# Electronic Supplementary Material (ESI) for New Journal of Chemistry.
# This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 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_shelx
_audit_block_doi                 10.5517/cc13pwk7
_database_code_depnum_ccdc_archive 'CCDC 1033929'
_audit_update_record             
;
2014-11-13 deposited with the CCDC.
2015-01-27 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         '2(C7 H7 N2), Co H12 O6, 2(O4 S), 4(H2 O)'
_chemical_formula_sum            'C14 H34 Co N4 O18 S2'
_chemical_formula_weight         669.50

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'
Co Co 0.3494 0.9721 '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
_symmetry_space_group_name_Hall  -P1

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   6.7203(2)
_cell_length_b                   8.2504(3)
_cell_length_c                   12.3358(4)
_cell_angle_alpha                84.4690(10)
_cell_angle_beta                 79.593(2)
_cell_angle_gamma                85.310(2)
_cell_volume                     668.13(4)
_cell_formula_units_Z            1
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    4074
_cell_measurement_theta_min      2.910
_cell_measurement_theta_max      40.250

_exptl_crystal_description       Polyhedral
_exptl_crystal_colour            red
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.11
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.664
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             349
_exptl_absorpt_coefficient_mu    0.886
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_correction_T_min  0.7887
_exptl_absorpt_correction_T_max  0.9421
_exptl_absorpt_process_details   
; 
(c.f. r.h. blessing, acta cryst. (1995), a51, 33-38) 
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_measurement_device_type  KappaCCD
_diffrn_measurement_device       '95mm CCD camera on κ-goniostat'
_diffrn_detector_area_resol_mean 9
_diffrn_radiation_monochromator  'horizonally mounted graphite crystal'
_computing_data_collection       'Collect (Bruker AXS BV, 1997-2004)'
_diffrn_measurement_method       CCD
_diffrn_reflns_number            14518
_diffrn_reflns_av_R_equivalents  0.0487
_diffrn_reflns_av_sigmaI/netI    0.0466
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         3.09
_diffrn_reflns_theta_max         40.32
_reflns_number_total             8328
_reflns_number_gt                6573
_reflns_threshold_expression     >2sigma(I)

_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0523P)²+0.1864P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.86(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         8328
_refine_ls_number_parameters     219
_refine_ls_number_restraints     15
_refine_ls_R_factor_all          0.0565
_refine_ls_R_factor_gt           0.0421
_refine_ls_wR_factor_ref         0.1183
_refine_ls_wR_factor_gt          0.1085
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_restrained_S_all      1.028
_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
Co1 Co 0.5000 0.0000 1.0000 0.02069(6) Uani 1 2 d S . .
S1 S 0.10146(4) 0.35918(3) 0.77738(2) 0.02270(6) Uani 1 1 d . . .
OW3 O 0.36072(14) -0.04387(11) 0.86737(8) 0.02895(16) Uani 1 1 d D . .
O1 O 0.30634(15) 0.39905(13) 0.78895(9) 0.0364(2) Uani 1 1 d . . .
OW1 O 0.41420(17) 0.39339(12) 1.15287(10) 0.0364(2) Uani 1 1 d D . .
O2 O 0.06301(18) 0.40859(13) 0.66547(8) 0.0374(2) Uani 1 1 d . . .
OW4 O 0.78306(13) -0.02627(12) 0.89275(9) 0.03215(18) Uani 1 1 d D . .
OW2 O -0.07437(17) 0.27329(12) 1.06955(9) 0.03548(19) Uani 1 1 d D . .
O3 O -0.04779(18) 0.44835(16) 0.85781(10) 0.0441(3) Uani 1 1 d . . .
OW5 O 0.48367(17) 0.24893(11) 0.95837(9) 0.03401(19) Uani 1 1 d D . .
N1 N 0.27788(18) 0.14832(16) 0.33206(9) 0.0347(2) Uani 1 1 d . . .
HN1 H 0.3079 0.1611 0.2611 0.042 Uiso 1 1 calc R . .
O4 O 0.08408(18) 0.18205(12) 0.80243(11) 0.0427(3) Uani 1 1 d . . .
C2 C 0.29464(17) 0.00210(16) 0.39591(10) 0.0288(2) Uani 1 1 d . . .
C7 C 0.23168(17) 0.03855(15) 0.50589(9) 0.02714(19) Uani 1 1 d . . .
C5 C 0.2945(3) -0.2382(2) 0.56572(16) 0.0448(3) Uani 1 1 d . . .
H5 H 0.2958 -0.3220 0.6217 0.054 Uiso 1 1 calc R . .
C1 C 0.2079(2) 0.26570(18) 0.39822(12) 0.0353(2) Uani 1 1 d . . .
H1 H 0.1831 0.3748 0.3747 0.042 Uiso 1 1 calc R . .
C6 C 0.2311(2) -0.08131(19) 0.59342(11) 0.0364(3) Uani 1 1 d . . .
H6 H 0.1903 -0.0573 0.6666 0.044 Uiso 1 1 calc R . .
C3 C 0.3580(2) -0.1559(2) 0.36843(14) 0.0391(3) Uani 1 1 d . . .
H3 H 0.3988 -0.1804 0.2954 0.047 Uiso 1 1 calc R . .
C4 C 0.3570(3) -0.2738(2) 0.45515(18) 0.0458(4) Uani 1 1 d . . .
H4 H 0.3991 -0.3807 0.4401 0.055 Uiso 1 1 calc R . .
N2 N 0.17868(17) 0.20458(14) 0.50237(9) 0.03136(19) Uani 1 1 d . . .
HN2 H 0.1340 0.2590 0.5588 0.038 Uiso 1 1 calc R . .
H21 H 0.305(3) 0.467(3) 1.154(2) 0.056(7) Uiso 1 1 d D . .
H14 H 0.874(3) -0.110(2) 0.9078(17) 0.041(5) Uiso 1 1 d D . .
H15 H 0.456(3) 0.308(3) 1.0180(14) 0.045(6) Uiso 1 1 d D . .
H25 H 0.419(3) 0.300(3) 0.9042(15) 0.055(7) Uiso 1 1 d D . .
H22 H -0.085(4) 0.317(3) 0.9993(14) 0.056(7) Uiso 1 1 d D . .
H12 H -0.036(5) 0.356(3) 1.105(2) 0.098(11) Uiso 1 1 d D . .
H11 H 0.516(3) 0.448(3) 1.174(2) 0.066(8) Uiso 1 1 d D . .
H13 H 0.277(3) 0.041(2) 0.841(2) 0.059(7) Uiso 1 1 d D . .
H23 H 0.282(3) -0.134(2) 0.882(2) 0.062(7) Uiso 1 1 d D . .
H24 H 0.844(4) 0.064(2) 0.866(2) 0.074(8) Uiso 1 1 d 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
Co1 OW5 2.0673(9) . ?
Co1 OW5 2.0673(9) 2_657 ?
Co1 OW3 2.0993(9) 2_657 ?
Co1 OW3 2.0993(9) . ?
Co1 OW4 2.1200(9) 2_657 ?
Co1 OW4 2.1200(9) . ?
S1 O2 1.4635(9) 1 ?
S1 O2 1.4635(9) . ?
S1 O4 1.4739(10) 1 ?
S1 O4 1.4739(10) . ?
S1 O1 1.4759(10) . ?
S1 O1 1.4759(10) 1 ?
S1 O3 1.4807(11) . ?
S1 O3 1.4807(11) 1 ?
OW3 H13 0.928(15) . ?
OW3 H23 0.931(15) . ?
O1 O1 0.000(3) 1 ?
OW1 OW1 0.000(3) 1 ?
OW1 H21 0.915(15) . ?
OW1 H11 0.934(16) . ?
O2 O2 0.000(2) 1 ?
OW4 H14 0.912(14) . ?
OW4 H24 0.888(16) . ?
OW2 H22 0.919(15) . ?
OW2 H12 0.926(17) . ?
O3 O3 0.000(2) 1 ?
OW5 H15 0.904(14) . ?
OW5 H25 0.912(15) . ?
N1 C1 1.3282(19) . ?
N1 C2 1.3839(18) . ?
N1 HN1 0.8600 . ?
O4 O4 0.000(3) 1 ?
C2 C3 1.3923(19) . ?
C2 C7 1.4002(16) . ?
C7 N2 1.3854(17) . ?
C7 C6 1.3918(18) . ?
C5 C6 1.384(2) . ?
C5 C4 1.405(3) . ?
C5 H5 0.9300 . ?
C1 N2 1.3204(18) . ?
C1 H1 0.9300 . ?
C6 H6 0.9300 . ?
C3 C4 1.374(3) . ?
C3 H3 0.9300 . ?
C4 H4 0.9300 . ?
N2 HN2 0.8600 . ?

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
OW5 Co1 OW5 180.0 . 2_657 ?
OW5 Co1 OW3 88.14(4) . 2_657 ?
OW5 Co1 OW3 91.86(4) 2_657 2_657 ?
OW5 Co1 OW3 91.86(4) . . ?
OW5 Co1 OW3 88.14(4) 2_657 . ?
OW3 Co1 OW3 180.0 2_657 . ?
OW5 Co1 OW4 89.29(4) . 2_657 ?
OW5 Co1 OW4 90.71(4) 2_657 2_657 ?
OW3 Co1 OW4 87.88(4) 2_657 2_657 ?
OW3 Co1 OW4 92.12(4) . 2_657 ?
OW5 Co1 OW4 90.71(4) . . ?
OW5 Co1 OW4 89.29(4) 2_657 . ?
OW3 Co1 OW4 92.12(4) 2_657 . ?
OW3 Co1 OW4 87.88(4) . . ?
OW4 Co1 OW4 180.0 2_657 . ?
O2 S1 O2 0.00(9) 1 . ?
O2 S1 O4 110.18(7) 1 1 ?
O2 S1 O4 110.18(7) . 1 ?
O2 S1 O4 110.18(7) 1 . ?
O2 S1 O4 110.18(7) . . ?
O4 S1 O4 0.00(9) 1 . ?
O2 S1 O1 110.83(7) 1 . ?
O2 S1 O1 110.83(7) . . ?
O4 S1 O1 108.81(6) 1 . ?
O4 S1 O1 108.81(6) . . ?
O2 S1 O1 110.83(7) 1 1 ?
O2 S1 O1 110.83(7) . 1 ?
O4 S1 O1 108.81(6) 1 1 ?
O4 S1 O1 108.81(6) . 1 ?
O1 S1 O1 0.00(8) . 1 ?
O2 S1 O3 109.26(7) 1 . ?
O2 S1 O3 109.26(7) . . ?
O4 S1 O3 109.63(8) 1 . ?
O4 S1 O3 109.63(8) . . ?
O1 S1 O3 108.10(7) . . ?
O1 S1 O3 108.10(7) 1 . ?
O2 S1 O3 109.26(7) 1 1 ?
O2 S1 O3 109.26(7) . 1 ?
O4 S1 O3 109.63(8) 1 1 ?
O4 S1 O3 109.63(8) . 1 ?
O1 S1 O3 108.10(7) . 1 ?
O1 S1 O3 108.10(7) 1 1 ?
O3 S1 O3 0.00(8) . 1 ?
Co1 OW3 H13 117.0(15) . . ?
Co1 OW3 H23 113.6(16) . . ?
H13 OW3 H23 105.1(18) . . ?
O1 O1 S1 0(10) 1 . ?
OW1 OW1 H21 0(10) 1 . ?
OW1 OW1 H11 0(10) 1 . ?
H21 OW1 H11 106.0(18) . . ?
O2 O2 S1 0(10) 1 . ?
Co1 OW4 H14 119.4(13) . . ?
Co1 OW4 H24 117.6(17) . . ?
H14 OW4 H24 111.7(19) . . ?
H22 OW2 H12 106(2) . . ?
O3 O3 S1 0(10) 1 . ?
Co1 OW5 H15 113.0(14) . . ?
Co1 OW5 H25 124.7(15) . . ?
H15 OW5 H25 108.8(17) . . ?
C1 N1 C2 108.88(11) . . ?
C1 N1 HN1 125.6 . . ?
C2 N1 HN1 125.6 . . ?
O4 O4 S1 0(9) 1 . ?
N1 C2 C3 132.19(13) . . ?
N1 C2 C7 106.03(11) . . ?
C3 C2 C7 121.78(13) . . ?
N2 C7 C6 132.17(12) . . ?
N2 C7 C2 106.21(11) . . ?
C6 C7 C2 121.62(12) . . ?
C6 C5 C4 121.63(14) . . ?
C6 C5 H5 119.2 . . ?
C4 C5 H5 119.2 . . ?
N2 C1 N1 109.95(12) . . ?
N2 C1 H1 125.0 . . ?
N1 C1 H1 125.0 . . ?
C5 C6 C7 116.39(13) . . ?
C5 C6 H6 121.8 . . ?
C7 C6 H6 121.8 . . ?
C4 C3 C2 116.35(14) . . ?
C4 C3 H3 121.8 . . ?
C2 C3 H3 121.8 . . ?
C3 C4 C5 122.23(15) . . ?
C3 C4 H4 118.9 . . ?
C5 C4 H4 118.9 . . ?
C1 N2 C7 108.93(11) . . ?
C1 N2 HN2 125.5 . . ?
C7 N2 HN2 125.5 . . ?

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
OW3 H13 O4 0.928(15) 1.774(16) 2.6936(14) 170(2) 1
OW3 H23 OW2 0.931(15) 1.859(17) 2.7681(14) 165(2) 2_557
OW4 H24 O4 0.888(16) 1.95(2) 2.7700(14) 153(2) 1_655
OW4 H14 OW2 0.912(14) 1.864(15) 2.7741(15) 175.5(19) 2_657
OW5 H15 OW1 0.904(14) 1.836(14) 2.7296(16) 170(2) 1
OW5 H25 O1 0.912(15) 1.825(15) 2.7353(14) 176(2) 1
OW1 H21 O3 0.915(15) 1.834(15) 2.7100(16) 160(2) 2_567
OW1 H11 O1 0.934(16) 1.948(17) 2.8678(14) 168(2) 2_667
OW2 H22 O3 0.919(15) 1.950(17) 2.8437(17) 164(2) 1
OW2 H12 O3 0.926(17) 1.873(19) 2.7789(17) 166(3) 2_567
N1 HN1 OW1 0.86 2.31 2.9195(16) 127.7 1_554
N2 HN2 O2 0.86 1.86 2.7128(15) 169.3 1

_diffrn_measured_fraction_theta_max 0.985
_diffrn_reflns_theta_full        40.32
_diffrn_measured_fraction_theta_full 0.985
_refine_diff_density_max         0.764
_refine_diff_density_min         -1.052
_refine_diff_density_rms         0.076
####################################################################### 
# 
# 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_shelxl
_audit_block_doi                 10.5517/cc13pwl8
_database_code_depnum_ccdc_archive 'CCDC 1033930'
_audit_update_record             
;
2014-11-13 deposited with the CCDC.
2015-01-27 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         '2(C7 H7 N2), Cu H12 O6, 2(O4 S), 4(H2 O)'
_chemical_formula_sum            'C14 H34 Cu N4 O18 S2'
_chemical_formula_weight         674.11

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'

_symmetry_cell_setting           triclinic
_symmetry_space_group_name_H-M   P-1
_symmetry_space_group_name_Hall  -P1

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   6.82920(10)
_cell_length_b                   8.1314(2)
_cell_length_c                   12.3445(3)
_cell_angle_alpha                85.4290(10)
_cell_angle_beta                 81.4370(10)
_cell_angle_gamma                85.4360(10)
_cell_volume                     674.11(3)
_cell_formula_units_Z            1
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    2477
_cell_measurement_theta_min      2.910
_cell_measurement_theta_max      32.032

_exptl_crystal_description       Polyhedral
_exptl_crystal_colour            blue
_exptl_crystal_size_max          0.263
_exptl_crystal_size_mid          0.197
_exptl_crystal_size_min          0.019
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.661
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             351
_exptl_absorpt_coefficient_mu    1.052
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_correction_T_min  0.8503
_exptl_absorpt_correction_T_max  0.9914
_exptl_absorpt_process_details   
;
(c.f. r.h. blessing, acta cryst. (1995), a51, 33-38) 
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_measurement_device_type  KappaCCD
_diffrn_measurement_device       '95mm CCD camera on κ-goniostat'
_diffrn_detector_area_resol_mean 9
_diffrn_radiation_monochromator  'horizonally mounted graphite crystal'
_computing_data_collection       'Collect (Bruker AXS BV, 1997-2004)'
_diffrn_measurement_method       CCD
_diffrn_reflns_number            8898
_diffrn_reflns_av_R_equivalents  0.0430
_diffrn_reflns_av_sigmaI/netI    0.0410
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         2.93
_diffrn_reflns_theta_max         32.03
_reflns_number_total             4622
_reflns_number_gt                4067
_reflns_threshold_expression     >2sigma(I)

_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
 Refinement of F² against ALL reflections.  The weighted R-factor wR and
 goodness of fit S are based on F², conventional R-factors R are based
 on F, with F set to zero for negative F². The threshold expression of
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is
 not relevant to the choice of reflections for refinement.  R-factors based
 on F² are statistically about twice as large as those based on F, and R-
 factors based on ALL data will be even larger.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0559P)²+0.5805P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.093(10)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         4622
_refine_ls_number_parameters     247
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0537
_refine_ls_R_factor_gt           0.0475
_refine_ls_wR_factor_ref         0.1278
_refine_ls_wR_factor_gt          0.1225
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_restrained_S_all      1.060
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu1 Cu 0.5000 0.0000 1.5000 0.02500(12) Uani 1 2 d S . .
S1 S 0.11407(7) 0.35608(6) 1.27653(4) 0.02668(13) Uani 1 1 d . . .
OW3 O 0.3660(2) -0.0452(2) 1.37571(13) 0.0315(3) Uani 1 1 d . . .
OW4 O 0.8078(3) -0.0312(3) 1.38068(15) 0.0385(4) Uani 1 1 d . . .
O1 O 0.3068(3) 0.4033(3) 1.29974(18) 0.0545(5) Uani 1 1 d . . .
O3 O 0.0833(3) 0.4119(2) 1.16463(13) 0.0390(4) Uani 1 1 d . . .
OW5 O 0.4739(3) 0.23996(19) 1.46615(15) 0.0356(3) Uani 1 1 d . . .
OW1 O 0.3950(3) 0.3957(2) 1.65357(17) 0.0408(4) Uani 1 1 d . . .
OW2 O 0.0975(3) -0.2774(2) 1.43496(17) 0.0415(4) Uani 1 1 d . . .
O2 O 0.1115(3) 0.1763(2) 1.2931(2) 0.0548(5) Uani 1 1 d . . .
O4 O -0.0394(4) 0.4370(4) 1.35438(19) 0.0753(8) Uani 1 1 d . . .
N1 N 0.2543(3) 0.1390(3) 0.83198(17) 0.0410(4) Uani 1 1 d . . .
N2 N 0.1795(3) 0.1998(2) 1.00181(16) 0.0341(4) Uani 1 1 d . . .
C2 C 0.2358(3) 0.0322(3) 1.00408(16) 0.0291(4) Uani 1 1 d . . .
C7 C 0.2829(3) -0.0070(3) 0.89499(18) 0.0329(4) Uani 1 1 d . . .
C3 C 0.2500(4) -0.0871(3) 1.0904(2) 0.0394(5) Uani 1 1 d . . .
C4 C 0.3112(4) -0.2459(3) 1.0619(3) 0.0482(6) Uani 1 1 d . . .
C5 C 0.3579(4) -0.2838(3) 0.9520(3) 0.0508(6) Uani 1 1 d . . .
C1 C 0.1918(4) 0.2588(3) 0.8987(2) 0.0395(5) Uani 1 1 d . . .
C6 C 0.3453(4) -0.1668(3) 0.8663(2) 0.0447(5) Uani 1 1 d . . .
H1 H 0.164(5) 0.363(4) 0.878(3) 0.047(8) Uiso 1 1 d . . .
H3 H 0.213(5) -0.060(4) 1.159(3) 0.046(8) Uiso 1 1 d . . .
H6 H 0.381(5) -0.191(5) 0.793(3) 0.059(10) Uiso 1 1 d . . .
H4 H 0.313(6) -0.331(5) 1.116(3) 0.068(11) Uiso 1 1 d . . .
H5 H 0.401(6) -0.390(5) 0.937(3) 0.067(11) Uiso 1 1 d . . .
HN2 H 0.149(5) 0.267(5) 1.065(3) 0.063(10) Uiso 1 1 d . . .
HN1 H 0.271(6) 0.152(5) 0.762(3) 0.064(11) Uiso 1 1 d . . .
H1W1 H 0.308(6) 0.458(5) 1.657(3) 0.050(10) Uiso 1 1 d . . .
H2W1 H 0.482(6) 0.434(5) 1.668(3) 0.061(11) Uiso 1 1 d . . .
H1W2 H 0.092(7) -0.310(5) 1.501(4) 0.082(14) Uiso 1 1 d . . .
H2W2 H 0.076(6) -0.344(5) 1.405(4) 0.065(12) Uiso 1 1 d . . .
H1W4 H 0.889(5) -0.100(4) 1.406(3) 0.046(9) Uiso 1 1 d . . .
H2W4 H 0.861(5) 0.034(5) 1.361(3) 0.051(10) Uiso 1 1 d . . .
H1W3 H 0.302(5) 0.029(4) 1.354(3) 0.046(9) Uiso 1 1 d . . .
H2W3 H 0.299(6) -0.121(5) 1.391(3) 0.062(11) Uiso 1 1 d . . .
H1W5 H 0.413(6) 0.288(5) 1.420(3) 0.063(11) Uiso 1 1 d . . .
H2W5 H 0.443(5) 0.288(4) 1.521(3) 0.042(8) Uiso 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 OW5 1.9623(15) . ?
Cu1 OW5 1.9623(15) 2_658 ?
Cu1 OW3 1.9719(15) . ?
Cu1 OW3 1.9719(15) 2_658 ?
Cu1 OW4 2.3884(17) . ?
Cu1 OW4 2.3884(17) 2_658 ?
S1 O3 1.4594(16) . ?
S1 O2 1.4612(18) 1 ?
S1 O2 1.4612(18) . ?
S1 O4 1.465(2) . ?
S1 O1 1.474(2) 1 ?
S1 O1 1.474(2) . ?
OW3 H1W3 0.77(4) . ?
OW3 H2W3 0.79(4) . ?
OW4 H1W4 0.83(4) . ?
OW4 H2W4 0.68(4) . ?
O1 O1 0.000(4) 1 ?
OW5 H1W5 0.81(4) . ?
OW5 H2W5 0.80(3) . ?
OW1 OW1 0.000(4) 1 ?
OW1 H1W1 0.75(4) . ?
OW1 H2W1 0.74(4) . ?
OW2 OW2 0.000(6) 1 ?
OW2 H1W2 0.83(5) . ?
OW2 H2W2 0.71(4) . ?
O2 O2 0.000(6) 1 ?
N1 C1 1.329(3) . ?
N1 C7 1.383(3) . ?
N1 HN1 0.86(4) . ?
N2 C1 1.317(3) . ?
N2 C2 1.386(3) . ?
N2 HN2 0.97(4) . ?
C2 C3 1.392(3) . ?
C2 C7 1.393(3) . ?
C7 C6 1.392(3) . ?
C3 C4 1.381(4) . ?
C3 H3 0.89(3) . ?
C4 C5 1.400(5) . ?
C4 H4 0.92(4) . ?
C5 C6 1.373(4) . ?
C5 H5 0.91(4) . ?
C1 H1 0.88(3) . ?
C6 H6 0.93(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
OW5 Cu1 OW5 180.000(1) . 2_658 ?
OW5 Cu1 OW3 92.64(7) . . ?
OW5 Cu1 OW3 87.36(7) 2_658 . ?
OW5 Cu1 OW3 87.36(7) . 2_658 ?
OW5 Cu1 OW3 92.64(7) 2_658 2_658 ?
OW3 Cu1 OW3 180.000(1) . 2_658 ?
OW5 Cu1 OW4 92.89(8) . . ?
OW5 Cu1 OW4 87.11(7) 2_658 . ?
OW3 Cu1 OW4 87.79(7) . . ?
OW3 Cu1 OW4 92.21(7) 2_658 . ?
OW5 Cu1 OW4 87.11(7) . 2_658 ?
OW5 Cu1 OW4 92.89(8) 2_658 2_658 ?
OW3 Cu1 OW4 92.21(7) . 2_658 ?
OW3 Cu1 OW4 87.79(7) 2_658 2_658 ?
OW4 Cu1 OW4 180.000(1) . 2_658 ?
O3 S1 O2 110.67(11) . 1 ?
O3 S1 O2 110.67(11) . . ?
O2 S1 O2 0.0(2) 1 . ?
O3 S1 O4 109.37(12) . . ?
O2 S1 O4 110.85(17) 1 . ?
O2 S1 O4 110.85(17) . . ?
O3 S1 O1 110.95(12) . 1 ?
O2 S1 O1 108.08(12) 1 1 ?
O2 S1 O1 108.08(12) . 1 ?
O4 S1 O1 106.85(16) . 1 ?
O3 S1 O1 110.95(12) . . ?
O2 S1 O1 108.08(12) 1 . ?
O2 S1 O1 108.08(12) . . ?
O4 S1 O1 106.85(16) . . ?
O1 S1 O1 0.00(15) 1 . ?
Cu1 OW3 H1W3 114(3) . . ?
Cu1 OW3 H2W3 111(3) . . ?
H1W3 OW3 H2W3 109(4) . . ?
Cu1 OW4 H1W4 113(2) . . ?
Cu1 OW4 H2W4 122(3) . . ?
H1W4 OW4 H2W4 105(4) . . ?
O1 O1 S1 0(10) 1 . ?
Cu1 OW5 H1W5 126(3) . . ?
Cu1 OW5 H2W5 112(2) . . ?
H1W5 OW5 H2W5 107(4) . . ?
OW1 OW1 H1W1 0(10) 1 . ?
OW1 OW1 H2W1 0(10) 1 . ?
H1W1 OW1 H2W1 109(4) . . ?
OW2 OW2 H1W2 0(10) 1 . ?
OW2 OW2 H2W2 0(10) 1 . ?
H1W2 OW2 H2W2 109(4) . . ?
O2 O2 S1 0(10) 1 . ?
C1 N1 C7 108.6(2) . . ?
C1 N1 HN1 125(3) . . ?
C7 N1 HN1 127(3) . . ?
C1 N2 C2 108.69(19) . . ?
C1 N2 HN2 124(2) . . ?
C2 N2 HN2 127(2) . . ?
N2 C2 C3 132.1(2) . . ?
N2 C2 C7 106.40(18) . . ?
C3 C2 C7 121.5(2) . . ?
N1 C7 C6 131.8(2) . . ?
N1 C7 C2 106.15(19) . . ?
C6 C7 C2 122.1(2) . . ?
C4 C3 C2 116.4(2) . . ?
C4 C3 H3 124(2) . . ?
C2 C3 H3 120(2) . . ?
C3 C4 C5 121.6(3) . . ?
C3 C4 H4 120(3) . . ?
C5 C4 H4 118(3) . . ?
C6 C5 C4 122.4(3) . . ?
C6 C5 H5 119(3) . . ?
C4 C5 H5 119(3) . . ?
N2 C1 N1 110.2(2) . . ?
N2 C1 H1 124(2) . . ?
N1 C1 H1 126(2) . . ?
C5 C6 C7 116.0(2) . . ?
C5 C6 H6 122(2) . . ?
C7 C6 H6 122(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
OW3 H1W3 O2 0.77(4) 1.90(4) 2.654(2) 168(4) 1
OW3 H2W3 OW2 0.79(4) 1.94(4) 2.719(2) 170(4) 1
OW4 H2W4 O2 0.68(4) 2.17(4) 2.813(3) 160(4) 1_655
OW4 H1W4 OW2 0.83(4) 2.00(4) 2.814(3) 168(3) 1_655
OW5 H2W5 OW1 0.80(3) 1.89(3) 2.690(3) 174(3) 1
OW5 H1W5 O1 0.81(4) 1.90(4) 2.704(2) 172(4) 1
N1 HN1 OW1 0.86(4) 2.44(4) 3.014(3) 125(3) 1_554
N2 HN2 O3 0.97(4) 1.76(4) 2.725(3) 172(3) .
OW1 H2W1 O1 0.74(4) 2.13(4) 2.860(3) 167(4) 2_668
OW1 H1W1 O4 0.75(4) 1.98(4) 2.698(3) 161(4) 2_568
OW2 H1W2 O4 0.83(5) 1.99(5) 2.800(3) 164(4) 2_558
OW2 H2W2 O4 0.71(4) 2.18(4) 2.872(4) 165(5) 1_545

_diffrn_measured_fraction_theta_max 0.983
_diffrn_reflns_theta_full        32.03
_diffrn_measured_fraction_theta_full 0.983
_refine_diff_density_max         1.542
_refine_diff_density_min         -0.987
_refine_diff_density_rms         0.080
####################################################################### 
# 
# 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_shelxl
_audit_block_doi                 10.5517/cc13pwm9
_database_code_depnum_ccdc_archive 'CCDC 1033931'
_audit_update_record             
;
2014-11-13 deposited with the CCDC.
2015-01-27 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         '2(C7 H7 N2), Fe H12 O6, 2(O4 S), 3(H2 O)'
_chemical_formula_sum            'C14 H32 Fe N4 O17 S2'
_chemical_formula_weight         648.41

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'
Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   P21/n
_symmetry_space_group_name_Hall  -P2yn

loop_
_symmetry_equiv_pos_as_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                   6.67060(10)
_cell_length_b                   26.5804(4)
_cell_length_c                   15.2009(2)
_cell_angle_alpha                90.00
_cell_angle_beta                 92.2540(10)
_cell_angle_gamma                90.00
_cell_volume                     2693.14(7)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    6227
_cell_measurement_theta_min      2.910
_cell_measurement_theta_max      27.485

_exptl_crystal_description       Polyhedral
_exptl_crystal_colour            yellow
_exptl_crystal_size_max          0.462
_exptl_crystal_size_mid          0.119
_exptl_crystal_size_min          0.11
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.599
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1352
_exptl_absorpt_coefficient_mu    0.797
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_correction_T_min  0.7846
_exptl_absorpt_correction_T_max  0.9290
_exptl_absorpt_process_details   
;
(c.f. r.h. blessing, acta cryst. (1995), a51, 33-38)
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_measurement_device_type  KappaCCD
_diffrn_measurement_device       '95mm CCD camera on κ-goniostat'
_diffrn_detector_area_resol_mean 9
_diffrn_radiation_monochromator  'horizonally mounted graphite crystal'
_computing_data_collection       'Collect (Bruker AXS BV, 1997-2004)'
_diffrn_measurement_method       CCD
_diffrn_reflns_number            32822
_diffrn_reflns_av_R_equivalents  0.0707
_diffrn_reflns_av_sigmaI/netI    0.0388
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_theta_min         3.07
_diffrn_reflns_theta_max         27.49
_reflns_number_total             6172
_reflns_number_gt                4982
_reflns_threshold_expression     >2sigma(I)

_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
 Refinement of F² against ALL reflections.  The weighted R-factor wR and
 goodness of fit S are based on F², conventional R-factors R are based
 on F, with F set to zero for negative F². The threshold expression of
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is
 not relevant to the choice of reflections for refinement.  R-factors based
 on F² are statistically about twice as large as those based on F, and R-
 factors based on ALL data will be even larger.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0559P)²+1.7740P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.0024(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         6172
_refine_ls_number_parameters     416
_refine_ls_number_restraints     27
_refine_ls_R_factor_all          0.0573
_refine_ls_R_factor_gt           0.0432
_refine_ls_wR_factor_ref         0.1184
_refine_ls_wR_factor_gt          0.1082
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_restrained_S_all      1.056
_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
Fe1 Fe 0.55162(4) 0.768058(12) 0.27202(2) 0.02888(12) Uani 1 1 d . . .
S1 S 0.16586(8) 0.85546(2) 0.05572(4) 0.03032(15) Uani 1 1 d . . .
S2 S 1.66832(8) 0.64253(2) -0.01543(4) 0.03050(15) Uani 1 1 d . . .
OW9 O 0.4425(3) 0.71321(7) 0.17746(11) 0.0405(4) Uani 1 1 d D . .
O1 O 0.3438(3) 0.87506(7) 0.10486(12) 0.0461(4) Uani 1 1 d . . .
OW5 O 0.4573(3) 0.71730(8) 0.37055(12) 0.0425(4) Uani 1 1 d D . .
O5 O 1.8689(3) 0.62706(8) -0.04059(13) 0.0508(5) Uani 1 1 d . . .
OW2 O 1.0424(3) 0.72288(9) 0.12212(14) 0.0476(5) Uani 1 1 d D . .
O6 O 1.5570(3) 0.65969(9) -0.09413(13) 0.0564(6) Uani 1 1 d . . .
O2 O 0.2342(3) 0.82115(8) -0.01229(13) 0.0565(6) Uani 1 1 d . . .
OW3 O 1.0683(3) 0.72572(8) 0.43109(13) 0.0440(4) Uani 1 1 d D . .
OW4 O 0.8329(3) 0.73097(8) 0.27615(13) 0.0443(5) Uani 1 1 d D . .
OW7 O 0.2664(3) 0.80234(8) 0.26965(12) 0.0419(4) Uani 1 1 d D . .
OW8 O 0.6442(3) 0.81457(8) 0.16879(14) 0.0505(5) Uani 1 1 d D . .
O3 O 0.0527(3) 0.89667(8) 0.01518(12) 0.0529(5) Uani 1 1 d . . .
O7 O 1.5619(3) 0.60119(9) 0.02421(14) 0.0616(6) Uani 1 1 d . . .
O4 O 0.0424(3) 0.82808(8) 0.11785(14) 0.0538(5) Uani 1 1 d . . .
OW1 O 1.1698(4) 0.56076(9) 0.01874(16) 0.0586(6) Uani 1 1 d D . .
OW6 O 0.6549(3) 0.81998(9) 0.36857(15) 0.0556(6) Uani 1 1 d D . .
N2 N 0.5891(3) 0.57996(8) 0.34435(13) 0.0367(5) Uani 1 1 d . . .
HN2 H 0.5788 0.5888 0.3984 0.044 Uiso 1 1 calc R . .
N1 N 0.6013(3) 0.58464(9) 0.20278(14) 0.0428(5) Uani 1 1 d . . .
HN1 H 0.6001 0.5970 0.1505 0.051 Uiso 1 1 calc R . .
N4 N 1.1415(3) 0.50575(9) 0.16863(14) 0.0440(5) Uani 1 1 d . . .
HN4 H 1.1383 0.5172 0.1157 0.053 Uiso 1 1 calc R . .
C4 C 0.6713(5) 0.44718(13) 0.2178(3) 0.0740(12) Uani 1 1 d . . .
H4 H 0.6903 0.4177 0.1861 0.089 Uiso 1 1 calc R . .
O8 O 1.6870(4) 0.68473(11) 0.04617(17) 0.0854(9) Uani 1 1 d . . .
N3 N 1.1625(3) 0.45381(9) 0.27782(15) 0.0432(5) Uani 1 1 d . . .
HN3 H 1.1746 0.4261 0.3069 0.052 Uiso 1 1 calc R . .
C9 C 1.1372(3) 0.50081(10) 0.31381(16) 0.0368(5) Uani 1 1 d . . .
C14 C 1.1227(3) 0.53418(10) 0.24402(17) 0.0395(6) Uani 1 1 d . . .
C2 C 0.6268(3) 0.53441(10) 0.22424(16) 0.0351(5) Uani 1 1 d . . .
C7 C 0.6186(3) 0.53149(9) 0.31486(15) 0.0313(5) Uani 1 1 d . . .
C6 C 0.6341(4) 0.48571(11) 0.3594(2) 0.0484(7) Uani 1 1 d . . .
H6 H 0.6261 0.4837 0.4203 0.058 Uiso 1 1 calc R . .
C13 C 1.0954(4) 0.58542(12) 0.2577(2) 0.0545(7) Uani 1 1 d . . .
H13 H 1.0860 0.6081 0.2112 0.065 Uiso 1 1 calc R . .
C10 C 1.1274(4) 0.51646(13) 0.40067(19) 0.0511(7) Uani 1 1 d . . .
H10 H 1.1393 0.4939 0.4473 0.061 Uiso 1 1 calc R . .
C1 C 0.5792(4) 0.61042(10) 0.27610(18) 0.0435(6) Uani 1 1 d . . .
H1 H 0.5595 0.6450 0.2790 0.052 Uiso 1 1 calc R . .
C12 C 1.0832(5) 0.60054(13) 0.3436(3) 0.0673(10) Uani 1 1 d . . .
H12 H 1.0633 0.6345 0.3553 0.081 Uiso 1 1 calc R . .
C3 C 0.6541(4) 0.49154(14) 0.1733(2) 0.0582(9) Uani 1 1 d . . .
H3 H 0.6602 0.4931 0.1124 0.070 Uiso 1 1 calc R . .
C11 C 1.0994(5) 0.56682(15) 0.4141(2) 0.0647(9) Uani 1 1 d . . .
H11 H 1.0911 0.5789 0.4712 0.078 Uiso 1 1 calc R . .
C5 C 0.6615(4) 0.44430(12) 0.3090(3) 0.0668(10) Uani 1 1 d . . .
H5 H 0.6742 0.4131 0.3362 0.080 Uiso 1 1 calc R . .
C8 C 1.1650(4) 0.45824(12) 0.19154(19) 0.0480(7) Uani 1 1 d . . .
H8 H 1.1811 0.4317 0.1525 0.058 Uiso 1 1 calc R . .
HW28 H 0.559(4) 0.8345(11) 0.148(2) 0.064(10) Uiso 1 1 d D . .
HW25 H 0.342(3) 0.7186(12) 0.390(2) 0.059(10) Uiso 1 1 d D . .
HW27 H 0.203(4) 0.8141(12) 0.3118(14) 0.060(10) Uiso 1 1 d D . .
HW29 H 0.324(3) 0.7165(13) 0.160(2) 0.060(10) Uiso 1 1 d D . .
HW18 H 0.756(3) 0.8190(11) 0.151(2) 0.053(9) Uiso 1 1 d D . .
HW16 H 0.769(3) 0.8257(12) 0.383(2) 0.055(9) Uiso 1 1 d D . .
HW24 H 0.902(4) 0.7277(13) 0.2315(13) 0.061(10) Uiso 1 1 d D . .
HW26 H 0.576(3) 0.8356(11) 0.3990(18) 0.049(9) Uiso 1 1 d D . .
HW14 H 0.910(4) 0.7307(13) 0.3211(13) 0.062(10) Uiso 1 1 d D . .
HW15 H 0.537(4) 0.7084(13) 0.4119(17) 0.062(10) Uiso 1 1 d D . .
HW17 H 0.202(5) 0.8116(13) 0.2243(13) 0.069(11) Uiso 1 1 d D . .
HW19 H 0.510(4) 0.7057(14) 0.1337(17) 0.069(11) Uiso 1 1 d D . .
HW12 H 1.041(6) 0.7528(8) 0.105(3) 0.088(15) Uiso 1 1 d D . .
HW13 H 0.993(5) 0.7068(11) 0.459(2) 0.087(13) Uiso 1 1 d D . .
HW23 H 1.074(6) 0.7533(8) 0.454(3) 0.090(15) Uiso 1 1 d D . .
HW22 H 0.960(6) 0.7071(13) 0.091(3) 0.104(16) Uiso 1 1 d D . .
HW11 H 1.274(4) 0.5780(14) 0.023(3) 0.108(17) Uiso 1 1 d D . .
HW21 H 1.071(4) 0.5790(12) 0.007(2) 0.073(12) Uiso 1 1 d 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
Fe1 OW7 2.1084(16) . ?
Fe1 OW8 2.1092(19) . ?
Fe1 OW6 2.1105(19) . ?
Fe1 OW4 2.1182(18) . ?
Fe1 OW5 2.1292(18) . ?
Fe1 OW9 2.1538(18) . ?
S1 O3 1.4534(19) . ?
S1 O2 1.4646(19) . ?
S1 O4 1.470(2) 1 ?
S1 O4 1.470(2) . ?
S1 O1 1.4726(18) 1 ?
S1 O1 1.4726(18) . ?
S2 O7 1.452(2) 1 ?
S2 O7 1.452(2) . ?
S2 O6 1.4563(19) . ?
S2 O8 1.463(2) . ?
S2 O5 1.4646(18) . ?
OW9 HW29 0.828(17) . ?
OW9 HW19 0.843(17) . ?
O1 O1 0.000(4) 1 ?
OW5 HW25 0.840(17) . ?
OW5 HW15 0.841(17) . ?
OW2 HW12 0.836(18) . ?
OW2 HW22 0.828(18) . ?
OW3 HW13 0.840(18) . ?
OW3 HW23 0.814(18) . ?
OW4 HW24 0.839(17) . ?
OW4 HW14 0.837(17) . ?
OW7 HW27 0.841(17) . ?
OW7 HW17 0.834(17) . ?
OW8 HW28 0.830(17) . ?
OW8 HW18 0.809(17) . ?
O7 O7 0.000(4) 1 ?
O4 O4 0.000(6) 1 ?
OW1 OW1 0.000(7) 1 ?
OW1 HW11 0.834(18) . ?
OW1 HW21 0.830(18) . ?
OW6 HW16 0.798(17) . ?
OW6 HW26 0.826(16) . ?
N2 C1 1.316(3) . ?
N2 C7 1.381(3) . ?
N2 HN2 0.8600 . ?
N1 C1 1.322(4) . ?
N1 C2 1.383(3) . ?
N1 HN1 0.8600 . ?
N4 C8 1.318(4) . ?
N4 C14 1.383(3) . ?
N4 HN4 0.8600 . ?
C4 C3 1.362(5) . ?
C4 C5 1.393(6) . ?
C4 H4 0.9300 . ?
N3 C8 1.318(4) . ?
N3 C9 1.377(4) . ?
N3 HN3 0.8600 . ?
C9 C14 1.383(4) . ?
C9 C10 1.388(4) . ?
C14 C13 1.391(4) . ?
C2 C7 1.383(3) . ?
C2 C3 1.393(4) . ?
C7 C6 1.395(4) . ?
C6 C5 1.358(5) . ?
C6 H6 0.9300 . ?
C13 C12 1.372(5) . ?
C13 H13 0.9300 . ?
C10 C11 1.368(5) . ?
C10 H10 0.9300 . ?
C1 H1 0.9300 . ?
C12 C11 1.398(5) . ?
C12 H12 0.9300 . ?
C3 H3 0.9300 . ?
C11 H11 0.9300 . ?
C5 H5 0.9300 . ?
C8 H8 0.9300 . ?

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
OW7 Fe1 OW8 91.40(8) . . ?
OW7 Fe1 OW6 89.95(8) . . ?
OW8 Fe1 OW6 92.11(10) . . ?
OW7 Fe1 OW4 177.74(8) . . ?
OW8 Fe1 OW4 90.56(8) . . ?
OW6 Fe1 OW4 91.09(8) . . ?
OW7 Fe1 OW5 89.69(7) . . ?
OW8 Fe1 OW5 176.42(9) . . ?
OW6 Fe1 OW5 91.29(9) . . ?
OW4 Fe1 OW5 88.28(7) . . ?
OW7 Fe1 OW9 90.01(7) . . ?
OW8 Fe1 OW9 90.08(8) . . ?
OW6 Fe1 OW9 177.81(9) . . ?
OW4 Fe1 OW9 88.88(8) . . ?
OW5 Fe1 OW9 86.51(8) . . ?
O3 S1 O2 109.93(12) . . ?
O3 S1 O4 110.53(12) . 1 ?
O2 S1 O4 110.07(14) . 1 ?
O3 S1 O4 110.53(12) . . ?
O2 S1 O4 110.07(14) . . ?
O4 S1 O4 0.00(19) 1 . ?
O3 S1 O1 110.07(12) . 1 ?
O2 S1 O1 108.14(11) . 1 ?
O4 S1 O1 108.05(12) 1 1 ?
O4 S1 O1 108.05(12) . 1 ?
O3 S1 O1 110.07(12) . . ?
O2 S1 O1 108.14(11) . . ?
O4 S1 O1 108.05(12) 1 . ?
O4 S1 O1 108.05(12) . . ?
O1 S1 O1 0.00(18) 1 . ?
O7 S2 O7 0.0(2) 1 . ?
O7 S2 O6 109.64(12) 1 . ?
O7 S2 O6 109.64(12) . . ?
O7 S2 O8 110.20(15) 1 . ?
O7 S2 O8 110.20(15) . . ?
O6 S2 O8 108.26(17) . . ?
O7 S2 O5 111.25(13) 1 . ?
O7 S2 O5 111.25(13) . . ?
O6 S2 O5 108.35(12) . . ?
O8 S2 O5 109.06(13) . . ?
Fe1 OW9 HW29 116(2) . . ?
Fe1 OW9 HW19 121(2) . . ?
HW29 OW9 HW19 108(2) . . ?
O1 O1 S1 0(10) 1 . ?
Fe1 OW5 HW25 122(2) . . ?
Fe1 OW5 HW15 120(2) . . ?
HW25 OW5 HW15 108(2) . . ?
HW12 OW2 HW22 108(3) . . ?
HW13 OW3 HW23 110(3) . . ?
Fe1 OW4 HW24 122(2) . . ?
Fe1 OW4 HW14 123(2) . . ?
HW24 OW4 HW14 109(2) . . ?
Fe1 OW7 HW27 129(2) . . ?
Fe1 OW7 HW17 125(2) . . ?
HW27 OW7 HW17 105(2) . . ?
Fe1 OW8 HW28 116(2) . . ?
Fe1 OW8 HW18 129(2) . . ?
HW28 OW8 HW18 114(2) . . ?
O7 O7 S2 0(10) 1 . ?
O4 O4 S1 0(10) 1 . ?
OW1 OW1 HW11 0(10) 1 . ?
OW1 OW1 HW21 0(10) 1 . ?
HW11 OW1 HW21 110(3) . . ?
Fe1 OW6 HW16 126(2) . . ?
Fe1 OW6 HW26 121(2) . . ?
HW16 OW6 HW26 112(2) . . ?
C1 N2 C7 108.7(2) . . ?
C1 N2 HN2 125.6 . . ?
C7 N2 HN2 125.6 . . ?
C1 N1 C2 108.6(2) . . ?
C1 N1 HN1 125.7 . . ?
C2 N1 HN1 125.7 . . ?
C8 N4 C14 108.6(2) . . ?
C8 N4 HN4 125.7 . . ?
C14 N4 HN4 125.7 . . ?
C3 C4 C5 122.4(3) . . ?
C3 C4 H4 118.8 . . ?
C5 C4 H4 118.8 . . ?
C8 N3 C9 108.7(2) . . ?
C8 N3 HN3 125.6 . . ?
C9 N3 HN3 125.6 . . ?
N3 C9 C14 106.4(2) . . ?
N3 C9 C10 131.4(3) . . ?
C14 C9 C10 122.2(3) . . ?
N4 C14 C9 106.2(2) . . ?
N4 C14 C13 132.5(3) . . ?
C9 C14 C13 121.3(3) . . ?
C7 C2 N1 106.2(2) . . ?
C7 C2 C3 121.2(3) . . ?
N1 C2 C3 132.5(3) . . ?
N2 C7 C2 106.4(2) . . ?
N2 C7 C6 131.7(2) . . ?
C2 C7 C6 121.9(2) . . ?
C5 C6 C7 116.2(3) . . ?
C5 C6 H6 121.9 . . ?
C7 C6 H6 121.9 . . ?
C12 C13 C14 116.2(3) . . ?
C12 C13 H13 121.9 . . ?
C14 C13 H13 121.9 . . ?
C11 C10 C9 116.5(3) . . ?
C11 C10 H10 121.7 . . ?
C9 C10 H10 121.7 . . ?
N2 C1 N1 110.0(2) . . ?
N2 C1 H1 125.0 . . ?
N1 C1 H1 125.0 . . ?
C13 C12 C11 122.4(3) . . ?
C13 C12 H12 118.8 . . ?
C11 C12 H12 118.8 . . ?
C4 C3 C2 116.3(3) . . ?
C4 C3 H3 121.9 . . ?
C2 C3 H3 121.9 . . ?
C10 C11 C12 121.3(3) . . ?
C10 C11 H11 119.3 . . ?
C12 C11 H11 119.3 . . ?
C6 C5 C4 122.0(3) . . ?
C6 C5 H5 119.0 . . ?
C4 C5 H5 119.0 . . ?
N3 C8 N4 110.0(3) . . ?
N3 C8 H8 125.0 . . ?
N4 C8 H8 125.0 . . ?

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
OW1 HW21 O5 0.830(18) 1.97(2) 2.794(3) 169(4) 1_455
OW1 HW11 O7 0.834(18) 2.015(19) 2.826(3) 164(4) 1
OW2 HW22 O8 0.828(18) 2.01(3) 2.787(3) 157(4) 1_455
OW2 HW12 O4 0.836(18) 2.01(2) 2.797(3) 156(4) 1_655
OW3 HW13 O2 0.840(18) 1.94(2) 2.722(3) 154(4) 4_676
OW3 HW23 O8 0.814(18) 2.27(2) 3.040(4) 159(4) 4_576
OW3 HW23 O6 0.814(18) 2.43(3) 3.070(3) 136(4) 4_576
OW4 HW24 OW2 0.839(17) 1.945(17) 2.782(3) 175(3) .
OW4 HW14 OW3 0.837(17) 1.948(17) 2.782(3) 174(3) .
OW5 HW15 O2 0.841(17) 1.886(18) 2.714(3) 168(3) 4_676
OW5 HW25 OW3 0.840(17) 1.958(17) 2.796(3) 176(3) 1_455
OW6 HW16 O6 0.798(17) 1.977(17) 2.773(3) 175(3) 4_576
OW6 HW26 O5 0.826(16) 1.959(17) 2.782(3) 174(3) 4_476
OW7 HW27 O6 0.841(17) 1.895(18) 2.736(3) 179(3) 4_476
OW7 HW17 O4 0.834(17) 1.953(18) 2.785(3) 175(4) 1
OW8 HW28 O1 0.830(17) 1.893(17) 2.719(3) 174(3) 1
OW8 HW18 O4 0.809(17) 2.011(17) 2.819(3) 175(3) 1_655
OW9 HW19 O8 0.843(17) 1.896(17) 2.733(3) 172(3) 1_455
OW9 HW29 OW2 0.828(17) 1.950(17) 2.778(3) 178(4) 1_455
N1 HN1 O7 0.86 1.93 2.752(3) 159.6 1_455
N2 HN2 O3 0.86 1.83 2.690(3) 176.3 4_676
N3 HN3 O1 0.86 1.92 2.751(3) 163.4 2_645
N4 HN4 OW1 0.86 1.89 2.720(3) 161.0 1

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        27.49
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         0.652
_refine_diff_density_min         -0.567
_refine_diff_density_rms         0.067
####################################################################### 
# 
# 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_shelxl
_audit_block_doi                 10.5517/cc13pwsg
_database_code_depnum_ccdc_archive 'CCDC 1033936'
_audit_update_record             
;
2014-11-13 deposited with the CCDC.
2015-01-27 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         '2(C7 H7 N2), Ni H12 O6, 2(O4 S), 4(H2 O)'
_chemical_formula_sum            'C14 H34 N4 Ni O18 S2'
_chemical_formula_weight         669.28

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'
Ni Ni 0.3393 1.1124 '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
_symmetry_space_group_name_Hall  -P1

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   6.6415(3)
_cell_length_b                   8.2264(4)
_cell_length_c                   12.2601(6)
_cell_angle_alpha                84.337(2)
_cell_angle_beta                 79.491(2)
_cell_angle_gamma                85.886(2)
_cell_volume                     654.40(5)
_cell_formula_units_Z            1
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    3439
_cell_measurement_theta_min      2.49
_cell_measurement_theta_max      27.33

_exptl_crystal_description       polyhedral
_exptl_crystal_colour            green
_exptl_crystal_size_max          0.43
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.05
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.698
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             350
_exptl_absorpt_coefficient_mu    0.990
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6462
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_process_details   
;
(c.f. r.h. blessing, acta cryst. (1995), a51, 33-38) 
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_measurement_device_type  KappaCCD
_diffrn_measurement_device       '95mm CCD camera on κ-goniostat'
_diffrn_detector_area_resol_mean 9
_diffrn_radiation_monochromator  'horizonally mounted graphite crystal'
_computing_data_collection       'Collect (Bruker AXS BV, 1997-2004)'
_diffrn_measurement_method       CCD
_diffrn_reflns_number            10712
_diffrn_reflns_av_R_equivalents  0.0441
_diffrn_reflns_av_sigmaI/netI    0.0502
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         1.70
_diffrn_reflns_theta_max         27.49
_reflns_number_total             2988
_reflns_number_gt                2523
_reflns_threshold_expression     >2sigma(I)

_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
 Refinement of F² against ALL reflections.  The weighted R-factor wR and
 goodness of fit S are based on F², conventional R-factors R are based
 on F, with F set to zero for negative F². The threshold expression of
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is
 not relevant to the choice of reflections for refinement.  R-factors based
 on F² are statistically about twice as large as those based on F, and R-
 factors based on ALL data will be even larger.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0630P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         2988
_refine_ls_number_parameters     218
_refine_ls_number_restraints     15
_refine_ls_R_factor_all          0.0446
_refine_ls_R_factor_gt           0.0359
_refine_ls_wR_factor_ref         0.1138
_refine_ls_wR_factor_gt          0.0991
_refine_ls_goodness_of_fit_ref   1.119
_refine_ls_restrained_S_all      1.121
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Ni1 Ni 0.5000 0.5000 1.0000 0.00842(15) Uani 1 2 d S . .
S1 S 0.10579(8) 0.85964(7) 0.77660(5) 0.00957(17) Uani 1 1 d . . .
O1 O -0.0455(2) 0.9496(2) 0.85733(14) 0.0153(4) Uani 1 1 d . . .
O2 O 0.0817(3) 0.6819(2) 0.80337(15) 0.0164(4) Uani 1 1 d . . .
OW1 O 0.5835(3) 0.1091(2) 0.85273(15) 0.0153(4) Uani 1 1 d D . .
O4 O 0.3139(2) 0.8981(2) 0.78784(14) 0.0145(4) Uani 1 1 d . . .
OW4 O 0.5026(3) 0.2562(2) 1.04466(15) 0.0139(4) Uani 1 1 d D . .
O3 O 0.0679(3) 0.9093(2) 0.66346(14) 0.0164(4) Uani 1 1 d . . .
OW5 O 0.3617(2) 0.4570(2) 0.86822(14) 0.0126(4) Uani 1 1 d D . .
OW2 O 0.0738(3) 0.2246(2) 0.93273(15) 0.0151(4) Uani 1 1 d D . .
C5 C 0.2965(4) 0.2633(3) 0.5676(2) 0.0200(6) Uani 1 1 d . . .
H5 H 0.2996 0.1804 0.6248 0.024 Uiso 1 1 calc R . .
OW3 O 0.2192(2) 0.5313(2) 1.10498(14) 0.0133(4) Uani 1 1 d D . .
N2 N 0.2764(3) 0.6468(3) 0.32882(17) 0.0155(5) Uani 1 1 d . . .
HN2 H 0.3059 0.6585 0.2573 0.019 Uiso 1 1 calc R . .
C1 C 0.2077(4) 0.7650(3) 0.3940(2) 0.0164(6) Uani 1 1 d . . .
H1 H 0.1830 0.8739 0.3692 0.020 Uiso 1 1 calc R . .
N1 N 0.1795(3) 0.7057(2) 0.49932(17) 0.0140(5) Uani 1 1 d . . .
HN1 H 0.1355 0.7611 0.5556 0.017 Uiso 1 1 calc R . .
C3 C 0.3562(4) 0.3422(3) 0.3686(2) 0.0193(6) Uani 1 1 d . . .
H3 H 0.3965 0.3164 0.2954 0.023 Uiso 1 1 calc R . .
C2 C 0.2933(3) 0.5006(3) 0.3945(2) 0.0124(5) Uani 1 1 d . . .
C7 C 0.2326(3) 0.5392(3) 0.5043(2) 0.0120(5) Uani 1 1 d . . .
C6 C 0.2336(4) 0.4204(3) 0.5939(2) 0.0174(6) Uani 1 1 d . . .
H6 H 0.1941 0.4458 0.6672 0.021 Uiso 1 1 calc R . .
C4 C 0.3558(4) 0.2258(3) 0.4568(2) 0.0215(6) Uani 1 1 d . . .
H4 H 0.3963 0.1182 0.4425 0.026 Uiso 1 1 calc R . .
H1W1 H 0.694(3) 0.039(3) 0.850(2) 0.024(8) Uiso 1 1 d D . .
H2W1 H 0.483(3) 0.061(3) 0.826(3) 0.037(9) Uiso 1 1 d D . .
H2W2 H 0.063(5) 0.135(3) 0.892(2) 0.044(10) Uiso 1 1 d D . .
H1W2 H 0.076(5) 0.176(4) 1.0055(15) 0.048(11) Uiso 1 1 d D . .
H1W4 H 0.578(4) 0.201(3) 1.0976(18) 0.034(9) Uiso 1 1 d D . .
H2W4 H 0.538(5) 0.197(4) 0.9813(18) 0.044(10) Uiso 1 1 d D . .
H1W5 H 0.285(4) 0.367(2) 0.886(3) 0.044(10) Uiso 1 1 d D . .
H2W5 H 0.273(4) 0.543(3) 0.844(2) 0.037(9) Uiso 1 1 d D . .
H2W3 H 0.150(4) 0.440(2) 1.134(2) 0.035(9) Uiso 1 1 d D . .
H1W3 H 0.127(4) 0.617(2) 1.091(2) 0.022(8) Uiso 1 1 d 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
Ni1 OW4 2.0261(17) . ?
Ni1 OW4 2.0261(17) 2_667 ?
Ni1 OW5 2.0686(17) . ?
Ni1 OW5 2.0686(17) 2_667 ?
Ni1 OW3 2.0789(16) 2_667 ?
Ni1 OW3 2.0789(16) . ?
S1 O3 1.4680(18) 1 ?
S1 O3 1.4680(18) . ?
S1 O4 1.4733(17) . ?
S1 O2 1.4798(17) 1 ?
S1 O2 1.4798(17) . ?
S1 O1 1.4872(17) . ?
O2 O2 0.000(5) 1 ?
OW1 H1W1 0.898(16) . ?
OW1 H2W1 0.929(17) . ?
OW4 H1W4 0.951(17) . ?
OW4 H2W4 0.944(17) . ?
O3 O3 0.000(5) 1 ?
OW5 H1W5 0.913(17) . ?
OW5 H2W5 0.950(17) . ?
OW2 H2W2 0.938(17) . ?
OW2 H1W2 0.943(17) . ?
C5 C6 1.380(4) . ?
C5 C4 1.403(4) . ?
C5 H5 0.9300 . ?
OW3 H2W3 0.917(17) . ?
OW3 H1W3 0.922(16) . ?
N2 C1 1.322(3) . ?
N2 C2 1.389(3) . ?
N2 HN2 0.8600 . ?
C1 N1 1.320(3) . ?
C1 H1 0.9300 . ?
N1 C7 1.388(3) . ?
N1 HN1 0.8600 . ?
C3 C4 1.371(4) . ?
C3 C2 1.388(4) . ?
C3 H3 0.9300 . ?
C2 C7 1.394(3) . ?
C7 C6 1.397(3) . ?
C6 H6 0.9300 . ?
C4 H4 0.9300 . ?

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
OW4 Ni1 OW4 180.000(1) . 2_667 ?
OW4 Ni1 OW5 88.03(7) . . ?
OW4 Ni1 OW5 91.97(7) 2_667 . ?
OW4 Ni1 OW5 91.97(7) . 2_667 ?
OW4 Ni1 OW5 88.03(7) 2_667 2_667 ?
OW5 Ni1 OW5 180.000(1) . 2_667 ?
OW4 Ni1 OW3 90.01(7) . 2_667 ?
OW4 Ni1 OW3 89.99(7) 2_667 2_667 ?
OW5 Ni1 OW3 87.60(7) . 2_667 ?
OW5 Ni1 OW3 92.40(7) 2_667 2_667 ?
OW4 Ni1 OW3 89.99(7) . . ?
OW4 Ni1 OW3 90.01(7) 2_667 . ?
OW5 Ni1 OW3 92.40(7) . . ?
OW5 Ni1 OW3 87.60(7) 2_667 . ?
OW3 Ni1 OW3 180.0 2_667 . ?
O3 S1 O3 0.00(18) 1 . ?
O3 S1 O4 110.83(10) 1 . ?
O3 S1 O4 110.83(10) . . ?
O3 S1 O2 110.23(10) 1 1 ?
O3 S1 O2 110.23(10) . 1 ?
O4 S1 O2 109.23(10) . 1 ?
O3 S1 O2 110.23(10) 1 . ?
O3 S1 O2 110.23(10) . . ?
O4 S1 O2 109.23(10) . . ?
O2 S1 O2 0.00(13) 1 . ?
O3 S1 O1 109.07(10) 1 . ?
O3 S1 O1 109.07(10) . . ?
O4 S1 O1 108.69(10) . . ?
O2 S1 O1 108.75(10) 1 . ?
O2 S1 O1 108.75(10) . . ?
O2 O2 S1 0(10) 1 . ?
H1W1 OW1 H2W1 109(2) . . ?
Ni1 OW4 H1W4 124.9(19) . . ?
Ni1 OW4 H2W4 110.6(19) . . ?
H1W4 OW4 H2W4 105(2) . . ?
O3 O3 S1 0(10) 1 . ?
Ni1 OW5 H1W5 111(2) . . ?
Ni1 OW5 H2W5 116.5(19) . . ?
H1W5 OW5 H2W5 106(2) . . ?
H2W2 OW2 H1W2 104(2) . . ?
C6 C5 C4 121.5(2) . . ?
C6 C5 H5 119.3 . . ?
C4 C5 H5 119.3 . . ?
Ni1 OW3 H2W3 118.1(18) . . ?
Ni1 OW3 H1W3 121.0(17) . . ?
H2W3 OW3 H1W3 110(2) . . ?
C1 N2 C2 109.0(2) . . ?
C1 N2 HN2 125.5 . . ?
C2 N2 HN2 125.5 . . ?
N1 C1 N2 110.0(2) . . ?
N1 C1 H1 125.0 . . ?
N2 C1 H1 125.0 . . ?
C1 N1 C7 108.8(2) . . ?
C1 N1 HN1 125.6 . . ?
C7 N1 HN1 125.6 . . ?
C4 C3 C2 116.5(2) . . ?
C4 C3 H3 121.7 . . ?
C2 C3 H3 121.7 . . ?
C3 C2 N2 132.4(2) . . ?
C3 C2 C7 121.8(2) . . ?
N2 C2 C7 105.8(2) . . ?
N1 C7 C2 106.4(2) . . ?
N1 C7 C6 132.1(2) . . ?
C2 C7 C6 121.6(2) . . ?
C5 C6 C7 116.4(2) . . ?
C5 C6 H6 121.8 . . ?
C7 C6 H6 121.8 . . ?
C3 C4 C5 122.3(2) . . ?
C3 C4 H4 118.9 . . ?
C5 C4 H4 118.9 . . ?

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
OW4 H1W4 O4 0.951(17) 1.792(17) 2.737(2) 172(3) 2_667
OW5 H2W5 O2 0.950(17) 1.752(18) 2.696(2) 172(3) 1
OW3 H2W3 O2 0.917(17) 1.90(2) 2.762(2) 156(2) 2_567
OW1 H1W1 O1 0.898(16) 1.844(17) 2.714(2) 163(3) 1_645
OW1 H2W1 O4 0.929(17) 1.95(2) 2.844(2) 162(3) 1_545
OW2 H2W2 O1 0.938(17) 1.86(2) 2.746(2) 157(3) 1_545
OW2 H1W2 O1 0.943(17) 1.872(19) 2.801(2) 168(3) 2_567
N2 HN2 OW1 0.86 2.31 2.913(3) 127.1 2_666
N1 HN1 O3 0.86 1.86 2.711(3) 170.1 1

_diffrn_measured_fraction_theta_max 0.991
_diffrn_reflns_theta_full        27.49
_diffrn_measured_fraction_theta_full 0.991
_refine_diff_density_max         0.535
_refine_diff_density_min         -0.431
_refine_diff_density_rms         0.106
