A green and cascade synthesis of functionalized 2-aminothiophenes from ketene dithioacetals.
Chahal, Mohit; Shaw, Ranjay; Yadav, Pratik; Bhardwaj, Vishnu; Althagafi, Ismail; Pratap, Ramendra; Organic & biomolecular chemistry 23 (2025) 10106–10117; doi:10.1039/d5ob01121c

data_7160799
_publ_section_title
;
 A green and cascade synthesis of functionalized 2-aminothiophenes from
 ketene dithioacetals.
;
_journal_issue                   44
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              10106
_journal_page_last               10117
_journal_paper_doi               10.1039/d5ob01121c
_journal_volume                  23
_journal_year                    2025
_chemical_absolute_configuration unk
_chemical_formula_moiety         '0.286(C8 H8 N2 O2 S2)'
_chemical_formula_sum            'C2.286 H2.286 N0.571 O0.571 S0.571'
_chemical_formula_weight         65.228
_chemical_name_systematic
'methyl 3-amino-4-cyano-5-(methylthio)thiophene-2-carboxylate'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_symmetry_Int_Tables_number      33
_atom_sites_solution_primary     iterative
_audit_creation_date             2025-08-25
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-08-27 deposited with the CCDC.	2025-09-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            14
_cell_length_a                   7.5261(7)
_cell_length_b                   13.4983(9)
_cell_length_c                   10.0289(8)
_cell_measurement_reflns_used    3099
_cell_measurement_temperature    298
_cell_measurement_theta_max      29.5600
_cell_measurement_theta_min      2.5110
_cell_volume                     1018.83(14)
_computing_cell_refinement       'CrysAlisPro 1.171.43.106a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.106a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.106a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5-alpha (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve 1.5-alpha (Bourhis et al., 2015)'
_diffrn_ambient_temperature      298
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9969
_diffrn_measured_fraction_theta_max 0.8122
_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     -6.00  22.00   0.50    2.25    --    6.15 -60.00  21.00   56
  2  \w    -14.00  19.00   0.50    2.25    --   -5.06 -99.00  30.00   66
  3  \w    -12.00  18.00   0.50    2.25    --   -5.06 -99.00-120.00   60
  4  \w    -30.00  -4.00   0.50    2.25    --    6.15 -57.00-120.00   52
  5  \w     32.00  67.00   0.50    2.25    --   -5.06  38.00-180.00   70
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0026523000
_diffrn_orient_matrix_UB_12      0.0006103000
_diffrn_orient_matrix_UB_13      0.0707025000
_diffrn_orient_matrix_UB_21      0.0664477000
_diffrn_orient_matrix_UB_22      -0.0372677000
_diffrn_orient_matrix_UB_23      -0.0008135000
_diffrn_orient_matrix_UB_31      0.0667461000
_diffrn_orient_matrix_UB_32      0.0370517000
_diffrn_orient_matrix_UB_33      -0.0019290000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0377
_diffrn_reflns_av_unetI/netI     0.0451
_diffrn_reflns_Laue_measured_fraction_full 0.9969
_diffrn_reflns_Laue_measured_fraction_max 0.8122
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            4864
_diffrn_reflns_point_group_measured_fraction_full 0.8812
_diffrn_reflns_point_group_measured_fraction_max 0.6595
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         31.01
_diffrn_reflns_theta_min         2.53
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.497
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45654
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.106a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.488
_exptl_crystal_description       block
_exptl_crystal_F_000             473.253
_exptl_crystal_preparation       'slow evaporation in DCM and ethylacetate'
_exptl_crystal_recrystallization_method NA
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.2684
_refine_diff_density_min         -0.2622
_refine_diff_density_rms         0.0409
_refine_ls_abs_structure_details
'Hooft, R.W.W., Straver, L.H., Spek, A.L. (2010). J. Appl. Cryst., 43, 665-668.'
_refine_ls_abs_structure_Flack   -0.04(6)
_refine_ls_d_res_high            0.6897
_refine_ls_d_res_low             8.0502
_refine_ls_goodness_of_fit_ref   1.0491
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    11
_refine_ls_number_parameters     130
_refine_ls_number_reflns         2144
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.0491
_refine_ls_R_factor_all          0.0389
_refine_ls_R_factor_gt           0.0332
_refine_ls_shift/su_max          0.0005
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0408P)^2^+0.1466P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0844
_refine_ls_wR_factor_ref         0.0889
_reflns_Friedel_coverage         0.490
_reflns_limit_h_max              10
_reflns_limit_h_min              -10
_reflns_limit_k_max              18
_reflns_limit_k_min              -18
_reflns_limit_l_max              10
_reflns_limit_l_min              -13
_reflns_number_gt                1906
_reflns_number_total             2144
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5ob01121c3.cif
_cod_data_source_block           3A_auto
_cod_depositor_comments
'Adding full bibliography for 7160799--7160802.cif.'
_cod_original_sg_symbol_Hall     ' P 2c -2n'
_cod_database_code               7160799
_chemical_oxdiff_formula         'C 8 H 8 O 2 N 2 S 2'
_chemical_oxdiff_usercomment     22-08-2025
_cell_oxdiff_angle_alpha         90.030(4)
_cell_oxdiff_angle_beta          90.040(6)
_cell_oxdiff_angle_gamma         89.980(4)
_cell_oxdiff_length_a            7.5281(6)
_cell_oxdiff_length_b            13.4962(5)
_cell_oxdiff_length_c            10.0278(7)
_cell_oxdiff_measurement_reflns_used 3099
_cell_oxdiff_volume              1018.83(11)
_diffrn_oxdiff_digest_hkl
;
01f2c3a60518e81c74d8868851d68e43f88e9b
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Rotating group:
 N4(H4a,H4b)
2.b Idealised Me refined as rotating group:
 C1(H1a,H1b,H1c), C(Ha,Hb,Hc)
;
_olex2_submission_original_sample_id 3a
_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 1.712
_oxdiff_exptl_absorpt_empirical_full_min 0.613