Solvent-free and Catalyst-free Reaction of o-Amino Benzophenone with Aryl Isothiocyanates: Expedient Access to Congested 4-Phenyl-4-Hydroxyquinazolin-2-thione Derivatives
Nguyen, Le Anh; Nguyen, Thi Thu Tram; Ngo, Quoc Anh; Retailleau, Pascal; Nguyen, Thanh Binh; Organic & Biomolecular Chemistry  (2024) –; doi:10.1039/D4OB01452A

data_7160191
_publ_section_title
;
 Solvent-free and Catalyst-free Reaction of o-Amino Benzophenone with Aryl
 Isothiocyanates: Expedient Access to Congested
 4-Phenyl-4-Hydroxyquinazolin-2-thione Derivatives
;
_journal_name_full               'Organic &amp; Biomolecular Chemistry'
_journal_paper_doi               10.1039/D4OB01452A
_journal_year                    2024
_chemical_formula_moiety         'C15 H14 N2 O S, C2 H6 O S'
_chemical_formula_sum            'C17 H20 N2 O2 S2'
_chemical_formula_weight         348.493
_chemical_name_systematic
"'rac-(R)-4-hydroxy-4-methyl-3-phenyl-3,4-dihydroquinazoline-2(1H)-thione, dmso solvate'"
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_Int_Tables_number      14
_audit_creation_date             2024-07-08
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-07-08 deposited with the CCDC.	2024-10-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.794(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.4378(7)
_cell_length_b                   7.5087(5)
_cell_length_c                   19.5257(11)
_cell_measurement_reflns_used    6348
_cell_measurement_temperature    292.46(15)
_cell_measurement_theta_max      27.8930
_cell_measurement_theta_min      2.8750
_cell_volume                     1810.73(19)
_computing_cell_refinement       'CrysAlisPro 1.171.43.109a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.109a 64-bit (release 21-02-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.109a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      292.46(15)
_diffrn_detector                 'Dectris PILATUS3 R 200K-A area detector'
_diffrn_detector_area_resol_mean 5.811
_diffrn_detector_type            'Hybrid Photon Counting area detector'
_diffrn_measured_fraction_theta_full 0.9957
_diffrn_measured_fraction_theta_max 0.9470
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \f      0.00 180.00   1.00   10.00   0.00   0.00   0.00    --   180
  2  \f    180.00 360.00   1.00   10.00   0.00   0.00   5.00    --   180
;
_diffrn_measurement_device       'kappa gonio four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB PRO'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0114685000
_diffrn_orient_matrix_UB_12      0.0265053000
_diffrn_orient_matrix_UB_13      -0.0349732000
_diffrn_orient_matrix_UB_21      0.0289615000
_diffrn_orient_matrix_UB_22      -0.0748939000
_diffrn_orient_matrix_UB_23      -0.0103193000
_diffrn_orient_matrix_UB_31      -0.0482337000
_diffrn_orient_matrix_UB_32      -0.0511138000
_diffrn_orient_matrix_UB_33      -0.0030234000
_diffrn_radiation_collimation    '0.3 mm'
_diffrn_radiation_monochromator
'Rigaku Integrated Confocal MaxFlux double bounce multi-layer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0449
_diffrn_reflns_av_unetI/netI     0.0321
_diffrn_reflns_Laue_measured_fraction_full 0.9957
_diffrn_reflns_Laue_measured_fraction_max 0.9470
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            24181
_diffrn_reflns_point_group_measured_fraction_full 0.9957
_diffrn_reflns_point_group_measured_fraction_max 0.9470
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         27.48
_diffrn_reflns_theta_min         2.82
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku micromax 003'
_exptl_absorpt_coefficient_mu    0.304
_exptl_absorpt_correction_T_max  0.91108
_exptl_absorpt_correction_T_min  0.91108
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.109a (Rigaku Oxford Diffraction, 2024)
Spherical absorption correction
using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.278
_exptl_crystal_description       tab
_exptl_crystal_F_000             736
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: DMSO'
_exptl_crystal_size_max          0.40
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.15
_exptl_crystal_size_rad          0.201
_refine_diff_density_max         0.2929
_refine_diff_density_min         -0.2293
_refine_diff_density_rms         0.0465
_refine_ls_d_res_high            0.7701
_refine_ls_d_res_low             7.2220
_refine_ls_goodness_of_fit_ref   1.0824
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    11
_refine_ls_number_parameters     311
_refine_ls_number_reflns         3933
_refine_ls_number_restraints     66
_refine_ls_restrained_S_all      1.0726
_refine_ls_R_factor_all          0.0533
_refine_ls_R_factor_gt           0.0389
_refine_ls_shift/su_max          -0.0010
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0269P)^2^+0.4973P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0869
_refine_ls_wR_factor_ref         0.0929
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              15
_reflns_limit_h_min              -15
_reflns_limit_k_max              9
_reflns_limit_k_min              0
_reflns_limit_l_max              23
_reflns_limit_l_min              0
_reflns_number_gt                3156
_reflns_number_total             3933
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d4ob01452a2.cif
_cod_data_source_block           B21093
_cod_original_cell_volume        1810.74(18)
_cod_database_code               7160191
_chemical_oxdiff_formula         'C17 H20 N2 O2 S2'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 O2, S2, C16, C17
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O2B, S2B, C16B, C17B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
O2 \\sim C16 \\sim C17 \\sim S2B \\sim O2B \\sim C16B \\sim C17B: within 2A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
4. Others
 Sof(H17E)=Sof(S2B)=Sof(O2B)=Sof(C17B)=Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(C16B)=
 Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(1)
 Sof(S2)=Sof(O2)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C17)=Sof(H17A)=
 Sof(H17B)=Sof(H17C)=FVAR(1)
5.a Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C17B(H17D,H17E,H17F), C16B(H16D,
 H16E,H16F)
;
_olex2_refine_details
;
Refinement using NoSpherA2, an implementation of
NOn-SPHERical Atom-form-factors in Olex2.
Please cite:
F. Kleemiss et al. Chem. Sci. DOI 10.1039/D0SC05526C - 2021
NoSpherA2 implementation of HAR makes use of
tailor-made aspherical atomic form factors calculated
on-the-fly from a Hirshfeld-partitioned electron density (ED) - not from
spherical-atom form factors.

The ED is calculated from a gaussian basis set single determinant SCF
wavefunction - either Hartree-Fock or DFT using selected funtionals
 - for a fragment of the crystal.
This fragment can be embedded in an electrostatic crystal field by employing cluster charges
or modelled using implicit solvation models, depending on the software used.
The following options were used:
   SOFTWARE:       discambMATTS
   PARTITIONING:   NoSpherA2
   INT ACCURACY:   Normal
   METHOD:         B3LYP
   BASIS SET:      def2-SVP
   CHARGE:         0
   MULTIPLICITY:   1
   DATE:           2024-07-08_14-59-43
;
_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 7.320
_oxdiff_exptl_absorpt_empirical_full_min 0.490