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_1573136
_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 H87 Er N6 O Si, 0.5(C6 H14)'
_chemical_formula_sum            'C63 H94 Er N6 O Si'
_chemical_formula_weight         1146.79
_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                103.08(4)
_cell_angle_beta                 94.75(4)
_cell_angle_gamma                94.70(3)
_cell_formula_units_Z            2
_cell_length_a                   10.554(9)
_cell_length_b                   12.716(12)
_cell_length_c                   23.25(2)
_cell_measurement_reflns_used    9682
_cell_measurement_temperature    300
_cell_measurement_theta_max      27.52
_cell_measurement_theta_min      2.87
_cell_volume                     3013(5)
_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 0.992
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71076
_diffrn_reflns_av_R_equivalents  0.1155
_diffrn_reflns_av_unetI/netI     0.0595
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            95245
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.885
_exptl_absorpt_coefficient_mu    1.456
_exptl_absorpt_correction_T_max  0.770
_exptl_absorpt_correction_T_min  0.740
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS 2014/5'
_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    1.264
_exptl_crystal_description       block
_exptl_crystal_F_000             1208
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.19
_refine_diff_density_max         1.587
_refine_diff_density_min         -1.591
_refine_diff_density_rms         0.106
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.184
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     951
_refine_ls_number_reflns         10554
_refine_ls_number_restraints     1214
_refine_ls_restrained_S_all      1.153
_refine_ls_R_factor_all          0.1006
_refine_ls_R_factor_gt           0.0774
_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^)+(0.0410P)^2^+16.4104P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1476
_refine_ls_wR_factor_ref         0.1589
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8625
_reflns_number_total             10554
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04197f3.cif
_cod_data_source_block           3b
_cod_depositor_comments
'Adding full bibliography for 1573095--1573138.cif.'
_cod_database_code               1573136
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.769
_shelx_estimated_absorpt_t_min   0.740
_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
 C1A-C1B = C1B-C1C = C1C-C1D = C1D-C1E = C1E-C1F
 1.52 with sigma of 0.02
 C1A-C1C = C1D-C1F
 2.53 with sigma of 0.04
 C1B-C1D = C1C-C1E
 2.54 with sigma of 0.04
 O1-C53A \\sim O1-C53 \\sim O1-C56A \\sim O1-C56
 with sigma of 0.02
 N4-C35 \\sim N4-C35A
 with sigma of 0.02
 C45-C48 \\sim C45-C50 \\sim C48-C50
 with sigma of 0.04
 C1A-C1B \\sim C1B-C1C \\sim C1C-C1D \\sim C1D-C1E \\sim C1E-C1F
 with sigma of 0.02
 C36A-C35A \\sim C36-C35
 with sigma of 0.02
 C1A-C1C \\sim C1C-C1E \\sim C1B-C1D \\sim C1D-C1F
 with sigma of 0.04
 C49-C45 \\sim C49-C48 \\sim C49-C50
 with sigma of 0.02
 N5-C36A \\sim N5-C36 \\sim N5-C41 \\sim N5-C41A \\sim N5-C37A \\sim N5-C37
 with sigma of 0.02
 C41-C40 \\sim C41A-C40A \\sim C40A-C39A \\sim C40-C39 \\sim C39-C38 \\sim
C39A-C38A \\sim C38A-C37A ~
 C38-C37
 with sigma of 0.02
 Er1-C57 \\sim Er1-C57A
 with sigma of 0.02
 Si1-C57A \\sim Si1-C57 \\sim Si1-C60A \\sim Si1-C60 \\sim Si1-C58 \\sim
Si1-C58A \\sim Si1-C59 \\sim Si1-
 C59A
 with sigma of 0.02
 N2-C11 \\sim N2-C11A \\sim N2-C15A \\sim N2-C15
 with sigma of 0.02
 C12-C11 \\sim C12A-C11A \\sim C13-C12 \\sim C13A-C12A \\sim C14-C13 \\sim
C14A-C13A \\sim C15A-C14A ~
 C15-C14
 with sigma of 0.02
 N6-C43 \\sim N6-C43A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C1A \\sim C1B \\sim C1C \\sim C1D \\sim C1E \\sim C1F: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
O1 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C53A \\sim C54A \\sim C55A
\\sim C56A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
N4 \\sim N5 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim
C41 \\sim C35A \\sim C36A \\sim C37A \\sim C38A \\sim C39A \\sim C40A \\sim
C41A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
Si1 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C57A \\sim C58A \\sim C59A
\\sim C60A: 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
C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim
C51 \\sim C52 \\sim C43A \\sim C44A \\sim C45A \\sim C46A \\sim C47A \\sim C48A
\\sim C49A \\sim C50A \\sim C51A \\sim C52A \\sim N6: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 C1A, C1B, C1C, C1D, C1E, C1F
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{Er1, Si1, C57A, C58A, C59A, C60A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{Er1, Si1, C57, C58, C59, C60}
{N2, C11A, C12A, C13A, C14A, C15A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N2, C11, C12, C13, C14, C15}
{N4, N5, C35A, C36A, C37A, C38A, C39A, C40A, C41A} sigma for 1-2: 0.02, 1-3:
0.04
as in
{N4, N5, C35, C36, C37, C38, C39, C40, C41}
{O1, C53A, C54A, C55A, C56A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O1, C53, C54, C55, C56}
{N6, C43A, C44A, C45A, C46A, C47A, C48A, C49A, C50A, C51A, C52A} sigma for 1-2:
0.02, 1-3: 0.04
as in
{N6, C43, C44, C45, C46, C47, C48, C49, C50, C51, C52}
6. Others
 Sof(C53A)=Sof(H53C)=Sof(H53D)=Sof(C54A)=Sof(H54C)=Sof(H54D)=Sof(C55A)=
 Sof(H55C)=Sof(H55D)=Sof(C56A)=Sof(H56C)=Sof(H56D)=1-FVAR(1)
 Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(C55)=Sof(H55A)=
 Sof(H55B)=Sof(C56)=Sof(H56A)=Sof(H56B)=FVAR(1)
 Sof(C35A)=Sof(H35C)=Sof(H35D)=Sof(C36A)=Sof(H36C)=Sof(H36D)=Sof(C37A)=
 Sof(H37C)=Sof(H37D)=Sof(C38A)=Sof(H38C)=Sof(H38D)=Sof(C39A)=Sof(H39C)=
 Sof(H39D)=Sof(C40A)=Sof(H40C)=Sof(H40D)=Sof(C41A)=Sof(H41C)=Sof(H41D)=1-FVAR(2)
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(C37)=Sof(H37A)=
 Sof(H37B)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(C40)=
 Sof(H40A)=Sof(H40B)=Sof(C41)=Sof(H41A)=Sof(H41B)=FVAR(2)
 Sof(C57A)=Sof(H57C)=Sof(H57D)=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(C57)=Sof(H57A)=Sof(H57B)=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)
 Sof(C43A)=Sof(C44A)=Sof(H44C)=Sof(H44D)=Sof(C45A)=Sof(H45C)=Sof(H45D)=
 Sof(C46A)=Sof(H46C)=Sof(H46D)=Sof(C47A)=Sof(H47A)=Sof(C48A)=Sof(H48C)=
 Sof(H48D)=Sof(C49A)=Sof(H49A)=Sof(C50A)=Sof(H50C)=Sof(H50D)=Sof(C51A)=
 Sof(H51A)=Sof(C52A)=Sof(H52C)=Sof(H52D)=1-FVAR(4)
 Sof(C43)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(C46)=
 Sof(H46A)=Sof(H46B)=Sof(C47)=Sof(H47)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(C49)=
 Sof(H49)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(C51)=Sof(H51)=Sof(C52)=Sof(H52A)=
 Sof(H52B)=FVAR(4)
 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(5)
 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(5)
 Fixed Sof: C1A(0.5) H1AA(0.5) H1AB(0.5) H1AC(0.5) C1B(0.5) H1BA(0.5)
 H1BB(0.5) C1C(0.5) H1CA(0.5) H1CB(0.5) C1D(0.5) H1DA(0.5) H1DB(0.5) C1E(0.5)
 H1EA(0.5) H1EB(0.5) C1F(0.5) H1FA(0.5) H1FB(0.5) H1FC(0.5)
 Fixed Y: C35A(0.484369)
7.a Riding coordinates:
 C1F(H1FA,H1FB,H1FC)
7.b Ternary CH refined with riding coordinates:
 C47(H47), C49(H49), C51(H51), C21(H21), C23(H23), C25(H25), C47A(H47A),
 C49A(H49A), C51A(H51A)
7.c Secondary CH2 refined with riding coordinates:
 C57(H57A,H57B), C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B), C56(H56A,
 H56B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B),
 C15(H15A,H15B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B), C38(H38A,H38B),
  C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C44(H44A,H44B), C45(H45A,
 H45B), C46(H46A,H46B), C48(H48A,H48B), C50(H50A,H50B), C52(H52A,H52B), C9(H9A,
 H9B), C10(H10A,H10B), C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B), C22(H22A,
 H22B), C24(H24A,H24B), C26(H26A,H26B), C44A(H44C,H44D), C45A(H45C,H45D),
 C46A(H46C,H46D), C48A(H48C,H48D), C50A(H50C,H50D), C52A(H52C,H52D), C11A(H11C,
 H11D), C12A(H12C,H12D), C13A(H13C,H13D), C14A(H14C,H14D), C15A(H15C,H15D),
 C35A(H35C,H35D), C36A(H36C,H36D), C37A(H37C,H37D), C38A(H38C,H38D), C39A(H39C,
 H39D), C40A(H40C,H40D), C41A(H41C,H41D), C53A(H53C,H53D), C54A(H54C,H54D),
 C55A(H55C,H55D), C56A(H56C,H56D), C57A(H57C,H57D), C1B(H1BA,H1BB), C1C(H1CA,
 H1CB), C1D(H1DA,H1DB), C1E(H1EA,H1EB)
7.d Me refined with riding coordinates:
 C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C58A(H58D,H58E,
 H58F), C59A(H59D,H59E,H59F), C60A(H60D,H60E,H60F)
7.e Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C16(H16), C30(H30), C31(H31), C32(H32),
 C33(H33), C42(H42)
7.f Idealised Me refined as rotating group:
 C1A(H1AA,H1AB,H1AC)
;
_shelx_res_checksum              65201
_shelx_hkl_checksum              92614
_olex2_submission_special_instructions 'No special instructions were received'