A
 with sigma of 0.01
 O4-C26 \\sim O4A-C26A
 with sigma of 0.01
 Eu1-C28 \\sim Eu1-C28A
 with sigma of 0.04
 Eu1-C26 \\sim Eu1-C26A
 with sigma of 0.04
 C28-C26 \\sim C28A-C26A
 with sigma of 0.04
 Eu1-O5 \\sim Eu1-O5A
 with sigma of 0.01
 Eu1-O4 \\sim Eu1-O4A
 with sigma of 0.01
4. Restrained planarity
 O4, C26, C27, C28, O5, C25A, C29
 with sigma of 0.01
 O4A, C28A, C26A, C27A, O5A, C25B, C29A
 with sigma of 0.01
5. Uiso/Uaniso restraints and constraints
Uanis(F6) \\sim Ueq, Uanis(F4) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(C29) \\sim
Ueq, Uanis(F6A) \\sim Ueq, Uanis(F4A) \\sim Ueq, Uanis(F5A) \\sim Ueq,
Uanis(C29A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F3A) \\sim Ueq, Uanis(F3B) \\sim Ueq, Uanis(F1A) \\sim Ueq, Uanis(F1B)
\\sim Ueq, Uanis(F2B) \\sim Ueq, Uanis(F2A) \\sim Ueq: with sigma of 0.003 and
sigma for terminal atoms of 0.006
Uanis(O5) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C28A) \\sim Ueq, Uanis(O5A)
\\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C27A) \\sim Ueq, Uanis(C26) \\sim Ueq,
Uanis(C26A) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(O4A) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C29) = Uanis(C29A)
Uanis(C25B) = Uanis(C25A)
Uanis(C28) = Uanis(C28A)
Uanis(C26) = Uanis(C26A)
Uanis(O5) = Uanis(O5A)
Uanis(C27) = Uanis(C27A)
Uanis(O4) = Uanis(O4A)
Uanis(F6A) = Uanis(F6)
Uanis(F4) = Uanis(F4A)
Uanis(F5) = Uanis(F5A)
6. Others
 Sof(O4A)=Sof(C28A)=Sof(C26A)=Sof(C27A)=Sof(H27A)=Sof(C25B)=Sof(F1B)=Sof(F2B)=
 Sof(F3B)=Sof(O5A)=Sof(F6A)=Sof(F4A)=Sof(F5A)=Sof(C29A)=1-FVAR(1)
 Sof(O5)=Sof(O4)=Sof(C28)=Sof(C26)=Sof(C27)=Sof(H27)=Sof(F6)=Sof(F4)=Sof(F5)=
 Sof(C29)=Sof(C25A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C1(H1), C10(H10)
7.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C2(H2A,H2B), C11(H11A,H11B), C9(H9A,H9B)
7.c Aromatic/amide H refined with riding coordinates:
 C24(H24), C21(H21), C20(H20), C23(H23), C22(H22), C27(H27), C32(H32),
 C27A(H27A)
7.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C7(H7A,H7B,H7C), C13(H13A,H13B,H13C), C16(H16A,H16B,H16C),
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C14(H14A,H14B,H14C), C17(H17A,H17B,H17C)
;
_shelx_res_checksum              86720
_olex2_submission_special_instructions 'No special instructions were received'