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


data_Compound_1

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C18 H14 Cu N2 O4 S, 2(H2O)'
_chemical_formula_sum            'C18 H18 Cu N2 O6 S'
_chemical_formula_weight         453.956

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'
Cu Cu 0.3201 1.2651 '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'
H H 0.0000 0.0000 '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                   10.0921(3)
_cell_length_b                   10.4958(3)
_cell_length_c                   10.8431(3)
_cell_angle_alpha                86.403(2)
_cell_angle_beta                 79.041(2)
_cell_angle_gamma                81.993(2)
_cell_volume                     1115.84(6)
_cell_formula_units_Z            2
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    365
_cell_measurement_theta_min      7.50
_cell_measurement_theta_max      25.39

_exptl_crystal_description       block
_exptl_crystal_colour            blue
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.37
_exptl_crystal_size_min          0.24
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.339
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             458
_exptl_absorpt_coefficient_mu    1.104
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.635
_exptl_absorpt_correction_T_max  0.767
_exptl_absorpt_process_details   'SADABS (Sheldrick, 1997)'

_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  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            6023
_diffrn_reflns_av_R_equivalents  0.0376
_diffrn_reflns_av_sigmaI/netI    0.0637
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         7.51
_diffrn_reflns_theta_max         28.71
_reflns_number_total             5772
_reflns_number_gt                3450
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
; 
loop_
  _platon_squeeze_void_nr
  _platon_squeeze_void_average_x
  _platon_squeeze_void_average_y
  _platon_squeeze_void_average_z
  _platon_squeeze_void_volume
  _platon_squeeze_void_count_electrons
  _platon_squeeze_void_content
   1  0.000  0.500  0.500       136        11 ' '
   2  0.371  0.745  0.852        12         1 ' '
   3  0.629  0.255  0.148        12         1 ' '
_platon_squeeze_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)+(0.0524P)²+2.8944P] 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         5772
_refine_ls_number_parameters     248
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1059
_refine_ls_R_factor_gt           0.0823
_refine_ls_wR_factor_ref         0.2467
_refine_ls_wR_factor_gt          0.2273
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_restrained_S_all      1.054
_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 1.13648(8) 0.11383(9) 0.08810(7) 0.0190(5) Uani 1 1 d . . .
S1 S 0.88202(17) 0.4235(2) -0.07980(18) 0.0239(7) Uani 1 1 d . . .
O1 O 0.9728(5) 0.1496(6) -0.0284(5) 0.0284(19) Uani 1 1 d . . .
O3 O 0.8676(5) 0.7013(6) -0.0988(5) 0.0261(18) Uani 1 1 d . . .
O4 O 0.6789(6) 0.7456(7) -0.1793(6) 0.038(2) Uani 1 1 d . . .
O2 O 0.8116(5) 0.0717(6) -0.1071(5) 0.0246(18) Uani 1 1 d . . .
N2 N 1.0027(6) 0.1081(7) 0.2517(6) 0.023(2) Uani 1 1 d . . .
N1 N 1.2791(5) 0.1197(7) -0.0718(6) 0.019(2) Uani 1 1 d . . .
C1 C 0.8682(6) 0.1618(8) -0.0749(6) 0.019(3) Uani 1 1 d . . .
C2 C 0.8033(7) 0.2949(9) -0.1007(7) 0.025(3) Uani 1 1 d . . .
C3 C 0.6826(8) 0.3325(10) -0.1412(9) 0.035(3) Uani 1 1 d . . .
H3 H 0.6258 0.2752 -0.1568 0.042 Uiso 1 1 calc R . .
C4 C 0.6543(8) 0.4650(10) -0.1566(9) 0.034(3) Uani 1 1 d . . .
H4 H 0.5756 0.5059 -0.1821 0.040 Uiso 1 1 calc R . .
C5 C 0.7555(7) 0.5307(9) -0.1299(7) 0.025(3) Uani 1 1 d . . .
C6 C 0.7649(7) 0.6668(9) -0.1366(8) 0.029(3) Uani 1 1 d . . .
C16 C 1.0079(8) 0.1732(11) 0.3508(8) 0.042(3) Uani 1 1 d . . .
H16 H 1.0733 0.2288 0.3441 0.051 Uiso 1 1 calc R . .
C15 C 0.9192(8) 0.1615(12) 0.4647(8) 0.046(4) Uani 1 1 d . . .
H15 H 0.9276 0.2069 0.5332 0.056 Uiso 1 1 calc R . .
C14 C 0.8177(7) 0.0816(11) 0.4761(7) 0.037(3) Uani 1 1 d . . .
C13 C 0.8118(8) 0.0201(13) 0.3703(8) 0.044(4) Uani 1 1 d . . .
H13 H 0.7443 -0.0323 0.3719 0.053 Uiso 1 1 calc R . .
C12 C 0.9048(7) 0.0349(10) 0.2611(7) 0.030(3) Uani 1 1 d . . .
H12 H 0.8981 -0.0086 0.1909 0.036 Uiso 1 1 calc R . .
C17 C 0.7186(9) 0.0598(13) 0.5985(7) 0.043(4) Uani 1 1 d . . .
H17A H 0.7010 -0.0292 0.6067 0.052 Uiso 1 1 calc R . .
H17B H 0.7579 0.0775 0.6697 0.052 Uiso 1 1 calc R . .
C11 C 1.2730(7) 0.2171(10) -0.1528(7) 0.027(3) Uani 1 1 d . . .
H11 H 1.1989 0.2812 -0.1373 0.032 Uiso 1 1 calc R . .
C10 C 1.3708(8) 0.2310(10) -0.2611(8) 0.0332(16) Uiso 1 1 d . . .
H10 H 1.3631 0.3029 -0.3153 0.040 Uiso 1 1 calc R . .
C9 C 1.4804(7) 0.1335(10) -0.2853(7) 0.026(3) Uani 1 1 d . . .
C8 C 1.4855(7) 0.0308(10) -0.2016(7) 0.025(3) Uani 1 1 d . . .
H8 H 1.5574 -0.0355 -0.2157 0.030 Uiso 1 1 calc R . .
C7 C 1.3845(6) 0.0245(9) -0.0955(7) 0.024(3) Uani 1 1 d . . .
H7 H 1.3895 -0.0464 -0.0399 0.028 Uiso 1 1 calc R . .
C18 C 0.5874(8) 0.1481(12) 0.5971(7) 0.035(3) Uani 1 1 d . . .
H18A H 0.5507 0.1308 0.5244 0.042 Uiso 1 1 calc R . .
H18B H 0.6068 0.2366 0.5884 0.042 Uiso 1 1 calc R . .
O5 O 0.6293(14) 0.7037(16) 0.5913(11) 0.115(5) Uani 1 1 d . . .
O6 O 0.365(3) 0.587(2) 0.659(3) 0.225(14) Uani 1 1 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
Cu1 O3 1.945(7) 2_765 ?
Cu1 O2 1.953(6) 2_755 ?
Cu1 N2 2.017(6) . ?
Cu1 N1 2.036(6) . ?
Cu1 O1 2.242(5) . ?
S1 C2 1.706(9) . ?
S1 C5 1.726(7) . ?
O1 C1 1.242(7) . ?
O3 C6 1.287(9) . ?
O3 Cu1 1.945(7) 2_765 ?
O4 C6 1.248(9) . ?
O2 C1 1.268(10) . ?
O2 Cu1 1.953(6) 2_755 ?
N2 C12 1.319(13) . ?
N2 C16 1.323(8) . ?
N1 C11 1.308(13) . ?
N1 C7 1.352(8) . ?
C1 C2 1.492(12) . ?
C2 C3 1.371(9) . ?
C3 C4 1.387(15) . ?
C3 H3 0.9300 . ?
C4 C5 1.392(13) . ?
C4 H4 0.9300 . ?
C5 C6 1.441(15) . ?
C16 C15 1.390(14) . ?
C16 H16 0.9300 . ?
C15 C14 1.395(16) . ?
C15 H15 0.9300 . ?
C14 C13 1.367(10) . ?
C14 C17 1.528(13) . ?
C13 C12 1.380(13) . ?
C13 H13 0.9300 . ?
C12 H12 0.9300 . ?
C17 C18 1.509(11) . ?
C17 H17A 0.9700 . ?
C17 H17B 0.9700 . ?
C11 C10 1.397(13) . ?
C11 H11 0.9300 . ?
C10 C9 1.396(10) . ?
C10 H10 0.9300 . ?
C9 C8 1.367(14) . ?
C9 C18 1.521(12) 1_654 ?
C8 C7 1.389(11) . ?
C8 H8 0.9300 . ?
C7 H7 0.9300 . ?
C18 C9 1.521(12) 1_456 ?
C18 H18A 0.9700 . ?
C18 H18B 0.9700 . ?

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
O3 Cu1 O2 161.4(2) 2_765 2_755 ?
O3 Cu1 N2 90.7(3) 2_765 . ?
O2 Cu1 N2 89.4(3) 2_755 . ?
O3 Cu1 N1 88.8(3) 2_765 . ?
O2 Cu1 N1 90.2(3) 2_755 . ?
N2 Cu1 N1 177.1(2) . . ?
O3 Cu1 O1 89.7(2) 2_765 . ?
O2 Cu1 O1 108.8(2) 2_755 . ?
N2 Cu1 O1 93.5(2) . . ?
N1 Cu1 O1 89.4(2) . . ?
C2 S1 C5 91.9(4) . . ?
C1 O1 Cu1 169.1(6) . . ?
C6 O3 Cu1 115.0(5) . 2_765 ?
C1 O2 Cu1 128.1(4) . 2_755 ?
C12 N2 C16 117.8(7) . . ?
C12 N2 Cu1 118.5(4) . . ?
C16 N2 Cu1 123.7(6) . . ?
C11 N1 C7 118.3(7) . . ?
C11 N1 Cu1 120.9(4) . . ?
C7 N1 Cu1 120.8(6) . . ?
O1 C1 O2 126.6(7) . . ?
O1 C1 C2 117.9(7) . . ?
O2 C1 C2 115.5(6) . . ?
C3 C2 C1 128.5(8) . . ?
C3 C2 S1 111.9(7) . . ?
C1 C2 S1 119.7(5) . . ?
C2 C3 C4 112.8(8) . . ?
C2 C3 H3 123.6 . . ?
C4 C3 H3 123.6 . . ?
C3 C4 C5 113.2(6) . . ?
C3 C4 H4 123.4 . . ?
C5 C4 H4 123.4 . . ?
C4 C5 C6 129.9(7) . . ?
C4 C5 S1 110.1(7) . . ?
C6 C5 S1 120.0(5) . . ?
O4 C6 O3 122.5(9) . . ?
O4 C6 C5 121.1(7) . . ?
O3 C6 C5 116.4(7) . . ?
N2 C16 C15 122.4(10) . . ?
N2 C16 H16 118.8 . . ?
C15 C16 H16 118.8 . . ?
C16 C15 C14 119.9(7) . . ?
C16 C15 H15 120.0 . . ?
C14 C15 H15 120.0 . . ?
C13 C14 C15 116.1(8) . . ?
C13 C14 C17 120.4(10) . . ?
C15 C14 C17 123.5(7) . . ?
C14 C13 C12 120.7(10) . . ?
C14 C13 H13 119.7 . . ?
C12 C13 H13 119.7 . . ?
N2 C12 C13 123.0(7) . . ?
N2 C12 H12 118.5 . . ?
C13 C12 H12 118.5 . . ?
C18 C17 C14 109.0(9) . . ?
C18 C17 H17A 109.9 . . ?
C14 C17 H17A 109.9 . . ?
C18 C17 H17B 109.9 . . ?
C14 C17 H17B 109.9 . . ?
H17A C17 H17B 108.3 . . ?
N1 C11 C10 124.1(7) . . ?
N1 C11 H11 118.0 . . ?
C10 C11 H11 118.0 . . ?
C9 C10 C11 117.8(10) . . ?
C9 C10 H10 121.1 . . ?
C11 C10 H10 121.1 . . ?
C8 C9 C10 118.0(8) . . ?
C8 C9 C18 123.9(7) . 1_654 ?
C10 C9 C18 118.0(9) . 1_654 ?
C9 C8 C7 120.7(7) . . ?
C9 C8 H8 119.6 . . ?
C7 C8 H8 119.6 . . ?
N1 C7 C8 121.1(9) . . ?
N1 C7 H7 119.5 . . ?
C8 C7 H7 119.5 . . ?
C17 C18 C9 113.4(8) . 1_456 ?
C17 C18 H18A 108.9 . . ?
C9 C18 H18A 108.9 1_456 . ?
C17 C18 H18B 108.9 . . ?
C9 C18 H18B 108.9 1_456 . ?
H18A C18 H18B 107.7 . . ?

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
O3 Cu1 O1 C1 -109(3) 2_765 . . . ?
O2 Cu1 O1 C1 73(3) 2_755 . . . ?
N2 Cu1 O1 C1 -18(3) . . . . ?
N1 Cu1 O1 C1 163(3) . . . . ?
O3 Cu1 N2 C12 139.0(7) 2_765 . . . ?
O2 Cu1 N2 C12 -59.6(7) 2_755 . . . ?
O1 Cu1 N2 C12 49.2(7) . . . . ?
O3 Cu1 N2 C16 -41.4(7) 2_765 . . . ?
O2 Cu1 N2 C16 120.0(7) 2_755 . . . ?
O1 Cu1 N2 C16 -131.2(7) . . . . ?
O3 Cu1 N1 C11 -37.1(6) 2_765 . . . ?
O2 Cu1 N1 C11 161.4(6) 2_755 . . . ?
O1 Cu1 N1 C11 52.6(6) . . . . ?
O3 Cu1 N1 C7 141.2(5) 2_765 . . . ?
O2 Cu1 N1 C7 -20.3(5) 2_755 . . . ?
O1 Cu1 N1 C7 -129.1(5) . . . . ?
Cu1 O1 C1 O2 -72(3) . . . . ?
Cu1 O1 C1 C2 111(3) . . . . ?
Cu1 O2 C1 O1 3.0(11) 2_755 . . . ?
Cu1 O2 C1 C2 -179.3(5) 2_755 . . . ?
O1 C1 C2 C3 -174.0(8) . . . . ?
O2 C1 C2 C3 8.1(12) . . . . ?
O1 C1 C2 S1 6.0(9) . . . . ?
O2 C1 C2 S1 -171.9(5) . . . . ?
C5 S1 C2 C3 -1.6(7) . . . . ?
C5 S1 C2 C1 178.4(6) . . . . ?
C1 C2 C3 C4 -179.4(8) . . . . ?
S1 C2 C3 C4 0.6(10) . . . . ?
C2 C3 C4 C5 1.1(12) . . . . ?
C3 C4 C5 C6 178.8(9) . . . . ?
C3 C4 C5 S1 -2.3(11) . . . . ?
C2 S1 C5 C4 2.2(7) . . . . ?
C2 S1 C5 C6 -178.8(7) . . . . ?
Cu1 O3 C6 O4 9.4(10) 2_765 . . . ?
Cu1 O3 C6 C5 -172.1(5) 2_765 . . . ?
C4 C5 C6 O4 -5.4(14) . . . . ?
S1 C5 C6 O4 175.8(6) . . . . ?
C4 C5 C6 O3 176.0(8) . . . . ?
S1 C5 C6 O3 -2.8(10) . . . . ?
C12 N2 C16 C15 3.5(14) . . . . ?
Cu1 N2 C16 C15 -176.1(7) . . . . ?
N2 C16 C15 C14 -1.9(16) . . . . ?
C16 C15 C14 C13 -0.9(15) . . . . ?
C16 C15 C14 C17 178.1(9) . . . . ?
C15 C14 C13 C12 1.9(15) . . . . ?
C17 C14 C13 C12 -177.1(10) . . . . ?
C16 N2 C12 C13 -2.5(14) . . . . ?
Cu1 N2 C12 C13 177.2(8) . . . . ?
C14 C13 C12 N2 -0.3(17) . . . . ?
C13 C14 C17 C18 -84.1(13) . . . . ?
C15 C14 C17 C18 97.0(11) . . . . ?
C7 N1 C11 C10 -1.8(12) . . . . ?
Cu1 N1 C11 C10 176.5(6) . . . . ?
N1 C11 C10 C9 1.2(13) . . . . ?
C11 C10 C9 C8 -0.2(12) . . . . ?
C11 C10 C9 C18 -179.9(8) . . . 1_654 ?
C10 C9 C8 C7 -0.2(12) . . . . ?
C18 C9 C8 C7 179.5(8) 1_654 . . . ?
C11 N1 C7 C8 1.3(10) . . . . ?
Cu1 N1 C7 C8 -177.0(5) . . . . ?
C9 C8 C7 N1 -0.4(11) . . . . ?
C14 C17 C18 C9 179.5(9) . . . 1_456 ?

_diffrn_measured_fraction_theta_max 1.00
_diffrn_reflns_theta_full        28.71
_diffrn_measured_fraction_theta_full 1.00
_refine_diff_density_max         0.549
_refine_diff_density_min         -0.685
_refine_diff_density_rms         0.122
_database_code_depnum_ccdc_archive 'CCDC 929621'
