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_7717945
_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         'C82 H116 K2 N6 O4'
_chemical_formula_sum            'C82 H116 K2 N6 O4'
_chemical_formula_weight         1328.00
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-25
_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                 102.170(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.6214(5)
_cell_length_b                   12.9345(4)
_cell_length_c                   22.6282(7)
_cell_measurement_reflns_used    7103
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.56
_cell_measurement_theta_min      2.19
_cell_volume                     4183.3(2)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device_type  'Bruker Quest D8'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0690
_diffrn_reflns_av_unetI/netI     0.0787
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            34480
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.999
_diffrn_reflns_theta_min         1.841
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.161
_exptl_absorpt_correction_T_max  0.4330
_exptl_absorpt_correction_T_min  0.3372
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1295 before and 0.0595 after correction.
The Ratio of minimum to maximum transmission is 0.7788.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.054
_exptl_crystal_description       plate
_exptl_crystal_F_000             1440
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.678
_refine_diff_density_min         -0.467
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     434
_refine_ls_number_reflns         8997
_refine_ls_number_restraints     14
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.1078
_refine_ls_R_factor_gt           0.0717
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0613P)^2^+3.4054P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1564
_refine_ls_wR_factor_ref         0.1727
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5918
_reflns_number_total             8997
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03326d2.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 7717941--7717948.cif.'
_cod_database_code               7717945
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.998
_shelx_estimated_absorpt_t_min   0.969
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H2SC,H2SA,H2SB} of C2S, All C(H,H) groups
 At 1.5 times of:
  {H4SA,H4SB,H4SC} of C4S', {H4SD,H4SE,H4SF} of C4S
2. Restrained distances
 O1S-C3S \\sim O1S-C3S'
 with sigma of 0.02
 C4S-C3S \\sim C3S'-C4S'
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C3S') \\sim Ueq, Uanis(C4S') \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C3S') = Uanis(C3S)
Uanis(C4S') = Uanis(C4S)
4. Others
 Sof(C3S)=Sof(H3SA)=Sof(H3SB)=Sof(C4S)=Sof(H4SD)=Sof(H4SE)=Sof(H4SF)=1-FVAR(1)
 Sof(C3S')=Sof(H3SC)=Sof(H3SD)=Sof(C4S')=Sof(H4SA)=Sof(H4SB)=Sof(H4SC)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C1S(H1SA,H1SB), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B),
 C12(H12A,H12B), C13(H13A,H13B), C20(H20A,H20B), C21(H21B,H21A), C22(H22A,H22B),
  C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), C32(H32B,H32A), C33(H33A,
 H33B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B),
 C3S(H3SA,H3SB), C3S'(H3SC,H3SD)
5.b 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)
5.c Idealised Me refined as rotating group:
 C2S(H2SC,H2SA,H2SB), C4S(H4SD,H4SE,H4SF), C4S'(H4SA,H4SB,H4SC)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              96494
_shelx_fab_checksum              79236
_olex2_submission_special_instructions 'No special instructions were received'