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_1573110
_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         'C70 H91 Dy N10, 0.25(C6 H14), 0.5(C7 H8)'
_chemical_formula_sum            'C75 H98.5 Dy N10'
_chemical_formula_weight         1302.63
_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                 95.6000(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   30.753(3)
_cell_length_b                   22.844(2)
_cell_length_c                   21.5677(19)
_cell_measurement_reflns_used    9987
_cell_measurement_temperature    300
_cell_measurement_theta_max      22.17
_cell_measurement_theta_min      2.19
_cell_volume                     15079(2)
_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  0.1104
_diffrn_reflns_av_unetI/netI     0.0832
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            71987
_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         1.112
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.036
_exptl_absorpt_correction_T_max  0.828
_exptl_absorpt_correction_T_min  0.418
_exptl_absorpt_correction_type   none
_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    1.148
_exptl_crystal_description       block
_exptl_crystal_F_000             5476
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.677
_refine_diff_density_min         -0.676
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1152
_refine_ls_number_reflns         13275
_refine_ls_number_restraints     1379
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.1186
_refine_ls_R_factor_gt           0.0556
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0877P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1348
_refine_ls_wR_factor_ref         0.1651
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7586
_reflns_number_total             13275
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04197f4.cif
_cod_data_source_block           8c
_cod_depositor_comments
'Adding full bibliography for 1573095--1573138.cif.'
_cod_original_cell_volume        15080(2)
_cod_original_formula_sum        'C75 H98.50 Dy N10'
_cod_database_code               1573110
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.828
_shelx_estimated_absorpt_t_min   0.812
_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
 C1A-C1B = C1B-C1C = C1C-C1D = C1D-C1E = C1E-C1F
 1.52 with sigma of 0.02
 C41A-C40A = C40-C39 = C40A-C39A = C41-C40 = C42-C41 = C42A-C41A = C43-C42 =
 C43A-C42A
 1.54 with sigma of 0.01
 C15A-C14A = C14A-C13A = C13A-C12A = C15-C14 = C12A-C11A = C14-C13 = C13-C12 =
 C12-C11
 1.54 with sigma of 0.01
 N2A-C15A = N2A-C11A = N2-C15 = N2-C11 = N2-C10 = N2A-C10A
 1.48 with sigma of 0.01
 C49-C14A
 2.5 with sigma of 0.01
 C1H-C1I = C1H-C1M = C1J-C1K
 1.39 with sigma of 0.02
 C1I-C1J = C1K-C1L = C1L-C1M
 1.38 with sigma of 0.02
 C1G-C1H
 1.51 with sigma of 0.02
 C1A-C1C = C1D-C1F
 2.53 with sigma of 0.04
 C1B-C1D = C1C-C1E
 2.54 with sigma of 0.04
 C1H-C1J
 2.42 with sigma of 0.04
 C1J-C1L = C1K-C1M
 2.4 with sigma of 0.04
 C1H-C1L
 2.41 with sigma of 0.04
 C1I-C1K
 2.39 with sigma of 0.04
 C1G-C1I = C1G-C1M
 2.52 with sigma of 0.04
 C38-C37 \\sim C38A-C37
 with sigma of 0.02
 C1A-C1B \\sim C1B-C1C \\sim C1C-C1D \\sim C1D-C1E \\sim C1E-C1F
 with sigma of 0.02
 N5-C38 \\sim N5A-C38A \\sim N5-C39 \\sim N5A-C43A \\sim N5A-C39A \\sim N5-C43
 with sigma of 0.02
 C1A-C1C \\sim C1C-C1E \\sim C1B-C1D \\sim C1D-C1F
 with sigma of 0.04
 C55A-C54 \\sim C55-C54 \\sim C56-C54 \\sim C56A-C54
 with sigma of 0.02
 C53A-C51 \\sim C53-C51 \\sim C52-C51 \\sim C52A-C51
 with sigma of 0.02
 C26-C22 \\sim C26A-C22A \\sim C23A-C18A \\sim C23-C18
 with sigma of 0.02
 C27-C26 \\sim C27A-C26A \\sim C28A-C26A \\sim C28-C26 \\sim C25A-C23A \\sim
C25-C23 \\sim C24A-C23A ~
 C24-C23
 with sigma of 0.02
 N3-C17A \\sim N3-C17
 with sigma of 0.02
 C9-C10 \\sim C9A-C10A
 with sigma of 0.02
 C15-C14 \\sim C15A-C14A \\sim C14A-C13A \\sim C13A-C12A \\sim C12A-C11A \\sim
C12-C11 \\sim C13-C12 ~
 C14-C13
 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
 N1-C9 \\sim N1-C9A
 with sigma of 0.02
 C1H-C1L \\sim C1H-C1J \\sim C1M-C1K \\sim C1I-C1M \\sim C1J-C1L \\sim C1I-C1K
 with sigma of 0.04
 C1G-C1M \\sim C1G-C1I
 with sigma of 0.04
 C1H-C1I \\sim C1I-C1J \\sim C1J-C1K \\sim C1K-C1L \\sim C1L-C1M \\sim C1M-C1H
 with sigma of 0.02
3. Restrained planarity
 C1A, C1B, C1C, C1D, C1E, C1F
 with sigma of 0.1
 N3, C17A, C18A, C19A, C20A, C21A, C22A, C23A, C26A
 with sigma of 0.1
 N3, C17, C18, C19, C20, C21, C22, C23, C26
 with sigma of 0.1
 C1G, C1H, C1I, C1J, C1K, C1L, C1M
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
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
C1A \\sim C1B \\sim C1C \\sim C1D \\sim C1E \\sim C1F: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C54 \\sim C55 \\sim C56 \\sim C55A \\sim C56A: 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
N3 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim
C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim C17A \\sim C18A \\sim C19A
\\sim C20A \\sim C21A \\sim C22A \\sim C23A \\sim C24A \\sim C25A \\sim C26A
\\sim C27A \\sim C28A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
N2 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim
N2A \\sim C9A \\sim C10A \\sim C11A \\sim C12A \\sim C13A \\sim C14A \\sim C15A
\\sim N1: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C70 \\sim N10 \\sim C69: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C1G \\sim C1H \\sim C1I \\sim C1J \\sim C1K \\sim C1L \\sim C1M: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C1A) \\sim Ueq, Uanis(C1B) \\sim Ueq, Uanis(C1C) \\sim Ueq, Uanis(C1D)
\\sim Ueq, Uanis(C1E) \\sim Ueq, Uanis(C1F) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C1G) \\sim Ueq, Uanis(C1H) \\sim Ueq, Uanis(C1I) \\sim Ueq, Uanis(C1J)
\\sim Ueq, Uanis(C1K) \\sim Ueq, Uanis(C1L) \\sim Ueq, Uanis(C1M) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C1A, C1B, C1C, C1D, C1E, C1F
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1G, C1H, C1I, C1J, C1K, C1L, C1M
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
{N1, N2A, C9A, C10A, C11A, C12A, C13A, C14A, C15A} sigma for 1-2: 0.02, 1-3:
0.04
as in
{N1, N2, C9, C10, C11, C12, C13, C14, 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}
{N3, C17A, C18A, C19A, C20A, C21A, C22A, C23A, C24A, C25A, C26A, C27A, C28A}
sigma for 1-2: 0.02, 1-3: 0.04
as in
{N3, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28}
{C54, C55A, C56A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C54, C55, C56}
7. Others
 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(1)
 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(1)
 Sof(H51A)=Sof(C52A)=Sof(H52D)=Sof(H52E)=Sof(H52F)=Sof(C53A)=Sof(H53D)=
 Sof(H53E)=Sof(H53F)=1-FVAR(2)
 Sof(H51)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(C53)=Sof(H53A)=Sof(H53B)=
 Sof(H53C)=FVAR(2)
 Sof(H54A)=Sof(C55A)=Sof(H55D)=Sof(H55E)=Sof(H55F)=Sof(C56A)=Sof(H56D)=
 Sof(H56E)=Sof(H56F)=1-FVAR(3)
 Sof(H54)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=Sof(C56)=Sof(H56A)=Sof(H56B)=
 Sof(H56C)=FVAR(3)
 Sof(C17A)=Sof(C18A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(H20A)=Sof(C21A)=
 Sof(H21A)=Sof(C22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24D)=Sof(H24E)=
 Sof(H24F)=Sof(C25A)=Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(C26A)=Sof(H26A)=
 Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=Sof(C28A)=Sof(H28D)=Sof(H28E)=
 Sof(H28F)=1-FVAR(4)
 Sof(C17)=Sof(C18)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21)=
 Sof(C22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25)=
 Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27A)=Sof(H27B)=
 Sof(H27C)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=FVAR(4)
 Sof(N2A)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=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(5)
 Sof(N2)=Sof(C9)=Sof(H9A)=Sof(H9B)=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(5)
 Fixed Sof: C1A(0.25) H1AA(0.25) H1AB(0.25) H1AC(0.25) C1B(0.25) H1BA(0.25)
 H1BB(0.25) C1C(0.25) H1CA(0.25) H1CB(0.25) C1D(0.25) H1DA(0.25) H1DB(0.25)
 C1E(0.25) H1EA(0.25) H1EB(0.25) C1F(0.25) H1FA(0.25) H1FB(0.25) H1FC(0.25)
 C1G(0.5) H1GA(0.5) H1GB(0.5) H1GC(0.5) C1H(0.5) C1I(0.5) H1I(0.5) C1J(0.5)
 H1J(0.5) C1K(0.5) H1K(0.5) C1L(0.5) H1L(0.5) C1M(0.5) H1M(0.5)
8.a Ternary CH refined with riding coordinates:
 C23(H23), C26(H26), C44(H44), C51(H51), C51(H51A), C54(H54), C54(H54A),
 C23A(H23A), C26A(H26A)
8.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B),
 C14(H14A,H14B), 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), C9A(H9AA,H9AB), C10A(H10C,H10D), C11A(H11C,H11D), C12A(H12C,H12D),
 C13A(H13C,H13D), C14A(H14C,H14D), C15A(H15C,H15D), C38A(H38C,H38D), C39A(H39C,
 H39D), C40A(H40C,H40D), C41A(H41C,H41D), C42A(H42C,H42D), C43A(H43C,H43D),
 C1B(H1BA,H1BB), C1C(H1CA,H1CB), C1D(H1DA,H1DB), C1E(H1EA,H1EB)
8.c Me refined with riding coordinates:
 C1A(H1AA,H1AB,H1AC), C1F(H1FA,H1FB,H1FC)
8.d Aromatic/amide H refined with riding coordinates:
 C19(H19), C20(H20), C21(H21), C4(H4), C5(H5), C6(H6), C7(H7), C16(H16),
 C32(H32), C33(H33), C34(H34), C35(H35), C47(H47), C48(H48), C49(H49), C58(H58),
  C60(H60), C61(H61), C64(H64), C65(H65), C67(H67), C68(H68), C19A(H19A),
 C20A(H20A), C21A(H21A), C1I(H1I), C1J(H1J), C1K(H1K), C1L(H1L), C1M(H1M)
8.e 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), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C69(H69A,H69B,H69C),
 C70(H70A,H70B,H70C), C24A(H24D,H24E,H24F), C25A(H25D,H25E,H25F), C27A(H27D,
 H27E,H27F), C28A(H28D,H28E,H28F), C52A(H52D,H52E,H52F), C53A(H53D,H53E,H53F),
 C55A(H55D,H55E,H55F), C56A(H56D,H56E,H56F), C1G(H1GA,H1GB,H1GC)
;
_shelx_res_checksum              80784
_shelx_hkl_checksum              92612
_olex2_submission_special_instructions 'No special instructions were received'