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


data_global
_journal_name_full               'Chemical Science'
_journal_coden_cambridge         1475
_journal_year                    ?
_journal_volume                  ?
_journal_page_first              ?
loop_
_publ_author_name
C.Brozek
M.Dinca

data_a
_database_code_depnum_ccdc_archive 'CCDC 874342'
#TrackingRef '- CB1_225.cif'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C6 H3 N4 Ni0.10 O3.25 Zn'
_chemical_formula_weight         247.91

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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Zn Zn 0.2839 1.4301 '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'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           cubic
_symmetry_space_group_name_H-M   f_m_-3_m

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

_cell_length_a                   25.8380(16)
_cell_length_b                   25.8380(16)
_cell_length_c                   25.8380(16)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     17249.5(19)
_cell_formula_units_Z            32
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    80165
_cell_measurement_theta_min      1.37
_cell_measurement_theta_max      26.82

_exptl_crystal_description       ?
_exptl_crystal_colour            purple
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.20
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    0.764
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             3930.2
_exptl_absorpt_coefficient_mu    1.113
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  0.7925
_exptl_absorpt_correction_T_max  0.7925
_exptl_absorpt_process_details   ?

_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_reflns_number            80165
_diffrn_reflns_av_R_equivalents  0.0604
_diffrn_reflns_av_sigmaI/netI    0.0104
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_theta_min         1.37
_diffrn_reflns_theta_max         26.82
_reflns_number_total             991
_reflns_number_gt                780
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_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^)+(0.2000P)^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    mixed
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.00006(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_number_reflns         991
_refine_ls_number_parameters     35
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1063
_refine_ls_R_factor_gt           0.0905
_refine_ls_wR_factor_ref         0.3424
_refine_ls_wR_factor_gt          0.2759
_refine_ls_goodness_of_fit_ref   1.571
_refine_ls_restrained_S_all      1.571
_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
Ni1 Ni 0.20654(2) 0.20654(2) 0.20654(2) 0.0324(7) Uani 0.09 6 d SP . .
Zn1 Zn 0.20654(2) 0.20654(2) 0.20654(2) 0.0324(7) Uani 0.91 6 d SP . .
O2 O 0.2500 0.2500 0.2500 0.038(3) Uani 1 24 d S . .
O1 O 0.21893(12) 0.21893(12) 0.13338(15) 0.0517(12) Uani 1 2 d S . .
C1 C 0.2500 0.2500 0.1108(2) 0.0454(18) Uani 1 4 d S . .
C2 C 0.2500 0.2500 0.0532(3) 0.050(2) Uani 1 4 d S . .
C3 C 0.21749(17) 0.21749(17) 0.0271(3) 0.061(2) Uani 1 2 d S . .
H3 H 0.1950 0.1950 0.0455 0.073 Uiso 1 2 calc SR . .
N4 N 0.3446(13) 0.1554(13) 0.1554(13) 0.26(2) Uani 1 6 d S . .
N3 N 0.0783(10) 0.2567(10) 0.0783(10) 0.42(3) Uani 1 2 d S . .

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 0.0324(7) 0.0324(7) 0.0324(7) 0.00011(18) 0.00011(18) 0.00011(18)
Zn1 0.0324(7) 0.0324(7) 0.0324(7) 0.00011(18) 0.00011(18) 0.00011(18)
O2 0.038(3) 0.038(3) 0.038(3) 0.000 0.000 0.000
O1 0.0592(16) 0.0592(16) 0.037(2) 0.0017(11) 0.0017(11) -0.018(2)
C1 0.053(3) 0.053(3) 0.029(3) 0.000 0.000 -0.005(3)
C2 0.061(3) 0.061(3) 0.028(3) 0.000 0.000 -0.005(4)
C3 0.072(3) 0.072(3) 0.039(3) 0.0067(17) 0.0067(17) -0.035(3)
N4 0.26(2) 0.26(2) 0.26(2) 0.08(3) -0.08(3) -0.08(3)
N3 0.32(2) 0.62(6) 0.32(2) 0.23(4) 0.14(2) 0.23(4)

_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 O1 1.944(4) . ?
Ni1 O1 1.944(4) 9 ?
Ni1 O1 1.944(4) 5 ?
Ni1 O2 1.9449(10) . ?
O2 Zn1 1.9448(10) 74 ?
O2 Ni1 1.9448(10) 74 ?
O2 Zn1 1.9448(10) 28 ?
O2 Zn1 1.9448(10) 51 ?
O2 Ni1 1.9448(10) 51 ?
O2 Ni1 1.9448(10) 28 ?
O1 C1 1.276(5) . ?
C1 O1 1.276(5) 74 ?
C1 C2 1.488(10) . ?
C2 C3 1.367(8) 74 ?
C2 C3 1.367(8) . ?
C3 C3 1.398(13) 98 ?

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
O1 Ni1 O1 107.05(14) . 9 ?
O1 Ni1 O1 107.05(14) . 5 ?
O1 Ni1 O1 107.05(14) 9 5 ?
O1 Ni1 O2 111.80(13) . . ?
O1 Ni1 O2 111.80(13) 9 . ?
O1 Ni1 O2 111.80(13) 5 . ?
Zn1 O2 Ni1 0.00(9) 74 74 ?
Zn1 O2 Zn1 109.5 74 28 ?
Ni1 O2 Zn1 109.5 74 28 ?
Zn1 O2 Zn1 109.5 74 51 ?
Ni1 O2 Zn1 109.5 74 51 ?
Zn1 O2 Zn1 109.5 28 51 ?
Zn1 O2 Ni1 109.5 74 51 ?
Ni1 O2 Ni1 109.5 74 51 ?
Zn1 O2 Ni1 109.5 28 51 ?
Zn1 O2 Ni1 0.00(6) 51 51 ?
Zn1 O2 Ni1 109.5 74 28 ?
Ni1 O2 Ni1 109.5 74 28 ?
Zn1 O2 Ni1 0.00(6) 28 28 ?
Zn1 O2 Ni1 109.5 51 28 ?
Ni1 O2 Ni1 109.5 51 28 ?
Zn1 O2 Ni1 109.5 74 . ?
Ni1 O2 Ni1 109.5 74 . ?
Zn1 O2 Ni1 109.5 28 . ?
Zn1 O2 Ni1 109.5 51 . ?
Ni1 O2 Ni1 109.5 51 . ?
Ni1 O2 Ni1 109.5 28 . ?
C1 O1 Ni1 130.6(4) . . ?
O1 C1 O1 125.6(6) 74 . ?
O1 C1 C2 117.2(3) 74 . ?
O1 C1 C2 117.2(3) . . ?
C3 C2 C3 120.7(7) 74 . ?
C3 C2 C1 119.7(4) 74 . ?
C3 C2 C1 119.7(4) . . ?
C2 C3 C3 119.7(4) . 98 ?

_diffrn_measured_fraction_theta_max 1.000
_diffrn_reflns_theta_full        26.82
_diffrn_measured_fraction_theta_full 1.000
_refine_diff_density_max         2.047
_refine_diff_density_min         -0.450
_refine_diff_density_rms         0.177