# Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.
# This journal is © The Royal Society of Chemistry 2015

####################################################################### 
# 
# 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_p21c
_database_code_depnum_ccdc_archive 'CCDC 1400689'
_audit_update_record             
;
2015-05-13 deposited with the CCDC.
2015-07-01 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            
'N-Methyl-N-(8-dimethylaminonaphth-1-yl)aminoacetic acid hydrobromide'
_chemical_melting_point          '236-238 deg.C (decomp.)'
_chemical_formula_moiety         'C15 H19 N2 O2, Br'
_chemical_formula_sum            'C15 H19 Br N2 O2'
_chemical_formula_weight         339.23

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'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   'P 21/c'
_symmetry_space_group_name_Hall  '-P 2ybc'

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'

_cell_length_a                   7.4871(8)
_cell_length_b                   12.1721(12)
_cell_length_c                   16.4565(17)
_cell_angle_alpha                90.00
_cell_angle_beta                 94.653(2)
_cell_angle_gamma                90.00
_cell_volume                     1494.8(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    219
_cell_measurement_theta_min      3
_cell_measurement_theta_max      28

_exptl_crystal_description       plate
_exptl_crystal_colour            grey
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.15
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.507
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             696
_exptl_absorpt_coefficient_mu    2.753
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.446
_exptl_absorpt_correction_T_max  0.683
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker APEX II CCD area detector'
_diffrn_measurement_method       'omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            10993
_diffrn_reflns_av_R_equivalents  0.0629
_diffrn_reflns_av_sigmaI/netI    0.0692
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_theta_min         2.48
_diffrn_reflns_theta_max         28.00
_reflns_number_total             3567
_reflns_number_gt                2827
_reflns_threshold_expression     I>2σ(I)

_computing_data_collection       'Bruker APEX II'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXTL  (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXTL  (Sheldrick, 2008)'
_computing_molecular_graphics    'SHELXTL  (Sheldrick, 2008)'
_computing_publication_material  'SHELXTL  (Sheldrick, 2008)'

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0626P)²+0.5020P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3567
_refine_ls_number_parameters     189
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0580
_refine_ls_R_factor_gt           0.0448
_refine_ls_wR_factor_ref         0.1213
_refine_ls_wR_factor_gt          0.1157
_refine_ls_goodness_of_fit_ref   1.009
_refine_ls_restrained_S_all      1.009
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000

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
_atom_site_disorder_assembly
_atom_site_disorder_group
N1 N 0.3608(4) 1.1948(2) 0.47021(15) 0.0142(5) Uani 1 1 d . . .
Br1 Br -0.28519(4) 1.05210(3) 0.679131(18) 0.02191(13) Uani 1 1 d . . .
N2 N 0.1657(4) 1.2760(2) 0.34594(15) 0.0182(6) Uani 1 1 d . . .
H2N H 0.240(6) 1.224(4) 0.389(3) 0.033(11) Uiso 1 1 d . . .
O1 O 0.0104(3) 1.1773(2) 0.51349(15) 0.0278(6) Uani 1 1 d . . .
O2 O 0.0904(4) 1.0466(2) 0.60516(15) 0.0275(6) Uani 1 1 d . . .
H2O H -0.029(8) 1.057(4) 0.620(3) 0.051(15) Uiso 1 1 d . . .
C1 C 0.3530(4) 1.3006(2) 0.51077(17) 0.0141(6) Uani 1 1 d . . .
C2 C 0.4333(4) 1.3148(3) 0.58824(18) 0.0161(6) Uani 1 1 d . . .
H2A H 0.4940 1.2550 0.6154 0.019 Uiso 1 1 calc R . .
C3 C 0.4265(4) 1.4169(3) 0.62754(18) 0.0168(6) Uani 1 1 d . . .
H3A H 0.4807 1.4255 0.6814 0.020 Uiso 1 1 calc R . .
C4 C 0.3425(4) 1.5036(3) 0.58875(18) 0.0166(6) Uani 1 1 d . . .
H4A H 0.3381 1.5722 0.6160 0.020 Uiso 1 1 calc R . .
C5 C 0.2612(4) 1.4930(2) 0.50802(18) 0.0140(6) Uani 1 1 d . . .
C6 C 0.1755(4) 1.5841(3) 0.4678(2) 0.0178(6) Uani 1 1 d . . .
H6A H 0.1752 1.6532 0.4947 0.021 Uiso 1 1 calc R . .
C7 C 0.0934(4) 1.5738(3) 0.3910(2) 0.0192(7) Uani 1 1 d . . .
H7A H 0.0372 1.6358 0.3648 0.023 Uiso 1 1 calc R . .
C8 C 0.0917(4) 1.4732(3) 0.35093(19) 0.0189(6) Uani 1 1 d . . .
H8A H 0.0351 1.4668 0.2973 0.023 Uiso 1 1 calc R . .
C9 C 0.1712(4) 1.3833(2) 0.38842(17) 0.0146(6) Uani 1 1 d . . .
C10 C 0.2638(4) 1.3891(2) 0.46822(17) 0.0125(6) Uani 1 1 d . . .
C11 C 0.5412(4) 1.1742(3) 0.4423(2) 0.0203(7) Uani 1 1 d . . .
H11A H 0.5761 1.2362 0.4091 0.030 Uiso 1 1 calc R . .
H11B H 0.5386 1.1068 0.4096 0.030 Uiso 1 1 calc R . .
H11C H 0.6281 1.1659 0.4898 0.030 Uiso 1 1 calc R . .
C12 C 0.3072(4) 1.1020(3) 0.51967(18) 0.0180(6) Uani 1 1 d . . .
H12A H 0.3914 1.0959 0.5690 0.022 Uiso 1 1 calc R . .
H12B H 0.3148 1.0333 0.4880 0.022 Uiso 1 1 calc R . .
C13 C 0.1204(5) 1.1148(3) 0.54481(19) 0.0200(7) Uani 1 1 d . . .
C14 C 0.2671(5) 1.2766(3) 0.2722(2) 0.0289(8) Uani 1 1 d . . .
H14A H 0.2882 1.2009 0.2552 0.043 Uiso 1 1 calc R . .
H14B H 0.3822 1.3138 0.2845 0.043 Uiso 1 1 calc R . .
H14C H 0.1978 1.3157 0.2281 0.043 Uiso 1 1 calc R . .
C15 C -0.0221(5) 1.2349(3) 0.3261(2) 0.0243(7) Uani 1 1 d . . .
H15A H -0.0864 1.2348 0.3757 0.037 Uiso 1 1 calc R . .
H15B H -0.0182 1.1600 0.3044 0.037 Uiso 1 1 calc R . .
H15C H -0.0843 1.2830 0.2853 0.037 Uiso 1 1 calc R . .


_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
N1 C1 1.454(4) . ?
N1 C12 1.467(4) . ?
N1 C11 1.483(4) . ?
N2 C9 1.480(4) . ?
N2 C14 1.483(4) . ?
N2 C15 1.503(4) . ?
N2 H2N 1.08(4) . ?
O1 C13 1.205(4) . ?
O2 C13 1.328(4) . ?
O2 H2O 0.95(6) . ?
C1 C2 1.376(4) . ?
C1 C10 1.422(4) . ?
C2 C3 1.404(4) . ?
C2 H2A 0.9500 . ?
C3 C4 1.360(5) . ?
C3 H3A 0.9500 . ?
C4 C5 1.422(4) . ?
C4 H4A 0.9500 . ?
C5 C6 1.417(4) . ?
C5 C10 1.425(4) . ?
C6 C7 1.366(4) . ?
C6 H6A 0.9500 . ?
C7 C8 1.391(4) . ?
C7 H7A 0.9500 . ?
C8 C9 1.368(4) . ?
C8 H8A 0.9500 . ?
C9 C10 1.436(4) . ?
C11 H11A 0.9800 . ?
C11 H11B 0.9800 . ?
C11 H11C 0.9800 . ?
C12 C13 1.498(5) . ?
C12 H12A 0.9900 . ?
C12 H12B 0.9900 . ?
C14 H14A 0.9800 . ?
C14 H14B 0.9800 . ?
C14 H14C 0.9800 . ?
C15 H15A 0.9800 . ?
C15 H15B 0.9800 . ?
C15 H15C 0.9800 . ?

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
C1 N1 C12 113.8(2) . . ?
C1 N1 C11 111.3(2) . . ?
C12 N1 C11 109.8(2) . . ?
C9 N2 C14 112.7(3) . . ?
C9 N2 C15 112.7(2) . . ?
C14 N2 C15 110.8(3) . . ?
C9 N2 H2N 103(2) . . ?
C14 N2 H2N 106(2) . . ?
C15 N2 H2N 112(2) . . ?
C13 O2 H2O 109(3) . . ?
C2 C1 C10 120.9(3) . . ?
C2 C1 N1 120.4(3) . . ?
C10 C1 N1 118.7(2) . . ?
C1 C2 C3 120.6(3) . . ?
C1 C2 H2A 119.7 . . ?
C3 C2 H2A 119.7 . . ?
C4 C3 C2 120.2(3) . . ?
C4 C3 H3A 119.9 . . ?
C2 C3 H3A 119.9 . . ?
C3 C4 C5 121.0(3) . . ?
C3 C4 H4A 119.5 . . ?
C5 C4 H4A 119.5 . . ?
C6 C5 C4 120.6(3) . . ?
C6 C5 C10 120.1(3) . . ?
C4 C5 C10 119.3(3) . . ?
C7 C6 C5 120.9(3) . . ?
C7 C6 H6A 119.6 . . ?
C5 C6 H6A 119.6 . . ?
C6 C7 C8 120.4(3) . . ?
C6 C7 H7A 119.8 . . ?
C8 C7 H7A 119.8 . . ?
C9 C8 C7 120.2(3) . . ?
C9 C8 H8A 119.9 . . ?
C7 C8 H8A 119.9 . . ?
C8 C9 C10 122.2(3) . . ?
C8 C9 N2 119.8(3) . . ?
C10 C9 N2 117.9(3) . . ?
C1 C10 C5 118.0(3) . . ?
C1 C10 C9 125.8(3) . . ?
C5 C10 C9 116.1(3) . . ?
N1 C11 H11A 109.5 . . ?
N1 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
N1 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
N1 C12 C13 112.1(3) . . ?
N1 C12 H12A 109.2 . . ?
C13 C12 H12A 109.2 . . ?
N1 C12 H12B 109.2 . . ?
C13 C12 H12B 109.2 . . ?
H12A C12 H12B 107.9 . . ?
O1 C13 O2 124.3(3) . . ?
O1 C13 C12 124.6(3) . . ?
O2 C13 C12 111.1(3) . . ?
N2 C14 H14A 109.5 . . ?
N2 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
N2 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
N2 C15 H15A 109.5 . . ?
N2 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
N2 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 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
C12 N1 C1 C2 50.4(4) . . . . ?
C11 N1 C1 C2 -74.4(3) . . . . ?
C12 N1 C1 C10 -130.8(3) . . . . ?
C11 N1 C1 C10 104.5(3) . . . . ?
C10 C1 C2 C3 1.0(5) . . . . ?
N1 C1 C2 C3 179.8(3) . . . . ?
C1 C2 C3 C4 -1.1(5) . . . . ?
C2 C3 C4 C5 -0.3(5) . . . . ?
C3 C4 C5 C6 -179.4(3) . . . . ?
C3 C4 C5 C10 1.7(5) . . . . ?
C4 C5 C6 C7 -178.4(3) . . . . ?
C10 C5 C6 C7 0.5(5) . . . . ?
C5 C6 C7 C8 0.4(5) . . . . ?
C6 C7 C8 C9 0.5(5) . . . . ?
C7 C8 C9 C10 -2.1(5) . . . . ?
C7 C8 C9 N2 178.8(3) . . . . ?
C14 N2 C9 C8 65.5(4) . . . . ?
C15 N2 C9 C8 -60.9(4) . . . . ?
C14 N2 C9 C10 -113.6(3) . . . . ?
C15 N2 C9 C10 120.0(3) . . . . ?
C2 C1 C10 C5 0.4(4) . . . . ?
N1 C1 C10 C5 -178.5(3) . . . . ?
C2 C1 C10 C9 -178.1(3) . . . . ?
N1 C1 C10 C9 3.0(5) . . . . ?
C6 C5 C10 C1 179.4(3) . . . . ?
C4 C5 C10 C1 -1.7(4) . . . . ?
C6 C5 C10 C9 -2.0(4) . . . . ?
C4 C5 C10 C9 176.9(3) . . . . ?
C8 C9 C10 C1 -178.6(3) . . . . ?
N2 C9 C10 C1 0.4(4) . . . . ?
C8 C9 C10 C5 2.8(4) . . . . ?
N2 C9 C10 C5 -178.1(3) . . . . ?
C1 N1 C12 C13 58.4(3) . . . . ?
C11 N1 C12 C13 -176.1(3) . . . . ?
N1 C12 C13 O1 17.1(4) . . . . ?
N1 C12 C13 O2 -164.2(2) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_site_symmetry_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_publ_flag


N2 H2N N1 1_555 1.08(4) 1.59(4) 2.610(4) 156(2) ?
O2 H2O Br1 1_555 0.95(6) 2.22(5) 3.154(4) 165(3) ?

_diffrn_measured_fraction_theta_max 0.989
_diffrn_reflns_theta_full        28.00
_diffrn_measured_fraction_theta_full 0.989
_refine_diff_density_max         1.756
_refine_diff_density_min         -0.580
_refine_diff_density_rms         0.112
_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: Methanol'
_exptl_crystal_preparation       Luminescent
####################################################################### 
# 
# 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_s8d
_database_code_depnum_ccdc_archive 'CCDC 1400690'
_audit_update_record             
;
2015-05-13 deposited with the CCDC.
2015-07-01 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            
'1,1,3-Trimethyl-2,3-dihydro-1H-perimidin-1-ium bromide'
_chemical_melting_point          '167-169 deg.C (decomp.)'
_chemical_formula_moiety         'C14 H17 N2 +, Br -, 2(H2 O)'
_chemical_formula_sum            'C14 H21 Br N2 O2'
_chemical_formula_weight         329.24
_chemical_absolute_configuration ad

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'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'

_cell_length_a                   7.0938(3)
_cell_length_b                   11.5502(5)
_cell_length_c                   18.1965(9)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1490.93(12)
_cell_formula_units_Z            4
_cell_measurement_temperature    120(2)
_cell_measurement_reflns_used    9960
_cell_measurement_theta_min      2.24
_cell_measurement_theta_max      30.02

_exptl_crystal_description       prizm
_exptl_crystal_colour            'light brown'
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.18
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.467
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             680
_exptl_absorpt_coefficient_mu    2.758
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.436
_exptl_absorpt_correction_T_max  0.609
_exptl_absorpt_process_details   'SADABS-2008/1 (Bruker,2008)'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      120(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        0
_diffrn_reflns_number            25728
_diffrn_reflns_av_R_equivalents  0.0361
_diffrn_reflns_av_sigmaI/netI    0.0341
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_theta_min         2.09
_diffrn_reflns_theta_max         30.19
_reflns_number_total             4383
_reflns_number_gt                4051
_reflns_threshold_expression     I>2σ(I)

_computing_data_collection       'APEX (Bruker, 2009)'
_computing_cell_refinement       'SAINT (Bruker, 2009)'
_computing_data_reduction        'SAINT (Bruker, 2009)'
_computing_structure_solution    'SHELXTL (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXTL (Sheldrick, 2008)'
_computing_molecular_graphics    'SHELXTL (Sheldrick, 2008)'
_computing_publication_material  
'SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009)'

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0207P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.005(5)
_refine_ls_number_reflns         4383
_refine_ls_number_parameters     191
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0275
_refine_ls_R_factor_gt           0.0228
_refine_ls_wR_factor_ref         0.0476
_refine_ls_wR_factor_gt          0.0460
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_restrained_S_all      1.015
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

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
_atom_site_disorder_assembly
_atom_site_disorder_group
Br1 Br 0.28414(2) 0.646347(14) 0.691760(9) 0.02122(4) Uani 1 1 d . . .
N1 N -0.19879(18) 0.77461(10) 0.79270(6) 0.0159(3) Uani 1 1 d . . .
N2 N -0.2310(2) 0.57614(12) 0.83226(8) 0.0233(3) Uani 1 1 d . . .
C1 C -0.0340(2) 0.78633(14) 0.84327(8) 0.0152(3) Uani 1 1 d . . .
C2 C 0.0227(2) 0.68649(14) 0.88294(8) 0.0155(3) Uani 1 1 d . . .
C3 C -0.0768(2) 0.57901(14) 0.87967(9) 0.0182(3) Uani 1 1 d . . .
C4 C -0.0246(3) 0.48872(15) 0.92437(9) 0.0235(3) Uani 1 1 d . . .
H4A H -0.0949 0.4187 0.9240 0.028 Uiso 1 1 calc R . .
C5 C 0.1337(3) 0.49997(16) 0.97087(10) 0.0267(4) Uani 1 1 d . . .
H5A H 0.1716 0.4359 1.0001 0.032 Uiso 1 1 calc R . .
C6 C 0.2334(3) 0.60060(16) 0.97472(8) 0.0248(4) Uani 1 1 d . . .
H6A H 0.3406 0.6055 1.0059 0.030 Uiso 1 1 calc R . .
C7 C 0.1781(2) 0.69808(15) 0.93249(8) 0.0190(3) Uani 1 1 d . . .
C8 C 0.2645(2) 0.80778(15) 0.94018(8) 0.0217(3) Uani 1 1 d . . .
H8A H 0.3687 0.8159 0.9725 0.026 Uiso 1 1 calc R . .
C9 C 0.2018(3) 0.90235(15) 0.90226(9) 0.0234(3) Uani 1 1 d . . .
H9A H 0.2604 0.9755 0.9093 0.028 Uiso 1 1 calc R . .
C10 C 0.0497(2) 0.89135(14) 0.85267(9) 0.0196(3) Uani 1 1 d . . .
H10A H 0.0061 0.9568 0.8260 0.024 Uiso 1 1 calc R . .
C11 C -0.1722(2) 0.84396(15) 0.72331(8) 0.0215(3) Uani 1 1 d . . .
H11A H -0.1850 0.9266 0.7344 0.032 Uiso 1 1 calc R . .
H11B H -0.2680 0.8214 0.6872 0.032 Uiso 1 1 calc R . .
H11C H -0.0465 0.8290 0.7032 0.032 Uiso 1 1 calc R . .
C12 C -0.3754(2) 0.81091(16) 0.83145(9) 0.0212(4) Uani 1 1 d . . .
H12A H -0.3666 0.8930 0.8447 0.032 Uiso 1 1 calc R . .
H12B H -0.3914 0.7644 0.8760 0.032 Uiso 1 1 calc R . .
H12C H -0.4838 0.7992 0.7989 0.032 Uiso 1 1 calc R . .
C13 C -0.2137(2) 0.64782(13) 0.76897(8) 0.0200(3) Uani 1 1 d . . .
H13A H -0.3250 0.6374 0.7368 0.024 Uiso 1 1 calc R . .
H13B H -0.0999 0.6256 0.7408 0.024 Uiso 1 1 calc R . .
C14 C -0.3663(3) 0.48247(17) 0.83400(12) 0.0348(5) Uani 1 1 d . . .
H14A H -0.4062 0.4688 0.8848 0.052 Uiso 1 1 calc R . .
H14B H -0.3081 0.4121 0.8143 0.052 Uiso 1 1 calc R . .
H14C H -0.4761 0.5031 0.8041 0.052 Uiso 1 1 calc R . .
O1 O 0.6272(2) 0.71819(14) 0.57645(8) 0.0340(3) Uani 1 1 d . . .
H1A H 0.542(3) 0.6986(19) 0.6001(12) 0.034(6) Uiso 1 1 d . . .
H2A H 1.058(3) 0.667(2) 0.5847(13) 0.043(7) Uiso 1 1 d . . .
O2 O 0.9982(2) 0.66752(15) 0.54507(8) 0.0373(4) Uani 1 1 d . . .
H1B H 0.587(3) 0.758(2) 0.5383(13) 0.042(7) Uiso 1 1 d . . .
H2B H 0.909(4) 0.680(2) 0.5587(13) 0.036(7) Uiso 1 1 d . . .


_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
N1 C1 1.4937(19) . ?
N1 C12 1.498(2) . ?
N1 C11 1.5071(19) . ?
N1 C13 1.5304(19) . ?
N2 C3 1.393(2) . ?
N2 C13 1.424(2) . ?
N2 C14 1.446(2) . ?
C1 C10 1.361(2) . ?
C1 C2 1.419(2) . ?
C2 C3 1.429(2) . ?
C2 C7 1.430(2) . ?
C3 C4 1.374(2) . ?
C4 C5 1.412(3) . ?
C4 H4A 0.9500 . ?
C5 C6 1.362(3) . ?
C5 H5A 0.9500 . ?
C6 C7 1.419(2) . ?
C6 H6A 0.9500 . ?
C7 C8 1.414(2) . ?
C8 C9 1.366(2) . ?
C8 H8A 0.9500 . ?
C9 C10 1.412(2) . ?
C9 H9A 0.9500 . ?
C10 H10A 0.9500 . ?
C11 H11A 0.9800 . ?
C11 H11B 0.9800 . ?
C11 H11C 0.9800 . ?
C12 H12A 0.9800 . ?
C12 H12B 0.9800 . ?
C12 H12C 0.9800 . ?
C13 H13A 0.9900 . ?
C13 H13B 0.9900 . ?
C14 H14A 0.9800 . ?
C14 H14B 0.9800 . ?
C14 H14C 0.9800 . ?
O1 H1A 0.78(2) . ?
O1 H1B 0.88(2) . ?
O2 H2A 0.83(2) . ?
O2 H2B 0.69(3) . ?

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
C1 N1 C12 109.84(11) . . ?
C1 N1 C11 111.72(12) . . ?
C12 N1 C11 110.50(12) . . ?
C1 N1 C13 108.33(11) . . ?
C12 N1 C13 110.06(13) . . ?
C11 N1 C13 106.31(11) . . ?
C3 N2 C13 114.77(13) . . ?
C3 N2 C14 121.67(15) . . ?
C13 N2 C14 120.66(15) . . ?
C10 C1 C2 122.45(14) . . ?
C10 C1 N1 119.97(14) . . ?
C2 C1 N1 117.49(13) . . ?
C1 C2 C3 123.01(13) . . ?
C1 C2 C7 117.59(15) . . ?
C3 C2 C7 119.22(14) . . ?
C4 C3 N2 124.08(15) . . ?
C4 C3 C2 120.10(15) . . ?
N2 C3 C2 115.73(13) . . ?
C3 C4 C5 119.97(17) . . ?
C3 C4 H4A 120.0 . . ?
C5 C4 H4A 120.0 . . ?
C6 C5 C4 121.48(16) . . ?
C6 C5 H5A 119.3 . . ?
C4 C5 H5A 119.3 . . ?
C5 C6 C7 120.38(16) . . ?
C5 C6 H6A 119.8 . . ?
C7 C6 H6A 119.8 . . ?
C8 C7 C6 122.52(15) . . ?
C8 C7 C2 118.69(15) . . ?
C6 C7 C2 118.71(16) . . ?
C9 C8 C7 121.68(15) . . ?
C9 C8 H8A 119.2 . . ?
C7 C8 H8A 119.2 . . ?
C8 C9 C10 119.96(15) . . ?
C8 C9 H9A 120.0 . . ?
C10 C9 H9A 120.0 . . ?
C1 C10 C9 119.59(15) . . ?
C1 C10 H10A 120.2 . . ?
C9 C10 H10A 120.2 . . ?
N1 C11 H11A 109.5 . . ?
N1 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
N1 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
N1 C12 H12A 109.5 . . ?
N1 C12 H12B 109.5 . . ?
H12A C12 H12B 109.5 . . ?
N1 C12 H12C 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
N2 C13 N1 109.53(11) . . ?
N2 C13 H13A 109.8 . . ?
N1 C13 H13A 109.8 . . ?
N2 C13 H13B 109.8 . . ?
N1 C13 H13B 109.8 . . ?
H13A C13 H13B 108.2 . . ?
N2 C14 H14A 109.5 . . ?
N2 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
N2 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
H1A O1 H1B 109(2) . . ?
H2A O2 H2B 99(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
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C12 N1 C1 C10 -82.02(18) . . . . ?
C11 N1 C1 C10 40.97(19) . . . . ?
C13 N1 C1 C10 157.74(14) . . . . ?
C12 N1 C1 C2 94.71(16) . . . . ?
C11 N1 C1 C2 -142.31(13) . . . . ?
C13 N1 C1 C2 -25.53(17) . . . . ?
C10 C1 C2 C3 172.92(15) . . . . ?
N1 C1 C2 C3 -3.7(2) . . . . ?
C10 C1 C2 C7 -2.1(2) . . . . ?
N1 C1 C2 C7 -178.78(13) . . . . ?
C13 N2 C3 C4 -151.75(15) . . . . ?
C14 N2 C3 C4 9.1(3) . . . . ?
C13 N2 C3 C2 31.68(19) . . . . ?
C14 N2 C3 C2 -167.46(16) . . . . ?
C1 C2 C3 C4 -174.20(15) . . . . ?
C7 C2 C3 C4 0.8(2) . . . . ?
C1 C2 C3 N2 2.5(2) . . . . ?
C7 C2 C3 N2 177.50(14) . . . . ?
N2 C3 C4 C5 -179.73(16) . . . . ?
C2 C3 C4 C5 -3.3(2) . . . . ?
C3 C4 C5 C6 2.5(3) . . . . ?
C4 C5 C6 C7 1.0(3) . . . . ?
C5 C6 C7 C8 173.27(16) . . . . ?
C5 C6 C7 C2 -3.5(2) . . . . ?
C1 C2 C7 C8 1.0(2) . . . . ?
C3 C2 C7 C8 -174.29(14) . . . . ?
C1 C2 C7 C6 177.84(14) . . . . ?
C3 C2 C7 C6 2.6(2) . . . . ?
C6 C7 C8 C9 -175.97(15) . . . . ?
C2 C7 C8 C9 0.8(2) . . . . ?
C7 C8 C9 C10 -1.4(2) . . . . ?
C2 C1 C10 C9 1.5(2) . . . . ?
N1 C1 C10 C9 178.09(14) . . . . ?
C8 C9 C10 C1 0.3(2) . . . . ?
C3 N2 C13 N1 -62.76(17) . . . . ?
C14 N2 C13 N1 136.17(16) . . . . ?
C1 N1 C13 N2 57.32(16) . . . . ?
C12 N1 C13 N2 -62.78(16) . . . . ?
C11 N1 C13 N2 177.53(13) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_site_symmetry_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_publ_flag
O1 H1A Br1 1_555 0.78(2) 2.55(2) 3.319(2) 173(2) ?
O2 H2A Br1 1_655 0.84(2) 2.54(2) 3.361(2) 170(2) ?
O1 H1B O2 4_466 0.88(2) 1.85(2) 2.733(2) 176(2) ?
O2 H2B O1 1_555 0.69(3) 2.07(3) 2.756(3) 168(3) ?

_diffrn_measured_fraction_theta_max 0.994
_diffrn_reflns_theta_full        30.19
_diffrn_measured_fraction_theta_full 0.994
_refine_diff_density_max         0.471
_refine_diff_density_min         -0.243
_refine_diff_density_rms         0.054

_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: Pyridine/ethanol'
_chemical_properties_physical    Hygroscopic
_exptl_crystal_preparation       Luminescent
