# Electronic Supplementary Material (ESI) for Green Chemistry.
# 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_a
_database_code_depnum_ccdc_archive 'CCDC 1506227'
_audit_update_record             
;
2016-09-25 deposited with the CCDC.
2017-01-18 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
3-(4-phenoxyphenyl)-6-(p-tolyl)-1,2,4,5-tetrazine
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C24 H22 N4 O'
_chemical_formula_weight         382.46

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'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   P21/c

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                   44.778(5)
_cell_length_b                   5.5195(6)
_cell_length_c                   8.2452(9)
_cell_angle_alpha                90.00
_cell_angle_beta                 93.029(9)
_cell_angle_gamma                90.00
_cell_volume                     2035.0(4)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    3503
_cell_measurement_theta_min      3.5327
_cell_measurement_theta_max      29.3396

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.20
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.248
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             808
_exptl_absorpt_coefficient_mu    0.079
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9768
_exptl_absorpt_correction_T_max  0.9844
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      293(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'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            18910
_diffrn_reflns_av_R_equivalents  0.1244
_diffrn_reflns_av_sigmaI/netI    0.0707
_diffrn_reflns_limit_h_min       -54
_diffrn_reflns_limit_h_max       54
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_theta_min         3.65
_diffrn_reflns_theta_max         25.50
_reflns_number_total             3760
_reflns_number_gt                2626
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_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)+(0.1069P)²+1.9527P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.007(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         3760
_refine_ls_number_parameters     264
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1254
_refine_ls_R_factor_gt           0.0942
_refine_ls_wR_factor_ref         0.2688
_refine_ls_wR_factor_gt          0.2486
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_restrained_S_all      1.085
_refine_ls_shift/su_max          0.000
_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
O1 O 0.13553(5) 0.4684(5) 0.0791(3) 0.0586(7) Uani 1 1 d . . .
N1 N 0.29834(7) 0.2974(6) 0.0423(4) 0.0647(9) Uani 1 1 d . . .
N2 N 0.27615(7) 0.3500(6) 0.1357(4) 0.0652(9) Uani 1 1 d . . .
N3 N 0.32449(7) 0.6430(6) 0.1391(4) 0.0665(9) Uani 1 1 d . . .
N4 N 0.30218(7) 0.6933(6) 0.2341(4) 0.0629(9) Uani 1 1 d . . .
C1 C 0.46850(12) 0.5945(17) 0.1750(8) 0.145(3) Uani 1 1 d . . .
H1A H 0.4817 0.5646 0.0892 0.217 Uiso 1 1 calc R . .
H1B H 0.4739 0.4918 0.2658 0.217 Uiso 1 1 calc R . .
H1C H 0.4701 0.7611 0.2079 0.217 Uiso 1 1 calc R . .
C2 C 0.43635(10) 0.5407(11) 0.1148(6) 0.0810(14) Uani 1 1 d . . .
C3 C 0.42177(11) 0.3361(10) 0.1630(5) 0.0810(14) Uani 1 1 d . . .
H3 H 0.4316 0.2286 0.2346 0.097 Uiso 1 1 calc R . .
C4 C 0.39255(10) 0.2873(8) 0.1062(5) 0.0658(11) Uani 1 1 d . . .
H4 H 0.3831 0.1476 0.1400 0.079 Uiso 1 1 calc R . .
C5 C 0.37762(8) 0.4437(7) 0.0007(4) 0.0546(9) Uani 1 1 d . . .
C6 C 0.39211(10) 0.6490(8) -0.0465(5) 0.0668(11) Uani 1 1 d . . .
H6 H 0.3824 0.7568 -0.1180 0.080 Uiso 1 1 calc R . .
C7 C 0.42092(12) 0.6967(10) 0.0111(6) 0.0840(14) Uani 1 1 d . . .
H7 H 0.4302 0.8383 -0.0210 0.101 Uiso 1 1 calc R . .
C8 C 0.34593(9) 0.3857(9) -0.0649(5) 0.0707(12) Uani 1 1 d . . .
H8A H 0.3421 0.4742 -0.1654 0.085 Uiso 1 1 calc R . .
H8B H 0.3448 0.2142 -0.0904 0.085 Uiso 1 1 calc R . .
C9 C 0.32190(8) 0.4446(7) 0.0469(4) 0.0550(9) Uani 1 1 d . . .
C10 C 0.27891(7) 0.5465(7) 0.2293(4) 0.0505(9) Uani 1 1 d . . .
C11 C 0.25432(8) 0.6023(8) 0.3413(4) 0.0570(10) Uani 1 1 d . . .
H11A H 0.2563 0.7696 0.3761 0.068 Uiso 1 1 calc R . .
H11B H 0.2570 0.5011 0.4371 0.068 Uiso 1 1 calc R . .
C12 C 0.22302(7) 0.5642(7) 0.2678(4) 0.0488(9) Uani 1 1 d . . .
C13 C 0.20614(8) 0.3652(7) 0.3047(4) 0.0552(9) Uani 1 1 d . . .
H13 H 0.2144 0.2471 0.3739 0.066 Uiso 1 1 calc R . .
C14 C 0.17713(8) 0.3371(6) 0.2409(5) 0.0552(9) Uani 1 1 d . . .
H14 H 0.1660 0.2021 0.2683 0.066 Uiso 1 1 calc R . .
C15 C 0.16465(7) 0.5105(6) 0.1361(4) 0.0458(8) Uani 1 1 d . . .
C16 C 0.18124(8) 0.7106(7) 0.0979(4) 0.0510(9) Uani 1 1 d . . .
H16 H 0.1731 0.8279 0.0277 0.061 Uiso 1 1 calc R . .
C17 C 0.21013(7) 0.7361(7) 0.1646(4) 0.0514(9) Uani 1 1 d . . .
H17 H 0.2211 0.8727 0.1392 0.062 Uiso 1 1 calc R . .
C18 C 0.12198(8) 0.6475(7) -0.0264(5) 0.0570(10) Uani 1 1 d . . .
H18A H 0.1334 0.6654 -0.1223 0.068 Uiso 1 1 calc R . .
H18B H 0.1217 0.8026 0.0289 0.068 Uiso 1 1 calc R . .
C19 C 0.09063(8) 0.5691(7) -0.0744(4) 0.0497(8) Uani 1 1 d . . .
C20 C 0.08505(10) 0.3640(7) -0.1657(5) 0.0659(11) Uani 1 1 d . . .
H20 H 0.1009 0.2681 -0.1955 0.079 Uiso 1 1 calc R . .
C21 C 0.05614(12) 0.2986(9) -0.2137(6) 0.0769(13) Uani 1 1 d . . .
H21 H 0.0526 0.1600 -0.2760 0.092 Uiso 1 1 calc R . .
C22 C 0.03258(10) 0.4391(10) -0.1692(6) 0.0768(13) Uani 1 1 d . . .
H22 H 0.0131 0.3958 -0.2018 0.092 Uiso 1 1 calc R . .
C23 C 0.03769(9) 0.6427(9) -0.0769(6) 0.0721(12) Uani 1 1 d . . .
H23 H 0.0218 0.7370 -0.0458 0.086 Uiso 1 1 calc R . .
C24 C 0.06685(9) 0.7069(8) -0.0302(5) 0.0604(10) Uani 1 1 d . . .
H24 H 0.0703 0.8456 0.0320 0.072 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
O1 C15 1.382(4) . ?
O1 C18 1.431(4) . ?
N1 N2 1.321(4) . ?
N1 C9 1.330(5) . ?
N2 C10 1.333(5) . ?
N3 N4 1.331(4) . ?
N3 C9 1.335(5) . ?
N4 C10 1.319(5) . ?
C1 C2 1.527(7) . ?
C1 H1A 0.9600 . ?
C1 H1B 0.9600 . ?
C1 H1C 0.9600 . ?
C2 C3 1.373(7) . ?
C2 C7 1.374(7) . ?
C3 C4 1.392(6) . ?
C3 H3 0.9300 . ?
C4 C5 1.374(5) . ?
C4 H4 0.9300 . ?
C5 C6 1.372(6) . ?
C5 C8 1.526(5) . ?
C6 C7 1.376(7) . ?
C6 H6 0.9300 . ?
C7 H7 0.9300 . ?
C8 C9 1.489(5) . ?
C8 H8A 0.9700 . ?
C8 H8B 0.9700 . ?
C10 C11 1.506(5) . ?
C11 C12 1.512(5) . ?
C11 H11A 0.9700 . ?
C11 H11B 0.9700 . ?
C12 C13 1.377(5) . ?
C12 C17 1.380(5) . ?
C13 C14 1.384(5) . ?
C13 H13 0.9300 . ?
C14 C15 1.387(5) . ?
C14 H14 0.9300 . ?
C15 C16 1.377(5) . ?
C16 C17 1.386(5) . ?
C16 H16 0.9300 . ?
C17 H17 0.9300 . ?
C18 C19 1.502(5) . ?
C18 H18A 0.9700 . ?
C18 H18B 0.9700 . ?
C19 C24 1.374(5) . ?
C19 C20 1.375(5) . ?
C20 C21 1.381(6) . ?
C20 H20 0.9300 . ?
C21 C22 1.375(7) . ?
C21 H21 0.9300 . ?
C22 C23 1.370(7) . ?
C22 H22 0.9300 . ?
C23 C24 1.388(5) . ?
C23 H23 0.9300 . ?
C24 H24 0.9300 . ?

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
C15 O1 C18 116.9(3) . . ?
N2 N1 C9 118.0(3) . . ?
N1 N2 C10 117.8(3) . . ?
N4 N3 C9 117.5(3) . . ?
C10 N4 N3 118.1(3) . . ?
C2 C1 H1A 109.5 . . ?
C2 C1 H1B 109.5 . . ?
H1A C1 H1B 109.5 . . ?
C2 C1 H1C 109.5 . . ?
H1A C1 H1C 109.5 . . ?
H1B C1 H1C 109.5 . . ?
C3 C2 C7 117.7(4) . . ?
C3 C2 C1 121.4(6) . . ?
C7 C2 C1 121.0(6) . . ?
C2 C3 C4 121.0(4) . . ?
C2 C3 H3 119.5 . . ?
C4 C3 H3 119.5 . . ?
C5 C4 C3 120.6(4) . . ?
C5 C4 H4 119.7 . . ?
C3 C4 H4 119.7 . . ?
C6 C5 C4 118.5(4) . . ?
C6 C5 C8 121.2(4) . . ?
C4 C5 C8 120.3(4) . . ?
C5 C6 C7 120.6(4) . . ?
C5 C6 H6 119.7 . . ?
C7 C6 H6 119.7 . . ?
C2 C7 C6 121.8(5) . . ?
C2 C7 H7 119.1 . . ?
C6 C7 H7 119.1 . . ?
C9 C8 C5 115.1(3) . . ?
C9 C8 H8A 108.5 . . ?
C5 C8 H8A 108.5 . . ?
C9 C8 H8B 108.5 . . ?
C5 C8 H8B 108.5 . . ?
H8A C8 H8B 107.5 . . ?
N1 C9 N3 124.2(3) . . ?
N1 C9 C8 116.5(3) . . ?
N3 C9 C8 119.2(4) . . ?
N4 C10 N2 124.5(3) . . ?
N4 C10 C11 117.3(3) . . ?
N2 C10 C11 118.2(3) . . ?
C10 C11 C12 114.7(3) . . ?
C10 C11 H11A 108.6 . . ?
C12 C11 H11A 108.6 . . ?
C10 C11 H11B 108.6 . . ?
C12 C11 H11B 108.6 . . ?
H11A C11 H11B 107.6 . . ?
C13 C12 C17 117.9(3) . . ?
C13 C12 C11 122.0(3) . . ?
C17 C12 C11 120.0(3) . . ?
C12 C13 C14 121.4(3) . . ?
C12 C13 H13 119.3 . . ?
C14 C13 H13 119.3 . . ?
C13 C14 C15 119.9(3) . . ?
C13 C14 H14 120.1 . . ?
C15 C14 H14 120.1 . . ?
C16 C15 O1 124.6(3) . . ?
C16 C15 C14 119.5(3) . . ?
O1 C15 C14 115.9(3) . . ?
C15 C16 C17 119.6(3) . . ?
C15 C16 H16 120.2 . . ?
C17 C16 H16 120.2 . . ?
C12 C17 C16 121.7(3) . . ?
C12 C17 H17 119.1 . . ?
C16 C17 H17 119.1 . . ?
O1 C18 C19 108.8(3) . . ?
O1 C18 H18A 109.9 . . ?
C19 C18 H18A 109.9 . . ?
O1 C18 H18B 109.9 . . ?
C19 C18 H18B 109.9 . . ?
H18A C18 H18B 108.3 . . ?
C24 C19 C20 118.7(4) . . ?
C24 C19 C18 119.8(3) . . ?
C20 C19 C18 121.5(3) . . ?
C19 C20 C21 120.8(4) . . ?
C19 C20 H20 119.6 . . ?
C21 C20 H20 119.6 . . ?
C22 C21 C20 119.8(4) . . ?
C22 C21 H21 120.1 . . ?
C20 C21 H21 120.1 . . ?
C23 C22 C21 120.2(4) . . ?
C23 C22 H22 119.9 . . ?
C21 C22 H22 119.9 . . ?
C22 C23 C24 119.4(4) . . ?
C22 C23 H23 120.3 . . ?
C24 C23 H23 120.3 . . ?
C19 C24 C23 121.1(4) . . ?
C19 C24 H24 119.5 . . ?
C23 C24 H24 119.5 . . ?

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
C9 N1 N2 C10 -0.4(5) . . . . ?
C9 N3 N4 C10 -0.9(5) . . . . ?
C7 C2 C3 C4 1.1(7) . . . . ?
C1 C2 C3 C4 -179.4(4) . . . . ?
C2 C3 C4 C5 -0.2(6) . . . . ?
C3 C4 C5 C6 -0.3(6) . . . . ?
C3 C4 C5 C8 178.3(4) . . . . ?
C4 C5 C6 C7 -0.1(6) . . . . ?
C8 C5 C6 C7 -178.7(4) . . . . ?
C3 C2 C7 C6 -1.5(7) . . . . ?
C1 C2 C7 C6 178.9(4) . . . . ?
C5 C6 C7 C2 1.1(7) . . . . ?
C6 C5 C8 C9 -100.7(5) . . . . ?
C4 C5 C8 C9 80.8(5) . . . . ?
N2 N1 C9 N3 -0.4(6) . . . . ?
N2 N1 C9 C8 -177.5(3) . . . . ?
N4 N3 C9 N1 1.1(6) . . . . ?
N4 N3 C9 C8 178.2(4) . . . . ?
C5 C8 C9 N1 -145.8(4) . . . . ?
C5 C8 C9 N3 36.9(6) . . . . ?
N3 N4 C10 N2 0.1(6) . . . . ?
N3 N4 C10 C11 178.2(3) . . . . ?
N1 N2 C10 N4 0.6(6) . . . . ?
N1 N2 C10 C11 -177.5(3) . . . . ?
N4 C10 C11 C12 140.2(4) . . . . ?
N2 C10 C11 C12 -41.6(5) . . . . ?
C10 C11 C12 C13 103.4(4) . . . . ?
C10 C11 C12 C17 -78.9(4) . . . . ?
C17 C12 C13 C14 -0.1(5) . . . . ?
C11 C12 C13 C14 177.7(3) . . . . ?
C12 C13 C14 C15 0.7(6) . . . . ?
C18 O1 C15 C16 -0.2(5) . . . . ?
C18 O1 C15 C14 178.7(3) . . . . ?
C13 C14 C15 C16 -0.7(5) . . . . ?
C13 C14 C15 O1 -179.6(3) . . . . ?
O1 C15 C16 C17 178.8(3) . . . . ?
C14 C15 C16 C17 0.0(5) . . . . ?
C13 C12 C17 C16 -0.7(5) . . . . ?
C11 C12 C17 C16 -178.4(3) . . . . ?
C15 C16 C17 C12 0.7(5) . . . . ?
C15 O1 C18 C19 -179.9(3) . . . . ?
O1 C18 C19 C24 116.9(4) . . . . ?
O1 C18 C19 C20 -64.7(4) . . . . ?
C24 C19 C20 C21 0.7(6) . . . . ?
C18 C19 C20 C21 -177.8(4) . . . . ?
C19 C20 C21 C22 -0.4(7) . . . . ?
C20 C21 C22 C23 -0.3(7) . . . . ?
C21 C22 C23 C24 0.6(7) . . . . ?
C20 C19 C24 C23 -0.3(6) . . . . ?
C18 C19 C24 C23 178.1(4) . . . . ?
C22 C23 C24 C19 -0.3(6) . . . . ?

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        25.50
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         0.211
_refine_diff_density_min         -0.252
_refine_diff_density_rms         0.054
####################################################################### 
# 
# 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_fz1
_database_code_depnum_ccdc_archive 'CCDC 1506226'
_audit_update_record             
;
2016-09-25 deposited with the CCDC.
2017-01-18 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        3,6-bis(4-bromophenyl)-1,2,4,5-tetrazine
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         (C2N4)(C7H6Br)2
_chemical_formula_sum            'C16 H12 Br2 N4'
_chemical_formula_weight         420.12

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'
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   P2(1)/n
_symmetry_space_group_name_Hall  -P2yn

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

_cell_length_a                   4.8044(3)
_cell_length_b                   34.603(3)
_cell_length_c                   9.8785(7)
_cell_angle_alpha                90.00
_cell_angle_beta                 100.443(7)
_cell_angle_gamma                90.00
_cell_volume                     1615.09(19)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    3503
_cell_measurement_theta_min      3.5327
_cell_measurement_theta_max      29.3396

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.15
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.728
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             824
_exptl_absorpt_coefficient_mu    5.020
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.3787
_exptl_absorpt_correction_T_max  0.5197
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      293(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'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            12743
_diffrn_reflns_av_R_equivalents  0.0520
_diffrn_reflns_av_sigmaI/netI    0.0589
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         3.53
_diffrn_reflns_theta_max         25.50
_reflns_number_total             2996
_reflns_number_gt                2010
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_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)+(0.1294P)²+2.5938P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.0040(14)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         2996
_refine_ls_number_parameters     200
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1105
_refine_ls_R_factor_gt           0.0744
_refine_ls_wR_factor_ref         0.2436
_refine_ls_wR_factor_gt          0.2029
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_restrained_S_all      1.040
_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 1.43698(18) 1.02016(3) 0.72418(10) 0.0760(4) Uani 1 1 d . . .
Br2 Br 0.5817(2) 0.60258(3) 0.79538(9) 0.0817(5) Uani 1 1 d . . .
C1 C 1.1997(15) 0.9777(2) 0.7501(8) 0.0553(19) Uani 1 1 d . . .
C8 C 0.7853(14) 0.8490(3) 0.8662(7) 0.0549(19) Uani 1 1 d . . .
C7 C 0.6350(17) 0.8854(3) 0.8100(10) 0.074(3) Uani 1 1 d . . .
H7A H 0.5152 0.8941 0.8732 0.089 Uiso 1 1 calc R . .
H7B H 0.5136 0.8795 0.7228 0.089 Uiso 1 1 calc R . .
C9 C 1.0540(14) 0.7881(2) 0.9632(7) 0.0526(18) Uani 1 1 d . . .
C3 C 0.9764(15) 0.9396(3) 0.9000(8) 0.065(2) Uani 1 1 d . . .
H3 H 0.9479 0.9337 0.9883 0.078 Uiso 1 1 calc R . .
C4 C 0.8355(14) 0.9180(3) 0.7885(8) 0.058(2) Uani 1 1 d . . .
C2 C 1.1542(16) 0.9689(3) 0.8817(7) 0.059(2) Uani 1 1 d . . .
H2 H 1.2453 0.9830 0.9570 0.071 Uiso 1 1 calc R . .
C6 C 1.0649(16) 0.9564(3) 0.6396(7) 0.058(2) Uani 1 1 d . . .
H6 H 1.0980 0.9618 0.5516 0.070 Uiso 1 1 calc R . .
C13 C 0.7350(16) 0.6638(3) 0.9862(7) 0.056(2) Uani 1 1 d . . .
H13 H 0.6135 0.6515 1.0358 0.067 Uiso 1 1 calc R . .
N4 N 1.1091(13) 0.8019(2) 0.8452(7) 0.0627(17) Uani 1 1 d . . .
C12 C 0.8758(14) 0.6967(2) 1.0366(7) 0.0526(18) Uani 1 1 d . . .
H12 H 0.8487 0.7064 1.1210 0.063 Uiso 1 1 calc R . .
C14 C 0.7746(15) 0.6491(2) 0.8621(7) 0.0510(17) Uani 1 1 d . . .
C15 C 0.9562(17) 0.6672(3) 0.7893(7) 0.063(2) Uani 1 1 d . . .
H15 H 0.9847 0.6570 0.7059 0.076 Uiso 1 1 calc R . .
C16 C 1.0932(16) 0.6999(3) 0.8386(8) 0.069(3) Uani 1 1 d . . .
H16 H 1.2130 0.7120 0.7877 0.083 Uiso 1 1 calc R . .
C10 C 1.2114(18) 0.7519(3) 1.0195(10) 0.076(3) Uani 1 1 d . . .
H10A H 1.3979 0.7520 0.9949 0.091 Uiso 1 1 calc R . .
H10B H 1.2357 0.7521 1.1191 0.091 Uiso 1 1 calc R . .
C11 C 1.0579(14) 0.7158(3) 0.9652(7) 0.0546(19) Uani 1 1 d . . .
N1 N 0.7267(15) 0.8347(3) 0.9813(7) 0.072(2) Uani 1 1 d . . .
N2 N 0.8677(15) 0.8030(3) 1.0322(6) 0.071(2) Uani 1 1 d . . .
N3 N 0.9692(14) 0.8338(2) 0.7951(6) 0.0632(18) Uani 1 1 d . . .
C5 C 0.8836(16) 0.9275(2) 0.6585(8) 0.060(2) Uani 1 1 d . . .
H5 H 0.7902 0.9138 0.5826 0.072 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
Br1 C1 1.904(8) . ?
Br2 C14 1.913(8) . ?
C1 C6 1.379(11) . ?
C1 C2 1.391(11) . ?
C8 N1 1.316(10) . ?
C8 N3 1.331(9) . ?
C8 C7 1.507(12) . ?
C7 C4 1.524(12) . ?
C7 H7A 0.9700 . ?
C7 H7B 0.9700 . ?
C9 N2 1.324(10) . ?
C9 N4 1.328(9) . ?
C9 C10 1.516(11) . ?
C3 C2 1.359(11) . ?
C3 C4 1.399(11) . ?
C3 H3 0.9300 . ?
C4 C5 1.384(11) . ?
C2 H2 0.9300 . ?
C6 C5 1.362(12) . ?
C6 H6 0.9300 . ?
C13 C12 1.370(11) . ?
C13 C14 1.372(10) . ?
C13 H13 0.9300 . ?
N4 N3 1.341(9) . ?
C12 C11 1.388(10) . ?
C12 H12 0.9300 . ?
C14 C15 1.378(11) . ?
C15 C16 1.354(13) . ?
C15 H15 0.9300 . ?
C16 C11 1.405(11) . ?
C16 H16 0.9300 . ?
C10 C11 1.500(12) . ?
C10 H10A 0.9700 . ?
C10 H10B 0.9700 . ?
N1 N2 1.339(11) . ?
C5 H5 0.9300 . ?

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
C6 C1 C2 119.4(8) . . ?
C6 C1 Br1 120.9(6) . . ?
C2 C1 Br1 119.7(6) . . ?
N1 C8 N3 125.1(8) . . ?
N1 C8 C7 117.9(7) . . ?
N3 C8 C7 117.0(7) . . ?
C8 C7 C4 113.5(6) . . ?
C8 C7 H7A 108.9 . . ?
C4 C7 H7A 108.9 . . ?
C8 C7 H7B 108.9 . . ?
C4 C7 H7B 108.9 . . ?
H7A C7 H7B 107.7 . . ?
N2 C9 N4 125.0(8) . . ?
N2 C9 C10 118.1(7) . . ?
N4 C9 C10 116.9(7) . . ?
C2 C3 C4 121.3(7) . . ?
C2 C3 H3 119.4 . . ?
C4 C3 H3 119.4 . . ?
C5 C4 C3 117.8(8) . . ?
C5 C4 C7 121.4(8) . . ?
C3 C4 C7 120.8(7) . . ?
C3 C2 C1 119.8(7) . . ?
C3 C2 H2 120.1 . . ?
C1 C2 H2 120.1 . . ?
C5 C6 C1 120.4(7) . . ?
C5 C6 H6 119.8 . . ?
C1 C6 H6 119.8 . . ?
C12 C13 C14 119.5(7) . . ?
C12 C13 H13 120.2 . . ?
C14 C13 H13 120.2 . . ?
C9 N4 N3 116.9(6) . . ?
C13 C12 C11 121.8(7) . . ?
C13 C12 H12 119.1 . . ?
C11 C12 H12 119.1 . . ?
C13 C14 C15 120.0(8) . . ?
C13 C14 Br2 118.9(6) . . ?
C15 C14 Br2 121.1(6) . . ?
C16 C15 C14 120.4(7) . . ?
C16 C15 H15 119.8 . . ?
C14 C15 H15 119.8 . . ?
C15 C16 C11 121.2(7) . . ?
C15 C16 H16 119.4 . . ?
C11 C16 H16 119.4 . . ?
C11 C10 C9 112.1(6) . . ?
C11 C10 H10A 109.2 . . ?
C9 C10 H10A 109.2 . . ?
C11 C10 H10B 109.2 . . ?
C9 C10 H10B 109.2 . . ?
H10A C10 H10B 107.9 . . ?
C12 C11 C16 117.0(8) . . ?
C12 C11 C10 122.1(7) . . ?
C16 C11 C10 120.9(7) . . ?
C8 N1 N2 117.3(7) . . ?
C9 N2 N1 117.9(7) . . ?
C8 N3 N4 117.7(6) . . ?
C6 C5 C4 121.3(7) . . ?
C6 C5 H5 119.4 . . ?
C4 C5 H5 119.4 . . ?

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 C8 C7 C4 123.8(8) . . . . ?
N3 C8 C7 C4 -55.8(10) . . . . ?
C2 C3 C4 C5 0.1(12) . . . . ?
C2 C3 C4 C7 -179.6(8) . . . . ?
C8 C7 C4 C5 103.5(9) . . . . ?
C8 C7 C4 C3 -76.8(10) . . . . ?
C4 C3 C2 C1 -0.3(12) . . . . ?
C6 C1 C2 C3 -0.5(12) . . . . ?
Br1 C1 C2 C3 177.5(6) . . . . ?
C2 C1 C6 C5 1.5(12) . . . . ?
Br1 C1 C6 C5 -176.4(6) . . . . ?
N2 C9 N4 N3 1.8(11) . . . . ?
C10 C9 N4 N3 179.7(7) . . . . ?
C14 C13 C12 C11 0.3(11) . . . . ?
C12 C13 C14 C15 0.4(11) . . . . ?
C12 C13 C14 Br2 178.8(6) . . . . ?
C13 C14 C15 C16 -1.0(12) . . . . ?
Br2 C14 C15 C16 -179.3(6) . . . . ?
C14 C15 C16 C11 0.9(12) . . . . ?
N2 C9 C10 C11 89.7(9) . . . . ?
N4 C9 C10 C11 -88.4(9) . . . . ?
C13 C12 C11 C16 -0.3(10) . . . . ?
C13 C12 C11 C10 179.7(7) . . . . ?
C15 C16 C11 C12 -0.3(11) . . . . ?
C15 C16 C11 C10 179.7(8) . . . . ?
C9 C10 C11 C12 -94.6(9) . . . . ?
C9 C10 C11 C16 85.4(10) . . . . ?
N3 C8 N1 N2 1.5(12) . . . . ?
C7 C8 N1 N2 -178.1(7) . . . . ?
N4 C9 N2 N1 -1.3(12) . . . . ?
C10 C9 N2 N1 -179.2(7) . . . . ?
C8 N1 N2 C9 -0.4(11) . . . . ?
N1 C8 N3 N4 -1.0(12) . . . . ?
C7 C8 N3 N4 178.6(7) . . . . ?
C9 N4 N3 C8 -0.7(11) . . . . ?
C1 C6 C5 C4 -1.8(12) . . . . ?
C3 C4 C5 C6 0.9(12) . . . . ?
C7 C4 C5 C6 -179.4(8) . . . . ?

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        25.50
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         0.844
_refine_diff_density_min         -0.595
_refine_diff_density_rms         0.136
