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_7061554
_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         'C75 H105 N6 Nd'
_chemical_formula_sum            'C75 H105 N6 Nd'
_chemical_formula_weight         1234.88
_chemical_name_systematic
'tris-(bis-(2,6-diisopropylphenyl)formanidinate) neodymium (III)'
_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             2021-04-07
_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                 100.0750(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.0830(3)
_cell_length_b                   20.4856(5)
_cell_length_c                   26.3710(6)
_cell_measurement_reflns_used    9901
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      28.49
_cell_measurement_theta_min      2.25
_cell_volume                     6958.8(3)
_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(2)
_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 0.998
_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  0.0627
_diffrn_reflns_av_unetI/netI     0.0465
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            139058
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.534
_diffrn_reflns_theta_min         1.637
_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    0.790
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6904
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1048 before and 0.0535 after correction.
The Ratio of minimum to maximum transmission is 0.9253.
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    1.179
_exptl_crystal_description       needle
_exptl_crystal_F_000             2628
_exptl_crystal_preparation       'Schlenk technique'
_exptl_crystal_recrystallization_method 'by crystallization from hot toluene'
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.083
_refine_diff_density_min         -1.087
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.301
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     739
_refine_ls_number_reflns         21263
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.301
_refine_ls_R_factor_all          0.1073
_refine_ls_R_factor_gt           0.0763
_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^)+27.1598P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1403
_refine_ls_wR_factor_ref         0.1490
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15080
_reflns_number_total             21263
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj01589g2.cif
_cod_data_source_block           mo_kds458_0m
_cod_depositor_comments
'Adding full bibliography for 7061550--7061554.cif.'
_cod_database_code               7061554
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.939
_shelx_estimated_absorpt_t_min   0.904
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C8(H8), C11(H11), C20(H20), C23(H23), C36(H36), C33(H33), C45(H45), C48(H48),
 C70(H70), C73(H73), C58(H58), C61(H61)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C5(H5), C6(H6), C18(H18), C17(H17), C16(H16), C26(H26),
 C29(H29), C30(H30), C31(H31), C41(H41), C42(H42), C43(H43), C51(H51), C66(H66),
  C67(H67), C68(H68), C56(H56), C55(H55), C54(H54)
2.c Fitted hexagon refined as free rotating group:
 C15(C14,C19,C18,C17,C16), C57(C56,C55,C54,C53,C52)
2.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C13(H13A,H13B,
 H13C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C24(H24A,H24B,H24C), C25(H25A,
 H25B,H25C), C38(H38A,H38B,H38C), C37(H37A,H37B,H37C), C34(H34A,H34B,H34C),
 C35(H35A,H35B,H35C), C47(H47A,H47B,H47C), C46(H46A,H46B,H46C), C49(H49A,H49B,
 H49C), C50(H50A,H50B,H50C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C75(H75A,
 H75B,H75C), C74(H74A,H74B,H74C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C),
 C63(H63A,H63B,H63C), C62(H62A,H62B,H62C)
;
_shelx_res_checksum              15367
_olex2_submission_special_instructions 'No special instructions were received'