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_1573108
_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         'C63 H85 N8 O Y'
_chemical_formula_sum            'C63 H85 N8 O Y'
_chemical_formula_weight         1059.29
_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                74.5490(10)
_cell_angle_beta                 86.700(2)
_cell_angle_gamma                80.2920(10)
_cell_formula_units_Z            2
_cell_length_a                   11.1074(3)
_cell_length_b                   14.1540(3)
_cell_length_c                   18.9061(5)
_cell_measurement_reflns_used    9983
_cell_measurement_temperature    300
_cell_measurement_theta_max      67.24
_cell_measurement_theta_min      2.42
_cell_volume                     2823.61(12)
_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 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0911
_diffrn_reflns_av_unetI/netI     0.0670
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            52987
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.437
_diffrn_reflns_theta_min         2.425
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.821
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.2925
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1511 before and 0.0753 after correction.
The Ratio of minimum to maximum transmission is 0.3884.
The \l/2 correction factor is Not present.
;
_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    1.246
_exptl_crystal_description       block
_exptl_crystal_F_000             1132
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.19
_refine_diff_density_max         1.066
_refine_diff_density_min         -1.223
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     980
_refine_ls_number_reflns         10357
_refine_ls_number_restraints     1276
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0820
_refine_ls_R_factor_gt           0.0535
_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^)+(0.0826P)^2^+0.0221P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1322
_refine_ls_wR_factor_ref         0.1520
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7523
_reflns_number_total             10357
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04197f4.cif
_cod_data_source_block           7b
_cod_depositor_comments
'Adding full bibliography for 1573095--1573138.cif.'
_cod_database_code               1573108
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.724
_shelx_estimated_absorpt_t_min   0.701
_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
 C36A-C35 \\sim C36-C35
 with sigma of 0.02
 N2A-C10 \\sim N2-C10 \\sim N2-C11 \\sim N2A-C11A \\sim N2A-C15A \\sim N2-C15
 with sigma of 0.02
 N5-C36 \\sim N5A-C36A \\sim N5-C41 \\sim N5A-C41A \\sim N5-C37 \\sim N5A-C37A
 with sigma of 0.02
 O1-C60 \\sim O1-C60A \\sim O1-C63A \\sim O1-C63
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C10 \\sim N2 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim N2A \\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
C35 \\sim N5 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim
N5A \\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
N6 \\sim 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
N3 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim
C24 \\sim C25 \\sim C26 \\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
O1 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim C60A \\sim C61A \\sim C62A
\\sim C63A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
4. Same fragment restrains
{O1, C60A, C61A, C62A, C63A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O1, C60, C61, C62, C63}
{N6, C43, 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}
{C10, N2A, C11A, C12A, C13A, C14A, C15A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C10, N2, C11, C12, C13, C14, C15}
{N3, C17, 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}
{C35, N5A, C36A, C37A, C38A, C39A, C40A, C41A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C35, N5, C36, C37, C38, C39, C40, C41}
5. Others
 Sof(H35C)=Sof(H35D)=Sof(N5A)=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(1)
 Sof(H35A)=Sof(H35B)=Sof(N5)=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(1)
 Sof(H10C)=Sof(H10D)=Sof(N2A)=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(H10A)=Sof(H10B)=Sof(N2)=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(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(3)
 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(3)
 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(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(C60A)=Sof(H60C)=Sof(H60D)=Sof(C61A)=Sof(H61C)=Sof(H61D)=Sof(C62A)=
 Sof(H62C)=Sof(H62D)=Sof(C63A)=Sof(H63C)=Sof(H63D)=1-FVAR(5)
 Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(C62)=Sof(H62A)=
 Sof(H62B)=Sof(C63)=Sof(H63A)=Sof(H63B)=FVAR(5)
6.a Ternary CH refined with riding coordinates:
 C21(H21), C23(H23), C25(H25), 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:
 C60(H60A,H60B), C61(H61A,H61B), C62(H62A,H62B), C63(H63A,H63B), C18(H18A,
 H18B), C19(H19A,H19B), C20(H20A,H20B), C22(H22A,H22B), C24(H24A,H24B),
 C26(H26A,H26B), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B), C48(H48A,H48B),
  C50(H50A,H50B), C52(H52A,H52B), C9(H9A,H9B), C10(H10A,H10B), C10(H10C,H10D),
 C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B),
  C35(H35A,H35B), C35(H35C,H35D), C36(H36A,H36B), C37(H37A,H37B), C38(H38A,
 H38B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C60A(H60C,H60D),
 C61A(H61C,H61D), C62A(H62C,H62D), C63A(H63C,H63D), 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), C18A(H18C,H18D), C19A(H19C,H19D), C20A(H20C,H20D), C22A(H22C,H22D),
 C24A(H24C,H24D), C26A(H26C,H26D), 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), C42(H42), C54(H54), C55(H55), C56(H56)
6.d Idealised Me refined as rotating group:
 C58(H58A,H58B,H58C), C59(H59A,H59B,H59C)
;
_shelx_res_checksum              48844
_shelx_hkl_checksum              4225
_olex2_submission_special_instructions 'No special instructions were received'