Experimental and Computational Study of the 1,5-O →N Carbamoyl Snieckus-Fries-Type Rearrangement.
Feberero, Claudia; Sedano, Carlos; Suárez-Pantiga, Samuel; López, Carlos Silva; Sanz, Roberto; The Journal of organic chemistry 85 (2020) 12561–12578; doi:10.1021/acs.joc.0c01732

data_4038772
_publ_section_title
;
 Experimental and Computational Study of the 1,5-O \\rightarrow N
 Carbamoyl Snieckus-Fries-Type Rearrangement.
;
_journal_issue                   19
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              12561
_journal_page_last               12578
_journal_paper_doi               10.1021/acs.joc.0c01732
_journal_volume                  85
_journal_year                    2020
_chemical_formula_moiety
'0.5(C18 H17 Cl F N2 O2 S), 0.5(C18 H17.68 Cl F0.98 N2 O2 S)'
_chemical_formula_sum            'C18 H17 Cl F N2 O2 S'
_chemical_formula_weight         379.84
_chemical_name_systematic
'O-4-Chloro-2-((2-fluorophenyl)carbamothioyl)phenyl N,N-diethylcarbamate'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-05-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-05-04 deposited with the CCDC.	2020-06-11 downloaded from the CCDC.
;
_cell_angle_alpha                88.740(4)
_cell_angle_beta                 82.005(4)
_cell_angle_gamma                79.455(4)
_cell_formula_units_Z            4
_cell_length_a                   9.2440(6)
_cell_length_b                   12.1783(8)
_cell_length_c                   16.9973(11)
_cell_measurement_reflns_used    7272
_cell_measurement_temperature    283(2)
_cell_measurement_theta_max      25.157
_cell_measurement_theta_min      2.414
_cell_volume                     1862.9(2)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      283(2)
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0767
_diffrn_reflns_av_unetI/netI     0.0576
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            32476
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.312
_diffrn_reflns_theta_min         2.420
_exptl_absorpt_coefficient_mu    0.340
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8875
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1298 before and 0.0681 after correction.
The Ratio of minimum to maximum transmission is 0.8875.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            yellowish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.354
_exptl_crystal_description       needle
_exptl_crystal_F_000             788
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.241
_refine_diff_density_min         -0.283
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.080
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     477
_refine_ls_number_reflns         6676
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.1003
_refine_ls_R_factor_gt           0.0599
_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^)+(0.0207P)^2^+1.3213P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1043
_refine_ls_wR_factor_ref         0.1202
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4464
_reflns_number_total             6676
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            2001019.cif
_cod_data_source_block           mo_scan_0m
_cod_depositor_comments
'Adding full bibliography for 4038765--4038772.cif.'
_cod_database_code               4038772
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.967
_shelx_estimated_absorpt_t_min   0.935
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{F1A, H14}
{F1B, H10}
{F2B, H33}
{F2A, H31}
3. Uiso/Uaniso restraints and constraints
Uanis(F1B) = Uiso(H10)
Uanis(F2B) = Uiso(H33)
Uanis(F2A) = Uiso(H31)
Uanis(F1A) = Uiso(H14)
4. Others
 Fixed Sof: F1A(0.34) H14(0.66) H10(0.34) H33(0.47) H31(0.53) F1B(0.66)
 F2B(0.53)
5.a Secondary CH2 refined with riding coordinates:
 C21(H21a,H21b), C17(H17a,H17b), C23(H23a,H23b), C16(H16a,H16b)
5.b Aromatic/amide H refined with riding coordinates:
 C26(H26), C29(H29), C27(H27), C5(H5), C8(H8), C7(H7), C36(H36), C13(H13),
 C11(H11), C35(H35), C12(H12), C34(H34)
5.c Idealised Me refined as rotating group:
 C22(H22a,H22b,H22c), C18(H18a,H18b,H18c), C24(H24a,H24b,H24c), C15(H15a,H15b,
 H15c)
;
_shelx_res_checksum              89129
_shelx_hkl_checksum              35958
_olex2_submission_special_instructions 'No special instructions were received'