Synthesis of Homoleptic, Divalent Lanthanide (Sm, Eu) Complexes via Oxidative Transmetallation
Gompa, Thaige P.; Jiang, Ningxin; Bacsa, John; La Pierre, Henry Storms; Dalton Transactions  (2019) –; doi:10.1039/C9DT04230J

data_7701803
_publ_section_title
;
 Synthesis of Homoleptic, Divalent Lanthanide (Sm, Eu) Complexes via
 Oxidative Transmetallation
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/C9DT04230J
_journal_year                    2019
_chemical_formula_moiety         '0.67(C48 H108 Eu N2 O12 Si4)'
_chemical_formula_sum            'C32 H72 Eu0.67 N1.33 O8 Si2.67'
_chemical_formula_weight         779.79
_chemical_name_systematic        Eu
_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             2018-12-03
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-09-05 deposited with the CCDC.	2019-11-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 111.428(5)
_cell_angle_gamma                90
_cell_formula_units_Z            6
_cell_length_a                   21.372(3)
_cell_length_b                   15.061(2)
_cell_length_c                   21.461(3)
_cell_measurement_reflns_used    9408
_cell_measurement_temperature    102.5
_cell_measurement_theta_max      29.555
_cell_measurement_theta_min      2.347
_cell_volume                     6430.5(15)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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      102.5
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0794
_diffrn_reflns_av_unetI/netI     0.0383
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            169239
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.130
_diffrn_reflns_theta_min         2.302
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    1.100
_exptl_absorpt_correction_T_max  0.9310
_exptl_absorpt_correction_T_min  0.6173
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1144 before and 0.0832 after correction. The Ratio of minimum to maximum transmission is 0.6631. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.208
_exptl_crystal_description       prism
_exptl_crystal_F_000             2500
_exptl_crystal_preparation       N.A
_exptl_crystal_recrystallization_method N.A.
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.258
_exptl_crystal_size_min          0.154
_refine_diff_density_max         0.892
_refine_diff_density_min         -0.742
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     684
_refine_ls_number_reflns         17268
_refine_ls_number_restraints     29
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0431
_refine_ls_R_factor_gt           0.0321
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0215P)^2^+6.3303P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0673
_refine_ls_wR_factor_ref         0.0728
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14571
_reflns_number_total             17268
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt04230j2.cif
_cod_data_source_block           mo_a363_0ma
_cod_original_cell_volume        6430.3(16)
_cod_database_code               7701803
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.849
_shelx_estimated_absorpt_t_min   0.763
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Si4-O10B \\sim Si4-O10A
 with sigma of 0.002
 Eu1-O10B \\sim Eu1-O10A
 with sigma of 0.002
 C39A-C37A \\sim C38A-C37A \\sim C40A-C37A
 with sigma of 0.005
 Eu1-O4B \\sim Eu1-O4A
 with sigma of 0.005
 Si2-O4B \\sim Si2-O4A
 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(C37A) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(O10B) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(O10A) = Uanis(O10B)
Uanis(C37B) = Uanis(C37A)
Uanis(C40A) = Uanis(C40B)
Uanis(C38B) = Uanis(C38A)
Uanis(O4B) = Uanis(O4A)
Uanis(C13B) = Uanis(C13A)
Uanis(C14B) = Uanis(C14A)
Uanis(C15A) = Uanis(C15B)
Uanis(C16A) = Uanis(C16B)
4. Same fragment restrains
{O10B, C37B, C38B, C39B, C40B} sigma for 1-2: 0.002, 1-3: 0.004
as
{O10A, C37A, C38A, C39A, C40A}
5. Others
 Sof(O10B)=Sof(C37B)=Sof(C38B)=Sof(H38D)=Sof(H38E)=Sof(H38F)=Sof(C39B)=
 Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C40B)=Sof(H40D)=Sof(H40E)=Sof(H40F)=1-FVAR(1)
 Sof(O10A)=Sof(C37A)=Sof(C38A)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C39A)=
 Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C40A)=Sof(H40A)=Sof(H40B)=Sof(H40C)=FVAR(1)
 Sof(O4B)=Sof(C13B)=Sof(C14B)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C15B)=
 Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C16B)=Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(2)
 Sof(O4A)=Sof(C13A)=Sof(C14A)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15A)=
 Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16A)=Sof(H16A)=Sof(H16B)=Sof(H16C)=FVAR(2)
6.a Idealised Me refined as rotating group:
 C38A(H38A,H38B,H38C), C39A(H39A,H39B,H39C), C40A(H40A,H40B,H40C), C42(H42A,
 H42B,H42C), C20(H20A,H20B,H20C), C2(H2A,H2B,H2C), C26(H26A,H26B,H26C),
 C22(H22A,H22B,H22C), C27(H27A,H27B,H27C), C32(H32A,H32B,H32C), C11(H11A,H11B,
 H11C), C44(H44A,H44B,H44C), C24(H24A,H24B,H24C), C3(H3A,H3B,H3C), C10(H10A,
 H10B,H10C), C8(H8A,H8B,H8C), C19(H19A,H19B,H19C), C6(H6A,H6B,H6C), C48(H48A,
 H48B,H48C), C30(H30A,H30B,H30C), C46(H46A,H46B,H46C), C43(H43A,H43B,H43C),
 C31(H31A,H31B,H31C), C47(H47A,H47B,H47C), C38B(H38D,H38E,H38F), C39B(H39D,H39E,
 H39F), C40B(H40D,H40E,H40F), C14A(H14A,H14B,H14C), C14B(H14D,H14E,H14F),
 C15A(H15A,H15B,H15C), C15B(H15D,H15E,H15F), C16A(H16A,H16B,H16C), C16B(H16D,
 H16E,H16F), C18(H18A,H18B,H18C), C4(H4A,H4B,H4C), C34(H34A,H34B,H34C),
 C23(H23A,H23B,H23C), C28(H28A,H28B,H28C), C36(H36A,H36B,H36C), C12(H12A,H12B,
 H12C), C7(H7A,H7B,H7C), C35(H35A,H35B,H35C)
;
_olex2_exptl_crystal_mounting_method N.A.
_olex2_submission_original_sample_id Eu(BTTSA)2
_olex2_submission_special_instructions 'No special instructions were received'