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_1573129
_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 H83 Lu N6 Si, 0.5(C7 H8)'
_chemical_formula_sum            'C63.5 H87 Lu N6 Si'
_chemical_formula_weight         1137.45
_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                73.0950(10)
_cell_angle_beta                 84.8970(10)
_cell_angle_gamma                70.2030(10)
_cell_formula_units_Z            2
_cell_length_a                   13.4249(7)
_cell_length_b                   13.4551(7)
_cell_length_c                   18.9550(10)
_cell_measurement_reflns_used    9954
_cell_measurement_temperature    300
_cell_measurement_theta_max      23.25
_cell_measurement_theta_min      2.25
_cell_volume                     3082.2(3)
_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 0.987
_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  0.0494
_diffrn_reflns_av_unetI/netI     0.0713
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            36378
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.502
_diffrn_reflns_theta_min         1.123
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.662
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.4418
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1047 before and 0.0496 after correction. The Ratio of minimum to maximum transmission is 0.5925. The \l/2 correction factor is Not present.'
_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    1.226
_exptl_crystal_description       block
_exptl_crystal_F_000             1190
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.19
_refine_diff_density_max         1.306
_refine_diff_density_min         -0.653
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.992
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     818
_refine_ls_number_reflns         13993
_refine_ls_number_restraints     628
_refine_ls_restrained_S_all      0.999
_refine_ls_R_factor_all          0.0775
_refine_ls_R_factor_gt           0.0490
_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^)+(0.0577P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1023
_refine_ls_wR_factor_ref         0.1120
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10270
_reflns_number_total             13993
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04197f3.cif
_cod_data_source_block           2a
_cod_depositor_comments
'Adding full bibliography for 1573095--1573138.cif.'
_cod_original_formula_sum        'C63.50 H87 Lu N6 Si'
_cod_database_code               1573129
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.743
_shelx_estimated_absorpt_t_min   0.722
_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
 C61-C66 = C61-C62 = C65-C64
 1.39 with sigma of 0.02
 C67-C61
 1.5 with sigma of 0.01
 C66-C65 = C64-C63 = C63-C62
 1.38 with sigma of 0.02
 C67-C66 = C67-C62
 2.52 with sigma of 0.04
 C61-C65
 2.42 with sigma of 0.04
 C61-C63
 2.41 with sigma of 0.04
 C66-C64
 2.39 with sigma of 0.04
 C65-C63 = C64-C62
 2.4 with sigma of 0.04
 Si1-C57 \\sim Si1A-C57
 with sigma of 0.02
 C67-C62 \\sim C67-C66
 with sigma of 0.04
 Si1A-C59A \\sim Si1-C59 \\sim Si1-C60 \\sim Si1A-C60A \\sim Si1-C58 \\sim
Si1A-C58A
 with sigma of 0.02
 Si1-C58 \\sim Si1A-C58A
 with sigma of 0.02
 Si1A-C59A \\sim Si1-C59
 with sigma of 0.02
 Si1A-C60A \\sim Si1-C60
 with sigma of 0.02
 C61-C66 \\sim C66-C65 \\sim C65-C64 \\sim C64-C63 \\sim C63-C62 \\sim C62-C61
 with sigma of 0.02
 C61-C63 \\sim C61-C65 \\sim C62-C64 \\sim C66-C62 \\sim C65-C63 \\sim C66-C64
 with sigma of 0.04
 N2-C15A \\sim N2-C15 \\sim N2-C11A \\sim N2-C11
 with sigma of 0.02
 N5-C39A \\sim N5-C39 \\sim N5-C43A \\sim N5-C43
 with sigma of 0.02
3. Restrained planarity
 C61, C62, C63, C64, C65, C66, C67
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C57 \\sim Si1 \\sim C58 \\sim C60 \\sim Si1A \\sim C58A \\sim C60A \\sim C59
\\sim C59A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67: 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
N5 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim C39A \\sim C40A
\\sim C41A \\sim C42A \\sim C43A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(C67) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C63)
\\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C65) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C61, C62, C63, C64, C65, C66, C67
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
{C57, Si1A, C58A, C59A, C60A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C57, Si1, C58, C59, C60}
{N5, C39A, C40A, C41A, C42A, C43A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N5, C39, C40, C41, C42, C43}
{N2, C11A, C12A, C13A, C14A, C15A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N2, C11, C12, C13, C14, C15}
7. Others
 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(1)
 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(1)
 Sof(C39A)=Sof(H39C)=Sof(H39D)=Sof(C40A)=Sof(H40C)=Sof(H40D)=Sof(C41A)=
 Sof(H41C)=Sof(H41D)=Sof(C42A)=Sof(H42C)=Sof(H42D)=Sof(C43A)=Sof(H43C)=
 Sof(H43D)=1-FVAR(2)
 Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(C41)=Sof(H41A)=
 Sof(H41B)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C43)=Sof(H43A)=Sof(H43B)=FVAR(2)
 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(3)
 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(3)
 Fixed Sof: C61(0.5) C62(0.5) H62(0.5) C63(0.5) H63(0.5) C64(0.5) H64(0.5)
 C65(0.5) H65(0.5) C66(0.5) H66(0.5) C67(0.5) H67A(0.5) H67B(0.5) H67C(0.5)
 Fixed X: C67(0.42342)
8.a Riding coordinates:
 C58A(H58D,H58E,H58F)
8.b Ternary CH refined with riding coordinates:
 C23(H23), C26(H26), C51(H51), C54(H54)
8.c Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,
 H15B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C42(H42A,H42B),
 C43(H43A,H43B), C9(H9A,H9B), C10(H10A,H10B), C37(H37A,H37B), C38(H38A,H38B),
 C57(H57A,H57B), C11A(H11C,H11D), C12A(H12C,H12D), C13A(H13C,H13D), C14A(H14C,
 H14D), C15A(H15C,H15D), C39A(H39C,H39D), C40A(H40C,H40D), C41A(H41C,H41D),
 C42A(H42C,H42D), C43A(H43C,H43D)
8.d Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C16(H16), C19(H19), C20(H20), C21(H21),
 C32(H32), C33(H33), C34(H34), C35(H35), C44(H44), C47(H47), C48(H48), C49(H49),
  C62(H62), C63(H63), C64(H64), C65(H65), C66(H66)
8.e Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C28(H28A,H28B,
 H28C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C55(H55A,H55B,H55C), C56(H56A,
 H56B,H56C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C),
 C59A(H59D,H59E,H59F), C60A(H60D,H60E,H60F), C67(H67A,H67B,H67C)
;
_shelx_res_checksum              87216
_shelx_hkl_checksum              57148
_olex2_submission_special_instructions 'No special instructions were received'