Direct synthesis of 2-substituted benzonitriles via alkylcyanation of arynes with N,N-disubstituted aminomalononitriles.
Bao, Wen; Gao, Zhu-Peng; Jin, Da-Ping; Xue, Cao-Gen; Liang, Huan; Lei, Ling-Sheng; Xu, Xue-Tao; Zhang, Kun; Wang, Shao-Hua; Chemical communications (Cambridge, England) 56 (2020) 7641–7644; doi:10.1039/d0cc01591a

data_7126672
_publ_section_title
;
 Direct synthesis of 2-substituted benzonitriles via alkylcyanation of
 arynes with N,N-disubstituted aminomalononitriles.
;
_journal_issue                   55
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              7641
_journal_page_last               7644
_journal_paper_doi               10.1039/d0cc01591a
_journal_volume                  56
_journal_year                    2020
_chemical_formula_moiety         'C18 H15 N3'
_chemical_formula_sum            'C18 H15 N3'
_chemical_formula_weight         273.33
_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     direct
_audit_creation_date             2020-05-06
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2020-05-07 deposited with the CCDC.	2020-06-10 downloaded from the CCDC.
;
_cell_angle_alpha                93.111(9)
_cell_angle_beta                 96.047(10)
_cell_angle_gamma                91.869(9)
_cell_formula_units_Z            2
_cell_length_a                   8.0685(11)
_cell_length_b                   8.5074(8)
_cell_length_c                   10.8878(13)
_cell_measurement_reflns_used    2323
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      69.8100
_cell_measurement_theta_min      5.2090
_cell_volume                     741.55(15)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_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     42.00  69.00   1.50    1.50    --    0.00  57.00   0.00   18
  2  \w     28.00 100.00   1.50    1.50    --   54.00  38.00 -60.00   48
  3  \w     94.00 137.50   1.50    1.50    --  108.00 -25.00  30.00   29
  4  \w    120.00 178.50   1.50    1.50    --  108.00  38.00  90.00   39
  5  \w    125.00 170.00   1.50    1.50    --  108.00 111.00  60.00   30
  6  \w    111.00 153.00   1.50    1.50    --  108.00 111.00 -60.00   28
  7  \w    111.00 178.50   1.50    1.50    --  108.00 111.00   0.00   45
  8  \w    102.00 171.00   1.50    1.50    --  108.00 111.00 -30.00   46
  9  \w    100.00 155.50   1.50    1.50    --  108.00 111.00  30.00   37
 10  \w     87.00 115.50   1.50    1.50    --  108.00  38.00  90.00   19
 11  \w     78.00 111.00   1.50    1.50    --  108.00  77.00 120.00   22
 12  \w     40.00  79.00   1.50    1.50    --  108.00 -25.00  30.00   26
 13  \w     43.00 106.00   1.50    1.50    --  108.00 -77.00  60.00   42
 14  \w     79.00 115.00   1.50    1.50    --  108.00-111.00  30.00   24
 15  \w     75.00 111.00   1.50    1.50    --  108.00-111.00 -60.00   24
 16  \w     46.00 109.00   1.50    1.50    --  108.00-111.00-180.00   42
 17  \w     43.00 124.00   1.50    1.50    --  108.00 -63.00 -60.00   54
 18  \w     40.00  74.50   1.50    1.50    --   54.00-125.00 -90.00   23
 19  \w     36.00 135.00   1.50    1.50    --  108.00 -25.00 -90.00   66
 20  \w     33.00 106.50   1.50    1.50    --   54.00  57.00 -30.00   49
 21  \w     25.00 121.00   1.50    1.50    --   54.00  77.00-180.00   64
 22  \w      2.00  27.50   1.50    1.50    --    0.00  57.00   0.00   17
 23  \w     -9.00  76.50   1.50    1.50    --   54.00 -38.00  30.00   57
 24  \w     23.00 110.00   1.50    1.50    --   54.00-125.00  60.00   58
 25  \w    -22.00   5.00   1.50    1.50    --    0.00 -57.00-120.00   18
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1499655000
_diffrn_orient_matrix_UB_12      0.0885102000
_diffrn_orient_matrix_UB_13      -0.0447679000
_diffrn_orient_matrix_UB_21      0.1028421000
_diffrn_orient_matrix_UB_22      -0.0211874000
_diffrn_orient_matrix_UB_23      0.1250584000
_diffrn_orient_matrix_UB_31      0.0620846000
_diffrn_orient_matrix_UB_32      -0.1570182000
_diffrn_orient_matrix_UB_33      -0.0516737000
_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  0.0218
_diffrn_reflns_av_unetI/netI     0.0289
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            4474
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        66.583
_diffrn_reflns_theta_max         66.583
_diffrn_reflns_theta_min         4.090
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.579
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54064
_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            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.224
_exptl_crystal_description       block
_exptl_crystal_F_000             288
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.205
_refine_diff_density_min         -0.165
_refine_diff_density_rms         0.030
_refine_ls_extinction_coef       0.033(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     192
_refine_ls_number_reflns         2598
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0466
_refine_ls_R_factor_gt           0.0410
_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^)+(0.0656P)^2^+0.0697P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1161
_refine_ls_wR_factor_ref         0.1220
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2232
_reflns_number_total             2598
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc01591a4.cif
_cod_data_source_block           liangh_0504_2
_cod_depositor_comments
'Adding full bibliography for 7126672--7126675.cif.'
_cod_database_code               7126672
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.28
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Ternary CH refined with riding coordinates:
 C9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C11(H11), C12(H12), C14(H14)
2.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C)
;
_shelx_res_checksum              28411
_olex2_date_sample_data_collection 2020-05-05
_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 1.871
_oxdiff_exptl_absorpt_empirical_full_min 0.586