Reaction of unsymmetrical α-bromo-1,3-diketones with N-substituted thioureas: regioselective access to 2-(N-arylamino)-5-acyl-4-methylthiazoles and/or rearranged 2-(N-acylimino)-3-N-aryl-4-methylthiazoles
Aggarwal, Ranjana; Sharma, Shilpa; Jain, Naman; Sanz, Dionisia; Claramunt, Rosa M.; Delgado, Patricia; Torralba, M. Carmen; RSC Advances 14 (2024) 35585–35600; doi:10.1039/D4RA05436A

data_7249561
_publ_section_title
;
 Reaction of unsymmetrical \a-bromo-1,3-diketones with N-substituted
 thioureas: regioselective access to
 2-(N-arylamino)-5-acyl-4-methylthiazoles and/or rearranged
 2-(N-acylimino)-3-N-aryl-4-methylthiazoles
;
_journal_issue                   48
_journal_name_full               'RSC Advances'
_journal_page_first              35585
_journal_page_last               35600
_journal_paper_doi               10.1039/D4RA05436A
_journal_volume                  14
_journal_year                    2024
_chemical_formula_moiety         '1.333(C17 H14 N2 O S)'
_chemical_formula_sum            'C22.67 H18.67 N2.67 O1.33 S1.33'
_chemical_formula_weight         392.48
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2023-12-04
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-12-05 deposited with the CCDC.	2024-08-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.509(3)
_cell_angle_gamma                90
_cell_formula_units_Z            6
_cell_length_a                   19.262(3)
_cell_length_b                   4.9631(9)
_cell_length_c                   30.819(5)
_cell_measurement_reflns_used    2243
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      26.0921
_cell_measurement_theta_min      2.3478
_cell_volume                     2913.8(8)
_computing_cell_refinement       'SAINT v6.28A (Bruker, 2002)'
_computing_data_reduction        'SAINT v6.28A (Bruker, 2002)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS-1997  (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.913
_diffrn_measurement_device_type  'Bruker P4'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0849
_diffrn_reflns_av_unetI/netI     0.0951
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.913
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            13672
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.913
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.944
_diffrn_reflns_theta_min         1.336
_diffrn_source_current           40.0
_diffrn_source_power             2.0
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.222
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.576010
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS v.2.10 (Bruker,2003) was used for absorption correction. R(int) was 0.0507 before and 0.0352 after correction. The Ratio of minimum to maximum transmission is 0.5760. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.342
_exptl_crystal_description       block
_exptl_crystal_F_000             1232
_exptl_crystal_size_max          0.64
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.288
_refine_diff_density_min         -0.363
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.967
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     233
_refine_ls_number_reflns         3533
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.967
_refine_ls_R_factor_all          0.1173
_refine_ls_R_factor_gt           0.0580
_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^)+(0.0731P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1336
_refine_ls_wR_factor_ref         0.1535
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1877
_reflns_number_total             3533
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ra05436a2.cif
_cod_data_source_block           shp-9
_cod_original_cell_volume        2913.8(9)
_cod_database_code               7249561
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(H16A)=Sof(H17A)=Sof(C18A)=Sof(H18A)=
 Sof(C19A)=Sof(H19A)=1-FVAR(1)
 Sof(C15)=Sof(H15)=Sof(C16)=Sof(H16)=Sof(H17)=Sof(C18)=Sof(H18)=Sof(C19)=
 Sof(H19)=FVAR(1)
3.a Aromatic/amide H refined with riding coordinates:
 N6(H6), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C15(H15), C15A(H15A),
 C16(H16), C16A(H16A), C17(H17), C17(H17A), C18(H18), C18A(H18A), C19(H19),
 C19A(H19A)
3.b Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C)
;
_shelx_res_checksum              67125
_shelx_hkl_checksum              82949
_olex2_submission_original_sample_id 'shp 9'
_olex2_submission_special_instructions 'No special instructions were received'