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_1573121
_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         'C66 H80 N8 Y'
_chemical_formula_sum            'C66 H80 N8 Y'
_chemical_formula_weight         1074.29
_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
_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                82.481(4)
_cell_angle_beta                 72.614(4)
_cell_angle_gamma                68.205(4)
_cell_formula_units_Z            2
_cell_length_a                   13.275(4)
_cell_length_b                   13.391(4)
_cell_length_c                   19.241(6)
_cell_measurement_reflns_used    7876
_cell_measurement_temperature    300
_cell_measurement_theta_max      22.96
_cell_measurement_theta_min      2.22
_cell_volume                     3030.0(16)
_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 0.999
_diffrn_measured_fraction_theta_max 0.983
_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  0.0829
_diffrn_reflns_av_unetI/netI     0.1078
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            35200
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.488
_diffrn_reflns_theta_min         1.638
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.008
_exptl_absorpt_correction_T_max  0.718
_exptl_absorpt_correction_T_min  0.417
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            'dull light black'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.178
_exptl_crystal_description       block
_exptl_crystal_F_000             1142
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.19
_refine_diff_density_max         1.380
_refine_diff_density_min         -0.885
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.986
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     845
_refine_ls_number_reflns         13684
_refine_ls_number_restraints     550
_refine_ls_restrained_S_all      0.992
_refine_ls_R_factor_all          0.1186
_refine_ls_R_factor_gt           0.0682
_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^)+(0.1009P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1601
_refine_ls_wR_factor_ref         0.1871
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8560
_reflns_number_total             13684
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04197f4.cif
_cod_data_source_block           12c
_cod_depositor_comments
'Adding full bibliography for 1573095--1573138.cif.'
_cod_original_cell_volume        3029.9(15)
_cod_database_code               1573121
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.832
_shelx_estimated_absorpt_t_min   0.816
_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
 C9-C10A \\sim C9-C10
 with sigma of 0.02
 N2-C10 \\sim N2A-C10A \\sim N2A-C15A \\sim N2-C15 \\sim N2A-C11A \\sim N2-C11
 with sigma of 0.02
 N5A-C38A \\sim N5-C38 \\sim N5-C43 \\sim N5A-C43A \\sim N5A-C39A \\sim N5-C39
 with sigma of 0.02
 C38A-C37 \\sim C38-C37
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C9 \\sim C14 \\sim N2 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C15 \\sim
N2A \\sim C10A \\sim C11A \\sim C12A \\sim C13A \\sim C15A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C37 \\sim N5 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim
N5A \\sim C38A \\sim C39A \\sim C40A \\sim C41A \\sim C42A \\sim C43A: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C51 \\sim C52 \\sim C53 \\sim C52A \\sim C53A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C26 \\sim C27 \\sim C28 \\sim C27A \\sim C28A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
4. Same fragment restrains
{C9, C14, N2A, C10A, C11A, C12A, C13A, C15A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C9, C14, N2, C10, C11, C12, C13, C15}
{C37, N5A, C38A, C39A, C40A, C41A, C42A, C43A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C37, N5, C38, C39, C40, C41, C42, C43}
{C51, C52A, C53A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C51, C52, C53}
{C26, C27A, C28A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C26, C27, C28}
5. Others
 Sof(H9BC)=Sof(H9BD)=Sof(H14C)=Sof(H14D)=Sof(N2A)=Sof(C10A)=Sof(H10C)=
 Sof(H10D)=Sof(C11A)=Sof(H11C)=Sof(H11D)=Sof(C12A)=Sof(H12C)=Sof(H12D)=
 Sof(C13A)=Sof(H13C)=Sof(H13D)=Sof(C15A)=Sof(H15C)=Sof(H15D)=1-FVAR(1)
 Sof(H9AA)=Sof(H9AB)=Sof(H14A)=Sof(H14B)=Sof(N2)=Sof(C10)=Sof(H10A)=Sof(H10B)=
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(C13)=Sof(H13A)=
 Sof(H13B)=Sof(C15)=Sof(H15A)=Sof(H15B)=FVAR(1)
 Sof(H37C)=Sof(H37D)=Sof(N5A)=Sof(C38A)=Sof(H38C)=Sof(H38D)=Sof(C39A)=
 Sof(H39C)=Sof(H39D)=Sof(C40A)=Sof(H40C)=Sof(H40D)=Sof(C41A)=Sof(H41C)=
 Sof(H41D)=Sof(C42A)=Sof(H42C)=Sof(H42D)=Sof(C43A)=Sof(H43C)=Sof(H43D)=1-FVAR(2)
 Sof(H37A)=Sof(H37B)=Sof(N5)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C39)=Sof(H39A)=
 Sof(H39B)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(C42)=
 Sof(H42A)=Sof(H42B)=Sof(C43)=Sof(H43A)=Sof(H43B)=FVAR(2)
 Sof(H26A)=Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=Sof(C28A)=Sof(H28D)=
 Sof(H28E)=Sof(H28F)=1-FVAR(3)
 Sof(H26)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C28)=Sof(H28A)=Sof(H28B)=
 Sof(H28C)=FVAR(3)
 Sof(H51A)=Sof(C52A)=Sof(H52D)=Sof(H52E)=Sof(H52F)=Sof(C53A)=Sof(H53D)=
 Sof(H53E)=Sof(H53F)=1-FVAR(4)
 Sof(H51)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(C53)=Sof(H53A)=Sof(H53B)=
 Sof(H53C)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C23(H23), C26(H26), C26(H26A), C51(H51), C51(H51A), C54(H54)
6.b Secondary CH2 refined with riding coordinates:
 C9(H9AA,H9AB), C9(H9BC,H9BD), C14(H14A,H14B), C14(H14C,H14D), C10(H10A,H10B),
 C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C15(H15A,H15B), C37(H37A,H37B),
  C37(H37C,H37D), C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,
 H41B), C42(H42A,H42B), C43(H43A,H43B), C10A(H10C,H10D), C11A(H11C,H11D),
 C12A(H12C,H12D), C13A(H13C,H13D), C15A(H15C,H15D), C38A(H38C,H38D), C39A(H39C,
 H39D), C40A(H40C,H40D), C41A(H41C,H41D), C42A(H42C,H42D), C43A(H43C,H43D)
6.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C16(H16), C19(H19), C20(H20), C21(H21),
 C32(H32), C33(H33), C34(H34), C35(H35), C44(H44), C47(H47), C48(H48), C49(H49),
  C57(H57), C58(H58), C59(H59), C60(H60), C63(H63), C64(H64), C65(H65), C66(H66)
6.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C28(H28A,H28B,
 H28C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C55(H55A,H55B,H55C), C56(H56A,
 H56B,H56C), C27A(H27D,H27E,H27F), C28A(H28D,H28E,H28F), C52A(H52D,H52E,H52F),
 C53A(H53D,H53E,H53F)
;
_shelx_res_checksum              27334
_shelx_hkl_checksum              44152
_olex2_submission_special_instructions 'No special instructions were received'