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_1573137
_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         'C60 H87 N6 O Si Y, 0.5(C6 H14)'
_chemical_formula_sum            'C63 H94 N6 O Si Y'
_chemical_formula_weight         1068.44
_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                102.763(2)
_cell_angle_beta                 94.670(2)
_cell_angle_gamma                94.644(2)
_cell_formula_units_Z            2
_cell_length_a                   10.5911(5)
_cell_length_b                   12.7677(7)
_cell_length_c                   23.3687(13)
_cell_measurement_reflns_used    9946
_cell_measurement_temperature    300
_cell_measurement_theta_max      27.64
_cell_measurement_theta_min      2.88
_cell_volume                     3055.7(3)
_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 0.985
_diffrn_measured_fraction_theta_max 0.985
_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  0.1177
_diffrn_reflns_av_unetI/netI     0.0499
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            124009
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.877
_exptl_absorpt_coefficient_mu    1.017
_exptl_absorpt_correction_T_max  0.822
_exptl_absorpt_correction_T_min  0.807
_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    1.161
_exptl_crystal_description       block
_exptl_crystal_F_000             1150
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.587
_refine_diff_density_min         -0.441
_refine_diff_density_rms         0.052
_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     1050
_refine_ls_number_reflns         10603
_refine_ls_number_restraints     1613
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0830
_refine_ls_R_factor_gt           0.0559
_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^)+(0.0649P)^2^+2.4707P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1270
_refine_ls_wR_factor_ref         0.1410
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8184
_reflns_number_total             10603
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04197f3.cif
_cod_data_source_block           3c
_cod_depositor_comments
'Adding full bibliography for 1573095--1573138.cif.'
_cod_database_code               1573137
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.822
_shelx_estimated_absorpt_t_min   0.807
_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
 N2-C10 = N2-C15 = N2-C11
 1.48 with sigma of 0.01
 C15-C14 = C14-C13 = C12-C11 = C13-C12
 1.54 with sigma of 0.01
 N2-C10 = N2-C11 = N2-C15
 1.48 with sigma of 0.01
 C9-C10
 1.54 with sigma of 0.01
 C66-C65 = C65-C64 = C64-C63 = C63-C62 = C62-C61
 1.52 with sigma of 0.02
 C66-C64 = C63-C61
 2.53 with sigma of 0.04
 C65-C63 = C64-C62
 2.54 with sigma of 0.04
 C36A-C35 \\sim C36-C35
 with sigma of 0.02
 N2-C10 \\sim N2-C11 \\sim N2-C15
 with sigma of 0.02
 C12-C11 \\sim C13-C12 \\sim C14-C13 \\sim C15-C14
 with sigma of 0.02
 C38-C37 \\sim C38A-C37A \\sim C39-C38 \\sim C39A-C38A \\sim C40-C39 \\sim
C40A-C39A \\sim C41A-C40A ~
 C41-C40
 with sigma of 0.02
 Y1-N3A \\sim Y1-N3
 with sigma of 0.02
 C10-C11 \\sim C10-C15
 with sigma of 0.02
 Si1A-C57 \\sim Si1-C57 \\sim Si1A-C59A \\sim Si1-C60 \\sim Si1-C59 \\sim
Si1A-C60A \\sim Si1A-C58A ~
 Si1-C58
 with sigma of 0.02
 C57-C58A \\sim C57-C59A \\sim C57-C60A
 with sigma of 0.02
 N3A-C17A \\sim N3-C17
 with sigma of 0.02
 N3A-C16 \\sim N3-C16
 with sigma of 0.02
 O1-C56 \\sim O1-C56A \\sim O1-C53 \\sim O1-C53A
 with sigma of 0.02
 C54A-C53A \\sim C54-C53 \\sim C55A-C54A \\sim C55-C54 \\sim C56A-C55A \\sim
C56-C55
 with sigma of 0.02
 N6-C43A \\sim N6-C43
 with sigma of 0.02
 N2-C10 \\sim N2-C11 \\sim N2-C11A \\sim N2-C15A \\sim N2-C15
 with sigma of 0.02
 C12-C11 \\sim C12A-C11A \\sim C13-C12 \\sim C13A-C12A \\sim C14A-C13A \\sim
C14-C13 \\sim C15A-C14A ~
 C15-C14
 with sigma of 0.02
 C66-C65 \\sim C65-C64 \\sim C64-C63 \\sim C63-C62 \\sim C62-C61
 with sigma of 0.02
 C66-C64 \\sim C64-C62 \\sim C65-C63 \\sim C63-C61
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
N2: 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 N3A \\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
N2 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
N5 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim
C36A \\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
C57 \\sim Si1 \\sim C58 \\sim C59 \\sim C60 \\sim Si1A \\sim C58A \\sim C59A
\\sim C60A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
O1 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C53A \\sim C54A \\sim C55A
\\sim C56A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
N6 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim
C50 \\sim C51 \\sim C52 \\sim C43A \\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
N2 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\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
C66 \\sim C65 \\sim C64 \\sim C63 \\sim C62 \\sim C61: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 C66, C65, C64, C63, C62, C61
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{O1, C53A, C54A, C55A, C56A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O1, C53, C54, C55, C56}
{N6, C43A, C44A, C45A, C46A, C47A, C48A, C49A, C50A, C51A, C52A} sigma for 1-2:
0.02, 1-3: 0.04
as in
{N6, C43, C44, C45, C46, C47, C48, C49, C50, C51, C52}
{C57, Si1A, C58A, C59A, C60A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C57, Si1, C58, C59, C60}
{N5, C35, C36A, C37A, C38A, C39A, C40A, C41A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N5, C35, C36, C37, C38, C39, C40, C41}
{N3A, 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}
6. Others
 Sof(C53A)=Sof(H53C)=Sof(H53D)=Sof(C54A)=Sof(H54C)=Sof(H54D)=Sof(C55A)=
 Sof(H55C)=Sof(H55D)=Sof(C56A)=Sof(H56C)=Sof(H56D)=1-FVAR(1)
 Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(C55)=Sof(H55A)=
 Sof(H55B)=Sof(C56)=Sof(H56A)=Sof(H56B)=FVAR(1)
 Sof(H57C)=Sof(H57D)=Sof(Si1A)=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(2)
 Sof(H57A)=Sof(H57B)=Sof(Si1)=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(2)
 Sof(H35C)=Sof(H35D)=Sof(C36A)=Sof(H36C)=Sof(H36D)=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(H35A)=Sof(H35B)=Sof(C36)=Sof(H36A)=Sof(H36B)=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(H16A)=Sof(N3A)=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(4)
 Sof(H16)=Sof(N3)=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(4)
 Sof(C43A)=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(C43)=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(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(6)
 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(6)
 Fixed Sof: C66(0.5) H66A(0.5) H66B(0.5) H66C(0.5) C65(0.5) H65A(0.5)
 H65B(0.5) C64(0.5) H64A(0.5) H64B(0.5) C63(0.5) H63A(0.5) H63B(0.5) C62(0.5)
 H62A(0.5) H62B(0.5) C61(0.5) H61A(0.5) H61B(0.5) H61C(0.5)
7.a Ternary CH refined with riding coordinates:
 C47(H47), C49(H49), C51(H51), C21(H21), C23(H23), C25(H25), C21A(H21A),
 C23A(H23A), C25A(H25A), C47A(H47A), C49A(H49A), C51A(H51A)
7.b Secondary CH2 refined with riding coordinates:
 C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B), C35(H35A,
 H35B), C35(H35C,H35D), C36(H36A,H36B), C37(H37A,H37B), C38(H38A,H38B),
 C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C44(H44A,H44B), C45(H45A,H45B),
  C46(H46A,H46B), C48(H48A,H48B), C50(H50A,H50B), C52(H52A,H52B), C9(H9A,H9B),
 C10(H10A,H10B), C57(H57A,H57B), C57(H57C,H57D), C18(H18A,H18B), C19(H19A,H19B),
  C20(H20A,H20B), C22(H22A,H22B), C24(H24A,H24B), C26(H26A,H26B), C11(H11A,
 H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B),
 C18A(H18C,H18D), C19A(H19C,H19D), C20A(H20C,H20D), C22A(H22C,H22D), C24A(H24C,
 H24D), C26A(H26C,H26D), C11A(H11C,H11D), C12A(H12C,H12D), C13A(H13C,H13D),
 C14A(H14C,H14D), C15A(H15C,H15D), C36A(H36C,H36D), 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), C53A(H53C,H53D), C54A(H54C,H54D), C55A(H55C,H55D), C56A(H56C,H56D),
 C65(H65A,H65B), C64(H64A,H64B), C63(H63A,H63B), C62(H62A,H62B)
7.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C16(H16), C16(H16A), C30(H30), C31(H31),
 C32(H32), C33(H33), C42(H42)
7.d Idealised Me refined as rotating group:
 C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C58A(H58D,H58E,
 H58F), C59A(H59D,H59E,H59F), C60A(H60D,H60E,H60F), C66(H66A,H66B,H66C),
 C61(H61A,H61B,H61C)
;
_shelx_res_checksum              82201
_shelx_hkl_checksum              4597
_olex2_submission_special_instructions 'No special instructions were received'