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_1573095
_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 Lu N5 O'
_chemical_formula_sum            'C39 H52 Lu N5 O'
_chemical_formula_weight         781.82
_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                 91.1100(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   13.6267(10)
_cell_length_b                   20.1993(15)
_cell_length_c                   26.817(2)
_cell_measurement_reflns_used    8067
_cell_measurement_temperature    300
_cell_measurement_theta_max      22.11
_cell_measurement_theta_min      2.34
_cell_volume                     7380.0(9)
_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  0.0748
_diffrn_reflns_av_unetI/netI     0.0546
_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            35887
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         1.519
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.711
_exptl_absorpt_correction_T_max  0.814
_exptl_absorpt_correction_T_min  0.418
_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    1.407
_exptl_crystal_description       block
_exptl_crystal_F_000             3200
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.687
_refine_diff_density_min         -0.623
_refine_diff_density_rms         0.091
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     616
_refine_ls_number_reflns         6506
_refine_ls_number_restraints     749
_refine_ls_restrained_S_all      1.004
_refine_ls_R_factor_all          0.0702
_refine_ls_R_factor_gt           0.0415
_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^)+(0.0411P)^2^+12.9290P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0824
_refine_ls_wR_factor_ref         0.0916
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4718
_reflns_number_total             6506
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04197f4.cif
_cod_data_source_block           4a
_cod_depositor_comments
'Adding full bibliography for 1573095--1573138.cif.'
_cod_original_cell_volume        7380.1(9)
_cod_database_code               1573095
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.627
_shelx_estimated_absorpt_t_min   0.600
_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-C39 \\sim O1-C39A \\sim O1-C36A \\sim O1-C36
 with sigma of 0.02
 N2-C11 \\sim N2A-C11 \\sim N2-C12 \\sim N2A-C12A \\sim N2A-C16A \\sim N2-C16
 with sigma of 0.02
3. Restrained planarity
 C23A, C21A, C20A, C18, C22A, C19A, C27A, C24A, N3
 with sigma of 0.1
 C22, C20, C19, C23, C21, C18, C24, C27, N3
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
O1 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C36A \\sim C37A \\sim C38A
\\sim C39A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C11 \\sim N2 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim N2A \\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 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
{C11, N2A, C12A, C13A, C14A, C15A, C16A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C11, N2, C12, C13, C14, C15, C16}
{N3, C18, 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, C36A, C37A, C38A, C39A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O1, C36, C37, C38, C39}
6. Others
 Sof(C36A)=Sof(H36C)=Sof(H36D)=Sof(C37A)=Sof(H37C)=Sof(H37D)=Sof(C38A)=
 Sof(H38C)=Sof(H38D)=Sof(C39A)=Sof(H39C)=Sof(H39D)=1-FVAR(1)
 Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(C38)=Sof(H38A)=
 Sof(H38B)=Sof(C39)=Sof(H39A)=Sof(H39B)=FVAR(1)
 Sof(H11C)=Sof(H11D)=Sof(N2A)=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(H11A)=Sof(H11B)=Sof(N2)=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(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(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:
 C36(H36A,H36B), C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B), C10(H10A,
 H10B), C11(H11A,H11B), C11(H11C,H11D), C12(H12A,H12B), C13(H13A,H13B),
 C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C12A(H12C,H12D), C13A(H13C,
 H13D), C14A(H14C,H14D), C15A(H15C,H15D), C16A(H16C,H16D), C36A(H36C,H36D),
 C37A(H37C,H37D), 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              92741
_shelx_hkl_checksum              48537
_olex2_submission_special_instructions 'No special instructions were received'