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_1573102
_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 H83 N8 Yb'
_chemical_formula_sum            'C64 H83 N8 Yb'
_chemical_formula_weight         1137.42
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 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                90
_cell_angle_beta                 91.093(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.140(4)
_cell_length_b                   13.516(2)
_cell_length_c                   18.231(3)
_cell_measurement_reflns_used    9358
_cell_measurement_temperature    300
_cell_measurement_theta_max      21.04
_cell_measurement_theta_min      2.23
_cell_volume                     5947.3(16)
_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 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  0.1097
_diffrn_reflns_av_unetI/netI     0.0793
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            56385
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         1.727
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.617
_exptl_absorpt_correction_T_max  0.814
_exptl_absorpt_correction_T_min  0.418
_exptl_absorpt_correction_type   none
_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    1.270
_exptl_crystal_description       block
_exptl_crystal_F_000             2372
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.19
_refine_diff_density_max         1.183
_refine_diff_density_min         -0.628
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     715
_refine_ls_number_reflns         10453
_refine_ls_number_restraints     669
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.1310
_refine_ls_R_factor_gt           0.0640
_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^)+(0.0811P)^2^+8.9153P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1489
_refine_ls_wR_factor_ref         0.1803
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5827
_reflns_number_total             10453
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04197f4.cif
_cod_data_source_block           5b
_cod_depositor_comments
'Adding full bibliography for 1573095--1573138.cif.'
_cod_original_cell_volume        5947.3(18)
_cod_database_code               1573102
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.749
_shelx_estimated_absorpt_t_min   0.728
_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
 N8-C63
 1.4 with sigma of 0.01
 N8-C64 = N8A-C64A
 1.47 with sigma of 0.01
 C63-N8 = C63A-N8A
 1.4 with sigma of 0.01
 C63-C64 = C63A-C64A
 2.486 with sigma of 0.02
 N7-C62 \\sim N8-C62
 with sigma of 0.02
 Yb1-N8 \\sim Yb1-N8A
 with sigma of 0.02
 Yb1-N7A \\sim Yb1-N7
 with sigma of 0.02
 N8A-N7A \\sim N8A-C62A
 with sigma of 0.02
3. Restrained planarity
 N7, C63, C62, C61, C60, C59, N8
 with sigma of 0.1
 C60A, C62A, C63A, C59A, C61A, N7A, N8A
 with sigma of 0.1
4. 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
Uanis(C47) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C56)
\\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C54) \\sim Ueq,
Uanis(C51) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C58)
\\sim Ueq, Uanis(C57) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
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: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(N5) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C41)
\\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C43) \\sim Ueq,
Uanis(C44) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C18) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C26)
\\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C23) \\sim Ueq,
Uanis(C21) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C28)
\\sim Ueq, Uanis(C29) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
5. Rigid body (RIGU) restrains
 N7A, C60A, N8A, C63A, C59A, C62A, C64A, C61A, Yb1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 N7, C60, N8, C63, C59, C62, C64, C61, Yb1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
6. Others
 Sof(N7A)=Sof(C63A)=Sof(C62A)=Sof(H62A)=Sof(C61A)=Sof(H61A)=Sof(C60A)=
 Sof(H60A)=Sof(C59A)=Sof(H59A)=Sof(N8A)=Sof(C64A)=Sof(H64D)=Sof(H64E)=Sof(H64F)=
 1-FVAR(1)
 Sof(N7)=Sof(C63)=Sof(C62)=Sof(H62)=Sof(C61)=Sof(H61)=Sof(C60)=Sof(H60)=
 Sof(C59)=Sof(H59)=Sof(N8)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=FVAR(1)
 Fixed X: C64A(0.81289)
7.a Ternary CH refined with riding coordinates:
 C24(H24), C56(H56), C53(H53), C27(H27)
7.b Secondary CH2 refined with riding coordinates:
 C39(H39A,H39B), C40(H40A,H40B), C30(H30A,H30B), C10(H10A,H10B), C1(H1A,H1B),
 C11(H11A,H11B), C41(H41A,H41B), C16(H16A,H16B), C12(H12A,H12B), C15(H15A,H15B),
  C13(H13A,H13B), C45(H45A,H45B), C42(H42A,H42B), C14(H14A,H14B), C43(H43A,
 H43B), C44(H44A,H44B)
7.c Me refined with riding coordinates:
 C64A(H64D,H64E,H64F)
7.d Aromatic/amide H refined with riding coordinates:
 C46(H46), C17(H17), C5(H5), C34(H34), C37(H37), C8(H8), C6(H6), C7(H7),
 C49(H49), C50(H50), C36(H36), C51(H51), C22(H22), C20(H20), C35(H35), C21(H21),
  C62(H62), C61(H61), C60(H60), C59(H59), C62A(H62A), C61A(H61A), C60A(H60A),
 C59A(H59A)
7.e Fitted hexagon refined as free rotating group:
 N7(C63,C62,C61,C60,C59), N7A(C63A,C62A,C61A,C60A,C59A)
7.f Idealised Me refined as rotating group:
 C54(H54A,H54B,H54C), C26(H26A,H26B,H26C), C55(H55A,H55B,H55C), C58(H58A,H58B,
 H58C), C25(H25A,H25B,H25C), C57(H57A,H57B,H57C), C28(H28A,H28B,H28C), C29(H29A,
 H29B,H29C), C64(H64A,H64B,H64C)
;
_shelx_res_checksum              86732
_shelx_hkl_checksum              10104
_olex2_submission_special_instructions 'No special instructions were received'