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_7160801
_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_formula_moiety
'0.075(C12 H13 N2 O4 S), 0.075(C4 H10 N O), 0.019[C4H9NO]'
_chemical_formula_sum            'C1.288 H1.906 N0.246 O0.397 S0.075'
_chemical_formula_weight         29.594
_chemical_name_systematic
'ethyl 4-cyano-3-hydroxy-5-morpholinothiophene-2-carboxylate'
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2025-08-30
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-08-30 deposited with the CCDC.	2025-09-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.111(6)
_cell_angle_gamma                90
_cell_formula_units_Z            53
_cell_length_a                   13.8922(8)
_cell_length_b                   19.2825(11)
_cell_length_c                   7.2587(4)
_cell_measurement_reflns_used    6019
_cell_measurement_temperature    293
_cell_measurement_theta_max      29.3290
_cell_measurement_theta_min      1.8370
_cell_volume                     1877.20(19)
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_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 0.9780
_diffrn_measured_fraction_theta_max 0.7474
_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      1.00  73.00   0.50    6.00    --    6.31  57.00  60.00  144
  2  \w     29.00  65.00   0.50    6.00    --   -5.22   9.00 -15.00   72
  3  \w    -10.00  17.00   0.50    6.00    --   -5.22   9.00 -15.00   54
  4  \w      6.00  38.00   0.50    6.00    --    6.31 -99.00-150.00   64
;
_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      -0.0304414000
_diffrn_orient_matrix_UB_12      -0.0300778000
_diffrn_orient_matrix_UB_13      -0.0169663000
_diffrn_orient_matrix_UB_21      -0.0428808000
_diffrn_orient_matrix_UB_22      0.0211169000
_diffrn_orient_matrix_UB_23      -0.0325822000
_diffrn_orient_matrix_UB_31      0.0055192000
_diffrn_orient_matrix_UB_32      -0.0018862000
_diffrn_orient_matrix_UB_33      -0.0943362000
_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  0.0268
_diffrn_reflns_av_unetI/netI     0.0363
_diffrn_reflns_Laue_measured_fraction_full 0.9780
_diffrn_reflns_Laue_measured_fraction_max 0.7474
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            10994
_diffrn_reflns_point_group_measured_fraction_full 0.9780
_diffrn_reflns_point_group_measured_fraction_max 0.7474
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         31.14
_diffrn_reflns_theta_min         1.85
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.208
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.95273
_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    1.387
_exptl_crystal_description       block
_exptl_crystal_F_000             834.855
_exptl_crystal_preparation       'isolated in microscope'
_exptl_crystal_recrystallization_method
'slow evaporation in ethylacetate in MeOH'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.6504
_refine_diff_density_min         -0.3962
_refine_diff_density_rms         0.0605
_refine_ls_d_res_high            0.6872
_refine_ls_d_res_low             11.0104
_refine_ls_goodness_of_fit_ref   1.0738
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    31
_refine_ls_number_parameters     235
_refine_ls_number_reflns         4534
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0738
_refine_ls_R_factor_all          0.0641
_refine_ls_R_factor_gt           0.0484
_refine_ls_shift/su_max          -0.0008
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0741P)^2^+0.3437P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1346
_refine_ls_wR_factor_ref         0.1444
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              17
_reflns_limit_h_min              -19
_reflns_limit_k_max              27
_reflns_limit_k_min              0
_reflns_limit_l_max              10
_reflns_limit_l_min              0
_reflns_number_gt                3412
_reflns_number_total             4534
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5ob01121c3.cif
_cod_data_source_block           7C_auto
_cod_depositor_comments
'Adding full bibliography for 7160799--7160802.cif.'
_cod_database_code               7160801
_chemical_oxdiff_formula         'C H N O S'
_chemical_oxdiff_usercomment     28-08-2025
_diffrn_oxdiff_digest_hkl
;
0109d762d0eefe454399ed7621adeb6523bb3d
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 N008(H00n,H00o), C00I(H00a,H00b), C00J(H00r,H00s), C00L(H00t,H00u), C00M(H00f,
 H00g), C00N(H00v,H00w), C00O(H00h,H00i), C00P(H00j,H00k), C00Q(H00l,H00m)
2.b Idealised Me refined as rotating group:
 C00K(H00c,H00d,H00e)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 36 electrons were 
found in a volume of 98\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
0.019[C4H9NO] per Unit Cell 
which account for 48 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_olex2_submission_original_sample_id 7c
_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 1.218
_oxdiff_exptl_absorpt_empirical_full_min 0.788