# Electronic Supplementary Material (ESI) for Dalton Transactions
# This journal is © The Royal Society of Chemistry 2012


data_global
_journal_name_full               'Dalton Trans.'
_journal_coden_cambridge         0222
_journal_year                    ?
_journal_volume                  ?
_journal_page_first              ?
loop_
_publ_author_name
B.Sarkar
D.Schweinfurth
C.-Y.Su
P.Braunstein
_publ_contact_author_name        'Biprajit Sarkar'
_publ_contact_author_email       iacbipro@iac.uni-stuttgart.de

data_ni
_database_code_depnum_ccdc_archive 'CCDC 851805'
#TrackingRef '- ni-rev.cif'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C52 H64 Br4 N16 Ni2'
_chemical_formula_weight         1350.25

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'
Ni Ni -3.0029 0.5091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           ORTHORHOMBIC
_symmetry_space_group_name_H-M   Pbca

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'
'-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                   13.0158(2)
_cell_length_b                   9.8575(2)
_cell_length_c                   20.8946(5)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     2680.85(9)
_cell_formula_units_Z            2
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    4154
_cell_measurement_theta_min      3.3929
_cell_measurement_theta_max      62.5099

_exptl_crystal_description       Block
_exptl_crystal_colour            Colorless
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.18
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.673
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1368
_exptl_absorpt_coefficient_mu    4.790
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.3806
_exptl_absorpt_correction_T_max  0.4793
_exptl_absorpt_process_details   
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET)
(compiled Oct 25 2010,18:11:34)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_type           CuK\a
_diffrn_radiation_source         'Enhance Ultra (Cu) X-ray Source'
_diffrn_radiation_monochromator  mirror
_diffrn_measurement_device_type  'Xcalibur, Sapphire3, Gemini ultra'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_detector_area_resol_mean 16.0855
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            6634
_diffrn_reflns_av_R_equivalents  0.0281
_diffrn_reflns_av_sigmaI/netI    0.0260
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_theta_min         4.23
_diffrn_reflns_theta_max         62.60
_reflns_number_total             2115
_reflns_number_gt                1919
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET)
(compiled Oct 25 2010,18:11:34)
;
_computing_cell_refinement       
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET)
(compiled Oct 25 2010,18:11:34)
;
_computing_data_reduction        
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET)
(compiled Oct 25 2010,18:11:34)
;
_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 F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ 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/[\s^2^(Fo^2^)+(0.0388P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/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         2115
_refine_ls_number_parameters     169
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0269
_refine_ls_R_factor_gt           0.0238
_refine_ls_wR_factor_ref         0.0616
_refine_ls_wR_factor_gt          0.0591
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_restrained_S_all      1.018
_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
Ni1 Ni 0.5000 0.0000 0.5000 0.01841(14) Uani 1 2 d S . .
Br1 Br 0.526293(16) 0.16216(2) 0.403171(11) 0.02311(11) Uani 1 1 d . . .
N1 N 0.34529(13) -0.02131(16) 0.47639(9) 0.0197(4) Uani 1 1 d . . .
N2 N 0.43632(13) 0.15875(16) 0.55245(9) 0.0202(4) Uani 1 1 d . . .
N3 N 0.46888(13) 0.25449(19) 0.59105(9) 0.0229(4) Uani 1 1 d . . .
N4 N 0.38443(14) 0.32033(17) 0.61180(9) 0.0214(4) Uani 1 1 d . . .
C1 C 0.30543(17) -0.1126(2) 0.43603(10) 0.0215(4) Uani 1 1 d . . .
H1A H 0.3505 -0.1746 0.4154 0.026 Uiso 1 1 calc R . .
C2 C 0.20120(17) -0.1206(2) 0.42304(11) 0.0248(5) Uani 1 1 d . . .
H2A H 0.1753 -0.1869 0.3942 0.030 Uiso 1 1 calc R . .
C3 C 0.13541(17) -0.0299(2) 0.45292(11) 0.0258(5) Uani 1 1 d . . .
H3A H 0.0636 -0.0339 0.4451 0.031 Uiso 1 1 calc R . .
C4 C 0.17518(16) 0.0663(2) 0.49420(11) 0.0224(5) Uani 1 1 d . . .
H4A H 0.1315 0.1304 0.5145 0.027 Uiso 1 1 calc R . .
C5 C 0.28089(16) 0.06734(19) 0.50542(10) 0.0200(4) Uani 1 1 d . . .
C6 C 0.33193(16) 0.16343(19) 0.54749(11) 0.0197(4) Uani 1 1 d . . .
C7 C 0.29825(16) 0.2678(2) 0.58576(10) 0.0217(5) Uani 1 1 d . . .
H7A H 0.2294 0.2966 0.5924 0.026 Uiso 1 1 calc R . .
C8 C 0.39515(16) 0.4415(2) 0.65390(11) 0.0229(5) Uani 1 1 d . . .
H8A H 0.4116 0.5215 0.6263 0.027 Uiso 1 1 calc R . .
C9 C 0.29356(17) 0.4696(2) 0.68815(12) 0.0293(5) Uani 1 1 d . . .
H9A H 0.2740 0.3902 0.7145 0.035 Uiso 1 1 calc R . .
H9B H 0.2386 0.4856 0.6563 0.035 Uiso 1 1 calc R . .
C10 C 0.30610(19) 0.5948(2) 0.73087(12) 0.0338(6) Uani 1 1 d . . .
H10A H 0.3200 0.6752 0.7038 0.041 Uiso 1 1 calc R . .
H10B H 0.2413 0.6113 0.7545 0.041 Uiso 1 1 calc R . .
C11 C 0.39338(19) 0.5767(2) 0.77836(12) 0.0335(6) Uani 1 1 d . . .
H11A H 0.3768 0.5014 0.8080 0.040 Uiso 1 1 calc R . .
H11B H 0.4013 0.6605 0.8040 0.040 Uiso 1 1 calc R . .
C12 C 0.49368(19) 0.5460(2) 0.74382(13) 0.0318(5) Uani 1 1 d . . .
H12A H 0.5486 0.5296 0.7757 0.038 Uiso 1 1 calc R . .
H12B H 0.5139 0.6253 0.7176 0.038 Uiso 1 1 calc R . .
C13 C 0.48282(17) 0.4220(2) 0.70083(13) 0.0292(5) Uani 1 1 d . . .
H13A H 0.5476 0.4073 0.6770 0.035 Uiso 1 1 calc R . .
H13B H 0.4696 0.3407 0.7274 0.035 Uiso 1 1 calc R . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Ni1 0.0113(2) 0.0188(3) 0.0251(3) -0.00316(19) 0.00025(19) 0.0004(2)
Br1 0.01599(15) 0.02450(15) 0.02884(17) 0.00136(8) 0.00000(8) -0.00112(8)
N1 0.0161(9) 0.0203(8) 0.0227(10) -0.0004(7) 0.0020(7) -0.0002(7)
N2 0.0134(9) 0.0199(9) 0.0273(10) -0.0022(7) -0.0001(7) 0.0013(7)
N3 0.0157(9) 0.0225(10) 0.0304(11) -0.0054(7) 0.0004(7) 0.0024(7)
N4 0.0157(9) 0.0210(9) 0.0275(10) -0.0032(7) 0.0004(7) 0.0020(7)
C1 0.0206(11) 0.0202(10) 0.0236(12) 0.0005(8) 0.0019(9) 0.0022(9)
C2 0.0218(11) 0.0248(11) 0.0280(12) -0.0023(9) -0.0035(9) -0.0045(9)
C3 0.0156(10) 0.0278(11) 0.0339(13) 0.0033(9) -0.0037(9) -0.0011(9)
C4 0.0140(10) 0.0240(11) 0.0293(12) 0.0008(9) -0.0003(9) 0.0015(8)
C5 0.0183(11) 0.0183(10) 0.0234(12) 0.0024(8) 0.0025(8) 0.0001(8)
C6 0.0138(10) 0.0200(10) 0.0254(12) 0.0011(8) 0.0013(9) 0.0003(8)
C7 0.0142(10) 0.0257(11) 0.0252(12) -0.0010(8) 0.0000(8) 0.0001(9)
C8 0.0212(11) 0.0190(10) 0.0283(12) -0.0034(8) 0.0010(9) 0.0005(9)
C9 0.0207(11) 0.0307(12) 0.0364(14) -0.0084(10) 0.0014(10) 0.0024(10)
C10 0.0295(12) 0.0323(13) 0.0397(15) -0.0124(10) 0.0042(11) 0.0035(10)
C11 0.0393(14) 0.0327(12) 0.0285(13) -0.0062(10) 0.0030(11) -0.0047(11)
C12 0.0307(12) 0.0309(12) 0.0338(15) -0.0060(10) -0.0058(11) -0.0032(10)
C13 0.0231(12) 0.0288(12) 0.0357(14) -0.0050(10) -0.0018(10) 0.0011(9)

_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
Ni1 N2 2.0825(17) 5_656 ?
Ni1 N2 2.0825(17) . ?
Ni1 N1 2.0838(17) . ?
Ni1 N1 2.0838(17) 5_656 ?
Ni1 Br1 2.6011(2) . ?
Ni1 Br1 2.6011(2) 5_656 ?
N1 C1 1.338(3) . ?
N1 C5 1.354(3) . ?
N2 N3 1.312(3) . ?
N2 C6 1.363(3) . ?
N3 N4 1.348(3) . ?
N4 C7 1.350(3) . ?
N4 C8 1.490(3) . ?
C1 C2 1.386(3) . ?
C1 H1A 0.9500 . ?
C2 C3 1.386(3) . ?
C2 H2A 0.9500 . ?
C3 C4 1.383(3) . ?
C3 H3A 0.9500 . ?
C4 C5 1.396(3) . ?
C4 H4A 0.9500 . ?
C5 C6 1.453(3) . ?
C6 C7 1.375(3) . ?
C7 H7A 0.9500 . ?
C8 C13 1.517(3) . ?
C8 C9 1.529(3) . ?
C8 H8A 1.0000 . ?
C9 C10 1.532(3) . ?
C9 H9A 0.9900 . ?
C9 H9B 0.9900 . ?
C10 C11 1.519(4) . ?
C10 H10A 0.9900 . ?
C10 H10B 0.9900 . ?
C11 C12 1.522(4) . ?
C11 H11A 0.9900 . ?
C11 H11B 0.9900 . ?
C12 C13 1.523(3) . ?
C12 H12A 0.9900 . ?
C12 H12B 0.9900 . ?
C13 H13A 0.9900 . ?
C13 H13B 0.9900 . ?

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
N2 Ni1 N2 180.00(9) 5_656 . ?
N2 Ni1 N1 100.62(7) 5_656 . ?
N2 Ni1 N1 79.38(7) . . ?
N2 Ni1 N1 79.38(7) 5_656 5_656 ?
N2 Ni1 N1 100.62(7) . 5_656 ?
N1 Ni1 N1 180.00(10) . 5_656 ?
N2 Ni1 Br1 90.01(5) 5_656 . ?
N2 Ni1 Br1 89.99(5) . . ?
N1 Ni1 Br1 90.28(5) . . ?
N1 Ni1 Br1 89.72(5) 5_656 . ?
N2 Ni1 Br1 89.99(5) 5_656 5_656 ?
N2 Ni1 Br1 90.01(5) . 5_656 ?
N1 Ni1 Br1 89.72(5) . 5_656 ?
N1 Ni1 Br1 90.28(5) 5_656 5_656 ?
Br1 Ni1 Br1 180.0 . 5_656 ?
C1 N1 C5 118.44(18) . . ?
C1 N1 Ni1 126.27(14) . . ?
C5 N1 Ni1 115.28(14) . . ?
N3 N2 C6 110.15(17) . . ?
N3 N2 Ni1 137.36(14) . . ?
C6 N2 Ni1 112.46(13) . . ?
N2 N3 N4 106.31(16) . . ?
N3 N4 C7 111.28(17) . . ?
N3 N4 C8 119.97(17) . . ?
C7 N4 C8 128.57(18) . . ?
N1 C1 C2 122.8(2) . . ?
N1 C1 H1A 118.6 . . ?
C2 C1 H1A 118.6 . . ?
C1 C2 C3 118.7(2) . . ?
C1 C2 H2A 120.7 . . ?
C3 C2 H2A 120.7 . . ?
C4 C3 C2 119.5(2) . . ?
C4 C3 H3A 120.3 . . ?
C2 C3 H3A 120.3 . . ?
C3 C4 C5 118.6(2) . . ?
C3 C4 H4A 120.7 . . ?
C5 C4 H4A 120.7 . . ?
N1 C5 C4 122.0(2) . . ?
N1 C5 C6 114.11(18) . . ?
C4 C5 C6 123.86(19) . . ?
N2 C6 C7 107.39(18) . . ?
N2 C6 C5 118.67(18) . . ?
C7 C6 C5 133.94(19) . . ?
N4 C7 C6 104.87(18) . . ?
N4 C7 H7A 127.6 . . ?
C6 C7 H7A 127.6 . . ?
N4 C8 C13 110.53(17) . . ?
N4 C8 C9 109.92(17) . . ?
C13 C8 C9 111.8(2) . . ?
N4 C8 H8A 108.2 . . ?
C13 C8 H8A 108.2 . . ?
C9 C8 H8A 108.2 . . ?
C8 C9 C10 109.07(19) . . ?
C8 C9 H9A 109.9 . . ?
C10 C9 H9A 109.9 . . ?
C8 C9 H9B 109.9 . . ?
C10 C9 H9B 109.9 . . ?
H9A C9 H9B 108.3 . . ?
C11 C10 C9 111.4(2) . . ?
C11 C10 H10A 109.3 . . ?
C9 C10 H10A 109.3 . . ?
C11 C10 H10B 109.3 . . ?
C9 C10 H10B 109.3 . . ?
H10A C10 H10B 108.0 . . ?
C10 C11 C12 110.8(2) . . ?
C10 C11 H11A 109.5 . . ?
C12 C11 H11A 109.5 . . ?
C10 C11 H11B 109.5 . . ?
C12 C11 H11B 109.5 . . ?
H11A C11 H11B 108.1 . . ?
C11 C12 C13 111.1(2) . . ?
C11 C12 H12A 109.4 . . ?
C13 C12 H12A 109.4 . . ?
C11 C12 H12B 109.4 . . ?
C13 C12 H12B 109.4 . . ?
H12A C12 H12B 108.0 . . ?
C8 C13 C12 110.46(19) . . ?
C8 C13 H13A 109.6 . . ?
C12 C13 H13A 109.6 . . ?
C8 C13 H13B 109.6 . . ?
C12 C13 H13B 109.6 . . ?
H13A C13 H13B 108.1 . . ?

_diffrn_measured_fraction_theta_max 0.985
_diffrn_reflns_theta_full        62.60
_diffrn_measured_fraction_theta_full 0.985
_refine_diff_density_max         0.432
_refine_diff_density_min         -0.331
_refine_diff_density_rms         0.066