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_7717941
_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         'C90 H118 K2 N8 O2'
_chemical_formula_sum            'C90 H118 K2 N8 O2'
_chemical_formula_weight         1422.12
_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     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                117.7860(10)
_cell_angle_beta                 103.1450(10)
_cell_angle_gamma                95.3970(10)
_cell_formula_units_Z            1
_cell_length_a                   12.1575(2)
_cell_length_b                   13.7797(3)
_cell_length_c                   13.9883(3)
_cell_measurement_reflns_used    9957
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.58
_cell_measurement_theta_min      2.37
_cell_volume                     1963.69(7)
_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 0.997
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker Quest D8'
_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  0.0281
_diffrn_reflns_av_unetI/netI     0.0358
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            22435
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.998
_diffrn_reflns_theta_min         2.058
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.175
_exptl_absorpt_correction_T_max  0.4330
_exptl_absorpt_correction_T_min  0.3714
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0683 before and 0.0442 after correction.
The Ratio of minimum to maximum transmission is 0.8577.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.203
_exptl_crystal_description       prism
_exptl_crystal_F_000             768
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.303
_refine_diff_density_min         -0.251
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     481
_refine_ls_number_reflns         8557
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0523
_refine_ls_R_factor_gt           0.0422
_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^)+(0.0445P)^2^+0.8008P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1017
_refine_ls_wR_factor_ref         0.1085
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7152
_reflns_number_total             8557
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03326d2.cif
_cod_data_source_block           6
_cod_depositor_comments
'Adding full bibliography for 7717941--7717948.cif.'
_cod_database_code               7717941
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.958
_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
 C10'-C11' \\sim C11-C10
 with sigma of 0.02
 N1-C9 \\sim N1'-C9'
 with sigma of 0.02
 C11'-C12' \\sim C11-C12
 with sigma of 0.02
 C9'-C10' \\sim C10-C9
 with sigma of 0.02
 C12-C13 \\sim C13'-C12'
 with sigma of 0.02
 N1-C13 \\sim N1'-C13'
 with sigma of 0.02
 N1'-C8 \\sim N1-C8
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C13') = Uanis(C13)
Uanis(C9) = Uanis(C9')
Uanis(C10') = Uanis(C10)
Uanis(N1) = Uanis(N1')
Uanis(C12') = Uanis(C12)
Uanis(C11) = Uanis(C11')
4. Others
 Sof(H8BC)=Sof(H8BD)=Sof(N1')=Sof(C9')=Sof(H9'A)=Sof(H9'B)=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(N1)=Sof(C9)=Sof(H9A)=Sof(H9B)=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)
5.a 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(H9A,H9B),
 C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C9'(H9'A,H9'B),
  C10'(H10C,H10D), C11'(H11C,H11D), C12'(H12C,H12D), C13'(H13C,H13D)
5.b Aromatic/amide H refined with riding coordinates:
 C2S(H2S), C3S(H3S), C4(H4), C4S(H4S), C5(H5), C5S(H5S), C6(H6), C6S(H6S),
 C7(H7), C16(H16), C17(H17), C18(H18), C19(H19), C28(H28), C29(H29), C30(H30),
 C31(H31)
5.c Idealised Me refined as rotating group:
 C7S(H7SA,H7SB,H7SC), C8S(H8SA,H8SB,H8SC)
;
_shelx_res_checksum              56408
_olex2_submission_special_instructions 'No special instructions were received'