Low-coordinate potassium alkoxide – an efficient trap for arenes: the role of ηn non-covalent bonding in substrate activation for C–H bond metalation
Selikhov, Alexander N.; Nelyubina, Yulia V.; Aysin, Rinat R.; Trifonov, Alexander A.; Dalton Transactions 54 (2025) 4503–4517; doi:10.1039/D4DT03326D

data_7717943
_publ_section_title
;
 Low-coordinate potassium alkoxide -- an efficient trap for arenes: the
 role of \hn non-covalent bonding in substrate activation for C--H bond
 metalation
;
_journal_issue                   11
_journal_name_full               'Dalton Transactions'
_journal_page_first              4503
_journal_page_last               4517
_journal_paper_doi               10.1039/D4DT03326D
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C78 H100 K2 N6 O2 S'
_chemical_formula_sum            'C78 H100 K2 N6 O2 S'
_chemical_formula_weight         1263.89
_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     dual
_audit_creation_date             2024-03-26
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-03-26 deposited with the CCDC.	2024-12-30 downloaded from the CCDC.
;
_cell_angle_alpha                113.687(4)
_cell_angle_beta                 92.326(4)
_cell_angle_gamma                105.616(4)
_cell_formula_units_Z            1
_cell_length_a                   9.5095(17)
_cell_length_b                   13.644(2)
_cell_length_c                   16.946(3)
_cell_measurement_reflns_used    1209
_cell_measurement_temperature    100
_cell_measurement_theta_max      29.67
_cell_measurement_theta_min      2.26
_cell_volume                     1911.4(6)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.970
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1090
_diffrn_reflns_av_unetI/netI     0.2172
_diffrn_reflns_Laue_measured_fraction_full 0.970
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            17505
_diffrn_reflns_point_group_measured_fraction_full 0.970
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         1.331
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.197
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6160
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0731 before and 0.0569 after correction.
The Ratio of minimum to maximum transmission is 0.8256.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.098
_exptl_crystal_description       plate
_exptl_crystal_F_000             680
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.681
_refine_diff_density_min         -0.527
_refine_diff_density_rms         0.068
_refine_ls_extinction_coef       0.019(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   0.897
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     429
_refine_ls_number_reflns         6724
_refine_ls_number_restraints     101
_refine_ls_restrained_S_all      0.927
_refine_ls_R_factor_all          0.1643
_refine_ls_R_factor_gt           0.0788
_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^)+(0.0664P)^2^+2.0724P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1895
_refine_ls_wR_factor_ref         0.2451
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3177
_reflns_number_total             6724
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03326d2.cif
_cod_data_source_block           8
_cod_depositor_comments
'Adding full bibliography for 7717941--7717948.cif.'
_cod_original_cell_volume        1911.3(6)
_cod_database_code               7717943
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.996
_shelx_estimated_absorpt_t_min   0.981
_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) groups, All C(H,H,H,H) groups
2. Restrained distances
 C1S-C2S
 2.2 with sigma of 0.02
 H2S_$1-H1S
 2.1 with sigma of 0.02
 H1S-H2S_$1
 2.2 with sigma of 0.02
 N006-C8 \\sim N1-C8
 with sigma of 0.02
 S1S-C2S \\sim S1S-C1S
 with sigma of 0.01
 C11'-C12' \\sim C12-C11
 with sigma of 0.02
 C10-C11 \\sim C11'-C10'
 with sigma of 0.02
 N1-C13 \\sim N006-C13'
 with sigma of 0.02
 C13-C12 \\sim C12'-C13'
 with sigma of 0.02
 C10'-C9' \\sim C9-C10
 with sigma of 0.02
 N006-C9' \\sim N1-C9
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C2S) \\sim Ueq, Uanis(S1S) \\sim Ueq, Uanis(C1S) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(N006) \\sim Ueq, Uanis(C9') \\sim Ueq, Uanis(C13') \\sim Ueq, Uanis(C10')
\\sim Ueq, Uanis(C12') \\sim Ueq, Uanis(C11') \\sim Ueq, Uanis(N1) \\sim Ueq,
Uanis(C9) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C12)
\\sim Ueq, Uanis(C11) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(C11') = Uanis(C11)
Uanis(C13) = Uanis(C13')
Uanis(C9') = Uanis(C9)
Uanis(N1) = Uanis(N006)
Uanis(C12') = Uanis(C12)
Uanis(C10') = Uanis(C10)
4. Others
 Sof(H8BC)=Sof(H8BD)=Sof(N1)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(C10)=Sof(H10C)=
 Sof(H10D)=Sof(C11)=Sof(H11C)=Sof(H11D)=Sof(C12)=Sof(H12C)=Sof(H12D)=Sof(C13)=
 Sof(H13C)=Sof(H13D)=1-FVAR(1)
 Sof(H8AA)=Sof(H8AB)=Sof(N006)=Sof(C9')=Sof(H9'A)=Sof(H9'B)=Sof(C10')=
 Sof(H10A)=Sof(H10B)=Sof(C11')=Sof(H11A)=Sof(H11B)=Sof(C12')=Sof(H12A)=
 Sof(H12B)=Sof(C13')=Sof(H13A)=Sof(H13B)=FVAR(1)
 Fixed Sof: S1S(0.5)
5.a Riding coordinates:
 C1S(H1S)
5.b Secondary CH2 refined with riding coordinates:
 C8(H8AA,H8AB), C8(H8BC,H8BD), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B),
 C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), C32(H32A,H32B), C33(H33A,H33B),
  C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B), C9'(H9'A,
 H9'B), C10'(H10A,H10B), C11'(H11A,H11B), C12'(H12A,H12B), C13'(H13A,H13B),
 C9(H9A,H9B), C10(H10C,H10D), C11(H11C,H11D), C12(H12C,H12D), C13(H13C,H13D)
5.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C16(H16), C17(H17), C18(H18), C19(H19),
 C28(H28), C29(H29), C30(H30), C31(H31)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              6424
_shelx_fab_checksum              93935
_olex2_submission_special_instructions 'No special instructions were received'