# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2014

#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
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# 
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#  data retrieval see:
#                         www.ccdc.cam.ac.uk
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#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_ligand1

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C20 H20 Br N5 O'
_chemical_formula_weight         426.32

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           Triclinic
_symmetry_space_group_name_H-M   'P -1'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   7.283(2)
_cell_length_b                   11.074(3)
_cell_length_c                   13.183(4)
_cell_angle_alpha                107.84(4)
_cell_angle_beta                 98.89(2)
_cell_angle_gamma                105.76(3)
_cell_volume                     940.7(3)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    3245
_cell_measurement_theta_min      4.1
_cell_measurement_theta_max      25

_exptl_crystal_description       block
_exptl_crystal_colour            'pale brown'
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.18
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.505
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             436
_exptl_absorpt_coefficient_mu    2.205
_exptl_absorpt_correction_type   psi-scan
_exptl_absorpt_correction_T_min  0.6545
_exptl_absorpt_correction_T_max  0.6923
_exptl_absorpt_process_details   '(North et al., 1968)'

_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  ?
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            4788
_diffrn_reflns_av_R_equivalents  0.0237
_diffrn_reflns_av_sigmaI/netI    0.0499
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         4.11
_diffrn_reflns_theta_max         25.02
_reflns_number_total             3245
_reflns_number_gt                2840
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_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)+(0.1946P)²+2.6322P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3245
_refine_ls_number_parameters     245
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0557
_refine_ls_R_factor_gt           0.0484
_refine_ls_wR_factor_ref         0.1584
_refine_ls_wR_factor_gt          0.1346
_refine_ls_goodness_of_fit_ref   0.649
_refine_ls_restrained_S_all      0.649
_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 -0.25708(5) 0.36348(4) 0.53911(3) 0.0250(2) Uani 1 1 d . . .
N3 N 0.2375(5) 0.1057(4) 0.6622(3) 0.0296(8) Uani 1 1 d . . .
N9 N 0.2161(5) 0.3085(4) 0.6320(3) 0.0241(7) Uani 1 1 d . . .
N7 N 0.2389(5) 0.2588(4) 0.4629(3) 0.0231(7) Uani 1 1 d . . .
N1 N 0.2636(5) -0.0528(4) 0.5021(3) 0.0319(9) Uani 1 1 d . . .
H1 H 0.2715 -0.1319 0.4750 0.038 Uiso 1 1 calc R . .
O1 O 0.2852(5) -0.1446(3) 0.3021(3) 0.0407(8) Uani 1 1 d . . .
C18 C -0.0810(6) 0.2822(4) 0.2937(3) 0.0247(9) Uani 1 1 d . . .
H18 H -0.0494 0.3575 0.3577 0.030 Uiso 1 1 calc R . .
C11 C 0.5707(6) 0.4903(4) 0.7942(3) 0.0267(9) Uani 1 1 d . . .
H11 H 0.5765 0.4293 0.7292 0.032 Uiso 1 1 calc R . .
C2 C 0.2514(6) -0.0087(5) 0.6090(4) 0.0312(10) Uani 1 1 d . . .
H2 H 0.2534 -0.0670 0.6468 0.037 Uiso 1 1 calc R . .
N6 N 0.2741(6) -0.0133(4) 0.3309(4) 0.0339(9) Uani 1 1 d . . .
C16 C 0.2562(7) 0.2733(5) 0.3567(4) 0.0289(9) Uani 1 1 d . . .
H16A H 0.3409 0.2257 0.3266 0.035 Uiso 1 1 calc R . .
H16B H 0.3173 0.3679 0.3692 0.035 Uiso 1 1 calc R . .
C17 C 0.0557(7) 0.2181(4) 0.2736(3) 0.0263(9) Uani 1 1 d . . .
C10 C 0.3918(6) 0.4854(4) 0.8186(3) 0.0256(9) Uani 1 1 d . . .
C19 C -0.2640(7) 0.2352(5) 0.2196(4) 0.0318(10) Uani 1 1 d . . .
H19 H -0.3570 0.2769 0.2341 0.038 Uiso 1 1 calc R . .
C9 C 0.1990(7) 0.3825(5) 0.7411(4) 0.0316(10) Uani 1 1 d . . .
H9A H 0.1468 0.3183 0.7746 0.038 Uiso 1 1 calc R . .
H9B H 0.1048 0.4281 0.7321 0.038 Uiso 1 1 calc R . .
C6 C 0.2638(6) 0.0219(4) 0.4346(4) 0.0279(9) Uani 1 1 d . . .
C8 C 0.2221(6) 0.3530(4) 0.5485(3) 0.0242(9) Uani 1 1 d . . .
H8 H 0.2157 0.4362 0.5501 0.029 Uiso 1 1 calc R . .
C4 C 0.2344(6) 0.1820(4) 0.5988(3) 0.0238(9) Uani 1 1 d . . .
C12 C 0.7440(7) 0.5892(5) 0.8696(4) 0.0343(10) Uani 1 1 d . . .
H12 H 0.8650 0.5945 0.8532 0.041 Uiso 1 1 calc R . .
C5 C 0.2462(5) 0.1499(4) 0.4926(4) 0.0228(8) Uani 1 1 d . . .
C21 C -0.1741(11) 0.0602(6) 0.1030(5) 0.0608(19) Uani 1 1 d . . .
H21 H -0.2063 -0.0150 0.0389 0.073 Uiso 1 1 calc R . .
C15 C 0.3837(8) 0.5751(5) 0.9172(4) 0.0336(10) Uani 1 1 d . . .
H15 H 0.2630 0.5711 0.9337 0.040 Uiso 1 1 calc R . .
C22 C 0.0092(9) 0.1064(5) 0.1781(4) 0.0459(13) Uani 1 1 d . . .
H22 H 0.1000 0.0625 0.1642 0.055 Uiso 1 1 calc R . .
C23 C 0.2893(8) -0.1856(6) 0.1883(5) 0.0464(13) Uani 1 1 d . . .
H23A H 0.1759 -0.1793 0.1451 0.070 Uiso 1 1 calc R . .
H23B H 0.2872 -0.2771 0.1627 0.070 Uiso 1 1 calc R . .
H23C H 0.4074 -0.1280 0.1811 0.070 Uiso 1 1 calc R . .
C13 C 0.7382(8) 0.6783(5) 0.9670(4) 0.0388(12) Uani 1 1 d . . .
H13 H 0.8539 0.7430 1.0165 0.047 Uiso 1 1 calc R . .
C14 C 0.5570(9) 0.6701(5) 0.9903(4) 0.0431(13) Uani 1 1 d . . .
H14 H 0.5520 0.7296 1.0563 0.052 Uiso 1 1 calc R . .
C20 C -0.3068(9) 0.1252(6) 0.1234(5) 0.0540(16) Uani 1 1 d . . .
H20 H -0.4277 0.0951 0.0719 0.065 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
N3 C2 1.286(6) . ?
N3 C4 1.361(6) . ?
N9 C8 1.339(5) . ?
N9 C4 1.384(6) . ?
N9 C9 1.464(6) . ?
N7 C8 1.328(5) . ?
N7 C5 1.389(5) . ?
N7 C16 1.478(5) . ?
N1 C6 1.389(6) . ?
N1 C2 1.368(6) . ?
O1 N6 1.413(5) . ?
O1 C23 1.435(7) . ?
C18 C19 1.383(6) . ?
C18 C17 1.384(6) . ?
C11 C10 1.381(6) . ?
C11 C12 1.405(6) . ?
N6 C6 1.321(6) . ?
C16 C17 1.521(6) . ?
C17 C22 1.384(7) . ?
C10 C15 1.395(6) . ?
C10 C9 1.512(6) . ?
C19 C20 1.383(7) . ?
C6 C5 1.440(6) . ?
C4 C5 1.357(6) . ?
C12 C13 1.374(7) . ?
C21 C20 1.365(9) . ?
C21 C22 1.390(8) . ?
C15 C14 1.381(8) . ?
C13 C14 1.386(8) . ?

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
C2 N3 C4 111.8(4) . . ?
C8 N9 C4 108.3(3) . . ?
C8 N9 C9 125.9(4) . . ?
C4 N9 C9 125.7(4) . . ?
C8 N7 C5 108.6(4) . . ?
C8 N7 C16 124.6(4) . . ?
C5 N7 C16 126.8(4) . . ?
C6 N1 C2 124.2(4) . . ?
N6 O1 C23 105.9(4) . . ?
C19 C18 C17 120.6(4) . . ?
C10 C11 C12 118.7(4) . . ?
N3 C2 N1 126.3(4) . . ?
C6 N6 O1 105.5(4) . . ?
N7 C16 C17 111.7(3) . . ?
C22 C17 C18 119.7(4) . . ?
C22 C17 C16 121.2(4) . . ?
C18 C17 C16 119.1(4) . . ?
C11 C10 C15 120.6(4) . . ?
C11 C10 C9 121.7(4) . . ?
C15 C10 C9 117.7(4) . . ?
C18 C19 C20 119.0(5) . . ?
N9 C9 C10 114.1(4) . . ?
N6 C6 N1 127.9(4) . . ?
N6 C6 C5 121.8(4) . . ?
N1 C6 C5 110.3(4) . . ?
N7 C8 N9 108.9(4) . . ?
N3 C4 C5 127.4(4) . . ?
N3 C4 N9 125.3(4) . . ?
C5 C4 N9 107.2(4) . . ?
C13 C12 C11 121.3(5) . . ?
C4 C5 N7 106.9(4) . . ?
C4 C5 C6 120.1(4) . . ?
N7 C5 C6 133.0(4) . . ?
C20 C21 C22 120.1(5) . . ?
C14 C15 C10 119.3(5) . . ?
C17 C22 C21 119.6(5) . . ?
C12 C13 C14 118.9(5) . . ?
C15 C14 C13 121.3(5) . . ?
C21 C20 C19 120.9(5) . . ?

_diffrn_measured_fraction_theta_max 0.973
_diffrn_reflns_theta_full        25.02
_diffrn_measured_fraction_theta_full 0.973
_refine_diff_density_max         0.846
_refine_diff_density_min         -0.684
_refine_diff_density_rms         0.157
_database_code_depnum_ccdc_archive 'CCDC 965785'
