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_1573117
_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         'C95 H102 Er N11, C6 H14'
_chemical_formula_sum            'C101 H116 Er N11'
_chemical_formula_weight         1651.30
_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             2024-04-17
_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                 114.6720(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.4080(19)
_cell_length_b                   20.7325(18)
_cell_length_c                   21.4331(18)
_cell_measurement_reflns_used    7378
_cell_measurement_temperature    300
_cell_measurement_theta_max      25.52
_cell_measurement_theta_min      2.23
_cell_volume                     9048.3(13)
_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  0.1268
_diffrn_reflns_av_unetI/netI     0.0919
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            43793
_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         1.402
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.979
_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    1.212
_exptl_crystal_description       block
_exptl_crystal_F_000             3468
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.19
_refine_diff_density_max         1.689
_refine_diff_density_min         -1.043
_refine_diff_density_rms         0.104
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     821
_refine_ls_number_reflns         7961
_refine_ls_number_restraints     1178
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0979
_refine_ls_R_factor_gt           0.0607
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0711P)^2^+7.5201P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1277
_refine_ls_wR_factor_ref         0.1448
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5768
_reflns_number_total             7961
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04197f4.cif
_cod_data_source_block           14b
_cod_depositor_comments
'Adding full bibliography for 1573095--1573138.cif.'
_cod_database_code               1573117
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.836
_shelx_estimated_absorpt_t_min   0.821
_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
 C1A-C1C = C1D-C1F
 2.53 with sigma of 0.04
 C1B-C1D = C1C-C1E
 2.54 with sigma of 0.04
 C9-C10A \\sim C9-C10
 with sigma of 0.02
 C1A-C1C \\sim C1C-C1E \\sim C1B-C1D \\sim C1D-C1F
 with sigma of 0.04
 N2-C10 \\sim N2A-C10A \\sim N2A-C15A \\sim N2A-C11A \\sim N2-C15 \\sim N2-C11
 with sigma of 0.02
 C1A-C1B \\sim C1B-C1C \\sim C1C-C1D \\sim C1D-C1E \\sim C1E-C1F
 with sigma of 0.02
 C43A-C42 \\sim C43-C42
 with sigma of 0.02
 N3-C17 \\sim N3-C17A
 with sigma of 0.02
3. Restrained planarity
 C29, C30, C31, C32, C33, C34, C35
 with sigma of 0.1
 C1A, C1B, C1C, C1D, C1E, C1F
 with sigma of 0.1
 C29, C30, C31A, C32A, C33A, C34A, C35A
 with sigma of 0.1
 C42, C43A_$1, C44A_$1, C45A_$1, C46A_$1, C47A_$1, C48A_$1
 with sigma of 0.1
 C42, C43_$1, C44_$1, C45_$1, C46_$1, C47_$1, C48_$1
 with sigma of 0.1
 C17, C19, C20, C18, C21, N3, C22, C26, C23
 with sigma of 0.1
 C19A, C17A, C22A, C20A, C18A, C21A, N3, C26A, C23A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
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
C30 \\sim C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C31A \\sim C32A
\\sim C33A \\sim C34A \\sim C35A: 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
0.01 and sigma for terminal atoms of 0.02 within 2A
C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C43A
\\sim C44A \\sim C45A \\sim C46A \\sim C47A \\sim C48A: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
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 \\sim N3: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 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
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
6. Same fragment restrains
{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}
{C30, C31A, C32A, C33A, C34A, C35A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C30, C31, C32, C33, C34, C35}
{C42, C43A, C44A, C45A, C46A, C47A, C48A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C42, C43, C44, C45, C46, C47, C48}
{C9, N2A, 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}
7. Others
 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(1)
 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(1)
 Sof(C31A)=Sof(H31A)=Sof(C32A)=Sof(H32A)=Sof(C33A)=Sof(H33A)=Sof(C34A)=
 Sof(H34A)=Sof(C35A)=Sof(H35A)=1-FVAR(2)
 Sof(C31)=Sof(H31)=Sof(C32)=Sof(H32)=Sof(C33)=Sof(H33)=Sof(C34)=Sof(H34)=
 Sof(C35)=Sof(H35)=FVAR(2)
 Sof(C43A)=Sof(C44A)=Sof(H44A)=Sof(C45A)=Sof(H45A)=Sof(C46A)=Sof(H46A)=
 Sof(C47A)=Sof(H47A)=Sof(C48A)=Sof(H48A)=1-FVAR(3)
 Sof(C43)=Sof(C44)=Sof(H44)=Sof(C45)=Sof(H45)=Sof(C46)=Sof(H46)=Sof(C47)=
 Sof(H47)=Sof(C48)=Sof(H48)=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)
 Fixed Sof: C1A(0.5) H1AA(0.5) H1AB(0.5) H1AC(0.5) C1B(0.5) H1BA(0.5)
 H1BB(0.5) C1C(0.5) H1CA(0.5) H1CB(0.5) C1D(0.5) H1DA(0.5) H1DB(0.5) C1E(0.5)
 H1EA(0.5) H1EB(0.5) C1F(0.5) H1FA(0.5) H1FB(0.5) H1FC(0.5)
8.a Ternary CH refined with riding coordinates:
 C23(H23), C26(H26), C23A(H23A), C26A(H26A)
8.b Secondary CH2 refined with riding coordinates:
 C9(H9AA,H9AB), C9(H9BC,H9BD), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B),
 C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C10A(H10C,H10D), C11A(H11C,
 H11D), C12A(H12C,H12D), C13A(H13C,H13D), C14A(H14C,H14D), C15A(H15C,H15D),
 C1B(H1BA,H1BB), C1C(H1CA,H1CB), C1D(H1DA,H1DB), C1E(H1EA,H1EB)
8.c Me refined with riding coordinates:
 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),
 C31(H31), C32(H32), C33(H33), C34(H34), C35(H35), C37(H37), C38(H38), C39(H39),
  C40(H40), C41(H41), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48),
 C19A(H19A), C20A(H20A), C21A(H21A), C31A(H31A), C32A(H32A), C33A(H33A),
 C34A(H34A), C35A(H35A), C44A(H44A), C45A(H45A), C46A(H46A), C47A(H47A),
 C48A(H48A)
8.e Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C28(H28A,H28B,
 H28C), C24A(H24D,H24E,H24F), C25A(H25D,H25E,H25F), C27A(H27D,H27E,H27F),
 C28A(H28D,H28E,H28F), C1A(H1AA,H1AB,H1AC)
;
_shelx_res_checksum              22878
_shelx_hkl_checksum              18240
_olex2_submission_special_instructions 'No special instructions were received'