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_7717946
_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         'C88 H111 K2 N6 O2, 2(C7 H8)'
_chemical_formula_sum            'C102 H127 K2 N6 O2'
_chemical_formula_weight         1547.29
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 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                90
_cell_angle_beta                 105.0040(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   16.1563(3)
_cell_length_b                   14.0953(3)
_cell_length_c                   19.3873(3)
_cell_measurement_reflns_used    214
_cell_measurement_temperature    100
_cell_measurement_theta_max      22.36
_cell_measurement_theta_min      2.59
_cell_volume                     4264.51(14)
_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      100.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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_R_equivalents  0.0751
_diffrn_reflns_av_unetI/netI     0.0617
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            52157
_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         27.999
_diffrn_reflns_theta_min         1.903
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.166
_exptl_absorpt_correction_T_max  0.2648
_exptl_absorpt_correction_T_min  0.1660
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1123 before and 0.0664 after correction.
The Ratio of minimum to maximum transmission is 0.6269.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.205
_exptl_crystal_description       prism
_exptl_crystal_F_000             1670
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.409
_refine_diff_density_min         -0.339
_refine_diff_density_rms         0.054
_refine_ls_extinction_coef       0.0013(2)
_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   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     507
_refine_ls_number_reflns         10311
_refine_ls_number_restraints     85
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0761
_refine_ls_R_factor_gt           0.0465
_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^)+(0.0385P)^2^+1.8020P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0978
_refine_ls_wR_factor_ref         0.1126
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7408
_reflns_number_total             10311
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03326d2.cif
_cod_data_source_block           3
_cod_depositor_comments
'Adding full bibliography for 7717941--7717948.cif.'
_cod_database_code               7717946
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.984
_shelx_estimated_absorpt_t_min   0.968
_olex2_refinement_description
;
1. 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
2. Restrained distances
 C8S'-C1E \\sim C14S-C8S
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C10S) \\sim Ueq, Uanis(C9S) \\sim Ueq, Uanis(C8S) \\sim Ueq, Uanis(C13S)
\\sim Ueq, Uanis(C12S) \\sim Ueq, Uanis(C11S) \\sim Ueq, Uanis(C9S') \\sim Ueq,
Uanis(C8S') \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C1B) \\sim Ueq, Uanis(C1C)
\\sim Ueq, Uanis(C1D) \\sim Ueq, Uanis(C1E) \\sim Ueq, Uanis(C14S) \\sim Ueq:
with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C1E) = Uanis(C14S)
Uanis(C1B) = Uanis(C12S)
Uanis(C1C) = Uanis(C11S)
Uanis(C8S) = Uanis(C8S')
Uanis(C1D) = Uanis(C10S)
Uanis(C9S) = Uanis(C9S')
Uanis(C1A) = Uanis(C13S)
4. Others
 Sof(C1E)=Sof(H1EA)=Sof(H1EB)=Sof(H1EC)=Sof(C9S')=Sof(H9S')=Sof(C8S')=Sof(C1A)=
 Sof(H1A)=Sof(C1B)=Sof(H1B)=Sof(C1C)=Sof(H1C)=Sof(C1D)=Sof(H1D)=1-FVAR(1)
 Sof(C10S)=Sof(H10S)=Sof(C9S)=Sof(H9S)=Sof(C8S)=Sof(C13S)=Sof(H13S)=Sof(C12S)=
 Sof(H12S)=Sof(C11S)=Sof(H11S)=Sof(C14S)=Sof(H14A)=Sof(H14B)=Sof(H14C)=FVAR(1)
 Fixed Sof: H18(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B),
 C13(H13A,H13B), 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)
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), C9S'(H9S'), C1A(H1A), C1B(H1B), C1C(H1C), C1D(H1D), C10S(H10S),
 C9S(H9S), C13S(H13S), C12S(H12S), C11S(H11S)
5.c Fitted hexagon refined as free rotating group:
 C9S'(C8S',C1A,C1B,C1C,C1D), C10S(C9S,C8S,C13S,C12S,C11S)
5.d Idealised Me refined as rotating group:
 C7S(H7SA,H7SB,H7SC), C1E(H1EA,H1EB,H1EC), C14S(H14A,H14B,H14C)
;
_shelx_res_checksum              13149
_olex2_submission_special_instructions 'No special instructions were received'