# Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.
# This journal is © The Royal Society of Chemistry 2016

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_3a
_database_code_depnum_ccdc_archive 'CCDC 1492337'
_audit_update_record             
;
2016-07-23 deposited with the CCDC.
2016-10-13 downloaded from the CCDC.
;
_audit_creation_date             2016-07-12
_audit_creation_method           
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C12 H11 Br N2 O'
_chemical_formula_sum            'C12 H11 Br N2 O'
_chemical_formula_weight         279.14
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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'
Br Br -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/c 1'
_space_group_name_Hall           '-P 2ybc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   8.473(2)
_cell_length_b                   19.517(4)
_cell_length_c                   7.043(2)
_cell_angle_alpha                90
_cell_angle_beta                 102.04(3)
_cell_angle_gamma                90
_cell_volume                     1139.2(5)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    9975
_cell_measurement_temperature    293.2
_cell_measurement_theta_max      71.9761
_cell_measurement_theta_min      5.3330
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    4.753
_exptl_absorpt_correction_T_max  0.753578
_exptl_absorpt_correction_T_min  0.510519
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.1164 before and 0.0485 after correction.
 The Ratio of minimum to maximum transmission not present.
 The λ/2 correction factor is Not present
 
For component 2:
 wR2(int) was 0.1358 before and 0.0399 after correction.
 The Ratio of minimum to maximum transmission is 0.68.
 The λ/2 correction factor is Not present

Final HKLF 4 output contains 19924 reflections, Rint = 0.0402
 (14944 with I > 3sig(I), Rint = 0.0387)
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.628
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             560
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.21
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0223
_diffrn_reflns_av_unetI/netI     0.0369
_diffrn_reflns_Laue_measured_fraction_full 0.978
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            4168
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        66.750
_diffrn_reflns_theta_max         72.061
_diffrn_reflns_theta_min         4.527
_diffrn_ambient_temperature      293.2
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.978
_diffrn_measured_fraction_theta_max 0.958
_diffrn_measurement_device_type  'Bruker D8 VENTURE PHOTON'
_diffrn_measurement_method       ?
_diffrn_radiation_type           'Cu Ka'
_diffrn_radiation_wavelength     1.54056
_diffrn_source                   ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1708
_reflns_number_total             2160
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'SAINT V8.34A (Bruker AXS Inc., 2013)'
_computing_data_collection       'Bruker D8 VENTURE PHOTON'
_computing_data_reduction        'SAINT V8.34A (Bruker AXS Inc., 2013)'
_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)'
_refine_diff_density_max         0.531
_refine_diff_density_min         -0.554
_refine_diff_density_rms         0.146
_refine_ls_extinction_coef       0.0050(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     147
_refine_ls_number_reflns         2160
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0594
_refine_ls_R_factor_gt           0.0432
_refine_ls_restrained_S_all      1.054
_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/[σ²(Fo²)+(0.0516P)²+0.5356P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0964
_refine_ls_wR_factor_ref         0.1026
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B)
2.b Aromatic/amide H refined with riding coordinates:
 N2(H2), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9)
2.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   ?
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
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Br1 Br 0.15753(4) 0.29712(2) 0.25372(6) 0.0690(2) Uani 1 1 d . . . . .
O1 O 0.8561(3) 0.48303(11) 0.6637(4) 0.0690(7) Uani 1 1 d . . . . .
N1 N 0.7773(3) 0.24090(12) 0.5264(4) 0.0506(6) Uani 1 1 d . . . . .
N2 N 0.8600(3) 0.37160(12) 0.5773(4) 0.0552(7) Uani 1 1 d . . . . .
H2 H 0.9250 0.3382 0.5718 0.066 Uiso 1 1 calc R . . . .
C1 C 0.3763(4) 0.32064(17) 0.3548(4) 0.0509(7) Uani 1 1 d . . . . .
C2 C 0.4943(4) 0.26792(15) 0.4026(4) 0.0447(6) Uani 1 1 d . . . . .
C3 C 0.6556(4) 0.28748(13) 0.4755(4) 0.0442(6) Uani 1 1 d . . . . .
C4 C 0.6972(3) 0.35825(14) 0.5012(4) 0.0477(7) Uani 1 1 d . . . . .
C5 C 0.5789(4) 0.40686(15) 0.4524(5) 0.0532(7) Uani 1 1 d . . . . .
H5 H 0.6055 0.4530 0.4681 0.064 Uiso 1 1 calc R . . . .
C6 C 0.4176(4) 0.38772(15) 0.3789(5) 0.0543(7) Uani 1 1 d . . . . .
H6 H 0.3388 0.4213 0.3465 0.065 Uiso 1 1 calc R . . . .
C7 C 0.4631(4) 0.19689(15) 0.3839(5) 0.0545(8) Uani 1 1 d . . . . .
H7 H 0.3586 0.1813 0.3357 0.065 Uiso 1 1 calc R . . . .
C8 C 0.5848(4) 0.15161(16) 0.4361(5) 0.0585(8) Uani 1 1 d . . . . .
H8 H 0.5648 0.1048 0.4246 0.070 Uiso 1 1 calc R . . . .
C9 C 0.7406(4) 0.17574(15) 0.5074(5) 0.0556(8) Uani 1 1 d . . . . .
H9 H 0.8230 0.1439 0.5434 0.067 Uiso 1 1 calc R . . . .
C10 C 0.9297(4) 0.43016(14) 0.6586(5) 0.0502(7) Uani 1 1 d . . . . .
C11 C 1.1083(4) 0.42276(17) 0.7409(6) 0.0641(9) Uani 1 1 d . . . . .
H11A H 1.1250 0.3835 0.8273 0.077 Uiso 1 1 calc R . . . .
H11B H 1.1624 0.4133 0.6351 0.077 Uiso 1 1 calc R . . . .
C12 C 1.1857(5) 0.4843(2) 0.8501(6) 0.0761(11) Uani 1 1 d . . . . .
H12A H 1.1641 0.5241 0.7688 0.114 Uiso 1 1 calc GR . . . .
H12B H 1.3001 0.4773 0.8871 0.114 Uiso 1 1 calc GR . . . .
H12C H 1.1423 0.4908 0.9643 0.114 Uiso 1 1 calc GR . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Br1 C1 1.898(3) . ?
O1 C10 1.210(3) . ?
N1 C3 1.365(4) . ?
N1 C9 1.309(4) . ?
N2 H2 0.8600 . ?
N2 C4 1.396(4) . ?
N2 C10 1.357(4) . ?
C1 C2 1.425(4) . ?
C1 C6 1.357(4) . ?
C2 C3 1.409(4) . ?
C2 C7 1.412(4) . ?
C3 C4 1.428(4) . ?
C4 C5 1.371(4) . ?
C5 H5 0.9300 . ?
C5 C6 1.407(4) . ?
C6 H6 0.9300 . ?
C7 H7 0.9300 . ?
C7 C8 1.350(5) . ?
C8 H8 0.9300 . ?
C8 C9 1.393(4) . ?
C9 H9 0.9300 . ?
C10 C11 1.511(4) . ?
C11 H11A 0.9700 . ?
C11 H11B 0.9700 . ?
C11 C12 1.501(5) . ?
C12 H12A 0.9600 . ?
C12 H12B 0.9600 . ?
C12 H12C 0.9600 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C9 N1 C3 118.1(3) . . ?
C4 N2 H2 115.6 . . ?
C10 N2 H2 115.6 . . ?
C10 N2 C4 128.8(2) . . ?
C2 C1 Br1 119.7(2) . . ?
C6 C1 Br1 119.1(2) . . ?
C6 C1 C2 121.1(3) . . ?
C3 C2 C1 118.0(3) . . ?
C3 C2 C7 116.6(3) . . ?
C7 C2 C1 125.3(3) . . ?
N1 C3 C2 122.5(2) . . ?
N1 C3 C4 117.3(3) . . ?
C2 C3 C4 120.2(3) . . ?
N2 C4 C3 115.3(2) . . ?
C5 C4 N2 125.4(3) . . ?
C5 C4 C3 119.3(3) . . ?
C4 C5 H5 119.6 . . ?
C4 C5 C6 120.8(3) . . ?
C6 C5 H5 119.6 . . ?
C1 C6 C5 120.5(3) . . ?
C1 C6 H6 119.7 . . ?
C5 C6 H6 119.7 . . ?
C2 C7 H7 120.0 . . ?
C8 C7 C2 120.0(3) . . ?
C8 C7 H7 120.0 . . ?
C7 C8 H8 120.3 . . ?
C7 C8 C9 119.3(3) . . ?
C9 C8 H8 120.3 . . ?
N1 C9 C8 123.5(3) . . ?
N1 C9 H9 118.3 . . ?
C8 C9 H9 118.3 . . ?
O1 C10 N2 123.3(3) . . ?
O1 C10 C11 123.5(3) . . ?
N2 C10 C11 113.2(2) . . ?
C10 C11 H11A 108.6 . . ?
C10 C11 H11B 108.6 . . ?
H11A C11 H11B 107.6 . . ?
C12 C11 C10 114.6(3) . . ?
C12 C11 H11A 108.6 . . ?
C12 C11 H11B 108.6 . . ?
C11 C12 H12A 109.5 . . ?
C11 C12 H12B 109.5 . . ?
C11 C12 H12C 109.5 . . ?
H12A C12 H12B 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?

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
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Br1 C1 C2 C3 179.4(2) . . . . ?
Br1 C1 C2 C7 -1.0(4) . . . . ?
Br1 C1 C6 C5 -179.6(2) . . . . ?
O1 C10 C11 C12 6.4(5) . . . . ?
N1 C3 C4 N2 -0.2(4) . . . . ?
N1 C3 C4 C5 -179.9(3) . . . . ?
N2 C4 C5 C6 -179.2(3) . . . . ?
N2 C10 C11 C12 -173.9(3) . . . . ?
C1 C2 C3 N1 179.6(3) . . . . ?
C1 C2 C3 C4 0.4(4) . . . . ?
C1 C2 C7 C8 -179.2(3) . . . . ?
C2 C1 C6 C5 -0.2(5) . . . . ?
C2 C3 C4 N2 179.0(3) . . . . ?
C2 C3 C4 C5 -0.6(5) . . . . ?
C2 C7 C8 C9 -0.2(5) . . . . ?
C3 N1 C9 C8 0.8(5) . . . . ?
C3 C2 C7 C8 0.4(5) . . . . ?
C3 C4 C5 C6 0.4(5) . . . . ?
C4 N2 C10 O1 -5.6(5) . . . . ?
C4 N2 C10 C11 174.7(3) . . . . ?
C4 C5 C6 C1 0.0(5) . . . . ?
C6 C1 C2 C3 0.0(5) . . . . ?
C6 C1 C2 C7 179.6(3) . . . . ?
C7 C2 C3 N1 0.0(4) . . . . ?
C7 C2 C3 C4 -179.2(3) . . . . ?
C7 C8 C9 N1 -0.4(5) . . . . ?
C9 N1 C3 C2 -0.6(5) . . . . ?
C9 N1 C3 C4 178.7(3) . . . . ?
C10 N2 C4 C3 -163.3(3) . . . . ?
C10 N2 C4 C5 16.4(5) . . . . ?

_shelx_SHELXL_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'
