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_1572341
_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         'C42 H92 K2 N6 O4 Zn2'
_chemical_formula_sum            'C42 H92 K2 N6 O4 Zn2'
_chemical_formula_weight         954.15
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_cell_setting           triclinic
_symmetry_Int_Tables_number      2
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-12-20T13:55:28-00:00
_audit_update_record
;
2024-05-26 deposited with the CCDC.	2024-08-09 downloaded from the CCDC.
;
_cell_angle_alpha                112.4692(14)
_cell_angle_beta                 92.8879(12)
_cell_angle_gamma                107.7984(13)
_cell_formula_units_Z            1
_cell_length_a                   10.92429(16)
_cell_length_b                   11.04872(16)
_cell_length_c                   13.15156(19)
_cell_measurement_reflns_used    46157
_cell_measurement_temperature    173.01(10)
_cell_measurement_theta_max      79.676
_cell_measurement_theta_min      3.699
_cell_volume                     1371.22(4)
_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 2018/2 (Sheldrick, 2018)'
_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 0.999
_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    -95.00  -6.00   1.00    0.50    --  -23.00 -63.00 -29.00   89
  2  \w    -40.00  50.00   1.00    0.50    --  -23.00  63.00 107.00   90
  3  \w     31.00 120.00   1.00    0.50    --   47.95  63.00 107.00   89
  4  \w     96.00 177.00   1.00    4.00    --  113.25  63.00 107.00   81
  5  \w     42.00  71.00   1.00    4.00    --  113.25 -63.00 -29.00   29
  6  \w    -70.00 -12.00   1.00    0.50    --  -23.00 125.00  60.00   58
  7  \w    -95.00   0.00   1.00    0.50    --  -23.00 -77.00 150.00   95
  8  \w    -95.00 -10.00   1.00    0.50    --  -23.00 -45.00 150.00   85
  9  \w      9.00  42.00   1.00    0.50    --   38.00  91.00 116.34   33
 10  \w     15.00  43.00   1.00    0.50    --   42.00  87.00-179.86   28
 11  \w     17.00  43.00   1.00    0.50    --   46.00  90.00  59.44   26
 12  \w     17.00  43.00   1.00    0.50    --   46.00  90.00 -88.97   26
 13  \w     -1.00  81.00   1.00    0.50    --   47.95 -99.00 -60.00   82
 14  \w    -24.00  65.00   1.00    0.50    --   47.95 -63.00 -29.00   89
 15  \w     29.00 122.00   1.00    0.50    --   50.00  74.00  32.18   93
 16  \w     28.00 122.00   1.00    0.50    --   50.00  76.00  -1.45   94
 17  \w     35.00 131.00   1.00    0.50    --   58.00  77.00  60.28   96
 18  \w     35.00 131.00   1.00    0.50    --   58.00  77.00  84.38   96
 19  \w     39.00 135.00   1.00    0.50    --   62.00  77.00-170.00   96
 20  \w     41.00 135.00   1.00    0.50    --   62.00  73.00 -23.90   94
 21  \w     40.00 135.00   1.00    0.50    --   62.00  75.00 -85.32   95
 22  \w     39.00 135.00   1.00    0.50    --   62.00  77.00-142.50   96
 23  \w     40.00 135.00   1.00    0.50    --   62.00  76.00 120.28   95
 24  \w     44.00 139.00   1.00    0.50    --   66.00  76.00 145.95   95
 25  \w     44.00 139.00   1.00    0.50    --   66.00  75.00 -59.02   95
 26  \w     44.00 139.00   1.00    0.50    --   66.00  76.00-119.05   95
 27  \w     44.00 139.00   1.00    0.50    --   66.00  76.00  10.67   95
 28  \w     51.00 143.00   1.00    0.50    --   70.00  67.00 105.25   92
 29  \w     47.00 143.00   1.00    0.50    --   70.00  77.00  51.05   96
 30  \w     51.00 143.00   1.00    0.50    --   70.00  69.00 174.14   92
 31  \w     48.00 143.00   1.00    0.50    --   70.00  75.00 -19.04   95
 32  \w     57.00 146.00   1.00    0.50    --   74.00  64.00-110.73   89
 33  \w     55.00 146.00   1.00    0.50    --   74.00  69.00  63.40   91
 34  \w     55.00 146.00   1.00    0.50    --   74.00  69.00 121.36   91
 35  \w     59.00 151.00   1.00    0.50    --   78.00  67.00 -53.21   92
 36  \w     62.00 150.00   1.00    0.50    --   78.00  60.00 -58.94   88
 37  \w     55.00 151.00   1.00    0.50    --   78.00  77.00   3.36   96
 38  \w     62.00 154.00   1.00    4.00    --   82.00  71.00  23.37   92
 39  \w     64.00 159.00   1.00    4.00    --   86.00  76.00-177.58   95
 40  \w     70.00 162.00   1.00    4.00    --   90.00  71.00 -41.47   92
 41  \w     80.00 170.00   1.00    4.00    --   98.00  65.00  60.01   90
 42  \w     86.00 175.00   1.00    4.00    --  102.00  61.00  -1.43   89
 43  \w    136.00 173.00   1.00    4.00    --  113.25  77.00-120.00   37
 44  \w    142.00 171.00   1.00    4.00    --  113.25  61.00  90.00   29
 45  \w     53.00 103.00   1.00    4.00    --  113.25 -94.00 150.00   50
 46  \w     99.00 127.00   1.00    4.00    --  113.25  61.00  90.00   28
 47  \w     91.00 176.00   1.00    4.00    --  113.25  77.00   0.00   85
 48  \w     44.00 106.00   1.00    4.00    --  113.25 -94.00 -30.00   62
 49  \w     97.00 175.00   1.00    4.00    --  113.25  61.00 150.00   78
 50  \w    135.00 170.00   1.00    4.00    --  113.25  61.00  30.00   35
 51  \w     98.00 130.00   1.00    4.00    --  113.25  61.00  30.00   32
 52  \w     97.00 130.00   1.00    4.00    --  113.25  61.00 120.00   33
 53  \w     93.00 177.00   1.00    4.00    --  113.25  77.00 -60.00   84
 54  \w     83.00 109.00   1.00    4.00    --  113.25-113.00 -67.43   26
 55  \w     81.00 106.00   1.00    4.00    --  113.25 -94.00  60.00   25
 56  \w     45.00  88.00   1.00    4.00    --  113.25 -77.00  30.00   43
 57  \w     91.00 130.00   1.00    4.00    --  113.25  77.00-120.00   39
 58  \w     44.00  97.00   1.00    4.00    --  113.25 -77.00   0.00   53
 59  \w    132.00 167.00   1.00    4.00    --  113.25  77.00  60.00   35
 60  \w     43.00  69.00   1.00    4.00    --  113.25-113.00 -67.43   26
 61  \w     91.00 122.00   1.00    4.00    --  113.25  77.00  60.00   31
 62  \w    144.00 176.00   1.00    4.00    --  113.25  77.00 -90.00   32
 63  \w    141.00 177.00   1.00    4.00    --  113.25  70.00-100.54   36
 64  \w     94.00 126.00   1.00    4.00    --  113.25  77.00 -90.00   32
 65  \w     91.00 137.00   1.00    4.00    --  113.25  77.00 -15.41   46
 66  \w    150.00 177.00   1.00    4.00    --  113.25  77.00-150.00   27
 67  \w     95.00 135.00   1.00    4.00    --  113.25  70.00-100.54   40
 68  \w     91.00 117.00   1.00    4.00    --  113.25  77.00-150.00   26
 69  \w     98.00 163.00   1.00    4.00    --  113.25  61.00-150.00   65
 70  \w     97.00 159.00   1.00    4.00    --  113.25  61.00-180.00   62
 71  \w    138.00 164.00   1.00    4.00    --  113.25  61.00 -60.00   26
 72  \w     81.00 106.00   1.00    4.00    --  113.25 -94.00  90.00   25
 73  \w     98.00 134.00   1.00    4.00    --  113.25  61.00 -60.00   36
 74  \w     46.00  90.00   1.00    4.00    --  113.25 -77.00-180.00   44
 75  \w    150.00 176.00   1.00    4.00    --  113.25  77.00 150.00   26
 76  \w     42.00  68.00   1.00    4.00    --  113.25 -61.00 -90.00   26
 77  \w     93.00 140.00   1.00    4.00    --  113.25  77.00 150.00   47
 78  \w    142.00 168.00   1.00    4.00    --  113.25  77.00 120.00   26
 79  \w    137.00 165.00   1.00    4.00    --  113.25  61.00 -30.00   28
 80  \w     92.00 136.00   1.00    4.00    --  113.25  77.00 120.00   44
 81  \w    100.00 133.00   1.00    4.00    --  113.25  61.00 -30.00   33
 82  \w    109.00 135.00   1.00    4.00    --  113.25  45.00  60.00   26
 83  \w    144.00 172.00   1.00    4.00    --  113.25  45.00  60.00   28
 84  \w     79.00 105.00   1.00    4.00    --  113.25 -94.00-150.00   26
 85  \w     76.00 102.00   1.00    4.00    --  113.25 -94.00 120.00   26
 86  \w    142.00 171.00   1.00    4.00    --  113.25  77.00 -15.41   29
 87  \w     44.00  70.00   1.00    4.00    --  113.25 -94.00 120.00   26
 88  \w     42.00  68.00   1.00    4.00    --  113.25 -61.00 -60.00   26
 89  \w    136.00 162.00   1.00    4.00    --  113.25  61.00-120.00   26
 90  \w     50.00  94.00   1.00    4.00    --  113.25 -77.00-150.00   44
 91  \w     48.00  93.00   1.00    4.00    --  113.25 -77.00 -90.00   45
 92  \w     43.00  69.00   1.00    4.00    --  113.25 -94.00-150.00   26
 93  \w    131.00 176.00   1.00    4.00    --  113.25  77.00-180.00   45
 94  \w     45.00  71.00   1.00    4.00    --  113.25 -94.00 -90.00   26
 95  \w     80.00 106.00   1.00    4.00    --  113.25 -94.00 -90.00   26
 96  \w     77.00 105.00   1.00    4.00    --  113.25 -94.00   0.00   28
 97  \w     97.00 123.00   1.00    4.00    --  113.25  61.00-120.00   26
 98  \w     92.00 117.00   1.00    4.00    --  113.25  77.00-180.00   25
 99  \w     42.00  67.00   1.00    4.00    --  113.25 -61.00 150.00   25
100  \w     43.00  77.00   1.00    4.00    --  113.25 -94.00  90.00   34
;
_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      0.1036969
_diffrn_orient_matrix_UB_12      -0.0151851
_diffrn_orient_matrix_UB_13      0.0734103
_diffrn_orient_matrix_UB_21      -0.1061198
_diffrn_orient_matrix_UB_22      -0.0569506
_diffrn_orient_matrix_UB_23      0.0594753
_diffrn_orient_matrix_UB_31      -0.0272797
_diffrn_orient_matrix_UB_32      -0.1500485
_diffrn_orient_matrix_UB_33      -0.0880018
_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  0.0224
_diffrn_reflns_av_unetI/netI     0.0228
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            51627
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.904
_diffrn_reflns_theta_min         3.705
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.733
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.74293
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.41.112a (Rigaku Oxford Diffraction, 2021)
        Empirical absorption correction using spherical harmonics,
        implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.155
_exptl_crystal_description       needle
_exptl_crystal_F_000             516
_exptl_crystal_size_max          0.236
_exptl_crystal_size_mid          0.183
_exptl_crystal_size_min          0.122
_refine_diff_density_max         0.377
_refine_diff_density_min         -0.382
_refine_diff_density_rms         0.031
_refine_ls_extinction_coef       0.00142(13)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     443
_refine_ls_number_reflns         4979
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0215
_refine_ls_R_factor_gt           0.0213
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0267P)^2^+0.4182P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0562
_refine_ls_wR_factor_ref         0.0564
_reflns_Friedel_coverage         0
_reflns_number_gt                4919
_reflns_number_total             4979
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03892d2.cif
_cod_data_source_block           21EH222_NJ-3-99
_cod_depositor_comments
'Adding full bibliography for 1572338--1572342.cif.'
_cod_database_code               1572341
_shelx_estimated_absorpt_t_min   0.565
_shelx_estimated_absorpt_t_max   0.732
_oxdiff_exptl_absorpt_empirical_details
;
        Empirical correction (ABSPACK) includes:
        - Absorption correction using spherical harmonics
        - Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.551
_oxdiff_exptl_absorpt_empirical_full_min 0.797
_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. Rigid bond restraints
 C18, C19A, C20A, C21A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
        3. Others
 Sof(H18A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(H20A)=Sof(C21A)=Sof(H21C)=
 Sof(H21D)=1-FVAR(1)
 Sof(H18)=Sof(C19)=Sof(C20)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H19)=Sof(H20)=
 FVAR(1)
        4.a Ternary CH refined with riding coordinates:
 C18(H18), C18(H18A), C19A(H19A)
        4.b Aromatic/amide H refined with riding coordinates:
 C20A(H20A)
        4.c X=CH2 refined with riding coordinates:
 C21(H21A,H21B), C21A(H21C,H21D)
        4.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_shelx_res_checksum              95427
_shelx_hkl_checksum              69957