Novel bimetallic LnIII/VIV (Ln = Gd, Tb, Dy, Er, Yb, Lu) compounds with cyclopropane-1,1-dicarboxylate anions and bulky tetrabutylammonium cations: synthesis, structure, magnetic properties, and thermal decomposition
Bazhina, Evgeniya S.; Shmelev, Maxim A.; Gogoleva, Natalia V.; Matiukhina, Anna K.; Vasilev, Pavel N.; Efimov, Nikolay N.; Kiskin, Mikhail A.; Eremenko, Igor L.; New Journal of Chemistry 49 (2025) 20754–20767; doi:10.1039/D5NJ03452C

data_7064132
_publ_section_title
;
 Novel bimetallic LnIII/VIV (Ln = Gd, Tb, Dy, Er, Yb, Lu) compounds with
 cyclopropane-1,1-dicarboxylate anions and bulky tetrabutylammonium
 cations: synthesis, structure, magnetic properties, and thermal
 decomposition
;
_journal_issue                   47
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              20754
_journal_page_last               20767
_journal_paper_doi               10.1039/D5NJ03452C
_journal_volume                  49
_journal_year                    2025
_chemical_formula_moiety
'Dy H16 O8, 2(C10 H10 O10 V), C16 H36 N, 0.667(H2 O)'
_chemical_formula_sum            'C36 H73.33 Dy N O28.67 V2'
_chemical_formula_weight         1243.34
_space_group_crystal_system      orthorhombic
_space_group_IT_number           52
_space_group_name_Hall           '-P 2a 2bc'
_space_group_name_H-M_alt        'P n n a'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2024-10-02
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-07-14 deposited with the CCDC.	2025-11-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.7781(12)
_cell_length_b                   21.2907(15)
_cell_length_c                   15.4105(10)
_cell_measurement_reflns_used    6316
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      30.45
_cell_measurement_theta_min      2.66
_cell_volume                     5176.8(6)
_computing_cell_refinement       'SAINT V8.35A (?, 2016)'
_computing_data_reduction        'SAINT V8.35A (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0984
_diffrn_reflns_av_unetI/netI     0.0526
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            36809
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        24.712
_diffrn_reflns_theta_max         24.712
_diffrn_reflns_theta_min         1.631
_exptl_absorpt_coefficient_mu    1.871
_exptl_absorpt_correction_T_max  0.2657
_exptl_absorpt_correction_T_min  0.1877
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1046 before and 0.0893 after correction.
The Ratio of minimum to maximum transmission is 0.7064.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.595
_exptl_crystal_description       block
_exptl_crystal_F_000             2551
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.874
_refine_diff_density_min         -1.227
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     352
_refine_ls_number_reflns         4418
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0816
_refine_ls_R_factor_gt           0.0537
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0259P)^2^+40.2510P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1124
_refine_ls_wR_factor_ref         0.1275
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3099
_reflns_number_total             4418
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj03452c2.cif
_cod_data_source_block           104
_cod_depositor_comments
'Adding full bibliography for 7064131--7064133.cif.'
_cod_database_code               7064132
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.896
_shelx_estimated_absorpt_t_min   0.807
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 Dy1-H12E_$1 \\sim Dy1-H12F_$1
 with sigma of 0.02
 Dy1-H14G_$1 \\sim Dy1-H14H_$1
 with sigma of 0.02
 Dy1-H11E_$1 \\sim Dy1-H11F_$1
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C13A) = Uanis(C13B)
Uanis(C12A) = Uanis(C12B)
Uanis(C14A) = Uanis(C13A)
Uanis(C10A) = Uanis(C9A)
Uiso(C9B) = Uiso(C10B)
Uanis(C18) = Uanis(C19B)
Uanis(C19A) = Uanis(C18)
4. Others
 Sof(H11C)=Sof(H11D)=Sof(C12B)=Sof(H12A)=Sof(H12B)=Sof(C14B)=Sof(H14A)=
 Sof(H14B)=Sof(H14C)=Sof(C13B)=Sof(H13A)=Sof(H13B)=1-FVAR(1)
 Sof(H11A)=Sof(H11B)=Sof(C13A)=Sof(H13C)=Sof(H13D)=Sof(C12A)=Sof(H12C)=
 Sof(H12D)=Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=FVAR(1)
 Sof(H2A)=Sof(H2B)=Sof(V1A)=1-FVAR(2)
 Sof(V1B)=Sof(H1A)=Sof(H1B)=FVAR(2)
 Sof(C10B)=Sof(H10A)=Sof(H10B)=Sof(C9B)=Sof(H9BA)=Sof(H9BB)=1-FVAR(3)
 Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(C10A)=Sof(H10C)=Sof(H10D)=FVAR(3)
 Sof(O6A)=1-FVAR(4)
 Sof(O6B)=FVAR(4)
 Fixed Sof: H18C(0.5) H18D(0.5) H18A(0.5) H18B(0.5) O1S(0.333333)
 H1SA(0.333333) H1SB(0.333333) C19B(0.5) H19A(0.5) H19B(0.5) H19C(0.5)
 C19A(0.5) H19D(0.5) H19E(0.5) H19F(0.5)
5.a Riding coordinates:
 O12(H12E,H12F), O13(H13E,H13F), O14(H14G,H14H), O11(H11E,H11F), O1S(H1SA,H1SB)
5.b Rotating group:
 O1(H1A,H1B), O2(H2A,H2B)
5.c Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C16(H16A,H16B), C10B(H10A,H10B), C4(H4A,H4B), C9B(H9BA,H9BB),
 C18(H18C,H18D), C18(H18A,H18B), C17(H17A,H17B), C11(H11C,H11D), C11(H11A,H11B),
  C12B(H12A,H12B), C13B(H13A,H13B), C13A(H13C,H13D), C12A(H12C,H12D), C9A(H9AA,
 H9AB), C10A(H10C,H10D)
5.d Idealised Me refined as rotating group:
 C19B(H19A,H19B,H19C), C14B(H14A,H14B,H14C), C14A(H14D,H14E,H14F), C19A(H19D,
 H19E,H19F)
;
_shelx_res_checksum              74420
_olex2_submission_special_instructions 'No special instructions were received'