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_7251649
_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         'C34 H43 Cu F12 N4 O7 P'
_chemical_formula_sum            'C34 H43 Cu F12 N4 O7 P'
_chemical_formula_weight         942.23
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2026-02-14
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2026-02-14 deposited with the CCDC.	2026-02-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 111.217(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   38.926(2)
_cell_length_b                   12.0395(6)
_cell_length_c                   20.6680(10)
_cell_measurement_reflns_used    9690
_cell_measurement_temperature    100
_cell_measurement_theta_max      72.16
_cell_measurement_theta_min      3.87
_cell_volume                     9029.5(8)
_computing_cell_refinement       'Bruker APEX2 (Bruker AXS, 2012)'
_computing_data_collection       'Bruker APEX2 (Bruker AXS, 2012)'
_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-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0769
_diffrn_reflns_av_unetI/netI     0.0336
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       48
_diffrn_reflns_limit_h_min       -48
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            192100
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.643
_diffrn_reflns_theta_min         3.868
_exptl_absorpt_coefficient_mu    1.881
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.5292
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS, Bruker Analytical X-ray Systems,Inc., Madison WI, 1997.'
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.386
_exptl_crystal_description       plate
_exptl_crystal_F_000             3864
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.053
_refine_diff_density_max         1.049
_refine_diff_density_min         -0.835
_refine_diff_density_rms         0.080
_refine_ls_extinction_coef       0.000210(19)
_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   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     632
_refine_ls_number_reflns         8906
_refine_ls_number_restraints     509
_refine_ls_restrained_S_all      1.130
_refine_ls_R_factor_all          0.0778
_refine_ls_R_factor_gt           0.0597
_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^)+(0.0566P)^2^+50.4372P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1420
_refine_ls_wR_factor_ref         0.1519
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7492
_reflns_number_total             8906
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce01150g2.cif
_cod_data_source_block           yn279
_cod_depositor_comments
'Adding full bibliography for 7251645--7251649.cif.'
_cod_original_cell_volume        9029.4(8)
_cod_database_code               7251649
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.907
_shelx_estimated_absorpt_t_min   0.559
_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
 C30A-F7A \\sim C30A-F8A \\sim C30A-F9A \\sim C30B-F7B \\sim C30B-F8B \\sim
C30B-F9B
 with sigma of 0.01
 C34A-F10A \\sim C34A-F11A \\sim C34A-F12A \\sim C34B-F10B \\sim C34B-F11B
\\sim C34B-F12B
 with sigma of 0.01
 C31A-O6A \\sim C31B-O6B \\sim C33A-O7A \\sim C33B-O7B
 with sigma of 0.02
 F7A-F8A \\sim F7A-F9A \\sim F8A-F9A \\sim F7B-F8B \\sim F7B-F9B \\sim F8B-F9B
 with sigma of 0.02
 F10A-F11A \\sim F10A-F12A \\sim F11A-F12A \\sim F10B-F11B \\sim F10B-F12B
\\sim F11B-F12B
 with sigma of 0.02
 C34A-C33A \\sim C34B-C33B \\sim C30A-C31A \\sim C30B-C31B
 with sigma of 0.02
 C31A-C32A \\sim C31B-C32B \\sim C32A-C33A \\sim C32B-C33B
 with sigma of 0.02
 F4B-F5B \\sim F4B-F6B \\sim F5B-F6B
 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
 F1A-F2A \\sim F1A-F3A \\sim F2A-F3A \\sim F1B-F2B \\sim F1B-F3B \\sim F2B-F3B
\\sim F1C-F2C \\sim F1C-F3C
 \\sim F2C-F3C
 with sigma of 0.02
 C25-F1A \\sim C25-F2A \\sim C25-F3A \\sim C25-F1B \\sim C25-F2B \\sim C25-F3B
\\sim C25-F1C \\sim C25-F2C
 \\sim C25-F3C
 with sigma of 0.008
3. Restrained planarity
 C26, C27A, C28A, C29A, O4, O5A, C25
 with sigma of 0.1
 C26, C27B, C28B, C29B, O4, O5B, C25
 with sigma of 0.1
 C30B, C31B, C32B, C33B, C34B, O6B, O7B
 with sigma of 0.1
 C30A, C31A, C32A, C33A, C34A, O6A, O7A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C30A) \\sim Ueq, Uanis(F7A) \\sim Ueq, Uanis(F8A) \\sim Ueq, Uanis(F9A)
\\sim Ueq, Uanis(C30B) \\sim Ueq, Uanis(F7B) \\sim Ueq, Uanis(F8B) \\sim Ueq,
Uanis(F9B) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(C34A) \\sim Ueq, Uanis(F10A) \\sim Ueq, Uanis(F11A) \\sim Ueq,
Uanis(F12A) \\sim Ueq, Uanis(C34B) \\sim Ueq, Uanis(F10B) \\sim Ueq,
Uanis(F11B) \\sim Ueq, Uanis(F12B) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.006
Uanis(C33A) \\sim Ueq, Uanis(C33B) \\sim Ueq, Uanis(O7A) \\sim Ueq, Uanis(O7B)
\\sim Ueq, Uanis(C32A) \\sim Ueq, Uanis(C32B) \\sim Ueq, Uanis(C31A) \\sim Ueq,
Uanis(C31B) \\sim Ueq, Uanis(O6A) \\sim Ueq, Uanis(O6B) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(F4A) \\sim Ueq, Uanis(F5A) \\sim Ueq, Uanis(F6A) \\sim Ueq, Uanis(C29A)
\\sim Ueq, Uanis(F4B) \\sim Ueq, Uanis(F5B) \\sim Ueq, Uanis(F6B) \\sim Ueq,
Uanis(C29B) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(C28A) \\sim Ueq, Uanis(C28B) \\sim Ueq, Uanis(O5A) \\sim Ueq, Uanis(O5B)
\\sim Ueq, Uanis(C27A) \\sim Ueq, Uanis(C27B) \\sim Ueq, Uanis(C26) \\sim Ueq,
Uanis(O4) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
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(F1C) \\sim Ueq,
Uanis(F2C) \\sim Ueq, Uanis(F3C) \\sim Ueq, Uanis(C25) \\sim Ueq: with sigma of
0.003 and sigma for terminal atoms of 0.006
Uanis(F7A) = Uanis(F7B)
Uanis(F8A) = Uanis(F8B)
Uanis(F9A) = Uanis(F9B)
Uanis(F10A) = Uanis(F10B)
Uanis(F11A) = Uanis(F11B)
Uanis(F12A) = Uanis(F12B)
Uanis(C30A) = Uanis(C30B)
Uanis(C31A) = Uanis(C31B)
Uanis(C32A) = Uanis(C32B)
Uanis(C33A) = Uanis(C33B)
Uanis(C34A) = Uanis(C34B)
Uanis(O6A) = Uanis(O6B)
Uanis(O7A) = Uanis(O7B)
Uanis(F1A) = Uanis(F1B) = Uanis(F1C)
Uanis(F2A) = Uanis(F2B) = Uanis(F2C)
Uanis(F3A) = Uanis(F3B) = Uanis(F3C)
Uanis(F4A) = Uanis(F4B)
Uanis(F5A) = Uanis(F5B)
Uanis(F6A) = Uanis(F6B)
Uanis(C29A) = Uanis(C29B)
Uanis(C28A) = Uanis(C28B)
Uanis(C27A) = Uanis(C27B)
Uanis(O5A) = Uanis(O5B)
5. Others
 1*[Sof(F1A)+Sof(F2A)+Sof(F3A)]+1*[Sof(F1B)+Sof(F2B)+Sof(F3B)]+1*[Sof(F1C)+
 Sof(F2C)+Sof(F3C)]=1 with esd of 0.0001
 Sof(C27B)=Sof(H27B)=Sof(C28B)=Sof(C29B)=Sof(F4B)=Sof(F5B)=Sof(F6B)=Sof(O5B)=1-
 FVAR(1)
 Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(C29A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(O5A)=
 FVAR(1)
 Sof(C30B)=Sof(C31B)=Sof(C32B)=Sof(H32B)=Sof(C33B)=Sof(C34B)=Sof(F7B)=Sof(F8B)=
 Sof(F9B)=Sof(F10B)=Sof(F11B)=Sof(F12B)=Sof(O6B)=Sof(O7B)=1-FVAR(2)
 Sof(C30A)=Sof(C31A)=Sof(C32A)=Sof(H32A)=Sof(C33A)=Sof(C34A)=Sof(F7A)=Sof(F8A)=
 Sof(F9A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=Sof(O6A)=Sof(O7A)=FVAR(2)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=FVAR(3)
 Sof(F1B)=Sof(F2B)=Sof(F3B)=FVAR(4)
 Sof(F1C)=Sof(F2C)=Sof(F3C)=FVAR(5)
6.a Ternary CH refined with riding coordinates:
 C5(H5), C14(H14)
6.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C6(H6A,H6B), C13(H13A,H13B), C15(H15A,H15B)
6.c Aromatic/amide H refined with riding coordinates:
 C22(H22), C24(H24), C20(H20), C23(H23), C21(H21), C27A(H27A), C27B(H27B),
 C32A(H32A), C32B(H32B)
6.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C11(H11A,H11B,H11C), C3(H3A,H3B,H3C), C8(H8A,H8B,H8C),
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C2(H2A,H2B,H2C), C9(H9A,H9B,H9C)
;
_smtbx_masks_void_probe_radius   1.8
_smtbx_masks_void_truncation_radius 2.0
_shelx_res_checksum              4994
_shelx_fab_checksum              80956
_olex2_submission_special_instructions 'No special instructions were received'