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_7064133
_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
'H16 O8 Tb, 2(C10 H10 O10 V), C16 H36 N, 0.667(H2 O)'
_chemical_formula_sum            'C36 H73.33 N O28.67 Tb V2'
_chemical_formula_weight         1239.76
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2024-08-28
_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                   15.7396(9)
_cell_length_b                   21.3320(10)
_cell_length_c                   15.4082(7)
_cell_measurement_reflns_used    9982
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      30.81
_cell_measurement_theta_min      2.64
_cell_volume                     5173.4(4)
_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    'XT  (Sheldrick, 2015)'
_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  0.0564
_diffrn_reflns_av_unetI/netI     0.0292
_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       -24
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            37267
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        24.713
_diffrn_reflns_theta_max         24.713
_diffrn_reflns_theta_min         1.630
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.795
_exptl_absorpt_correction_T_max  0.2681
_exptl_absorpt_correction_T_min  0.1915
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0911 before and 0.0703 after correction.
The Ratio of minimum to maximum transmission is 0.7143.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.592
_exptl_crystal_description       block
_exptl_crystal_F_000             2547
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.348
_refine_diff_density_min         -2.350
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.192
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     388
_refine_ls_number_reflns         4419
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.191
_refine_ls_R_factor_all          0.0573
_refine_ls_R_factor_gt           0.0506
_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^)+34.7288P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0990
_refine_ls_wR_factor_ref         0.1018
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3881
_reflns_number_total             4419
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj03452c2.cif
_cod_data_source_block           001
_cod_depositor_comments
'Adding full bibliography for 7064131--7064133.cif.'
_cod_database_code               7064133
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.900
_shelx_estimated_absorpt_t_min   0.775
_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
 Tb1-H11E \\sim Tb1-H11F
 with sigma of 0.02
 C14B-C13B \\sim C14A-C13A
 with sigma of 0.02
 Tb1-H12E \\sim Tb1-H12F
 with sigma of 0.02
 Tb1-H13E \\sim Tb1-H13F
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C13A) = Uanis(C14A)
Uanis(C13B) = Uanis(C14B)
Uanis(C9B) = Uanis(C10B)
Uanis(C10A) = Uanis(C9A)
Uanis(O4A) = Uanis(O4B)
Uanis(C17A) = Uanis(C17B)
Uanis(C17B) = Uanis(C18B)
Uanis(C17A) = Uanis(C18A)
Uanis(O8A) = Uanis(O8B)
Uanis(O4B) = Uanis(O4A)
4. Others
 Sof(C10B)=Sof(H10C)=Sof(H10D)=Sof(C9B)=Sof(H9BA)=Sof(H9BB)=1-FVAR(1)
 Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(C10A)=Sof(H10A)=Sof(H10B)=FVAR(1)
 Sof(H1A)=Sof(H1B)=Sof(O4A)=Sof(V1B)=1-FVAR(2)
 Sof(H2A)=Sof(H2B)=Sof(V1A)=Sof(O4B)=FVAR(2)
 Sof(O8A)=1-FVAR(3)
 Sof(O8B)=FVAR(3)
 Fixed Sof: C11A(0.5) H11A(0.5) H11B(0.5) C17B(0.5) H17A(0.5) H17B(0.5)
 C16B(0.5) H16A(0.5) H16B(0.5) C18B(0.5) H18A(0.5) H18B(0.5) H18C(0.5)
 C14B(0.5) H14A(0.5) H14B(0.5) H14C(0.5) C12B(0.5) H12A(0.5) H12B(0.5)
 C13B(0.5) H13A(0.5) H13B(0.5) O1S(0.333333) H1SA(0.333333) H1SB(0.333333)
 C11B(0.5) H11C(0.5) H11D(0.5) H15A(0.5) H15B(0.5) H15C(0.5) H15D(0.5)
 C16A(0.5) H16C(0.5) H16D(0.5) C12A(0.5) H12C(0.5) H12D(0.5) C17A(0.5)
 H17C(0.5) H17D(0.5) C13A(0.5) H13C(0.5) H13D(0.5) C18A(0.5) H18D(0.5)
 H18E(0.5) H18F(0.5) C14A(0.5) H14D(0.5) H14E(0.5) H14F(0.5)
5.a Riding coordinates:
 O1(H1A,H1B), O2(H2A,H2B), O1S(H1SA,H1SB)
5.b Free rotating group:
 O11(H11E,H11F), O12(H12E,H12F), O13(H13E,H13F)
5.c Rotating group:
 O14(H14G,H14H)
5.d Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C4(H4A,H4B), C9A(H9AA,H9AB), C11A(H11A,H11B), C10A(H10A,H10B),
 C17B(H17A,H17B), C16B(H16A,H16B), C12B(H12A,H12B), C13B(H13A,H13B), C10B(H10C,
 H10D), C9B(H9BA,H9BB), C11B(H11C,H11D), C15(H15A,H15B), C15(H15C,H15D),
 C16A(H16C,H16D), C12A(H12C,H12D), C17A(H17C,H17D), C13A(H13C,H13D)
5.e Idealised Me refined as rotating group:
 C18B(H18A,H18B,H18C), C14B(H14A,H14B,H14C), C18A(H18D,H18E,H18F), C14A(H14D,
 H14E,H14F)
;
_shelx_res_checksum              90856
_olex2_submission_special_instructions 'No special instructions were received'