# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2017

####################################################################### 
# 
# 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_shelx
_database_code_depnum_ccdc_archive 'CCDC 1539452'
_audit_update_record             
;
2017-03-21 deposited with the CCDC.
2017-05-30 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        
2-(4-nitropyrazol-1-yl)-6-(pyrazol-1-yl)pyridine
_chemical_name_common            NO2-bppy
_chemical_melting_point          440.15
_chemical_formula_moiety         'C11 H8 N6 O2'
_chemical_formula_sum            'C11 H8 N6 O2'
_chemical_formula_weight         256.23

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'

_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_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.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   6.0442(17)
_cell_length_b                   8.393(2)
_cell_length_c                   11.447(3)
_cell_angle_alpha                72.362(7)
_cell_angle_beta                 89.297(7)
_cell_angle_gamma                78.103(7)
_cell_volume                     540.7(3)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    2418
_cell_measurement_theta_min      3.0
_cell_measurement_theta_max      25.0

_exptl_crystal_description       prism
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.574
_exptl_crystal_F_000             264
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.620
_exptl_crystal_size_mid          0.420
_exptl_crystal_size_min          0.300
_exptl_absorpt_coefficient_mu    0.116
_shelx_estimated_absorpt_T_min   0.931
_shelx_estimated_absorpt_T_max   0.966
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.901
_exptl_absorpt_correction_T_max  1.00
_exptl_absorpt_process_details   
;
Abscor. T. Higashi (2001). The Rigaku Corporation, Tokyo, Japan.
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine focus sealed tube'
_diffrn_measurement_device_type  'Rigaku AFC-12 with Saturn 724+ CCD'
_diffrn_measurement_method       ω-scans
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            7034
_diffrn_reflns_av_unetI/netI     0.0174
_diffrn_reflns_av_R_equivalents  0.0191
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         3.450
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measured_fraction_theta_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_point_group_measured_fraction_full 0.992
_reflns_number_total             2419
_reflns_number_gt                2221
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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.
;




_computing_data_collection       'CrystalClear (Rigaku Inc., 2008)'
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2008)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2008)'

_computing_structure_solution    
;

Sir2004.  Burla M.C., Caliandro, R., Camalli M., Carrozzini, B., Cascarano G.L., 
De Caro, L., Giacovazzo C., Polidori G., Spagna R. 
;
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2015)'
_computing_molecular_graphics    'XP SHELXTL/PC, Siemens Analytical'
_computing_publication_material  'XP SHELXTL/PC, Siemens Analytical'






_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0457P)²+0.2349P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2419
_refine_ls_number_parameters     172
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0357
_refine_ls_R_factor_gt           0.0332
_refine_ls_wR_factor_ref         0.0919
_refine_ls_wR_factor_gt          0.0904
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_restrained_S_all      1.057
_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_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
C1 C 1.07317(18) 0.98655(14) 0.19211(10) 0.0137(2) Uani 1 1 d . . . . .
C2 C 1.26880(19) 1.01573(14) 0.23892(11) 0.0165(2) Uani 1 1 d . . . . .
H2 H 1.304558 1.125785 0.214645 0.020 Uiso 1 1 calc R U . . .
C3 C 1.40791(19) 0.87659(15) 0.32233(11) 0.0184(2) Uani 1 1 d . . . . .
H3 H 1.542515 0.890546 0.356400 0.022 Uiso 1 1 calc R U . . .
C4 C 1.35173(19) 0.71630(15) 0.35659(10) 0.0166(2) Uani 1 1 d . . . . .
H4 H 1.446131 0.618981 0.412519 0.020 Uiso 1 1 calc R U . . .
C5 C 1.15060(18) 0.70642(14) 0.30468(10) 0.0132(2) Uani 1 1 d . . . . .
C6 C 0.71923(19) 1.11441(14) 0.05874(10) 0.0166(2) Uani 1 1 d . . . . .
H6 H 0.650780 1.018037 0.077038 0.020 Uiso 1 1 calc R U . . .
C7 C 0.6317(2) 1.27511(15) -0.01889(11) 0.0198(2) Uani 1 1 d . . . . .
H7 H 0.490920 1.313424 -0.065101 0.024 Uiso 1 1 calc R U . . .
C8 C 0.7963(2) 1.37139(15) -0.01530(11) 0.0193(2) Uani 1 1 d . . . . .
H8 H 0.781532 1.488657 -0.060866 0.023 Uiso 1 1 calc R U . . .
C9 C 0.89105(18) 0.52279(14) 0.28470(10) 0.0140(2) Uani 1 1 d . . . . .
H9 H 0.787539 0.603141 0.222214 0.017 Uiso 1 1 calc R U . . .
C10 C 0.88494(18) 0.35476(14) 0.34349(10) 0.0146(2) Uani 1 1 d . . . . .
C11 C 1.07354(19) 0.28696(14) 0.42786(10) 0.0164(2) Uani 1 1 d . . . . .
H11 H 1.111573 0.172284 0.480435 0.020 Uiso 1 1 calc R U . . .
N1 N 0.97404(17) 1.27856(12) 0.05932(9) 0.0183(2) Uani 1 1 d . . . . .
N2 N 0.92412(16) 1.11996(12) 0.10465(9) 0.0145(2) Uani 1 1 d . . . . .
N3 N 1.01079(15) 0.83629(12) 0.22504(8) 0.0134(2) Uani 1 1 d . . . . .
N4 N 1.07587(15) 0.54890(12) 0.33494(8) 0.0135(2) Uani 1 1 d . . . . .
N5 N 1.19063(16) 0.40590(12) 0.42354(9) 0.0161(2) Uani 1 1 d . . . . .
N6 N 0.71511(16) 0.26917(12) 0.32187(9) 0.0160(2) Uani 1 1 d . . . . .
O1 O 0.55850(14) 0.35123(11) 0.24556(8) 0.0203(2) Uani 1 1 d . . . . .
O2 O 0.73516(16) 0.11662(11) 0.38190(8) 0.0250(2) Uani 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
C1 N3 1.3338(14) . ?
C1 C2 1.3999(15) . ?
C1 N2 1.4123(14) . ?
C2 C3 1.3861(16) . ?
C2 H2 0.9500 . ?
C3 C4 1.3944(16) . ?
C3 H3 0.9500 . ?
C4 C5 1.3882(15) . ?
C4 H4 0.9500 . ?
C5 N3 1.3304(14) . ?
C5 N4 1.4271(14) . ?
C6 N2 1.3662(15) . ?
C6 C7 1.3710(16) . ?
C6 H6 0.9500 . ?
C7 C8 1.4130(17) . ?
C7 H7 0.9500 . ?
C8 N1 1.3287(15) . ?
C8 H8 0.9500 . ?
C9 N4 1.3490(14) . ?
C9 C10 1.3743(15) . ?
C9 H9 0.9500 . ?
C10 C11 1.4080(15) . ?
C10 N6 1.4314(14) . ?
C11 N5 1.3268(15) . ?
C11 H11 0.9500 . ?
N1 N2 1.3694(13) . ?
N4 N5 1.3735(13) . ?
N6 O1 1.2330(13) . ?
N6 O2 1.2374(13) . ?

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
N3 C1 C2 124.32(10) . . ?
N3 C1 N2 114.86(10) . . ?
C2 C1 N2 120.82(10) . . ?
C3 C2 C1 116.91(10) . . ?
C3 C2 H2 121.5 . . ?
C1 C2 H2 121.5 . . ?
C2 C3 C4 120.49(10) . . ?
C2 C3 H3 119.8 . . ?
C4 C3 H3 119.8 . . ?
C5 C4 C3 116.49(10) . . ?
C5 C4 H4 121.8 . . ?
C3 C4 H4 121.8 . . ?
N3 C5 C4 125.26(10) . . ?
N3 C5 N4 113.77(9) . . ?
C4 C5 N4 120.97(10) . . ?
N2 C6 C7 106.59(10) . . ?
N2 C6 H6 126.7 . . ?
C7 C6 H6 126.7 . . ?
C6 C7 C8 105.08(10) . . ?
C6 C7 H7 127.5 . . ?
C8 C7 H7 127.5 . . ?
N1 C8 C7 112.02(10) . . ?
N1 C8 H8 124.0 . . ?
C7 C8 H8 124.0 . . ?
N4 C9 C10 105.06(9) . . ?
N4 C9 H9 127.5 . . ?
C10 C9 H9 127.5 . . ?
C9 C10 C11 106.93(10) . . ?
C9 C10 N6 125.39(10) . . ?
C11 C10 N6 127.68(10) . . ?
N5 C11 C10 110.39(10) . . ?
N5 C11 H11 124.8 . . ?
C10 C11 H11 124.8 . . ?
C8 N1 N2 104.20(9) . . ?
C6 N2 N1 112.12(9) . . ?
C6 N2 C1 127.30(10) . . ?
N1 N2 C1 120.54(9) . . ?
C5 N3 C1 116.49(10) . . ?
C9 N4 N5 113.10(9) . . ?
C9 N4 C5 125.79(9) . . ?
N5 N4 C5 121.11(9) . . ?
C11 N5 N4 104.51(9) . . ?
O1 N6 O2 124.16(10) . . ?
O1 N6 C10 118.42(10) . . ?
O2 N6 C10 117.42(10) . . ?

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
N3 C1 C2 C3 1.87(17) . . . . ?
N2 C1 C2 C3 -178.62(10) . . . . ?
C1 C2 C3 C4 -0.04(17) . . . . ?
C2 C3 C4 C5 -1.10(17) . . . . ?
C3 C4 C5 N3 0.64(17) . . . . ?
C3 C4 C5 N4 -179.11(10) . . . . ?
N2 C6 C7 C8 0.26(12) . . . . ?
C6 C7 C8 N1 -0.19(13) . . . . ?
N4 C9 C10 C11 -0.42(12) . . . . ?
N4 C9 C10 N6 178.96(10) . . . . ?
C9 C10 C11 N5 0.65(13) . . . . ?
N6 C10 C11 N5 -178.71(10) . . . . ?
C7 C8 N1 N2 0.03(12) . . . . ?
C7 C6 N2 N1 -0.26(13) . . . . ?
C7 C6 N2 C1 177.36(10) . . . . ?
C8 N1 N2 C6 0.14(12) . . . . ?
C8 N1 N2 C1 -177.66(9) . . . . ?
N3 C1 N2 C6 5.42(16) . . . . ?
C2 C1 N2 C6 -174.14(10) . . . . ?
N3 C1 N2 N1 -177.15(9) . . . . ?
C2 C1 N2 N1 3.29(15) . . . . ?
C4 C5 N3 C1 1.02(16) . . . . ?
N4 C5 N3 C1 -179.22(9) . . . . ?
C2 C1 N3 C5 -2.32(16) . . . . ?
N2 C1 N3 C5 178.14(9) . . . . ?
C10 C9 N4 N5 0.07(12) . . . . ?
C10 C9 N4 C5 -178.82(10) . . . . ?
N3 C5 N4 C9 4.37(15) . . . . ?
C4 C5 N4 C9 -175.86(10) . . . . ?
N3 C5 N4 N5 -174.44(9) . . . . ?
C4 C5 N4 N5 5.34(15) . . . . ?
C10 C11 N5 N4 -0.58(12) . . . . ?
C9 N4 N5 C11 0.32(12) . . . . ?
C5 N4 N5 C11 179.27(9) . . . . ?
C9 C10 N6 O1 -0.88(16) . . . . ?
C11 C10 N6 O1 178.37(10) . . . . ?
C9 C10 N6 O2 179.38(11) . . . . ?
C11 C10 N6 O2 -1.38(17) . . . . ?

_refine_diff_density_max         0.295
_refine_diff_density_min         -0.273
_refine_diff_density_rms         0.046


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: dichloromethane'
_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_shelx
_database_code_depnum_ccdc_archive 'CCDC 1539453'
_audit_update_record             
;
2017-03-21 deposited with the CCDC.
2017-05-30 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        
2-(4-aminopyrazol-1-yl)-6-(pyrazol-1-yl)pyridine
_chemical_name_common            NH2-bppy
_chemical_melting_point          '423.35 - 431.55'
_chemical_formula_moiety         'C12 H11 N5'
_chemical_formula_sum            'C12 H11 N5'
_chemical_formula_weight         225.26

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'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

_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.
;

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                   22.9809(16)
_cell_length_b                   3.7881(3)
_cell_length_c                   12.2183(9)
_cell_angle_alpha                90
_cell_angle_beta                 104.812(7)
_cell_angle_gamma                90
_cell_volume                     1028.31(14)
_cell_formula_units_Z            4
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    1704
_cell_measurement_theta_min      4.01
_cell_measurement_theta_max      75.2

_exptl_crystal_description       acicular
_exptl_crystal_colour            Yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.455
_exptl_crystal_F_000             472
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.180
_exptl_crystal_size_mid          0.060
_exptl_crystal_size_min          0.060
_exptl_absorpt_coefficient_mu    0.759
_shelx_estimated_absorpt_T_min   0.875
_shelx_estimated_absorpt_T_max   0.956
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.485
_exptl_absorpt_correction_T_max  1.00
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      173(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   'sealed microfocus tube'
_diffrn_measurement_device_type  'Agilent SuperNova with AtlasS2 CCD'
_diffrn_measurement_method       ω-scans
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            5061
_diffrn_reflns_av_unetI/netI     0.0531
_diffrn_reflns_av_R_equivalents  0.0500
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_k_min       -4
_diffrn_reflns_limit_k_max       3
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         3.979
_diffrn_reflns_theta_max         75.692
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.964
_diffrn_measured_fraction_theta_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_point_group_measured_fraction_full 0.993
_reflns_number_total             2060
_reflns_number_gt                1624
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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.
;



_computing_data_collection       
'CrysAlisPro V 1.171.37.31, Agilent Technologies'
_computing_cell_refinement       
'CrysAlisPro V 1.171.37.31, Agilent Technologies'
_computing_data_reduction        
'CrysAlisPro V 1.171.37.31, Agilent Technologies'

_computing_structure_solution    
;

SHELXT. Sheldrick, G. M. (2015). Acta Cryst. A71, 3-8. 
;
_computing_structure_refinement  'Shelxl-2014/7, Sheldrick, G. M.'
_computing_molecular_graphics    'XP SHELXTL/PC, Siemens Analytical'
_computing_publication_material  'Shelxl-2014/7, Sheldrick, G. M.'





_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1350P)²+0.1913P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2060
_refine_ls_number_parameters     162
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0803
_refine_ls_R_factor_gt           0.0670
_refine_ls_wR_factor_ref         0.2137
_refine_ls_wR_factor_gt          0.1865
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_restrained_S_all      1.050
_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_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
C1 C 0.68720(10) 0.5198(6) 0.33140(18) 0.0250(5) Uani 1 1 d . . . . .
C2 C 0.68254(10) 0.6797(6) 0.43145(19) 0.0290(5) Uani 1 1 d . . . . .
H2 H 0.644572 0.736473 0.444345 0.035 Uiso 1 1 calc R U . . .
C3 C 0.73596(11) 0.7520(6) 0.51130(19) 0.0299(6) Uani 1 1 d . . . . .
H3 H 0.734956 0.860252 0.580940 0.036 Uiso 1 1 calc R U . . .
C4 C 0.79043(10) 0.6685(6) 0.49056(19) 0.0289(5) Uani 1 1 d . . . . .
H4 H 0.827304 0.718957 0.544405 0.035 Uiso 1 1 calc R U . . .
C5 C 0.78948(10) 0.5066(6) 0.38739(18) 0.0243(5) Uani 1 1 d . . . . .
C6 C 0.63185(11) 0.2818(6) 0.1442(2) 0.0297(6) Uani 1 1 d . . . . .
H6 H 0.664950 0.212957 0.115769 0.036 Uiso 1 1 calc R U . . .
C7 C 0.57258(11) 0.2497(7) 0.0897(2) 0.0347(6) Uani 1 1 d . . . . .
H7 H 0.555534 0.158334 0.016043 0.042 Uiso 1 1 calc R U . . .
C8 C 0.54211(11) 0.3842(7) 0.1681(2) 0.0378(6) Uani 1 1 d . . . . .
H8 H 0.499525 0.394316 0.153938 0.045 Uiso 1 1 calc R U . . .
C9 C 0.85145(10) 0.2872(6) 0.26113(18) 0.0263(5) Uani 1 1 d . . . . .
H9 H 0.821408 0.264917 0.191783 0.032 Uiso 1 1 calc R U . . .
C10 C 0.91132(10) 0.2104(6) 0.27932(18) 0.0282(6) Uani 1 1 d . . . . .
C11 C 0.93605(10) 0.2816(7) 0.39525(19) 0.0325(6) Uani 1 1 d . . . . .
H11 H 0.977337 0.250142 0.432805 0.039 Uiso 1 1 calc R U . . .
N1 N 0.57957(9) 0.4941(6) 0.26319(18) 0.0344(5) Uani 1 1 d . . . . .
N2 N 0.63506(8) 0.4305(5) 0.24697(16) 0.0277(5) Uani 1 1 d . . . . .
N3 N 0.73906(8) 0.4342(5) 0.30808(15) 0.0251(5) Uani 1 1 d . . . . .
N4 N 0.84324(8) 0.4027(5) 0.36268(15) 0.0252(5) Uani 1 1 d . . . . .
N5 N 0.89514(8) 0.3970(6) 0.44569(16) 0.0335(5) Uani 1 1 d . . . . .
N6 N 0.94460(9) 0.1071(7) 0.20353(18) 0.0362(6) Uani 1 1 d . . . . .
H6A H 0.9716(18) -0.069(12) 0.224(4) 0.084(14) Uiso 1 1 d . . . . .
H6B H 0.9189(15) 0.083(10) 0.121(3) 0.067(11) 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
C1 N3 1.334(3) . ?
C1 C2 1.393(3) . ?
C1 N2 1.408(3) . ?
C2 C3 1.386(3) . ?
C2 H2 0.9500 . ?
C3 C4 1.376(3) . ?
C3 H3 0.9500 . ?
C4 C5 1.397(3) . ?
C4 H4 0.9500 . ?
C5 N3 1.335(3) . ?
C5 N4 1.401(3) . ?
C6 C7 1.360(3) . ?
C6 N2 1.361(3) . ?
C6 H6 0.9500 . ?
C7 C8 1.418(4) . ?
C7 H7 0.9500 . ?
C8 N1 1.324(3) . ?
C8 H8 0.9500 . ?
C9 C10 1.368(3) . ?
C9 N4 1.373(3) . ?
C9 H9 0.9500 . ?
C10 N6 1.399(3) . ?
C10 C11 1.411(3) . ?
C11 N5 1.323(3) . ?
C11 H11 0.9500 . ?
N1 N2 1.361(3) . ?
N4 N5 1.354(2) . ?
N6 H6A 0.90(4) . ?
N6 H6B 1.04(4) . ?

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
N3 C1 C2 124.5(2) . . ?
N3 C1 N2 115.1(2) . . ?
C2 C1 N2 120.4(2) . . ?
C3 C2 C1 116.8(2) . . ?
C3 C2 H2 121.6 . . ?
C1 C2 H2 121.6 . . ?
C4 C3 C2 120.6(2) . . ?
C4 C3 H3 119.7 . . ?
C2 C3 H3 119.7 . . ?
C3 C4 C5 117.5(2) . . ?
C3 C4 H4 121.2 . . ?
C5 C4 H4 121.2 . . ?
N3 C5 C4 123.7(2) . . ?
N3 C5 N4 115.81(19) . . ?
C4 C5 N4 120.44(19) . . ?
C7 C6 N2 107.5(2) . . ?
C7 C6 H6 126.3 . . ?
N2 C6 H6 126.3 . . ?
C6 C7 C8 104.0(2) . . ?
C6 C7 H7 128.0 . . ?
C8 C7 H7 128.0 . . ?
N1 C8 C7 112.5(2) . . ?
N1 C8 H8 123.7 . . ?
C7 C8 H8 123.7 . . ?
C10 C9 N4 106.60(19) . . ?
C10 C9 H9 126.7 . . ?
N4 C9 H9 126.7 . . ?
C9 C10 N6 130.5(2) . . ?
C9 C10 C11 104.6(2) . . ?
N6 C10 C11 124.7(2) . . ?
N5 C11 C10 112.3(2) . . ?
N5 C11 H11 123.9 . . ?
C10 C11 H11 123.9 . . ?
C8 N1 N2 103.9(2) . . ?
C6 N2 N1 112.07(19) . . ?
C6 N2 C1 127.6(2) . . ?
N1 N2 C1 120.3(2) . . ?
C1 N3 C5 116.9(2) . . ?
N5 N4 C9 111.94(18) . . ?
N5 N4 C5 119.97(18) . . ?
C9 N4 C5 128.06(18) . . ?
C11 N5 N4 104.53(18) . . ?
C10 N6 H6A 119(3) . . ?
C10 N6 H6B 114(2) . . ?
H6A N6 H6B 113(3) . . ?

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
N3 C1 C2 C3 -0.1(4) . . . . ?
N2 C1 C2 C3 178.6(2) . . . . ?
C1 C2 C3 C4 0.2(4) . . . . ?
C2 C3 C4 C5 -0.6(4) . . . . ?
C3 C4 C5 N3 1.0(3) . . . . ?
C3 C4 C5 N4 -177.6(2) . . . . ?
N2 C6 C7 C8 -0.8(3) . . . . ?
C6 C7 C8 N1 0.6(3) . . . . ?
N4 C9 C10 N6 -175.0(2) . . . . ?
N4 C9 C10 C11 1.0(3) . . . . ?
C9 C10 C11 N5 -0.6(3) . . . . ?
N6 C10 C11 N5 175.7(2) . . . . ?
C7 C8 N1 N2 -0.1(3) . . . . ?
C7 C6 N2 N1 0.9(3) . . . . ?
C7 C6 N2 C1 -178.7(2) . . . . ?
C8 N1 N2 C6 -0.5(3) . . . . ?
C8 N1 N2 C1 179.1(2) . . . . ?
N3 C1 N2 C6 -2.8(3) . . . . ?
C2 C1 N2 C6 178.4(2) . . . . ?
N3 C1 N2 N1 177.72(18) . . . . ?
C2 C1 N2 N1 -1.2(3) . . . . ?
C2 C1 N3 C5 0.5(3) . . . . ?
N2 C1 N3 C5 -178.34(17) . . . . ?
C4 C5 N3 C1 -0.9(3) . . . . ?
N4 C5 N3 C1 177.76(18) . . . . ?
C10 C9 N4 N5 -1.1(3) . . . . ?
C10 C9 N4 C5 -178.8(2) . . . . ?
N3 C5 N4 N5 -166.33(19) . . . . ?
C4 C5 N4 N5 12.4(3) . . . . ?
N3 C5 N4 C9 11.2(3) . . . . ?
C4 C5 N4 C9 -170.1(2) . . . . ?
C10 C11 N5 N4 -0.1(3) . . . . ?
C9 N4 N5 C11 0.8(3) . . . . ?
C5 N4 N5 C11 178.7(2) . . . . ?

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
N6 H6A N6 0.90(4) 2.27(4) 3.144(3) 165(4) 2_745
N6 H6B N5 1.04(4) 2.07(4) 3.064(3) 160(3) 4_565

_refine_diff_density_max         0.340
_refine_diff_density_min         -0.358
_refine_diff_density_rms         0.079


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: dichloromethane'
_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_shelx
_database_code_depnum_ccdc_archive 'CCDC 1539454'
_audit_update_record             
;
2017-03-21 deposited with the CCDC.
2017-05-30 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT431_shelx               
;
PROBLEM: Short Inter HL..A  Contact Br1    ..  O2      ..       3.00 Ang.  
RESPONSE: A non-bonded contact of 3.00 Ang between a Br ion and an oxygen 
atom on a nitro group is not unusual.  There are numerous examples of 
contacts this close and closer in the Cambridge Crystallographic 
Database.
;
# end Validation Reply Form

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        2-bromo-6-(4-pyrazol-1-yl)pyridine
_chemical_name_common            NO2-pz-py-Br
_chemical_melting_point          '409.25 - 410.65'
_chemical_formula_moiety         'C8 H5 Br N4 O2'
_chemical_formula_sum            'C8 H5 Br N4 O2'
_chemical_formula_weight         269.07

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'
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 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_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.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   5.1820(14)
_cell_length_b                   8.556(3)
_cell_length_c                   11.285(3)
_cell_angle_alpha                77.698(7)
_cell_angle_beta                 81.398(7)
_cell_angle_gamma                75.758(7)
_cell_volume                     471.3(2)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    6902
_cell_measurement_theta_min      3.00
_cell_measurement_theta_max      27.5

_exptl_crystal_description       bladed
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.896
_exptl_crystal_F_000             264
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.390
_exptl_crystal_size_mid          0.180
_exptl_crystal_size_min          0.046
_exptl_absorpt_coefficient_mu    4.344
_shelx_estimated_absorpt_T_min   0.282
_shelx_estimated_absorpt_T_max   0.825
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.576
_exptl_absorpt_correction_T_max  1.00
_exptl_absorpt_process_details   
;
Abscor. T. Higashi (2001). The Rigaku Corporation, Tokyo, Japan.
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'sealed fine focus tube'
_diffrn_measurement_device_type  'Rigaku AFC-12 with Saturn 724+ CCD'
_diffrn_measurement_method       ω-scans
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            6902
_diffrn_reflns_av_unetI/netI     0.0368
_diffrn_reflns_av_R_equivalents  0.0408
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         3.377
_diffrn_reflns_theta_max         27.367
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measured_fraction_theta_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_point_group_measured_fraction_full 0.996
_reflns_number_total             2125
_reflns_number_gt                2010
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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.
;




_computing_data_collection       'CrystalClear (Rigaku Inc., 2008)'
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2008)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2008)'

_computing_structure_solution    
;

Sir2004.  Burla M.C., Caliandro, R., Camalli M., Carrozzini, B., Cascarano G.L., 
De Caro, L., Giacovazzo C., Polidori G., Spagna R. 
;
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2015)'
_computing_molecular_graphics    'XP SHELXTL/PC, Siemens Analytical'
_computing_publication_material  'XP SHELXTL/PC, Siemens Analytical'





_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0328P)²+0.2750P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    refall
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2125
_refine_ls_number_parameters     156
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0288
_refine_ls_R_factor_gt           0.0269
_refine_ls_wR_factor_ref         0.0680
_refine_ls_wR_factor_gt          0.0666
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_restrained_S_all      1.096
_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_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
C1 C 0.4769(4) 0.7291(3) 0.36887(19) 0.0158(4) Uani 1 1 d . . . . .
C2 C 0.6689(4) 0.8200(3) 0.3185(2) 0.0182(4) Uani 1 1 d . . . . .
C3 C 0.8305(4) 0.7763(3) 0.2159(2) 0.0193(4) Uani 1 1 d . . . . .
C4 C 0.7966(4) 0.6464(3) 0.1674(2) 0.0165(4) Uani 1 1 d . . . . .
C5 C 0.5981(4) 0.5664(2) 0.22787(19) 0.0138(4) Uani 1 1 d . . . . .
C6 C 0.3538(4) 0.3485(3) 0.23385(19) 0.0142(4) Uani 1 1 d . . . . .
C7 C 0.3819(4) 0.2339(2) 0.16113(19) 0.0142(4) Uani 1 1 d . . . . .
C8 C 0.5993(4) 0.2543(3) 0.0720(2) 0.0166(4) Uani 1 1 d . . . . .
Br1 Br 0.24568(4) 0.78655(2) 0.50822(2) 0.01953(9) Uani 1 1 d . . . . .
N1 N 0.4360(3) 0.6056(2) 0.32615(16) 0.0155(3) Uani 1 1 d . . . . .
N2 N 0.5472(3) 0.4314(2) 0.18610(16) 0.0141(3) Uani 1 1 d . . . . .
N3 N 0.7025(4) 0.3744(2) 0.08742(16) 0.0166(4) Uani 1 1 d . . . . .
N4 N 0.2168(3) 0.1181(2) 0.17358(16) 0.0154(3) Uani 1 1 d . . . . .
O1 O 0.2461(3) 0.0395(2) 0.09099(15) 0.0220(3) Uani 1 1 d . . . . .
O2 O 0.0544(3) 0.1039(2) 0.26464(14) 0.0205(3) Uani 1 1 d . . . . .
H2 H 0.692(5) 0.906(3) 0.351(2) 0.019(6) Uiso 1 1 d . . . . .
H3 H 0.959(6) 0.836(4) 0.180(3) 0.026(7) Uiso 1 1 d . . . . .
H4 H 0.892(5) 0.608(4) 0.099(3) 0.024(7) Uiso 1 1 d . . . . .
H6 H 0.237(5) 0.377(3) 0.299(3) 0.017(6) Uiso 1 1 d . . . . .
H8 H 0.678(6) 0.195(4) 0.007(3) 0.030(8) 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
C1 N1 1.324(3) . ?
C1 C2 1.393(3) . ?
C1 Br1 1.904(2) . ?
C2 C3 1.386(3) . ?
C2 H2 0.93(3) . ?
C3 C4 1.397(3) . ?
C3 H3 0.93(3) . ?
C4 C5 1.389(3) . ?
C4 H4 0.93(3) . ?
C5 N1 1.337(3) . ?
C5 N2 1.430(3) . ?
C6 N2 1.350(3) . ?
C6 C7 1.376(3) . ?
C6 H6 0.91(3) . ?
C7 C8 1.412(3) . ?
C7 N4 1.434(3) . ?
C8 N3 1.321(3) . ?
C8 H8 0.97(3) . ?
N2 N3 1.377(2) . ?
N4 O2 1.232(2) . ?
N4 O1 1.232(2) . ?

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
N1 C1 C2 125.2(2) . . ?
N1 C1 Br1 116.03(16) . . ?
C2 C1 Br1 118.77(16) . . ?
C3 C2 C1 117.1(2) . . ?
C3 C2 H2 120.0(17) . . ?
C1 C2 H2 122.9(17) . . ?
C2 C3 C4 120.1(2) . . ?
C2 C3 H3 118.7(18) . . ?
C4 C3 H3 121.2(19) . . ?
C5 C4 C3 116.4(2) . . ?
C5 C4 H4 116.5(17) . . ?
C3 C4 H4 127.1(17) . . ?
N1 C5 C4 125.50(19) . . ?
N1 C5 N2 113.51(18) . . ?
C4 C5 N2 120.98(18) . . ?
N2 C6 C7 104.66(18) . . ?
N2 C6 H6 121.1(18) . . ?
C7 C6 H6 134.2(18) . . ?
C6 C7 C8 107.12(18) . . ?
C6 C7 N4 125.84(19) . . ?
C8 C7 N4 127.04(19) . . ?
N3 C8 C7 110.38(19) . . ?
N3 C8 H8 119.1(19) . . ?
C7 C8 H8 130.5(19) . . ?
C1 N1 C5 115.75(18) . . ?
C6 N2 N3 113.33(17) . . ?
C6 N2 C5 126.49(18) . . ?
N3 N2 C5 120.17(17) . . ?
C8 N3 N2 104.49(17) . . ?
O2 N4 O1 124.15(18) . . ?
O2 N4 C7 118.60(17) . . ?
O1 N4 C7 117.25(18) . . ?

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
N1 C1 C2 C3 -0.4(3) . . . . ?
Br1 C1 C2 C3 -178.97(16) . . . . ?
C1 C2 C3 C4 0.2(3) . . . . ?
C2 C3 C4 C5 -0.6(3) . . . . ?
C3 C4 C5 N1 1.3(3) . . . . ?
C3 C4 C5 N2 -179.78(19) . . . . ?
N2 C6 C7 C8 0.7(2) . . . . ?
N2 C6 C7 N4 -178.44(19) . . . . ?
C6 C7 C8 N3 0.0(3) . . . . ?
N4 C7 C8 N3 179.1(2) . . . . ?
C2 C1 N1 C5 1.1(3) . . . . ?
Br1 C1 N1 C5 179.65(14) . . . . ?
C4 C5 N1 C1 -1.6(3) . . . . ?
N2 C5 N1 C1 179.48(18) . . . . ?
C7 C6 N2 N3 -1.1(2) . . . . ?
C7 C6 N2 C5 178.57(19) . . . . ?
N1 C5 N2 C6 1.9(3) . . . . ?
C4 C5 N2 C6 -177.1(2) . . . . ?
N1 C5 N2 N3 -178.41(17) . . . . ?
C4 C5 N2 N3 2.6(3) . . . . ?
C7 C8 N3 N2 -0.6(2) . . . . ?
C6 N2 N3 C8 1.1(2) . . . . ?
C5 N2 N3 C8 -178.60(19) . . . . ?
C6 C7 N4 O2 -9.2(3) . . . . ?
C8 C7 N4 O2 171.9(2) . . . . ?
C6 C7 N4 O1 170.3(2) . . . . ?
C8 C7 N4 O1 -8.6(3) . . . . ?

_refine_diff_density_max         0.662
_refine_diff_density_min         -0.446
_refine_diff_density_rms         0.091


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: dichloromethane'
