Combining two relatively weak bases (Zn(TMP)<sub>2</sub> and KO<i>t</i>Bu) for the regioselective metalation of non-activated arenes and heteroarenes.
Judge, Neil R.; Hevia, Eva; Chemical science 15 (2024) 14757–14765; doi:10.1039/d4sc03892d

data_1572339
_publ_section_title
;
 Combining two relatively weak bases (Zn(TMP)<sub>2</sub> and
 KO<i>t</i>Bu) for the regioselective metalation of non-activated arenes
 and heteroarenes.
;
_journal_issue                   36
_journal_name_full               'Chemical science'
_journal_page_first              14757
_journal_page_last               14765
_journal_paper_doi               10.1039/d4sc03892d
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C52 H82 K2 O8 Zn2'
_chemical_formula_sum            'C52 H82 K2 O8 Zn2'
_chemical_formula_weight         1044.11
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      15
_symmetry_space_group_name_Hall  '-I 2ya'
_symmetry_space_group_name_H-M   'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-02-23T19:00:21-00:00
_audit_update_record
;
2024-05-26 deposited with the CCDC.	2024-08-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.7772(18)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.2697(3)
_cell_length_b                   17.0018(3)
_cell_length_c                   20.8902(3)
_cell_measurement_reflns_used    24674
_cell_measurement_temperature    173.01(10)
_cell_measurement_theta_max      76.88
_cell_measurement_theta_min      3.451
_cell_volume                     5982.85(19)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
        List of Runs (angles in degrees, time in seconds):
  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -97.00  -9.00   0.50    3.00    --  -23.00 -16.00  36.00  176
  2  \w    -28.00  52.00   0.50    3.00    --  -23.00  16.00-153.00  160
  3  \w     35.00 122.00   0.50    3.00    --   47.92  16.00-153.00  174
  4  \w    -26.00  22.00   0.50    3.00    --   47.92 -16.00  36.00   96
  5  \w    100.00 177.00   0.50   21.00    --  113.25  16.00-153.00  154
  6  \w    -30.00  53.00   0.50    3.00    --  -23.00  19.00 -60.00  166
  7  \w    -36.00  49.00   0.50    3.00    --  -23.00  45.00  90.00  170
  8  \w     -1.00  81.00   0.50    3.00    --   47.92 -99.00 -60.00  164
  9  \w    -26.00  23.00   0.50    3.00    --   47.92 -19.00-180.00   98
 10  \w     -1.00  81.00   0.50    3.00    --   47.92 -99.00-150.00  164
 11  \w     -1.00  81.00   0.50    3.00    --   47.92 -99.00  30.00  164
 12  \w    -26.00  23.00   0.50    3.00    --   47.92 -19.00 -90.00   98
 13  \w    -26.00  23.00   0.50    3.00    --   47.92 -19.00-120.00   98
 14  \w    -23.00  63.00   0.50    3.00    --   47.92 -57.00   0.00  172
 15  \w     42.00 106.00   0.50   21.00    --  113.25 -94.00-120.00  128
 16  \w    101.00 177.00   0.50   21.00    --  113.25  30.00   0.00  152
 17  \w     42.00 106.00   0.50   21.00    --  113.25 -94.00 120.00  128
 18  \w     42.00 106.00   0.50   21.00    --  113.25 -94.00  30.00  128
 19  \w    100.00 177.00   0.50   21.00    --  113.25  15.00 -90.00  154
 20  \w     91.00 177.00   0.50   21.00    --  113.25  77.00 120.00  172
 21  \w     42.00 102.00   0.50   21.00    --  113.25 -77.00 -60.00  120
 22  \w     42.00 102.00   0.50   21.00    --  113.25 -77.00 -90.00  120
 23  \w     42.00 106.00   0.50   21.00    --  113.25 -94.00  60.00  128
 24  \w     42.00 106.00   0.50   21.00    --  113.25 -94.00-180.00  128
 25  \w     42.00 106.00   0.50   21.00    --  113.25 -94.00 -30.00  128
 26  \w     42.00 102.00   0.50   21.00    --  113.25 -77.00-120.00  120
 27  \w    101.00 177.00   0.50   21.00    --  113.25  30.00 120.00  152
 28  \w     42.00 106.00   0.50   21.00    --  113.25 -94.00-150.00  128
 29  \w    101.00 177.00   0.50   21.00    --  113.25  45.00  30.00  152
 30  \w     42.00  68.00   0.50   21.00    --  113.25 -61.00 120.00   52
 31  \w     91.00 177.00   0.50   21.00    --  113.25  77.00  30.00  172
 32  \w     42.00 106.00   0.50   21.00    --  113.25 -94.00   0.00  128
 33  \w     42.00 102.00   0.50   21.00    --  113.25 -77.00  30.00  120
 34  \w     42.00 102.00   0.50   21.00    --  113.25 -77.00 120.00  120
 35  \w     42.00  68.00   0.50   21.00    --  113.25 -61.00 150.00   52
 36  \w     42.00  68.00   0.50   21.00    --  113.25 -61.00  30.00   52
 37  \w    101.00 177.00   0.50   21.00    --  113.25  45.00  90.00  152
 38  \w     42.00 106.00   0.50   21.00    --  113.25 -94.00 150.00  128
 39  \w     42.00  68.00   0.50   21.00    --  113.25 -61.00-150.00   52
 40  \w     42.00 102.00   0.50   21.00    --  113.25 -77.00 -30.00  120
 41  \w     42.00  68.00   0.50   21.00    --  113.25 -61.00-180.00   52
 42  \w     42.00 106.00   0.50   21.00    --  113.25-100.00 108.96  128
 43  \w     42.00  68.00   0.50   21.00    --  113.25 -61.00  60.00   52
 44  \w     42.00 106.00   0.50   21.00    --  113.25 -94.00 -90.00  128
 45  \w    101.00 177.00   0.50   21.00    --  113.25  30.00 -30.00  152
 46  \w    101.00 177.00   0.50   21.00    --  113.25  45.00 -90.00  152
 47  \w     42.00 108.00   0.50   21.00    --  113.25-111.00-147.12  132
 48  \w     25.00 121.00   0.50    3.00    --   47.92  77.00   0.00  192
 49  \w     25.00 121.00   0.50    3.00    --   47.92  77.00 -90.00  192
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0594015
_diffrn_orient_matrix_UB_12      0.0674234
_diffrn_orient_matrix_UB_13      -0.0089082
_diffrn_orient_matrix_UB_21      0.0675161
_diffrn_orient_matrix_UB_22      0.0603814
_diffrn_orient_matrix_UB_23      0.0148706
_diffrn_orient_matrix_UB_31      -0.0166768
_diffrn_orient_matrix_UB_32      0.0037036
_diffrn_orient_matrix_UB_33      -0.078115
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0602
_diffrn_reflns_av_unetI/netI     0.0698
_diffrn_reflns_Laue_measured_fraction_full 1
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            59420
_diffrn_reflns_point_group_measured_fraction_full 1
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.265
_diffrn_reflns_theta_min         3.467
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.577
_exptl_absorpt_correction_T_max  0.883
_exptl_absorpt_correction_T_min  0.832
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.41.112a (Rigaku Oxford Diffraction, 2021)
Analytical numeric absorption correction using a multifaceted crystal
        model based on expressions derived by R.C. Clark & J.S. Reid.
        (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
        Empirical absorption correction using spherical harmonics,
        implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.159
_exptl_crystal_description       block
_exptl_crystal_F_000             2224
_exptl_crystal_size_max          0.131
_exptl_crystal_size_mid          0.069
_exptl_crystal_size_min          0.067
_refine_diff_density_max         0.749
_refine_diff_density_min         -0.478
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     295
_refine_ls_number_reflns         5794
_refine_ls_number_restraints     115
_refine_ls_restrained_S_all      1.108
_refine_ls_R_factor_all          0.0691
_refine_ls_R_factor_gt           0.0625
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1303P)^2^+4.8608P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1977
_refine_ls_wR_factor_ref         0.2066
_reflns_Friedel_coverage         0
_reflns_number_gt                4850
_reflns_number_total             5794
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03892d2.cif
_cod_data_source_block           22EH021_NJ-3-118
_cod_depositor_comments
'Adding full bibliography for 1572338--1572342.cif.'
_cod_original_cell_volume        5982.84(18)
_cod_database_code               1572339
_shelx_estimated_absorpt_t_min   0.729
_shelx_estimated_absorpt_t_max   0.846
_oxdiff_exptl_absorpt_empirical_details
;
        Empirical correction (ABSPACK) includes:
        - Absorption correction using spherical harmonics
        - Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.634
_oxdiff_exptl_absorpt_empirical_full_min 0.599
_shelx_shelxl_version_number     2018/3
_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
 C22-C21 = C20-C19
 1.53 with sigma of 0.02
 C24-C25
 1.54 with sigma of 0.001
 O3-C22 = O3-C19
 1.44 with sigma of 0.02
 C25-C26 = C23-C24
 1.53 with sigma of 0.001
 C21-C20
 1.54 with sigma of 0.001
 O3-C21 = O3-C20 = C22-C20 = C21-C19
 2.38 with sigma of 0.04
 O4-C26 \\sim O4-C23
 with sigma of 0.002
 O3-C22 \\sim O3-C19
 with sigma of 0.02
 C22-C21 \\sim C21-C20 \\sim C20-C19
 with sigma of 0.02
 C21-C19 \\sim C22-C20
 with sigma of 0.04
 O3-C21 \\sim O3-C20
 with sigma of 0.04
        3. Uiso/Uaniso restraints and constraints
O3 \\sim C22 \\sim C21 \\sim C20 \\sim C19: within 2A with sigma of 0.04 and
        sigma for terminal atoms of 0.08 within 2A
Uanis(C25) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C3) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C26) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C2) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.01
Uanis(C4) \\sim Ueq, Uanis(C19) \\sim Ueq: with sigma of 0.02 and sigma for
        terminal atoms of 0.01
        4. Rigid body (RIGU) restrains
 O3, C22, C21, C20, C19
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
        5.a Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,H26B), C22(H22A,
 H22B), C21(H21A,H21B), C20(H20A,H20B), C19(H19A,H19B)
        5.b Aromatic/amide H refined with riding coordinates:
 C18(H18), C11(H11), C10(H10), C16(H16), C13(H13), C15(H15), C14(H14)
        5.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C3(H3A,H3B,H3C), C2(H2A,
 H2B,H2C), C4(H4A,H4B,H4C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              54862
_shelx_hkl_checksum              66035
_shelx_fab_checksum              5050