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

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#
#                 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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data_1

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C48 H32 Co2 N24 O9 Zn5'
_chemical_formula_weight         1535.85

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'
Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Trigonal
_symmetry_space_group_name_H-M   R-3c

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'y, x, -z+1/2'
'x-y, -y, -z+1/2'
'-x, -x+y, -z+1/2'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'y+2/3, x+1/3, -z+5/6'
'x-y+2/3, -y+1/3, -z+5/6'
'-x+2/3, -x+y+1/3, -z+5/6'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'y+1/3, x+2/3, -z+7/6'
'x-y+1/3, -y+2/3, -z+7/6'
'-x+1/3, -x+y+2/3, -z+7/6'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'-y, -x, z-1/2'
'-x+y, y, z-1/2'
'x, x-y, z-1/2'
'-x+2/3, -y+1/3, -z+1/3'
'y+2/3, -x+y+1/3, -z+1/3'
'x-y+2/3, x+1/3, -z+1/3'
'-y+2/3, -x+1/3, z-1/6'
'-x+y+2/3, y+1/3, z-1/6'
'x+2/3, x-y+1/3, z-1/6'
'-x+1/3, -y+2/3, -z+2/3'
'y+1/3, -x+y+2/3, -z+2/3'
'x-y+1/3, x+2/3, -z+2/3'
'-y+1/3, -x+2/3, z+1/6'
'-x+y+1/3, y+2/3, z+1/6'
'x+1/3, x-y+2/3, z+1/6'

_cell_length_a                   13.988(2)
_cell_length_b                   13.988(2)
_cell_length_c                   47.981(10)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_volume                     8130(2)
_cell_formula_units_Z            6
_cell_measurement_temperature    298(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       block
_exptl_crystal_colour            red
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.20
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.880
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             4584
_exptl_absorpt_coefficient_mu    2.853
_exptl_absorpt_correction_type   'multi-scan(SADABS; Sheldrick,1996)'
_exptl_absorpt_correction_T_min  0.5022
_exptl_absorpt_correction_T_max  0.5992
_exptl_absorpt_process_details   ?

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      298(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            21852
_diffrn_reflns_av_R_equivalents  0.0545
_diffrn_reflns_av_sigmaI/netI    0.0210
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -57
_diffrn_reflns_limit_l_max       57
_diffrn_reflns_theta_min         3.18
_diffrn_reflns_theta_max         24.97
_reflns_number_total             1597
_reflns_number_gt                1466
_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)+(0.0257P)²+56.1461P] 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_number_reflns         1597
_refine_ls_number_parameters     148
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0444
_refine_ls_R_factor_gt           0.0382
_refine_ls_wR_factor_ref         0.0783
_refine_ls_wR_factor_gt          0.0759
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_restrained_S_all      1.095
_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
Zn2 Zn 0.6667 0.54092(4) 0.0833 0.03318(19) Uani 0.71 2 d SP . 1
Zn3 Zn 0.3333 0.6667 0.039749(14) 0.0263(2) Uani 0.71 3 d SP . 1
Zn1 Zn 0.6667 0.3333 0.039643(15) 0.0336(2) Uani 0.71 3 d SP . 1
Co2 Co 0.6667 0.54092(4) 0.0833 0.03318(19) Uani 0.29 2 d SP . 2
Co3 Co 0.3333 0.6667 0.039749(14) 0.0263(2) Uani 0.29 3 d SP . 2
Co1 Co 0.6667 0.3333 0.039643(15) 0.0336(2) Uani 0.29 3 d SP . 2
N1 N 0.5521(3) 0.5872(3) 0.07558(6) 0.0340(7) Uani 1 1 d . . .
C6 C 0.5744(3) 0.6146(3) 0.00481(7) 0.0268(8) Uani 1 1 d . . .
O1 O 0.7100(3) 0.4831(2) 0.05215(6) 0.0469(7) Uani 1 1 d D . .
N2 N 0.5389(3) 0.6484(3) 0.09576(6) 0.0412(8) Uani 1 1 d . . .
N4 N 0.4582(2) 0.6593(3) 0.05846(6) 0.0305(7) Uani 1 1 d . . .
C7 C 0.5005(3) 0.5476(3) 0.02552(7) 0.0252(8) Uani 1 1 d . . .
C5 C 0.5736(3) 0.5652(3) -0.02148(7) 0.0266(8) Uani 1 1 d . . .
C3 C 0.7227(3) 0.7415(3) -0.03789(8) 0.0404(10) Uani 1 1 d . . .
H3 H 0.7734 0.7837 -0.0516 0.048 Uiso 1 1 calc R . .
C4 C 0.6514(3) 0.6326(3) -0.04231(8) 0.0343(9) Uani 1 1 d . . .
H4 H 0.6531 0.6012 -0.0592 0.041 Uiso 1 1 calc R . .
N3 N 0.4819(3) 0.6903(3) 0.08565(6) 0.0399(8) Uani 1 1 d . . .
C2 C 0.7200(3) 0.7910(3) -0.01229(8) 0.0394(10) Uani 1 1 d . . .
H2 H 0.7672 0.8662 -0.0096 0.047 Uiso 1 1 calc R . .
C8 C 0.5033(3) 0.5970(3) 0.05307(7) 0.0267(8) Uani 1 1 d . . .
C1 C 0.6494(3) 0.7298(3) 0.00817(8) 0.0354(9) Uani 1 1 d . . .
H1 H 0.6497 0.7637 0.0249 0.043 Uiso 1 1 calc R . .
O1W O 0.3333 0.6667 0.1400(3) 0.115(6) Uani 0.50 3 d SP . .
O2 O 0.676(8) 0.3654(16) -0.00036(12) 0.033(3) Uani 0.33 1 d PD . .
H2A H 0.6827 0.4289 -0.0004 0.039 Uiso 0.33 1 d PRD . .
H1A H 0.753(4) 0.537(3) 0.0422(10) 0.10(2) Uiso 1 1 d 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
Zn2 O1 1.937(3) 18_654 ?
Zn2 O1 1.937(3) . ?
Zn2 N1 2.041(3) 18_654 ?
Zn2 N1 2.041(3) . ?
Zn3 O2 1.931(6) 21 ?
Zn3 O2 1.931(6) 19_665 ?
Zn3 O2 1.931(6) 20_565 ?
Zn3 N4 2.012(3) 2_665 ?
Zn3 N4 2.012(3) 3_565 ?
Zn3 N4 2.012(3) . ?
Zn1 O2 1.961(6) 3_665 ?
Zn1 O2 1.961(6) 2_655 ?
Zn1 O2 1.961(6) . ?
Zn1 O1 1.961(3) 3_665 ?
Zn1 O1 1.961(3) 2_655 ?
Zn1 O1 1.961(3) . ?
N1 C8 1.321(4) . ?
N1 N2 1.365(4) . ?
C6 C7 1.402(5) . ?
C6 C1 1.426(5) . ?
C6 C5 1.436(5) . ?
O1 H1A 0.839(10) . ?
N2 N3 1.296(5) . ?
N4 C8 1.332(5) . ?
N4 N3 1.362(4) . ?
C7 C5 1.402(5) 19_665 ?
C7 C8 1.484(5) . ?
C5 C7 1.402(5) 19_665 ?
C5 C4 1.430(5) . ?
C3 C4 1.357(5) . ?
C3 C2 1.420(5) . ?
C3 H3 0.9300 . ?
C4 H4 0.9300 . ?
C2 C1 1.351(5) . ?
C2 H2 0.9300 . ?
C1 H1 0.9300 . ?
O2 O2 0.691(14) 2_655 ?
O2 O2 0.691(14) 3_665 ?
O2 Co3 1.931(6) 19_665 ?
O2 Zn3 1.931(6) 19_665 ?
O2 H2A 0.8474 . ?

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 Zn2 O1 109.90(19) 18_654 . ?
O1 Zn2 N1 116.82(13) 18_654 18_654 ?
O1 Zn2 N1 111.37(12) . 18_654 ?
O1 Zn2 N1 111.37(12) 18_654 . ?
O1 Zn2 N1 116.82(13) . . ?
N1 Zn2 N1 89.52(18) 18_654 . ?
O2 Zn3 O2 20.6(4) 21 19_665 ?
O2 Zn3 O2 20.6(4) 21 20_565 ?
O2 Zn3 O2 20.6(4) 19_665 20_565 ?
O2 Zn3 N4 108(2) 21 2_665 ?
O2 Zn3 N4 128.0(10) 19_665 2_665 ?
O2 Zn3 N4 113(3) 20_565 2_665 ?
O2 Zn3 N4 113(3) 21 3_565 ?
O2 Zn3 N4 108(2) 19_665 3_565 ?
O2 Zn3 N4 128.0(10) 20_565 3_565 ?
N4 Zn3 N4 101.61(10) 2_665 3_565 ?
O2 Zn3 N4 128.0(10) 21 . ?
O2 Zn3 N4 113(3) 19_665 . ?
O2 Zn3 N4 108(2) 20_565 . ?
N4 Zn3 N4 101.61(10) 2_665 . ?
N4 Zn3 N4 101.61(10) 3_565 . ?
O2 Zn1 O2 20.3(4) 3_665 2_655 ?
O2 Zn1 O2 20.3(4) 3_665 . ?
O2 Zn1 O2 20.3(4) 2_655 . ?
O2 Zn1 O1 96.1(3) 3_665 3_665 ?
O2 Zn1 O1 113(3) 2_655 3_665 ?
O2 Zn1 O1 113(3) . 3_665 ?
O2 Zn1 O1 113(3) 3_665 2_655 ?
O2 Zn1 O1 96.1(3) 2_655 2_655 ?
O2 Zn1 O1 113(3) . 2_655 ?
O1 Zn1 O1 111.07(9) 3_665 2_655 ?
O2 Zn1 O1 113(3) 3_665 . ?
O2 Zn1 O1 113(3) 2_655 . ?
O2 Zn1 O1 96.1(3) . . ?
O1 Zn1 O1 111.07(9) 3_665 . ?
O1 Zn1 O1 111.07(9) 2_655 . ?
C8 N1 N2 106.0(3) . . ?
C8 N1 Zn2 135.3(2) . . ?
N2 N1 Zn2 116.4(2) . . ?
C7 C6 C1 123.7(3) . . ?
C7 C6 C5 118.4(3) . . ?
C1 C6 C5 117.9(3) . . ?
Zn2 O1 Zn1 133.52(17) . . ?
Zn2 O1 H1A 107(4) . . ?
Zn1 O1 H1A 119(4) . . ?
N3 N2 N1 108.9(3) . . ?
C8 N4 N3 106.0(3) . . ?
C8 N4 Zn3 130.8(2) . . ?
N3 N4 Zn3 119.4(2) . . ?
C6 C7 C5 122.5(3) . 19_665 ?
C6 C7 C8 118.8(3) . . ?
C5 C7 C8 118.7(3) 19_665 . ?
C7 C5 C4 122.4(3) 19_665 . ?
C7 C5 C6 119.1(3) 19_665 . ?
C4 C5 C6 118.4(3) . . ?
C4 C3 C2 119.9(4) . . ?
C4 C3 H3 120.1 . . ?
C2 C3 H3 120.1 . . ?
C3 C4 C5 121.4(3) . . ?
C3 C4 H4 119.3 . . ?
C5 C4 H4 119.3 . . ?
N2 N3 N4 108.7(3) . . ?
C1 C2 C3 120.6(4) . . ?
C1 C2 H2 119.7 . . ?
C3 C2 H2 119.7 . . ?
N1 C8 N4 110.3(3) . . ?
N1 C8 C7 125.1(3) . . ?
N4 C8 C7 124.6(3) . . ?
C2 C1 C6 121.7(4) . . ?
C2 C1 H1 119.1 . . ?
C6 C1 H1 119.2 . . ?
O2 O2 O2 60.000(17) 2_655 3_665 ?
O2 O2 Co3 79.7(2) 2_655 19_665 ?
O2 O2 Co3 79.7(2) 3_665 19_665 ?
O2 O2 Zn3 79.7(2) 2_655 19_665 ?
O2 O2 Zn3 79.7(2) 3_665 19_665 ?
Co3 O2 Zn3 0.000(8) 19_665 19_665 ?
O2 O2 Zn1 79.85(19) 2_655 . ?
O2 O2 Zn1 79.9(2) 3_665 . ?
Co3 O2 Zn1 156.3(5) 19_665 . ?
Zn3 O2 Zn1 156.3(5) 19_665 . ?
O2 O2 H2A 138.3 2_655 . ?
O2 O2 H2A 161.7 3_665 . ?
Co3 O2 H2A 101.7 19_665 . ?
Zn3 O2 H2A 101.7 19_665 . ?
Zn1 O2 H2A 101.5 . . ?

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        24.97
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         0.462
_refine_diff_density_min         -0.542
_refine_diff_density_rms         0.066
_database_code_depnum_ccdc_archive 'CCDC 955704'
