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_1573104
_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         'C62 H79 Er N8'
_chemical_formula_sum            'C62 H79 Er N8'
_chemical_formula_weight         1103.59
_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                83.839(10)
_cell_angle_beta                 71.754(10)
_cell_angle_gamma                69.498(10)
_cell_formula_units_Z            2
_cell_length_a                   13.255(10)
_cell_length_b                   13.375(10)
_cell_length_c                   18.831(14)
_cell_measurement_reflns_used    8552
_cell_measurement_temperature    300
_cell_measurement_theta_max      22.15
_cell_measurement_theta_min      2.28
_cell_volume                     2970(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 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  0.0580
_diffrn_reflns_av_unetI/netI     0.0740
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            28901
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         1.139
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.456
_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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.234
_exptl_crystal_description       block
_exptl_crystal_F_000             1150
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.19
_refine_diff_density_max         1.826
_refine_diff_density_min         -1.290
_refine_diff_density_rms         0.119
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.002
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     833
_refine_ls_number_reflns         10432
_refine_ls_number_restraints     692
_refine_ls_restrained_S_all      1.001
_refine_ls_R_factor_all          0.0711
_refine_ls_R_factor_gt           0.0506
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0922P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1334
_refine_ls_wR_factor_ref         0.1455
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8207
_reflns_number_total             10432
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04197f4.cif
_cod_data_source_block           6c
_cod_depositor_comments
'Adding full bibliography for 1573095--1573138.cif.'
_cod_database_code               1573104
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.769
_shelx_estimated_absorpt_t_min   0.750
_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
 C38A-C37 \\sim C38-C37
 with sigma of 0.02
 N5-C38A \\sim N5-C38 \\sim N5-C43 \\sim N5-C43A \\sim N5-C39A \\sim N5-C39
 with sigma of 0.02
 N2-C10 \\sim N2A-C10A \\sim N2-C15 \\sim N2A-C15A \\sim N2A-C11A \\sim N2-C11
 with sigma of 0.02
 C9-C10 \\sim C9-C10A
 with sigma of 0.02
 Er1-N7A \\sim Er1-N7
 with sigma of 0.02
 Er1-N8 \\sim Er1-N8A
 with sigma of 0.02
3. Restrained planarity
 C59, C57, N7, C60, C58, C61, N8, C62, Er1
 with sigma of 0.1
 C59A, C58A, C57A, N7A, C61A, C60A, N8A, C62A, Er1
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
N5 \\sim C37 \\sim C41 \\sim C38 \\sim C39 \\sim C40 \\sim C42 \\sim C43 \\sim
C38A \\sim C39A \\sim C40A \\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
N7 \\sim N8 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim
N7A \\sim N8A \\sim C57A \\sim C58A \\sim C59A \\sim C60A \\sim C61A \\sim C62A
\\sim Er1: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
5. Same fragment restrains
{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}
{N5, C37, C41, C38A, C39A, C40A, C42A, C43A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N5, C37, C41, C38, C39, C40, C42, C43}
{Er1, N7A, N8A, C57A, C58A, C59A, C60A, C61A, C62A} sigma for 1-2: 0.02, 1-3:
0.04
as in
{Er1, N7, N8, C57, C58, C59, C60, C61, C62}
6. Others
 Sof(H37C)=Sof(H37D)=Sof(H41C)=Sof(H41D)=Sof(C38A)=Sof(H38C)=Sof(H38D)=
 Sof(C39A)=Sof(H39C)=Sof(H39D)=Sof(C40A)=Sof(H40C)=Sof(H40D)=Sof(C42A)=
 Sof(H42C)=Sof(H42D)=Sof(C43A)=Sof(H43C)=Sof(H43D)=1-FVAR(1)
 Sof(H37A)=Sof(H37B)=Sof(H41A)=Sof(H41B)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C39)=
 Sof(H39A)=Sof(H39B)=Sof(C40)=Sof(H40A)=Sof(H40B)=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(N7A)=Sof(N8A)=Sof(C57A)=Sof(H57A)=Sof(C58A)=Sof(H58A)=Sof(C59A)=Sof(H59A)=
 Sof(C60A)=Sof(H60A)=Sof(C61A)=Sof(C62A)=Sof(H62D)=Sof(H62E)=Sof(H62F)=1-FVAR(3)
 Sof(N7)=Sof(N8)=Sof(C57)=Sof(H57)=Sof(C58)=Sof(H58)=Sof(C59)=Sof(H59)=
 Sof(C60)=Sof(H60)=Sof(C61)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=FVAR(3)
7.a Ternary CH refined with riding coordinates:
 C23(H23), C26(H26), C51(H51), C54(H54)
7.b Secondary CH2 refined with riding coordinates:
 C37(H37A,H37B), C37(H37C,H37D), C41(H41A,H41B), C41(H41C,H41D), C38(H38A,
 H38B), C39(H39A,H39B), C40(H40A,H40B), C42(H42A,H42B), C43(H43A,H43B), C9(H9AA,
 H9AB), C9(H9BC,H9BD), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,
 H13B), C14(H14A,H14B), C15(H15A,H15B), 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), C42A(H42C,H42D), C43A(H43C,H43D)
7.c Aromatic/amide H refined with riding coordinates:
 C57(H57), C58(H58), C59(H59), C60(H60), 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), C57A(H57A), C58A(H58A), C59A(H59A),
 C60A(H60A)
7.d Idealised Me refined as rotating group:
 C62(H62A,H62B,H62C), 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), C62A(H62D,H62E,H62F)
;
_shelx_res_checksum              34034
_shelx_hkl_checksum              34573
_olex2_submission_special_instructions 'No special instructions were received'