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_1573111
_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 H87 Dy N10, 2(C4 H8 O)'
_chemical_formula_sum            'C74 H103 Dy N10 O2'
_chemical_formula_weight         1327.16
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/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                 93.6530(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.8231(6)
_cell_length_b                   23.6040(11)
_cell_length_c                   23.0899(10)
_cell_measurement_reflns_used    9925
_cell_measurement_temperature    300
_cell_measurement_theta_max      21.25
_cell_measurement_theta_min      2.35
_cell_volume                     6974.6(6)
_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 0.998
_diffrn_measured_fraction_theta_max 0.998
_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  0.0771
_diffrn_reflns_av_unetI/netI     0.0580
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            67930
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         1.235
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.123
_exptl_absorpt_correction_T_max  0.840
_exptl_absorpt_correction_T_min  0.440
_exptl_absorpt_correction_type   multi-scan
_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    1.264
_exptl_crystal_description       block
_exptl_crystal_F_000             2796
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.423
_refine_diff_density_min         -0.349
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1184
_refine_ls_number_reflns         12261
_refine_ls_number_restraints     1581
_refine_ls_restrained_S_all      0.984
_refine_ls_R_factor_all          0.0795
_refine_ls_R_factor_gt           0.0422
_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^)+(0.0295P)^2^+5.3693P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0762
_refine_ls_wR_factor_ref         0.0890
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8335
_reflns_number_total             12261
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04197f4.cif
_cod_data_source_block           9
_cod_depositor_comments
'Adding full bibliography for 1573095--1573138.cif.'
_cod_database_code               1573111
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.815
_shelx_estimated_absorpt_t_min   0.798
_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
 N3-C17 \\sim N3-C17A
 with sigma of 0.02
 C15-C14 \\sim C15A-C14A \\sim C14-C13 \\sim C14A-C13A \\sim C13-C12 \\sim
C13A-C12A \\sim C12-C11 ~
 C12A-C11A
 with sigma of 0.02
 C9-C10 \\sim C9-C10A
 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
 N5-C41 \\sim N5-C41A \\sim N5-C37A \\sim N5-C37
 with sigma of 0.02
 C41-C40 \\sim C41A-C40A \\sim C40A-C39A \\sim C40-C39 \\sim C39-C38 \\sim
C39A-C38A \\sim C38A-C37A ~
 C38-C37
 with sigma of 0.02
 N10-C65A \\sim N10-C65 \\sim N10-C66 \\sim N10-C66A
 with sigma of 0.02
 O1-C67 \\sim O1A-C67A \\sim O1-C70 \\sim O1A-C70A
 with sigma of 0.02
 C68A-C67A \\sim C68-C67 \\sim C69A-C68A \\sim C69-C68 \\sim C70A-C69A \\sim
C70-C69
 with sigma of 0.02
 O2-C71A \\sim O2A-C71 \\sim O2-C74A \\sim O2A-C74
 with sigma of 0.02
 C71-C72 \\sim C72-C73 \\sim C71A-C72A \\sim C74-C73 \\sim C72A-C73A \\sim
C74A-C73A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
N3 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim
C24 \\sim C25 \\sim C26 \\sim C17A \\sim C18A \\sim C19A \\sim C20A \\sim C21A
\\sim C22A \\sim C23A \\sim C24A \\sim C25A \\sim C26A: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C9 \\sim N2 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim
N2A \\sim C10A \\sim C11A \\sim C12A \\sim C13A \\sim C14A \\sim C15A: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
N5 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C37A \\sim C38A
\\sim C39A \\sim C40A \\sim C41A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
N10 \\sim C65 \\sim C66 \\sim C65A \\sim C66A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim
C51 \\sim C52 \\sim C44A \\sim C45A \\sim C46A \\sim C47A \\sim C48A \\sim C49A
\\sim C50A \\sim C51A \\sim C52A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
O1 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim O1A \\sim C67A \\sim C68A
\\sim C69A \\sim C70A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O2A \\sim C73 \\sim C72 \\sim C71 \\sim C74 \\sim O2 \\sim C73A \\sim C72A
\\sim C71A \\sim C74A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
4. Same fragment restrains
{N3, C17A, C18A, C19A, C20A, C21A, C22A, C23A, C24A, C25A, C26A} sigma for 1-2:
0.02, 1-3: 0.04
as in
{N3, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26}
{O2, C73A, C72A, C71A, C74A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O2A, C73, C72, C71, C74}
{C43, C44A, C45A, C46A, C47A, C48A, C49A, C50A, C51A, C52A} sigma for 1-2:
0.02, 1-3: 0.04
as in
{C43, C44, C45, C46, C47, C48, C49, C50, C51, C52}
{O1A, C67A, C68A, C69A, C70A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O1, C67, C68, C69, C70}
{C9, N2, C10A, C11A, C12A, C13A, C14A, C15A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C9, N2, C10, C11, C12, C13, C14, C15}
{N10, C65A, C66A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N10, C65, C66}
{N5, C37A, C38A, C39A, C40A, C41A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N5, C37, C38, C39, C40, C41}
5. Others
 Sof(C17A)=Sof(C18A)=Sof(H18C)=Sof(H18D)=Sof(C19A)=Sof(H19C)=Sof(H19D)=
 Sof(C20A)=Sof(H20C)=Sof(H20D)=Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(H22C)=
 Sof(H22D)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24C)=Sof(H24D)=Sof(C25A)=
 Sof(H25A)=Sof(C26A)=Sof(H26C)=Sof(H26D)=1-FVAR(1)
 Sof(C17)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C20)=
 Sof(H20A)=Sof(H20B)=Sof(C21)=Sof(H21)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(C23)=
 Sof(H23)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(C25)=Sof(H25)=Sof(C26)=Sof(H26A)=
 Sof(H26B)=FVAR(1)
 Sof(H9BC)=Sof(H9BD)=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(C14A)=Sof(H14C)=Sof(H14D)=Sof(C15A)=Sof(H15C)=Sof(H15D)=1-FVAR(2)
 Sof(H9AA)=Sof(H9AB)=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(C14)=
 Sof(H14A)=Sof(H14B)=Sof(C15)=Sof(H15A)=Sof(H15B)=FVAR(2)
 Sof(C37A)=Sof(H37C)=Sof(H37D)=Sof(C38A)=Sof(H38C)=Sof(H38D)=Sof(C39A)=
 Sof(H39C)=Sof(H39D)=Sof(C40A)=Sof(H40C)=Sof(H40D)=Sof(C41A)=Sof(H41C)=
 Sof(H41D)=1-FVAR(3)
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C39)=Sof(H39A)=
 Sof(H39B)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(C41)=Sof(H41A)=Sof(H41B)=FVAR(3)
 Sof(C65A)=Sof(H65D)=Sof(H65E)=Sof(H65F)=Sof(C66A)=Sof(H66D)=Sof(H66E)=
 Sof(H66F)=1-FVAR(4)
 Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(H65C)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=
 FVAR(4)
 Sof(C44A)=Sof(H44C)=Sof(H44D)=Sof(C45A)=Sof(H45C)=Sof(H45D)=Sof(C46A)=
 Sof(H46C)=Sof(H46D)=Sof(C47A)=Sof(H47A)=Sof(C48A)=Sof(H48C)=Sof(H48D)=
 Sof(C49A)=Sof(H49A)=Sof(C50A)=Sof(H50C)=Sof(H50D)=Sof(C51A)=Sof(H51A)=
 Sof(C52A)=Sof(H52C)=Sof(H52D)=1-FVAR(5)
 Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(C46)=Sof(H46A)=
 Sof(H46B)=Sof(C47)=Sof(H47)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(C49)=Sof(H49)=
 Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(C51)=Sof(H51)=Sof(C52)=Sof(H52A)=Sof(H52B)=
 FVAR(5)
 Sof(O1A)=Sof(C67A)=Sof(H67C)=Sof(H67D)=Sof(C68A)=Sof(H68C)=Sof(H68D)=
 Sof(C69A)=Sof(H69C)=Sof(H69D)=Sof(C70A)=Sof(H70C)=Sof(H70D)=1-FVAR(6)
 Sof(O1)=Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(C69)=
 Sof(H69A)=Sof(H69B)=Sof(C70)=Sof(H70A)=Sof(H70B)=FVAR(6)
 Sof(O2)=Sof(C73A)=Sof(H73C)=Sof(H73D)=Sof(C72A)=Sof(H72C)=Sof(H72D)=Sof(C71A)=
 Sof(H71C)=Sof(H71D)=Sof(C74A)=Sof(H74C)=Sof(H74D)=1-FVAR(7)
 Sof(O2A)=Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(C71)=
 Sof(H71A)=Sof(H71B)=Sof(C74)=Sof(H74A)=Sof(H74B)=FVAR(7)
6.a Ternary CH refined with riding coordinates:
 C21(H21), C23(H23), C25(H25), C42(H42), C47(H47), C49(H49), C51(H51),
 C21A(H21A), C23A(H23A), C25A(H25A), C47A(H47A), C49A(H49A), C51A(H51A)
6.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B), C22(H22A,H22B), C24(H24A,
 H24B), C26(H26A,H26B), C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B),
 C40(H40A,H40B), C41(H41A,H41B), C9(H9AA,H9AB), C9(H9BC,H9BD), C10(H10A,H10B),
 C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B),
  C35(H35A,H35B), C36(H36A,H36B), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,
 H46B), C48(H48A,H48B), C50(H50A,H50B), C52(H52A,H52B), C73(H73A,H73B),
 C72(H72A,H72B), C71(H71A,H71B), C74(H74A,H74B), C67(H67A,H67B), C68(H68A,H68B),
  C69(H69A,H69B), C70(H70A,H70B), C67A(H67C,H67D), C68A(H68C,H68D), C69A(H69C,
 H69D), C70A(H70C,H70D), C73A(H73C,H73D), C72A(H72C,H72D), C71A(H71C,H71D),
 C74A(H74C,H74D), C10A(H10C,H10D), C11A(H11C,H11D), C12A(H12C,H12D), C13A(H13C,
 H13D), C14A(H14C,H14D), C15A(H15C,H15D), C18A(H18C,H18D), C19A(H19C,H19D),
 C20A(H20C,H20D), C22A(H22C,H22D), C24A(H24C,H24D), C26A(H26C,H26D), C37A(H37C,
 H37D), C38A(H38C,H38D), C39A(H39C,H39D), C40A(H40C,H40D), C41A(H41C,H41D),
 C44A(H44C,H44D), C45A(H45C,H45D), C46A(H46C,H46D), C48A(H48C,H48D), C50A(H50C,
 H50D), C52A(H52C,H52D)
6.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C16(H16), C30(H30), C31(H31), C32(H32),
 C33(H33), C54(H54), C56(H56), C57(H57), C60(H60), C61(H61), C63(H63), C64(H64)
6.d Idealised Me refined as rotating group:
 C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C58(H58A,H58B,H58C), C59(H59A,H59B,
 H59C), C65A(H65D,H65E,H65F), C66A(H66D,H66E,H66F)
;
_shelx_res_checksum              1803
_shelx_hkl_checksum              65808
_olex2_submission_special_instructions 'No special instructions were received'