Zinc amidinate-catalysed cyclization reaction of carbodiimides and alkynes. An insight into the mechanism.
Parra-Cadenas, Blanca; Ginés, Carlos; García-Vivó, Daniel; Elorriaga, David; Carrillo-Hermosilla, Fernando; Dalton transactions (Cambridge, England : 2003) 53 (2024) 10050–10054; doi:10.1039/d4dt01265h

data_7716184
_publ_section_title
;
 Zinc amidinate-catalysed cyclization reaction of carbodiimides and
 alkynes. An insight into the mechanism.
;
_journal_issue                   24
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              10050
_journal_page_last               10054
_journal_paper_doi               10.1039/d4dt01265h
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         '4(C66 H78 N4 Zn)'
_chemical_formula_sum            'C264 H312 N16 Zn4'
_chemical_formula_weight         3970.76
_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_Hall           '-P 2n 2ab'
_space_group_name_H-M_alt        'P b c n'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-02-09
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-04-09 deposited with the CCDC.	2024-05-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   20.6268(7)
_cell_length_b                   16.0836(6)
_cell_length_c                   18.5709(6)
_cell_measurement_reflns_used    9178
_cell_measurement_temperature    250.0
_cell_measurement_theta_max      20.211
_cell_measurement_theta_min      2.719
_cell_volume                     6161.0(4)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      250.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker P4'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0519
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            55520
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.403
_diffrn_reflns_theta_min         1.606
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.438
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6874
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0570 before and 0.0489 after correction.
The Ratio of minimum to maximum transmission is 0.9224.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.070
_exptl_crystal_description       prism
_exptl_crystal_F_000             2128
_exptl_crystal_size_max          0.245
_exptl_crystal_size_mid          0.181
_exptl_crystal_size_min          0.176
_refine_diff_density_max         0.478
_refine_diff_density_min         -1.079
_refine_diff_density_rms         0.186
_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     420
_refine_ls_number_reflns         5669
_refine_ls_number_restraints     438
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.1392
_refine_ls_R_factor_gt           0.0805
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1919P)^2^+1.2193P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2314
_refine_ls_wR_factor_ref         0.2956
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3294
_reflns_number_total             5669
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01265h2.cif
_cod_data_source_block           bp19
_cod_depositor_comments
'Adding full bibliography for 7716182--7716185.cif.'
_cod_database_code               7716184
_shelx_shelxl_version_number     2017/1
_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. Uiso/Uaniso restraints and constraints
C4 \\sim C4A \\sim C5 \\sim C5A \\sim C6 \\sim C6A \\sim C7 \\sim C7A \\sim C8
\\sim C8A \\sim C9 \\sim C9A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.01 within 2A
C22 \\sim C22A \\sim C23 \\sim C23A \\sim C24 \\sim C24A \\sim C25 \\sim C25A
\\sim C26 \\sim C26A \\sim C27 \\sim C27A \\sim C29 \\sim C29A \\sim C28 \\sim
C28A \\sim C30 \\sim C30A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.01 within 2A
3. Others
 Sof(C4A)=Sof(C9A)=Sof(H9A)=Sof(C8A)=Sof(H8A)=Sof(C7A)=Sof(H7A)=Sof(C6A)=
 Sof(H6A)=Sof(C5A)=Sof(H5A)=1-FVAR(1)
 Sof(C4)=Sof(C9)=Sof(H9)=Sof(C8)=Sof(H8)=Sof(C7)=Sof(H7)=Sof(C6)=Sof(H6)=
 Sof(C5)=Sof(H5)=FVAR(1)
 Sof(C28A)=Sof(H28A)=Sof(H31A)=Sof(C29A)=Sof(H29A)=Sof(H29B)=Sof(H29C)=
 Sof(C22A)=Sof(C27A)=Sof(C26A)=Sof(H26A)=Sof(C25A)=Sof(H25A)=Sof(C24A)=
 Sof(H24A)=Sof(C23A)=Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=1-FVAR(2)
 Sof(C22)=Sof(C27)=Sof(C26)=Sof(H26)=Sof(C25)=Sof(H25)=Sof(C24)=Sof(H24)=
 Sof(C23)=Sof(H31)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C28)=Sof(H28)=
 Sof(C29)=Sof(H29D)=Sof(H29E)=Sof(H29F)=FVAR(2)
4.a Ternary CH refined with riding coordinates:
 C19(H19), C16(H16), C28A(H28A), C31(H31), C31(H31A), C28(H28)
4.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C8(H8), C7(H7), C6(H6), C5(H5), C26(H26), C25(H25), C24(H24),
 C12(H12), C14(H14), C13(H13), C9A(H9A), C8A(H8A), C7A(H7A), C6A(H6A), C5A(H5A),
  C26A(H26A), C25A(H25A), C24A(H24A)
4.c Fitted hexagon refined as free rotating group:
 C4(C9,C8,C7,C6,C5), C22(C27,C26,C25,C24,C23), C4A(C9A,C8A,C7A,C6A,C5A),
 C22A(C27A,C26A,C25A,C24A,C23A)
4.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C17(H17A,H17B,H17C), C20(H20A,H20B,H20C), C32(H32A,H32B,
 H32C), C33(H33A,H33B,H33C), C30(H30A,H30B,H30C), C18(H18A,H18B,H18C),
 C29A(H29A,H29B,H29C), C29(H29D,H29E,H29F), C30A(H30D,H30E,H30F)
;
_shelx_res_checksum              59489
_olex2_submission_special_instructions 'No special instructions were received'