On the usability of salt metathesis reactions for the synthesis of sterically crowded tris-formamidinate Ln(iii) complexes: success and limits. Spontaneous reduction of Eu(iii) to Eu(ii)
Bashirov, Denis A.; Kolybalov, Dmitry S.; Mironova, Olga A.; Sukhikh, Taisiya S.; Konchenko, Sergey N.; New Journal of Chemistry 46 (2022) 11994–12001; doi:10.1039/D2NJ01589G

data_7061553
_publ_section_title
;
 On the usability of salt metathesis reactions for the synthesis of
 sterically crowded tris-formamidinate Ln(iii) complexes: success and
 limits. Spontaneous reduction of Eu(iii) to Eu(ii)
;
_journal_issue                   25
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              11994
_journal_page_last               12001
_journal_paper_doi               10.1039/D2NJ01589G
_journal_volume                  46
_journal_year                    2022
_chemical_formula_moiety         'C58 H86 Cl N4 Nd O2, 2(C4 H8 O)'
_chemical_formula_sum            'C66 H102 Cl N4 Nd O4'
_chemical_formula_weight         1195.20
_chemical_name_systematic
'bis(N,N'-bis(2,6-diisopropylphenyl)formamidinato-chloro-bis(tetrahydrofuran)-neodimium(iii) di-tetrahydrofuran solvate'
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-02-04
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2022-01-11 deposited with the CCDC.	2022-05-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.8470(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.7849(5)
_cell_length_b                   27.0152(13)
_cell_length_c                   21.9212(10)
_cell_measurement_reflns_used    9996
_cell_measurement_temperature    150(4)
_cell_measurement_theta_max      25.05
_cell_measurement_theta_min      2.17
_cell_volume                     6364.0(5)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX3'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      150(4)
_diffrn_detector                 PIXEL
_diffrn_detector_area_resol_mean 7.41
_diffrn_detector_type            'Bruker PHOTON III area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture diffractometer'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'Incoatec HELIOS multilayer mirrors'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0700
_diffrn_reflns_av_unetI/netI     0.0515
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            70871
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.419
_diffrn_reflns_theta_min         2.011
_diffrn_source                   'Incoatec IuS3.0 microfocus X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.906
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6571
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0727 before and 0.0632 after correction.
The Ratio of minimum to maximum transmission is 0.8815.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.247
_exptl_crystal_description       prism
_exptl_crystal_F_000             2540
_exptl_crystal_preparation       'Schlenk technique'
_exptl_crystal_recrystallization_method 'slow evaporation THF'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.944
_refine_diff_density_min         -2.000
_refine_diff_density_rms         0.100
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.103
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     651
_refine_ls_number_reflns         13055
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.107
_refine_ls_R_factor_all          0.0735
_refine_ls_R_factor_gt           0.0590
_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^)+(0.0402P)^2^+22.5872P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1287
_refine_ls_wR_factor_ref         0.1354
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10742
_reflns_number_total             13055
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj01589g2.cif
_cod_data_source_block           mo_kds450_0m
_cod_depositor_comments
'Adding full bibliography for 7061550--7061554.cif.'
_cod_database_code               7061553
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.931
_shelx_estimated_absorpt_t_min   0.876
_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
 C57-C56
 1.54 with sigma of 0.02
 C61-C60
 1.54 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C29(H29), C20(H20), C10(H10), C45(H45), C23(H23), C28(H28), C48(H48), C2(H2)
3.b Secondary CH2 refined with riding coordinates:
 C51(H51A,H51B), C58(H58A,H58B), C54(H54A,H54B), C52(H52A,H52B), C55(H55A,
 H55B), C53(H53A,H53B), C64(H64A,H64B), C57(H57A,H57B), C56(H56A,H56B),
 C65(H65A,H65B), C66(H66A,H66B), C63(H63A,H63B), C59(H59A,H59B), C62(H62A,H62B),
  C61(H61A,H61B), C60(H60A,H60B)
3.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C43(H43), C38(H38), C42(H42), C41(H41), C33(H33), C18(H18), C7(H7),
 C5(H5), C16(H16), C6(H6), C17(H17), C35(H35), C34(H34)
3.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C31(H31A,H31B,H31C), C47(H47A,H47B,H47C), C1(H1A,H1B,
 H1C), C50(H50A,H50B,H50C), C11(H11A,H11B,H11C), C22(H22A,H22B,H22C), C3(H3A,
 H3B,H3C), C27(H27A,H27B,H27C), C21(H21A,H21B,H21C), C46(H46A,H46B,H46C),
 C49(H49A,H49B,H49C), C30(H30A,H30B,H30C), C26(H26A,H26B,H26C), C25(H25A,H25B,
 H25C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              7285
_olex2_submission_special_instructions 'No special instructions were received'