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_1573107
_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         '2(C64 H83 N8 Y)'
_chemical_formula_sum            'C128 H166 N16 Y2'
_chemical_formula_weight         2106.58
_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                71.129(2)
_cell_angle_beta                 81.630(2)
_cell_angle_gamma                89.722(2)
_cell_formula_units_Z            2
_cell_length_a                   13.6160(16)
_cell_length_b                   18.253(2)
_cell_length_c                   25.838(3)
_cell_measurement_reflns_used    9931
_cell_measurement_temperature    300
_cell_measurement_theta_max      22.41
_cell_measurement_theta_min      2.23
_cell_volume                     6005.6(12)
_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 0.999
_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  0.0823
_diffrn_reflns_av_unetI/netI     0.1167
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            58706
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.180
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.015
_exptl_absorpt_correction_T_max  0.814
_exptl_absorpt_correction_T_min  0.418
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.165
_exptl_crystal_description       block
_exptl_crystal_F_000             2248
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.19
_refine_diff_density_max         1.332
_refine_diff_density_min         -0.471
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1479
_refine_ls_number_reflns         21140
_refine_ls_number_restraints     1201
_refine_ls_restrained_S_all      1.008
_refine_ls_R_factor_all          0.1901
_refine_ls_R_factor_gt           0.0811
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1344P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2042
_refine_ls_wR_factor_ref         0.2621
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9375
_reflns_number_total             21140
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04197f4.cif
_cod_data_source_block           5d
_cod_depositor_comments
'Adding full bibliography for 1573095--1573138.cif.'
_cod_original_cell_volume        6005.5(12)
_cod_database_code               1573107
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.830
_shelx_estimated_absorpt_t_min   0.815
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N16-C128 = N16A-C1E = N8-C64 = N8A-C64A
 1.47 with sigma of 0.01
 C41A-C40A = C42A-C41A = C43A-C42A = C44A-C43A = C44-C45 = C43-C44 = C42-C43 =
 C41-C42
 1.54 with sigma of 0.01
 N8-C64 = N8A-C64A
 1.47 with sigma of 0.02
 C59-N8 = C59A-N8A
 1.41 with sigma of 0.02
 C44-C42
 2.515 with sigma of 0.02
 C43-C45
 2.515 with sigma of 0.02
 C43-C41
 2.515 with sigma of 0.02
 C59-C64 = C59A-C64A
 2.494 with sigma of 0.04
 Y1-N7 \\sim Y1-N8
 with sigma of 0.02
 Y1-N7A \\sim Y1-N8A
 with sigma of 0.02
 Y2-N15 \\sim Y2-N15A
 with sigma of 0.02
 Y2-N16 \\sim Y2-N16A
 with sigma of 0.02
 C123-C128 \\sim C129-C1E
 with sigma of 0.02
 C44A-C40A \\sim C41-C45
 with sigma of 0.02
 N5-C40A \\sim N5-C45
 with sigma of 0.02
 N5-C41 \\sim N5-C44A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
N7 \\sim C63 \\sim C62 \\sim C61 \\sim C60 \\sim C59 \\sim N8 \\sim C64 \\sim
N7A \\sim C63A \\sim C62A \\sim C61A \\sim C60A \\sim C59A \\sim N8A \\sim
C64A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
N15 \\sim C123 \\sim C124 \\sim C125 \\sim C126 \\sim C127 \\sim N16 \\sim C128
\\sim N15A \\sim C129 \\sim C1A \\sim C1B \\sim C1C \\sim C1D \\sim N16A \\sim
C1E: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
N5 \\sim C39 \\sim C40 \\sim C45 \\sim C44 \\sim C43 \\sim C42 \\sim C40A \\sim
C41A \\sim C42A \\sim C43A \\sim C44A \\sim C41: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
Uanis(N7) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C61)
\\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(N8) \\sim Ueq,
Uanis(C64) \\sim Ueq, Uanis(N7A) \\sim Ueq, Uanis(C63A) \\sim Ueq, Uanis(C62A)
\\sim Ueq, Uanis(C61A) \\sim Ueq, Uanis(C60A) \\sim Ueq, Uanis(C59A) \\sim Ueq,
Uanis(N8A) \\sim Ueq, Uanis(C64A) \\sim Ueq, Uanis(N15) \\sim Ueq, Uanis(C123)
\\sim Ueq, Uanis(C124) \\sim Ueq, Uanis(C125) \\sim Ueq, Uanis(C126) \\sim Ueq,
Uanis(C127) \\sim Ueq, Uanis(N16) \\sim Ueq, Uanis(C128) \\sim Ueq, Uanis(N15A)
\\sim Ueq, Uanis(C129) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C1B) \\sim Ueq,
Uanis(C1C) \\sim Ueq, Uanis(C1D) \\sim Ueq, Uanis(N16A) \\sim Ueq, Uanis(C1E)
\\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
4. Rigid body (RIGU) restrains
 Y1, N7, C63, C62, C61, C60, C59, N8, C64
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 Y1, N7A, C63A, C62A, C61A, C60A, C59A, N8A, C64A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 N15, C123, C124, C125, C126, C127, N16, C128, Y2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 N15A, C129, C1A, C1B, C1C, C1D, N16A, C1E, Y2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C43A, C41A, C40A, C44A, C42A, N4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C41, C43, C44, N5, C42, C45, C40, C39, N4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
5. Others
 Sof(N15A)=Sof(C129)=Sof(C1A)=Sof(H1AA)=Sof(C1B)=Sof(H1BA)=Sof(C1C)=Sof(H1C)=
 Sof(C1D)=Sof(H1D)=Sof(N16A)=Sof(C1E)=Sof(H1EA)=Sof(H1EB)=Sof(H1EC)=1-FVAR(1)
 Sof(N15)=Sof(C123)=Sof(C124)=Sof(H124)=Sof(C125)=Sof(H125)=Sof(C126)=
 Sof(H126)=Sof(C127)=Sof(H127)=Sof(N16)=Sof(C128)=Sof(H12I)=Sof(H12J)=Sof(H12K)=
 FVAR(1)
 Sof(N7A)=Sof(C63A)=Sof(H63A)=Sof(C62A)=Sof(H62A)=Sof(C61A)=Sof(H61A)=
 Sof(C60A)=Sof(H60A)=Sof(C59A)=Sof(N8A)=Sof(C64A)=Sof(H64D)=Sof(H64E)=Sof(H64F)=
 1-FVAR(2)
 Sof(N7)=Sof(C63)=Sof(H63)=Sof(C62)=Sof(H62)=Sof(C61)=Sof(H61)=Sof(C60)=
 Sof(H60)=Sof(C59)=Sof(N8)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=FVAR(2)
 Sof(C40A)=Sof(H40C)=Sof(H40D)=Sof(C41A)=Sof(H41C)=Sof(H41D)=Sof(C42A)=
 Sof(H42C)=Sof(H42D)=Sof(C43A)=Sof(H43C)=Sof(H43D)=Sof(C44A)=Sof(H44C)=
 Sof(H44D)=1-FVAR(3)
 Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(C43)=Sof(H43A)=
 Sof(H43B)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C41)=Sof(H41A)=Sof(H41B)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C24(H24), C27(H27), C53(H53), C56(H56), C88(H88), C91(H91), C117(H117),
 C120(H120)
6.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C16(H16A,H16B), C15(H15A,H15B), C14(H14A,
 H14B), C13(H13A,H13B), C12(H12A,H12B), C1(H1A,H1B), C39(H39A,H39B), C40(H40A,
 H40B), C45(H45A,H45B), C44(H44A,H44B), C43(H43A,H43B), C42(H42A,H42B),
 C41(H41A,H41B), C30(H30A,H30B), C73(H73A,H73B), C74(H74A,H74B), C75(H75A,H75B),
  C76(H76A,H76B), C77(H77A,H77B), C78(H78A,H78B), C79(H79A,H79B), C80(H80A,
 H80B), C102(H10C,H10D), C103(H10E,H10F), C104(H10G,H10H), C105(H10I,H10J),
 C106(H10K,H10L), C107(H10M,H10N), C108(H10O,H10P), C109(H10Q,H10R), C40A(H40C,
 H40D), C41A(H41C,H41D), C42A(H42C,H42D), C43A(H43C,H43D), C44A(H44C,H44D)
6.c Aromatic/amide H refined with riding coordinates:
 C63(H63), C62(H62), C61(H61), C60(H60), C5(H5), C6(H6), C7(H7), C8(H8),
 C17(H17), C20(H20), C21(H21), C22(H22), C34(H34), C35(H35), C36(H36), C37(H37),
  C46(H46), C49(H49), C50(H50), C51(H51), C124(H124), C125(H125), C126(H126),
 C127(H127), C68(H68), C69(H69), C70(H70), C71(H71), C81(H81), C84(H84),
 C85(H85), C86(H86), C97(H97), C98(H98), C99(H99), C100(H100), C110(H110),
 C113(H113), C114(H114), C115(H115), C1A(H1AA), C1B(H1BA), C1C(H1C), C1D(H1D),
 C63A(H63A), C62A(H62A), C61A(H61A), C60A(H60A)
6.d Fitted hexagon refined as free rotating group:
 N7(C63,C62,C61,C60,C59), N15(C123,C124,C125,C126,C127), N15A(C129,C1A,C1B,C1C,
 C1D), N7A(C63A,C62A,C61A,C60A,C59A)
6.e Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C57(H57A,H57B,H57C), C58(H58A,
 H58B,H58C), C64(H64A,H64B,H64C), C89(H89A,H89B,H89C), C90(H90A,H90B,H90C),
 C92(H92A,H92B,H92C), C93(H93A,H93B,H93C), C118(H11C,H11D,H11E), C119(H11F,H11G,
 H11H), C121(H12C,H12D,H12E), C122(H12F,H12G,H12H), C128(H12I,H12J,H12K),
 C1E(H1EA,H1EB,H1EC), C64A(H64D,H64E,H64F)
;
_shelx_res_checksum              68210
_shelx_hkl_checksum              96077
_olex2_submission_special_instructions 'No special instructions were received'