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_4038767
_publ_section_title
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 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         'C18 H18 Cl2 N2 O3'
_chemical_formula_sum            'C18 H18 Cl2 N2 O3'
_chemical_formula_weight         381.24
_chemical_name_systematic
'O-4-Chloro-2-((3-chlorophenyl)carbamoyl)phenyl N,N-diethylcarbamate'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-05-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-05-08 deposited with the CCDC.	2020-06-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   13.8795(16)
_cell_length_b                   11.3828(13)
_cell_length_c                   23.518(3)
_cell_measurement_reflns_used    7013
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      25.514
_cell_measurement_theta_min      2.270
_cell_volume                     3715.6(8)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_collection       'SMART v5.625 (Bruker, 2001)'
_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      298(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  Parallel,graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0348
_diffrn_reflns_av_unetI/netI     0.0185
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            37500
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.414
_diffrn_reflns_theta_min         1.732
_diffrn_source_current           20.0
_diffrn_source_power             1.0
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.368
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6606
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1233 before and 0.0433 after correction. The Ratio of minimum to maximum transmission is 0.8862. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.363
_exptl_crystal_description       prism
_exptl_crystal_F_000             1584
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.365
_refine_diff_density_min         -0.181
_refine_diff_density_rms         0.033
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     275
_refine_ls_number_reflns         3807
_refine_ls_number_restraints     28
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0627
_refine_ls_R_factor_gt           0.0416
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0531P)^2^+1.1509P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1067
_refine_ls_wR_factor_ref         0.1207
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2685
_reflns_number_total             3807
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            2002768.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 4038765--4038772.cif.'
_cod_original_cell_volume        3715.6(7)
_cod_database_code               4038767
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N2B-C15A \\sim N2A-C15A
 with sigma of 0.02
 O3-N2B \\sim O3-N2A
 with sigma of 0.04
 O2-N2B \\sim O2-N2A
 with sigma of 0.04
 N2B-C18 \\sim N2A-C18
 with sigma of 0.04
 C16A-C15A \\sim C16B-C15B
 with sigma of 0.02
 N2B-C16A \\sim N2B-C16B
 with sigma of 0.04
 N2B-C15A \\sim N2B-C15B
 with sigma of 0.04
 O3-C5B \\sim O3-C5A
 with sigma of 0.02
 O2-C5B \\sim O2-C5A
 with sigma of 0.02
 C5B-N2B \\sim C5A-N2A
 with sigma of 0.02
 C5B-C15A \\sim C5A-C15A
 with sigma of 0.04
3. Rigid body (RIGU) restrains
 C5B, N2B, C17
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C16A, C15A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C16B, C15B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C17, C18
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C5A, N2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(H17C)=Sof(H17D)=Sof(C5A)=Sof(N2A)=1-FVAR(1)
 Sof(C5B)=Sof(N2B)=Sof(H17A)=Sof(H17B)=FVAR(1)
 Sof(C15B)=Sof(H15C)=Sof(H15D)=Sof(C16B)=Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(2)
 Sof(C16A)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C15A)=Sof(H15A)=Sof(H15B)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C17(H17C,H17D), C15A(H15A,H15B), C15B(H15C,H15D)
5.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C10(H10), C7(H7), C8(H8), C13(H13), C12(H12)
5.c Idealised Me refined as rotating group:
 C16A(H16A,H16B,H16C), C18(H18A,H18B,H18C), C16B(H16D,H16E,H16F)
;
_shelx_res_checksum              29263
_shelx_hkl_checksum              18509
_olex2_submission_special_instructions 'No special instructions were received'