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_7061551
_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 Eu N6, 2.5(C7 H8)'
_chemical_formula_sum            'C92.5 H125 Eu N6'
_chemical_formula_weight         1472.94
_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   mixed
_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                90
_cell_angle_beta                 96.3750(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.1230(3)
_cell_length_b                   37.9400(7)
_cell_length_c                   16.4938(3)
_cell_measurement_reflns_used    9884
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      63.73
_cell_measurement_theta_min      5.39
_cell_volume                     8161.3(3)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX3'
_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                 PIXEL
_diffrn_detector_area_resol_mean 7.41
_diffrn_detector_type            'Bruker PHOTON III area detector'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'Incoatec HELIOS multilayer mirrors'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0655
_diffrn_reflns_av_unetI/netI     0.0523
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       44
_diffrn_reflns_limit_k_min       -44
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            64727
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        63.950
_diffrn_reflns_theta_max         63.950
_diffrn_reflns_theta_min         2.329
_diffrn_source                   'Incoatec IuS3.0 microfocus X-ray tube'
_exptl_absorpt_coefficient_mu    5.854
_exptl_absorpt_correction_T_max  0.7524
_exptl_absorpt_correction_T_min  0.4383
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1297 before and 0.0692 after correction. The Ratio of minimum to maximum transmission is 0.5825. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'bluish green'
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.199
_exptl_crystal_description       prism
_exptl_crystal_F_000             3140
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.007
_refine_diff_density_min         -0.775
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.135
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     821
_refine_ls_number_reflns         13430
_refine_ls_number_restraints     85
_refine_ls_restrained_S_all      1.132
_refine_ls_R_factor_all          0.0672
_refine_ls_R_factor_gt           0.0586
_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^)+(0.0223P)^2^+32.6444P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1367
_refine_ls_wR_factor_ref         0.1409
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11838
_reflns_number_total             13430
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj01589g2.cif
_cod_data_source_block           kds299
_cod_depositor_comments
'Adding full bibliography for 7061550--7061554.cif.'
_cod_original_formula_sum        'C92.50 H125 Eu N6'
_cod_database_code               7061551
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.592
_shelx_estimated_absorpt_t_min   0.234
_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. Restrained distances
 C31S-C36S \\sim C36S-C35S \\sim C35S-C34S \\sim C34S-C33S \\sim C33S-C32S
\\sim C32S-C31S
 with sigma of 0.02
 C31S-C33S \\sim C31S-C35S \\sim C32S-C34S \\sim C36S-C32S \\sim C35S-C33S
\\sim C36S-C34S
 with sigma of 0.04
 C37S-C32S \\sim C37S-C36S
 with sigma of 0.04
 C41S-C46S \\sim C46S-C45S \\sim C45S-C44S \\sim C44S-C43S \\sim C43S-C42S
\\sim C42S-C41S
 with sigma of 0.02
 C41S-C43S \\sim C41S-C45S \\sim C42S-C44S \\sim C46S-C42S \\sim C45S-C43S
\\sim C46S-C44S
 with sigma of 0.04
 C47S-C42S \\sim C47S-C46S
 with sigma of 0.04
 C21S-C23S \\sim C23S-C24S_$1
 with sigma of 0.02
3. Restrained planarity
 C31S, C32S, C33S, C34S, C35S, C36S, C37S
 with sigma of 0.1
 C41S, C42S, C43S, C44S, C45S, C46S, C47S
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C31S \\sim C32S \\sim C33S \\sim C34S \\sim C35S \\sim C36S \\sim C37S: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C41S \\sim C42S \\sim C43S \\sim C44S \\sim C45S \\sim C46S \\sim C47S: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uiso(C34S) = Uiso(C35S) = Uiso(C33S) = Uiso(C36S) = Uiso(C32S) = Uiso(C31S) =
Uiso(C37S)
Uiso(C43S) = Uiso(C47S) = Uiso(C41S) = Uiso(C46S) = Uiso(C42S) = Uiso(C45S) =
Uiso(C44S) = Uiso(C35S) = Uiso(C37S) = Uiso(C31S) = Uiso(C36S) = Uiso(C32S) =
Uiso(C33S) = Uiso(C34S)
5. Rigid body (RIGU) restrains
 C31S, C32S, C33S, C34S, C35S, C36S, C37S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C41S, C42S, C43S, C44S, C45S, C46S, C47S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: H22S(0.5) C23S(0.5) H23M(0.5) H23N(0.5) H23O(0.5) C37S(0.5)
 H37A(0.5) H37B(0.5) H37C(0.5) C31S(0.5) C32S(0.5) H32S(0.5) C33S(0.5)
 H33S(0.5) C34S(0.5) H34S(0.5) C35S(0.5) H35S(0.5) C36S(0.5) H36S(0.5)
 C47S(0.5) H47A(0.5) H47B(0.5) H47C(0.5) C41S(0.5) C42S(0.5) H42S(0.5)
 C43S(0.5) H43S(0.5) C44S(0.5) H44S(0.5) C45S(0.5) H45S(0.5) C46S(0.5) H46S(0.5)
7.a Riding coordinates:
 C22S(H22S)
7.b Free rotating group:
 C37S(C31S,C32S,C33S,C34S,C35S,C36S), C47S(C41S,C42S,C43S,C44S,C45S,C46S)
7.c Ternary CH refined with riding coordinates:
 C117(H117), C120(H120), C129(H129), C132(H132), C217(H217), C220(H220),
 C229(H229), C232(H232), C317(H317), C320(H320), C329(H329), C332(H332)
7.d Aromatic/amide H refined with riding coordinates:
 C11(H11), C21(H21), C31(H31), C113(H113), C114(H114), C115(H115), C125(H125),
 C126(H126), C127(H127), C213(H213), C214(H214), C215(H215), C225(H225),
 C226(H226), C227(H227), C313(H313), C314(H314), C315(H315), C325(H325),
 C326(H326), C327(H327), C12S(H12S), C13S(H13S), C14S(H14S), C15S(H15S),
 C16S(H16S), C21S(H21S), C24S(H24S), C32S(H32S), C33S(H33S), C34S(H34S),
 C35S(H35S), C36S(H36S), C42S(H42S), C43S(H43S), C44S(H44S), C45S(H45S),
 C46S(H46S)
7.e Idealised Me refined with riding coordinates:
 C23S(H23M,H23N,H23O), C37S(H37A,H37B,H37C), C47S(H47A,H47B,H47C)
7.f Idealised Me refined as rotating group:
 C118(H11A,H11B,H11C), C119(H11D,H11E,H11F), C121(H12A,H12B,H12C), C122(H12D,
 H12E,H12F), C130(H13A,H13B,H13C), C131(H13D,H13E,H13F), C133(H13G,H13H,H13I),
 C134(H13J,H13K,H13L), 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), C318(H31A,H31B,H31C), C319(H31D,
 H31E,H31F), C321(H32A,H32B,H32C), C322(H32D,H32E,H32F), C330(H33A,H33B,H33C),
 C331(H33D,H33E,H33F), C333(H33G,H33H,H33I), C334(H33J,H33K,H33L), C17S(H17A,
 H17B,H17C)
;
_shelx_res_checksum              65759
_olex2_submission_special_instructions 'No special instructions were received'