# 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
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  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_1

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C48 H46 Cl4 Cu4 N14 O28'
_chemical_formula_weight         1662.95

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'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           70
_space_group_name_H-M_alt        'F d d d'
_space_group_name_Hall           '-F 2uv 2vw'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+3/4, -y+3/4, z'
'-x+3/4, y, -z+3/4'
'x, -y+3/4, -z+3/4'
'x, y+1/2, z+1/2'
'-x+3/4, -y+5/4, z+1/2'
'-x+3/4, y+1/2, -z+5/4'
'x, -y+5/4, -z+5/4'
'x+1/2, y, z+1/2'
'-x+5/4, -y+3/4, z+1/2'
'-x+5/4, y, -z+5/4'
'x+1/2, -y+3/4, -z+5/4'
'x+1/2, y+1/2, z'
'-x+5/4, -y+5/4, z'
'-x+5/4, y+1/2, -z+3/4'
'x+1/2, -y+5/4, -z+3/4'
'-x, -y, -z'
'x-3/4, y-3/4, -z'
'x-3/4, -y, z-3/4'
'-x, y-3/4, z-3/4'
'-x, -y+1/2, -z+1/2'
'x-3/4, y-1/4, -z+1/2'
'x-3/4, -y+1/2, z-1/4'
'-x, y-1/4, z-1/4'
'-x+1/2, -y, -z+1/2'
'x-1/4, y-3/4, -z+1/2'
'x-1/4, -y, z-1/4'
'-x+1/2, y-3/4, z-1/4'
'-x+1/2, -y+1/2, -z'
'x-1/4, y-1/4, -z'
'x-1/4, -y+1/2, z-3/4'
'-x+1/2, y-1/4, z-3/4'

_cell_length_a                   14.6315(16)
_cell_length_b                   24.776(3)
_cell_length_c                   33.169(4)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     12024(2)
_cell_formula_units_Z            8
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    4724
_cell_measurement_theta_min      2.45
_cell_measurement_theta_max      24.52

_exptl_crystal_description       pole
_exptl_crystal_colour            'dark green'
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.837
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             6720
_exptl_absorpt_coefficient_mu    1.676
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.630
_exptl_absorpt_correction_T_max  0.851
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      296(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  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        2.5
_diffrn_reflns_number            16212
_diffrn_reflns_av_R_equivalents  0.0394
_diffrn_reflns_av_unetI/netI     0.0292
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_theta_min         2.05
_diffrn_reflns_theta_max         26.07
_reflns_number_total             2972
_reflns_number_gt                2483
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SHELXTL'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_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)+(0.0491P)²+249.6704P] 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         2972
_refine_ls_number_parameters     253
_refine_ls_number_restraints     10
_refine_ls_R_factor_all          0.0688
_refine_ls_R_factor_gt           0.0573
_refine_ls_wR_factor_ref         0.1578
_refine_ls_wR_factor_gt          0.1519
_refine_ls_goodness_of_fit_ref   1.181
_refine_ls_restrained_S_all      1.190
_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
Cu1 Cu 0.56113(4) 0.17568(2) 0.590361(18) 0.0250(2) Uani 1 1 d . . .
C1 C 0.5078(5) 0.0799(2) 0.54442(19) 0.0459(16) Uani 1 1 d . . .
C2 C 0.4293(6) 0.0528(3) 0.5215(3) 0.078(3) Uani 1 1 d . . .
H2A H 0.4539 0.0336 0.4985 0.093 Uiso 1 1 calc R . .
H2B H 0.4001 0.0266 0.5390 0.093 Uiso 1 1 calc R . .
C3 C 0.3596(5) 0.1057(3) 0.4685(3) 0.072(3) Uani 1 1 d . . .
H3A H 0.4023 0.0904 0.4512 0.087 Uiso 1 1 calc R . .
C4 C 0.3005(5) 0.1140(2) 0.5329(2) 0.0472(16) Uani 1 1 d . . .
H4A H 0.3023 0.1046 0.5600 0.057 Uiso 1 1 calc R . .
C5 C 0.2969(4) 0.1420(3) 0.4537(2) 0.0540(19) Uani 1 1 d . . .
H5A H 0.2974 0.1512 0.4266 0.065 Uiso 1 1 calc R . .
C6 C 0.2369(4) 0.1498(2) 0.51971(19) 0.0398(14) Uani 1 1 d . . .
H6A H 0.1953 0.1646 0.5379 0.048 Uiso 1 1 calc R . .
C7 C 0.2333(4) 0.1647(2) 0.47930(18) 0.0355(13) Uani 1 1 d . . .
C8 C 0.1612(4) 0.2016(2) 0.46360(16) 0.0288(11) Uani 1 1 d . . .
C9 C 0.1437(4) 0.2044(3) 0.42270(18) 0.0418(15) Uani 1 1 d . . .
H9A H 0.1773 0.1834 0.4048 0.050 Uiso 1 1 calc R . .
C10 C 0.1078(4) 0.2335(2) 0.48844(16) 0.0325(12) Uani 1 1 d . . .
H10A H 0.1169 0.2326 0.5162 0.039 Uiso 1 1 calc R . .
C11 C 0.0766(4) 0.2382(3) 0.40847(17) 0.0384(14) Uani 1 1 d . . .
H11A H 0.0657 0.2394 0.3809 0.046 Uiso 1 1 calc R . .
C12 C 0.0417(4) 0.2663(2) 0.47258(17) 0.0325(12) Uani 1 1 d . . .
H12A H 0.0063 0.2870 0.4900 0.039 Uiso 1 1 calc R . .
N1 N 0.6250 0.2289(3) 0.6250 0.052(2) Uani 1 2 d S . .
N2 N 0.6250 0.2767(3) 0.6250 0.0355(15) Uani 1 2 d S . .
N3 N 0.6250 0.3228(3) 0.6250 0.066(3) Uani 1 2 d S . .
N4 N 0.3600(4) 0.0922(2) 0.50743(19) 0.0591(18) Uani 1 1 d . . .
N5 N 0.0261(3) 0.26955(17) 0.43273(13) 0.0280(10) Uani 1 1 d . . .
O1 O 0.6250 0.1250 0.6250 0.0205(13) Uani 1 4 d S . .
O2 O 0.4861(3) 0.12220(16) 0.56270(13) 0.0424(10) Uani 1 1 d . . .
O3 O 0.5818(3) 0.05592(19) 0.54412(14) 0.0534(13) Uani 1 1 d . . .
O4 O 0.649(3) 0.1345(15) 0.4055(4) 0.145(14) Uani 0.50 1 d P A -1
O5 O 0.5533(17) 0.1553(11) 0.4574(8) 0.114(4) Uani 0.50 1 d P A -1
O6 O 0.6849(17) 0.1079(12) 0.4694(8) 0.114(4) Uani 0.50 1 d P A -1
O7 O 0.5665(18) 0.0680(12) 0.4294(10) 0.209(8) Uani 0.50 1 d P A -1
O8 O 0.4135(13) 0.2175(5) 0.3708(8) 0.209(8) Uani 0.50 1 d PD B -1
O9 O 0.5002(9) 0.2942(9) 0.3843(8) 0.209(8) Uani 0.50 1 d PD B -1
O10 O 0.3739(15) 0.2981(10) 0.3467(5) 0.209(8) Uani 0.50 1 d PD B -1
O11 O 0.3548(15) 0.2786(9) 0.4133(5) 0.209(8) Uani 0.50 1 d PD B -1
Cl1 Cl 0.6217(15) 0.1137(5) 0.44000(13) 0.093(4) Uani 0.50 1 d P A -1
Cl2 Cl 0.4140(4) 0.2724(2) 0.38084(17) 0.102(2) Uani 0.50 1 d PD B -1
O12 O 0.530(2) 0.2508(8) 0.4242(6) 0.190(12) Uani 0.50 1 d P C 2
O13 O 0.524(4) 0.3750 0.3750 0.34(3) Uani 0.50 2 d SP D 2


_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
Cu1 O1 1.9416(6) . ?
Cu1 O2 1.950(4) . ?
Cu1 N1 1.983(5) . ?
Cu1 N5 2.014(4) 29_556 ?
Cu1 O3 2.240(4) 14_545 ?
Cu1 Cu1 2.9620(12) 11 ?
C1 O3 1.236(7) . ?
C1 O2 1.251(7) . ?
C1 C2 1.532(9) . ?
C2 N4 1.482(8) . ?
C2 H2A 0.9700 . ?
C2 H2B 0.9700 . ?
C3 N4 1.332(11) . ?
C3 C5 1.375(9) . ?
C3 H3A 0.9300 . ?
C4 N4 1.329(9) . ?
C4 C6 1.359(8) . ?
C4 H4A 0.9300 . ?
C5 C7 1.379(8) . ?
C5 H5A 0.9300 . ?
C6 C7 1.391(8) . ?
C6 H6A 0.9300 . ?
C7 C8 1.489(7) . ?
C8 C10 1.383(7) . ?
C8 C9 1.382(8) . ?
C9 C11 1.375(8) . ?
C9 H9A 0.9300 . ?
C10 C12 1.368(7) . ?
C10 H10A 0.9300 . ?
C11 N5 1.339(7) . ?
C11 H11A 0.9300 . ?
C12 N5 1.344(7) . ?
C12 H12A 0.9300 . ?
N1 N2 1.184(10) . ?
N1 Cu1 1.983(5) 11 ?
N2 N3 1.141(10) . ?
N5 Cu1 2.015(4) 29_556 ?
O1 Cu1 1.9416(6) 14_545 ?
O1 Cu1 1.9417(6) 11 ?
O1 Cu1 1.9417(6) 8_545 ?
O3 Cu1 2.240(4) 14_545 ?
O4 Cl1 1.316(19) . ?
O5 Cl1 1.55(3) . ?
O6 Cl1 1.35(3) . ?
O7 Cl1 1.44(3) . ?
O8 Cl2 1.402(9) . ?
O9 Cl2 1.376(9) . ?
O10 Cl2 1.426(9) . ?
O11 Cl2 1.389(9) . ?

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 Cu1 O2 96.31(12) . . ?
O1 Cu1 N1 81.99(15) . . ?
O2 Cu1 N1 171.80(14) . . ?
O1 Cu1 N5 164.93(13) . 29_556 ?
O2 Cu1 N5 85.53(17) . 29_556 ?
N1 Cu1 N5 94.06(19) . 29_556 ?
O1 Cu1 O3 101.54(11) . 14_545 ?
O2 Cu1 O3 102.1(2) . 14_545 ?
N1 Cu1 O3 86.08(15) . 14_545 ?
N5 Cu1 O3 92.64(17) 29_556 14_545 ?
O1 Cu1 Cu1 40.292(18) . 11 ?
O2 Cu1 Cu1 136.08(12) . 11 ?
N1 Cu1 Cu1 41.69(15) . 11 ?
N5 Cu1 Cu1 134.02(12) 29_556 11 ?
O3 Cu1 Cu1 95.15(13) 14_545 11 ?
O3 C1 O2 129.0(6) . . ?
O3 C1 C2 116.2(5) . . ?
O2 C1 C2 114.7(5) . . ?
N4 C2 C1 112.4(5) . . ?
N4 C2 H2A 109.1 . . ?
C1 C2 H2A 109.1 . . ?
N4 C2 H2B 109.1 . . ?
C1 C2 H2B 109.1 . . ?
H2A C2 H2B 107.9 . . ?
N4 C3 C5 120.9(7) . . ?
N4 C3 H3A 119.6 . . ?
C5 C3 H3A 119.6 . . ?
N4 C4 C6 120.7(6) . . ?
N4 C4 H4A 119.7 . . ?
C6 C4 H4A 119.7 . . ?
C7 C5 C3 119.8(7) . . ?
C7 C5 H5A 120.1 . . ?
C3 C5 H5A 120.1 . . ?
C4 C6 C7 120.6(6) . . ?
C4 C6 H6A 119.7 . . ?
C7 C6 H6A 119.7 . . ?
C5 C7 C6 117.3(6) . . ?
C5 C7 C8 120.9(6) . . ?
C6 C7 C8 121.7(5) . . ?
C10 C8 C9 116.8(5) . . ?
C10 C8 C7 122.8(5) . . ?
C9 C8 C7 120.4(5) . . ?
C11 C9 C8 120.0(5) . . ?
C11 C9 H9A 120.0 . . ?
C8 C9 H9A 120.0 . . ?
C12 C10 C8 120.6(5) . . ?
C12 C10 H10A 119.7 . . ?
C8 C10 H10A 119.7 . . ?
N5 C11 C9 122.7(5) . . ?
N5 C11 H11A 118.6 . . ?
C9 C11 H11A 118.6 . . ?
N5 C12 C10 122.3(5) . . ?
N5 C12 H12A 118.8 . . ?
C10 C12 H12A 118.8 . . ?
N2 N1 Cu1 131.70(15) . . ?
N2 N1 Cu1 131.69(15) . 11 ?
Cu1 N1 Cu1 96.6(3) . 11 ?
N3 N2 N1 180.000(3) . . ?
C4 N4 C3 120.7(6) . . ?
C4 N4 C2 121.0(7) . . ?
C3 N4 C2 118.3(7) . . ?
C12 N5 C11 117.5(5) . . ?
C12 N5 Cu1 121.5(3) . 29_556 ?
C11 N5 Cu1 120.7(4) . 29_556 ?
Cu1 O1 Cu1 107.44(4) 14_545 . ?
Cu1 O1 Cu1 122.46(4) 14_545 11 ?
Cu1 O1 Cu1 99.42(4) . 11 ?
Cu1 O1 Cu1 99.42(4) 14_545 8_545 ?
Cu1 O1 Cu1 122.46(4) . 8_545 ?
Cu1 O1 Cu1 107.44(4) 11 8_545 ?
C1 O2 Cu1 130.9(4) . . ?
C1 O3 Cu1 120.6(4) . 14_545 ?
O4 Cl1 O6 118(3) . . ?
O4 Cl1 O7 105.4(19) . . ?
O6 Cl1 O7 119(2) . . ?
O4 Cl1 O5 105(3) . . ?
O6 Cl1 O5 104.2(12) . . ?
O7 Cl1 O5 104.6(19) . . ?
O9 Cl2 O11 117.8(12) . . ?
O9 Cl2 O8 113.8(11) . . ?
O11 Cl2 O8 106.7(11) . . ?
O9 Cl2 O10 105.6(12) . . ?
O11 Cl2 O10 108.1(11) . . ?
O8 Cl2 O10 104.0(11) . . ?

_diffrn_measured_fraction_theta_max 0.997
_diffrn_reflns_theta_full        26.07
_diffrn_measured_fraction_theta_full 0.997
_refine_diff_density_max         0.723
_refine_diff_density_min         -0.557
_refine_diff_density_rms         0.101
_database_code_depnum_ccdc_archive 'CCDC 1006282'
#######################################################################
#
#                 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
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  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_2

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C28 H28 Cu7 N46 O4'
_chemical_formula_weight         1517.74

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'
Cu Cu 0.3201 1.2651 '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                   10.677(2)
_cell_length_b                   11.349(2)
_cell_length_c                   13.181(3)
_cell_angle_alpha                115.25(3)
_cell_angle_beta                 96.79(3)
_cell_angle_gamma                106.40(3)
_cell_volume                     1332.3(5)
_cell_formula_units_Z            1
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    2165
_cell_measurement_theta_min      2.36
_cell_measurement_theta_max      26.96

_exptl_crystal_description       prism
_exptl_crystal_colour            green
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.892
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             753
_exptl_absorpt_coefficient_mu    2.824
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.4845
_exptl_absorpt_correction_T_max  0.7654
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      293(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  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        2.5
_diffrn_reflns_number            6065
_diffrn_reflns_av_R_equivalents  0.0408
_diffrn_reflns_av_unetI/netI     0.0756
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         1.78
_diffrn_reflns_theta_max         26.00
_reflns_number_total             5094
_reflns_number_gt                3376
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SHELXTL'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_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)+(0.0379P)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    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         5094
_refine_ls_number_parameters     385
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0627
_refine_ls_R_factor_gt           0.0376
_refine_ls_wR_factor_ref         0.0855
_refine_ls_wR_factor_gt          0.0797
_refine_ls_goodness_of_fit_ref   0.861
_refine_ls_restrained_S_all      0.861
_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
Cu1 Cu 0.39776(5) 0.51243(6) 0.57655(4) 0.02986(15) Uani 1 1 d . . .
Cu2 Cu 0.47311(5) 0.81826(6) 0.87369(5) 0.03144(15) Uani 1 1 d . . .
Cu3 Cu 0.22754(5) 0.89833(6) 0.93047(4) 0.02796(14) Uani 1 1 d . . .
O1 O 0.5225(3) 0.5284(4) 0.7338(3) 0.0520(10) Uani 1 1 d . . .
O2 O 0.5624(3) 0.7087(3) 0.9110(3) 0.0406(8) Uani 1 1 d . . .
N1 N 0.4599(4) 0.3701(4) 0.4613(3) 0.0395(10) Uani 1 1 d . . .
N2 N 0.4403(4) 0.2533(5) 0.4481(3) 0.0356(9) Uani 1 1 d . . .
N3 N 0.4189(5) 0.1429(5) 0.4341(4) 0.0595(12) Uani 1 1 d . . .
N4 N 0.3400(4) 0.6669(4) 0.6690(3) 0.0410(10) Uani 1 1 d . . .
N5 N 0.2242(4) 0.6540(4) 0.6652(3) 0.0385(10) Uani 1 1 d . . .
N6 N 0.1164(4) 0.6487(5) 0.6683(4) 0.0682(14) Uani 1 1 d . . .
N7 N 0.3123(3) 0.7653(4) 0.9329(3) 0.0324(9) Uani 1 1 d . . .
N8 N 0.2663(4) 0.6604(5) 0.9404(3) 0.0377(9) Uani 1 1 d . . .
N9 N 0.2249(6) 0.5619(5) 0.9483(5) 0.0763(16) Uani 1 1 d . . .
N10 N 0.3899(3) 0.9586(4) 0.8811(3) 0.0314(9) Uani 1 1 d . . .
N11 N 0.4219(4) 1.0318(4) 0.8360(3) 0.0328(9) Uani 1 1 d . . .
N12 N 0.4545(5) 1.0988(5) 0.7942(4) 0.0632(13) Uani 1 1 d . . .
N13 N 0.6375(3) 0.9194(4) 0.8474(3) 0.0397(10) Uani 1 1 d . . .
N14 N 0.7227(3) 0.8728(4) 0.8231(3) 0.0323(9) Uani 1 1 d . . .
N15 N 0.8118(4) 0.8355(4) 0.8047(3) 0.0423(10) Uani 1 1 d . . .
N16 N 0.0657(3) 0.8437(4) 0.9881(3) 0.0300(8) Uani 1 1 d . . .
N17 N 0.0791(4) 0.8144(5) 1.0663(4) 0.0432(10) Uani 1 1 d . . .
N18 N 0.0913(5) 0.7858(7) 1.1384(5) 0.0887(19) Uani 1 1 d . . .
N19 N 0.1346(3) 1.0181(4) 0.9117(3) 0.0334(9) Uani 1 1 d . . .
N20 N 0.1637(4) 1.0942(4) 0.8694(3) 0.0323(9) Uani 1 1 d . . .
N21 N 0.1907(5) 1.1672(5) 0.8313(4) 0.0607(13) Uani 1 1 d . . .
N22 N 0.7319(3) 0.4701(4) 0.7930(3) 0.0299(8) Uani 1 1 d . . .
N23 N 1.2322(3) 0.3656(4) 0.5618(3) 0.0313(9) Uani 1 1 d . . .
C1 C 0.5852(4) 0.6078(5) 0.8367(4) 0.0326(10) Uani 1 1 d . . .
C2 C 0.7102(4) 0.5871(5) 0.8859(3) 0.0338(11) Uani 1 1 d . . .
H2A H 0.7896 0.6723 0.9167 0.041 Uiso 1 1 calc R . .
H2B H 0.6964 0.5669 0.9491 0.041 Uiso 1 1 calc R . .
C3 C 0.6614(5) 0.3400(5) 0.7693(4) 0.0387(11) Uani 1 1 d . . .
H3A H 0.6101 0.3250 0.8180 0.046 Uiso 1 1 calc R . .
C4 C 0.8078(4) 0.4939(5) 0.7251(4) 0.0407(12) Uani 1 1 d . . .
H4A H 0.8586 0.5856 0.7443 0.049 Uiso 1 1 calc R . .
C5 C 0.8115(4) 0.3845(5) 0.6274(4) 0.0383(11) Uani 1 1 d . . .
H5A H 0.8645 0.4019 0.5806 0.046 Uiso 1 1 calc R . .
C6 C 0.6642(4) 0.2280(5) 0.6734(4) 0.0378(11) Uani 1 1 d . . .
H6A H 0.6168 0.1375 0.6590 0.045 Uiso 1 1 calc R . .
C7 C 0.7355(4) 0.2470(5) 0.5984(4) 0.0319(10) Uani 1 1 d . . .
C8 C 0.7322(4) 0.1228(5) 0.4914(4) 0.0395(12) Uani 1 1 d . . .
H8A H 0.7421 0.1481 0.4304 0.047 Uiso 1 1 calc R . .
H8B H 0.6445 0.0476 0.4643 0.047 Uiso 1 1 calc R . .
C9 C 0.8441(4) 0.0700(5) 0.5131(4) 0.0418(12) Uani 1 1 d . . .
H9A H 0.8423 0.0570 0.5811 0.050 Uiso 1 1 calc R . .
H9B H 0.8268 -0.0203 0.4466 0.050 Uiso 1 1 calc R . .
C10 C 0.9827(4) 0.1705(4) 0.5322(4) 0.0316(10) Uani 1 1 d . . .
C11 C 1.0719(4) 0.2613(5) 0.6410(4) 0.0379(11) Uani 1 1 d . . .
H11A H 1.0501 0.2589 0.7066 0.046 Uiso 1 1 calc R . .
C12 C 1.0238(4) 0.1786(5) 0.4390(4) 0.0413(12) Uani 1 1 d . . .
H12A H 0.9678 0.1174 0.3636 0.050 Uiso 1 1 calc R . .
C13 C 1.1447(4) 0.2750(5) 0.4568(4) 0.0381(12) Uani 1 1 d . . .
H13A H 1.1682 0.2784 0.3921 0.046 Uiso 1 1 calc R . .
C14 C 1.1947(4) 0.3566(5) 0.6525(4) 0.0378(11) Uani 1 1 d . . .
H14A H 1.2539 0.4172 0.7267 0.045 Uiso 1 1 calc R . .
Cu4 Cu 0.0000 1.0000 1.0000 0.02865(19) Uani 1 2 d S . .


_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
Cu1 N4 1.976(4) . ?
Cu1 N23 1.979(4) 1_455 ?
Cu1 N1 1.985(4) 2_666 ?
Cu1 N1 2.026(3) . ?
Cu1 O1 2.234(3) . ?
Cu2 O2 1.943(3) . ?
Cu2 N13 1.966(4) . ?
Cu2 N10 2.006(3) . ?
Cu2 N7 2.013(4) . ?
Cu2 N4 2.451(4) . ?
Cu3 N10 1.968(3) . ?
Cu3 N19 1.971(3) . ?
Cu3 N7 1.976(3) . ?
Cu3 N16 2.014(3) . ?
Cu3 Cu4 3.0464(9) . ?
O1 C1 1.225(5) . ?
O2 C1 1.259(5) . ?
N1 N2 1.212(5) . ?
N1 Cu1 1.985(4) 2_666 ?
N2 N3 1.135(5) . ?
N4 N5 1.195(5) . ?
N5 N6 1.142(5) . ?
N7 N8 1.204(5) . ?
N8 N9 1.135(6) . ?
N10 N11 1.212(5) . ?
N11 N12 1.122(5) . ?
N13 N14 1.186(4) . ?
N14 N15 1.157(4) . ?
N16 N17 1.216(5) . ?
N16 Cu4 2.038(3) . ?
N17 N18 1.132(5) . ?
N19 N20 1.206(5) . ?
N19 Cu4 1.973(3) . ?
N20 N21 1.130(5) . ?
N22 C3 1.330(6) . ?
N22 C4 1.336(5) . ?
N22 C2 1.474(5) . ?
N23 C13 1.336(5) . ?
N23 C14 1.339(5) . ?
N23 Cu1 1.979(4) 1_655 ?
C1 C2 1.536(5) . ?
C2 H2A 0.9700 . ?
C2 H2B 0.9700 . ?
C3 C6 1.369(6) . ?
C3 H3A 0.9300 . ?
C4 C5 1.369(6) . ?
C4 H4A 0.9300 . ?
C5 C7 1.393(6) . ?
C5 H5A 0.9300 . ?
C6 C7 1.367(6) . ?
C6 H6A 0.9300 . ?
C7 C8 1.497(6) . ?
C8 C9 1.529(6) . ?
C8 H8A 0.9700 . ?
C8 H8B 0.9700 . ?
C9 C10 1.505(6) . ?
C9 H9A 0.9700 . ?
C9 H9B 0.9700 . ?
C10 C11 1.375(6) . ?
C10 C12 1.382(6) . ?
C11 C14 1.388(6) . ?
C11 H11A 0.9300 . ?
C12 C13 1.353(6) . ?
C12 H12A 0.9300 . ?
C13 H13A 0.9300 . ?
C14 H14A 0.9300 . ?
Cu4 N19 1.973(3) 2_577 ?
Cu4 N16 2.038(3) 2_577 ?
Cu4 Cu3 3.0464(9) 2_577 ?

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
N4 Cu1 N23 93.40(15) . 1_455 ?
N4 Cu1 N1 94.44(16) . 2_666 ?
N23 Cu1 N1 162.36(15) 1_455 2_666 ?
N4 Cu1 N1 169.13(17) . . ?
N23 Cu1 N1 92.78(15) 1_455 . ?
N1 Cu1 N1 77.24(18) 2_666 . ?
N4 Cu1 O1 93.77(14) . . ?
N23 Cu1 O1 95.07(15) 1_455 . ?
N1 Cu1 O1 100.15(15) 2_666 . ?
N1 Cu1 O1 94.58(14) . . ?
O2 Cu2 N13 91.59(14) . . ?
O2 Cu2 N10 164.82(14) . . ?
N13 Cu2 N10 91.96(15) . . ?
O2 Cu2 N7 95.80(14) . . ?
N13 Cu2 N7 165.04(15) . . ?
N10 Cu2 N7 77.65(14) . . ?
O2 Cu2 N4 105.41(13) . . ?
N13 Cu2 N4 97.75(15) . . ?
N10 Cu2 N4 88.72(14) . . ?
N7 Cu2 N4 92.81(14) . . ?
N10 Cu3 N19 100.10(15) . . ?
N10 Cu3 N7 79.43(14) . . ?
N19 Cu3 N7 174.40(15) . . ?
N10 Cu3 N16 177.47(15) . . ?
N19 Cu3 N16 79.73(14) . . ?
N7 Cu3 N16 100.99(15) . . ?
N10 Cu3 Cu4 137.71(10) . . ?
N19 Cu3 Cu4 39.45(10) . . ?
N7 Cu3 Cu4 142.18(11) . . ?
N16 Cu3 Cu4 41.55(10) . . ?
C1 O1 Cu1 143.9(3) . . ?
C1 O2 Cu2 124.5(3) . . ?
N2 N1 Cu1 129.0(3) . 2_666 ?
N2 N1 Cu1 125.2(3) . . ?
Cu1 N1 Cu1 102.76(18) 2_666 . ?
N3 N2 N1 178.4(5) . . ?
N5 N4 Cu1 123.9(3) . . ?
N5 N4 Cu2 107.4(3) . . ?
Cu1 N4 Cu2 115.68(17) . . ?
N6 N5 N4 175.8(5) . . ?
N8 N7 Cu3 129.8(3) . . ?
N8 N7 Cu2 127.1(3) . . ?
Cu3 N7 Cu2 101.10(17) . . ?
N9 N8 N7 179.0(6) . . ?
N11 N10 Cu3 133.0(3) . . ?
N11 N10 Cu2 122.8(3) . . ?
Cu3 N10 Cu2 101.65(17) . . ?
N12 N11 N10 178.2(5) . . ?
N14 N13 Cu2 122.4(3) . . ?
N15 N14 N13 175.7(4) . . ?
N17 N16 Cu3 118.9(3) . . ?
N17 N16 Cu4 122.8(3) . . ?
Cu3 N16 Cu4 97.50(16) . . ?
N18 N17 N16 179.4(5) . . ?
N20 N19 Cu3 128.6(3) . . ?
N20 N19 Cu4 129.7(3) . . ?
Cu3 N19 Cu4 101.15(17) . . ?
N21 N20 N19 178.9(5) . . ?
C3 N22 C4 120.9(4) . . ?
C3 N22 C2 118.5(4) . . ?
C4 N22 C2 120.1(4) . . ?
C13 N23 C14 116.1(4) . . ?
C13 N23 Cu1 119.5(3) . 1_655 ?
C14 N23 Cu1 124.1(3) . 1_655 ?
O1 C1 O2 128.7(4) . . ?
O1 C1 C2 118.1(4) . . ?
O2 C1 C2 113.2(4) . . ?
N22 C2 C1 109.7(3) . . ?
N22 C2 H2A 109.7 . . ?
C1 C2 H2A 109.7 . . ?
N22 C2 H2B 109.7 . . ?
C1 C2 H2B 109.7 . . ?
H2A C2 H2B 108.2 . . ?
N22 C3 C6 120.2(4) . . ?
N22 C3 H3A 119.9 . . ?
C6 C3 H3A 119.9 . . ?
N22 C4 C5 120.6(4) . . ?
N22 C4 H4A 119.7 . . ?
C5 C4 H4A 119.7 . . ?
C4 C5 C7 119.8(4) . . ?
C4 C5 H5A 120.1 . . ?
C7 C5 H5A 120.1 . . ?
C7 C6 C3 121.1(4) . . ?
C7 C6 H6A 119.5 . . ?
C3 C6 H6A 119.5 . . ?
C6 C7 C5 117.3(4) . . ?
C6 C7 C8 120.1(4) . . ?
C5 C7 C8 122.6(4) . . ?
C7 C8 C9 112.6(4) . . ?
C7 C8 H8A 109.1 . . ?
C9 C8 H8A 109.1 . . ?
C7 C8 H8B 109.1 . . ?
C9 C8 H8B 109.1 . . ?
H8A C8 H8B 107.8 . . ?
C10 C9 C8 112.0(4) . . ?
C10 C9 H9A 109.2 . . ?
C8 C9 H9A 109.2 . . ?
C10 C9 H9B 109.2 . . ?
C8 C9 H9B 109.2 . . ?
H9A C9 H9B 107.9 . . ?
C11 C10 C12 116.7(4) . . ?
C11 C10 C9 122.8(4) . . ?
C12 C10 C9 120.5(4) . . ?
C10 C11 C14 119.5(4) . . ?
C10 C11 H11A 120.2 . . ?
C14 C11 H11A 120.2 . . ?
C13 C12 C10 120.6(4) . . ?
C13 C12 H12A 119.7 . . ?
C10 C12 H12A 119.7 . . ?
N23 C13 C12 123.8(4) . . ?
N23 C13 H13A 118.1 . . ?
C12 C13 H13A 118.1 . . ?
N23 C14 C11 123.2(4) . . ?
N23 C14 H14A 118.4 . . ?
C11 C14 H14A 118.4 . . ?
N19 Cu4 N19 180.000(2) . 2_577 ?
N19 Cu4 N16 100.90(14) . 2_577 ?
N19 Cu4 N16 79.10(14) 2_577 2_577 ?
N19 Cu4 N16 79.10(14) . . ?
N19 Cu4 N16 100.90(14) 2_577 . ?
N16 Cu4 N16 180.000(2) 2_577 . ?
N19 Cu4 Cu3 39.40(10) . . ?
N19 Cu4 Cu3 140.60(10) 2_577 . ?
N16 Cu4 Cu3 139.05(10) 2_577 . ?
N16 Cu4 Cu3 40.95(10) . . ?
N19 Cu4 Cu3 140.60(10) . 2_577 ?
N19 Cu4 Cu3 39.40(10) 2_577 2_577 ?
N16 Cu4 Cu3 40.95(10) 2_577 2_577 ?
N16 Cu4 Cu3 139.05(10) . 2_577 ?
Cu3 Cu4 Cu3 180.000(1) . 2_577 ?

_diffrn_measured_fraction_theta_max 0.971
_diffrn_reflns_theta_full        26.00
_diffrn_measured_fraction_theta_full 0.971
_refine_diff_density_max         0.642
_refine_diff_density_min         -0.407
_refine_diff_density_rms         0.118
_database_code_depnum_ccdc_archive 'CCDC 1006283'
