# Electronic Supplementary Material (ESI) for RSC Advances.
# This journal is © The Royal Society of Chemistry 2016

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_Compound1
_database_code_depnum_ccdc_archive 'CCDC 1471702'
_audit_update_record             
;
2016-07-26 deposited with the CCDC.
2016-08-29 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C15 H12 Cu N2 O7 S, H2 O'
_chemical_formula_sum            'C15 H14 Cu N2 O8 S'
_chemical_formula_weight         445.88

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      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

_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, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   8.9126(7)
_cell_length_b                   10.0253(7)
_cell_length_c                   18.9226(16)
_cell_angle_alpha                90
_cell_angle_beta                 90.499(3)
_cell_angle_gamma                90
_cell_volume                     1690.7(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    3516
_cell_measurement_theta_min      2.96
_cell_measurement_theta_max      24.57


_exptl_crystal_description       prism
_exptl_crystal_colour            red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.752
_exptl_crystal_F_000             908
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.120
_exptl_absorpt_coefficient_mu    1.465
_shelx_estimated_absorpt_T_min   0.758
_shelx_estimated_absorpt_T_max   0.844
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.770
_exptl_absorpt_correction_T_max  0.841
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71069
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II photon 100 detector'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            21696
_diffrn_reflns_av_unetI/netI     0.0426
_diffrn_reflns_av_R_equivalents  0.0789
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_theta_min         2.285
_diffrn_reflns_theta_max         25.193
_diffrn_reflns_theta_full        25.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             3035
_reflns_number_gt                2288
_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       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SIR97 (Giacovazzo et al, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Ortep-3 for Windows (Farrugia, 1997)'
_computing_publication_material  'WinGX publication routines (Farrugia, 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)+(0.0825P)²+0.6179P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3035
_refine_ls_number_parameters     262
_refine_ls_number_restraints     7
_refine_ls_R_factor_all          0.0741
_refine_ls_R_factor_gt           0.0491
_refine_ls_wR_factor_ref         0.1329
_refine_ls_wR_factor_gt          0.1246
_refine_ls_goodness_of_fit_ref   1.051
_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_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
C1 C 0.8405(5) -0.0152(4) 0.8404(2) 0.0247(9) Uani 1 1 d . . . . .
C2 C 0.9532(5) -0.1121(5) 0.8336(3) 0.0391(12) Uani 1 1 d . . . . .
H2 H 0.9964 -0.1264 0.7896 0.047 Uiso 1 1 calc R U . . .
C3 C 1.0010(6) -0.1862(5) 0.8905(3) 0.0452(13) Uani 1 1 d . . . . .
H3 H 1.0764 -0.2495 0.8853 0.054 Uiso 1 1 calc R U . . .
C4 C 0.9355(6) -0.1653(5) 0.9553(3) 0.0411(12) Uani 1 1 d . . . . .
H4 H 0.9667 -0.2158 0.9940 0.049 Uiso 1 1 calc R U . . .
C5 C 0.8248(5) -0.0709(4) 0.9637(2) 0.0312(10) Uani 1 1 d . . . . .
H5 H 0.7814 -0.0592 1.0078 0.037 Uiso 1 1 calc R U . . .
C6 C 0.7772(4) 0.0071(4) 0.9070(2) 0.0221(9) Uani 1 1 d . . . . .
C7 C 0.5383(5) 0.2210(4) 1.0033(2) 0.0240(9) Uani 1 1 d . . . . .
C8 C 0.5116(5) 0.2450(4) 1.0783(2) 0.0265(10) Uani 1 1 d . . . . .
C9 C 0.3946(5) 0.3525(4) 1.0817(2) 0.0263(10) Uani 1 1 d . . . . .
C10 C 0.3231(5) 0.4079(5) 1.1392(2) 0.0361(11) Uani 1 1 d . . . . .
H10 H 0.3472 0.3819 1.1851 0.043 Uiso 1 1 calc R U . . .
C11 C 0.2135(6) 0.5042(5) 1.1258(3) 0.0421(13) Uani 1 1 d . . . . .
H11 H 0.1630 0.5431 1.1634 0.051 Uiso 1 1 calc R U . . .
C12 C 0.1792(6) 0.5424(5) 1.0575(3) 0.0437(13) Uani 1 1 d . . . . .
H12 H 0.1062 0.6073 1.0499 0.052 Uiso 1 1 calc R U . . .
C13 C 0.2504(5) 0.4870(4) 1.0002(2) 0.0326(10) Uani 1 1 d . . . . .
H13 H 0.2263 0.5134 0.9544 0.039 Uiso 1 1 calc R U . . .
C14 C 0.3588(5) 0.3908(4) 1.0129(2) 0.0249(9) Uani 1 1 d . . . . .
C15 C 0.4485(5) 0.3119(4) 0.9634(2) 0.0230(9) Uani 1 1 d . . . . .
N1 N 0.6630(4) 0.1085(3) 0.91675(17) 0.0204(7) Uani 1 1 d . . . . .
N2 N 0.6402(4) 0.1313(3) 0.98294(17) 0.0227(8) Uani 1 1 d . . . . .
O1 O 0.4449(4) 0.3244(3) 0.89767(15) 0.0321(7) Uani 1 1 d . . . . .
O2 O 0.5717(4) 0.1896(3) 1.12860(15) 0.0366(8) Uani 1 1 d . . . . .
O1W O 0.1047(5) 0.2486(5) 0.8638(2) 0.0640(11) Uani 1 1 d D . . . .
O3 O 0.4773(5) 0.3136(3) 0.76192(17) 0.0419(9) Uani 1 1 d D . . . .
O4 O 0.3334(4) 0.0716(4) 0.8409(3) 0.0616(12) Uani 1 1 d D . . . .
O11 O 0.6230(3) 0.0768(3) 0.76504(15) 0.0298(7) Uani 1 1 d . . . . .
O12 O 0.8445(4) 0.2119(3) 0.77665(18) 0.0386(8) Uani 1 1 d . . . . .
O13 O 0.8474(4) 0.0112(3) 0.70392(16) 0.0448(9) Uani 1 1 d . . . . .
S1 S 0.79046(12) 0.07834(11) 0.76510(5) 0.0262(3) Uani 1 1 d . . . . .
Cu1 Cu 0.54094(6) 0.19289(5) 0.83844(3) 0.0265(2) Uani 1 1 d . . . . .
H4B H 0.244(3) 0.113(4) 0.839(3) 0.040 Uiso 1 1 d D U . . .
H3B H 0.524(5) 0.323(5) 0.7257(17) 0.040 Uiso 1 1 d D U . . .
H3A H 0.446(5) 0.390(3) 0.764(3) 0.040 Uiso 1 1 d D U . . .
H4A H 0.318(5) -0.009(2) 0.850(3) 0.040 Uiso 1 1 d D U . . .
H1W H 0.022(3) 0.238(5) 0.838(2) 0.040 Uiso 1 1 d D U . . .
H2W H 0.162(4) 0.311(4) 0.843(2) 0.040 Uiso 1 1 d D 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
C1 C6 1.403(6) . ?
C1 C2 1.404(6) . ?
C1 S1 1.760(4) . ?
C2 C3 1.372(7) . ?
C2 H2 0.9300 . ?
C3 C4 1.380(7) . ?
C3 H3 0.9300 . ?
C4 C5 1.377(6) . ?
C4 H4 0.9300 . ?
C5 C6 1.391(6) . ?
C5 H5 0.9300 . ?
C6 N1 1.451(5) . ?
C7 N2 1.338(5) . ?
C7 C15 1.426(6) . ?
C7 C8 1.460(6) . ?
C8 O2 1.222(5) . ?
C8 C9 1.501(6) . ?
C9 C10 1.382(6) . ?
C9 C14 1.392(6) . ?
C10 C11 1.395(7) . ?
C10 H10 0.9300 . ?
C11 C12 1.381(7) . ?
C11 H11 0.9300 . ?
C12 C13 1.378(6) . ?
C12 H12 0.9300 . ?
C13 C14 1.384(6) . ?
C13 H13 0.9300 . ?
C14 C15 1.467(6) . ?
C15 O1 1.250(5) . ?
N1 N2 1.291(4) . ?
N1 Cu1 2.017(3) . ?
O1 Cu1 1.935(3) . ?
O1W H1W 0.888(19) . ?
O1W H2W 0.897(19) . ?
O3 Cu1 1.967(3) . ?
O3 H3B 0.81(2) . ?
O3 H3A 0.82(2) . ?
O4 Cu1 2.214(4) . ?
O4 H4B 0.90(2) . ?
O4 H4A 0.84(2) . ?
O11 S1 1.493(3) . ?
O11 Cu1 1.958(3) . ?
O12 S1 1.439(3) . ?
O13 S1 1.436(3) . ?

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
C6 C1 C2 119.1(4) . . ?
C6 C1 S1 122.7(3) . . ?
C2 C1 S1 118.1(3) . . ?
C3 C2 C1 121.3(4) . . ?
C3 C2 H2 119.4 . . ?
C1 C2 H2 119.4 . . ?
C2 C3 C4 119.0(4) . . ?
C2 C3 H3 120.5 . . ?
C4 C3 H3 120.5 . . ?
C5 C4 C3 121.0(5) . . ?
C5 C4 H4 119.5 . . ?
C3 C4 H4 119.5 . . ?
C4 C5 C6 120.8(4) . . ?
C4 C5 H5 119.6 . . ?
C6 C5 H5 119.6 . . ?
C5 C6 C1 118.7(4) . . ?
C5 C6 N1 120.3(4) . . ?
C1 C6 N1 120.9(4) . . ?
N2 C7 C15 131.1(4) . . ?
N2 C7 C8 120.6(4) . . ?
C15 C7 C8 108.3(3) . . ?
O2 C8 C7 127.4(4) . . ?
O2 C8 C9 126.4(4) . . ?
C7 C8 C9 106.2(4) . . ?
C10 C9 C14 121.5(4) . . ?
C10 C9 C8 130.3(4) . . ?
C14 C9 C8 108.2(4) . . ?
C9 C10 C11 117.5(4) . . ?
C9 C10 H10 121.2 . . ?
C11 C10 H10 121.2 . . ?
C12 C11 C10 120.7(4) . . ?
C12 C11 H11 119.6 . . ?
C10 C11 H11 119.6 . . ?
C13 C12 C11 121.7(4) . . ?
C13 C12 H12 119.2 . . ?
C11 C12 H12 119.2 . . ?
C12 C13 C14 118.1(4) . . ?
C12 C13 H13 121.0 . . ?
C14 C13 H13 121.0 . . ?
C13 C14 C9 120.5(4) . . ?
C13 C14 C15 130.4(4) . . ?
C9 C14 C15 109.0(4) . . ?
O1 C15 C7 126.9(4) . . ?
O1 C15 C14 124.8(4) . . ?
C7 C15 C14 108.3(3) . . ?
N2 N1 C6 111.3(3) . . ?
N2 N1 Cu1 123.4(3) . . ?
C6 N1 Cu1 125.1(2) . . ?
N1 N2 C7 120.8(3) . . ?
C15 O1 Cu1 120.0(3) . . ?
H1W O1W H2W 109(3) . . ?
Cu1 O3 H3B 123(4) . . ?
Cu1 O3 H3A 130(4) . . ?
H3B O3 H3A 97(5) . . ?
Cu1 O4 H4B 119(3) . . ?
Cu1 O4 H4A 132(4) . . ?
H4B O4 H4A 108(5) . . ?
S1 O11 Cu1 111.90(17) . . ?
O13 S1 O12 116.0(2) . . ?
O13 S1 O11 110.8(2) . . ?
O12 S1 O11 110.04(19) . . ?
O13 S1 C1 108.3(2) . . ?
O12 S1 C1 106.9(2) . . ?
O11 S1 C1 103.98(18) . . ?
O1 Cu1 O11 170.21(12) . . ?
O1 Cu1 O3 83.16(13) . . ?
O11 Cu1 O3 87.17(13) . . ?
O1 Cu1 N1 95.67(12) . . ?
O11 Cu1 N1 93.99(12) . . ?
O3 Cu1 N1 161.69(16) . . ?
O1 Cu1 O4 89.32(15) . . ?
O11 Cu1 O4 90.32(15) . . ?
O3 Cu1 O4 96.77(17) . . ?
N1 Cu1 O4 101.49(15) . . ?

_refine_diff_density_max         0.726
_refine_diff_density_min         -0.488
_refine_diff_density_rms         0.141

_shelxl_version_number           2013-4

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_Compound2
_database_code_depnum_ccdc_archive 'CCDC 1471703'
_audit_update_record             
;
2016-07-26 deposited with the CCDC.
2016-08-29 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C19 H18 Cu N3 O7 S'
_chemical_formula_sum            'C19 H18 Cu N3 O7 S'
_chemical_formula_weight         495.96

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      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

_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+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   7.4989(3)
_cell_length_b                   19.3512(6)
_cell_length_c                   13.6935(5)
_cell_angle_alpha                90
_cell_angle_beta                 94.3580(10)
_cell_angle_gamma                90
_cell_volume                     1981.36(12)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    9997
_cell_measurement_theta_min      2.58
_cell_measurement_theta_max      25.41

_exptl_crystal_description       plate
_exptl_crystal_colour            bronze
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.663
_exptl_crystal_F_000             1016
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.250
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.090
_exptl_absorpt_coefficient_mu    1.257
_shelx_estimated_absorpt_T_min   0.744
_shelx_estimated_absorpt_T_max   0.895
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.747
_exptl_absorpt_correction_T_max  0.893
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            20735
_diffrn_reflns_av_unetI/netI     0.0224
_diffrn_reflns_av_R_equivalents  0.0340
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         2.580
_diffrn_reflns_theta_max         25.424
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             3644
_reflns_number_gt                3063
_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       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SIR97 (Giacovazzo et al, 1999)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    ?
_computing_publication_material  'WinGX publication routines (Farrugia, 1999)'

_refine_special_details          
;
 All H-atoms were introduced in calculated positions and refined on a
 riding model, except H3N, H6O and H7O (the ones attached to N- and O-atoms)
 which were located in difference map positions and refined positionally 
 (H6O with DFIX restraints), and with Uiso = 1.5Ueq of their parent N-atom.
 To accomplish H-bond interactions as well as the oxidation state of the metal, 
 the hydrogen atoms attached to O6 and O7 have half s.o.f..  
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0579P)²+2.5373P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3644
_refine_ls_number_parameters     289
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0536
_refine_ls_R_factor_gt           0.0432
_refine_ls_wR_factor_ref         0.1158
_refine_ls_wR_factor_gt          0.1066
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_restrained_S_all      1.097
_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_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
C1 C 0.8131(4) 0.97224(15) 0.8901(2) 0.0274(6) Uani 1 1 d . . . . .
C2 C 0.7401(4) 0.91618(15) 0.9419(2) 0.0285(6) Uani 1 1 d . . . . .
C3 C 0.6925(4) 0.94170(15) 1.0381(2) 0.0288(6) Uani 1 1 d . . . . .
C4 C 0.7358(4) 1.01159(16) 1.0449(2) 0.0293(6) Uani 1 1 d . . . . .
C5 C 0.7030(4) 1.04878(17) 1.1276(2) 0.0343(7) Uani 1 1 d . . . . .
H4 H 0.7316 1.0955 1.1331 0.041 Uiso 1 1 calc R U . . .
C6 C 0.6256(5) 1.01379(19) 1.2023(2) 0.0393(8) Uani 1 1 d . . . . .
H1 H 0.6018 1.0376 1.2589 0.047 Uiso 1 1 calc R U . . .
C7 C 0.5834(5) 0.94461(19) 1.1946(2) 0.0406(8) Uani 1 1 d . . . . .
H2 H 0.5316 0.9228 1.2459 0.049 Uiso 1 1 calc R U . . .
C8 C 0.6162(5) 0.90687(17) 1.1121(2) 0.0365(7) Uani 1 1 d . . . . .
H3 H 0.5882 0.8601 1.1069 0.044 Uiso 1 1 calc R U . . .
C9 C 0.8109(4) 1.03409(15) 0.9519(2) 0.0290(6) Uani 1 1 d . . . . .
C10 C 0.8430(4) 0.92999(16) 0.6426(2) 0.0299(7) Uani 1 1 d . . . . .
C11 C 0.9302(4) 0.88641(17) 0.5811(2) 0.0327(7) Uani 1 1 d . . . . .
C12 C 0.9165(5) 0.8979(2) 0.4808(2) 0.0435(8) Uani 1 1 d . . . . .
H8 H 0.9736 0.8682 0.4398 0.052 Uiso 1 1 calc R U . . .
C13 C 0.8193(5) 0.9528(2) 0.4414(3) 0.0492(9) Uani 1 1 d . . . . .
H7 H 0.8116 0.9604 0.3741 0.059 Uiso 1 1 calc R U . . .
C14 C 0.7339(5) 0.9965(2) 0.5015(3) 0.0460(9) Uani 1 1 d . . . . .
H6 H 0.6694 1.0340 0.4751 0.055 Uiso 1 1 calc R U . . .
C15 C 0.7437(4) 0.98485(18) 0.6010(2) 0.0385(8) Uani 1 1 d . . . . .
H5 H 0.6830 1.0141 0.6410 0.046 Uiso 1 1 calc R U . . .
C17 C 0.9605(6) 0.6955(2) 0.8892(3) 0.0529(10) Uani 1 1 d . . . . .
H17A H 1.0370 0.6886 0.8360 0.063 Uiso 1 1 calc R U . . .
H17B H 0.9372 0.6507 0.9175 0.063 Uiso 1 1 calc R U . . .
C18 C 1.0526(7) 0.7416(2) 0.9658(3) 0.0619(11) Uani 1 1 d . . . . .
H9 H 0.9765 0.7486 1.0191 0.074 Uiso 1 1 calc R U . . .
H10 H 1.1632 0.7204 0.9920 0.074 Uiso 1 1 calc R U . . .
C19 C 0.6881(6) 0.68475(19) 0.7754(3) 0.0489(9) Uani 1 1 d . . . . .
H12 H 0.6638 0.6395 0.8018 0.059 Uiso 1 1 calc R U . . .
H13 H 0.7580 0.6785 0.7193 0.059 Uiso 1 1 calc R U . . .
C20 C 0.5148(6) 0.7201(2) 0.7438(3) 0.0603(11) Uani 1 1 d . . . . .
H14 H 0.4515 0.6945 0.6911 0.072 Uiso 1 1 calc R U . . .
H15 H 0.4394 0.7228 0.7982 0.072 Uiso 1 1 calc R U . . .
N1 N 0.8484(3) 0.91809(12) 0.74571(18) 0.0283(5) Uani 1 1 d . . . . .
N2 N 0.8438(3) 0.97495(13) 0.79541(17) 0.0281(5) Uani 1 1 d . . . . .
N3 N 0.7920(4) 0.72715(14) 0.8517(2) 0.0357(6) Uani 1 1 d . . . . .
O1 O 0.7111(3) 0.85604(11) 0.91206(16) 0.0389(5) Uani 1 1 d . . . . .
O2 O 0.8604(3) 1.09234(11) 0.93262(17) 0.0404(6) Uani 1 1 d . . . . .
O3 O 1.1106(4) 0.77612(14) 0.5462(2) 0.0567(7) Uani 1 1 d . . . . .
O4 O 1.2262(3) 0.85257(14) 0.6760(2) 0.0550(7) Uani 1 1 d . . . . .
O5 O 0.9682(3) 0.78097(12) 0.69606(17) 0.0437(6) Uani 1 1 d . . . . .
O6 O 1.0897(4) 0.80649(15) 0.9216(2) 0.0527(7) Uani 1 1 d D . . . .
O7 O 0.5567(4) 0.78825(15) 0.7113(2) 0.0541(7) Uani 1 1 d . . . . .
S1 S 1.07272(11) 0.81927(4) 0.62725(6) 0.0340(2) Uani 1 1 d . . . . .
Cu1 Cu 0.82839(5) 0.82255(2) 0.79805(3) 0.03130(15) Uani 1 1 d . . . . .
H7O H 0.462(12) 0.815(4) 0.696(6) 0.047 Uiso 0.5 1 d . U P . .
H6O H 1.106(11) 0.837(3) 0.971(4) 0.047 Uiso 0.5 1 d D U P . .
H3N H 0.737(6) 0.732(2) 0.896(3) 0.047 Uiso 1 1 d . 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
C1 N2 1.335(4) . ?
C1 C2 1.428(4) . ?
C1 C9 1.467(4) . ?
C2 O1 1.247(4) . ?
C2 C3 1.476(4) . ?
C3 C8 1.377(5) . ?
C3 C4 1.392(4) . ?
C4 C5 1.379(4) . ?
C4 C9 1.496(4) . ?
C5 C6 1.391(5) . ?
C5 H4 0.9300 . ?
C6 C7 1.378(5) . ?
C6 H1 0.9300 . ?
C7 C8 1.382(5) . ?
C7 H2 0.9300 . ?
C8 H3 0.9300 . ?
C9 O2 1.222(4) . ?
C10 C11 1.390(4) . ?
C10 C15 1.393(5) . ?
C10 N1 1.428(4) . ?
C11 C12 1.388(4) . ?
C11 S1 1.768(3) . ?
C12 C13 1.376(6) . ?
C12 H8 0.9300 . ?
C13 C14 1.372(6) . ?
C13 H7 0.9300 . ?
C14 C15 1.377(5) . ?
C14 H6 0.9300 . ?
C15 H5 0.9300 . ?
C17 N3 1.462(5) . ?
C17 C18 1.505(6) . ?
C17 H17A 0.9700 . ?
C17 H17B 0.9700 . ?
C18 O6 1.429(5) . ?
C18 H9 0.9700 . ?
C18 H10 0.9700 . ?
C19 N3 1.499(5) . ?
C19 C20 1.503(6) . ?
C19 H12 0.9700 . ?
C19 H13 0.9700 . ?
C20 O7 1.434(5) . ?
C20 H14 0.9700 . ?
C20 H15 0.9700 . ?
N1 N2 1.296(3) . ?
N1 Cu1 1.993(2) . ?
N3 Cu1 2.013(3) . ?
N3 H3N 0.77(4) . ?
O1 Cu1 1.960(2) . ?
O3 S1 1.435(3) . ?
O4 S1 1.438(3) . ?
O5 S1 1.471(3) . ?
O5 Cu1 1.980(2) . ?
O6 H6O 0.90(2) . ?
O7 Cu1 2.374(3) . ?
O7 H7O 0.89(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
N2 C1 C2 127.8(3) . . ?
N2 C1 C9 122.6(3) . . ?
C2 C1 C9 108.2(3) . . ?
O1 C2 C1 127.6(3) . . ?
O1 C2 C3 123.8(3) . . ?
C1 C2 C3 108.5(3) . . ?
C8 C3 C4 122.3(3) . . ?
C8 C3 C2 129.4(3) . . ?
C4 C3 C2 108.3(3) . . ?
C5 C4 C3 120.4(3) . . ?
C5 C4 C9 130.5(3) . . ?
C3 C4 C9 109.1(3) . . ?
C4 C5 C6 117.4(3) . . ?
C4 C5 H4 121.3 . . ?
C6 C5 H4 121.3 . . ?
C7 C6 C5 121.5(3) . . ?
C7 C6 H1 119.2 . . ?
C5 C6 H1 119.2 . . ?
C6 C7 C8 121.5(3) . . ?
C6 C7 H2 119.3 . . ?
C8 C7 H2 119.3 . . ?
C3 C8 C7 116.9(3) . . ?
C3 C8 H3 121.6 . . ?
C7 C8 H3 121.6 . . ?
O2 C9 C1 127.7(3) . . ?
O2 C9 C4 126.3(3) . . ?
C1 C9 C4 106.0(3) . . ?
C11 C10 C15 118.4(3) . . ?
C11 C10 N1 121.5(3) . . ?
C15 C10 N1 120.1(3) . . ?
C12 C11 C10 120.0(3) . . ?
C12 C11 S1 118.0(3) . . ?
C10 C11 S1 121.9(2) . . ?
C13 C12 C11 120.6(3) . . ?
C13 C12 H8 119.7 . . ?
C11 C12 H8 119.7 . . ?
C14 C13 C12 119.8(3) . . ?
C14 C13 H7 120.1 . . ?
C12 C13 H7 120.1 . . ?
C13 C14 C15 120.1(3) . . ?
C13 C14 H6 120.0 . . ?
C15 C14 H6 120.0 . . ?
C14 C15 C10 121.0(3) . . ?
C14 C15 H5 119.5 . . ?
C10 C15 H5 119.5 . . ?
N3 C17 C18 109.6(3) . . ?
N3 C17 H17A 109.8 . . ?
C18 C17 H17A 109.8 . . ?
N3 C17 H17B 109.8 . . ?
C18 C17 H17B 109.8 . . ?
H17A C17 H17B 108.2 . . ?
O6 C18 C17 108.7(3) . . ?
O6 C18 H9 110.0 . . ?
C17 C18 H9 110.0 . . ?
O6 C18 H10 110.0 . . ?
C17 C18 H10 110.0 . . ?
H9 C18 H10 108.3 . . ?
N3 C19 C20 110.1(3) . . ?
N3 C19 H12 109.6 . . ?
C20 C19 H12 109.6 . . ?
N3 C19 H13 109.6 . . ?
C20 C19 H13 109.6 . . ?
H12 C19 H13 108.2 . . ?
O7 C20 C19 107.7(3) . . ?
O7 C20 H14 110.2 . . ?
C19 C20 H14 110.2 . . ?
O7 C20 H15 110.2 . . ?
C19 C20 H15 110.2 . . ?
H14 C20 H15 108.5 . . ?
N2 N1 C10 112.5(2) . . ?
N2 N1 Cu1 126.40(19) . . ?
C10 N1 Cu1 120.53(19) . . ?
N1 N2 C1 119.3(2) . . ?
C17 N3 C19 113.9(3) . . ?
C17 N3 Cu1 112.0(2) . . ?
C19 N3 Cu1 109.0(2) . . ?
C17 N3 H3N 106(3) . . ?
C19 N3 H3N 110(3) . . ?
Cu1 N3 H3N 106(3) . . ?
C2 O1 Cu1 119.5(2) . . ?
S1 O5 Cu1 125.70(14) . . ?
C18 O6 H6O 106(5) . . ?
C20 O7 Cu1 107.5(2) . . ?
C20 O7 H7O 114(5) . . ?
Cu1 O7 H7O 127(5) . . ?
O3 S1 O4 114.90(18) . . ?
O3 S1 O5 110.42(16) . . ?
O4 S1 O5 112.05(17) . . ?
O3 S1 C11 107.51(16) . . ?
O4 S1 C11 106.10(15) . . ?
O5 S1 C11 105.19(15) . . ?
O1 Cu1 O5 172.01(10) . . ?
O1 Cu1 N1 91.73(10) . . ?
O5 Cu1 N1 93.73(10) . . ?
O1 Cu1 N3 86.06(10) . . ?
O5 Cu1 N3 88.75(11) . . ?
N1 Cu1 N3 176.45(11) . . ?
O1 Cu1 O7 94.09(11) . . ?
O5 Cu1 O7 90.77(11) . . ?
N1 Cu1 O7 99.47(10) . . ?
N3 Cu1 O7 77.95(11) . . ?

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
N2 C1 C2 O1 9.5(5) . . . . ?
C9 C1 C2 O1 176.1(3) . . . . ?
N2 C1 C2 C3 -167.2(3) . . . . ?
C9 C1 C2 C3 -0.7(3) . . . . ?
O1 C2 C3 C8 2.1(5) . . . . ?
C1 C2 C3 C8 179.0(3) . . . . ?
O1 C2 C3 C4 -177.1(3) . . . . ?
C1 C2 C3 C4 -0.2(3) . . . . ?
C8 C3 C4 C5 0.0(5) . . . . ?
C2 C3 C4 C5 179.2(3) . . . . ?
C8 C3 C4 C9 -178.4(3) . . . . ?
C2 C3 C4 C9 0.9(3) . . . . ?
C3 C4 C5 C6 -0.2(5) . . . . ?
C9 C4 C5 C6 177.8(3) . . . . ?
C4 C5 C6 C7 0.1(5) . . . . ?
C5 C6 C7 C8 0.0(6) . . . . ?
C4 C3 C8 C7 0.2(5) . . . . ?
C2 C3 C8 C7 -178.9(3) . . . . ?
C6 C7 C8 C3 -0.2(5) . . . . ?
N2 C1 C9 O2 -11.7(5) . . . . ?
C2 C1 C9 O2 -179.1(3) . . . . ?
N2 C1 C9 C4 168.6(3) . . . . ?
C2 C1 C9 C4 1.2(3) . . . . ?
C5 C4 C9 O2 0.9(5) . . . . ?
C3 C4 C9 O2 179.0(3) . . . . ?
C5 C4 C9 C1 -179.4(3) . . . . ?
C3 C4 C9 C1 -1.3(3) . . . . ?
C15 C10 C11 C12 -0.3(5) . . . . ?
N1 C10 C11 C12 177.5(3) . . . . ?
C15 C10 C11 S1 175.3(2) . . . . ?
N1 C10 C11 S1 -7.0(4) . . . . ?
C10 C11 C12 C13 1.0(5) . . . . ?
S1 C11 C12 C13 -174.7(3) . . . . ?
C11 C12 C13 C14 -0.5(6) . . . . ?
C12 C13 C14 C15 -0.8(6) . . . . ?
C13 C14 C15 C10 1.5(5) . . . . ?
C11 C10 C15 C14 -1.0(5) . . . . ?
N1 C10 C15 C14 -178.8(3) . . . . ?
N3 C17 C18 O6 -60.9(5) . . . . ?
N3 C19 C20 O7 55.6(4) . . . . ?
C11 C10 N1 N2 147.7(3) . . . . ?
C15 C10 N1 N2 -34.5(4) . . . . ?
C11 C10 N1 Cu1 -40.5(4) . . . . ?
C15 C10 N1 Cu1 137.2(3) . . . . ?
C10 N1 N2 C1 167.1(3) . . . . ?
Cu1 N1 N2 C1 -4.0(4) . . . . ?
C2 C1 N2 N1 -17.0(5) . . . . ?
C9 C1 N2 N1 178.2(3) . . . . ?
C18 C17 N3 C19 -179.3(3) . . . . ?
C18 C17 N3 Cu1 56.4(4) . . . . ?
C20 C19 N3 C17 178.1(3) . . . . ?
C20 C19 N3 Cu1 -56.0(4) . . . . ?
C1 C2 O1 Cu1 17.7(4) . . . . ?
C3 C2 O1 Cu1 -166.0(2) . . . . ?
C19 C20 O7 Cu1 -28.5(4) . . . . ?
Cu1 O5 S1 O3 -162.42(19) . . . . ?
Cu1 O5 S1 O4 68.1(2) . . . . ?
Cu1 O5 S1 C11 -46.7(2) . . . . ?
C12 C11 S1 O3 -16.0(3) . . . . ?
C10 C11 S1 O3 168.4(3) . . . . ?
C12 C11 S1 O4 107.4(3) . . . . ?
C10 C11 S1 O4 -68.2(3) . . . . ?
C12 C11 S1 O5 -133.7(3) . . . . ?
C10 C11 S1 O5 50.7(3) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
C17 H17A O5 0.97 2.64 3.123(5) 111.0 .
C19 H13 O5 0.97 2.57 3.067(5) 112.1 .
O7 H7O O4 0.89(9) 1.92(9) 2.783(4) 165(7) 1_455
O6 H6O O2 0.90(2) 1.90(2) 2.801(4) 174(7) 3_777
N3 H3N O3 0.77(4) 2.33(4) 3.082(4) 166(4) 4_576
C17 H17A O5 0.97 2.64 3.123(5) 111.0 .
C19 H13 O5 0.97 2.57 3.067(5) 112.1 .
O7 H7O O4 0.89(9) 1.92(9) 2.783(4) 165(7) 1_455
O7 H7O S1 0.89(9) 3.00(9) 3.771(3) 146(6) 1_455
O6 H6O O2 0.90(2) 1.90(2) 2.801(4) 174(7) 3_777
N3 H3N O3 0.77(4) 2.33(4) 3.082(4) 166(4) 4_576

_refine_diff_density_max         0.639
_refine_diff_density_min         -0.282
_refine_diff_density_rms         0.097

_shelxl_version_number           2013-4

