Hypervalent zinc(I) complexes with an <i>NNNN</i>-macrocycle: C-H bond activation across the zinc(I)-zinc(I) bond.
Mahawar, Pritam; Rajeshkumar, Thayalan; Spaniol, Thomas P.; Maron, Laurent; Okuda, Jun; Chemical communications (Cambridge, England) 60 (2024) 11359–11362; doi:10.1039/d4cc04266b

data_7133709
_publ_section_title
;
 Hypervalent zinc(I) complexes with an <i>NNNN</i>-macrocycle: C-H bond
 activation across the zinc(I)-zinc(I) bond.
;
_journal_issue                   80
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              11359
_journal_page_last               11362
_journal_paper_doi               10.1039/d4cc04266b
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety
'2(C32 H36 B), 2(C22 H43 N4 Zn2), 3(C2 H3 N), 2(C5 H12)'
_chemical_formula_sum            'C124 H191 B2 N11 Zn4'
_chemical_formula_weight         2118.97
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-08-08
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-08-19 deposited with the CCDC.	2024-09-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.0970(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.5774(2)
_cell_length_b                   14.25140(10)
_cell_length_c                   34.1633(5)
_cell_measurement_reflns_used    86876
_cell_measurement_temperature    100
_cell_measurement_theta_max      70.90
_cell_measurement_theta_min      4.72
_cell_volume                     6062.57(14)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100
_diffrn_detector                 Pilatus200K
_diffrn_detector_area_resol_mean 5.81
_diffrn_detector_type            'DECTRIS PILATUS 200K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_details
;
 5366 frames, detector distance = 60 mm
;
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '0.5 mm diameter'
_diffrn_radiation_monochromator  'Graded multilayer mirror'
_diffrn_radiation_polarisn_norm  270
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54186
_diffrn_reflns_av_R_equivalents  0.0146
_diffrn_reflns_av_unetI/netI     0.0064
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            98964
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.686
_diffrn_reflns_theta_max         71.076
_diffrn_reflns_theta_min         4.716
_diffrn_source                   'GeniX 3D HF Cu'
_diffrn_source_current           0.600
_diffrn_source_power             0.030
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.267
_exptl_absorpt_correction_T_max  0.9765
_exptl_absorpt_correction_T_min  0.8713
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE LANA, absorption correction by scaling of reflection intensities.
J. Koziskova, F. Hahn, J. Richter, J. Kozisek, "Comparison of different
absorption corrections on the model structure of tetrakis(\m~2~-acetato)-
diaqua-di-copper(II)", Acta Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
Afterwards a spherical absorption correction was performed within STOE LANA.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.161
_exptl_crystal_description       block
_exptl_crystal_F_000             2284
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.267
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.981
_refine_diff_density_min         -0.634
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     787
_refine_ls_number_reflns         11668
_refine_ls_number_restraints     253
_refine_ls_restrained_S_all      1.108
_refine_ls_R_factor_all          0.0407
_refine_ls_R_factor_gt           0.0400
_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^)+(0.0691P)^2^+4.2436P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1155
_refine_ls_wR_factor_ref         0.1161
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11331
_reflns_number_total             11668
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc04266b2.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 7133709--7133712.cif.'
_cod_database_code               7133709
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.768
_shelx_estimated_absorpt_t_min   0.665
_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
 C59-C60 = C62-C63
 1.48 with sigma of 0.02
 C63-C62 = C62A-C61A
 1.48 with sigma of 0.02
 C62-C61 = C61A-C60A
 1.48 with sigma of 0.02
 C61-C60 = C60A-C59A
 1.48 with sigma of 0.02
 C62-C63 = C61A-C62A
 1.38 with sigma of 0.02
 C59-C61 = C60-C62 = C61-C63
 2.4 with sigma of 0.02
 C59A-C61A = C60A-C62A = C61A-C63A
 2.4 with sigma of 0.02
 C59-C60 \\sim C59A-C60A \\sim C62-C63 \\sim C62A-C63A
 with sigma of 0.02
 C60-C61 \\sim C59A-C60A \\sim C61-C62 \\sim C60A-C61A
 with sigma of 0.02
 N1-C1 \\sim N1-C1A
 with sigma of 0.02
 N1-C8 \\sim N1-C8A
 with sigma of 0.02
 N2-C2 \\sim N2-C2A
 with sigma of 0.02
 N2-C3 \\sim N2-C3A
 with sigma of 0.02
 N3-C4 \\sim N3-C4A
 with sigma of 0.02
 N3-C5A \\sim N3-C5
 with sigma of 0.02
 N4-C6 \\sim N4-C6A
 with sigma of 0.02
 N4-C7A \\sim N4-C7
 with sigma of 0.02
 C1-C2 \\sim C1A-C2A
 with sigma of 0.02
 C3-C4 \\sim C3A-C4A
 with sigma of 0.02
 C5A-C6 \\sim C5-C6A
 with sigma of 0.02
 C7A-C8 \\sim C7-C8A
 with sigma of 0.02
 N1-C2 \\sim N1-C2A
 with sigma of 0.04
 N1-C7A \\sim N1-C7
 with sigma of 0.04
 N2-C1 \\sim N2-C1A
 with sigma of 0.04
 N2-C4 \\sim N2-C4A
 with sigma of 0.04
 N3-C3 \\sim N3-C3A
 with sigma of 0.04
 N3-C6 \\sim N3-C6A
 with sigma of 0.04
 N4-C5A \\sim N4-C5
 with sigma of 0.04
 N4-C8 \\sim N4-C8A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C1 \\sim C1A \\sim C2 \\sim C2A \\sim C3 \\sim C3A \\sim C4 \\sim C4A: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C5A \\sim C5 \\sim C6 \\sim C6A \\sim C7A \\sim C7 \\sim C8 \\sim C8A: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 C59, C60, C61, C62, C63, C59A, C60A, C61A, C62A, C63A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C59A)=Sof(H59D)=Sof(H59E)=Sof(H59F)=Sof(C60A)=Sof(H60C)=Sof(H60D)=
 Sof(C61A)=Sof(H61C)=Sof(H61D)=Sof(C62A)=Sof(H62C)=Sof(H62D)=Sof(C63A)=
 Sof(H63D)=Sof(H63E)=Sof(H63F)=1-FVAR(1)
 Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(C61)=
 Sof(H61A)=Sof(H61B)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(C63)=Sof(H63A)=Sof(H63B)=
 Sof(H63C)=FVAR(1)
 Sof(C1A)=Sof(H1C)=Sof(H1D)=Sof(C2A)=Sof(H2C)=Sof(H2D)=Sof(C3A)=Sof(H3C)=
 Sof(H3D)=Sof(C4A)=Sof(H4C)=Sof(H4D)=Sof(C5A)=Sof(H5C)=Sof(H5D)=Sof(C6A)=
 Sof(H6C)=Sof(H6D)=Sof(C7A)=Sof(H7C)=Sof(H7D)=Sof(C8A)=Sof(H8C)=Sof(H8D)=1-
 FVAR(2)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(H3A)=Sof(H3B)=
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C6)=Sof(H6A)=Sof(H6B)=
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(C8)=Sof(H8A)=Sof(H8B)=FVAR(2)
 Fixed Sof: N6(0.5) C57(0.5) C58(0.5) H58A(0.5) H58B(0.5) H58C(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B),
 C7(H7A,H7B), C8(H8A,H8B), C1A(H1C,H1D), C2A(H2C,H2D), C3A(H3C,H3D), C4A(H4C,
 H4D), C5A(H5C,H5D), C6A(H6C,H6D), C7A(H7C,H7D), C8A(H8C,H8D), C60(H60A,H60B),
 C61(H61A,H61B), C62(H62A,H62B), C60A(H60C,H60D), C61A(H61C,H61D), C62A(H62C,
 H62D)
6.b Me refined with riding coordinates:
 C59(H59A,H59B,H59C), C63(H63A,H63B,H63C), C59A(H59D,H59E,H59F), C63A(H63D,
 H63E,H63F)
6.c Aromatic/amide H refined with riding coordinates:
 C24(H24), C26(H26), C28(H28), C32(H32), C34(H34), C36(H36), C40(H40),
 C42(H42), C44(H44), C48(H48), C50(H50), C52(H52)
6.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,
 H12C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,
 H21B,H21C), C22(H22A,H22B,H22C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C),
 C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C45(H45A,H45B,H45C), C46(H46A,H46B,
 H46C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C56(H56A,H56B,H56C), C58(H58A,
 H58B,H58C)
;
_shelx_res_checksum              80548
_shelx_hkl_checksum              4785
_olex2_submission_special_instructions 'No special instructions were received'