#------------------------------------------------------------------------------
#$Date: 2019-11-04 14:39:32 +0200 (Mon, 04 Nov 2019) $
#$Revision: 223044 $
#$URL: file:///home/coder/svn-repositories/cod/cif/4/03/45/4034545.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_4034545
loop_
_publ_author_name
'Massaro, Nicholas P.'
'Chatterji, Aayushi'
'Sharma, Indrajeet'
_publ_section_title
;
 Three-Component Approach to Pyridine-Stabilized Ketenimines for the
 Synthesis of Diverse Heterocycles.
;
_journal_issue                   21
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              13676
_journal_page_last               13685
_journal_paper_doi               10.1021/acs.joc.9b01906
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C16 H9 Br N2 O'
_chemical_formula_sum            'C16 H9 Br N2 O'
_chemical_formula_weight         325.16
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2018/3
_cell_angle_alpha                90
_cell_angle_beta                 113.580(5)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   25.468(5)
_cell_length_b                   4.6287(8)
_cell_length_c                   23.093(4)
_cell_measurement_reflns_used    6223
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.82
_cell_measurement_theta_min      3.07
_cell_volume                     2495.0(8)
_computing_cell_refinement       'SAINT (Bruker, 2016)'
_computing_data_collection       'APEX3 (Bruker, 2018)'
_computing_data_reduction        'SAINT (Bruker, 2016)'
_computing_molecular_graphics    'Mercury (CCDC, 2018)'
_computing_publication_material  'SHELXL-2018/3 (Sheldrick, 2015b)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Bruker Photon II cpad'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0645
_diffrn_reflns_av_unetI/netI     0.0403
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            21838
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.928
_diffrn_reflns_theta_min         2.305
_exptl_absorpt_coefficient_mu    3.290
_exptl_absorpt_correction_T_max  0.869
_exptl_absorpt_correction_T_min  0.671
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
; 
 SADABS-2016/2 Krause, L., Herbst-Irmer, R., Sheldrick G.M. & Stalke D., 
 J. Appl. Cryst. 48 (2015) 3-10. 
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.731
_exptl_crystal_description       block
_exptl_crystal_F_000             1296
_exptl_crystal_size_max          0.132
_exptl_crystal_size_mid          0.066
_exptl_crystal_size_min          0.044
_refine_diff_density_max         1.964
_refine_diff_density_min         -1.006
_refine_diff_density_rms         0.156
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.005
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     188
_refine_ls_number_reflns         2960
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.005
_refine_ls_R_factor_all          0.0797
_refine_ls_R_factor_gt           0.0592
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[σ²(Fo²)+(0.1280P)²+20.5000P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1713
_refine_ls_wR_factor_ref         0.1984
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2356
_reflns_number_total             2960
_reflns_threshold_expression     'I > 2σ(I)'
_cod_data_source_file            jo9b01906_si_004.cif
_cod_data_source_block           19097
_cod_original_sg_symbol_H-M      'C 2/c'
_cod_database_code               4034545
_shelx_space_group_comment
; 
The symmetry employed for this shelxl refinement is uniquely defined 
by the following loop, which should always be used as a source of 
symmetry information in preference to the above space-group names. 
They are only intended as comments. 
;
_shelx_estimated_absorpt_t_min   0.671
_shelx_estimated_absorpt_t_max   0.869
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y, -z+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y, z-1/2'
'-x+1/2, -y+1/2, -z'
'x+1/2, -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_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
Br1 Br 0.63728(3) 0.52625(13) 0.16815(3) 0.0264(2) Uani 1 1 d . .
O1 O 0.60812(19) 0.6765(10) 0.53660(19) 0.0268(9) Uani 1 1 d . .
N1 N 0.7068(2) 1.0152(10) 0.4318(2) 0.0211(10) Uani 1 1 d . .
N2 N 0.6965(2) 1.0623(13) 0.5265(3) 0.0250(11) Uani 1 1 d . .
H2A H 0.723(3) 1.198(17) 0.540(3) 0.030 Uiso 1 1 d . U
H2B H 0.680(4) 1.021(15) 0.549(4) 0.030 Uiso 1 1 d . U
C1 C 0.6580(2) 0.6706(13) 0.2510(3) 0.0233(12) Uani 1 1 d . .
C2 C 0.7021(3) 0.8754(14) 0.2749(3) 0.0250(12) Uani 1 1 d . .
H2 H 0.721429 0.939618 0.249544 0.030 Uiso 1 1 calc R U
C3 C 0.7172(3) 0.9827(13) 0.3345(3) 0.0243(12) Uani 1 1 d . .
H3 H 0.746787 1.123410 0.349904 0.029 Uiso 1 1 calc R U
C4 C 0.6900(2) 0.8895(13) 0.3739(3) 0.0224(11) Uani 1 1 d . .
C5 C 0.6814(2) 0.9332(12) 0.4697(3) 0.0209(11) Uani 1 1 d . .
C6 C 0.6388(2) 0.7143(12) 0.4508(3) 0.0199(10) Uani 1 1 d . .
C7 C 0.6051(3) 0.6056(13) 0.4851(3) 0.0239(12) Uani 1 1 d . .
C8 C 0.5640(2) 0.3921(13) 0.4404(3) 0.0208(11) Uani 1 1 d . .
C9 C 0.5215(3) 0.2317(13) 0.4477(3) 0.0267(13) Uani 1 1 d . .
H9 H 0.515084 0.244725 0.485410 0.032 Uiso 1 1 calc R U
C10 C 0.4884(3) 0.0511(13) 0.3991(3) 0.0266(13) Uani 1 1 d . .
H10 H 0.458812 -0.059769 0.403467 0.032 Uiso 1 1 calc R U
C11 C 0.4977(3) 0.0292(13) 0.3441(3) 0.0268(13) Uani 1 1 d . .
H11 H 0.474891 -0.098561 0.311518 0.032 Uiso 1 1 calc R U
C12 C 0.5410(2) 0.1969(13) 0.3361(3) 0.0227(11) Uani 1 1 d . .
H12 H 0.547391 0.184409 0.298365 0.027 Uiso 1 1 calc R U
C13 C 0.5736(2) 0.3785(12) 0.3845(3) 0.0214(11) Uani 1 1 d . .
C14 C 0.6215(3) 0.5856(12) 0.3918(3) 0.0200(11) Uani 1 1 d . .
C15 C 0.6459(3) 0.6744(13) 0.3497(3) 0.0223(11) Uani 1 1 d . .
C16 C 0.6312(2) 0.5640(12) 0.2880(3) 0.0178(10) Uani 1 1 d . .
H16 H 0.603038 0.416923 0.272165 0.021 Uiso 1 1 calc R U
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 0.0000 0.0000 '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 0.0060 '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'
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
C5 N1 C4 118.6(5)
C5 N2 H2A 123(5)
C5 N2 H2B 120(6)
H2A N2 H2B 117(7)
C16 C1 C2 120.9(5)
C16 C1 Br1 119.5(4)
C2 C1 Br1 119.5(4)
C3 C2 C1 120.0(5)
C3 C2 H2 120.0
C1 C2 H2 120.0
C2 C3 C4 121.6(6)
C2 C3 H3 119.2
C4 C3 H3 119.2
N1 C4 C3 117.4(5)
N1 C4 C15 124.5(5)
C3 C4 C15 118.1(5)
N1 C5 N2 119.2(5)
N1 C5 C6 120.9(5)
N2 C5 C6 120.0(6)
C14 C6 C5 120.7(5)
C14 C6 C7 111.0(5)
C5 C6 C7 128.2(5)
O1 C7 C6 128.1(6)
O1 C7 C8 127.3(6)
C6 C7 C8 104.6(5)
C9 C8 C13 121.5(6)
C9 C8 C7 129.4(5)
C13 C8 C7 109.2(5)
C8 C9 C10 118.7(6)
C8 C9 H9 120.7
C10 C9 H9 120.7
C9 C10 C11 121.1(6)
C9 C10 H10 119.4
C11 C10 H10 119.4
C10 C11 C12 120.3(6)
C10 C11 H11 119.8
C12 C11 H11 119.8
C13 C12 C11 118.3(5)
C13 C12 H12 120.8
C11 C12 H12 120.8
C12 C13 C8 120.1(5)
C12 C13 C14 132.5(5)
C8 C13 C14 107.4(5)
C6 C14 C15 120.0(5)
C6 C14 C13 107.9(5)
C15 C14 C13 132.0(5)
C14 C15 C16 125.3(5)
C14 C15 C4 115.2(5)
C16 C15 C4 119.4(5)
C1 C16 C15 119.8(5)
C1 C16 H16 120.1
C15 C16 H16 120.1
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
Br1 C1 1.891(6)
O1 C7 1.207(7)
N1 C5 1.334(8)
N1 C4 1.361(7)
N2 C5 1.350(8)
N2 H2A 0.89(8)
N2 H2B 0.81(9)
C1 C16 1.382(7)
C1 C2 1.403(8)
C2 C3 1.367(8)
C2 H2 0.9500
C3 C4 1.413(8)
C3 H3 0.9500
C4 C15 1.438(8)
C5 C6 1.420(8)
C6 C14 1.387(8)
C6 C7 1.468(8)
C7 C8 1.508(8)
C8 C9 1.377(8)
C8 C13 1.407(8)
C9 C10 1.383(9)
C9 H9 0.9500
C10 C11 1.385(9)
C10 H10 0.9500
C11 C12 1.421(9)
C11 H11 0.9500
C12 C13 1.380(8)
C12 H12 0.9500
C13 C14 1.507(8)
C14 C15 1.408(7)
C15 C16 1.415(8)
C16 H16 0.9500
loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
_geom_hbond_publ_flag
N2 H2A N1 0.89(8) 2.10(8) 2.987(8) 172(7) 7_676 yes
N2 H2B O1 0.81(9) 2.36(8) 2.955(7) 131(7) . yes
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
C16 C1 C2 C3 -3.2(9)
Br1 C1 C2 C3 179.6(5)
C1 C2 C3 C4 0.9(10)
C5 N1 C4 C3 179.4(5)
C5 N1 C4 C15 0.9(9)
C2 C3 C4 N1 -178.0(6)
C2 C3 C4 C15 0.6(9)
C4 N1 C5 N2 -178.1(5)
C4 N1 C5 C6 1.5(8)
N1 C5 C6 C14 -1.6(8)
N2 C5 C6 C14 178.0(6)
N1 C5 C6 C7 -177.5(6)
N2 C5 C6 C7 2.1(9)
C14 C6 C7 O1 -178.1(6)
C5 C6 C7 O1 -1.9(10)
C14 C6 C7 C8 -0.3(7)
C5 C6 C7 C8 176.0(5)
O1 C7 C8 C9 -0.2(11)
C6 C7 C8 C9 -178.2(6)
O1 C7 C8 C13 178.2(6)
C6 C7 C8 C13 0.3(6)
C13 C8 C9 C10 0.8(9)
C7 C8 C9 C10 179.1(6)
C8 C9 C10 C11 0.4(9)
C9 C10 C11 C12 -1.1(9)
C10 C11 C12 C13 0.6(9)
C11 C12 C13 C8 0.6(9)
C11 C12 C13 C14 -179.0(6)
C9 C8 C13 C12 -1.4(9)
C7 C8 C13 C12 -180.0(5)
C9 C8 C13 C14 178.4(5)
C7 C8 C13 C14 -0.2(7)
C5 C6 C14 C15 -0.8(9)
C7 C6 C14 C15 175.7(5)
C5 C6 C14 C13 -176.4(5)
C7 C6 C14 C13 0.1(7)
C12 C13 C14 C6 179.8(6)
C8 C13 C14 C6 0.0(7)
C12 C13 C14 C15 4.9(11)
C8 C13 C14 C15 -174.8(6)
C6 C14 C15 C16 -178.8(6)
C13 C14 C15 C16 -4.5(11)
C6 C14 C15 C4 2.9(8)
C13 C14 C15 C4 177.3(6)
N1 C4 C15 C14 -3.1(9)
C3 C4 C15 C14 178.4(5)
N1 C4 C15 C16 178.5(6)
C3 C4 C15 C16 0.1(8)
C2 C1 C16 C15 3.8(9)
Br1 C1 C16 C15 -179.0(4)
C14 C15 C16 C1 179.6(6)
C4 C15 C16 C1 -2.2(9)
