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_1572340
_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         'C46 H76 K2 N2 O10 Zn2'
_chemical_formula_sum            'C46 H76 K2 N2 O10 Zn2'
_chemical_formula_weight         1026.02
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-07-12
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-05-26 deposited with the CCDC.	2024-08-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.3733(3)
_cell_length_b                   15.7455(3)
_cell_length_c                   18.5165(3)
_cell_measurement_reflns_used    14363
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      78.8650
_cell_measurement_theta_min      4.4050
_cell_volume                     5356.76(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -77.00 -20.00   0.50    0.40    --  -23.00 139.00 175.00  114
  2  \w    -74.00 -16.00   0.50    0.40    --  -23.00 131.00   1.00  116
  3  \w    -95.00   0.00   0.50    0.40    --  -23.00 -77.00 -90.00  190
  4  \w    -70.00 -12.00   0.50    0.40    --  -23.00 125.00-180.00  116
  5  \w    -30.00  53.00   0.50    0.40    --  -23.00  19.00 120.00  166
  6  \w    -27.00  23.00   0.50    0.40    --   47.42 -19.00 -60.00  100
  7  \w    -25.00  40.00   0.50    0.40    --   47.42 -38.00-120.00  130
  8  \w    -27.00  23.00   0.50    0.40    --   47.42 -19.00-150.00  100
  9  \w    101.00 177.00   0.50    4.00    --  113.25  45.00  30.00  152
 10  \w     42.00  68.00   0.50    4.00    --  113.25 -61.00   0.00   52
 11  \w     91.00 177.00   0.50    4.00    --  113.25  77.00 -90.00  172
 12  \w     96.00 177.00   0.50    4.00    --  113.25  64.00 141.86  162
 13  \w     42.00  68.00   0.50    4.00    --  113.25 -61.00  90.00   52
 14  \w     42.00  68.00   0.50    4.00    --  113.25 -61.00  60.00   52
 15  \w     42.00 106.00   0.50    4.00    --  113.25 -98.00-148.67  128
 16  \w     42.00 106.00   0.50    4.00    --  113.25 -94.00-180.00  128
 17  \w     42.00 106.00   0.50    4.00    --  113.25 -94.00-120.00  128
 18  \w     97.00 177.00   0.50    4.00    --  113.25  61.00-120.00  160
 19  \w     42.00  68.00   0.50    4.00    --  113.25 -61.00 -90.00   52
 20  \w     42.00 108.00   0.50    4.00    --  113.25-106.00 -56.58  132
 21  \w     42.00 106.00   0.50    4.00    --  113.25 -94.00 -60.00  128
 22  \w     42.00  68.00   0.50    4.00    --  113.25 -61.00-150.00   52
 23  \w     42.00  68.00   0.50    4.00    --  113.25 -61.00 -60.00   52
 24  \w     42.00 102.00   0.50    4.00    --  113.25 -77.00 150.00  120
 25  \w     42.00 102.00   0.50    4.00    --  113.25 -77.00-120.00  120
 26  \w    101.00 177.00   0.50    4.00    --  113.25  45.00 -60.00  152
 27  \w     91.00 177.00   0.50    4.00    --  113.25  75.00  -8.87  172
 28  \w     25.00  79.00   0.50    0.40    --   47.42  77.00 150.00  108
 29  \w     25.00 119.00   0.50    0.40    --   47.42  77.00   0.00  188
;
_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      -0.0022407000
_diffrn_orient_matrix_UB_12      -0.0552043000
_diffrn_orient_matrix_UB_13      0.0686137000
_diffrn_orient_matrix_UB_21      -0.0078288000
_diffrn_orient_matrix_UB_22      -0.0803302000
_diffrn_orient_matrix_UB_23      -0.0469853000
_diffrn_orient_matrix_UB_31      0.0834104000
_diffrn_orient_matrix_UB_32      -0.0090877000
_diffrn_orient_matrix_UB_33      -0.0024935000
_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  0.0375
_diffrn_reflns_av_unetI/netI     0.0176
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            50695
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.504
_diffrn_reflns_theta_min         4.402
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.909
_exptl_absorpt_correction_T_max  0.665
_exptl_absorpt_correction_T_min  0.577
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.61a (Rigaku Oxford Diffraction, 2019)
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_colour_primary    colourless
_exptl_crystal_density_diffrn    1.272
_exptl_crystal_description       block
_exptl_crystal_F_000             2176
_exptl_crystal_size_max          0.252
_exptl_crystal_size_mid          0.234
_exptl_crystal_size_min          0.197
_refine_diff_density_max         0.521
_refine_diff_density_min         -0.646
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     306
_refine_ls_number_reflns         5474
_refine_ls_number_restraints     48
_refine_ls_restrained_S_all      1.101
_refine_ls_R_factor_all          0.0525
_refine_ls_R_factor_gt           0.0473
_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^)+(0.0685P)^2^+4.0507P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1317
_refine_ls_wR_factor_ref         0.1367
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4842
_reflns_number_total             5474
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03892d2.cif
_cod_data_source_block           22eh088_nj-3-181
_cod_depositor_comments
'Adding full bibliography for 1572338--1572342.cif.'
_cod_original_cell_volume        5356.74(16)
_cod_database_code               1572340
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C23H34KNO5Zn
_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(C19) \\sim Ueq, Uanis(C19A) \\sim Ueq, Uanis(C18A) \\sim Ueq, Uanis(C18)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.2
Uanis(C22) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C23)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.2
3. Others
 Sof(C19A)=Sof(H19B)=Sof(H19A)=1-FVAR(1)
 Sof(C19)=Sof(H19C)=Sof(H19D)=FVAR(1)
 Sof(H17C)=Sof(H17D)=Sof(C18A)=Sof(H18A)=Sof(H18B)=1-FVAR(2)
 Sof(H17A)=Sof(H17B)=Sof(C18)=Sof(H18C)=Sof(H18D)=FVAR(2)
4.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C22(H22A,H22B), C17(H17C,H17D), C17(H17A,H17B), C19A(H19B,
 H19A), C23(H23A,H23B), C20(H20A,H20B), C21(H21A,H21B), C18A(H18A,H18B),
 C19(H19C,H19D), C18(H18C,H18D)
4.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C5(H5), C3(H3)
4.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C10(H10A,H10B,H10C), C14(H14A,H14B,H14C), C15(H15A,H15B,
 H15C), C13(H13A,H13B,H13C), C9(H9A,H9B,H9C)
;
_shelx_res_checksum              59350
_shelx_hkl_checksum              57456
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.802
_oxdiff_exptl_absorpt_empirical_full_min 0.589