Palladium-catalyzed double coupling reaction of terminal alkynes with isocyanides: a direct approach to symmetrical <i>N</i>-aryl dialkynylimines.
Xi, Zhi-Wei; He, Yan; Liu, Li-Qiu; Wang, Ying-Chun; Organic & biomolecular chemistry 18 (2020) 8089–8093; doi:10.1039/d0ob01604g

data_7157722
_publ_section_title
;
 Palladium-catalyzed double coupling reaction of terminal alkynes with
 isocyanides: a direct approach to symmetrical <i>N</i>-aryl
 dialkynylimines.
;
_journal_issue                   40
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              8089
_journal_page_last               8093
_journal_paper_doi               10.1039/d0ob01604g
_journal_volume                  18
_journal_year                    2020
_chemical_formula_moiety
'C18.5 H18 I0.5 N0.5 O, C18.5 H15.754 I0.5 N0.5 O'
_chemical_formula_sum            'C37 H34 I N O2'
_chemical_formula_weight         651.55
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-09-11
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2019.08.16 svn.r3652 for OlexSys, GUI svn.r5895)
;
_audit_update_record
;
2019-10-18 deposited with the CCDC.	2020-09-29 downloaded from the CCDC.
;
_cell_angle_alpha                93.058(5)
_cell_angle_beta                 90.358(4)
_cell_angle_gamma                92.480(5)
_cell_formula_units_Z            4
_cell_length_a                   5.8087(3)
_cell_length_b                   11.2608(7)
_cell_length_c                   47.001(2)
_cell_measurement_reflns_used    2437
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      71.9160
_cell_measurement_theta_min      3.7490
_cell_volume                     3067.0(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5368
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.953
_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     17.00 112.00   1.00    1.00    --   40.98  57.00 -90.00   95
  2  \w    101.00 175.00   1.00    2.50    --  106.95  45.00-120.00   74
  3  \w    152.00 178.00   1.00    2.50    --  106.95 125.00 -60.00   26
  4  \w     97.00 135.00   1.00    2.50    --  106.95  45.00 -90.00   38
  5  \w    110.00 140.00   1.00    2.50    --  106.95 -77.00 -90.00   30
  6  \w     82.00 134.00   1.00    2.50    --  106.95-150.00   5.00   52
  7  \w     37.00 130.00   1.00    2.50    --  106.95 -30.00  60.00   93
  8  \w     31.00 104.00   1.00    2.50    --  106.95 -94.00   0.00   73
  9  \w     37.00  64.00   1.00    2.50    --  106.95-125.00  90.00   27
 10  \w     35.00 132.00   1.00    2.50    --  106.95 -77.00  60.00   97
 11  \w     25.00 158.00   1.00    2.50    --  106.95 -15.00-120.00  133
 12  \w     36.00 136.00   1.00    2.50    --  106.95 -61.00-180.00  100
 13  \w      2.00  82.00   1.00    1.00    --   40.98 -99.00-180.00   80
 14  \w    -64.00  14.00   1.00    1.00    --  -40.98  37.00  90.00   78
 15  \w    -64.00  14.00   1.00    1.00    --  -40.98  37.00  30.00   78
 16  \w    -70.00 -14.00   1.00    4.00    --  -40.98 150.00  51.00   56
 17  \w    108.00 133.00   1.00    5.00    --  106.95 -45.00-180.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0381971000
_diffrn_orient_matrix_UB_12      0.0569673000
_diffrn_orient_matrix_UB_13      -0.0287728000
_diffrn_orient_matrix_UB_21      -0.0248681000
_diffrn_orient_matrix_UB_22      -0.1239490000
_diffrn_orient_matrix_UB_23      -0.0155131000
_diffrn_orient_matrix_UB_31      -0.2615319000
_diffrn_orient_matrix_UB_32      0.0140273000
_diffrn_orient_matrix_UB_33      -0.0030131000
_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  0.0960
_diffrn_reflns_av_unetI/netI     0.1392
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_limit_h_max       4
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       53
_diffrn_reflns_limit_l_min       -58
_diffrn_reflns_number            21375
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.964
_diffrn_reflns_theta_min         1.883
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.455
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49948
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
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    1.411
_exptl_crystal_description       block
_exptl_crystal_F_000             1328
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.711
_refine_diff_density_min         -1.801
_refine_diff_density_rms         0.155
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     808
_refine_ls_number_reflns         11868
_refine_ls_number_restraints     46
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.1386
_refine_ls_R_factor_gt           0.0949
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0800P)^2^+10.2645P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2192
_refine_ls_wR_factor_ref         0.2505
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7461
_reflns_number_total             11868
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0ob01604g2.cif
_cod_data_source_block           2w-36
_cod_depositor_comments
'Adding full bibliography for 7157722--7157724.cif.'
_cod_database_code               7157722
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.485
_shelx_estimated_absorpt_t_min   0.430
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H21B,H21A,H21C} of C21B, All C(H,H) groups
 At 1.5 times of:
  {H22A,H22B,H22C} of C22B, {H36A,H36B,H36C} of C36, {H01A,H01B,H01C} of C01Z,
   {H32A,H32B,H32C} of C32B
2. Rigid bond restraints
 C31B, C32B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C17B, C40
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C21B, C22B, C37
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C31B \\sim C32B: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004 within 2A
C17B \\sim C40: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004 within 2A
C21B \\sim C22B \\sim C37: within 2A with sigma of 0.002 and sigma for terminal
atoms of 0.004 within 2A
Uanis(C4B) \\sim Ueq, Uanis(C29B) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
4. Others
 Sof(H20A)=Sof(C6A)=Sof(H6A)=1-FVAR(1)
 Sof(H20B)=Sof(C19B)=Sof(H19B)=FVAR(1)
 Sof(H21A)=Sof(H21C)=Sof(C22B)=Sof(H22A)=Sof(H22B)=Sof(H22C)=1-FVAR(2)
 Sof(H21B)=Sof(C37)=Sof(H37A)=Sof(H37B)=FVAR(2)
 Sof(H15A)=Sof(C1A)=Sof(H1A)=1-FVAR(3)
 Sof(C39)=FVAR(3)
 Sof(H17B)=Sof(C10A)=1-FVAR(4)
 Sof(C40)=FVAR(4)
 Sof(C0)=Sof(H0)=1-FVAR(5)
 Sof(H15B)=Sof(C026)=Sof(H026)=FVAR(5)
 Sof(C41)=1-FVAR(6)
 Sof(C16B)=FVAR(6)
 Sof(C8A)=Sof(H8AA)=Sof(H8AB)=1-FVAR(7)
 Sof(C18B)=Sof(H18A)=Sof(H18B)=FVAR(7)
5.a Ternary CH refined with riding coordinates:
 C15B(H15B), C15B(H15A), C17B(H17B), C026(H026), C1A(H1A), C0(H0)
5.b Secondary CH2 refined with riding coordinates:
 C20(H20C,H20D), C21(H21D,H21E), C28B(H28A,H28B), C22(H22D,H22E), C29B(H29A,
 H29B), C32(H32D,H32E), C30B(H30A,H30B), C23(H23A,H23B), C34(H34A,H34B),
 C33(H33A,H33B), C35(H35A,H35B), C31B(H31A,H31B), C21B(H21A,H21C), C18B(H18A,
 H18B), C8A(H8AA,H8AB)
5.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C19(H19), C18(H18), C24B(H24B), C25B(H25B), C13(H13), C16(H16),
 C26B(H26B), C27B(H27B), C9B(H9B), C12(H12), C7(H7), C10(H10), C6(H6),
 C10B(H10B), C30(H30), C12B(H12B), C6B(H6B), C7B(H7B), C11B(H11B), C31(H31),
 C28(H28), C11(H11), C27(H27), C20B(H20B), C20B(H20A), C21B(H21B), C19B(H19B),
 C6A(H6A)
5.d X=CH2 refined with riding coordinates:
 C37(H37A,H37B)
5.e Idealised Me refined as rotating group:
 C01Z(H01A,H01B,H01C), C36(H36A,H36B,H36C), C32B(H32A,H32B,H32C), C22B(H22A,
 H22B,H22C)
;
_shelx_res_checksum              40890
_shelx_hkl_checksum              5631
_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 1.732
_oxdiff_exptl_absorpt_empirical_full_min 0.606