# Electronic Supplementary Material (ESI) for Inorganic Chemistry Frontiers.
# This journal is © the Partner Organisations 2014

#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_cd0821a

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C23 H14 Cu N6 O3 S, H2 O'
_chemical_formula_sum            'C23 H16 Cu N6 O4 S'
_chemical_formula_weight         536.04

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'

_symmetry_cell_setting           triclinic
_symmetry_space_group_name_H-M   P-1
_symmetry_space_group_name_Hall  '-P 1'

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

_cell_length_a                   8.886(2)
_cell_length_b                   10.307(3)
_cell_length_c                   12.913(3)
_cell_angle_alpha                68.732(11)
_cell_angle_beta                 70.997(18)
_cell_angle_gamma                85.639(18)
_cell_volume                     1040.9(5)
_cell_formula_units_Z            2
_cell_measurement_temperature    98(2)
_cell_measurement_reflns_used    5129
_cell_measurement_theta_min      2.1
_cell_measurement_theta_max      40.2

_exptl_crystal_description       chip
_exptl_crystal_colour            red
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.710
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             546
_exptl_absorpt_coefficient_mu    1.198
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.870
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_process_details   'ABSCOR (Higashi, 1995)'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      98(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  
;
Saturn724 (2x2 bin mode)
;
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean 28.5714
_diffrn_standards_number         0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        <1
_diffrn_reflns_number            7526
_diffrn_reflns_av_R_equivalents  0.0206
_diffrn_reflns_av_sigmaI/netI    0.0320
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         2.12
_diffrn_reflns_theta_max         27.50
_diffrn_reflns_reduction_process 'Lp corrections applied'
_reflns_number_total             4727
_reflns_number_gt                4545
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       
;
CrystalClear-SM Expert 2.0 r3 (Rigaku, 2009)
;
_computing_cell_refinement       
;
CrystalClear-SM Expert 2.0 r3 (Rigaku, 2009)
;
_computing_data_reduction        
;
CrystalClear-SM Expert 2.0 r3 (Rigaku, 2009)
;
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  'publCIF (Westrip, 2010)'

_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)+(0.0486P)²+1.3645P] 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         4727
_refine_ls_number_parameters     364
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0375
_refine_ls_R_factor_gt           0.0361
_refine_ls_wR_factor_ref         0.0947
_refine_ls_wR_factor_gt          0.0928
_refine_ls_goodness_of_fit_ref   0.996
_refine_ls_restrained_S_all      0.996
_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
Cu1 Cu -0.22941(3) 0.27649(3) 0.21955(2) 0.01437(9) Uani 1 1 d . . .
S1 S -0.01753(6) 0.47135(6) 0.30008(4) 0.01482(12) Uani 1 1 d . . .
O1 O -0.04588(18) 0.44286(18) 0.20450(14) 0.0197(3) Uani 1 1 d . . .
O2 O 0.06978(19) 0.36349(19) 0.36255(14) 0.0236(4) Uani 1 1 d . . .
O3 O 0.05084(19) 0.61188(18) 0.26083(15) 0.0217(3) Uani 1 1 d . . .
N1 N 0.5617(2) -0.12825(18) -0.17816(15) 0.0136(3) Uani 1 1 d . . .
N2 N 0.3760(2) 0.05152(18) -0.17822(16) 0.0138(3) Uani 1 1 d . . .
N3 N 0.3702(2) -0.12934(18) 0.00192(15) 0.0129(3) Uani 1 1 d . . .
N4 N -0.0747(2) 0.17275(18) 0.12578(15) 0.0132(3) Uani 1 1 d . . .
N5 N -0.3124(2) 0.17896(18) 0.39409(15) 0.0138(3) Uani 1 1 d . . .
N6 N -0.3370(2) 0.43479(18) 0.12813(15) 0.0130(3) Uani 1 1 d . . .
C1 C -0.2105(2) 0.4697(2) 0.40186(18) 0.0141(4) Uani 1 1 d . . .
C2 C -0.3306(2) 0.5345(2) 0.35969(18) 0.0143(4) Uani 1 1 d . . .
C3 C -0.4855(2) 0.5344(2) 0.43834(17) 0.0125(4) Uani 1 1 d . . .
C5 C -0.6131(3) 0.5988(2) 0.39847(19) 0.0160(4) Uani 1 1 d . . .
C4 C -0.2380(3) 0.4033(2) 0.5240(2) 0.0166(4) Uani 1 1 d . . .
C6 C 0.4976(2) -0.0117(2) -0.23176(18) 0.0130(4) Uani 1 1 d . . .
C7 C 0.4910(2) -0.1834(2) -0.06150(18) 0.0121(4) Uani 1 1 d . . .
C8 C 0.3181(2) -0.0116(2) -0.06144(18) 0.0120(4) Uani 1 1 d . . .
C11 C -0.0155(2) 0.2238(2) 0.00715(18) 0.0136(4) Uani 1 1 d . . .
C10 C 0.1115(2) 0.1675(2) -0.05652(18) 0.0129(4) Uani 1 1 d . . .
C9 C 0.1832(2) 0.0529(2) 0.00346(18) 0.0119(4) Uani 1 1 d . . .
C13 C 0.1203(2) -0.0031(2) 0.12585(18) 0.0139(4) Uani 1 1 d . . .
C12 C -0.0074(3) 0.0589(2) 0.18319(19) 0.0154(4) Uani 1 1 d . . .
C14 C 0.5643(2) 0.0529(2) -0.36096(18) 0.0132(4) Uani 1 1 d . . .
C16 C 0.7231(3) 0.0399(2) -0.42086(19) 0.0161(4) Uani 1 1 d . . .
C15 C 0.4678(2) 0.1304(2) -0.42580(18) 0.0135(4) Uani 1 1 d . . .
C17 C -0.4670(3) 0.1882(2) 0.45351(19) 0.0141(4) Uani 1 1 d . . .
C18 C -0.2198(3) 0.1067(2) 0.45827(19) 0.0165(4) Uani 1 1 d . . .
C22 C -0.4896(2) 0.4688(2) 0.16693(18) 0.0140(4) Uani 1 1 d . . .
C23 C -0.5492(2) 0.5928(2) 0.10936(18) 0.0140(4) Uani 1 1 d . . .
C19 C 0.5503(2) -0.3163(2) 0.00357(18) 0.0124(4) Uani 1 1 d . . .
C20 C 0.7056(2) -0.3536(2) -0.04085(18) 0.0129(4) Uani 1 1 d . . .
C21 C -0.2427(2) 0.5246(2) 0.02513(18) 0.0129(4) Uani 1 1 d . . .
O4 O 0.0928(2) 0.21427(19) 0.59247(17) 0.0262(4) Uani 1 1 d . . .
H17A H -0.524(4) 0.238(3) 0.406(3) 0.031 Uiso 1 1 d . . .
H2A H -0.306(4) 0.580(3) 0.272(3) 0.031 Uiso 1 1 d . . .
H15A H 0.359(4) 0.145(3) -0.390(3) 0.031 Uiso 1 1 d . . .
H4A H -0.153(4) 0.356(3) 0.550(3) 0.031 Uiso 1 1 d . . .
H22A H -0.560(4) 0.407(3) 0.234(3) 0.031 Uiso 1 1 d . . .
H20A H 0.777(4) -0.291(3) -0.114(3) 0.031 Uiso 1 1 d . . .
H23A H -0.653(4) 0.611(3) 0.139(3) 0.031 Uiso 1 1 d . . .
H5A H -0.596(4) 0.642(3) 0.317(3) 0.031 Uiso 1 1 d . . .
H11A H -0.063(4) 0.303(3) -0.035(3) 0.031 Uiso 1 1 d . . .
H18A H -0.104(4) 0.098(3) 0.416(3) 0.031 Uiso 1 1 d . . .
H16A H 0.790(4) -0.009(3) -0.380(3) 0.031 Uiso 1 1 d . . .
H13A H 0.161(4) -0.084(3) 0.170(3) 0.031 Uiso 1 1 d . . .
H21A H -0.132(4) 0.499(3) -0.003(3) 0.031 Uiso 1 1 d . . .
H4B H 0.086(4) 0.258(4) 0.530(3) 0.039 Uiso 1 1 d . . .
H10A H 0.145(4) 0.203(3) -0.135(3) 0.031 Uiso 1 1 d . . .
H4C H 0.067(4) 0.270(4) 0.627(3) 0.039 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 N5 2.0051(19) . ?
Cu1 N6 2.0175(18) . ?
Cu1 N4 2.0327(18) . ?
Cu1 O1 2.3696(17) . ?
S1 O2 1.4542(17) . ?
S1 O3 1.4576(18) . ?
S1 O1 1.4662(16) . ?
S1 C1 1.786(2) . ?
N1 C6 1.340(3) . ?
N1 C7 1.343(3) . ?
N2 C8 1.340(3) . ?
N2 C6 1.343(3) . ?
N3 C8 1.341(3) . ?
N3 C7 1.342(3) . ?
N4 C11 1.354(3) . ?
N4 C12 1.355(3) . ?
N5 C18 1.350(3) . ?
N5 C17 1.354(3) . ?
N6 C22 1.351(3) . ?
N6 C21 1.352(3) . ?
C1 C2 1.374(3) . ?
C1 C4 1.417(3) . ?
C2 C3 1.419(3) . ?
C2 H2A 1.01(3) . ?
C3 C5 1.418(3) . ?
C3 C3 1.430(4) 2_466 ?
C5 C4 1.371(3) 2_466 ?
C5 H5A 0.95(3) . ?
C4 C5 1.371(3) 2_466 ?
C4 H4A 0.96(3) . ?
C6 C14 1.479(3) . ?
C7 C19 1.485(3) . ?
C8 C9 1.487(3) . ?
C11 C10 1.388(3) . ?
C11 H11A 0.96(3) . ?
C10 C9 1.394(3) . ?
C10 H10A 0.90(3) . ?
C9 C13 1.398(3) . ?
C13 C12 1.389(3) . ?
C13 H13A 0.94(3) . ?
C14 C16 1.394(3) . ?
C14 C15 1.397(3) . ?
C16 C18 1.388(3) 1_654 ?
C16 H16A 0.92(3) . ?
C15 C17 1.382(3) 1_654 ?
C15 H15A 0.95(3) . ?
C17 C15 1.382(3) 1_456 ?
C17 H17A 0.91(3) . ?
C18 C16 1.388(3) 1_456 ?
C18 H18A 1.01(3) . ?
C22 C23 1.390(3) . ?
C22 H22A 0.92(3) . ?
C23 C19 1.392(3) 1_465 ?
C23 H23A 0.91(3) . ?
C19 C23 1.392(3) 1_645 ?
C19 C20 1.394(3) . ?
C20 C21 1.380(3) 1_645 ?
C20 H20A 0.97(3) . ?
C21 C20 1.380(3) 1_465 ?
C21 H21A 0.98(3) . ?
O4 H4B 0.79(4) . ?
O4 H4C 0.83(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
N5 Cu1 N6 124.11(7) . . ?
N5 Cu1 N4 116.93(7) . . ?
N6 Cu1 N4 115.91(7) . . ?
N5 Cu1 O1 100.53(7) . . ?
N6 Cu1 O1 88.44(7) . . ?
N4 Cu1 O1 98.55(7) . . ?
O2 S1 O3 113.75(11) . . ?
O2 S1 O1 112.82(10) . . ?
O3 S1 O1 111.73(10) . . ?
O2 S1 C1 107.04(10) . . ?
O3 S1 C1 105.26(10) . . ?
O1 S1 C1 105.46(10) . . ?
S1 O1 Cu1 127.82(9) . . ?
C6 N1 C7 114.24(17) . . ?
C8 N2 C6 114.61(18) . . ?
C8 N3 C7 114.35(18) . . ?
C11 N4 C12 117.25(17) . . ?
C11 N4 Cu1 122.97(14) . . ?
C12 N4 Cu1 118.93(14) . . ?
C18 N5 C17 116.87(18) . . ?
C18 N5 Cu1 123.22(15) . . ?
C17 N5 Cu1 119.87(14) . . ?
C22 N6 C21 116.98(18) . . ?
C22 N6 Cu1 125.81(15) . . ?
C21 N6 Cu1 116.67(14) . . ?
C2 C1 C4 120.91(19) . . ?
C2 C1 S1 118.92(16) . . ?
C4 C1 S1 120.17(16) . . ?
C1 C2 C3 120.24(19) . . ?
C1 C2 H2A 118.3(18) . . ?
C3 C2 H2A 121.4(18) . . ?
C5 C3 C2 122.06(19) . . ?
C5 C3 C3 118.8(2) . 2_466 ?
C2 C3 C3 119.1(2) . 2_466 ?
C4 C5 C3 121.1(2) 2_466 . ?
C4 C5 H5A 119.2(19) 2_466 . ?
C3 C5 H5A 119.7(19) . . ?
C5 C4 C1 119.8(2) 2_466 . ?
C5 C4 H4A 121.7(19) 2_466 . ?
C1 C4 H4A 118.3(19) . . ?
N1 C6 N2 125.52(19) . . ?
N1 C6 C14 117.82(17) . . ?
N2 C6 C14 116.66(18) . . ?
N3 C7 N1 125.74(19) . . ?
N3 C7 C19 116.77(18) . . ?
N1 C7 C19 117.49(17) . . ?
N2 C8 N3 125.49(18) . . ?
N2 C8 C9 117.45(18) . . ?
N3 C8 C9 117.05(18) . . ?
N4 C11 C10 123.27(19) . . ?
N4 C11 H11A 118.4(19) . . ?
C10 C11 H11A 118.3(19) . . ?
C11 C10 C9 119.09(19) . . ?
C11 C10 H10A 121(2) . . ?
C9 C10 H10A 120(2) . . ?
C10 C9 C13 118.16(18) . . ?
C10 C9 C8 120.78(18) . . ?
C13 C9 C8 121.01(18) . . ?
C12 C13 C9 119.30(19) . . ?
C12 C13 H13A 119.3(19) . . ?
C9 C13 H13A 121.4(19) . . ?
N4 C12 C13 122.90(19) . . ?
C16 C14 C15 118.42(19) . . ?
C16 C14 C6 121.59(19) . . ?
C15 C14 C6 119.99(18) . . ?
C18 C16 C14 119.0(2) 1_654 . ?
C18 C16 H16A 121(2) 1_654 . ?
C14 C16 H16A 120(2) . . ?
C17 C15 C14 118.63(19) 1_654 . ?
C17 C15 H15A 118.7(19) 1_654 . ?
C14 C15 H15A 122.7(19) . . ?
N5 C17 C15 123.7(2) . 1_456 ?
N5 C17 H17A 113(2) . . ?
C15 C17 H17A 123(2) 1_456 . ?
N5 C18 C16 123.25(19) . 1_456 ?
N5 C18 H18A 118.5(18) . . ?
C16 C18 H18A 118.2(18) 1_456 . ?
N6 C22 C23 123.18(19) . . ?
N6 C22 H22A 119.6(19) . . ?
C23 C22 H22A 117(2) . . ?
C22 C23 C19 118.68(19) . 1_465 ?
C22 C23 H23A 120(2) . . ?
C19 C23 H23A 122(2) 1_465 . ?
C23 C19 C20 118.73(19) 1_645 . ?
C23 C19 C7 120.46(18) 1_645 . ?
C20 C19 C7 120.80(18) . . ?
C21 C20 C19 118.65(19) 1_645 . ?
C21 C20 H20A 121.2(18) 1_645 . ?
C19 C20 H20A 120.0(18) . . ?
N6 C21 C20 123.59(19) . 1_465 ?
N6 C21 H21A 116.6(19) . . ?
C20 C21 H21A 119.8(19) 1_465 . ?
H4B O4 H4C 103(3) . . ?

_diffrn_measured_fraction_theta_max 0.989
_diffrn_reflns_theta_full        27.50
_diffrn_measured_fraction_theta_full 0.989
_refine_diff_density_max         0.956
_refine_diff_density_min         -0.493
_refine_diff_density_rms         0.078
_database_code_depnum_ccdc_archive 'CCDC 1013552'
