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

#######################################################################
#
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#                                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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# 
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#  data retrieval see:
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#  from this site to visualise CIF-encoded structures and 
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data_final

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C26 H32 Cu N6 O8 S2'
_chemical_formula_weight         684.23

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'
S S 0.1246 0.1234 '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           61
_space_group_name_H-M_alt        'P b c a'
_space_group_name_Hall           '-P 2ac 2ab'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_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                   10.607(2)
_cell_length_b                   15.644(3)
_cell_length_c                   17.786(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2951.3(10)
_cell_measurement_temperature    298
_cell_measurement_reflns_used    8118
_cell_measurement_theta_min      2.910
_cell_measurement_theta_max      27.485
_cell_formula_units_Z            4

_exptl_crystal_description       Prism
_exptl_crystal_colour            Green
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.540
_exptl_crystal_F_000             1420
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          3.24
_exptl_crystal_size_mid          0.84
_exptl_crystal_size_min          0.52
_exptl_absorpt_coefficient_mu    0.941
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.589
_exptl_absorpt_correction_T_max  0.708
_exptl_absorpt_process_details   'HKL Scalepack (Otwinowski & Minor 1997)'

loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
0 -5 -6 0.150000
0 5 6 0.400000
-3 0 1 0.260000
3 0 -1 0.220000
3 -1 0 0.100000
-3 1 0 0.260000

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      298(2)
_diffrn_radiation_wavelength     0.7107
_diffrn_radiation_type           MoK\a
_diffrn_radiation_monochromator  'horizonally mounted graphite crystal'
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  KappaCCD
_diffrn_measurement_device       '95mm CCD camera on κ-goniostat'
_diffrn_measurement_method       CCD
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            10593
_diffrn_reflns_av_unetI/netI     0.0590
_diffrn_reflns_av_R_equivalents  0.0653
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_theta_min         2.989
_diffrn_reflns_theta_max         27.478
_diffrn_reflns_theta_full        26.000
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measured_fraction_theta_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_point_group_measured_fraction_full 0.989
_reflns_number_total             3339
_reflns_number_gt                2072
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'Collect (Bruker AXS BV, 1997-2004)'
_computing_cell_refinement       'HKL Scalepack (Otwinowski & Minor 1997)'
_computing_data_reduction        
'HKL Denzo and Scalepack (Otwinowski & Minor 1997)'
_computing_structure_solution    'SHELXT (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    'Ortep (Johnson, 1976)'
_computing_publication_material  'maXus(Mackay et al., 1999)'

_refine_special_details          
;
 ?
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0534P)²+1.4107P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3339
_refine_ls_number_parameters     199
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0904
_refine_ls_R_factor_gt           0.0458
_refine_ls_wR_factor_ref         0.1279
_refine_ls_wR_factor_gt          0.1079
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_restrained_S_all      1.029
_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_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu1 Cu 0.5000 0.5000 0.5000 0.03808(17) Uani 1 2 d S . P . .
O2 O 0.34254(19) 0.49834(11) 0.43748(12) 0.0473(5) Uani 1 1 d . . . . .
N5 N 0.2665(3) 0.68538(17) 0.34371(15) 0.0600(8) Uani 1 1 d . . . . .
N4 N 0.2448(2) 0.59895(15) 0.35936(14) 0.0498(7) Uani 1 1 d . . . . .
C3 C 0.3374(3) 0.57173(19) 0.40688(16) 0.0440(7) Uani 1 1 d . . . . .
C7 C 0.4210(3) 0.63938(18) 0.41511(16) 0.0439(7) Uani 1 1 d . . . . .
C6 C 0.3770(3) 0.7085(2) 0.37605(18) 0.0528(8) Uani 1 1 d . . . . .
N9 N 0.5241(2) 0.62779(15) 0.46710(15) 0.0419(6) Uani 1 1 d . . . . .
C10 C 0.6511(3) 0.6392(2) 0.4317(2) 0.0565(9) Uani 1 1 d . . . . .
H10A H 0.6614 0.6977 0.4166 0.085 Uiso 1 1 calc R U . . .
H10B H 0.6578 0.6028 0.3884 0.085 Uiso 1 1 calc R U . . .
H10C H 0.7155 0.6243 0.4673 0.085 Uiso 1 1 calc R U . . .
C11 C 0.5119(3) 0.6819(2) 0.5353(2) 0.0541(8) Uani 1 1 d . . . . .
H11A H 0.5023 0.7411 0.5202 0.065 Uiso 1 1 calc R U . . .
H11B H 0.5886 0.6775 0.5648 0.065 Uiso 1 1 calc R U . . .
S12 S 0.38028(10) 0.65194(5) 0.59279(5) 0.0597(3) Uani 1 1 d . . . . .
O13 O 0.3951(2) 0.55996(14) 0.60164(12) 0.0572(6) Uani 1 1 d . . . . .
O14 O 0.2659(3) 0.67310(17) 0.55197(16) 0.0813(8) Uani 1 1 d . . . . .
O15 O 0.3988(3) 0.69849(18) 0.66118(15) 0.0940(10) Uani 1 1 d . . . . .
C16 C 0.1240(3) 0.56066(19) 0.34812(16) 0.0450(7) Uani 1 1 d . . . . .
C17 C 0.0937(3) 0.5260(2) 0.27912(19) 0.0558(9) Uani 1 1 d . . . . .
H17A H 0.1511 0.5290 0.2397 0.067 Uiso 1 1 calc R U . . .
C18 C -0.0217(4) 0.4868(2) 0.2684(2) 0.0671(11) Uani 1 1 d . . . . .
H18A H -0.0431 0.4649 0.2215 0.081 Uiso 1 1 calc R U . . .
C19 C -0.1041(4) 0.4803(3) 0.3273(3) 0.0745(12) Uani 1 1 d . . . . .
H19A H -0.1810 0.4529 0.3204 0.089 Uiso 1 1 calc R U . . .
C20 C -0.0748(4) 0.5137(3) 0.3959(2) 0.0739(12) Uani 1 1 d . . . . .
H20A H -0.1319 0.5088 0.4354 0.089 Uiso 1 1 calc R U . . .
C21 C 0.0397(4) 0.5551(2) 0.40736(18) 0.0602(9) Uani 1 1 d . . . . .
H21A H 0.0592 0.5786 0.4540 0.072 Uiso 1 1 calc R U . . .
C22 C 0.1974(4) 0.7276(3) 0.2837(2) 0.0771(12) Uani 1 1 d . . . . .
H22A H 0.2144 0.7879 0.2850 0.116 Uiso 1 1 calc R U . . .
H22B H 0.1086 0.7181 0.2903 0.116 Uiso 1 1 calc R U . . .
H22C H 0.2235 0.7047 0.2361 0.116 Uiso 1 1 calc R U . . .
C23 C 0.4292(4) 0.7968(2) 0.3655(2) 0.0754(11) Uani 1 1 d . . . . .
H23A H 0.5111 0.8003 0.3881 0.113 Uiso 1 1 calc R U . . .
H23B H 0.3740 0.8376 0.3888 0.113 Uiso 1 1 calc R U . . .
H23C H 0.4357 0.8091 0.3127 0.113 Uiso 1 1 calc R U . . .


_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 O2 2.007(2) 5_666 ?
Cu1 O2 2.007(2) . ?
Cu1 N9 2.099(2) 5_666 ?
Cu1 N9 2.099(2) . ?
Cu1 O13 2.321(2) 5_666 ?
Cu1 O13 2.321(2) . ?
O2 C3 1.272(3) . ?
N5 C6 1.356(4) . ?
N5 N4 1.399(3) . ?
N5 C22 1.454(4) . ?
N4 C3 1.364(4) . ?
N4 C16 1.428(4) . ?
C3 C7 1.388(4) . ?
C7 C6 1.367(4) . ?
C7 N9 1.443(4) . ?
C6 C23 1.500(5) . ?
N9 C11 1.486(4) . ?
N9 C10 1.498(4) . ?
C10 H10A 0.9600 . ?
C10 H10B 0.9600 . ?
C10 H10C 0.9600 . ?
C11 S12 1.792(3) . ?
C11 H11A 0.9700 . ?
C11 H11B 0.9700 . ?
S12 O15 1.431(3) . ?
S12 O14 1.453(3) . ?
S12 O13 1.456(2) . ?
C16 C17 1.380(4) . ?
C16 C21 1.385(4) . ?
C17 C18 1.382(5) . ?
C17 H17A 0.9300 . ?
C18 C19 1.367(6) . ?
C18 H18A 0.9300 . ?
C19 C20 1.364(6) . ?
C19 H19A 0.9300 . ?
C20 C21 1.391(5) . ?
C20 H20A 0.9300 . ?
C21 H21A 0.9300 . ?
C22 H22A 0.9600 . ?
C22 H22B 0.9600 . ?
C22 H22C 0.9600 . ?
C23 H23A 0.9600 . ?
C23 H23B 0.9600 . ?
C23 H23C 0.9600 . ?

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
O2 Cu1 O2 180.0 5_666 . ?
O2 Cu1 N9 87.66(8) 5_666 5_666 ?
O2 Cu1 N9 92.34(8) . 5_666 ?
O2 Cu1 N9 92.34(8) 5_666 . ?
O2 Cu1 N9 87.66(8) . . ?
N9 Cu1 N9 180.00(13) 5_666 . ?
O2 Cu1 O13 92.17(9) 5_666 5_666 ?
O2 Cu1 O13 87.82(9) . 5_666 ?
N9 Cu1 O13 83.71(9) 5_666 5_666 ?
N9 Cu1 O13 96.29(9) . 5_666 ?
O2 Cu1 O13 87.82(9) 5_666 . ?
O2 Cu1 O13 92.18(9) . . ?
N9 Cu1 O13 96.29(9) 5_666 . ?
N9 Cu1 O13 83.71(9) . . ?
O13 Cu1 O13 180.0 5_666 . ?
C3 O2 Cu1 105.14(18) . . ?
C6 N5 N4 108.4(2) . . ?
C6 N5 C22 128.8(3) . . ?
N4 N5 C22 120.2(3) . . ?
C3 N4 N5 107.9(2) . . ?
C3 N4 C16 127.0(2) . . ?
N5 N4 C16 121.6(2) . . ?
O2 C3 N4 125.3(3) . . ?
O2 C3 C7 128.0(3) . . ?
N4 C3 C7 106.7(3) . . ?
C6 C7 C3 109.4(3) . . ?
C6 C7 N9 133.1(3) . . ?
C3 C7 N9 117.1(3) . . ?
N5 C6 C7 107.5(3) . . ?
N5 C6 C23 120.7(3) . . ?
C7 C6 C23 131.8(3) . . ?
C7 N9 C11 112.7(2) . . ?
C7 N9 C10 113.4(2) . . ?
C11 N9 C10 110.8(2) . . ?
C7 N9 Cu1 101.89(17) . . ?
C11 N9 Cu1 107.7(2) . . ?
C10 N9 Cu1 109.88(18) . . ?
N9 C10 H10A 109.5 . . ?
N9 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
N9 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?
N9 C11 S12 112.6(2) . . ?
N9 C11 H11A 109.1 . . ?
S12 C11 H11A 109.1 . . ?
N9 C11 H11B 109.1 . . ?
S12 C11 H11B 109.1 . . ?
H11A C11 H11B 107.8 . . ?
O15 S12 O14 115.05(18) . . ?
O15 S12 O13 113.34(16) . . ?
O14 S12 O13 111.70(16) . . ?
O15 S12 C11 104.15(17) . . ?
O14 S12 C11 107.82(17) . . ?
O13 S12 C11 103.65(14) . . ?
S12 O13 Cu1 111.54(11) . . ?
C17 C16 C21 120.1(3) . . ?
C17 C16 N4 119.9(3) . . ?
C21 C16 N4 120.0(3) . . ?
C16 C17 C18 120.2(3) . . ?
C16 C17 H17A 119.9 . . ?
C18 C17 H17A 119.9 . . ?
C19 C18 C17 119.6(4) . . ?
C19 C18 H18A 120.2 . . ?
C17 C18 H18A 120.2 . . ?
C20 C19 C18 120.8(4) . . ?
C20 C19 H19A 119.6 . . ?
C18 C19 H19A 119.6 . . ?
C19 C20 C21 120.5(3) . . ?
C19 C20 H20A 119.8 . . ?
C21 C20 H20A 119.8 . . ?
C16 C21 C20 118.8(3) . . ?
C16 C21 H21A 120.6 . . ?
C20 C21 H21A 120.6 . . ?
N5 C22 H22A 109.5 . . ?
N5 C22 H22B 109.5 . . ?
H22A C22 H22B 109.5 . . ?
N5 C22 H22C 109.5 . . ?
H22A C22 H22C 109.5 . . ?
H22B C22 H22C 109.5 . . ?
C6 C23 H23A 109.5 . . ?
C6 C23 H23B 109.5 . . ?
H23A C23 H23B 109.5 . . ?
C6 C23 H23C 109.5 . . ?
H23A C23 H23C 109.5 . . ?
H23B C23 H23C 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C6 N5 N4 C3 5.2(3) . . . . ?
C22 N5 N4 C3 168.3(3) . . . . ?
C6 N5 N4 C16 165.4(3) . . . . ?
C22 N5 N4 C16 -31.5(4) . . . . ?
Cu1 O2 C3 N4 -179.9(3) . . . . ?
Cu1 O2 C3 C7 -0.7(4) . . . . ?
N5 N4 C3 O2 174.4(3) . . . . ?
C16 N4 C3 O2 15.5(5) . . . . ?
N5 N4 C3 C7 -4.9(3) . . . . ?
C16 N4 C3 C7 -163.7(3) . . . . ?
O2 C3 C7 C6 -176.4(3) . . . . ?
N4 C3 C7 C6 2.9(4) . . . . ?
O2 C3 C7 N9 -3.1(5) . . . . ?
N4 C3 C7 N9 176.2(3) . . . . ?
N4 N5 C6 C7 -3.4(4) . . . . ?
C22 N5 C6 C7 -164.6(3) . . . . ?
N4 N5 C6 C23 176.7(3) . . . . ?
C22 N5 C6 C23 15.5(6) . . . . ?
C3 C7 C6 N5 0.4(4) . . . . ?
N9 C7 C6 N5 -171.5(3) . . . . ?
C3 C7 C6 C23 -179.7(4) . . . . ?
N9 C7 C6 C23 8.4(6) . . . . ?
C6 C7 N9 C11 60.8(4) . . . . ?
C3 C7 N9 C11 -110.6(3) . . . . ?
C6 C7 N9 C10 -66.0(4) . . . . ?
C3 C7 N9 C10 122.6(3) . . . . ?
C6 C7 N9 Cu1 176.0(3) . . . . ?
C3 C7 N9 Cu1 4.6(3) . . . . ?
C7 N9 C11 S12 66.5(3) . . . . ?
C10 N9 C11 S12 -165.3(2) . . . . ?
Cu1 N9 C11 S12 -45.1(3) . . . . ?
N9 C11 S12 O15 168.9(2) . . . . ?
N9 C11 S12 O14 -68.4(3) . . . . ?
N9 C11 S12 O13 50.1(3) . . . . ?
O15 S12 O13 Cu1 -140.24(16) . . . . ?
O14 S12 O13 Cu1 87.84(16) . . . . ?
C11 S12 O13 Cu1 -27.99(18) . . . . ?
C3 N4 C16 C17 -115.4(4) . . . . ?
N5 N4 C16 C17 88.4(4) . . . . ?
C3 N4 C16 C21 61.9(4) . . . . ?
N5 N4 C16 C21 -94.4(4) . . . . ?
C21 C16 C17 C18 1.0(5) . . . . ?
N4 C16 C17 C18 178.2(3) . . . . ?
C16 C17 C18 C19 -1.9(5) . . . . ?
C17 C18 C19 C20 1.4(6) . . . . ?
C18 C19 C20 C21 0.0(6) . . . . ?
C17 C16 C21 C20 0.4(5) . . . . ?
N4 C16 C21 C20 -176.8(3) . . . . ?
C19 C20 C21 C16 -0.9(5) . . . . ?

_refine_diff_density_max         0.405
_refine_diff_density_min         -0.293
_refine_diff_density_rms         0.059

_shelxl_version_number           2013-4



_database_code_depnum_ccdc_archive 'CCDC 986306'
