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_1572338
_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         'C44 H78 K2 O8 Zn2'
_chemical_formula_sum            'C44 H78 K2 O8 Zn2'
_chemical_formula_weight         944
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-09-06T09:29:55-00:00
_audit_update_record
;
2024-05-26 deposited with the CCDC.	2024-08-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.0280(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.74441(7)
_cell_length_b                   14.35189(9)
_cell_length_c                   14.07101(7)
_cell_measurement_reflns_used    39426
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      79.745
_cell_measurement_theta_min      3.068
_cell_volume                     2567.32(2)
_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      173.00(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 1
_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    -45.00  50.00   0.50    0.10    --  -23.00  76.00-144.00  190
  2  \w     26.00 120.00   0.50    0.10    --   47.95  76.00-144.00  188
  3  \w     91.00 177.00   0.50    0.50    --  113.25  76.00-144.00  172
  4  \w    101.00 177.00   0.50    0.50    --  113.25  40.00 -39.10  152
  5  \w    101.00 177.00   0.50    0.50    --  113.25  45.00-125.01  152
  6  \w    101.00 177.00   0.50    0.50    --  113.25  45.00-180.00  152
  7  \w     99.00 177.00   0.50    0.50    --  113.25  56.00-164.78  156
  8  \w     97.00 177.00   0.50    0.50    --  113.25  61.00 -30.00  160
  9  \w    100.00 177.00   0.50    0.50    --  113.25  15.00  60.00  154
 10  \w    101.00 177.00   0.50    0.50    --  113.25  30.00 150.00  152
 11  \w    101.00 177.00   0.50    0.50    --  113.25  45.00 150.00  152
 12  \w     97.00 177.00   0.50    0.50    --  113.25  61.00 150.00  160
 13  \w    101.00 177.00   0.50    0.50    --  113.25  45.00   0.00  152
 14  \w    101.00 177.00   0.50    0.50    --  113.25  19.00 -63.30  152
 15  \w    101.00 177.00   0.50    0.50    --  113.25  45.00-150.00  152
 16  \w    101.00 177.00   0.50    0.50    --  113.25  45.00 -90.00  152
 17  \w    100.00 177.00   0.50    0.50    --  113.25  15.00 -30.00  154
 18  \w     91.00 177.00   0.50    0.50    --  113.25  77.00 -60.00  172
 19  \w     91.00 177.00   0.50    0.50    --  113.25  77.00-120.00  172
 20  \w     92.00 177.00   0.50    0.50    --  113.25  73.00 -18.17  170
 21  \w     42.00  98.00   0.50    0.50    --  113.25 -76.00  88.00  112
 22  \w     42.00 102.00   0.50    0.50    --  113.25 -77.00 120.00  120
 23  \w     42.00 102.00   0.50    0.50    --  113.25 -77.00   0.00  120
 24  \w     42.00 102.00   0.50    0.50    --  113.25 -77.00 -60.00  120
 25  \w     42.00  68.00   0.50    0.50    --  113.25 -61.00   0.00   52
 26  \w     42.00  95.00   0.50    0.50    --  113.25 -75.00   3.56  106
 27  \w     42.00 102.00   0.50    0.50    --  113.25 -77.00  30.00  120
 28  \w     42.00 106.00   0.50    0.50    --  113.25 -94.00 150.00  128
 29  \w     42.00  68.00   0.50    0.50    --  113.25 -61.00  90.00   52
 30  \w     42.00 106.00   0.50    0.50    --  113.25 -94.00  90.00  128
 31  \w     42.00 102.00   0.50    0.50    --  113.25 -77.00  60.00  120
 32  \w     42.00 102.00   0.50    0.50    --  113.25 -77.00 150.00  120
 33  \w     36.00 121.00   0.50    0.10    --   47.95  38.00 -30.00  170
 34  \w     42.00  68.00   0.50    0.50    --  113.25 -61.00-180.00   52
 35  \w     42.00 106.00   0.50    0.50    --  113.25 -94.00-180.00  128
 36  \w     42.00 102.00   0.50    0.50    --  113.25 -77.00-180.00  120
 37  \w    -24.00  70.00   0.50    0.10    --   47.95 -76.00  88.00  188
 38  \w    -26.00  23.00   0.50    0.10    --   47.95 -19.00  90.00   98
 39  \w    -26.00  23.00   0.50    0.10    --   47.95 -19.00 120.00   98
 40  \w     25.00  89.00   0.50    0.10    --   47.95  77.00  90.00  128
 41  \w    -26.00  23.00   0.50    0.10    --   47.95 -19.00 -30.00   98
 42  \w    -46.00  50.00   0.50    0.10    --  -23.00  77.00 -30.00  192
 43  \w    -70.00 -12.00   0.50    0.10    --  -23.00 125.00  60.00  116
 44  \w    -97.00 -10.00   0.50    0.10    --  -23.00 -19.00-150.00  174
 45  \w    -94.00  -8.00   0.50    0.10    --  -23.00 -57.00-180.00  172
 46  \w    -95.00   0.00   0.50    0.10    --  -23.00 -76.00  88.00  190
;
_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      -0.0816597
_diffrn_orient_matrix_UB_12      0.0792271
_diffrn_orient_matrix_UB_13      -0.0019806
_diffrn_orient_matrix_UB_21      -0.0464697
_diffrn_orient_matrix_UB_22      -0.0411943
_diffrn_orient_matrix_UB_23      0.0890125
_diffrn_orient_matrix_UB_31      0.0764454
_diffrn_orient_matrix_UB_32      0.0596715
_diffrn_orient_matrix_UB_33      0.0641618
_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  0.0323
_diffrn_reflns_av_unetI/netI     0.038
_diffrn_reflns_Laue_measured_fraction_full 1
_diffrn_reflns_Laue_measured_fraction_max 1
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            50337
_diffrn_reflns_point_group_measured_fraction_full 1
_diffrn_reflns_point_group_measured_fraction_max 1
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.459
_diffrn_reflns_theta_min         4.406
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.946
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.66057
_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    1.221
_exptl_crystal_description       block
_exptl_crystal_F_000             1008
_exptl_crystal_size_max          0.317
_exptl_crystal_size_mid          0.266
_exptl_crystal_size_min          0.186
_refine_diff_density_max         0.321
_refine_diff_density_min         -0.259
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     315
_refine_ls_number_reflns         4926
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.029
_refine_ls_R_factor_gt           0.0286
_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^)+(0.0427P)^2^+0.8791P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0784
_refine_ls_wR_factor_ref         0.0788
_reflns_Friedel_coverage         0
_reflns_number_gt                4810
_reflns_number_total             4926
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03892d2.cif
_cod_data_source_block           21EH173_NJ-3-50
_cod_depositor_comments
'Adding full bibliography for 1572338--1572342.cif.'
_cod_database_code               1572338
_shelx_estimated_absorpt_t_min   0.455
_shelx_estimated_absorpt_t_max   0.61
_oxdiff_exptl_absorpt_empirical_details
;
        Empirical correction (ABSPACK) includes:
        - Absorption correction using spherical harmonics
        - Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.407
_oxdiff_exptl_absorpt_empirical_full_min 0.783
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
        2. Uiso/Uaniso restraints and constraints
Uanis(C18A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C21A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C22A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
        3. Others
 Sof(O00C)=Sof(H20C)=Sof(H20D)=Sof(C19A)=Sof(H19C)=Sof(H19D)=Sof(C21A)=
 Sof(H21C)=Sof(H21D)=Sof(C22A)=Sof(H22C)=Sof(H22D)=1-FVAR(1)
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H20A)=Sof(H20B)=
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(O4)=FVAR(1)
 Sof(H15C)=Sof(H15D)=Sof(H17C)=Sof(H17D)=Sof(C18A)=Sof(H18C)=Sof(H18D)=Sof(O0)=
 1-FVAR(2)
 Sof(O3)=Sof(H15A)=Sof(H15B)=Sof(H17A)=Sof(H17B)=Sof(C18)=Sof(H18A)=Sof(H18B)=
 FVAR(2)
        4.a Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C15(H15C,H15D), C22(H22A,H22B), C21(H21A,H21B), C20(H20A,
 H20B), C20(H20C,H20D), C16(H16A,H16B), C17(H17A,H17B), C17(H17C,H17D),
 C18(H18A,H18B), C19(H19A,H19B), C19A(H19C,H19D), C18A(H18C,H18D), C21A(H21C,
 H21D), C22A(H22C,H22D)
        4.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C3(H3), C2(H2), C4(H4), C5(H5)
        4.c Idealised Me refined as rotating group:
 C10(H10C,H10A,H10B), C9(H9A,H9B,H9C), C13(H13A,H13B,H13C), C14(H14A,H14B,
 H14C), C8(H8A,H8B,H8C), C12(H12A,H12B,H12C)
;
_shelx_res_checksum              30087
_shelx_hkl_checksum              41308