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_1573125
_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         'C44 H74 Er N3 O2 Si2'
_chemical_formula_sum            'C44 H74 Er N3 O2 Si2'
_chemical_formula_weight         900.50
_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   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-11-03
_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                 113.507(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.905(4)
_cell_length_b                   39.957(11)
_cell_length_c                   10.506(3)
_cell_measurement_reflns_used    6632
_cell_measurement_temperature    300.00
_cell_measurement_theta_max      22.014
_cell_measurement_theta_min      2.175
_cell_volume                     4968(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'Bruker D8 Venture diffractometer'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      293.15
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1263
_diffrn_reflns_av_unetI/netI     0.1372
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       51
_diffrn_reflns_limit_k_min       -49
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            42868
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.492
_diffrn_reflns_theta_min         1.795
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.771
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.4489
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1140 before and 0.0518 after correction.
The Ratio of minimum to maximum transmission is 0.6021.
The \l/2 correction factor is 0.00150.
;
_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    1.204
_exptl_crystal_description       block
_exptl_crystal_F_000             1884
_exptl_crystal_recrystallization_method
'The crystals were growth by means of evaporation of a mixture of n-hexane and toluene at RT.'
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.19
_refine_diff_density_max         1.254
_refine_diff_density_min         -1.619
_refine_diff_density_rms         0.117
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     791
_refine_ls_number_reflns         11343
_refine_ls_number_restraints     1176
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.1819
_refine_ls_R_factor_gt           0.0829
_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^)+(0.0261P)^2^+22.3637P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1247
_refine_ls_wR_factor_ref         0.1528
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5938
_reflns_number_total             11343
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04197f2.cif
_cod_data_source_block           1c
_cod_depositor_comments
'Adding full bibliography for 1573095--1573138.cif.'
_cod_original_cell_volume        4968(2)
_cod_database_code               1573125
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.730
_shelx_estimated_absorpt_t_min   0.707
_exptl_crystal_mounting_method
'Crystals were removed from the crystallisation vial and immediately coated with polybutenes oil (CAS: 9003-29-6) on a glass slide. A suitable single crystal coated with polybutenes oil as less as possible was sealed in capillary tube filled with argon. The capillary tube with single crystal was mounted on copper pin with solid paraffin.'
_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. Shared sites
{C36, C36A}
3. Restrained planarity
 C21A, C17A, C18A, C20A, C22A, C19A, N3, C26A, C23A
 with sigma of 0.1
 C22, C18, C19, C21, C17, C20, N3, C23, C26
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Si1 \\sim C40A \\sim C23A \\sim N2 \\sim C14A \\sim C10 \\sim C31A \\sim C11
\\sim C10A \\sim C12 \\sim C19A \\sim C13 \\sim C27A \\sim C14 \\sim C35A \\sim
C15 \\sim Si1A \\sim C17 \\sim C12A \\sim C18 \\sim C17A \\sim C19 \\sim C21A
\\sim C20 \\sim C25A \\sim C21 \\sim C29A \\sim C22 \\sim C33A \\sim C23 \\sim
C38A \\sim C24 \\sim C43A \\sim C25 \\sim N2A \\sim C26 \\sim C11A \\sim C27
\\sim C13A \\sim C28 \\sim C15A \\sim C29 \\sim C18A \\sim C30 \\sim C20A \\sim
C31 \\sim C22A \\sim C32 \\sim C24A \\sim C33 \\sim C26A \\sim C34 \\sim C28A
\\sim C35 \\sim C30A \\sim C36 \\sim C32A \\sim C38 \\sim C34A \\sim C39 \\sim
C36A \\sim C40 \\sim C39A \\sim C42 \\sim C42A \\sim C43 \\sim C44A \\sim C44:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C30) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C29A)
\\sim Ueq, Uanis(C30A) \\sim Ueq, Uanis(C31A) \\sim Ueq, Uanis(C29) \\sim Ueq,
Uanis(C32A) \\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C11)
\\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq,
Uanis(C15) \\sim Ueq, Uanis(N2A) \\sim Ueq, Uanis(C10A) \\sim Ueq, Uanis(C11A)
\\sim Ueq, Uanis(C12A) \\sim Ueq, Uanis(C13A) \\sim Ueq, Uanis(C14A) \\sim Ueq,
Uanis(C15A) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C44)
\\sim Ueq, Uanis(C42A) \\sim Ueq, Uanis(C43A) \\sim Ueq, Uanis(C44A) \\sim Ueq,
Uanis(Si1) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C40)
\\sim Ueq, Uanis(Si1A) \\sim Ueq, Uanis(C38A) \\sim Ueq, Uanis(C39A) \\sim Ueq,
Uanis(C40A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C36) = Uanis(C36A)
5. Same fragment restrains
{Si2, C42A, C43A, C44A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{Si2, C42, C43, C44}
{C9, N2A, C10A, C11A, C12A, C13A, C14A, C15A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C9, N2, C10, C11, C12, C13, C14, C15}
{C37, Si1A, C38A, C39A, C40A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C37, Si1, C38, C39, C40}
{O1, C29A, C30A, C31A, C32A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O1, C29, C30, C31, C32}
{O2, C33A, C34A, C35A, C36A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O2, C33, C34, C35, C36}
{N3, C17A, C18A, C19A, C20A, C21A, C22A, C23A, C24A, C25A, C26A, C27A, C28A}
sigma for 1-2: 0.02, 1-3: 0.04
as in
{N3, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28}
6. Others
 Sof(H9BC)=Sof(H9BD)=Sof(N2A)=Sof(C10A)=Sof(H10C)=Sof(H10D)=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(H9AA)=Sof(H9AB)=Sof(N2)=Sof(C10)=Sof(H10A)=Sof(H10B)=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(C33A)=Sof(H33C)=Sof(H33D)=Sof(C34A)=Sof(H34C)=Sof(H34D)=Sof(C35A)=
 Sof(H35C)=Sof(H35D)=Sof(C36A)=Sof(H36C)=Sof(H36D)=1-FVAR(2)
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(C35)=Sof(H35A)=
 Sof(H35B)=Sof(C36)=Sof(H36A)=Sof(H36B)=FVAR(2)
 Sof(C29A)=Sof(H29C)=Sof(H29D)=Sof(C30A)=Sof(H30C)=Sof(H30D)=Sof(C31A)=
 Sof(H31C)=Sof(H31D)=Sof(C32A)=Sof(H32C)=Sof(H32D)=1-FVAR(3)
 Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(C31)=Sof(H31A)=
 Sof(H31B)=Sof(C32)=Sof(H32A)=Sof(H32B)=FVAR(3)
 Sof(C17A)=Sof(C18A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(H20A)=Sof(C21A)=
 Sof(H21A)=Sof(C22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24D)=Sof(H24E)=
 Sof(H24F)=Sof(C25A)=Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(C26A)=Sof(H26A)=
 Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=Sof(C28A)=Sof(H28D)=Sof(H28E)=
 Sof(H28F)=1-FVAR(4)
 Sof(C17)=Sof(C18)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21)=
 Sof(C22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25)=
 Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27A)=Sof(H27B)=
 Sof(H27C)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=FVAR(4)
 Sof(H37C)=Sof(H37D)=Sof(Si1A)=Sof(C38A)=Sof(H38D)=Sof(H38E)=Sof(H38F)=
 Sof(C39A)=Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C40A)=Sof(H40D)=Sof(H40E)=
 Sof(H40F)=1-FVAR(5)
 Sof(H37A)=Sof(H37B)=Sof(Si1)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C39)=
 Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=FVAR(5)
 Sof(C42A)=Sof(H42D)=Sof(H42E)=Sof(H42F)=Sof(C43A)=Sof(H43D)=Sof(H43E)=
 Sof(H43F)=Sof(C44A)=Sof(H44D)=Sof(H44E)=Sof(H44F)=1-FVAR(6)
 Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=
 Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=FVAR(6)
7.a Riding coordinates:
 C40(H40A,H40B,H40C)
7.b Ternary CH refined with riding coordinates:
 C23(H23), C26(H26), C23A(H23A), C26A(H26A)
7.c Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B), C33(H33A,
 H33B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C9(H9AA,H9AB), C9(H9BC,
 H9BD), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B),
 C14(H14A,H14B), C15(H15A,H15B), C37(H37C,H37D), C37(H37A,H37B), C41(H41A,H41B),
  C10A(H10C,H10D), C11A(H11C,H11D), C12A(H12C,H12D), C13A(H13C,H13D), C14A(H14C,
 H14D), C15A(H15C,H15D), C29A(H29C,H29D), C30A(H30C,H30D), C31A(H31C,H31D),
 C32A(H32C,H32D), C33A(H33C,H33D), C34A(H34C,H34D), C35A(H35C,H35D), C36A(H36C,
 H36D)
7.d Aromatic/amide H refined with riding coordinates:
 C19(H19), C20(H20), C21(H21), C4(H4), C5(H5), C6(H6), C7(H7), C16(H16),
 C19A(H19A), C20A(H20A), C21A(H21A)
7.e Idealised Me refined as rotating group:
 C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C24(H24A,H24B,
 H24C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C38(H38A,
 H38B,H38C), C39(H39A,H39B,H39C), C38A(H38D,H38E,H38F), C39A(H39D,H39E,H39F),
 C40A(H40D,H40E,H40F), C24A(H24D,H24E,H24F), C25A(H25D,H25E,H25F), C27A(H27D,
 H27E,H27F), C28A(H28D,H28E,H28F), C42A(H42D,H42E,H42F), C43A(H43D,H43E,H43F),
 C44A(H44D,H44E,H44F)
;
_shelx_res_checksum              61734
_shelx_hkl_checksum              65737
_olex2_submission_special_instructions 'No special instructions were received'