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_7064131
_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
'Gd H16 O8, 2(C10 H10 O10 V), 0.667(H2 O), C16 H36 N'
_chemical_formula_sum            'C36 H74 Gd N O29 V2'
_chemical_formula_weight         1244.09
_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                   15.8568(8)
_cell_length_b                   21.4138(11)
_cell_length_c                   15.4243(10)
_cell_measurement_reflns_used    9934
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      30.48
_cell_measurement_theta_min      2.64
_cell_volume                     5237.4(5)
_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)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  0.0583
_diffrn_reflns_av_unetI/netI     0.0380
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            31266
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.712
_diffrn_reflns_theta_max         24.712
_diffrn_reflns_theta_min         1.627
_exptl_absorpt_coefficient_mu    1.690
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.5654
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1307 before and 0.0724 after correction.
The Ratio of minimum to maximum transmission is 0.7578.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.578
_exptl_crystal_description       block
_exptl_crystal_F_000             2556
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.955
_refine_diff_density_min         -2.030
_refine_diff_density_rms         0.102
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.121
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     381
_refine_ls_number_reflns         4465
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.135
_refine_ls_R_factor_all          0.0617
_refine_ls_R_factor_gt           0.0484
_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^)+(0.0233P)^2^+33.4521P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1063
_refine_ls_wR_factor_ref         0.1137
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3560
_reflns_number_total             4465
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj03452c2.cif
_cod_data_source_block           op1_a
_cod_depositor_comments
'Adding full bibliography for 7064131--7064133.cif.'
_cod_database_code               7064131
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.920
_shelx_estimated_absorpt_t_min   0.786
_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
 C17B-C18B = C17A-C18A = C17A-C16B = C17B-C16A = C16B-C15 = C16A-C15
 1.5 with sigma of 0.02
 C14A-C13 = C14B-C13
 1.55 with sigma of 0.02
 Gd1-HF \\sim Gd1-HG
 with sigma of 0.02
 Gd1-HD \\sim Gd1-HE
 with sigma of 0.02
 Gd1-HB \\sim Gd1-HC
 with sigma of 0.02
 Gd1-H \\sim Gd1-HA
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C18A) \\sim Ueq, Uanis(C18B) \\sim Ueq: with sigma of 0.015 and sigma for
terminal atoms of 0.03
Uanis(C12) \\sim Ueq: with sigma of 0.015 and sigma for terminal atoms of 0.03
Uanis(C16B) = Uanis(C16A)
4. Others
 Sof(O4A)=1-FVAR(1)
 Sof(O4B)=FVAR(1)
 Sof(HR)=Sof(HS)=Sof(C14B)=Sof(H6)=Sof(H7)=Sof(H8)=1-FVAR(2)
 Sof(HP)=Sof(HQ)=Sof(C14A)=Sof(HV)=Sof(HW)=Sof(HX)=FVAR(2)
 Sof(HJ)=Sof(HK)=Sof(C16B)=Sof(HY)=Sof(HZ)=Sof(C17A)=Sof(H1)=Sof(H2)=Sof(C18A)=
 Sof(H3)=Sof(H4)=Sof(H5)=1-FVAR(3)
 Sof(HL)=Sof(HM)=Sof(C16A)=Sof(H9)=Sof(H10)=Sof(C17B)=Sof(H11)=Sof(H12)=
 Sof(C18B)=Sof(H13)=Sof(H14)=Sof(H15)=FVAR(3)
 Sof(C10A)=Sof(H10A)=Sof(H10B)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=1-FVAR(4)
 Sof(C10B)=Sof(H10C)=Sof(H10D)=Sof(C9B)=Sof(H9BA)=Sof(H9BB)=FVAR(4)
 Fixed Sof: O1S(0.333333) HH(0.333333) HI(0.333333) V1B(0.666667)
 H2A(0.333333) H2B(0.333333) V1A(0.333333) H1A(0.66666) H1B(0.66666)
5.a Riding coordinates:
 O11(H,HA), O14(HB,HC), O13(HD,HE), O12(HF,HG), O2(H2A,H2B), O1(H1A,H1B)
5.b Rotating group:
 O1S(HH,HI)
5.c Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C4(H4A,H4B), C15(HJ,HK), C15(HL,HM), C11(HN,HO), C10A(H10A,H10B),
  C9A(H9AA,H9AB), C13(HP,HQ), C13(HR,HS), C12(HT,HU), C16B(HY,HZ), C17A(H1,H2),
 C16A(H9,H10), C17B(H11,H12), C10B(H10C,H10D), C9B(H9BA,H9BB)
5.d Me refined with riding coordinates:
 C18A(H3,H4,H5)
5.e Idealised Me refined as rotating group:
 C14A(HV,HW,HX), C14B(H6,H7,H8), C18B(H13,H14,H15)
;
_shelx_res_checksum              95176
_shelx_fab_checksum              83246
_olex2_submission_special_instructions 'No special instructions were received'