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_7716183
_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         'C33 H30 N2'
_chemical_formula_sum            'C33 H30 N2'
_chemical_formula_weight         454.59
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2024-01-15
_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                 99.625(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.3909(2)
_cell_length_b                   15.7998(3)
_cell_length_c                   13.9004(2)
_cell_measurement_reflns_used    8098
_cell_measurement_temperature    298
_cell_measurement_theta_max      69.3070
_cell_measurement_theta_min      4.2620
_cell_volume                     2683.03(8)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      298
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.2640
_diffrn_detector_type            Onyx
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.985
_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   -123.00 -94.00   1.00   10.00    --  -43.35 -99.00 150.00   29
  2  \w     21.00 115.00   1.00   10.00    --   43.35  37.00  30.00   94
  3  \w     11.00  53.00   1.00   10.00    --   43.35 -57.00-150.00   42
  4  \w     98.00 126.00   1.00  125.00    --   94.50  61.00 -90.00   28
  5  \w     79.00 163.00   1.00  125.00    --   94.50  45.00  30.00   84
  6  \w     32.00 108.00   1.00  125.00    --   94.50-125.00 120.00   76
  7  \w     29.00 121.00   1.00  125.00    --   94.50 -30.00  90.00   92
  8  \w     24.00 109.00   1.00  125.00    --   94.50 -94.00 -90.00   85
  9  \w     59.00  86.00   1.00  125.00    --   94.50 -61.00-120.00   27
 10  \w    136.00 164.00   1.00  125.00    --   94.50  61.00 -90.00   28
 11  \w     64.00 105.00   1.00  125.00    --   94.50 -94.00 -30.00   41
 12  \w     28.00 114.00   1.00  125.00    --   94.50 -45.00 -90.00   86
 13  \w    -37.00 -12.00   1.00   10.00    --  -43.48 -77.00 120.00   25
 14  \w     12.00  83.00   1.00   10.00    --   43.48  77.00-120.00   71
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Onyx, Nova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0559083000
_diffrn_orient_matrix_UB_12      -0.0860615000
_diffrn_orient_matrix_UB_13      -0.0090015000
_diffrn_orient_matrix_UB_21      0.0816494000
_diffrn_orient_matrix_UB_22      0.0425290000
_diffrn_orient_matrix_UB_23      -0.0570513000
_diffrn_orient_matrix_UB_31      0.0780988000
_diffrn_orient_matrix_UB_32      0.0171346000
_diffrn_orient_matrix_UB_33      0.0964771000
_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  0.0274
_diffrn_reflns_av_unetI/netI     0.0238
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            14574
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.498
_diffrn_reflns_theta_min         4.270
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Nova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.497
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.495
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.125
_exptl_crystal_description       block
_exptl_crystal_F_000             968
_exptl_crystal_size_max          0.485
_exptl_crystal_size_mid          0.238
_exptl_crystal_size_min          0.163
_refine_diff_density_max         0.169
_refine_diff_density_min         -0.160
_refine_diff_density_rms         0.033
_refine_ls_extinction_coef       0.0019(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     350
_refine_ls_number_reflns         4968
_refine_ls_number_restraints     66
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0481
_refine_ls_R_factor_gt           0.0429
_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^)+(0.0756P)^2^+0.2242P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1224
_refine_ls_wR_factor_ref         0.1293
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4300
_reflns_number_total             4968
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01265h2.cif
_cod_data_source_block           24001_ciclo40
_cod_depositor_comments
'Adding full bibliography for 7716182--7716185.cif.'
_cod_database_code               7716183
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C33H30N2
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.29
_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
C31 \\sim C31A \\sim C32 \\sim C32A \\sim C30 \\sim C30A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
3. Others
 Sof(H29A)=Sof(C32A)=Sof(H32D)=Sof(H32E)=Sof(H32F)=Sof(C31A)=Sof(C30A)=
 Sof(H30A)=1-FVAR(1)
 Sof(H29)=Sof(C31)=Sof(C30)=Sof(H30)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=
 FVAR(1)
4.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C17(H17), C13(H13), C16(H16), C28(H28), C7(H7), C11(H11),
 C14(H14), C22(H22), C15(H15), C20(H20), C21(H21), C8(H8), C10(H10), C29(H29),
 C29(H29A), C9(H9), C30(H30), C30A(H30A)
4.b Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C24(H24A,H24B,H24C), C33(H33A,H33B,H33C), C32(H32A,H32B,
 H32C), C32A(H32D,H32E,H32F)
;
_shelx_res_checksum              31152
_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 1.438
_oxdiff_exptl_absorpt_empirical_full_min 0.683