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_7714550
_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         '2(C34 H50 Gd N3 O Si)'
_chemical_formula_sum            'C68 H100 Gd2 N6 O2 Si2'
_chemical_formula_weight         1404.21
_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   geom
_audit_creation_date             2023-08-02
_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                 129.8560(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   35.524(3)
_cell_length_b                   22.8423(16)
_cell_length_c                   23.6243(16)
_cell_measurement_reflns_used    9336
_cell_measurement_temperature    293.15
_cell_measurement_theta_max      23.639
_cell_measurement_theta_min      2.246
_cell_volume                     14715.9(19)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'SAINT v8.37A (Bruker, 2015)'
_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 (Sheldrick, 2015)'
_diffrn_ambient_temperature      293.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_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  0.0630
_diffrn_reflns_av_unetI/netI     0.0580
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       46
_diffrn_reflns_limit_h_min       -46
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            86252
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.528
_diffrn_reflns_theta_min         1.163
_exptl_absorpt_coefficient_mu    1.862
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.3877
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1114 before and 0.0603 after correction.
The Ratio of minimum to maximum transmission is 0.5200.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light black'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.268
_exptl_crystal_description       block
_exptl_crystal_F_000             5776
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.700
_refine_diff_density_min         -0.826
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     781
_refine_ls_number_reflns         16880
_refine_ls_number_restraints     142
_refine_ls_restrained_S_all      7.933
_refine_ls_R_factor_all          0.0811
_refine_ls_R_factor_gt           0.0394
_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^)+(0.0326P)^2^+4.7279P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0774
_refine_ls_wR_factor_ref         0.0891
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10468
_reflns_number_total             16880
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt03374k2.cif
_cod_data_source_block           2b
_cod_depositor_comments
'Adding full bibliography for 7714545--7714552.cif.'
_cod_original_cell_volume        14716.0(18)
_cod_database_code               7714550
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.707
_shelx_estimated_absorpt_t_min   0.685
_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
 Si2A-C33A_$1 \\sim Si2-C33A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Si2 \\sim Si2A \\sim C33A \\sim C31A \\sim C66A \\sim C32A \\sim C67A \\sim
C34A \\sim C68A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C3A \\sim C4A \\sim C5A \\sim C6A \\sim C7A \\sim C8A: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C11: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002 within
2A
Uanis(C11) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Si2) \\sim Ueq, Uanis(C31A) \\sim Ueq, Uanis(C32A) \\sim Ueq, Uanis(C34A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C66A) \\sim Ueq, Uanis(C67A) \\sim Ueq, Uanis(C68A) \\sim Ueq,
Uanis(Si2A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 Si2, C31A, C32A, C34A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 Si2A, C66A, C67A, C68A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Others
 Sof(Si2A)=Sof(H31C)=Sof(H31D)=Sof(C66A)=Sof(H66A)=Sof(H66B)=Sof(H66C)=
 Sof(C67A)=Sof(H67A)=Sof(H67B)=Sof(H67C)=Sof(C68A)=Sof(H68A)=Sof(H68B)=
 Sof(H68C)=1-FVAR(1)
 Sof(Si2)=Sof(H33C)=Sof(H33D)=Sof(C31A)=Sof(H31F)=Sof(H31G)=Sof(H31H)=
 Sof(C32A)=Sof(H32D)=Sof(H32E)=Sof(H32F)=Sof(C34A)=Sof(H34D)=Sof(H34E)=
 Sof(H34F)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C25(H25), C28(H28), C25A(H25A), C28A(H28A)
6.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C12(H12A,H12B), C13(H13A,H13B), C33(H33A,H33B),
 C9A(H9AA,H9AB), C10A(H10C,H10D), C12A(H12C,H12D), C13A(H13C,H13D), C33A(H33C,
 H33D), C33A(H31C,H31D)
6.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C15(H15), C21(H21), C22(H22), C23(H23),
 C4A(H4A), C5A(H5A), C6A(H6A), C7A(H7A), C15A(H15A), C23A(H23A), C22A(H22A),
 C21A(H21A)
6.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C26(H26A,H26B,
 H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C34(H34A,
 H34B,H34C), C32(H32A,H32B,H32C), C31(H31A,H31B,H31E), C11A(H11D,H11E,H11F),
 C17A(H17D,H17E,H17F), C18A(H18D,H18E,H18F), C27A(H27D,H27E,H27F), C26A(H26D,
 H26E,H26F), C30A(H30D,H30E,H30F), C29A(H29D,H29E,H29F), C31A(H31F,H31G,H31H),
 C66A(H66A,H66B,H66C), C32A(H32D,H32E,H32F), C67A(H67A,H67B,H67C), C34A(H34D,
 H34E,H34F), C68A(H68A,H68B,H68C)
;
_shelx_res_checksum              39257
_shelx_fab_checksum              30228
_olex2_submission_special_instructions 'No special instructions were received'