Using hyperpolarised NMR and DFT to rationalise the unexpected hydrogenation of quinazoline to 3,4-dihydroquinazoline.
Richards, Josh E.; Hooper, Alexander J. J.; Bayfield, Oliver W.; Cockett, Martin C. R.; Dear, Gordon J.; Holmes, A. Jonathon; John, Richard O.; Mewis, Ryan E.; Pridmore, Natalie; Roberts, Andy D.; Whitwood, Adrian C.; Duckett, Simon B.; Chemical communications (Cambridge, England) 54 (2018) 10375–10378; doi:10.1039/c8cc04826f

data_7122255
_publ_section_title
;
 Using hyperpolarised NMR and DFT to rationalise the unexpected
 hydrogenation of quinazoline to 3,4-dihydroquinazoline.
;
_journal_issue                   73
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              10375
_journal_page_last               10378
_journal_paper_doi               10.1039/c8cc04826f
_journal_volume                  54
_journal_year                    2018
_chemical_formula_moiety         'C8 H9 N2, Cl'
_chemical_formula_sum            'C8 H9 Cl N2'
_chemical_formula_weight         168.62
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2014-10-17
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_audit_update_record
;
2018-06-11 deposited with the CCDC.
2018-07-17 downloaded from the CCDC.
;
_cell_angle_alpha                82.068(6)
_cell_angle_beta                 76.113(6)
_cell_angle_gamma                80.977(8)
_cell_formula_units_Z            2
_cell_length_a                   5.5421(5)
_cell_length_b                   7.9319(9)
_cell_length_c                   9.4933(3)
_cell_measurement_reflns_used    1362
_cell_measurement_temperature    110.00(14)
_cell_measurement_theta_max      31.1120
_cell_measurement_theta_min      3.9580
_cell_volume                     397.91(6)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      110.00(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.875
_diffrn_measurement_details
;
  1 omega   59.00   94.00   1.0000   52.5000
omega____ theta____ kappa____ phi______ frames
    -       25.4797   57.0000   30.0000 35

  2 omega  -43.00   40.00   1.0000   52.5000
omega____ theta____ kappa____ phi______ frames
    -       25.4797  -57.0000 -120.0000 83

  3 omega   36.00   65.00   1.0000   52.5000
omega____ theta____ kappa____ phi______ frames
    -       25.4797  -99.0000 -120.0000 29

  4 omega   -8.00   66.00   1.0000   52.5000
omega____ theta____ kappa____ phi______ frames
    -       25.4797  -99.0000    0.0000 74

  5 omega  -18.00   67.00   1.0000   52.5000
omega____ theta____ kappa____ phi______ frames
    -       25.4797  -99.0000  120.0000 85

  6 omega  -17.00   93.00   1.0000   52.5000
omega____ theta____ kappa____ phi______ frames
    -       25.4797   19.0000 -120.0000 110

  7 omega  -96.00  -71.00   1.0000   52.5000
omega____ theta____ kappa____ phi______ frames
    -      -26.1047 -178.0000   90.0000 25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1089412000
_diffrn_orient_matrix_UB_12      0.0024497000
_diffrn_orient_matrix_UB_13      0.0573926000
_diffrn_orient_matrix_UB_21      -0.0221063000
_diffrn_orient_matrix_UB_22      0.0904897000
_diffrn_orient_matrix_UB_23      -0.0150498000
_diffrn_orient_matrix_UB_31      -0.0729156000
_diffrn_orient_matrix_UB_32      -0.0097358000
_diffrn_orient_matrix_UB_33      -0.0496879000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0273
_diffrn_reflns_av_unetI/netI     0.0494
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.875
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            4030
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.875
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.028
_diffrn_reflns_theta_min         3.605
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.410
_exptl_absorpt_correction_T_max  0.992
_exptl_absorpt_correction_T_min  0.937
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.407
_exptl_crystal_description       plank
_exptl_crystal_F_000             176
_exptl_crystal_size_max          0.2714
_exptl_crystal_size_mid          0.0838
_exptl_crystal_size_min          0.0192
_refine_diff_density_max         0.656
_refine_diff_density_min         -0.316
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.129
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     108
_refine_ls_number_reflns         2425
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.129
_refine_ls_R_factor_all          0.0648
_refine_ls_R_factor_gt           0.0562
_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^)+(0.0355P)^2^+0.6399P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1316
_refine_ls_wR_factor_ref         0.1363
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2118
_reflns_number_total             2425
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc04826f2.cif
_cod_data_source_block           sbd1415
_cod_depositor_comments          'Adding full bibliography for 7122255.cif.'
_cod_database_code               7122255
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C8 H9 Cl1 N2'
_chemical_oxdiff_usercomment     'Ryan Mewis SBD / REM 2'
_reflns_odcompleteness_completeness 98.39
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C4(H4), C5(H5), C6(H6)
;
_olex2_exptl_crystal_mounting_method 'Oil on loop'
_olex2_submission_special_instructions 'No special instructions were received'