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_7133712
_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
'4(C32 H36 B), 2(C24 H56 N8 Zn2), 5(C4 H10 O), 11(C2 H3 N)'
_chemical_formula_sum            'C218 H339 B4 N27 O5 Zn4'
_chemical_formula_weight         3722.86
_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   mixed
_audit_creation_date             2024-08-15
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.2793(3)
_cell_length_b                   19.2350(5)
_cell_length_c                   47.6175(10)
_cell_measurement_reflns_used    177759
_cell_measurement_temperature    100
_cell_measurement_theta_max      71.24
_cell_measurement_theta_min      2.60
_cell_volume                     22238.0(8)
_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 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0716
_diffrn_reflns_av_unetI/netI     0.0293
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       58
_diffrn_reflns_limit_l_min       -51
_diffrn_reflns_number            270691
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.859
_diffrn_reflns_theta_min         2.599
_exptl_absorpt_coefficient_mu    0.923
_exptl_absorpt_correction_T_max  0.9935
_exptl_absorpt_correction_T_min  0.7905
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE X-Red32, absorption correction by Gaussian integration, analogous to
P. Coppens in: F. R. Ahmed (Editor), "Crystallographic Computing", Munksgaard,
Copenhagen (1970), 255 - 270. Afterwards scaling of reflection intensities was
performed within STOE LANA. J. Koziskova, F. Hahn, J. Richter, J. Kozisek, Acta
Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
Finally a spherical absorption correction was done within STOE LANA.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.112
_exptl_crystal_description       block
_exptl_crystal_F_000             8064
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.163
_exptl_crystal_size_min          0.14
_refine_diff_density_max         1.341
_refine_diff_density_min         -0.644
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1280
_refine_ls_number_reflns         21322
_refine_ls_number_restraints     110
_refine_ls_restrained_S_all      7.652
_refine_ls_R_factor_all          0.1009
_refine_ls_R_factor_gt           0.0762
_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^)+(0.1506P)^2^+30.9336P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2227
_refine_ls_wR_factor_ref         0.2496
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15720
_reflns_number_total             21322
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc04266b2.cif
_cod_data_source_block           4
_cod_depositor_comments
'Adding full bibliography for 7133709--7133712.cif.'
_cod_database_code               7133712
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.882
_shelx_estimated_absorpt_t_min   0.837
_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
 C107-C108 = C108-O3 = O3-C109 = C109-C110
 1.48 with sigma of 0.02
 C107-O3 = C108-C109 = O3-C110
 2.2 with sigma of 0.02
 C111-C112 = C112-O2 = O2-C105 = C105-C106
 1.48 with sigma of 0.02
 C111-O2 = C112-C105 = O2-C106
 2.2 with sigma of 0.02
 C113-C114 = C114-O4 = O4-C115 = C115-C116
 1.48 with sigma of 0.02
 C113-O4 = C114-C115 = O4-C116
 2.2 with sigma of 0.02
 C95-C96 = C104-C103
 1.5 with sigma of 0.02
 N12-C95 = N14-C104
 1.15 with sigma of 0.02
 H52-H96C
 2.1 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O4 \\sim C113 \\sim C114 \\sim C115 \\sim C116: within 2A with sigma of 0.005
and sigma for terminal atoms of 0.01 within 2A
O2 \\sim C111 \\sim C112 \\sim C105 \\sim C106: within 2A with sigma of 0.005
and sigma for terminal atoms of 0.01 within 2A
O3 \\sim C107 \\sim C108 \\sim C109 \\sim C110: within 2A with sigma of 0.005
and sigma for terminal atoms of 0.01 within 2A
N14 \\sim C104 \\sim C103: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01 within 2A
4. Others
 Fixed Sof: O2(0.5) C111(0.5) H11D(0.5) H11E(0.5) H11F(0.5) C112(0.5)
 H11G(0.5) H11H(0.5) C105(0.5) H10K(0.5) H10L(0.5) C106(0.5) H10M(0.5)
 H10N(0.5) H10O(0.5) O3(0.5) C107(0.5) H10P(0.5) H10Q(0.5) H10R(0.5) C108(0.5)
 H10S(0.5) H10T(0.5) C109(0.5) H10U(0.5) H10V(0.5) C110(0.5) H11I(0.5)
 H11J(0.5) H11K(0.5) N14(0.5) C104(0.5) C103(0.5) H10W(0.5) H10X(0.5) H10Y(0.5)
 O4(0.5) C113(0.5) H11L(0.5) H11M(0.5) H11N(0.5) C114(0.5) H11O(0.5) H11P(0.5)
 C115(0.5) H11Q(0.5) H11R(0.5) C116(0.5) H11S(0.5) H11T(0.5) H11U(0.5)
5.a Riding coordinates:
 C103(H10W,H10X,H10Y)
5.b 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), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B),
 C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B),
  C100(H10D,H10E), C101(H10F,H10G), C112(H11G,H11H), C105(H10K,H10L), C108(H10S,
 H10T), C109(H10U,H10V), C114(H11O,H11P), C115(H11Q,H11R)
5.c Aromatic/amide H refined with riding coordinates:
 C26(H26), C28(H28), C30(H30), C34(H34), C36(H36), C38(H38), C42(H42),
 C44(H44), C46(H46), C50(H50), C52(H52), C54(H54), C58(H58), C60(H60), C62(H62),
  C66(H66), C68(H68), C70(H70), C74(H74), C76(H76), C78(H78), C82(H82),
 C84(H84), C86(H86)
5.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,
 H12C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,
 H24B,H24C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C39(H39A,H39B,H39C),
 C40(H40A,H40B,H40C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C55(H55A,H55B,
 H55C), C56(H56A,H56B,H56C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C71(H71A,
 H71B,H71C), C72(H72A,H72B,H72C), C79(H79A,H79B,H79C), C80(H80A,H80B,H80C),
 C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C90(H90A,H90B,H90C), C92(H92A,H92B,
 H92C), C94(H94A,H94B,H94C), C96(H96A,H96B,H96C), C98(H98A,H98B,H98C), C99(H99A,
 H99B,H99C), C102(H10H,H10I,H10J), C111(H11D,H11E,H11F), C106(H10M,H10N,H10O),
 C107(H10P,H10Q,H10R), C110(H11I,H11J,H11K), C113(H11L,H11M,H11N), C116(H11S,
 H11T,H11U)
;
_shelx_res_checksum              6852
_shelx_hkl_checksum              72233
_olex2_submission_special_instructions 'No special instructions were received'