# 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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#  data retrieval see:
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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.
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data_p

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C20 H23 Br N4 Ni'
_chemical_formula_weight         458.04

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'
Ni Ni 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   'Pna2(1) '

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

_cell_length_a                   19.216(6)
_cell_length_b                   10.729(4)
_cell_length_c                   9.506(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1959.7(11)
_cell_formula_units_Z            4
_cell_measurement_temperature    273(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       ?
_exptl_crystal_colour            ?
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.19
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.552
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             936
_exptl_absorpt_coefficient_mu    3.040
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      273(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            10965
_diffrn_reflns_av_R_equivalents  0.1054
_diffrn_reflns_av_sigmaI/netI    0.1166
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         2.17
_diffrn_reflns_theta_max         27.50
_reflns_number_total             4247
_reflns_number_gt                2615
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_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)+(0.0681P)²+0.0000P] 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     none
_refine_ls_extinction_coef       ?
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.10(2)
_refine_ls_number_reflns         4247
_refine_ls_number_parameters     239
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.1019
_refine_ls_R_factor_gt           0.0574
_refine_ls_wR_factor_ref         0.1416
_refine_ls_wR_factor_gt          0.1252
_refine_ls_goodness_of_fit_ref   0.922
_refine_ls_restrained_S_all      0.922
_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
Br1 Br 0.80045(4) 0.51636(7) 0.52689(11) 0.0537(3) Uani 1 1 d . . .
C1 C 0.6214(5) 0.2807(10) 0.3273(10) 0.059(3) Uani 1 1 d . . .
H1A H 0.5934 0.2099 0.3517 0.089 Uiso 1 1 calc R . .
H1B H 0.6396 0.2700 0.2340 0.089 Uiso 1 1 calc R . .
H1C H 0.5934 0.3548 0.3306 0.089 Uiso 1 1 calc R . .
C2 C 0.7280(5) 0.1774(8) 0.4319(11) 0.066(3) Uani 1 1 d . . .
H2A H 0.7665 0.1902 0.4946 0.098 Uiso 1 1 calc R . .
H2B H 0.7451 0.1627 0.3385 0.098 Uiso 1 1 calc R . .
H2C H 0.7015 0.1066 0.4625 0.098 Uiso 1 1 calc R . .
C3 C 0.6818(4) 0.2926(7) 0.4319(9) 0.0394(18) Uani 1 1 d . . .
H3 H 0.7103 0.3641 0.4035 0.047 Uiso 1 1 calc R . .
C4 C 0.6541(4) 0.4308(6) 0.6365(7) 0.0281(15) Uani 1 1 d . . .
C5 C 0.6157(4) 0.2364(7) 0.6522(9) 0.040(2) Uani 1 1 d . . .
H5 H 0.6094 0.1522 0.6327 0.048 Uiso 1 1 calc R . .
C6 C 0.5898(4) 0.2956(7) 0.7597(8) 0.037(2) Uani 1 1 d . . .
H6 H 0.5613 0.2620 0.8292 0.045 Uiso 1 1 calc R . .
C7 C 0.5941(4) 0.5185(7) 0.8412(7) 0.0314(16) Uani 1 1 d . . .
C8 C 0.5774(4) 0.4945(7) 0.9821(8) 0.0425(19) Uani 1 1 d . . .
H8 H 0.5793 0.4133 1.0161 0.051 Uiso 1 1 calc R . .
C9 C 0.5583(4) 0.5892(9) 1.0700(11) 0.058(2) Uani 1 1 d . . .
H9 H 0.5456 0.5728 1.1625 0.070 Uiso 1 1 calc R . .
C10 C 0.5584(4) 0.7100(8) 1.0190(9) 0.0459(19) Uani 1 1 d . . .
H10 H 0.5464 0.7753 1.0786 0.055 Uiso 1 1 calc R . .
C11 C 0.5759(4) 0.7351(7) 0.8811(8) 0.0414(19) Uani 1 1 d . . .
H11 H 0.5767 0.8173 0.8501 0.050 Uiso 1 1 calc R . .
C12 C 0.5926(3) 0.6384(7) 0.7860(8) 0.0332(17) Uani 1 1 d . . .
C13 C 0.5851(3) 0.7601(5) 0.5720(8) 0.0278(14) Uani 1 1 d . . .
C14 C 0.5202(4) 0.8171(6) 0.5889(8) 0.0370(18) Uani 1 1 d . . .
H14 H 0.4906 0.7907 0.6604 0.044 Uiso 1 1 calc R . .
C15 C 0.4997(4) 0.9116(6) 0.5010(8) 0.0389(18) Uani 1 1 d . . .
H15 H 0.4572 0.9509 0.5159 0.047 Uiso 1 1 calc R . .
C16 C 0.5404(4) 0.9483(6) 0.3934(9) 0.044(2) Uani 1 1 d . . .
H16 H 0.5248 1.0097 0.3320 0.052 Uiso 1 1 calc R . .
C17 C 0.6053(4) 0.8956(6) 0.3732(8) 0.0366(18) Uani 1 1 d . . .
H17 H 0.6340 0.9239 0.3012 0.044 Uiso 1 1 calc R . .
C18 C 0.6270(3) 0.8015(6) 0.4600(8) 0.0287(16) Uani 1 1 d . . .
C19 C 0.7500(4) 0.8251(7) 0.5037(11) 0.057(3) Uani 1 1 d . . .
H19A H 0.7407 0.8459 0.6001 0.086 Uiso 1 1 calc R . .
H19B H 0.7506 0.8997 0.4481 0.086 Uiso 1 1 calc R . .
H19C H 0.7943 0.7843 0.4972 0.086 Uiso 1 1 calc R . .
C20 C 0.7102(4) 0.7039(10) 0.3021(10) 0.057(2) Uani 1 1 d . . .
H20A H 0.7546 0.6632 0.2980 0.085 Uiso 1 1 calc R . .
H20B H 0.7110 0.7770 0.2440 0.085 Uiso 1 1 calc R . .
H20C H 0.6748 0.6480 0.2690 0.085 Uiso 1 1 calc R . .
N1 N 0.6537(3) 0.3183(4) 0.5721(7) 0.0308(12) Uani 1 1 d . . .
N2 N 0.6126(3) 0.4184(5) 0.7514(6) 0.0316(13) Uani 1 1 d . . .
N3 N 0.6112(3) 0.6597(5) 0.6491(6) 0.0289(13) Uani 1 1 d . . .
N4 N 0.6948(3) 0.7404(5) 0.4507(7) 0.0360(14) Uani 1 1 d . . .
Ni1 Ni 0.68703(4) 0.58373(7) 0.56628(9) 0.0276(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
Br1 Ni1 2.3266(13) . ?
C1 C3 1.534(12) . ?
C2 C3 1.522(11) . ?
C3 N1 1.464(10) . ?
C4 N1 1.353(8) . ?
C4 N2 1.359(8) . ?
C4 Ni1 1.881(7) . ?
C5 C6 1.302(11) . ?
C5 N1 1.373(9) . ?
C6 N2 1.390(9) . ?
C7 C12 1.389(10) . ?
C7 C8 1.401(10) . ?
C7 N2 1.418(9) . ?
C8 C9 1.365(12) . ?
C9 C10 1.383(12) . ?
C10 C11 1.381(11) . ?
C11 C12 1.413(10) . ?
C12 N3 1.369(9) . ?
C13 N3 1.396(8) . ?
C13 C14 1.398(9) . ?
C13 C18 1.407(9) . ?
C14 C15 1.371(10) . ?
C15 C16 1.348(11) . ?
C16 C17 1.382(10) . ?
C17 C18 1.369(9) . ?
C18 N4 1.462(8) . ?
C19 N4 1.485(9) . ?
C20 N4 1.495(11) . ?
N3 Ni1 1.847(5) . ?
N4 Ni1 2.013(6) . ?

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 C3 C2 111.6(7) . . ?
N1 C3 C1 109.1(6) . . ?
C2 C3 C1 111.9(7) . . ?
N1 C4 N2 105.8(6) . . ?
N1 C4 Ni1 128.3(5) . . ?
N2 C4 Ni1 124.6(5) . . ?
C6 C5 N1 109.1(7) . . ?
C5 C6 N2 107.2(6) . . ?
C12 C7 C8 121.8(7) . . ?
C12 C7 N2 118.6(6) . . ?
C8 C7 N2 119.6(6) . . ?
C9 C8 C7 120.6(7) . . ?
C8 C9 C10 118.8(8) . . ?
C11 C10 C9 121.0(8) . . ?
C10 C11 C12 121.3(8) . . ?
N3 C12 C7 120.6(6) . . ?
N3 C12 C11 123.0(7) . . ?
C7 C12 C11 116.3(7) . . ?
N3 C13 C14 126.7(6) . . ?
N3 C13 C18 115.8(5) . . ?
C14 C13 C18 117.4(6) . . ?
C15 C14 C13 120.6(7) . . ?
C16 C15 C14 120.8(7) . . ?
C15 C16 C17 120.6(7) . . ?
C18 C17 C16 119.5(7) . . ?
C17 C18 C13 121.0(6) . . ?
C17 C18 N4 124.5(6) . . ?
C13 C18 N4 114.5(6) . . ?
C4 N1 C5 108.9(6) . . ?
C4 N1 C3 125.3(6) . . ?
C5 N1 C3 125.5(6) . . ?
C4 N2 C6 108.9(6) . . ?
C4 N2 C7 123.8(5) . . ?
C6 N2 C7 127.2(6) . . ?
C12 N3 C13 122.3(6) . . ?
C12 N3 Ni1 122.5(5) . . ?
C13 N3 Ni1 113.6(4) . . ?
C18 N4 C19 110.0(5) . . ?
C18 N4 C20 110.5(6) . . ?
C19 N4 C20 109.9(7) . . ?
C18 N4 Ni1 106.0(4) . . ?
C19 N4 Ni1 112.2(5) . . ?
C20 N4 Ni1 108.2(5) . . ?
N3 Ni1 C4 88.2(3) . . ?
N3 Ni1 N4 85.6(2) . . ?
C4 Ni1 N4 161.2(3) . . ?
N3 Ni1 Br1 161.0(2) . . ?
C4 Ni1 Br1 95.8(2) . . ?
N4 Ni1 Br1 95.85(16) . . ?

_diffrn_measured_fraction_theta_max 0.992
_diffrn_reflns_theta_full        27.50
_diffrn_measured_fraction_theta_full 0.992
_refine_diff_density_max         1.104
_refine_diff_density_min         -0.879
_refine_diff_density_rms         0.124
_database_code_depnum_ccdc_archive 'CCDC 981371'
