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_7717947
_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         'C86 H108 K2 N6 O2, 2(C6 H6)'
_chemical_formula_sum            'C98 H120 K2 N6 O2'
_chemical_formula_weight         1492.19
_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             2024-03-25
_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                 103.263(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   16.6965(19)
_cell_length_b                   14.0000(17)
_cell_length_c                   18.5478(17)
_cell_measurement_reflns_used    7168
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.73
_cell_measurement_theta_min      2.26
_cell_volume                     4219.9(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 0.999
_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  0.4963
_diffrn_reflns_av_unetI/netI     0.2805
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            79604
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_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    0.165
_exptl_absorpt_correction_T_max  0.4330
_exptl_absorpt_correction_T_min  0.3038
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1655 before and 0.1080 after correction.
The Ratio of minimum to maximum transmission is 0.7016.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.174
_exptl_crystal_description       plate
_exptl_crystal_F_000             1608
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.519
_refine_diff_density_min         -0.585
_refine_diff_density_rms         0.137
_refine_ls_extinction_coef       0.028(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   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     483
_refine_ls_number_reflns         9214
_refine_ls_number_restraints     72
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.2601
_refine_ls_R_factor_gt           0.1177
_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^)+(0.1037P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2221
_refine_ls_wR_factor_ref         0.2899
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3579
_reflns_number_total             9214
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03326d2.cif
_cod_data_source_block           2
_cod_depositor_comments
'Adding full bibliography for 7717941--7717948.cif.'
_cod_database_code               7717947
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.995
_shelx_estimated_absorpt_t_min   0.976
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C9S) \\sim Ueq, Uanis(C10S) \\sim Ueq, Uanis(C11S) \\sim Ueq, Uanis(C8S)
\\sim Ueq, Uanis(C9S') \\sim Ueq, Uanis(C8S') \\sim Ueq, Uanis(C7S') \\sim Ueq,
Uanis(C1B) \\sim Ueq, Uanis(C1C) \\sim Ueq, Uanis(C12S) \\sim Ueq, Uanis(C7S)
\\sim Ueq, Uanis(C1A) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(C11S) = Uanis(C1C)
Uanis(C7S) = Uanis(C1A)
Uanis(C8S) = Uanis(C7S')
Uanis(C10S) = Uanis(C9S')
Uanis(C12S) = Uanis(C1B)
Uanis(C9S) = Uanis(C8S')
3. Others
 Sof(C9S')=Sof(H9S')=Sof(C8S')=Sof(H8S')=Sof(C7S')=Sof(H7S')=Sof(C1A)=Sof(H1A)=
 Sof(C1B)=Sof(H1B)=Sof(C1C)=Sof(H1C)=1-FVAR(1)
 Sof(C9S)=Sof(H9S)=Sof(C10S)=Sof(H10S)=Sof(C11S)=Sof(H11S)=Sof(C12S)=Sof(H12S)=
 Sof(C7S)=Sof(H7S)=Sof(C8S)=Sof(H8S)=FVAR(1)
4.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)
4.b Aromatic/amide H refined with riding coordinates:
 C1S(H1S), 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'), C8S'(H8S'), C7S'(H7S'), C1A(H1A), C1B(H1B),
 C1C(H1C), C9S(H9S), C10S(H10S), C11S(H11S), C12S(H12S), C7S(H7S), C8S(H8S)
4.c Fitted hexagon refined as free rotating group:
 C9S'(C8S',C7S',C1A,C1B,C1C), C9S(C10S,C11S,C12S,C7S,C8S)
;
_shelx_res_checksum              57923
_olex2_submission_special_instructions 'No special instructions were received'