#------------------------------------------------------------------------------
#$Date: 2025-08-19 22:06:29 +0200 (Tue 19 de Aug de 2025) $
#$Revision: 301812 $
#$URL: svn://www.crystallography.net/cod/cif/4/02/15/4021587.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_4021587
loop_
_publ_author_name
'Robert D. Dura'
'Leo A. Paquette'
_publ_section_title
;
 Ring Contraction of Bridgehead Sultams by Photoinduced
 Di-π-methane Rearrangement
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              2456
_journal_page_last               2459
_journal_paper_doi               10.1021/jo0526587
_journal_volume                  71
_journal_year                    2006
_chemical_compound_source        'synthesis as described'
_chemical_formula_moiety         'C10 H9 Br2 N1 O2 S1'
_chemical_formula_sum            'C10 H9 Br2 N O2 S'
_chemical_formula_weight         367.06
_chemical_name_common            'Paquette 1399'
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_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     heavy
_atom_sites_solution_secondary   difmap
_audit_conform_dict_location     ftp://ftp.iucr.org/pub/cif_core.dic
_audit_conform_dict_name         cif_core.dic
_audit_conform_dict_version      2.3
_audit_creation_date             2005-12-13T17:20:53-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90
_cell_angle_beta                 111.078(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.1336(10)
_cell_length_b                   8.6732(10)
_cell_length_c                   12.5840(10)
_cell_measurement_reflns_used    2782
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      27.485
_cell_measurement_theta_min      2.037
_cell_measurement_wavelength     0.71073
_cell_volume                     1133.86(19)
_computing_cell_refinement       'HKL Scalepack (Otwinowski & Minor 1997)'
_computing_data_collection       'Collect (Nonius BV, 1997-2000)'
_computing_data_reduction
'HKL Denzo and Scalepack (Otwinowski & Minor 1997)'
_computing_molecular_graphics    'Ortep-3 for Windows (Farrugia, 1997)'
_computing_publication_material  'WinGX publication routines (Farrugia, 1999)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1997)'
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 9
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       '95mm CCD camera on κ-goniostat'
_diffrn_measurement_device_type  KappaCCD
_diffrn_measurement_method       'CCD rotation images, thick slices'
_diffrn_orient_matrix_type       'by Nonius Collect from scalepack cell'
_diffrn_orient_matrix_UB_11      -0.283816E-1
_diffrn_orient_matrix_UB_12      0.683933E-1
_diffrn_orient_matrix_UB_13      -0.685608E-1
_diffrn_orient_matrix_UB_21      0.71235E-1
_diffrn_orient_matrix_UB_22      -0.408385E-1
_diffrn_orient_matrix_UB_23      -0.22768E-1
_diffrn_orient_matrix_UB_31      -0.581874E-1
_diffrn_orient_matrix_UB_32      -0.833555E-1
_diffrn_orient_matrix_UB_33      -0.450994E-1
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.040
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            23767
_diffrn_reflns_theta_full        27.5
_diffrn_reflns_theta_max         27.5
_diffrn_reflns_theta_min         2.92
_diffrn_source                   'Enraf Nonius FR590'
_exptl_absorpt_coefficient_mu    7.316
_exptl_absorpt_correction_T_max  0.249
_exptl_absorpt_correction_T_min  0.195
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'HKL Scalepack (Otwinowski & Minor, 1997)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    2.15
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       'triangular  chunk'
_exptl_crystal_F_000             712
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.704
_refine_diff_density_min         -0.835
_refine_diff_density_rms         0.152
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.168
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     145
_refine_ls_number_reflns         2605
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.168
_refine_ls_R_factor_all          0.0426
_refine_ls_R_factor_gt           0.0346
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
' w=1/[σ²(Fo²)+(0.0458P)²+0.7110P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0816
_refine_ls_wR_factor_ref         0.0857
_reflns_number_gt                2250
_reflns_number_total             2605
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo0526587si20051227_031816.cif
_cod_original_sg_symbol_H-M      ' P 21/c'
_cod_database_code               4021587
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
C1 C 0.7460(3) 0.5000(3) 0.1575(2) 0.0187(6) Uani 1 1 d .
H1 H 0.6513 0.4825 0.1193 0.022 Uiso 1 1 calc R
C2 C 0.8061(3) 0.3511(4) 0.2245(3) 0.0190(6) Uani 1 1 d .
H2 H 0.7371 0.2858 0.235 0.023 Uiso 1 1 calc R
C3 C 0.8615(3) 0.2704(3) 0.1436(3) 0.0183(6) Uani 1 1 d .
H3 H 0.9309 0.1956 0.1848 0.022 Uiso 1 1 calc R
C4 C 0.7525(3) 0.1931(3) 0.0478(3) 0.0186(6) Uani 1 1 d .
C5 C 0.7300(3) 0.0360(4) 0.0549(3) 0.0208(6) Uani 1 1 d .
H5 H 0.7818 -0.021 0.1196 0.025 Uiso 1 1 calc R
C6 C 0.6326(3) -0.0376(4) -0.0318(3) 0.0250(7) Uani 1 1 d .
H6 H 0.6192 -0.145 -0.0264 0.03 Uiso 1 1 calc R
C7 C 0.5545(3) 0.0441(4) -0.1263(3) 0.0251(7) Uani 1 1 d .
H7 H 0.4883 -0.0077 -0.1853 0.03 Uiso 1 1 calc R
C8 C 0.5729(3) 0.2004(4) -0.1348(3) 0.0224(7) Uani 1 1 d .
H8 H 0.5193 0.2572 -0.1989 0.027 Uiso 1 1 calc R
C9 C 0.6722(3) 0.2737(3) -0.0469(3) 0.0176(6) Uani 1 1 d .
C10 C 0.9140(3) 0.4077(3) 0.0989(3) 0.0194(6) Uani 1 1 d .
H10A H 0.9909 0.4521 0.1584 0.023 Uiso 1 1 calc R
H10B H 0.9358 0.3795 0.0317 0.023 Uiso 1 1 calc R
Br1 Br 0.77033(3) 0.68898(3) 0.24628(3) 0.02345(12) Uani 1 1 d .
Br2 Br 0.94501(3) 0.38372(4) 0.37152(3) 0.02471(12) Uani 1 1 d .
N N 0.8022(2) 0.5157(3) 0.0676(2) 0.0189(5) Uani 1 1 d .
O1 O 0.5819(2) 0.5571(3) -0.07868(19) 0.0257(5) Uani 1 1 d .
O2 O 0.7624(2) 0.4925(3) -0.14007(19) 0.0255(5) Uani 1 1 d .
S S 0.69839(7) 0.47248(9) -0.06051(6) 0.01944(18) Uani 1 1 d .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
C1 0.0197(14) 0.0197(14) 0.0167(14) -0.0018(12) 0.0066(12) -0.0031(12)
C2 0.0150(14) 0.0218(15) 0.0168(14) 0.0016(12) 0.0017(12) -0.0021(12)
C3 0.0184(14) 0.0167(14) 0.0185(15) 0.0013(12) 0.0049(12) -0.0002(12)
C4 0.0202(15) 0.0212(15) 0.0171(15) -0.0012(12) 0.0099(12) -0.0004(12)
C5 0.0215(15) 0.0193(15) 0.0230(16) 0.0026(12) 0.0095(13) 0.0020(12)
C6 0.0317(17) 0.0180(15) 0.0309(18) -0.0043(13) 0.0182(15) -0.0050(13)
C7 0.0254(16) 0.0263(17) 0.0221(16) -0.0071(14) 0.0070(13) -0.0078(14)
C8 0.0234(16) 0.0262(16) 0.0171(15) 0.0001(13) 0.0067(13) -0.0011(13)
C9 0.0178(14) 0.0158(14) 0.0191(15) 0.0016(12) 0.0063(12) -0.0014(12)
C10 0.0167(14) 0.0210(15) 0.0207(15) -0.0008(12) 0.0071(12) -0.0001(12)
Br1 0.0269(2) 0.01966(18) 0.02448(19) -0.00411(12) 0.01004(14) -0.00042(12)
Br2 0.02558(19) 0.0284(2) 0.01644(18) 0.00099(12) 0.00303(13) -0.00314(12)
N 0.0207(13) 0.0183(12) 0.0170(12) 0.0011(10) 0.0059(11) -0.0009(10)
O1 0.0254(11) 0.0238(11) 0.0238(12) 0.0028(10) 0.0038(9) 0.0064(10)
O2 0.0333(12) 0.0245(11) 0.0208(11) 0.0049(9) 0.0121(10) -0.0011(10)
S 0.0235(4) 0.0170(4) 0.0167(4) 0.0029(3) 0.0059(3) 0.0001(3)
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0 0 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.006 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
N C1 C2 105.8(2)
N C1 Br1 110.50(19)
C2 C1 Br1 116.4(2)
N C1 H1 108
C2 C1 H1 108
Br1 C1 H1 108
C3 C2 C1 102.5(2)
C3 C2 Br2 108.9(2)
C1 C2 Br2 115.6(2)
C3 C2 H2 109.9
C1 C2 H2 109.9
Br2 C2 H2 109.9
C10 C3 C4 110.7(2)
C10 C3 C2 100.9(2)
C4 C3 C2 109.3(2)
C10 C3 H3 111.8
C4 C3 H3 111.8
C2 C3 H3 111.8
C9 C4 C5 118.1(3)
C9 C4 C3 122.6(3)
C5 C4 C3 119.3(3)
C6 C5 C4 120.5(3)
C6 C5 H5 119.7
C4 C5 H5 119.7
C5 C6 C7 120.7(3)
C5 C6 H6 119.7
C7 C6 H6 119.7
C8 C7 C6 120.2(3)
C8 C7 H7 119.9
C6 C7 H7 119.9
C7 C8 C9 118.7(3)
C7 C8 H8 120.7
C9 C8 H8 120.7
C4 C9 C8 121.9(3)
C4 C9 S 119.7(2)
C8 C9 S 118.4(2)
N C10 C3 101.2(2)
N C10 H10A 111.5
C3 C10 H10A 111.5
N C10 H10B 111.5
C3 C10 H10B 111.5
H10A C10 H10B 109.4
C1 N C10 106.4(2)
C1 N S 112.59(19)
C10 N S 109.8(2)
O2 S O1 118.35(14)
O2 S N 107.75(13)
O1 S N 108.29(13)
O2 S C9 109.07(14)
O1 S C9 110.07(14)
N S C9 102.05(14)
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
C1 N 1.483(4)
C1 C2 1.556(4)
C1 Br1 1.947(3)
C1 H1 1
C2 C3 1.535(4)
C2 Br2 1.959(3)
C2 H2 1
C3 C10 1.521(4)
C3 C4 1.524(4)
C3 H3 1
C4 C9 1.394(4)
C4 C5 1.393(4)
C5 C6 1.386(4)
C5 H5 0.95
C6 C7 1.389(5)
C6 H6 0.95
C7 C8 1.381(5)
C7 H7 0.95
C8 C9 1.404(4)
C8 H8 0.95
C9 S 1.767(3)
C10 N 1.493(4)
C10 H10A 0.99
C10 H10B 0.99
N S 1.654(3)
O1 S 1.435(2)
O2 S 1.433(2)
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
N C1 C2 C3 -16.0(3)
Br1 C1 C2 C3 -139.2(2)
N C1 C2 Br2 102.2(2)
Br1 C1 C2 Br2 -21.0(3)
C1 C2 C3 C10 39.2(3)
Br2 C2 C3 C10 -83.7(2)
C1 C2 C3 C4 -77.5(3)
Br2 C2 C3 C4 159.6(2)
C10 C3 C4 C9 -29.4(4)
C2 C3 C4 C9 80.8(3)
C10 C3 C4 C5 151.6(3)
C2 C3 C4 C5 -98.1(3)
C9 C4 C5 C6 1.8(5)
C3 C4 C5 C6 -179.2(3)
C4 C5 C6 C7 -1.0(5)
C5 C6 C7 C8 -0.2(5)
C6 C7 C8 C9 0.6(5)
C5 C4 C9 C8 -1.5(5)
C3 C4 C9 C8 179.6(3)
C5 C4 C9 S -179.2(2)
C3 C4 C9 S 1.9(4)
C7 C8 C9 C4 0.3(5)
C7 C8 C9 S 178.0(2)
C4 C3 C10 N 67.5(3)
C2 C3 C10 N -48.1(3)
C2 C1 N C10 -14.0(3)
Br1 C1 N C10 112.8(2)
C2 C1 N S 106.3(2)
Br1 C1 N S -126.97(17)
C3 C10 N C1 38.9(3)
C3 C10 N S -83.2(2)
C1 N S O2 179.68(19)
C10 N S O2 -62.0(2)
C1 N S O1 50.6(2)
C10 N S O1 168.85(19)
C1 N S C9 -65.5(2)
C10 N S C9 52.7(2)
C4 C9 S O2 101.9(3)
C8 C9 S O2 -75.9(3)
C4 C9 S O1 -126.8(3)
C8 C9 S O1 55.5(3)
C4 C9 S N -11.9(3)
C8 C9 S N 170.3(2)
loop_
_cod_related_entry_id
_cod_related_entry_database
_cod_related_entry_code
1 PubChem 11646326
