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_7061552
_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 Eu N4 O2'
_chemical_formula_sum            'C58 H86 Eu N4 O2'
_chemical_formula_weight         1023.26
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-08-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-01-11 deposited with the CCDC.	2022-05-24 downloaded from the CCDC.
;
_cell_angle_alpha                84.194(2)
_cell_angle_beta                 86.763(2)
_cell_angle_gamma                64.066(2)
_cell_formula_units_Z            2
_cell_length_a                   12.0671(7)
_cell_length_b                   12.7845(8)
_cell_length_c                   19.7004(12)
_cell_measurement_reflns_used    5561
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      23.45
_cell_measurement_theta_min      2.29
_cell_volume                     2718.9(3)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'Bruker APEXII CCD area detector'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0429
_diffrn_reflns_av_unetI/netI     0.0762
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            22668
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.828
_diffrn_reflns_theta_min         1.778
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    1.196
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.6448
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0600 before and 0.0457 after correction. The Ratio of minimum to maximum transmission is 0.8652. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.250
_exptl_crystal_description       prism
_exptl_crystal_F_000             1082
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.535
_refine_diff_density_min         -0.488
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     621
_refine_ls_number_reflns         10342
_refine_ls_number_restraints     33
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0578
_refine_ls_R_factor_gt           0.0402
_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^)+(0.0262P)^2^+0.0280P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0687
_refine_ls_wR_factor_ref         0.0737
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8465
_reflns_number_total             10342
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj01589g2.cif
_cod_data_source_block           kds103h
_cod_depositor_comments
'Adding full bibliography for 7061550--7061554.cif.'
_cod_database_code               7061552
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.890
_shelx_estimated_absorpt_t_min   0.746
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O31-C31A \\sim O31-C31
 with sigma of 0.02
 C32A-C31A \\sim C32-C31
 with sigma of 0.02
 C33-C32 \\sim C33-C32A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C31A) \\sim Ueq, Uanis(C32A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 O31, C31A, C32A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O31, C31, C32
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H33C)=Sof(H33D)=Sof(C32A)=Sof(H32C)=Sof(H32D)=Sof(C31A)=Sof(H31C)=
 Sof(H31D)=1-FVAR(1)
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H33A)=Sof(H33B)=
 FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C117(H117), C120(H120), C128(H128), C131(H131), C217(H217), C220(H220),
 C229(H229), C232(H232)
6.b Secondary CH2 refined with riding coordinates:
 C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B), C33(H33C,H33D), C34(H34A,
 H34B), C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B), C44(H44A,H44B),
 C32A(H32C,H32D), C31A(H31C,H31D)
6.c Aromatic/amide H refined with riding coordinates:
 C01J(H01J), C11(H11), C21(H21), C113(H113), C114(H114), C115(H115),
 C125(H125), C126(H126), C213(H213), C214(H214), C215(H215), C225(H225),
 C226(H226), C227(H227)
6.d Idealised Me refined as rotating group:
 C118(H11A,H11B,H11C), C119(H11D,H11E,H11F), C121(H12A,H12B,H12C), C122(H12D,
 H12E,H12F), C129(H12G,H12H,H12I), C130(H13A,H13B,H13C), C132(H13D,H13E,H13F),
 C133(H13G,H13H,H13I), C218(H21A,H21B,H21C), C219(H21D,H21E,H21F), C221(H22A,
 H22B,H22C), C222(H22D,H22E,H22F), C230(H23A,H23B,H23C), C231(H23D,H23E,H23F),
 C233(H23G,H23H,H23I), C234(H23J,H23K,H23L)
;
_shelx_res_checksum              68223
_olex2_submission_special_instructions 'No special instructions were received'