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_1573099
_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 Lu N8)'
_chemical_formula_sum            'C128 H166 Lu2 N16'
_chemical_formula_weight         2278.70
_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   mixed
_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                70.931(5)
_cell_angle_beta                 81.514(5)
_cell_angle_gamma                89.800(5)
_cell_formula_units_Z            2
_cell_length_a                   13.584(5)
_cell_length_b                   18.222(7)
_cell_length_c                   25.760(10)
_cell_measurement_reflns_used    2065
_cell_measurement_temperature    300
_cell_measurement_theta_max      20.58
_cell_measurement_theta_min      2.37
_cell_volume                     5954(4)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Bruker SMART APEX II diffractometer'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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       'three-circle diffractometer'
_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_unetI/netI     0.1262
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            20036
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        24.737
_diffrn_reflns_theta_max         24.737
_diffrn_reflns_theta_min         1.184
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.703
_exptl_absorpt_correction_T_max  0.745068
_exptl_absorpt_correction_T_min  0.410987
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.1105 before and 0.0576 after correction.
 
For component 2:
 wR2(int) was 0.1164 before and 0.0486 after correction.
 The Ratio of minimum to maximum transmission is 0.55.

Final HKLF 4 output contains 56752 reflections, Rint = 0.0815
 (14842 with I > 3sig(I), Rint = 0.0538)
;
_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    1.271
_exptl_crystal_description       block
_exptl_crystal_F_000             2376
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.19
_refine_diff_density_max         1.793
_refine_diff_density_min         -1.606
_refine_diff_density_rms         0.138
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1430
_refine_ls_number_reflns         20036
_refine_ls_number_restraints     1490
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.2217
_refine_ls_R_factor_gt           0.0995
_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^)+(0.1841P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2720
_refine_ls_wR_factor_ref         0.3381
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7938
_reflns_number_total             20036
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04197f4.cif
_cod_data_source_block           5a
_cod_depositor_comments
'Adding full bibliography for 1573095--1573138.cif.'
_cod_database_code               1573099
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.738
_shelx_estimated_absorpt_t_min   0.716
_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
 N2-C12 = N2-C16 = N2-C11 = N5-C40 = N5-C41 = N5-C45 = N13-C104 = N13-C105 =
 N13-C109 = N10-C75 = N10-C80 = N10-C76
 1.48 with sigma of 0.001
 C13-C12 = C14-C13 = C15-C14 = C16-C15 = C42-C41 = C43-C42 = C44-C43 = C45-C44
 = C106-C105 = C107-C106 = C108-C107 = C109-C108 = C77-C76 = C78-C77 = C79-C78 =
  C80-C79
 1.54 with sigma of 0.001
 C23-C22 = C22-C21 = C20-C19 = C21-C20 = C19-C18 = C23-C18 = C52-C47 = C52-C51
 = C51-C50 = C50-C49 = C49-C48 = C48-C47 = C116-C115 = C115-C114 = C114-C113 =
 C113-C112 = C112-C111 = C116-C111 = C87-C82 = C87-C86 = C86-C85 = C85-C84 =
 C84-C83 = C83-C82
 1.4 with sigma of 0.02
 C104-C103 = C11-C10 = C40-C39 = C75-C74
 1.54 with sigma of 0.001
 C122-C120 = C121-C120 = C118-C117 = C119-C117 = C93-C91 = C92-C91 = C89-C88 =
 C90-C88 = C29-C27 = C28-C27 = C25-C24 = C26-C24 = C55-C53 = C54-C53 = C57-C56 =
  C58-C56
 1.54 with sigma of 0.001
 C56-C52 = C53-C48 = C24-C19 = C27-C23 = C91-C87 = C88-C83 = C120-C116 = C117-
 C112
 1.5 with sigma of 0.001
 N16A-C1F \\sim N16-C128
 with sigma of 0.001
 N8A-C64A \\sim N8-C64
 with sigma of 0.001
 N8A-C63A \\sim N8-C63
 with sigma of 0.001
 N7-C59 \\sim N7-C63 \\sim N7A-C63A \\sim N7A-C59A
 with sigma of 0.001
 C60-C59 \\sim C61-C60 \\sim C62-C61 \\sim C63-C62 \\sim C63A-C62A \\sim
C62A-C61A \\sim C61A-C60A ~
 C60A-C59A
 with sigma of 0.001
 N16-C127 \\sim N16A-C1A
 with sigma of 0.001
 N15-C123 \\sim N15-C127 \\sim N15A-C1A \\sim N15A-C1E
 with sigma of 0.001
 C124-C123 \\sim C125-C124 \\sim C126-C125 \\sim C127-C126 \\sim C1A-C1B \\sim
C1B-C1C \\sim C1D-C1C ~
 C1E-C1D
 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
4. Others
 Sof(N8A)=Sof(N7A)=Sof(C63A)=Sof(C62A)=Sof(H62A)=Sof(C61A)=Sof(H61A)=Sof(C60A)=
 Sof(H60A)=Sof(C59A)=Sof(H59A)=Sof(C64A)=Sof(H64D)=Sof(H64E)=Sof(H64F)=1-FVAR(1)
 Sof(N8)=Sof(N7)=Sof(C63)=Sof(C62)=Sof(H62)=Sof(C61)=Sof(H61)=Sof(C60)=
 Sof(H60)=Sof(C59)=Sof(H59)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=FVAR(1)
 Sof(N15A)=Sof(C1A)=Sof(C1B)=Sof(H1B)=Sof(C1C)=Sof(H1C)=Sof(C1D)=Sof(H1D)=
 Sof(C1E)=Sof(H1E)=Sof(N16A)=Sof(C1F)=Sof(H1FA)=Sof(H1FB)=Sof(H1FC)=1-FVAR(2)
 Sof(N15)=Sof(C127)=Sof(C126)=Sof(H126)=Sof(C125)=Sof(H125)=Sof(C124)=
 Sof(H124)=Sof(C123)=Sof(H123)=Sof(N16)=Sof(C128)=Sof(H12G)=Sof(H12H)=Sof(H12I)=
 FVAR(2)
 Fixed X: C1F(0.839419)
 Fixed Z: C64A(0.18456)
5.a Riding coordinates:
 C1F(H1FA,H1FB,H1FC)
5.b Ternary CH refined with riding coordinates:
 C56(H56), C91(H91), C53(H53), C24(H24), C120(H120), C117(H117), C88(H88),
 C27(H27)
5.c Secondary CH2 refined with riding coordinates:
 C75(H75A,H75B), C39(H39A,H39B), C40(H40A,H40B), C74(H74A,H74B), C65(H65A,
 H65B), C10(H10O,H10P), C30(H30A,H30B), C11(H11G,H11H), C45(H45A,H45B),
 C109(H10A,H10B), C12(H12J,H12K), C1(H1A,H1F), C105(H10C,H10D), C94(H94A,H94B),
 C103(H10E,H10F), C16(H16A,H16B), C104(H10G,H10H), C106(H10I,H10J), C76(H76A,
 H76B), C107(H10K,H10L), C77(H77A,H77B), C41(H41A,H41B), C80(H80A,H80B),
 C42(H42A,H42B), C14(H14A,H14B), C43(H43A,H43B), C44(H44A,H44B), C13(H13A,H13B),
  C108(H10M,H10N), C15(H15A,H15B), C78(H78A,H78B), C79(H79A,H79B)
5.d Aromatic/amide H refined with riding coordinates:
 C46(H46), C110(H110), C126(H126), C125(H125), C124(H124), C123(H123),
 C81(H81), C17(H17), C34(H34), C72(H72), C5(H5), C37(H37), C69(H69), C8(H8),
 C98(H98), C84(H84), C51(H51), C62(H62), C61(H61), C60(H60), C59(H59), C36(H36),
  C71(H71), C100(H100), C49(H49), C101(H101), C86(H86), C50(H50), C85(H85),
 C70(H70), C20(H20), C6(H6), C99(H99), C22(H22), C7(H7), C35(H35), C113(H113),
 C21(H21), C115(H115), C114(H114), C62A(H62A), C61A(H61A), C60A(H60A),
 C59A(H59A), C1B(H1B), C1C(H1C), C1D(H1D), C1E(H1E)
5.e Fitted hexagon refined as free rotating group:
 N15(C127,C126,C125,C124,C123), N7(C63,C62,C61,C60,C59), N7A(C63A,C62A,C61A,
 C60A,C59A), N15A(C1A,C1B,C1C,C1D,C1E)
5.f Idealised Me refined as rotating group:
 C55(H55A,H55B,H55C), C89(H89A,H89B,H89C), C93(H93A,H93B,H93C), C57(H57A,H57B,
 H57C), C54(H54A,H54B,H54C), C92(H92A,H92B,H92C), C25(H25A,H25B,H25C),
 C119(H11A,H11B,H11C), C118(H11D,H11E,H11F), C90(H90A,H90B,H90C), C58(H58A,H58B,
 H58C), C29(H29A,H29B,H29C), C121(H12A,H12B,H12C), C122(H12D,H12E,H12F),
 C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C64(H64A,H64B,H64C), C128(H12G,H12H,
 H12I), C64A(H64D,H64E,H64F)
;
_shelx_res_checksum              1004
_shelx_hkl_checksum              143
_olex2_submission_special_instructions 'No special instructions were received'