Synthesis and catalytic activity of tetradentate β-diketiminato rare-earth metal monoalkyl complexes in tandem Oppenauer oxidation and cross-aldol condensation.
Zou, Haiyan; Wang, Ziqian; Guo, Dianjun; Zhang, Lijun; Wang, Shaowu; Zhu, Xiancui; Dalton transactions (Cambridge, England : 2003) 53 (2023) 267–275; doi:10.1039/d3dt03374k

data_7714552
_publ_section_title
;
 Synthesis and catalytic activity of tetradentate &#x3b2;-diketiminato
 rare-earth metal monoalkyl complexes in tandem Oppenauer oxidation and
 cross-aldol condensation.
;
_journal_issue                   1
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              267
_journal_page_last               275
_journal_paper_doi               10.1039/d3dt03374k
_journal_volume                  53
_journal_year                    2023
_chemical_formula_moiety         '1(C34 H50 Lu N3 O Si)'
_chemical_formula_sum            'C34 H50 Lu N3 O Si'
_chemical_formula_weight         719.83
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2023-09-21
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-09-22 deposited with the CCDC.	2023-11-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 129.875(3)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   35.237(9)
_cell_length_b                   22.966(6)
_cell_length_c                   23.494(6)
_cell_measurement_reflns_used    9918
_cell_measurement_temperature    293.15
_cell_measurement_theta_max      21.97
_cell_measurement_theta_min      2.26
_cell_volume                     14591(7)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker SMART APEX II diffractometer'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293.15
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1559
_diffrn_reflns_av_unetI/netI     0.1406
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       45
_diffrn_reflns_limit_h_min       -45
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            81424
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.613
_diffrn_reflns_theta_min         1.163
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.766
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.2923
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1606 before and 0.1067 after correction. The Ratio of minimum to maximum transmission is 0.3920. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.311
_exptl_crystal_description       block
_exptl_crystal_F_000             5888
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         3.391
_refine_diff_density_min         -1.735
_refine_diff_density_rms         0.156
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.991
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     766
_refine_ls_number_reflns         16616
_refine_ls_number_restraints     286
_refine_ls_restrained_S_all      0.986
_refine_ls_R_factor_all          0.1597
_refine_ls_R_factor_gt           0.0761
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1188P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1948
_refine_ls_wR_factor_ref         0.2396
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7919
_reflns_number_total             16616
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt03374k2.cif
_cod_data_source_block           2d
_cod_depositor_comments
'Adding full bibliography for 7714545--7714552.cif.'
_cod_original_cell_volume        14592(6)
_cod_database_code               7714552
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.733
_shelx_estimated_absorpt_t_min   0.682
_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
 C60A-C28 = C29-C28 = C61A-C28 = C30-C28
 1.54 with sigma of 0.01
 C61A-C60A = C29-C30
 2.515 with sigma of 0.02
 Si1A-C32A \\sim Si1A-C36 \\sim Si1A-C34A \\sim Si1A-C38 \\sim Si1A-C31A \\sim
Si1A-C37
 with sigma of 0.02
 C34A-C32A \\sim C34A-C31A \\sim C32A-C31A
 with sigma of 0.02
 C36-C37 \\sim C36-C38 \\sim C37-C38
 with sigma of 0.02
 O1A-C11A \\sim O1A-C35
 with sigma of 0.02
3. Restrained planarity
 C5, C4, C3, C8, C7, C6, C2, N3
 with sigma of 0.1
4. Rigid bond restraints
 C28A, C29A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Uiso/Uaniso restraints and constraints
Si1A \\sim C34A \\sim C32A \\sim C31A \\sim C36 \\sim C38 \\sim C37: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C6 \\sim C7 \\sim C8 \\sim C3 \\sim C4 \\sim C5: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
C11A \\sim C35 \\sim O1A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C28 \\sim C29 \\sim C30 \\sim C60A \\sim C61A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
6. Rigid body (RIGU) restrains
 Si1A, C34A, C32A, C31A, C36, C38, C37
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C6, C7, C8, C3, C4, C5, N3, C2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 O1A, C35, C11A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C28, C29, C30, C60A, C61A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
7. Others
 Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=1-FVAR(1)
 Sof(C34A)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C32A)=Sof(H32A)=Sof(H32B)=
 Sof(H32C)=Sof(C31A)=Sof(H31A)=Sof(H31B)=Sof(H31C)=FVAR(1)
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=1-FVAR(2)
 Sof(C11A)=Sof(H11A)=Sof(H11B)=Sof(H11C)=FVAR(2)
 Sof(H28B)=Sof(C60A)=Sof(H60A)=Sof(H60B)=Sof(H60C)=Sof(C61A)=Sof(H61A)=
 Sof(H61B)=Sof(H61C)=1-FVAR(3)
 Sof(H28)=Sof(C29)=Sof(H29D)=Sof(H29E)=Sof(H29F)=Sof(C30)=Sof(H30D)=Sof(H30E)=
 Sof(H30F)=FVAR(3)
8.a Riding coordinates:
 C31A(H31A,H31B,H31C), C38(H38A,H38B,H38C)
8.b Ternary CH refined with riding coordinates:
 C25A(H25A), C28A(H28A), C28(H28), C28(H28B), C25(H25)
8.c Secondary CH2 refined with riding coordinates:
 C9A(H9AA,H9AB), C10A(H10A,H10B), C12A(H12A,H12B), C13A(H13A,H13B), C33A(H33A,
 H33B), C9(H9A,H9B), C10(H10C,H10D), C12(H12C,H12D), C13(H13C,H13D), C33(H33C,
 H33D)
8.d Aromatic/amide H refined with riding coordinates:
 C4A(H4A), C5A(H5A), C6A(H6A), C7A(H7A), C15A(H15A), C23A(H23A), C22A(H22A),
 C21A(H21A), C15(H15), C21(H21), C22(H22), C23(H23), C6(H6), C5(H5), C4(H4),
 C7(H7)
8.e Fitted hexagon refined as free rotating group:
 C19A(C24A,C23A,C22A,C21A,C20A), C19(C20,C21,C22,C23,C24), C6(C5,C4,C3,C8,C7)
8.f Idealised Me refined as rotating group:
 C11A(H11A,H11B,H11C), C18A(H18A,H18B,H18C), C17A(H17A,H17B,H17C), C26A(H26A,
 H26B,H26C), C27A(H27A,H27B,H27C), C29A(H29A,H29B,H29C), C30A(H30A,H30B,H30C),
 C34A(H34A,H34B,H34C), C32A(H32A,H32B,H32C), C11(H11D,H11E,H11F), C17(H17D,H17E,
 H17F), C18(H18D,H18E,H18F), C29(H29D,H29E,H29F), C30(H30D,H30E,H30F), C26(H26D,
 H26E,H26F), C27(H27D,H27E,H27F), C31(H31D,H31E,H31F), C32(H32D,H32E,H32F),
 C34(H34D,H34E,H34F), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C35(H35A,H35B,
 H35C), C60A(H60A,H60B,H60C), C61A(H61A,H61B,H61C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              20168
_shelx_fab_checksum              96992
_olex2_submission_special_instructions 'No special instructions were received'