A metal-free and a solvent-free synthesis of thio-amides and amides: An efficient Friedel-Crafts arylation of isothiocyanates and isocyanates
Prabhu, Kandikere Ramaiah; Varun, Begur Vasanthkumar; Sood, Ankush; RSC Adv.  (2014) –; doi:10.1039/C4RA12944J

data_7218647
_publ_section_title
;
 A metal-free and a solvent-free synthesis of thio-amides and amides: An
 efficient Friedel-Crafts arylation of isothiocyanates and isocyanates
;
_journal_name_full               'RSC Adv.'
_journal_paper_doi               10.1039/C4RA12944J
_journal_year                    2014
_chemical_formula_moiety         'C14 H13 N O2 S'
_chemical_formula_sum            'C14 H13 N O2 S'
_chemical_formula_weight         259.31
_chemical_name_systematic        4-hydroxy-3-methoxy-N-phenylbenzothioamide
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_symmetry_space_group_name_Hall  'C -2yc'
_symmetry_space_group_name_H-M   'C 1 c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2014-08-06
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.827(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.7799(16)
_cell_length_b                   12.8970(16)
_cell_length_c                   7.5173(9)
_cell_measurement_reflns_used    3890
_cell_measurement_temperature    293
_cell_measurement_theta_max      27.35
_cell_measurement_theta_min      2.26
_cell_volume                     1220.8(3)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_diffrn_ambient_temperature      293
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0565
_diffrn_reflns_av_unetI/netI     0.0488
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            7068
_diffrn_reflns_point_group_measured_fraction_full 0.967
_diffrn_reflns_point_group_measured_fraction_max 0.927
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.659
_diffrn_reflns_theta_min         2.260
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.257
_exptl_absorpt_correction_T_max  0.980
_exptl_absorpt_correction_T_min  0.913
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.411
_exptl_crystal_description       needle
_exptl_crystal_F_000             544
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: ethylacetate:pet ether'
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.300
_refine_diff_density_min         -0.163
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 1080 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.01(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     167
_refine_ls_number_reflns         2641
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0380
_refine_ls_R_factor_gt           0.0354
_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^)+(0.0459P)^2^+0.1112P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0844
_refine_ls_wR_factor_ref         0.0866
_reflns_Friedel_coverage         0.857
_reflns_Friedel_fraction_full    0.934
_reflns_Friedel_fraction_max     0.858
_reflns_number_gt                2494
_reflns_number_total             2641
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4ra12944j2.cif
_cod_data_source_block           new
_cod_database_code               7218647
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.913
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All N(H) groups, H11 of C11, H14 of C14, H9 of C9, H3 of C3, H8 of C8, H7
  of C7, H13 of C13, H12 of C12
 At 1.5 times of:
  All C(H,H,H) groups, H1 of C14
2.a Aromatic/amide H refined with riding coordinates:
 N1(H1A), C3(H3), C7(H7), C8(H8), C9(H9), C11(H11), C12(H12), C13(H13), C14(H14)
2.b Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C)
;
_shelx_res_checksum              34468
_shelx_hkl_checksum              53188
_olex2_submission_special_instructions 'No special instructions were received'