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_7251646
_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 O12 P2 Tb'
_chemical_formula_sum            'C63 H85 F18 N8 O12 P2 Tb'
_chemical_formula_weight         1709.24
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 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                 95.2292(11)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.2774(3)
_cell_length_b                   31.7772(6)
_cell_length_c                   20.0260(4)
_cell_measurement_reflns_used    9885
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      64.25
_cell_measurement_theta_min      4.30
_cell_volume                     7780.5(3)
_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 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.976
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0486
_diffrn_reflns_av_unetI/netI     0.0453
_diffrn_reflns_Laue_measured_fraction_full 0.976
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            54954
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        64.564
_diffrn_reflns_theta_max         64.564
_diffrn_reflns_theta_min         2.781
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.767
_exptl_absorpt_correction_T_max  0.7525
_exptl_absorpt_correction_T_min  0.4857
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1317 before and 0.0600 after correction.
The Ratio of minimum to maximum transmission is 0.6454.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.459
_exptl_crystal_description       block
_exptl_crystal_F_000             3488
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_size_max          0.324
_exptl_crystal_size_mid          0.085
_exptl_crystal_size_min          0.046
_refine_diff_density_max         1.050
_refine_diff_density_min         -0.711
_refine_diff_density_rms         0.064
_refine_ls_extinction_coef       0.000187(18)
_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   1.018
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1017
_refine_ls_number_reflns         12794
_refine_ls_number_restraints     407
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0506
_refine_ls_R_factor_gt           0.0389
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0313P)^2^+10.3036P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0814
_refine_ls_wR_factor_ref         0.0862
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10902
_reflns_number_total             12794
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce01150g2.cif
_cod_data_source_block           yn753_2b_0m
_cod_depositor_comments
'Adding full bibliography for 7251645--7251649.cif.'
_cod_database_code               7251646
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.777
_shelx_estimated_absorpt_t_min   0.257
_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
 N4-H4
 0.87 with sigma of 0.02
 N7-H7
 0.87 with sigma of 0.02
 N8-H8
 0.87 with sigma of 0.02
 N3-H3
 0.87 with sigma of 0.02
 F4A-F5A \\sim F4A-F6A \\sim F5A-F6A
 with sigma of 0.02
 O4A-N5A \\sim O4B-N5B
 with sigma of 0.02
 C31-N5A \\sim C31-N5B \\sim C25-N5A \\sim C25-N5B
 with sigma of 0.02
 F10A-F11A \\sim F10A-F12A \\sim F11A-F12A
 with sigma of 0.02
 F10B-F11B \\sim F10B-F12B \\sim F11B-F12B
 with sigma of 0.02
 C58-F10A \\sim C58-F11A \\sim C58-F12A \\sim C58-F10B \\sim C58-F11B \\sim
C58-F12B
 with sigma of 0.01
 C63-F13B \\sim C63-F14B \\sim C63-F15B \\sim C63-F13A \\sim C63-F14A \\sim
C63-F15A
 with sigma of 0.01
 F13A-F14A \\sim F13A-F15A \\sim F14A-F15A
 with sigma of 0.02
 F13B-F14B \\sim F13B-F15B \\sim F14B-F15B
 with sigma of 0.02
 F16A-F17A \\sim F16A-F18A \\sim F17A-F18A
 with sigma of 0.02
 F16B-F17B \\sim F16B-F18B \\sim F17B-F18B
 with sigma of 0.02
 C59-F16A \\sim C59-F17A \\sim C59-F18A \\sim C59-F16B \\sim C59-F17B \\sim
C59-F18B
 with sigma of 0.01
 F4B-F5B \\sim F4B-F6B \\sim F5B-F6B
 with sigma of 0.02
 C49-F4A \\sim C49-F5A \\sim C49-F6A \\sim C49-F4B \\sim C49-F5B \\sim C49-F6B
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C58 \\sim F10A \\sim F11A \\sim F12A \\sim F10B \\sim F11B \\sim F12B: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C59 \\sim F16B \\sim F16A \\sim F17A \\sim F17B \\sim F18A \\sim F18B: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C49 \\sim F5B \\sim F5A \\sim F4B \\sim F6A \\sim F6B \\sim F4A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C63 \\sim F13B \\sim F13A \\sim F15B \\sim F15A \\sim F14B \\sim F14A: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(O4A) \\sim Ueq, Uanis(N5A) \\sim Ueq, Uanis(O4B) \\sim Ueq, Uanis(N5B)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O4A) = Uanis(O4B)
Uanis(N5A) = Uanis(N5B)
Uanis(F10A) = Uanis(F10B)
Uanis(F11A) = Uanis(F11B)
Uanis(F12A) = Uanis(F12B)
Uanis(F13A) = Uanis(F13B)
Uanis(F14A) = Uanis(F14B)
Uanis(F15A) = Uanis(F15B)
Uanis(F4A) = Uanis(F4B)
Uanis(F5A) = Uanis(F5B)
Uanis(F6A) = Uanis(F6B)
Uanis(F16A) = Uanis(F16B)
Uanis(F17A) = Uanis(F17B)
Uanis(F18A) = Uanis(F18B)
4. Others
 Sof(F4B)=Sof(F5B)=Sof(F6B)=1-FVAR(1)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=FVAR(1)
 Sof(F16B)=Sof(F17B)=Sof(F18B)=1-FVAR(2)
 Sof(F16A)=Sof(F17A)=Sof(F18A)=FVAR(2)
 Sof(F13B)=Sof(F14B)=Sof(F15B)=1-FVAR(3)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=FVAR(3)
 Sof(F10B)=Sof(F11B)=Sof(F12B)=1-FVAR(4)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=FVAR(4)
 Sof(N5B)=Sof(O4B)=1-FVAR(5)
 Sof(N5A)=Sof(O4A)=FVAR(5)
5.a Ternary CH refined with riding coordinates:
 C14(H14), C5(H5), C29(H29), C38(H38)
5.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C13(H13A,H13B), C37(H37A,H37B), C39(H39A,H39B), C6(H6A,H6B),
 C4(H4A,H4B), C28(H28A,H28B), C30(H30A,H30B)
5.c Aromatic/amide H refined with riding coordinates:
 C21(H21), C56(H56), C22(H22), C23(H23), C46(H46), C20(H20), C43(H43),
 C47(H47), C24(H24), C51(H51), C44(H44), C61(H61), C45(H45)
5.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C9(H9A,H9B,
 H9C), C2(H2A,H2B,H2C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C11(H11A,H11B,
 H11C), C12(H12A,H12B,H12C), C17(H17A,H17B,H17C), C8(H8A,H8B,H8C), C41(H41A,
 H41B,H41C), C42(H42A,H42B,H42C), C3(H3A,H3B,H3C), C32(H32A,H32B,H32C),
 C33(H33A,H33B,H33C)
;
_shelx_res_checksum              81115
_olex2_submission_special_instructions 'No special instructions were received'