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_7717948
_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_absolute_configuration ad
_chemical_formula_moiety         'C88 H112 K2 N6 O4'
_chemical_formula_sum            'C88 H112 K2 N6 O4'
_chemical_formula_weight         1396.03
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_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                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.9048(12)
_cell_length_b                   14.7155(9)
_cell_length_c                   26.2038(15)
_cell_measurement_reflns_used    9858
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.45
_cell_measurement_theta_min      2.28
_cell_volume                     8446.5(8)
_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 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  0.2631
_diffrn_reflns_av_unetI/netI     0.1692
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            149530
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.999
_diffrn_reflns_theta_min         1.667
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.162
_exptl_absorpt_correction_T_max  0.4330
_exptl_absorpt_correction_T_min  0.3061
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1710 before and 0.1030 after correction.
The Ratio of minimum to maximum transmission is 0.7069.
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       prism
_exptl_crystal_F_000             3008
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.668
_refine_diff_density_min         -0.523
_refine_diff_density_rms         0.081
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.39(11)
_refine_ls_extinction_coef       0.0030(6)
_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   1.003
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     895
_refine_ls_number_reflns         18427
_refine_ls_number_restraints     27
_refine_ls_restrained_S_all      1.003
_refine_ls_R_factor_all          0.1866
_refine_ls_R_factor_gt           0.0870
_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^)+(0.1301P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2074
_refine_ls_wR_factor_ref         0.2749
_reflns_Friedel_coverage         0.956
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                8654
_reflns_number_total             18427
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03326d2.cif
_cod_data_source_block           5
_cod_depositor_comments
'Adding full bibliography for 7717941--7717948.cif.'
_cod_database_code               7717948
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.992
_shelx_estimated_absorpt_t_min   0.976
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.61(11)
 0.39(11)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H7SD,H7SE,H7SF} of C7SA, All C(H,H) groups
 At 1.5 times of:
  {H7SA,H7SB,H7SC} of C7S
3. Restrained distances
 O1S-C1S \\sim O1S-C1S'
 with sigma of 0.02
 O1SA-C1SB \\sim O1SA-C1SA
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C1SA) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C4SA) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C1S') \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C2SB) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C5S) = Uanis(C5S')
Uanis(C3S) = Uanis(C3S')
Uanis(C4S) = Uanis(C4S')
Uanis(C1S') = Uanis(C1S)
Uanis(C2S) = Uanis(C2S')
Uanis(C6S') = Uanis(C6S)
Uanis(C5SA) = Uanis(C5SB)
Uanis(C4SA) = Uanis(C4SB)
Uanis(C3SA) = Uanis(C3SB)
Uanis(C6SB) = Uanis(C6SA)
Uanis(C1SA) = Uanis(C1SB)
Uanis(C2SA) = Uanis(C2SB)
5. Others
 Sof(C1S')=Sof(C2S')=Sof(H2S')=Sof(C3S')=Sof(H3S')=Sof(C4S')=Sof(H4S')=
 Sof(C5S')=Sof(H5S')=Sof(C6S')=Sof(H6S')=1-FVAR(1)
 Sof(C1S)=Sof(C2S)=Sof(H2S)=Sof(C3S)=Sof(H3S)=Sof(C4S)=Sof(H4S)=Sof(C5S)=
 Sof(H5S)=Sof(C6S)=Sof(H6S)=FVAR(1)
 Sof(C2SB)=Sof(H2SB)=Sof(C3SB)=Sof(H3SB)=Sof(C4SB)=Sof(H4SB)=Sof(C5SB)=
 Sof(H5SB)=Sof(C6SB)=Sof(H6SB)=Sof(C1SB)=1-FVAR(2)
 Sof(C1SA)=Sof(C2SA)=Sof(H2SA)=Sof(C3SA)=Sof(H3SA)=Sof(C4SA)=Sof(H4SA)=
 Sof(C5SA)=Sof(H5SA)=Sof(C6SA)=Sof(H6SA)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C8A(H8AA,H8AB), C9(H9A,H9B), C9A(H9AA,H9AB), C10(H10A,H10B),
 C10A(H10C,H10D), C11(H11A,H11B), C11A(H11C,H11D), C12(H12A,H12B), C12A(H12C,
 H12D), C13(H13A,H13B), C13A(H13C,H13D), C20(H20A,H20B), C20A(H20C,H20D),
 C21(H21A,H21B), C21A(H21C,H21D), C22(H22A,H22B), C22A(H22C,H22D), C23(H23A,
 H23B), C23A(H23C,H23D), C24(H24A,H24B), C24A(H24C,H24D), C25(H25A,H25B),
 C25A(H25C,H25D), C32(H32A,H32B), C32A(H32C,H32D), C33(H33A,H33B), C33A(H33C,
 H33D), C34(H34A,H34B), C34A(H34C,H34D), C35(H35A,H35B), C35A(H35C,H35D),
 C36(H36A,H36B), C36A(H36C,H36D), C37(H37A,H37B), C37A(H37C,H37D)
6.b Aromatic/amide H refined with riding coordinates:
 C2SA(H2SA), C3SA(H3SA), C4SA(H4SA), C5SA(H5SA), C6SA(H6SA), C4(H4), C4A(H4A),
 C5(H5), C5A(H5A), C6(H6), C6A(H6A), C7(H7), C7A(H7A), C16(H16), C16A(H16A),
 C17(H17), C17A(H17A), C18(H18), C18A(H18A), C19(H19), C19A(H19A), C28(H28),
 C28A(H28A), C29(H29), C29A(H29A), C30(H30), C30A(H30A), C31(H31), C31A(H31A),
 C2S(H2S), C3S(H3S), C4S(H4S), C5S(H5S), C6S(H6S), C2S'(H2S'), C3S'(H3S'),
 C4S'(H4S'), C5S'(H5S'), C6S'(H6S'), C2SB(H2SB), C3SB(H3SB), C4SB(H4SB),
 C5SB(H5SB), C6SB(H6SB)
6.c Fitted hexagon refined as free rotating group:
 C1SA(C2SA,C3SA,C4SA,C5SA,C6SA), C1S(C2S,C3S,C4S,C5S,C6S), C1S'(C2S',C3S',C4S',
 C5S',C6S'), C2SB(C3SB,C4SB,C5SB,C6SB,C1SB)
6.d Idealised Me refined as rotating group:
 C7S(H7SA,H7SB,H7SC), C7SA(H7SD,H7SE,H7SF)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              63673
_shelx_fab_checksum              49005
_olex2_submission_special_instructions 'No special instructions were received'