Selective synthesis of pyrrolidin-2-ones and 3-iodopyrroles via the ring contraction and deformylative functionalization of piperidine derivatives.
Wang, Fang; Zhang, Xinying; He, Yan; Fan, Xuesen; Organic & biomolecular chemistry 17 (2018) 156–164; doi:10.1039/c8ob02640h

data_7156598
_publ_section_title
;
 Selective synthesis of pyrrolidin-2-ones and 3-iodopyrroles via the ring
 contraction and deformylative functionalization of piperidine
 derivatives.
;
_journal_issue                   1
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              156
_journal_page_last               164
_journal_paper_doi               10.1039/c8ob02640h
_journal_volume                  17
_journal_year                    2018
_chemical_formula_moiety         'C10 H7 Br I N'
_chemical_formula_sum            'C10 H7 Br I N'
_chemical_formula_weight         347.98
_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'
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-08-02
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-08-02 deposited with the CCDC.
2018-12-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.5281(10)
_cell_length_b                   7.7940(9)
_cell_length_c                   25.907(2)
_cell_measurement_reflns_used    2355
_cell_measurement_temperature    294.63(10)
_cell_measurement_theta_max      27.4420
_cell_measurement_theta_min      4.0040
_cell_volume                     2125.8(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.35c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.35c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.35c (Rigaku OD, 2017)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      294.63(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0528
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -51.00  33.00   1.00   10.00    --   15.98 -57.00 -60.00   84
  2  \w    -20.00  55.00   1.00   10.00    --   15.98 -99.00  30.00   75
  3  \w     34.00  89.00   1.00   10.00    --   15.98-178.00-180.00   55
  4  \w     -1.00  24.00   1.00   10.00    --   15.98  57.00  90.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0172878000
_diffrn_orient_matrix_UB_12      -0.0552130000
_diffrn_orient_matrix_UB_13      -0.0206490000
_diffrn_orient_matrix_UB_21      -0.0384044000
_diffrn_orient_matrix_UB_22      0.0486129000
_diffrn_orient_matrix_UB_23      -0.0171340000
_diffrn_orient_matrix_UB_31      0.0525561000
_diffrn_orient_matrix_UB_32      0.0535412000
_diffrn_orient_matrix_UB_33      -0.0056277000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1758
_diffrn_reflns_av_unetI/netI     0.1153
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            7533
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         3.613
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    6.724
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.01270
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.35c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    2.174
_exptl_crystal_description       plate
_exptl_crystal_F_000             1296
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.37
_exptl_crystal_size_min          0.03
_refine_diff_density_max         2.043
_refine_diff_density_min         -3.023
_refine_diff_density_rms         0.361
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     118
_refine_ls_number_reflns         1871
_refine_ls_number_restraints     343
_refine_ls_restrained_S_all      0.995
_refine_ls_R_factor_all          0.1534
_refine_ls_R_factor_gt           0.1155
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2883
_refine_ls_wR_factor_ref         0.3252
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1117
_reflns_number_total             1871
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8ob02640h2.cif
_cod_data_source_block           3d
_cod_depositor_comments          'Adding full bibliography for 7156598.cif.'
_cod_database_code               7156598
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C1 O1 N1'
_shelx_estimated_absorpt_t_max   0.824
_shelx_estimated_absorpt_t_min   0.152
_reflns_odcompleteness_completeness 99.01
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C8-I1
 2.13 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 3.8A with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(Br1) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C3) \\sim
Ueq, Uanis(C2) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(N1)
\\sim Ueq, Uanis(I1) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C7) \\sim Ueq,
Uanis(C9) \\sim Ueq, Uanis(C10) \\sim Ueq, : with sigma of 0.01 and sigma for
terminal atoms of 0.02
4.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C7(H7), C9(H9), C10(H10)
;
_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 20.177
_oxdiff_exptl_absorpt_empirical_full_min 0.231