# Electronic Supplementary Material (ESI) for RSC Advances.
# This journal is © The Royal Society of Chemistry 2015

####################################################################### 
# 
# 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 1023179'
_audit_update_record             
;
2014-09-06 deposited with the CCDC.
2015-03-04 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         '2(C9 H7 N4 O4 S), H12 Mn O6, 4(H2 O)'
_chemical_formula_sum            'C18 H34 Mn N8 O18 S2'
_chemical_formula_weight         769.59

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'
Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_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, -z'

_cell_length_a                   7.2288(4)
_cell_length_b                   9.9748(6)
_cell_length_c                   11.5954(6)
_cell_angle_alpha                85.652(3)
_cell_angle_beta                 82.940(3)
_cell_angle_gamma                76.401(3)
_cell_volume                     805.54(8)
_cell_formula_units_Z            1
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    7963
_cell_measurement_theta_min      2.92
_cell_measurement_theta_max      30.67

_exptl_crystal_description       prism
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.586
_exptl_crystal_F_000             399
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.420
_exptl_crystal_size_mid          0.330
_exptl_crystal_size_min          0.210
_exptl_absorpt_coefficient_mu    0.627
_shelx_estimated_absorpt_T_min   0.779
_shelx_estimated_absorpt_T_max   0.880
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.780
_exptl_absorpt_correction_T_max  0.877
_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         'sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker APEX-II Photon 100'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_reflns_number            13853
_diffrn_reflns_av_unetI/netI     0.0280
_diffrn_reflns_av_R_equivalents  0.0254
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         1.772
_diffrn_reflns_theta_max         30.702
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             4954
_reflns_number_gt                4434
_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 APEX 2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SIR97 (Giacovazzo et al, 1997)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    'Mercury CSD 3.3'
_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)+(0.0412P)²+0.2133P] 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         4954
_refine_ls_number_parameters     253
_refine_ls_number_restraints     10
_refine_ls_R_factor_all          0.0316
_refine_ls_R_factor_gt           0.0273
_refine_ls_wR_factor_ref         0.0774
_refine_ls_wR_factor_gt          0.0739
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_restrained_S_all      1.058
_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 0.26709(14) 0.50135(10) 0.43270(9) 0.01342(17) Uani 1 1 d . . . . .
C2 C 0.36200(15) 0.43555(10) 0.33228(9) 0.01376(18) Uani 1 1 d . . . . .
C3 C 0.48166(16) 0.30424(11) 0.34170(10) 0.0182(2) Uani 1 1 d . . . . .
H3 H 0.5430 0.2603 0.2749 0.022 Uiso 1 1 calc R U . . .
C4 C 0.50973(16) 0.23900(11) 0.44987(11) 0.0203(2) Uani 1 1 d . . . . .
H4 H 0.5887 0.1511 0.4559 0.024 Uiso 1 1 calc R U . . .
C5 C 0.41891(16) 0.30586(11) 0.54943(10) 0.0186(2) Uani 1 1 d . . . . .
H5 H 0.4402 0.2630 0.6222 0.022 Uiso 1 1 calc R U . . .
C6 C 0.29706(15) 0.43550(11) 0.54170(9) 0.01659(19) Uani 1 1 d . . . . .
H6 H 0.2355 0.4785 0.6089 0.020 Uiso 1 1 calc R U . . .
C7 C -0.05227(15) 0.81604(10) 0.51428(9) 0.01485(18) Uani 1 1 d . . . . .
C8 C -0.13503(16) 0.88264(11) 0.62516(9) 0.01622(19) Uani 1 1 d . . . . .
C9 C -0.11584(16) 0.88217(11) 0.40680(10) 0.0176(2) Uani 1 1 d . . . . .
N1 N 0.14414(13) 0.63304(9) 0.42364(8) 0.01511(16) Uani 1 1 d . . . . .
N2 N 0.06934(13) 0.69754(9) 0.51913(8) 0.01485(16) Uani 1 1 d . . . . .
N3 N -0.15900(17) 0.92563(12) 0.31728(9) 0.0261(2) Uani 1 1 d . . . . .
N4 N -0.07235(16) 0.81464(10) 0.72135(9) 0.0221(2) Uani 1 1 d . . . . .
O1 O 0.40956(14) 0.41318(9) 0.10914(7) 0.02364(18) Uani 1 1 d . . . . .
O2 O 0.48073(12) 0.61301(8) 0.18512(7) 0.01753(15) Uani 1 1 d . . . . .
O3 O 0.15173(12) 0.59778(9) 0.18949(7) 0.02049(16) Uani 1 1 d . . . . .
O4 O -0.25345(12) 0.99403(8) 0.62403(7) 0.02115(17) Uani 1 1 d . . . . .
O5 O 0.61077(14) 0.10011(9) -0.15952(7) 0.02372(18) Uani 1 1 d D . . . .
O6 O 0.30153(12) 0.19179(8) 0.03866(8) 0.02063(16) Uani 1 1 d D . . . .
O7 O 0.70862(14) 0.05752(10) 0.09512(8) 0.02504(18) Uani 1 1 d D . . . .
O8 O 0.07850(12) 0.74988(9) 0.98276(8) 0.02096(16) Uani 1 1 d D . . . .
O9 O 0.13964(13) 0.54512(9) 0.83048(8) 0.02412(18) Uani 1 1 d D . . . .
S2 S 0.35127(4) 0.51924(2) 0.19245(2) 0.01377(6) Uani 1 1 d . . . . .
Mn1 Mn 0.5000 0.0000 0.0000 0.01375(6) Uani 1 2 d S . P . .
H1N H 0.107(2) 0.6656(16) 0.3545(14) 0.021 Uiso 1 1 d . U . . .
H4A H -0.127(2) 0.8440(16) 0.7865(14) 0.021 Uiso 1 1 d . U . . .
H4B H 0.004(2) 0.7360(17) 0.7200(14) 0.021 Uiso 1 1 d . U . . .
H5A H 0.585(2) 0.1875(13) -0.1663(14) 0.021 Uiso 1 1 d D U . . .
H5B H 0.643(2) 0.0716(16) -0.2267(12) 0.021 Uiso 1 1 d D U . . .
H6A H 0.331(2) 0.2660(14) 0.0547(14) 0.021 Uiso 1 1 d D U . . .
H6B H 0.189(2) 0.2145(16) 0.0185(14) 0.021 Uiso 1 1 d D U . . .
H7A H 0.749(2) 0.0181(16) 0.1548(12) 0.021 Uiso 1 1 d D U . . .
H7B H 0.779(2) 0.1147(15) 0.0698(13) 0.021 Uiso 1 1 d D U . . .
H8A H 0.101(2) 0.6835(15) 0.9389(13) 0.021 Uiso 1 1 d D U . . .
H8B H 0.106(2) 0.7143(16) 1.0479(12) 0.021 Uiso 1 1 d D U . . .
H9A H 0.058(2) 0.4969(16) 0.8302(14) 0.021 Uiso 1 1 d D U . . .
H9B H 0.245(2) 0.4917(15) 0.8289(14) 0.021 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 1.3965(14) . ?
C1 C2 1.4018(14) . ?
C1 N1 1.4070(13) . ?
C2 C3 1.3944(14) . ?
C2 S2 1.7683(10) . ?
C3 C4 1.3837(16) . ?
C3 H3 0.9300 . ?
C4 C5 1.3904(16) . ?
C4 H4 0.9300 . ?
C5 C6 1.3865(15) . ?
C5 H5 0.9300 . ?
C6 H6 0.9300 . ?
C7 N2 1.2987(13) . ?
C7 C9 1.4399(14) . ?
C7 C8 1.4852(14) . ?
C8 O4 1.2332(13) . ?
C8 N4 1.3321(14) . ?
C9 N3 1.1448(15) . ?
N1 N2 1.3151(12) . ?
N1 H1N 0.892(16) . ?
N4 H4A 0.848(17) . ?
N4 H4B 0.847(16) . ?
O1 S2 1.4405(8) . ?
O2 S2 1.4621(8) . ?
O3 S2 1.4739(8) . ?
O5 Mn1 2.1890(8) . ?
O5 H5A 0.847(13) . ?
O5 H5B 0.837(13) . ?
O6 Mn1 2.1449(8) . ?
O6 H6A 0.856(13) . ?
O6 H6B 0.848(13) . ?
O7 Mn1 2.1752(9) . ?
O7 H7A 0.821(13) . ?
O7 H7B 0.864(13) . ?
O8 H8A 0.839(13) . ?
O8 H8B 0.836(13) . ?
O9 H9A 0.845(13) . ?
O9 H9B 0.821(13) . ?
Mn1 O6 2.1449(8) 2_655 ?
Mn1 O7 2.1752(9) 2_655 ?
Mn1 O5 2.1890(8) 2_655 ?

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 119.39(9) . . ?
C6 C1 N1 120.38(9) . . ?
C2 C1 N1 120.22(9) . . ?
C3 C2 C1 119.98(9) . . ?
C3 C2 S2 117.78(8) . . ?
C1 C2 S2 122.04(8) . . ?
C4 C3 C2 120.39(10) . . ?
C4 C3 H3 119.8 . . ?
C2 C3 H3 119.8 . . ?
C3 C4 C5 119.49(10) . . ?
C3 C4 H4 120.3 . . ?
C5 C4 H4 120.3 . . ?
C6 C5 C4 120.91(10) . . ?
C6 C5 H5 119.5 . . ?
C4 C5 H5 119.5 . . ?
C5 C6 C1 119.81(10) . . ?
C5 C6 H6 120.1 . . ?
C1 C6 H6 120.1 . . ?
N2 C7 C9 122.80(9) . . ?
N2 C7 C8 118.25(9) . . ?
C9 C7 C8 118.89(9) . . ?
O4 C8 N4 124.26(10) . . ?
O4 C8 C7 120.04(9) . . ?
N4 C8 C7 115.70(9) . . ?
N3 C9 C7 174.73(12) . . ?
N2 N1 C1 119.07(9) . . ?
N2 N1 H1N 121.4(10) . . ?
C1 N1 H1N 119.0(10) . . ?
C7 N2 N1 120.66(9) . . ?
C8 N4 H4A 118.2(11) . . ?
C8 N4 H4B 122.3(11) . . ?
H4A N4 H4B 118.4(15) . . ?
Mn1 O5 H5A 118.9(11) . . ?
Mn1 O5 H5B 130.8(11) . . ?
H5A O5 H5B 106.7(15) . . ?
Mn1 O6 H6A 125.7(11) . . ?
Mn1 O6 H6B 124.2(11) . . ?
H6A O6 H6B 107.2(15) . . ?
Mn1 O7 H7A 125.9(11) . . ?
Mn1 O7 H7B 125.5(10) . . ?
H7A O7 H7B 107.6(15) . . ?
H8A O8 H8B 105.1(15) . . ?
H9A O9 H9B 107.1(16) . . ?
O1 S2 O2 113.22(5) . . ?
O1 S2 O3 113.66(5) . . ?
O2 S2 O3 110.52(5) . . ?
O1 S2 C2 107.05(5) . . ?
O2 S2 C2 105.86(5) . . ?
O3 S2 C2 105.89(5) . . ?
O6 Mn1 O6 180.0 . 2_655 ?
O6 Mn1 O7 89.77(4) . 2_655 ?
O6 Mn1 O7 90.23(4) 2_655 2_655 ?
O6 Mn1 O7 90.23(4) . . ?
O6 Mn1 O7 89.77(4) 2_655 . ?
O7 Mn1 O7 180.0 2_655 . ?
O6 Mn1 O5 91.12(3) . 2_655 ?
O6 Mn1 O5 88.88(3) 2_655 2_655 ?
O7 Mn1 O5 90.35(4) 2_655 2_655 ?
O7 Mn1 O5 89.65(4) . 2_655 ?
O6 Mn1 O5 88.88(3) . . ?
O6 Mn1 O5 91.12(3) 2_655 . ?
O7 Mn1 O5 89.65(4) 2_655 . ?
O7 Mn1 O5 90.35(4) . . ?
O5 Mn1 O5 180.0 2_655 . ?

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
N1 H1N O3 0.892(16) 2.040(16) 2.7564(12) 136.5(13) .
N4 H4A O6 0.848(17) 2.302(16) 3.0630(14) 149.5(14) 2_566
N4 H4B O9 0.847(16) 2.299(16) 3.0332(13) 145.2(14) .
O5 H5A O2 0.847(13) 1.936(13) 2.7828(11) 177.7(15) 2_665
O5 H5B O4 0.837(13) 1.940(13) 2.7732(12) 173.2(15) 1_644
O6 H6A O1 0.856(13) 1.870(13) 2.7196(12) 171.5(15) .
O6 H6B O8 0.848(13) 1.884(14) 2.7095(12) 164.1(15) 2_566
O7 H7A N3 0.821(13) 2.143(13) 2.9635(14) 176.1(16) 1_645
O7 H7B O8 0.864(13) 1.905(13) 2.7677(13) 176.4(16) 2_666
O8 H8A O9 0.839(13) 1.886(13) 2.7231(13) 174.9(16) .
O8 H8B O3 0.836(13) 1.954(13) 2.7768(11) 167.8(15) 1_556
O8 H8B S2 0.836(13) 2.891(14) 3.6455(9) 151.2(14) 1_556
O9 H9A O3 0.845(13) 2.008(13) 2.8467(13) 171.4(15) 2_566
O9 H9B O2 0.821(13) 2.004(13) 2.8173(12) 170.9(16) 2_666
O9 H9B S2 0.821(13) 2.874(14) 3.5637(10) 143.0(14) 2_666

_refine_diff_density_max         0.462
_refine_diff_density_min         -0.372
_refine_diff_density_rms         0.060

_shelxl_version_number           2014-3


_exptl_crystal_recrystallization_method 
'Slow evaporation of a methanol solution'
####################################################################### 
# 
# 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 1023180'
_audit_update_record             
;
2014-09-06 deposited with the CCDC.
2015-03-04 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C28 H44 Cu4 N4 O28 S4, 2(H2 O)'
_chemical_formula_sum            'C28 H48 Cu4 N4 O30 S4'
_chemical_formula_weight         1303.10

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'
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'

_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                   9.9962(4)
_cell_length_b                   17.2664(8)
_cell_length_c                   13.1588(6)
_cell_angle_alpha                90
_cell_angle_beta                 107.705(2)
_cell_angle_gamma                90
_cell_volume                     2163.61(17)
_cell_formula_units_Z            2
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    9219
_cell_measurement_theta_min      2.87
_cell_measurement_theta_max      26.27


_exptl_crystal_description       block
_exptl_crystal_colour            orange
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.000
_exptl_crystal_F_000             1328
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.130
_exptl_crystal_size_mid          0.090
_exptl_crystal_size_min          0.050
_exptl_absorpt_coefficient_mu    2.242
_shelx_estimated_absorpt_T_min   0.759
_shelx_estimated_absorpt_T_max   0.896
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.783
_exptl_absorpt_correction_T_max  0.895
_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 Photon 100'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            41836
_diffrn_reflns_av_unetI/netI     0.0445
_diffrn_reflns_av_R_equivalents  0.0962
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         2.258
_diffrn_reflns_theta_max         26.382
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             4422
_reflns_number_gt                3213
_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)+(0.0627P)²+4.2496P] 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         4422
_refine_ls_number_parameters     327
_refine_ls_number_restraints     3
_refine_ls_R_factor_all          0.0766
_refine_ls_R_factor_gt           0.0445
_refine_ls_wR_factor_ref         0.1210
_refine_ls_wR_factor_gt          0.1030
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_restrained_S_all      1.024
_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
C1 C 0.6178(5) 0.4585(2) 0.6241(3) 0.0164(9) Uani 1 1 d . . . . .
C2 C 0.7570(5) 0.4809(2) 0.6320(3) 0.0174(9) Uani 1 1 d . . . . .
C3 C 0.7968(4) 0.5566(2) 0.6689(3) 0.0160(9) Uani 1 1 d . . . . .
C4 C 0.7045(5) 0.6058(2) 0.6970(4) 0.0190(9) Uani 1 1 d . . . . .
H4 H 0.7345 0.6545 0.7247 0.023 Uiso 1 1 calc R U . . .
C5 C 0.5672(5) 0.5826(2) 0.6840(4) 0.0189(9) Uani 1 1 d . . . . .
C6 C 0.5227(5) 0.5082(2) 0.6460(4) 0.0188(9) Uani 1 1 d . . . . .
H6 H 0.4305 0.4927 0.6358 0.023 Uiso 1 1 calc R U . . .
C7 C 0.4430(5) 0.2753(2) 0.5625(4) 0.0183(9) Uani 1 1 d . . . . .
C8 C 0.5332(5) 0.2206(2) 0.5338(4) 0.0185(9) Uani 1 1 d . . . . .
C9 C 0.4831(5) 0.1391(2) 0.5074(4) 0.0217(10) Uani 1 1 d . . . . .
H9A H 0.5112 0.1085 0.5723 0.026 Uiso 1 1 calc R U . . .
H9B H 0.5298 0.1176 0.4590 0.026 Uiso 1 1 calc R U . . .
C10 C 0.3245(5) 0.1310(2) 0.4565(4) 0.0197(9) Uani 1 1 d . . . . .
C11 C 0.2531(5) 0.1711(3) 0.5305(4) 0.0220(10) Uani 1 1 d . . . . .
H11A H 0.1533 0.1750 0.4933 0.026 Uiso 1 1 calc R U . . .
H11B H 0.2641 0.1386 0.5926 0.026 Uiso 1 1 calc R U . . .
C12 C 0.3073(5) 0.2502(2) 0.5676(3) 0.0178(9) Uani 1 1 d . . . . .
C13 C 0.2762(6) 0.1673(3) 0.3459(4) 0.0319(11) Uani 1 1 d . . . . .
H13A H 0.3032 0.2209 0.3507 0.048 Uiso 1 1 calc R U . . .
H13B H 0.1759 0.1634 0.3175 0.048 Uiso 1 1 calc R U . . .
H13C H 0.3190 0.1406 0.2998 0.048 Uiso 1 1 calc R U . . .
C14 C 0.2845(6) 0.0450(3) 0.4476(5) 0.0327(12) Uani 1 1 d . . . . .
H14A H 0.1847 0.0400 0.4166 0.049 Uiso 1 1 calc R U . . .
H14B H 0.3127 0.0220 0.5173 0.049 Uiso 1 1 calc R U . . .
H14C H 0.3310 0.0191 0.4032 0.049 Uiso 1 1 calc R U . . .
Cu1 Cu 0.74544(6) 0.33642(3) 0.55141(5) 0.02122(16) Uani 1 1 d . . . . .
Cu2 Cu 0.29456(6) 0.37273(3) 0.71308(5) 0.02224(16) Uani 1 1 d . . . . .
N1 N 0.4753(4) 0.3511(2) 0.5952(3) 0.0187(8) Uani 1 1 d . . . . .
N2 N 0.5883(4) 0.3809(2) 0.5893(3) 0.0177(8) Uani 1 1 d . . . . .
O1 O 0.8415(3) 0.43182(18) 0.6063(3) 0.0257(8) Uani 1 1 d . . . . .
O2 O 0.6556(3) 0.23573(18) 0.5331(3) 0.0243(7) Uani 1 1 d . . . . .
O1W O 0.3622(4) 0.3794(2) 0.9973(3) 0.0434(10) Uani 1 1 d . . . . .
O3 O 0.2310(3) 0.29123(18) 0.6061(3) 0.0232(7) Uani 1 1 d . . . . .
O4 O 0.9174(3) 0.29342(19) 0.5269(3) 0.0273(8) Uani 1 1 d . . . . .
O5 O 0.3787(4) 0.4496(2) 0.8235(3) 0.0337(9) Uani 1 1 d D . . . .
O6 O 0.3999(5) 0.2957(2) 0.8168(3) 0.0406(10) Uani 1 1 d D . . . .
O7 O 0.1063(4) 0.3630(2) 0.7746(3) 0.0368(9) Uani 1 1 d . . . . .
O8 O 0.2018(3) 0.45517(19) 0.6143(3) 0.0251(7) Uani 1 1 d D . . . .
O11 O 0.3214(4) 0.6463(2) 0.6306(3) 0.0388(9) Uani 1 1 d . . . . .
O12 O 0.5169(4) 0.7163(2) 0.7537(3) 0.0383(9) Uani 1 1 d . . . . .
O13 O 0.4180(4) 0.6040(2) 0.8108(3) 0.0309(8) Uani 1 1 d . . . . .
O14 O 0.9769(4) 0.5920(2) 0.5713(3) 0.0341(9) Uani 1 1 d . . . . .
O15 O 0.9795(4) 0.66638(18) 0.7276(3) 0.0288(8) Uani 1 1 d . . . . .
O16 O 1.0660(4) 0.5345(2) 0.7457(3) 0.0358(9) Uani 1 1 d . . . . .
S1 S 0.44662(12) 0.64263(6) 0.72112(9) 0.0196(2) Uani 1 1 d . . . . .
S3 S 0.96854(12) 0.58988(6) 0.68051(9) 0.0201(2) Uani 1 1 d . . . . .
H1W H 0.4398 0.3780 1.0627 0.030 Uiso 1 1 d . U . . .
H2W H 0.2778 0.3623 1.0021 0.030 Uiso 1 1 d . U . . .
H5A H 0.3585 0.4979 0.8011 0.030 Uiso 1 1 d . U . . .
H5B H 0.374(6) 0.434(3) 0.883(2) 0.030 Uiso 1 1 d D U . . .
H6A H 0.357(5) 0.296(3) 0.861(4) 0.030 Uiso 1 1 d D U . . .
H6B H 0.4171 0.2488 0.7961 0.030 Uiso 1 1 d . U . . .
H7A H 0.0549 0.3988 0.7399 0.030 Uiso 1 1 d . U . . .
H7B H 0.0563 0.3203 0.7699 0.030 Uiso 1 1 d . U . . .
H8A H 0.1338 0.4425 0.5568 0.030 Uiso 1 1 d . U . . .
H8B H 0.156(5) 0.483(3) 0.644(4) 0.030 Uiso 1 1 d D U . . .
H4A H 0.9582 0.3292 0.4945 0.030 Uiso 1 1 d . U . . .
H4B H 0.9912 0.2914 0.5942 0.030 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 C6 1.374(6) . ?
C1 C2 1.417(6) . ?
C1 N2 1.419(5) . ?
C2 O1 1.311(5) . ?
C2 C3 1.410(6) . ?
C3 C4 1.383(6) . ?
C3 S3 1.772(4) . ?
C4 C5 1.390(6) . ?
C5 C6 1.400(6) . ?
C5 S1 1.767(4) . ?
C7 N1 1.384(5) . ?
C7 C8 1.433(6) . ?
C7 C12 1.445(6) . ?
C8 O2 1.254(5) . ?
C8 C9 1.499(6) . ?
C9 C10 1.528(6) . ?
C10 C13 1.523(7) . ?
C10 C14 1.533(6) . ?
C10 C11 1.537(6) . ?
C11 C12 1.496(6) . ?
C12 O3 1.255(5) . ?
Cu1 O1 1.933(3) . ?
Cu1 O2 1.938(3) . ?
Cu1 N2 1.944(4) . ?
Cu1 O4 1.987(3) . ?
Cu1 O11 2.302(4) 3_666 ?
Cu2 O3 1.955(3) . ?
Cu2 O8 1.960(3) . ?
Cu2 O5 1.959(4) . ?
Cu2 O6 1.966(4) . ?
Cu2 O7 2.270(4) . ?
N1 N2 1.265(5) . ?
O11 S1 1.443(4) . ?
O11 Cu1 2.302(4) 3_666 ?
O12 S1 1.453(4) . ?
O13 S1 1.457(3) . ?
O14 S3 1.464(4) . ?
O15 S3 1.449(3) . ?
O16 S3 1.446(4) . ?

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 122.7(4) . . ?
C6 C1 N2 124.7(4) . . ?
C2 C1 N2 112.6(4) . . ?
O1 C2 C3 123.5(4) . . ?
O1 C2 C1 120.0(4) . . ?
C3 C2 C1 116.5(4) . . ?
C4 C3 C2 121.3(4) . . ?
C4 C3 S3 119.1(3) . . ?
C2 C3 S3 119.6(3) . . ?
C3 C4 C5 120.3(4) . . ?
C4 C5 C6 120.2(4) . . ?
C4 C5 S1 121.9(3) . . ?
C6 C5 S1 117.9(3) . . ?
C1 C6 C5 118.8(4) . . ?
N1 C7 C8 126.8(4) . . ?
N1 C7 C12 113.7(4) . . ?
C8 C7 C12 119.2(4) . . ?
O2 C8 C7 123.9(4) . . ?
O2 C8 C9 116.8(4) . . ?
C7 C8 C9 119.2(4) . . ?
C8 C9 C10 114.6(4) . . ?
C13 C10 C9 111.5(4) . . ?
C13 C10 C14 109.0(4) . . ?
C9 C10 C14 109.5(4) . . ?
C13 C10 C11 110.2(4) . . ?
C9 C10 C11 107.6(4) . . ?
C14 C10 C11 109.0(4) . . ?
C12 C11 C10 115.3(4) . . ?
O3 C12 C7 122.9(4) . . ?
O3 C12 C11 116.3(4) . . ?
C7 C12 C11 120.7(4) . . ?
O1 Cu1 O2 165.90(15) . . ?
O1 Cu1 N2 85.18(14) . . ?
O2 Cu1 N2 90.33(14) . . ?
O1 Cu1 O4 91.34(13) . . ?
O2 Cu1 O4 92.05(13) . . ?
N2 Cu1 O4 174.51(15) . . ?
O1 Cu1 O11 103.43(15) . 3_666 ?
O2 Cu1 O11 90.58(15) . 3_666 ?
N2 Cu1 O11 102.34(14) . 3_666 ?
O4 Cu1 O11 82.59(14) . 3_666 ?
O3 Cu2 O8 93.48(14) . . ?
O3 Cu2 O5 173.77(15) . . ?
O8 Cu2 O5 90.53(15) . . ?
O3 Cu2 O6 90.07(16) . . ?
O8 Cu2 O6 175.48(17) . . ?
O5 Cu2 O6 85.70(16) . . ?
O3 Cu2 O7 94.60(14) . . ?
O8 Cu2 O7 90.80(14) . . ?
O5 Cu2 O7 90.10(15) . . ?
O6 Cu2 O7 91.69(16) . . ?
N2 N1 C7 119.5(4) . . ?
N1 N2 C1 117.8(4) . . ?
N1 N2 Cu1 131.4(3) . . ?
C1 N2 Cu1 110.6(3) . . ?
C2 O1 Cu1 111.2(3) . . ?
C8 O2 Cu1 127.0(3) . . ?
C12 O3 Cu2 126.3(3) . . ?
S1 O11 Cu1 140.2(2) . 3_666 ?
O11 S1 O12 115.2(2) . . ?
O11 S1 O13 110.7(2) . . ?
O12 S1 O13 111.0(2) . . ?
O11 S1 C5 106.9(2) . . ?
O12 S1 C5 106.6(2) . . ?
O13 S1 C5 105.9(2) . . ?
O16 S3 O15 113.5(2) . . ?
O16 S3 O14 111.7(2) . . ?
O15 S3 O14 112.1(2) . . ?
O16 S3 C3 107.3(2) . . ?
O15 S3 C3 106.1(2) . . ?
O14 S3 C3 105.5(2) . . ?

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
C6 H6 O8 0.93 2.31 3.239(5) 178.7 .
C11 H11B O13 0.970 2.59 3.286(5) 129.1 2_546
O1W H1W O13 0.970 1.857(4) 2.813(6) 168.8(3) 3_667
O1W H1W S1 0.970 2.750 3.636(4) 153.0(2) 3_667
O1W H2W O2 0.910 2.200 3.005(5) 147.0(3) 4_566
O5 H5A O13 0.890 1.920 2.707(5) 147.0 .
O5 H5A S1 0.890 2.950 3.733(4) 149.0 .
O5 H5B O1W 0.85(2) 1.81(2) 2.639(5) 166(5) .
O6 H6A O1W 0.83(2) 2.28(4) 2.901(6) 132(5) .
O6 H6A O4 0.83(2) 2.59(5) 3.122(5) 124(5) 4_566
O6 H6B O15 0.890 1.840 2.685(5) 158.2(3) 2_646
O6 H6B S3 0.890) 2.950 3.786(4) 157.1(3) 2_646
O7 H7A O1 0.840 2.380 3.124(5) 146.6(3) 1_455
O7 H7A O16 0.840 2.350 2.998(5) 134.4(3) 1_455
O7 H7B O12 0.880 1.930 2.791(5) 165.6(3) 2_546
O8 H8A O14 0.880 1.810 2.677(5) 167.9(2) 3_666
O8 H8A S3 0.880 3.030 3.813(4) 150.0(2) 3_666
O8 H8B O14 0.834(19) 2.57(4) 3.192(5) 132(5) 1_455
O8 H8B O16 0.834(19) 2.04(2) 2.853(5) 166(5) 1_455
O8 H8B S3 0.834(19) 2.78(3) 3.584(3) 163(5) 1_455
O4 H4A O14 0.910 1.830 2.744(5) 173.6(2) 3_766
O4 H4A S3 0.910 2.970 3.834(4) 158.4(2) 3_766
C6 H6 O8 0.93 2.31 3.239(5) 178.7 .
C11 H11B O13 0.97 2.59 3.286(5) 129.1 2_546
O1W H1W O13 0.970 1.860 2.813(6) 168.8(3) 3_667
O1W H1W S1 0.970 2.750 3.636(4) 153.0(2) 3_667
O1W H2W O2 0.910 2.200 3.005(5) 147.0(3) 4_566
O5 H5A O13 0.890 1.920 2.707(5) 147.00 .
O5 H5A S1 0.890 2.950 3.733(4) 149.0 .
O5 H5B O1W 0.85(2) 1.81(2) 2.639(5) 166(5) .
O6 H6A O1W 0.83(2) 2.28(4) 2.901(6) 132(5) .
O6 H6A O4 0.83(2) 2.59(5) 3.122(5) 124(5) 4_566
O6 H6B O15 0.890 1.840 2.685(5) 158.2(3) 2_646
O6 H6B S3 0.890 2.950 3.786(4) 157.1(3) 2_646
O7 H7A O1 0.840 2.380 3.124(5) 146.6(3) 1_455
O7 H7A O16 0.840 2.350 2.998(5) 134.4(3) 1_455
O7 H7B O12 0.880 1.930 2.791(5) 165.6(3) 2_546
O8 H8A O14 0.880 1.810 2.677(5) 167.9(2) 3_666
O8 H8A S3 0.880 3.030 3.813(4) 150.0(2) 3_666
O8 H8B O14 0.834(19) 2.57(4) 3.192(5) 132(5) 1_455
O8 H8B O16 0.834(19) 2.04(2) 2.853(5) 166(5) 1_455
O8 H8B S3 0.834(19) 2.78(3) 3.584(3) 163(5) 1_455
O4 H4A O14 0.910 1.830 2.744(5) 173.6(2) 3_766
O4 H4A S3 0.910 2.970 3.834(4) 158.4(2) 3_766

_refine_diff_density_max         0.947
_refine_diff_density_min         -0.539
_refine_diff_density_rms         0.141

_shelxl_version_number           2013-4





