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_1573131
_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         'C64 H91 Er N6 O Si'
_chemical_formula_sum            'C64 H91 Er N6 O Si'
_chemical_formula_weight         1155.77
_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                73.486(2)
_cell_angle_beta                 84.862(2)
_cell_angle_gamma                71.051(2)
_cell_formula_units_Z            2
_cell_length_a                   13.1343(18)
_cell_length_b                   13.9845(19)
_cell_length_c                   18.709(3)
_cell_measurement_reflns_used    9371
_cell_measurement_temperature    300
_cell_measurement_theta_max      27.35
_cell_measurement_theta_min      2.27
_cell_volume                     3116.1(8)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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 0.987
_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  0.0307
_diffrn_reflns_av_unetI/netI     0.0401
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            36406
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.481
_diffrn_reflns_theta_min         1.135
_exptl_absorpt_coefficient_mu    1.409
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.3513
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1187 before and 0.0456 after correction. The Ratio of minimum to maximum transmission is 0.4712. The \l/2 correction factor is Not present.'
_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    1.232
_exptl_crystal_description       block
_exptl_crystal_F_000             1214
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.19
_refine_diff_density_max         1.765
_refine_diff_density_min         -0.896
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     985
_refine_ls_number_reflns         14091
_refine_ls_number_restraints     1227
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0472
_refine_ls_R_factor_gt           0.0373
_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^)+(0.0542P)^2^+0.9758P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0924
_refine_ls_wR_factor_ref         0.0972
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12035
_reflns_number_total             14091
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04197f3.cif
_cod_data_source_block           2c
_cod_depositor_comments
'Adding full bibliography for 1573095--1573138.cif.'
_cod_original_cell_volume        3116.1(7)
_cod_database_code               1573131
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.776
_shelx_estimated_absorpt_t_min   0.756
_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
 C12-C11 = C13-C12 = C14-C13 = C15-C14
 1.54 with sigma of 0.001
 N5-C39 = N5-C43 = N5-C38
 1.48 with sigma of 0.001
 N2-C11 = N2-C15 = N2-C10
 1.48 with sigma of 0.001
 C12-C13 = C13-C14
 1.54 with sigma of 0.02
 C40-C39 = C41-C40 = C42-C41 = C43-C42
 1.54 with sigma of 0.001
 C12-C14
 2.515 with sigma of 0.04
 C9-C10 \\sim C9-C10A
 with sigma of 0.02
 N2-C10 \\sim N2A-C10A \\sim N2-C15 \\sim N2A-C15A \\sim N2A-C11A \\sim N2-C11
 with sigma of 0.02
 C15-C14 \\sim C15A-C14A \\sim C14A-C13A \\sim C14-C13 \\sim C13A-C12A \\sim
C13-C12 \\sim C12A-C11A ~
 C12-C11
 with sigma of 0.02
 Er1-C57 \\sim Er1-C57A
 with sigma of 0.02
 Si1A-C57A \\sim Si1-C57 \\sim Si1-C60 \\sim Si1A-C59A \\sim Si1A-C58A \\sim
Si1-C58 \\sim Si1A-C60A ~
 Si1-C59
 with sigma of 0.02
 C57A-C58A \\sim C57A-C59A \\sim C57A-C60A
 with sigma of 0.02
 C58A-C59A \\sim C58A-C60A \\sim C59A-C60A
 with sigma of 0.02
 Er1-C57A \\sim Er1-C57
 with sigma of 0.02
 Si1-C57 \\sim Si1A-C57A
 with sigma of 0.02
 C38A-C37 \\sim C38-C37
 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
 C43-C42 \\sim C43A-C42A \\sim C42-C41 \\sim C42A-C41A \\sim C41-C40 \\sim
C41A-C40A \\sim C40A-C39A ~
 C40-C39
 with sigma of 0.02
 O1-C61A \\sim O1-C61 \\sim O1-C64A \\sim O1-C64
 with sigma of 0.02
 C62A-C61A \\sim C62-C61 \\sim C63A-C62A \\sim C63-C62 \\sim C64A-C63A \\sim
C64-C63
 with sigma of 0.02
3. Restrained planarity
 C22, C20, C19, C17, C21, C18, C23, C26, N3
 with sigma of 0.1
 C22A, C20A, C19A, C17, C21A, C18A, C23A, C26A, N3
 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
Si1 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim Si1A \\sim C57A \\sim C58A
\\sim C59A \\sim C60A: 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
O1 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C61A \\sim C62A \\sim C63A
\\sim C64A: 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 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
5. Same fragment restrains
{Er1, Si1A, C57A, C58A, C59A, C60A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{Er1, Si1, C57, C58, C59, C60}
{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}
{C17, C18A, C19A, C20A, C21A, C22A, C23A, C24A, C25A, C26A, C27A, C28A} sigma
for 1-2: 0.02, 1-3: 0.04
as in
{C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28}
{O1, C61A, C62A, C63A, C64A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O1, C61, C62, C63, C64}
{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}
6. Others
 Sof(Si1A)=Sof(C57A)=Sof(H57C)=Sof(H57D)=Sof(C58A)=Sof(H58D)=Sof(H58E)=
 Sof(H58F)=Sof(C59A)=Sof(H59D)=Sof(H59E)=Sof(H59F)=Sof(C60A)=Sof(H60D)=
 Sof(H60E)=Sof(H60F)=1-FVAR(1)
 Sof(Si1)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=
 Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=
 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(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(3)
 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(3)
 Sof(C61A)=Sof(H61C)=Sof(H61D)=Sof(C62A)=Sof(H62C)=Sof(H62D)=Sof(C63A)=
 Sof(H63C)=Sof(H63D)=Sof(C64A)=Sof(H64C)=Sof(H64D)=1-FVAR(4)
 Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(C63)=Sof(H63A)=
 Sof(H63B)=Sof(C64)=Sof(H64A)=Sof(H64B)=FVAR(4)
 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(5)
 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(5)
 Fixed X: C13(0.67372)
 Fixed Z: C13(0.04143)
7.a Ternary CH refined with riding coordinates:
 C23(H23), C26(H26), C51(H51), C54(H54), C23A(H23A), C26A(H26A)
7.b Secondary CH2 refined with riding coordinates:
 C57(H57A,H57B), C61(H61A,H61B), C62(H62A,H62B), C63(H63A,H63B), C64(H64A,
 H64B), C9(H9AA,H9AB), C9(H9BC,H9BD), 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), C57A(H57C,H57D), 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), C61A(H61C,H61D), C62A(H62C,H62D), C63A(H63C,H63D),
 C64A(H64C,H64D)
7.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),
  C19A(H19A), C20A(H20A), C21A(H21A)
7.d Idealised Me refined as rotating group:
 C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), 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),
 C24A(H24D,H24E,H24F), C25A(H25D,H25E,H25F), C27A(H27D,H27E,H27F), C28A(H28D,
 H28E,H28F), C58A(H58D,H58E,H58F), C59A(H59D,H59E,H59F), C60A(H60D,H60E,H60F)
;
_shelx_res_checksum              91304
_shelx_hkl_checksum              76649
_olex2_submission_special_instructions 'No special instructions were received'