# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 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_hyb

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         '3(C22 H8 Cu2 N2 O10 S), 2(O)'
_chemical_formula_sum            'C66 H24 Cu6 N6 O32 S3 '
_chemical_formula_weight         1890.42

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           trigonal
_symmetry_space_group_name_H-M   'R -3 m '
_symmetry_space_group_name_Hall  '-R 3 2" '

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'y, x, -z'
'x-y, -y, -z'
'-x, -x+y, -z'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'y+2/3, x+1/3, -z+1/3'
'x-y+2/3, -y+1/3, -z+1/3'
'-x+2/3, -x+y+1/3, -z+1/3'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'y+1/3, x+2/3, -z+2/3'
'x-y+1/3, -y+2/3, -z+2/3'
'-x+1/3, -x+y+2/3, -z+2/3'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'-y, -x, z'
'-x+y, y, z'
'x, x-y, z'
'-x+2/3, -y+1/3, -z+1/3'
'y+2/3, -x+y+1/3, -z+1/3'
'x-y+2/3, x+1/3, -z+1/3'
'-y+2/3, -x+1/3, z+1/3'
'-x+y+2/3, y+1/3, z+1/3'
'x+2/3, x-y+1/3, z+1/3'
'-x+1/3, -y+2/3, -z+2/3'
'y+1/3, -x+y+2/3, -z+2/3'
'x-y+1/3, x+2/3, -z+2/3'
'-y+1/3, -x+2/3, z+2/3'
'-x+y+1/3, y+2/3, z+2/3'
'x+1/3, x-y+2/3, z+2/3'

_cell_length_a                   18.819(4)
_cell_length_b                   18.819(4)
_cell_length_c                   38.603(15)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_volume                     11840(6)
_cell_formula_units_Z            3
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    3678
_cell_measurement_theta_min      2.1
_cell_measurement_theta_max      28.2

_exptl_crystal_description       blue
_exptl_crystal_colour            green
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.12
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    0.795
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             2820
_exptl_absorpt_coefficient_mu    0.877
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.839
_exptl_absorpt_correction_T_max  0.900
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean 16.2141
_diffrn_standards_number         0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            42313
_diffrn_reflns_av_R_equivalents  0.0339
_diffrn_reflns_av_sigmaI/netI    0.0144
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_l_min       -50
_diffrn_reflns_limit_l_max       50
_diffrn_reflns_theta_min         3.27
_diffrn_reflns_theta_max         27.56
_reflns_number_total             3293
_reflns_number_gt                2917
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_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)+(0.1249P)²+23.2032P] 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         3293
_refine_ls_number_parameters     124
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0612
_refine_ls_R_factor_gt           0.0544
_refine_ls_wR_factor_ref         0.1910
_refine_ls_wR_factor_gt          0.1823
_refine_ls_goodness_of_fit_ref   1.132
_refine_ls_restrained_S_all      1.132
_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
C1 C 0.76098(16) -0.02726(17) 0.30740(7) 0.0341(5) Uani 1 1 d . . .
C2 C 0.81992(17) 0.05228(18) 0.29015(7) 0.0383(6) Uani 1 1 d . . .
C3 C 0.89135(13) 0.10865(13) 0.30705(10) 0.0362(8) Uani 1 2 d S . .
H3 H 0.9014 0.0986 0.3296 0.043 Uiso 1 2 calc SR . .
C4 C 0.80553(19) 0.0668(2) 0.25632(8) 0.0477(8) Uani 1 1 d . . .
H4 H 0.7575 0.0290 0.2452 0.057 Uiso 1 1 calc R . .
C5 C 0.86235(19) 0.13765(19) 0.23871(12) 0.0531(13) Uani 1 2 d S . .
C6 C 0.8474(2) 0.1526(2) 0.20237(13) 0.0625(16) Uani 1 2 d S . .
C7 C 0.9102(6) 0.1870(7) 0.1781(2) 0.081(3) Uani 0.50 1 d P . .
C8 C 0.8679(8) 0.2298(6) 0.1901(2) 0.086(3) Uani 0.50 1 d P . .
N1 N 0.9926(14) 0.1970(19) 0.1817(6) 0.145(11) Uani 0.25 1 d P . .
N2 N 0.8974(18) 0.3019(12) 0.2104(4) 0.118(8) Uani 0.25 1 d P . .
O1 O 0.77750(12) -0.03833(13) 0.33775(5) 0.0418(5) Uani 1 1 d . . .
O2 O 0.69971(13) -0.07719(13) 0.28981(5) 0.0447(5) Uani 1 1 d . . .
O3 O 0.7803(3) -0.10985(13) 0.40982(10) 0.0733(12) Uani 1 2 d SD . .
H1A H 0.7499 -0.1251 0.4277 0.110 Uiso 1 2 d SRD . .
S1 S 1.0443(4) 0.2436(10) 0.14788(19) 0.216(8) Uani 0.25 1 d P . .
Cu1 Cu 0.71230(2) -0.143852(12) 0.361687(10) 0.0259(2) Uani 1 2 d S . .
O4 O 0.0000 0.0000 0.3663(16) 0.50(3) Uiso 1 6 d S . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
C1 0.0282(12) 0.0341(13) 0.0333(13) 0.0050(10) 0.0028(10) 0.0104(10)
C2 0.0321(13) 0.0387(14) 0.0321(13) 0.0066(11) -0.0018(10) 0.0085(11)
C3 0.0341(13) 0.0341(13) 0.0308(17) 0.0032(8) -0.0032(8) 0.0097(15)
C4 0.0383(14) 0.0418(16) 0.0371(15) 0.0074(12) -0.0116(12) 0.0007(12)
C5 0.0467(16) 0.0467(16) 0.035(2) 0.0138(11) -0.0138(11) 0.0004(19)
C6 0.0546(18) 0.0546(18) 0.040(3) 0.0162(14) -0.0162(14) -0.001(2)
C7 0.057(5) 0.099(7) 0.050(4) 0.030(5) -0.014(4) 0.011(5)
C8 0.099(7) 0.061(5) 0.048(4) 0.019(4) -0.028(5) 0.003(5)
N1 0.082(13) 0.21(3) 0.087(13) 0.056(16) -0.020(11) 0.034(15)
N2 0.21(2) 0.073(10) 0.061(9) -0.003(8) -0.059(13) 0.061(14)
O1 0.0366(10) 0.0373(10) 0.0349(10) 0.0072(8) -0.0034(8) 0.0061(8)
O2 0.0350(10) 0.0398(11) 0.0380(10) 0.0082(9) -0.0063(8) 0.0026(9)
O3 0.069(3) 0.095(2) 0.0471(19) -0.0110(9) -0.0220(19) 0.0343(13)
S1 0.068(3) 0.45(2) 0.083(4) 0.115(8) 0.016(3) 0.090(7)
Cu1 0.0193(2) 0.0323(2) 0.0217(3) -0.00034(7) -0.00068(13) 0.00967(12)

_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 O1 1.256(3) . ?
C1 O2 1.261(3) . ?
C1 C2 1.501(4) . ?
C2 C4 1.389(4) . ?
C2 C3 1.390(3) . ?
C3 C2 1.390(3) 22_665 ?
C4 C5 1.399(4) . ?
C5 C4 1.399(4) 22_665 ?
C5 C6 1.485(6) . ?
C6 C8 1.387(10) . ?
C6 C8 1.387(10) 22_665 ?
C6 C7 1.389(10) . ?
C6 C7 1.389(10) 22_665 ?
C7 C8 1.420(10) 10_545 ?
C7 C8 1.461(17) . ?
C7 N1 1.47(2) . ?
C7 C7 1.830(18) 22_665 ?
C8 C7 1.420(10) 10_545 ?
C8 N2 1.42(2) . ?
C8 C8 1.838(19) 22_665 ?
C8 C8 2.03(3) 10_545 ?
N1 S1 1.60(2) . ?
N2 S1 1.633(17) 10_545 ?
O1 Cu1 1.966(2) . ?
O2 Cu1 1.968(2) 31_645 ?
O3 Cu1 2.163(4) . ?
S1 N2 1.633(17) 10_545 ?
Cu1 O1 1.966(2) 24_545 ?
Cu1 O2 1.968(2) 18_655 ?
Cu1 O2 1.968(2) 31_645 ?
Cu1 Cu1 2.6466(11) 31_645 ?

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
O1 C1 O2 126.1(3) . . ?
O1 C1 C2 117.3(2) . . ?
O2 C1 C2 116.7(2) . . ?
C4 C2 C3 120.0(3) . . ?
C4 C2 C1 119.6(2) . . ?
C3 C2 C1 120.2(2) . . ?
C2 C3 C2 119.8(4) . 22_665 ?
C2 C4 C5 120.9(3) . . ?
C4 C5 C4 118.3(4) 22_665 . ?
C4 C5 C6 120.84(19) 22_665 . ?
C4 C5 C6 120.84(19) . . ?
C8 C6 C8 83.0(10) . 22_665 ?
C8 C6 C7 63.5(7) . . ?
C8 C6 C7 115.3(6) 22_665 . ?
C8 C6 C7 115.3(6) . 22_665 ?
C8 C6 C7 63.5(7) 22_665 22_665 ?
C7 C6 C7 82.4(10) . 22_665 ?
C8 C6 C5 122.8(5) . . ?
C8 C6 C5 122.8(5) 22_665 . ?
C7 C6 C5 121.9(5) . . ?
C7 C6 C5 121.9(5) 22_665 . ?
C6 C7 C8 122.3(9) . 10_545 ?
C6 C7 C8 58.2(7) . . ?
C8 C7 C8 89.7(11) 10_545 . ?
C6 C7 N1 126.3(10) . . ?
C8 C7 N1 110.2(12) 10_545 . ?
C8 C7 N1 136.8(16) . . ?
C6 C7 C7 48.8(5) . 22_665 ?
C8 C7 C7 90.2(6) 10_545 22_665 ?
C8 C7 C7 90.2(5) . 22_665 ?
N1 C7 C7 126.2(13) . 22_665 ?
C6 C8 C7 122.4(9) . 10_545 ?
C6 C8 N2 125.8(9) . . ?
C7 C8 N2 111.5(10) 10_545 . ?
C6 C8 C7 58.3(6) . . ?
C7 C8 C7 90.3(11) 10_545 . ?
N2 C8 C7 130.0(15) . . ?
C6 C8 C8 48.5(5) . 22_665 ?
C7 C8 C8 89.8(6) 10_545 22_665 ?
N2 C8 C8 132.4(13) . 22_665 ?
C7 C8 C8 89.8(5) . 22_665 ?
C6 C8 C8 90.0(9) . 10_545 ?
C7 C8 C8 46.0(7) 10_545 10_545 ?
N2 C8 C8 135.7(11) . 10_545 ?
C7 C8 C8 44.3(7) . 10_545 ?
C8 C8 C8 90.000(1) 22_665 10_545 ?
C7 N1 S1 107.8(13) . . ?
C8 N2 S1 109.0(10) . 10_545 ?
C1 O1 Cu1 121.65(18) . . ?
C1 O2 Cu1 123.83(18) . 31_645 ?
N1 S1 N2 98.8(10) . 10_545 ?
O1 Cu1 O1 88.51(14) 24_545 . ?
O1 Cu1 O2 168.22(8) 24_545 18_655 ?
O1 Cu1 O2 90.29(11) . 18_655 ?
O1 Cu1 O2 90.29(11) 24_545 31_645 ?
O1 Cu1 O2 168.22(8) . 31_645 ?
O2 Cu1 O2 88.50(15) 18_655 31_645 ?
O1 Cu1 O3 97.28(11) 24_545 . ?
O1 Cu1 O3 97.28(11) . . ?
O2 Cu1 O3 94.49(11) 18_655 . ?
O2 Cu1 O3 94.49(11) 31_645 . ?
O1 Cu1 Cu1 85.12(6) 24_545 31_645 ?
O1 Cu1 Cu1 85.12(6) . 31_645 ?
O2 Cu1 Cu1 83.11(6) 18_655 31_645 ?
O2 Cu1 Cu1 83.10(6) 31_645 31_645 ?
O3 Cu1 Cu1 176.63(13) . 31_645 ?

_diffrn_measured_fraction_theta_max 0.990
_diffrn_reflns_theta_full        27.56
_diffrn_measured_fraction_theta_full 0.990
_refine_diff_density_max         1.137
_refine_diff_density_min         -0.335
_refine_diff_density_rms         0.127
_database_code_depnum_ccdc_archive 'CCDC 1014276'
