# Electronic Supplementary Material (ESI) for RSC Advances.
# 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
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# 
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#  data retrieval see:
#                         www.ccdc.cam.ac.uk
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#  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_I
_chemical_name_systematic        ?
_chemical_name_common            {Cu2(HTyr-N-Dan)4(H2O)2].2(H2O)
_chemical_formula_moiety         'C84 H88 N8 Cu2 O22 S4, 2(H2 O)'
_chemical_formula_sum            'C84 H92 Cu2 N8 O24 S4'
_chemical_formula_iupac          ?
_chemical_formula_weight         1852.98
_chemical_absolute_configuration ?

_chemical_melting_point          ?

_space_group_crystal_system      tetragonal
_space_group_name_H-M_alt        'I 4'
_space_group_name_Hall           'I 4'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-y, x, z'
'y, -x, z'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-y+1/2, x+1/2, z+1/2'
'y+1/2, -x+1/2, z+1/2'

_cell_length_a                   20.3483(8)
_cell_length_b                   20.3483(8)
_cell_length_c                   11.0831(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4589.0(3)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    124
_cell_measurement_theta_min      4.1602
_cell_measurement_theta_max      20.0076
_cell_measurement_temperature    296.(2)

_exptl_crystal_description       block
_exptl_crystal_colour            green
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.100
_exptl_crystal_density_diffrn    1.338
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1924

_exptl_absorpt_coefficient_mu    0.630
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS V2012/1 (Bruker AXS Inc.)'
_exptl_absorpt_correction_T_min  0.6831
_exptl_absorpt_correction_T_max  0.7452

_exptl_special_details           
;
;

_diffrn_ambient_temperature      296.(2)

_diffrn_source                   'Sealed Tube'
_diffrn_source_type              'Fine Focus'

_diffrn_radiation_type           'Mo k\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_monochromator  Graphite

_diffrn_measurement_device_type  'Bruker Kappa Apex II'
_diffrn_measurement_method       'Phi and Omega Scan'


_diffrn_detector_area_resol_mean 8.3333

_diffrn_reflns_number            15737
_diffrn_reflns_av_R_equivalents  0.0423
_diffrn_reflns_av_sigmaI/netI    0.0497
_diffrn_reflns_theta_min         1.42
_diffrn_reflns_theta_max         25.02
_diffrn_reflns_theta_full        25.02
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_limit_l_max       12

_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.
;

_reflns_number_total             4021
_reflns_number_gt                3051
_reflns_threshold_expression     >2sigma(I)

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_R_factor_all          0.0770
_refine_ls_R_factor_gt           0.0540
_refine_ls_wR_factor_gt          0.1467
_refine_ls_wR_factor_ref         0.1693
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_restrained_S_all      1.017
_refine_ls_number_reflns         4021
_refine_ls_number_parameters     279
_refine_ls_number_restraints     1
_refine_ls_hydrogen_treatment    mixed
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.1000P)²+0.0000P] where P=(Fo²+2Fc²)/3'

_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap

_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_diff_density_max         0.526
_refine_diff_density_min         -0.315
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.03(2)

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'

_computing_data_collection       'APEX2 V2011.4-1 (Bruker AXS)'
_computing_cell_refinement       'SAINT V8.30C (Bruker AXS Inc., 2013)'
_computing_data_reduction        'SAINT V8.30C (Bruker AXS Inc., 2013)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    'SHELXTL (Bruker AXS)'
_computing_publication_material  'SHELXTL (Bruker AXS)'

loop_
_atom_site_type_symbol
_atom_site_label
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu Cu1 1.0 1.0 0.35977(9) 0.0464(3) Uani d S 1 . .
Cu Cu2 1.0 1.0 0.12171(9) 0.0517(4) Uani d S 1 . .
S S1 0.98607(7) 0.73386(8) 0.3778(2) 0.0845(6) Uani d . 1 . .
O O1 1.0 1.0 0.5520(9) 0.117(4) Uani d S 1 . .
O O2 1.0 1.0 -0.0733(10) 0.117(4) Uani d S 1 . .
O O3 0.9662(2) 0.90996(18) 0.1409(4) 0.0639(11) Uani d . 1 . .
O O4 0.9640(2) 0.91174(19) 0.3428(5) 0.0702(12) Uani d . 1 . .
O O5 1.0410(2) 0.7506(3) 0.3028(6) 0.119(2) Uani d . 1 . .
O O6 0.9954(3) 0.7274(3) 0.5047(6) 0.111(2) Uani d . 1 . .
O O7 0.7078(3) 0.5897(2) 0.1539(6) 0.1035(17) Uani d . 1 . .
H H7 0.7246 0.5668 0.1015 0.155 Uiso calc R 1 . .
O O8 0.5834(7) 0.6260(7) 0.0792(13) 0.139(5) Uiso d PG 0.5 . .
N N1 0.9262(2) 0.7861(2) 0.3585(5) 0.0705(12) Uani d . 1 . .
H H1 0.899 0.794 0.416 0.085 Uiso calc R 1 . .
N N2 0.8023(5) 0.4749(3) 0.3126(7) 0.124(3) Uani d . 1 . .
C C1 0.9538(2) 0.8857(2) 0.2422(7) 0.0558(11) Uani d . 1 . .
C C2 0.9194(2) 0.8193(2) 0.2427(7) 0.0603(12) Uani d . 1 . .
H H2 0.9391 0.7916 0.18 0.072 Uiso calc R 1 . .
C C3 0.8467(3) 0.8297(3) 0.2122(6) 0.0718(18) Uani d . 1 . .
H H3A 0.8266 0.8556 0.2758 0.086 Uiso calc R 1 . .
H H3B 0.8436 0.8548 0.138 0.086 Uiso calc R 1 . .
C C4 0.8085(3) 0.7665(2) 0.1976(5) 0.0594(14) Uani d . 1 . .
C C5 0.7605(3) 0.7481(3) 0.2786(8) 0.087(2) Uani d . 1 . .
H H5 0.7496 0.7752 0.3432 0.105 Uiso calc R 1 . .
C C6 0.7283(3) 0.6880(3) 0.2622(9) 0.089(2) Uani d . 1 . .
H H6 0.6968 0.6744 0.3178 0.107 Uiso calc R 1 . .
C C7 0.7427(3) 0.6487(3) 0.1643(7) 0.0729(17) Uani d . 1 . .
C C8 0.7882(4) 0.6670(4) 0.0870(7) 0.087(2) Uani d . 1 . .
H H8 0.7984 0.6407 0.021 0.105 Uiso calc R 1 . .
C C9 0.8205(4) 0.7252(3) 0.1045(7) 0.088(2) Uani d . 1 . .
H H9 0.8526 0.7371 0.049 0.106 Uiso calc R 1 . .
C C10 0.9541(3) 0.6588(3) 0.3205(6) 0.0744(19) Uani d . 1 . .
C C11 0.9811(4) 0.6351(4) 0.2162(8) 0.100(3) Uani d . 1 . .
H H11 1.0172 0.6564 0.1824 0.12 Uiso calc R 1 . .
C C12 0.9553(6) 0.5799(4) 0.1600(8) 0.134(4) Uani d . 1 . .
H H12 0.9737 0.5647 0.0884 0.161 Uiso calc R 1 . .
C C13 0.9053(5) 0.5491(3) 0.2076(6) 0.104(3) Uani d . 1 . .
H H13 0.8877 0.5128 0.1681 0.124 Uiso calc R 1 . .
C C14 0.8774(3) 0.5700(3) 0.3185(5) 0.0689(16) Uani d . 1 . .
C C15 0.8992(3) 0.6277(2) 0.3755(5) 0.0594(13) Uani d . 1 . .
C C16 0.8659(3) 0.6509(3) 0.4768(5) 0.0671(15) Uani d . 1 . .
H H16 0.8809 0.6883 0.5167 0.081 Uiso calc R 1 . .
C C17 0.8113(3) 0.6187(3) 0.5176(7) 0.0782(17) Uani d . 1 . .
H H17 0.7883 0.6351 0.5835 0.094 Uiso calc R 1 . .
C C18 0.7902(4) 0.5622(4) 0.4616(9) 0.090(2) Uani d . 1 . .
H H18 0.7522 0.542 0.4897 0.108 Uiso calc R 1 . .
C C19 0.8217(4) 0.5354(3) 0.3695(7) 0.089(2) Uani d . 1 . .
C C20 0.8550(5) 0.4211(6) 0.3260(10) 0.138(4) Uiso d . 1 . .
H H20A 0.8557 0.4056 0.4078 0.208 Uiso calc R 1 . .
H H20B 0.8973 0.4389 0.3056 0.208 Uiso calc R 1 . .
H H20C 0.845 0.3852 0.2728 0.208 Uiso calc R 1 . .
C C21 0.7376(5) 0.4547(5) 0.3273(14) 0.180(6) Uani d . 1 . .
H H21A 0.7326 0.434 0.4047 0.27 Uiso calc R 1 . .
H H21B 0.7264 0.4239 0.265 0.27 Uiso calc R 1 . .
H H21C 0.709 0.4921 0.3226 0.27 Uiso calc R 1 . .


_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_site_symmetry_2
_geom_bond_distance
_geom_bond_publ_flag
Cu1 O4 2_775 1.949(4) ?
Cu1 O4 4_575 1.949(4) ?
Cu1 O4 3_755 1.949(4) ?
Cu1 O4 . 1.949(4) ?
Cu1 O1 . 2.130(10) ?
Cu1 Cu2 . 2.6384(14) ?
Cu2 O3 2_775 1.968(4) ?
Cu2 O3 3_755 1.968(4) ?
Cu2 O3 4_575 1.968(4) ?
Cu2 O3 . 1.968(4) ?
Cu2 O2 . 2.161(11) ?
S1 O6 . 1.426(6) ?
S1 O5 . 1.433(6) ?
S1 N1 . 1.631(5) ?
S1 C10 . 1.777(7) ?
O3 C1 . 1.252(7) ?
O4 C1 . 1.252(8) ?
O7 C7 . 1.400(7) ?
O7 H7 . 0.82 ?
N1 C2 . 1.457(9) ?
N1 H1 . 0.86 ?
N2 C21 . 1.390(13) ?
N2 C19 . 1.438(9) ?
N2 C20 . 1.540(13) ?
C1 C2 . 1.523(6) ?
C2 C3 . 1.531(7) ?
C2 H2 . 0.98 ?
C3 C4 . 1.511(8) ?
C3 H3A . 0.97 ?
C3 H3B . 0.97 ?
C4 C9 . 1.353(9) ?
C4 C5 . 1.380(10) ?
C5 C6 . 1.400(10) ?
C5 H5 . 0.93 ?
C6 C7 . 1.379(11) ?
C6 H6 . 0.93 ?
C7 C8 . 1.316(9) ?
C8 C9 . 1.367(9) ?
C8 H8 . 0.93 ?
C9 H9 . 0.93 ?
C10 C11 . 1.367(10) ?
C10 C15 . 1.421(8) ?
C11 C12 . 1.389(12) ?
C11 H11 . 0.93 ?
C12 C13 . 1.307(13) ?
C12 H12 . 0.93 ?
C13 C14 . 1.420(9) ?
C13 H13 . 0.93 ?
C14 C15 . 1.406(8) ?
C14 C19 . 1.447(10) ?
C15 C16 . 1.394(8) ?
C16 C17 . 1.367(8) ?
C16 H16 . 0.93 ?
C17 C18 . 1.374(10) ?
C17 H17 . 0.93 ?
C18 C19 . 1.324(11) ?
C18 H18 . 0.93 ?
C20 H20A . 0.96 ?
C20 H20B . 0.96 ?
C20 H20C . 0.96 ?
C21 H21A . 0.96 ?
C21 H21B . 0.96 ?
C21 H21C . 0.96 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle
_geom_angle_publ_flag
O4 Cu1 O4 2_775 4_575 89.47(3) ?
O4 Cu1 O4 2_775 3_755 89.47(3) ?
O4 Cu1 O4 4_575 3_755 168.9(3) ?
O4 Cu1 O4 2_775 . 168.9(3) ?
O4 Cu1 O4 4_575 . 89.47(3) ?
O4 Cu1 O4 3_755 . 89.47(3) ?
O4 Cu1 O1 2_775 . 95.53(15) ?
O4 Cu1 O1 4_575 . 95.53(15) ?
O4 Cu1 O1 3_755 . 95.53(15) ?
O4 Cu1 O1 . . 95.53(15) ?
O4 Cu1 Cu2 2_775 . 84.47(15) ?
O4 Cu1 Cu2 4_575 . 84.47(15) ?
O4 Cu1 Cu2 3_755 . 84.47(15) ?
O4 Cu1 Cu2 . . 84.47(15) ?
O1 Cu1 Cu2 . . 180.000(2) ?
O3 Cu2 O3 2_775 3_755 89.33(3) ?
O3 Cu2 O3 2_775 4_575 89.33(3) ?
O3 Cu2 O3 3_755 4_575 167.6(3) ?
O3 Cu2 O3 2_775 . 167.6(3) ?
O3 Cu2 O3 3_755 . 89.33(3) ?
O3 Cu2 O3 4_575 . 89.33(3) ?
O3 Cu2 O2 2_775 . 96.21(13) ?
O3 Cu2 O2 3_755 . 96.21(13) ?
O3 Cu2 O2 4_575 . 96.21(13) ?
O3 Cu2 O2 . . 96.21(13) ?
O3 Cu2 Cu1 2_775 . 83.79(13) ?
O3 Cu2 Cu1 3_755 . 83.79(13) ?
O3 Cu2 Cu1 4_575 . 83.79(13) ?
O3 Cu2 Cu1 . . 83.79(13) ?
O2 Cu2 Cu1 . . 180.000(2) ?
O6 S1 O5 . . 119.3(4) ?
O6 S1 N1 . . 106.8(4) ?
O5 S1 N1 . . 110.6(3) ?
O6 S1 C10 . . 108.8(3) ?
O5 S1 C10 . . 106.4(4) ?
N1 S1 C10 . . 103.9(3) ?
C1 O3 Cu2 . . 122.3(3) ?
C1 O4 Cu1 . . 122.6(4) ?
C7 O7 H7 . . 109.5 ?
C2 N1 S1 . . 119.2(4) ?
C2 N1 H1 . . 120.4 ?
S1 N1 H1 . . 120.4 ?
C21 N2 C19 . . 117.5(10) ?
C21 N2 C20 . . 116.0(8) ?
C19 N2 C20 . . 112.0(7) ?
O3 C1 O4 . . 126.7(4) ?
O3 C1 C2 . . 116.5(6) ?
O4 C1 C2 . . 116.7(6) ?
N1 C2 C1 . . 111.7(5) ?
N1 C2 C3 . . 110.5(5) ?
C1 C2 C3 . . 108.7(4) ?
N1 C2 H2 . . 108.6 ?
C1 C2 H2 . . 108.6 ?
C3 C2 H2 . . 108.6 ?
C4 C3 C2 . . 113.7(4) ?
C4 C3 H3A . . 108.8 ?
C2 C3 H3A . . 108.8 ?
C4 C3 H3B . . 108.8 ?
C2 C3 H3B . . 108.8 ?
H3A C3 H3B . . 107.7 ?
C9 C4 C5 . . 117.1(5) ?
C9 C4 C3 . . 121.2(6) ?
C5 C4 C3 . . 121.7(6) ?
C4 C5 C6 . . 119.0(7) ?
C4 C5 H5 . . 120.5 ?
C6 C5 H5 . . 120.5 ?
C7 C6 C5 . . 120.6(7) ?
C7 C6 H6 . . 119.7 ?
C5 C6 H6 . . 119.7 ?
C8 C7 C6 . . 119.8(6) ?
C8 C7 O7 . . 123.2(6) ?
C6 C7 O7 . . 117.0(6) ?
C7 C8 C9 . . 119.4(6) ?
C7 C8 H8 . . 120.3 ?
C9 C8 H8 . . 120.3 ?
C4 C9 C8 . . 124.1(6) ?
C4 C9 H9 . . 118.0 ?
C8 C9 H9 . . 118.0 ?
C11 C10 C15 . . 121.5(7) ?
C11 C10 S1 . . 117.2(5) ?
C15 C10 S1 . . 121.1(5) ?
C10 C11 C12 . . 120.8(7) ?
C10 C11 H11 . . 119.6 ?
C12 C11 H11 . . 119.6 ?
C13 C12 C11 . . 120.1(8) ?
C13 C12 H12 . . 119.9 ?
C11 C12 H12 . . 119.9 ?
C12 C13 C14 . . 121.2(8) ?
C12 C13 H13 . . 119.4 ?
C14 C13 H13 . . 119.4 ?
C15 C14 C13 . . 120.8(6) ?
C15 C14 C19 . . 118.6(6) ?
C13 C14 C19 . . 120.3(7) ?
C16 C15 C14 . . 119.4(5) ?
C16 C15 C10 . . 125.2(5) ?
C14 C15 C10 . . 115.3(5) ?
C17 C16 C15 . . 119.9(6) ?
C17 C16 H16 . . 120.1 ?
C15 C16 H16 . . 120.1 ?
C16 C17 C18 . . 120.4(7) ?
C16 C17 H17 . . 119.8 ?
C18 C17 H17 . . 119.8 ?
C19 C18 C17 . . 122.8(7) ?
C19 C18 H18 . . 118.6 ?
C17 C18 H18 . . 118.6 ?
C18 C19 N2 . . 123.9(8) ?
C18 C19 C14 . . 118.6(6) ?
N2 C19 C14 . . 117.4(8) ?
N2 C20 H20A . . 109.5 ?
N2 C20 H20B . . 109.5 ?
H20A C20 H20B . . 109.5 ?
N2 C20 H20C . . 109.5 ?
H20A C20 H20C . . 109.5 ?
H20B C20 H20C . . 109.5 ?
N2 C21 H21A . . 109.5 ?
N2 C21 H21B . . 109.5 ?
H21A C21 H21B . . 109.5 ?
N2 C21 H21C . . 109.5 ?
H21A C21 H21C . . 109.5 ?
H21B C21 H21C . . 109.5 ?
#
_vrf_PLAT201_I                   
;
PROBLEM: Isotropic non-H Atoms in Main Residue(s)
RESPONSE: Numerous attempts to refine partially occupied (0.5) 
lattice water molecule (O8) anisotropically did not 
provide the converged refinement of the structure. 
Thus this atom was refined isotropically.
;
#
_database_code_depnum_ccdc_archive 'CCDC 1018411'
