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_1572342
_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         'C34 H56 K2 O4 Zn'
_chemical_formula_sum            'C34 H56 K2 O4 Zn'
_chemical_formula_weight         672.35
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-12-07T16:34:26-00:00
_audit_update_record
;
2024-05-26 deposited with the CCDC.	2024-08-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.2607(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.08965(17)
_cell_length_b                   26.6881(3)
_cell_length_c                   18.63986(19)
_cell_measurement_reflns_used    71422
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      31.823
_cell_measurement_theta_min      2.089
_cell_volume                     7335.32(14)
_computing_cell_refinement       'CrysAlisPro 1.171.43.95a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 42.102a 64-bit (release 15-09-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.95a (Rigaku OD, 2023)'
_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-Arc 100'
_diffrn_measured_fraction_theta_full 0.999
_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    -38.00  49.00   0.50    2.00    --   13.29 -88.00  -5.00  174
  2  \w    -22.00  41.00   0.50    2.00    --   13.29  88.00 110.00  126
  3  \w    -49.00  41.00   0.50    2.00    --  -13.44  88.00 110.00  180
  4  \w    -37.00  21.00   0.50    2.00    --  -13.44 -88.00  -5.00  116
  5  \w     -7.00  94.00   0.50    2.00    --   13.29  38.00-150.00  202
  6  \w    -68.00  28.00   0.50    2.00    --   13.29 -19.00 -90.00  192
  7  \w    -68.00  28.00   0.50    2.00    --   13.29 -19.00-180.00  192
  8  \w    -89.00 -40.00   0.50    2.00    --  -13.44 178.00-180.00   98
  9  \w    -87.00 -42.00   0.50    2.00    --  -13.44-178.00 -30.00   90
 10  \w    -42.00  56.00   0.50    2.00    --  -13.44  77.00-150.00  196
 11  \w     -8.00  66.00   0.50    2.00    --   13.29  57.00 -60.00  148
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0401191
_diffrn_orient_matrix_UB_12      -0.014605
_diffrn_orient_matrix_UB_13      -0.0048332
_diffrn_orient_matrix_UB_21      0.0242688
_diffrn_orient_matrix_UB_22      -0.0190604
_diffrn_orient_matrix_UB_23      0.0224618
_diffrn_orient_matrix_UB_31      -0.0108241
_diffrn_orient_matrix_UB_32      0.0113807
_diffrn_orient_matrix_UB_33      0.0314345
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0432
_diffrn_reflns_av_unetI/netI     0.0568
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 1
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            222585
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 1
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.508
_diffrn_reflns_theta_min         2.058
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Mova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.929
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.697
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.43.95a (Rigaku Oxford Diffraction, 2023)
        Numerical absorption correction based on gaussian integration over
        a multifaceted crystal model
        Empirical absorption correction using spherical harmonics,
        implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.218
_exptl_crystal_description       block
_exptl_crystal_F_000             2880
_exptl_crystal_size_max          0.257
_exptl_crystal_size_mid          0.226
_exptl_crystal_size_min          0.156
_refine_diff_density_max         0.624
_refine_diff_density_min         -0.47
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     848
_refine_ls_number_reflns         22397
_refine_ls_number_restraints     104
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0691
_refine_ls_R_factor_gt           0.0475
_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^)+(0.0651P)^2^+2.8509P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1172
_refine_ls_wR_factor_ref         0.1269
_reflns_Friedel_coverage         0
_reflns_number_gt                16804
_reflns_number_total             22397
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03892d2.cif
_cod_data_source_block           23EH377_NJ-3-378
_cod_depositor_comments
'Adding full bibliography for 1572338--1572342.cif.'
_cod_original_cell_volume        7335.31(14)
_cod_database_code               1572342
_shelx_estimated_absorpt_t_min   0.794
_shelx_estimated_absorpt_t_max   0.866
_oxdiff_exptl_absorpt_empirical_details
;
        Empirical correction (ABSPACK) includes:
        - Absorption correction using spherical harmonics
        - Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.162
_oxdiff_exptl_absorpt_empirical_full_min 0.831
_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. Restrained distances
 C33A-C32A \\sim C33-C32
 with sigma of 0.002
 C34-C33 \\sim C32A-C31A \\sim C32-C31 \\sim C34A-C33A
 with sigma of 0.002
        3. Rigid bond restraints
 O4, C31A, C32A, C33A, C34A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O3, C27A, C28A, C29, C30
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O3, C27, C28, C29, C30
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O7, C64, C63, C62, C61
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
        4. Uiso/Uaniso restraints and constraints
        Uanis(C31) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.02
        Uanis(C31A) \\sim Ueq, Uanis(C32A) \\sim Ueq, Uanis(C33A) \\sim Ueq,
        Uanis(C34A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
        Uanis(C28A) \\sim Ueq, Uanis(C27A) \\sim Ueq: with sigma of 0.01 and sigma for
        terminal atoms of 0.02
        Uanis(C64) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C61) \\sim Ueq: with sigma of
        0.01 and sigma for terminal atoms of 0.02
        5. Others
 Sof(C31A)=Sof(H31C)=Sof(H31D)=Sof(C34A)=Sof(H34C)=Sof(H34D)=Sof(C32A)=
 Sof(H32C)=Sof(H32D)=Sof(C33A)=Sof(H33C)=Sof(H33D)=1-FVAR(1)
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(C34)=Sof(H34A)=
 Sof(H34B)=Sof(C31)=Sof(H31A)=Sof(H31B)=FVAR(1)
 Sof(H29C)=Sof(H29D)=Sof(C28A)=Sof(H28C)=Sof(H28D)=1-FVAR(2)
 Sof(H29A)=Sof(H29B)=Sof(C28)=Sof(H28A)=Sof(H28B)=FVAR(2)
 Sof(C27A)=Sof(H27C)=Sof(H27D)=1-FVAR(3)
 Sof(C27)=Sof(H27A)=Sof(H27B)=FVAR(3)
        6.a Secondary CH2 refined with riding coordinates:
 C66(H66A,H66B), C67(H67A,H67B), C65(H65A,H65B), C68(H68A,H68B), C29(H29A,
 H29B), C29(H29C,H29D), C33(H33A,H33B), C30(H30A,H30B), C32(H32A,H32B),
 C34(H34A,H34B), C62(H62A,H62B), C61(H61A,H61B), C28(H28A,H28B), C27(H27A,H27B),
  C63(H63A,H63B), C64(H64A,H64B), C31(H31A,H31B), C31A(H31C,H31D), C34A(H34C,
 H34D), C32A(H32C,H32D), C33A(H33C,H33D), C28A(H28C,H28D), C27A(H27C,H27D)
        6.b Aromatic/amide H refined with riding coordinates:
 C41(H41), C16(H16), C50(H50), C12(H12), C37(H37), C3(H3), C39(H39), C14(H14),
 C46(H46), C7(H7), C48(H48), C5(H5)
        6.c Idealised Me refined as rotating group:
 C60(H60A,H60B,H60C), C24(H24B,H24A,H24C), C26(H26A,H26B,H26C), C20(H20C,H20B,
 H20A), C54(H54A,H54B,H54C), C25(H25A,H25C,H25B), C43(H43A,H43B,H43C), C59(H59A,
 H59B,H59C), C58(H58A,H58C,H58B), C56(H56C,H56B,H56A), C22(H22C,H22B,H22A),
 C21(H21A,H21B,H21C), C42(H42A,H42B,H42C), C55(H55A,H55B,H55C), C17(H17A,H17B,
 H17C), C18(H18A,H18B,H18C), C52(H52A,H52B,H52C), C51(H51A,H51B,H51C), C9(H9A,
 H9B,H9C), C8(H8A,H8B,H8C)
;
_shelx_res_checksum              96854
_shelx_hkl_checksum              67885