Transition Metal-Free One-Pot Synthesis of Fused 1,4-Thiazepin-5(4H)-ones and Theoretical Study of the S-N Type Smiles Rearrangement Process.
Yang, Bingchuan; Tan, Xiaochen; Guo, Ruiying; Chen, Shunwei; Zhang, Zeyuan; Chu, Xianglong; Xie, Caixia; Zhang, Dongju; Ma, Chen; The Journal of organic chemistry 79 (2014) 8040–8048; doi:10.1021/jo5011729

data_4029878
_publ_section_title
;
 Transition Metal-Free One-Pot Synthesis of Fused 1,4-Thiazepin-5(4H)-ones
 and Theoretical Study of the S-N Type Smiles Rearrangement Process.
;
_journal_issue                   17
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              8040
_journal_page_last               8048
_journal_paper_doi               10.1021/jo5011729
_journal_volume                  79
_journal_year                    2014
_chemical_formula_moiety         'C18 H10 Cl N3 O3 S, H2 O'
_chemical_formula_sum            'C18 H12 Cl N3 O4 S'
_chemical_formula_weight         401.82
_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_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-09-26
_audit_creation_method
;
Olex2 1.2
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 123.483(14)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   8.784(3)
_cell_length_b                   16.217(5)
_cell_length_c                   14.313(4)
_cell_measurement_reflns_used    3161
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      0.000
_cell_measurement_theta_min      0.000
_cell_volume                     1700.5(10)
_computing_data_reduction        'SAINT v7.23A (Bruker, 2003)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      298.15
_diffrn_measured_fraction_theta_full 0.965
_diffrn_measured_fraction_theta_max 0.965
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71000
_diffrn_reflns_av_R_equivalents  0.0500
_diffrn_reflns_av_unetI/netI     0.0640
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            9276
_diffrn_reflns_theta_full        27.53
_diffrn_reflns_theta_max         27.53
_diffrn_reflns_theta_min         2.12
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    0.379
_exptl_crystal_density_diffrn    1.569
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             824
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.555
_refine_diff_density_min         -0.678
_refine_diff_density_rms         0.158
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.111
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     244
_refine_ls_number_reflns         3792
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.111
_refine_ls_R_factor_all          0.0779
_refine_ls_R_factor_gt           0.0467
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1022P)^2^+0.1128P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1352
_refine_ls_wR_factor_ref         0.1765
_reflns_number_gt                2714
_reflns_number_total             3792
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo5011729_si_001.cif
_cod_data_source_block           p
_cod_depositor_comments          'Adding full bibliography for 4029878.cif.'
_cod_original_cell_volume        1700.5(9)
_cod_database_code               4029878
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H,H) groups
2.a Riding coordinates:
 O1W(H1WA,H1WB)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C10(H10), C11(H11), C12(H12), C15(H15),
 C16(H16), C18(H18)
;