Rare-earth metal complexes bearing electrophilic and nucleophilic carbon centres and their unique reactivity patterns towards pyridine derivatives.
Wu, Weikang; Rajeshkumar, Thayalan; Zhu, Shan; Chai, Fuxiang; Hong, Dongjing; Huang, Zeming; Yuan, Qingbing; Maron, Laurent; Wang, Shaowu; Chemical science 15 (2024) 20315–20327; doi:10.1039/d4sc04197f

data_1573096
_publ_section_title
;
 Rare-earth metal complexes bearing electrophilic and nucleophilic carbon
 centres and their unique reactivity patterns towards pyridine
 derivatives.
;
_journal_issue                   48
_journal_name_full               'Chemical science'
_journal_page_first              20315
_journal_page_last               20327
_journal_paper_doi               10.1039/d4sc04197f
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C39 H52 Er N5 O'
_chemical_formula_sum            'C39 H52 Er N5 O'
_chemical_formula_weight         774.11
_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
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-04-16
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-05-29 deposited with the CCDC.	2024-11-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.3400(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   13.6472(7)
_cell_length_b                   20.2383(10)
_cell_length_c                   26.8628(14)
_cell_measurement_reflns_used    7036
_cell_measurement_temperature    300
_cell_measurement_theta_max      22.06
_cell_measurement_theta_min      2.33
_cell_volume                     7417.4(7)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      300
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  0.0887
_diffrn_reflns_av_unetI/netI     0.0665
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            36004
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.517
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.299
_exptl_absorpt_correction_T_max  0.814
_exptl_absorpt_correction_T_min  0.417
_exptl_absorpt_correction_type   multi-scan
_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    1.386
_exptl_crystal_description       block
_exptl_crystal_F_000             3176
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.19
_refine_diff_density_max         1.417
_refine_diff_density_min         -0.553
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     625
_refine_ls_number_reflns         6538
_refine_ls_number_restraints     781
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0878
_refine_ls_R_factor_gt           0.0485
_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^)+(0.0395P)^2^+18.2561P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0888
_refine_ls_wR_factor_ref         0.1015
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4473
_reflns_number_total             6538
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04197f4.cif
_cod_data_source_block           4c
_cod_depositor_comments
'Adding full bibliography for 1573095--1573138.cif.'
_cod_database_code               1573096
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.669
_shelx_estimated_absorpt_t_min   0.644
_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
 O1-C36 \\sim O1-C36A \\sim O1-C39A \\sim O1-C39
 with sigma of 0.02
 C11-C10 \\sim C11A-C10
 with sigma of 0.02
 N2-C11 \\sim N2A-C11A \\sim N2-C16 \\sim N2A-C16A \\sim N2A-C12A \\sim N2-C12
 with sigma of 0.02
 N3-C18 \\sim N3-C18A
 with sigma of 0.02
3. Restrained planarity
 C21, C18, C20, C22, C19, C24, C23, C27, N3
 with sigma of 0.1
 C20A, C18A, C23A, C21A, C19A, C22A, C24A, N3, C27A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
O1 \\sim C37 \\sim C36 \\sim C38 \\sim C39 \\sim C36A \\sim C38A \\sim C39A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C10 \\sim N2 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim
N2A \\sim C11A \\sim C12A \\sim C13A \\sim C14A \\sim C15A \\sim C16A: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim
C26 \\sim C27 \\sim C28 \\sim C29 \\sim C18A \\sim C19A \\sim C20A \\sim C21A
\\sim C22A \\sim C23A \\sim C24A \\sim C25A \\sim C26A \\sim C27A \\sim C28A
\\sim C29A \\sim N3: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
5. Same fragment restrains
{C10, N2A, C11A, C12A, C13A, C14A, C15A, C16A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C10, N2, C11, C12, C13, C14, C15, C16}
{N3, C18A, C19A, C20A, C21A, C22A, C23A, C24A, C25A, C26A, C27A, C28A, C29A}
sigma for 1-2: 0.02, 1-3: 0.04
as in
{N3, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29}
{O1, C37, C36A, C38A, C39A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O1, C37, C36, C38, C39}
6. Others
 Sof(H37C)=Sof(H37D)=Sof(C36A)=Sof(H36C)=Sof(H36D)=Sof(C38A)=Sof(H38C)=
 Sof(H38D)=Sof(C39A)=Sof(H39C)=Sof(H39D)=1-FVAR(1)
 Sof(H37A)=Sof(H37B)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(C38)=Sof(H38A)=Sof(H38B)=
 Sof(C39)=Sof(H39A)=Sof(H39B)=FVAR(1)
 Sof(H10C)=Sof(H10D)=Sof(N2A)=Sof(C11A)=Sof(H11C)=Sof(H11D)=Sof(C12A)=
 Sof(H12C)=Sof(H12D)=Sof(C13A)=Sof(H13C)=Sof(H13D)=Sof(C14A)=Sof(H14C)=
 Sof(H14D)=Sof(C15A)=Sof(H15C)=Sof(H15D)=Sof(C16A)=Sof(H16C)=Sof(H16D)=1-FVAR(2)
 Sof(H10A)=Sof(H10B)=Sof(N2)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=
 Sof(H12B)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(C15)=
 Sof(H15A)=Sof(H15B)=Sof(C16)=Sof(H16A)=Sof(H16B)=FVAR(2)
 Sof(C18A)=Sof(C19A)=Sof(C20A)=Sof(H20A)=Sof(C21A)=Sof(H21A)=Sof(C22A)=
 Sof(H22A)=Sof(C23A)=Sof(C24A)=Sof(H24A)=Sof(C25A)=Sof(H25D)=Sof(H25E)=
 Sof(H25F)=Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(C27A)=Sof(H27A)=
 Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29A)=Sof(H29D)=Sof(H29E)=
 Sof(H29F)=1-FVAR(3)
 Sof(C18)=Sof(C19)=Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21)=Sof(C22)=Sof(H22)=
 Sof(C23)=Sof(C24)=Sof(H24)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C26)=
 Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28A)=Sof(H28B)=
 Sof(H28C)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=FVAR(3)
7.a Ternary CH refined with riding coordinates:
 C24(H24), C27(H27), C1(H1), C24A(H24A), C27A(H27A)
7.b Secondary CH2 refined with riding coordinates:
 C37(H37A,H37B), C37(H37C,H37D), C36(H36A,H36B), C38(H38A,H38B), C39(H39A,
 H39B), C10(H10A,H10B), C10(H10C,H10D), C11(H11A,H11B), C12(H12A,H12B),
 C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C11A(H11C,
 H11D), C12A(H12C,H12D), C13A(H13C,H13D), C14A(H14C,H14D), C15A(H15C,H15D),
 C16A(H16C,H16D), C36A(H36C,H36D), C38A(H38C,H38D), C39A(H39C,H39D)
7.c Aromatic/amide H refined with riding coordinates:
 C20(H20), C21(H21), C22(H22), C5(H5), C6(H6), C7(H7), C8(H8), C17(H17),
 C30(H30), C31(H31), C32(H32), C33(H33), C20A(H20A), C21A(H21A), C22A(H22A)
7.d Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C35(H35A,H35B,H35C), C25A(H25D,H25E,H25F), C26A(H26D,H26E,H26F),
 C28A(H28D,H28E,H28F), C29A(H29D,H29E,H29F)
;
_shelx_res_checksum              50170
_shelx_hkl_checksum              59712
_olex2_submission_special_instructions 'No special instructions were received'