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_1573119
_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         'C71 H88 Dy N7 O'
_chemical_formula_sum            'C71 H88 Dy N7 O'
_chemical_formula_weight         1217.98
_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                100.4060(10)
_cell_angle_beta                 90.2750(10)
_cell_angle_gamma                99.7910(10)
_cell_formula_units_Z            4
_cell_length_a                   13.5582(10)
_cell_length_b                   20.4707(15)
_cell_length_c                   23.6618(17)
_cell_measurement_reflns_used    9834
_cell_measurement_temperature    300
_cell_measurement_theta_max      25.108
_cell_measurement_theta_min      2.264
_cell_volume                     6360.9(8)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker SMART APEX II diffractometer'
_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_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_device       'three-circle diffractometer'
_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_unetI/netI     0.0982
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            28891
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.601
_diffrn_reflns_theta_min         1.221
_exptl_absorpt_coefficient_mu    1.223
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.3849
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1112 before and 0.0583 after correction.
The Ratio of minimum to maximum transmission is 0.5162.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.272
_exptl_crystal_description       block
_exptl_crystal_F_000             2548
_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         2.192
_refine_diff_density_min         -1.131
_refine_diff_density_rms         0.101
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.005
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1682
_refine_ls_number_reflns         28891
_refine_ls_number_restraints     757
_refine_ls_restrained_S_all      0.998
_refine_ls_R_factor_all          0.1124
_refine_ls_R_factor_gt           0.0586
_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^)+(0.0526P)^2^+3.6130P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1163
_refine_ls_wR_factor_ref         0.1356
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17786
_reflns_number_total             28891
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04197f4.cif
_cod_data_source_block           11_tw
_cod_depositor_comments
'Adding full bibliography for 1573095--1573138.cif.'
_cod_database_code               1573119
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.801
_shelx_estimated_absorpt_t_min   0.783
_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. Twinned data refinement
 Scales: 0.8898(15)
 0.1102(15)
2. 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
3. Restrained distances
 N2-C15 \\sim N2-C15A \\sim N2-C11 \\sim N2-C11A
 with sigma of 0.02
 N9-C86A \\sim N9-C86 \\sim N9-C82A \\sim N9-C82
 with sigma of 0.02
 C121-C120 \\sim C1C-C121
 with sigma of 0.02
 C117-C116 \\sim C143-C116
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
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
N9 \\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86 \\sim C82A \\sim C83A
\\sim C84A \\sim C85A \\sim C86A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C26 \\sim C27 \\sim C28 \\sim C27A \\sim C28A: 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
C117 \\sim C118 \\sim C119 \\sim C120 \\sim C122 \\sim C123 \\sim C1A \\sim C1B
\\sim C1C \\sim C1D \\sim C1E \\sim C143 \\sim C124 \\sim C1F \\sim C116 \\sim
C121: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
5. Same fragment restrains
{N2, C11A, C12A, C13A, C14A, C15A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N2, C11, C12, C13, C14, C15}
{C26, C27A, C28A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C26, C27, C28}
{N9, C82A, C83A, C84A, C85A, C86A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N9, C82, C83, C84, C85, C86}
{N5, C39A, C40A, C41A, C42A, C43A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N5, C39, C40, C41, C42, C43}
{C1C, C1B, C1A, C143, C1D, C1E, C1F} sigma for 1-2: 0.02, 1-3: 0.02
as in
{C120, C119, C118, C117, C122, C123, C124}
6. 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(C82A)=Sof(H82C)=Sof(H82D)=Sof(C83A)=Sof(H83C)=Sof(H83D)=Sof(C84A)=
 Sof(H84C)=Sof(H84D)=Sof(C85A)=Sof(H85C)=Sof(H85D)=Sof(C86A)=Sof(H86C)=
 Sof(H86D)=1-FVAR(2)
 Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(C83)=Sof(H83A)=Sof(H83B)=Sof(C84)=Sof(H84A)=
 Sof(H84B)=Sof(C85)=Sof(H85A)=Sof(H85B)=Sof(C86)=Sof(H86A)=Sof(H86B)=FVAR(2)
 Sof(H26A)=Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=Sof(C28A)=Sof(H28D)=
 Sof(H28E)=Sof(H28F)=1-FVAR(3)
 Sof(H26)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C28)=Sof(H28A)=Sof(H28B)=
 Sof(H28C)=FVAR(3)
 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(4)
 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(4)
 Sof(C1C)=Sof(H1C)=Sof(C1B)=Sof(H1B)=Sof(C1A)=Sof(H1A)=Sof(C143)=Sof(C1D)=
 Sof(H1D)=Sof(C1E)=Sof(H1EA)=Sof(H1EB)=Sof(H1EC)=Sof(C1F)=Sof(H1FA)=Sof(H1FB)=
 Sof(H1FC)=1-FVAR(5)
 Sof(C120)=Sof(H120)=Sof(C119)=Sof(H119)=Sof(C118)=Sof(H118)=Sof(C117)=
 Sof(C122)=Sof(H122)=Sof(C123)=Sof(H12K)=Sof(H12L)=Sof(H12M)=Sof(C124)=
 Sof(H12N)=Sof(H12O)=Sof(H12P)=FVAR(5)
 Fixed Z: C14(0.445439)
7.a Ternary CH refined with riding coordinates:
 C1(H1), C23(H23), C26(H26), C26(H26A), C51(H51), C54(H54), C72(H72), C94(H94),
  C97(H97), C125(H125), C122(H122), C1D(H1D)
7.b 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),
 C68(H68A,H68B), C69(H69A,H69B), C70(H70A,H70B), C71(H71A,H71B), C82(H82A,H82B),
  C83(H83A,H83B), C84(H84A,H84B), C85(H85A,H85B), C86(H86A,H86B), C80(H80A,
 H80B), C81(H81A,H81B), C108(H10C,H10D), C109(H10E,H10F), C110(H11E,H11F),
 C111(H11G,H11H), C112(H11I,H11J), C113(H11K,H11L), C114(H11M,H11N), C139(H13E,
 H13F), C140(H14E,H14F), C141(H14G,H14H), C142(H14I,H14J), 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),
 C82A(H82C,H82D), C83A(H83C,H83D), C84A(H84C,H84D), C85A(H85C,H85D), C86A(H86C,
 H86D)
7.c 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),
  C58(H58), C59(H59), C60(H60), C63(H63), C64(H64), C65(H65), C66(H66),
 C75(H75), C76(H76), C77(H77), C78(H78), C87(H87), C90(H90), C91(H91), C92(H92),
  C103(H103), C104(H104), C105(H105), C106(H106), C115(H115), C129(H129),
 C130(H130), C131(H131), C134(H134), C135(H135), C136(H136), C137(H137),
 C120(H120), C119(H119), C118(H118), C1C(H1C), C1B(H1B), C1A(H1A)
7.d 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), C95(H95A,H95B,H95C), C96(H96A,H96B,H96C), C98(H98A,H98B,H98C),
 C99(H99A,H99B,H99C), C126(H12E,H12F,H12G), C127(H12H,H12I,H12J), C123(H12K,
 H12L,H12M), C124(H12N,H12O,H12P), C1E(H1EA,H1EB,H1EC), C1F(H1FA,H1FB,H1FC),
 C27A(H27D,H27E,H27F), C28A(H28D,H28E,H28F)
;
_shelx_res_checksum              89524
_shelx_hkl_checksum              76143
_olex2_submission_special_instructions 'No special instructions were received'