Synthesis of rare-earth metal complexes with a morpholine-functionalized β-diketiminato ligand and their catalytic activities towards C–O and C–N bond formation
Zhu, Xiancui; He, Jinqiang; Yang, Yuanqing; Zhou, Shuangliu; Wei, Yun; Wang, Shaowu; Dalton Transactions  (2022) –; doi:10.1039/D2DT02053J

data_7710929
_publ_section_title
;
 Synthesis of rare-earth metal complexes with a morpholine-functionalized
 \b-diketiminato ligand and their catalytic activities towards C--O and
 C--N bond formation
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT02053J
_journal_year                    2022
_chemical_formula_moiety
'C81 H120 Cl Gd3 N9 O3 Si6, C16 H32 Li O4, 0.55[C7H8], 3.65[C7H8]'
_chemical_formula_sum            'C97 H152 Cl Gd3 Li N9 O7 Si6'
_chemical_formula_weight         2238.95
_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
_audit_block_doi                 10.5517/ccdc.csd.cc28p426
_audit_creation_date             2021-06-24
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-08-26 deposited with the CCDC.	2022-07-28 downloaded from the CCDC.
;
_cell_angle_alpha                67.2240(10)
_cell_angle_beta                 83.7930(10)
_cell_angle_gamma                61.7530(10)
_cell_formula_units_Z            2
_cell_length_a                   19.8493(16)
_cell_length_b                   20.2615(17)
_cell_length_c                   21.6207(18)
_cell_measurement_reflns_used    9915
_cell_measurement_temperature    298.15
_cell_measurement_theta_max      21.682
_cell_measurement_theta_min      2.180
_cell_volume                     7032.3(10)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      298.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.984
_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  0.1177
_diffrn_reflns_av_unetI/netI     0.1730
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            83693
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.551
_diffrn_reflns_theta_min         1.026
_exptl_absorpt_coefficient_mu    1.509
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.3182
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1337 before and 0.0683 after correction. The Ratio of minimum to maximum transmission is 0.4268. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.057
_exptl_crystal_description       block
_exptl_crystal_F_000             2298
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.407
_refine_diff_density_min         -0.523
_refine_diff_density_rms         0.106
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.938
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1111
_refine_ls_number_reflns         31936
_refine_ls_number_restraints     473
_refine_ls_restrained_S_all      0.945
_refine_ls_R_factor_all          0.1749
_refine_ls_R_factor_gt           0.0701
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0787P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1509
_refine_ls_wR_factor_ref         0.1922
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13444
_reflns_number_total             31936
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02053j2.cif
_cod_data_source_block           1c
_cod_database_code               7710929
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.864
_shelx_estimated_absorpt_t_min   0.840
_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
 O6-C90 = O6-C93 = O4-C82 = O4-C85 = O7-C94 = O7-C97 = O5-C89 = O5-C86
 1.43 with sigma of 0.01
 C95-C94 = C95-C96 = C97-C96 = C89-C88 = C87-C88 = C87-C86 = C91-C90 = C91-C92
 = C92-C93 = C83-C82 = C84-C83 = C84-C85
 1.54 with sigma of 0.01
 C58-C60
 1.54 with sigma of 0.01
 C59-C58
 1.54 with sigma of 0.01
 C93-C91 = C92-C90 = C82-C84 = C83-C85 = C94-C96 = C97-C95 = C88-C86 = C89-C87
 2.52 with sigma of 0.01
 C60-C59
 2.52 with sigma of 0.01
 O5-Li1 \\sim O6-Li1 \\sim O7-Li1 \\sim O4-Li1
 with sigma of 0.02
 O6-O4 \\sim O6-O7 \\sim O6-O5 \\sim O4-O7 \\sim O4-O5 \\sim O7-O5
 with sigma of 0.02
3. Rigid bond restraints
 C40, C42
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
Li1 \\sim O4 \\sim C82 \\sim C85 \\sim C83 \\sim C84 \\sim O5 \\sim O6 \\sim O7
\\sim C86 \\sim C89 \\sim C90 \\sim C93 \\sim C94 \\sim C97 \\sim C87 \\sim C88
\\sim C91 \\sim C92 \\sim C95 \\sim C96: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
Uanis(C53) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C59)
\\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C21) \\sim Ueq,
Uanis(C14) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C40)
\\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C34) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 Li1, O4, C82, C85, C83, C84, O7, O5, O6, C94, C95, C97, C86, C89, C90, C93,
 C96, C87, C88, C91, C92
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C53, C58, C59, C60
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
6.a Ternary CH refined with riding coordinates:
 C16(H16), C19(H19), C37(H37), C40(H40), C58(H58), C61(H61)
6.b Secondary CH2 refined with riding coordinates:
 C82(H82A,H82B), C83(H83A,H83B), C84(H84A,H84B), C85(H85A,H85B), C86(H86A,
 H86B), C87(H87A,H87B), C88(H88A,H88B), C89(H89A,H89B), C90(H90A,H90B),
 C91(H91A,H91B), C92(H92A,H92B), C93(H93A,H93B), C94(H94A,H94B), C95(H95A,H95B),
  C96(H96A,H96B), C97(H97A,H97B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C6(H6), C7(H7), C12(H12), C13(H13), C14(H14),
 C23(H23), C25(H25), C26(H26), C27(H27), C28(H28), C35(H35), C34(H34), C33(H33),
  C44(H44), C46(H46), C47(H47), C48(H48), C49(H49), C54(H54), C55(H55), C56(H56)
6.d Fitted hexagon refined as free rotating group:
 C10(C11,C12,C13,C14,C15), C35(C34,C33,C32,C31,C36), C52(C53,C54,C55,C56,C57)
6.e Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C41(H41A,H41B,H41C), C42(H42A,
 H42B,H42C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C62(H62A,H62B,H62C),
 C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C66(H66A,H66B,
 H66C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C70(H70A,
 H70B,H70C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C73(H73A,H73B,H73C),
 C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C76(H76A,H76B,H76C), C77(H77A,H77B,
 H77C), C78(H78A,H78B,H78C), C79(H79A,H79B,H79C), C80(H80A,H80B,H80C), C81(H81A,
 H81B,H81C)
;
_shelx_res_checksum              49043
_shelx_hkl_checksum              58159
_shelx_fab_checksum              53200
_platon_squeeze_special_details
;
A solvent mask was calculated and 419 electrons were 
found in a volume of 2020\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
0.55[C7H8], 3.65[C7H8] per Unit Cell 
which account for 420 electrons 
per unit cell.
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'