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_1573112
_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         'C67 H80 Er N7'
_chemical_formula_sum            'C67 H80 Er N7'
_chemical_formula_weight         1150.64
_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   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                82.2660(10)
_cell_angle_beta                 72.4560(10)
_cell_angle_gamma                68.2900(10)
_cell_formula_units_Z            2
_cell_length_a                   13.3096(11)
_cell_length_b                   13.3936(11)
_cell_length_c                   19.2327(16)
_cell_measurement_reflns_used    9782
_cell_measurement_temperature    300
_cell_measurement_theta_max      27.36
_cell_measurement_theta_min      2.22
_cell_volume                     3036.1(4)
_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 0.998
_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  0.0311
_diffrn_reflns_av_unetI/netI     0.0397
_diffrn_reflns_Laue_measured_fraction_full 0.998
_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            35673
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.459
_diffrn_reflns_theta_min         1.111
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.427
_exptl_absorpt_correction_T_max  0.814
_exptl_absorpt_correction_T_min  0.417
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            'clear light black'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.259
_exptl_crystal_description       block
_exptl_crystal_F_000             1198
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.19
_refine_diff_density_max         1.034
_refine_diff_density_min         -0.573
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1035
_refine_ls_number_reflns         13729
_refine_ls_number_restraints     1351
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0400
_refine_ls_R_factor_gt           0.0324
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0420P)^2^+0.9051P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0777
_refine_ls_wR_factor_ref         0.0808
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12004
_reflns_number_total             13729
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04197f4.cif
_cod_data_source_block           10a
_cod_depositor_comments
'Adding full bibliography for 1573095--1573138.cif.'
_cod_database_code               1573112
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.773
_shelx_estimated_absorpt_t_min   0.754
_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. Restrained distances
 C38-C37 \\sim C38A-C37
 with sigma of 0.02
 N5A-C38A \\sim N5-C38 \\sim N5A-C43A \\sim N5A-C39A \\sim N5-C43 \\sim N5-C39
 with sigma of 0.02
 N2-C10 \\sim N2A-C10A \\sim N2-C15 \\sim N2-C11 \\sim N2A-C15A \\sim N2A-C11A
 with sigma of 0.02
 C9-C10 \\sim C9-C10A
 with sigma of 0.02
 C24-C23 \\sim C24A-C23 \\sim C25-C23 \\sim C25A-C23
 with sigma of 0.02
 Er1-C67 \\sim Er1-C67A
 with sigma of 0.02
 Er1-N7A \\sim Er1-N7
 with sigma of 0.02
3. Restrained planarity
 N6, C45, C48, C46, C47, C49, C50, C51, C54
 with sigma of 0.1
 N6, C45, C48, C47, C46A, C49A, C50A, C51A, C54A
 with sigma of 0.1
 N7, Er1, C64, C57, C66, C59, C67, C61, C65, C60, C63, C62, C58
 with sigma of 0.1
 N7A, Er1, C65A, C57A, C63A, C59A, C67A, C61A, C66A, C60A, C64A, C62A, C58A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
N6 \\sim C45 \\sim C48 \\sim C46 \\sim C47 \\sim C49 \\sim C50 \\sim C51 \\sim
C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C46A \\sim C47A \\sim C49A
\\sim C50A \\sim C51A \\sim C52A \\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
C37 \\sim N5 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim
N5A \\sim C38A \\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
C9 \\sim N2 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim
N2A \\sim C10A \\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
C23 \\sim C24 \\sim C25 \\sim C24A \\sim C25A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
N7 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim
C64 \\sim C65 \\sim C66 \\sim C67 \\sim N7A \\sim C57A \\sim C58A \\sim C59A
\\sim C60A \\sim C61A \\sim C62A \\sim C63A \\sim C64A \\sim C65A \\sim C66A
\\sim C67A \\sim Er1: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
5. Same fragment restrains
{Er1, N7A, C57A, C58A, C59A, C60A, C61A, C62A, C63A, C64A, C65A, C66A, C67A}
sigma for 1-2: 0.02, 1-3: 0.04
as in
{Er1, N7, C57, C58, C59, C60, C61, C62, C63, C64, C65, C66, C67}
{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}
{C23, C24A, C25A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C23, C24, C25}
{N6, C45, C48, C46A, C47A, C49A, C50A, C51A, C52A, C53A, C54A, C55A, C56A}
sigma for 1-2: 0.02, 1-3: 0.04
as in
{N6, C45, C48, C46, C47, C49, C50, C51, C52, C53, C54, C55, C56}
{C37, N5A, C38A, C39A, C40A, C41A, C42A, C43A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C37, N5, C38, C39, C40, C41, C42, C43}
6. Others
 Sof(H37C)=Sof(H37D)=Sof(N5A)=Sof(C38A)=Sof(H38C)=Sof(H38D)=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(1)
 Sof(H37A)=Sof(H37B)=Sof(N5)=Sof(C38)=Sof(H38A)=Sof(H38B)=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(1)
 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(2)
 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(2)
 Sof(H23A)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C25A)=Sof(H25D)=
 Sof(H25E)=Sof(H25F)=1-FVAR(3)
 Sof(H23)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25)=Sof(H25A)=Sof(H25B)=
 Sof(H25C)=FVAR(3)
 Sof(H48A)=Sof(C46A)=Sof(C47A)=Sof(H47A)=Sof(C49A)=Sof(H49A)=Sof(C50A)=
 Sof(C51A)=Sof(H51A)=Sof(C52A)=Sof(H52D)=Sof(H52E)=Sof(H52F)=Sof(C53A)=
 Sof(H53D)=Sof(H53E)=Sof(H53F)=Sof(C54A)=Sof(H54A)=Sof(C55A)=Sof(H55D)=
 Sof(H55E)=Sof(H55F)=Sof(C56A)=Sof(H56D)=Sof(H56E)=Sof(H56F)=1-FVAR(4)
 Sof(H48)=Sof(C46)=Sof(C47)=Sof(H47)=Sof(C49)=Sof(H49)=Sof(C50)=Sof(C51)=
 Sof(H51)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(C53)=Sof(H53A)=Sof(H53B)=
 Sof(H53C)=Sof(C54)=Sof(H54)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=Sof(C56)=
 Sof(H56A)=Sof(H56B)=Sof(H56C)=FVAR(4)
 Sof(N7A)=Sof(C57A)=Sof(H57A)=Sof(C58A)=Sof(H58A)=Sof(C59A)=Sof(H59A)=
 Sof(C60A)=Sof(H60A)=Sof(C61A)=Sof(C62A)=Sof(C63A)=Sof(H63A)=Sof(C64A)=
 Sof(H64A)=Sof(C65A)=Sof(H65A)=Sof(C66A)=Sof(H66A)=Sof(C67A)=1-FVAR(5)
 Sof(N7)=Sof(C57)=Sof(H57)=Sof(C58)=Sof(H58)=Sof(C59)=Sof(H59)=Sof(C60)=
 Sof(H60)=Sof(C61)=Sof(C62)=Sof(C63)=Sof(H63)=Sof(C64)=Sof(H64)=Sof(C65)=
 Sof(H65)=Sof(C66)=Sof(H66)=Sof(C67)=FVAR(5)
 Fixed Z: C46A(0.27304)
7.a Ternary CH refined with riding coordinates:
 C51(H51), C54(H54), C23(H23), C23(H23A), C26(H26), C51A(H51A), C54A(H54A)
7.b Secondary CH2 refined with riding coordinates:
 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(H37A,H37B), C37(H37C,H37D),
  C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C42(H42A,
 H42B), C43(H43A,H43B), C10A(H10C,H10D), C11A(H11C,H11D), C12A(H12C,H12D),
 C13A(H13C,H13D), C14A(H14C,H14D), C15A(H15C,H15D), C38A(H38C,H38D), C39A(H39C,
 H39D), C40A(H40C,H40D), C41A(H41C,H41D), C42A(H42C,H42D), C43A(H43C,H43D)
7.c Me refined with riding coordinates:
 C55A(H55D,H55E,H55F)
7.d Aromatic/amide H refined with riding coordinates:
 C57(H57), C58(H58), C59(H59), C60(H60), C63(H63), C64(H64), C65(H65),
 C66(H66), C48(H48), C48(H48A), C47(H47), C49(H49), 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), C57A(H57A), C58A(H58A), C59A(H59A), C60A(H60A), C63A(H63A),
  C64A(H64A), C65A(H65A), C66A(H66A), C47A(H47A), C49A(H49A)
7.e Idealised Me refined as rotating group:
 C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C55(H55A,H55B,H55C), C56(H56A,H56B,
 H56C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C28(H28A,
 H28B,H28C), C24A(H24D,H24E,H24F), C25A(H25D,H25E,H25F), C52A(H52D,H52E,H52F),
 C53A(H53D,H53E,H53F), C56A(H56D,H56E,H56F)
;
_shelx_res_checksum              8501
_shelx_hkl_checksum              16447
_olex2_submission_special_instructions 'No special instructions were received'