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# 
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# 
#  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.
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#  fide research purposes only. It may contain copyright material
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data_ZJU-72

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C69 H27 Cu6 O36'
_chemical_formula_sum            'C69 H27 Cu6 O36'
_chemical_formula_weight         1813.14

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'
O O 0.0106 0.0060 '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'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           63
_space_group_name_H-M_alt        'C m c m'
_space_group_name_Hall           '-C 2c 2'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z+1/2'
'-x, y, -z+1/2'
'x, -y, -z'
'x+1/2, y+1/2, z'
'-x+1/2, -y+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'
'-x, -y, -z'
'x, y, -z-1/2'
'x, -y, z-1/2'
'-x, y, z'
'-x+1/2, -y+1/2, -z'
'x+1/2, y+1/2, -z-1/2'
'x+1/2, -y+1/2, z-1/2'
'-x+1/2, y+1/2, z'

_cell_length_a                   24.8319(17)
_cell_length_b                   33.5320(17)
_cell_length_c                   18.7099(16)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     15579.0(19)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    3143
_cell_measurement_theta_min      2.18
_cell_measurement_theta_max      19.92

_exptl_crystal_description       block
_exptl_crystal_colour            blue
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    0.773
_exptl_crystal_F_000             3612
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.270
_exptl_crystal_size_mid          0.220
_exptl_crystal_size_min          0.200
_exptl_absorpt_coefficient_mu    0.849
_shelx_estimated_absorpt_T_min   0.803
_shelx_estimated_absorpt_T_max   0.849
_exptl_absorpt_correction_type   psi-scan
_exptl_absorpt_correction_T_min  0.730
_exptl_absorpt_correction_T_max  0.825
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'sealed tube'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            64114
_diffrn_reflns_av_unetI/netI     0.1687
_diffrn_reflns_av_R_equivalents  0.2130
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_k_min       -41
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         1.020
_diffrn_reflns_theta_max         26.099
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measured_fraction_theta_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_point_group_measured_fraction_full 0.997
_reflns_number_total             8111
_reflns_number_gt                2873
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
 ?
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0822P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         8111
_refine_ls_number_parameters     282
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1459
_refine_ls_R_factor_gt           0.0587
_refine_ls_wR_factor_ref         0.1725
_refine_ls_wR_factor_gt          0.1512
_refine_ls_goodness_of_fit_ref   0.809
_refine_ls_restrained_S_all      0.809
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu1 Cu -0.20979(3) 0.73236(2) 0.53475(4) 0.0561(2) Uani 1 1 d . . . . .
Cu2 Cu 0.0000 0.85895(3) 0.7500 0.0592(4) Uani 1 4 d S T P . .
Cu3 Cu 0.0000 0.93796(3) 0.7500 0.0552(4) Uani 1 4 d S T P . .
O1 O -0.17798(18) 0.72896(12) 0.4398(2) 0.0815(13) Uani 1 1 d . . . . .
O2 O -0.24664(18) 0.75792(12) 0.3804(2) 0.0739(12) Uani 1 1 d . . . . .
O3 O -0.0420(6) 0.5706(7) 0.3707(16) 0.371(19) Uani 0.5 1 d . . P . .
O4 O -0.1455(2) 0.69870(17) 0.5829(3) 0.136(2) Uani 1 1 d . . . . .
O5 O -0.18153(16) 0.78646(10) 0.5453(2) 0.0729(12) Uani 1 1 d . . . . .
O6 O -0.24918(19) 0.81641(10) 0.4862(2) 0.0770(13) Uani 1 1 d . . . . .
O7 O -0.05491(16) 0.86501(11) 0.6776(3) 0.0842(14) Uani 1 1 d . . . . .
O8 O -0.05622(14) 0.93168(10) 0.6764(2) 0.0653(11) Uani 1 1 d . . . . .
O9 O 0.0000 0.7941(2) 0.7500 0.173(6) Uani 1 4 d S T P . .
O10 O 0.0000 1.0015(2) 0.7500 0.123(4) Uani 1 4 d S T P . .
O17 O -0.3886(3) 0.9704(2) 0.5157(7) 0.309(7) Uani 1 1 d . . . . .
C1 C -0.2016(3) 0.74111(17) 0.3838(3) 0.0634(17) Uani 1 1 d . . . . .
C2 C -0.1742(3) 0.73223(17) 0.3141(3) 0.0637(16) Uani 1 1 d . . . . .
C3 C -0.1976(4) 0.7417(2) 0.2500 0.060(2) Uani 1 2 d S T P . .
H3 H -0.2305 0.7550 0.2500 0.072 Uiso 1 2 calc R U P . .
C4 C -0.1244(3) 0.71164(18) 0.3118(4) 0.079(2) Uani 1 1 d . . . . .
H4 H -0.1080 0.7052 0.3550 0.095 Uiso 1 1 calc R U . . .
C5 C -0.0990(4) 0.7007(3) 0.2500 0.074(3) Uani 1 2 d S T P . .
C6 C -0.0485(4) 0.6791(3) 0.2500 0.115(4) Uani 1 2 d S T P . .
C7 C 0.0000 0.6958(3) 0.2500 0.065(3) Uani 1 4 d S T P . .
H7 H 0.0000 0.7235 0.2500 0.079 Uiso 1 4 calc R U P . .
C8 C -0.0487(5) 0.6424(4) 0.3009(9) 0.094(5) Uani 0.5 1 d . . P . .
H8 H -0.0813 0.6327 0.3180 0.112 Uiso 0.5 1 calc . U P . .
C9 C 0.0000 0.6235(7) 0.3220(18) 0.151(12) Uani 0.5 2 d S T P . .
C10 C 0.0000 0.5865(9) 0.366(2) 0.197(18) Uani 0.5 2 d S T P . .
C21 C -0.2057(3) 0.81635(16) 0.5223(3) 0.0618(16) Uani 1 1 d . . . . .
C22 C -0.1835(3) 0.85672(15) 0.5412(3) 0.0615(16) Uani 1 1 d . . . . .
C23 C -0.2091(2) 0.89130(15) 0.5186(3) 0.0648(17) Uani 1 1 d . . . . .
H23 H -0.2389 0.8893 0.4886 0.078 Uiso 1 1 calc R U . . .
C24 C -0.1916(2) 0.92850(15) 0.5397(3) 0.0604(16) Uani 1 1 d . . . . .
C25 C -0.1467(2) 0.93011(15) 0.5830(3) 0.0633(17) Uani 1 1 d . . . . .
H25 H -0.1340 0.9549 0.5975 0.076 Uiso 1 1 calc R U . . .
C26 C -0.1200(2) 0.89637(16) 0.6058(3) 0.0591(16) Uani 1 1 d . . . . .
C27 C -0.1392(2) 0.85943(15) 0.5840(3) 0.0611(16) Uani 1 1 d . . . . .
H27 H -0.1217 0.8363 0.5987 0.073 Uiso 1 1 calc R U . . .
C28 C -0.0732(2) 0.89856(19) 0.6568(3) 0.0615(16) Uani 1 1 d . . . . .
C29 C -0.2216(3) 0.96498(15) 0.5187(3) 0.0673(18) Uani 1 1 d . . . . .
C30 C -0.1945(3) 1.0000 0.5000 0.064(2) Uani 1 2 d S T P . .
H30 H -0.1570 1.0000 0.5000 0.076 Uiso 1 2 calc R U P . .
C31 C -0.2779(3) 0.96637(18) 0.5194(4) 0.094(2) Uani 1 1 d . . . . .
H31 H -0.2973 0.9440 0.5334 0.113 Uiso 1 1 calc R U . . .
C32 C -0.3046(4) 1.0000 0.5000 0.105(4) Uani 1 2 d S T P . .
C33 C -0.3652(5) 1.0000 0.5000 0.195(9) Uani 1 2 d S T P . .


_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 O1 1.948(4) . ?
Cu1 O2 1.949(4) 13_466 ?
Cu1 O5 1.955(3) . ?
Cu1 O6 1.966(4) 13_466 ?
Cu1 O4 2.153(4) . ?
Cu1 Cu1 2.6605(13) 13_466 ?
Cu2 O7 1.933(4) 3_556 ?
Cu2 O7 1.933(4) 12 ?
Cu2 O7 1.933(4) 10_557 ?
Cu2 O7 1.933(4) . ?
Cu2 O9 2.175(8) . ?
Cu2 Cu3 2.6494(16) . ?
Cu3 O8 1.972(4) 3_556 ?
Cu3 O8 1.972(4) 12 ?
Cu3 O8 1.972(4) 10_557 ?
Cu3 O8 1.972(4) . ?
Cu3 O10 2.131(8) . ?
O1 C1 1.267(7) . ?
O2 C1 1.255(7) . ?
O2 Cu1 1.949(4) 13_466 ?
O3 C10 1.174(18) . ?
O5 C21 1.245(6) . ?
O6 C21 1.273(6) . ?
O6 Cu1 1.966(4) 13_466 ?
O7 C28 1.274(6) . ?
O8 C28 1.244(6) . ?
O17 C33 1.188(8) . ?
C1 C2 1.500(8) . ?
C2 C3 1.371(7) . ?
C2 C4 1.417(8) . ?
C3 C2 1.371(7) 10_556 ?
C4 C5 1.368(8) . ?
C5 C4 1.368(8) 10_556 ?
C5 C6 1.450(12) . ?
C6 C7 1.328(11) . ?
C6 C8 1.554(14) 10_556 ?
C6 C8 1.554(14) . ?
C7 C6 1.328(11) 3 ?
C8 C9 1.421(17) . ?
C8 C8 1.91(3) 10_556 ?
C9 C8 1.421(17) 12 ?
C9 C10 1.49(3) . ?
C10 O3 1.174(18) 12 ?
C21 C22 1.504(7) . ?
C22 C27 1.363(7) . ?
C22 C23 1.389(7) . ?
C23 C24 1.379(7) . ?
C24 C25 1.379(7) . ?
C24 C29 1.485(7) . ?
C25 C26 1.379(7) . ?
C26 C27 1.389(7) . ?
C26 C28 1.505(8) . ?
C29 C30 1.399(6) . ?
C29 C31 1.399(7) . ?
C30 C29 1.399(6) 4_576 ?
C31 C32 1.358(7) . ?
C32 C31 1.358(7) 4_576 ?
C32 C33 1.504(15) . ?
C33 O17 1.188(8) 4_576 ?

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 Cu1 O2 168.00(17) . 13_466 ?
O1 Cu1 O5 90.03(18) . . ?
O2 Cu1 O5 87.83(17) 13_466 . ?
O1 Cu1 O6 88.84(18) . 13_466 ?
O2 Cu1 O6 90.79(17) 13_466 13_466 ?
O5 Cu1 O6 167.91(16) . 13_466 ?
O1 Cu1 O4 92.9(2) . . ?
O2 Cu1 O4 99.1(2) 13_466 . ?
O5 Cu1 O4 100.25(19) . . ?
O6 Cu1 O4 91.8(2) 13_466 . ?
O1 Cu1 Cu1 83.37(13) . 13_466 ?
O2 Cu1 Cu1 84.67(13) 13_466 13_466 ?
O5 Cu1 Cu1 84.61(12) . 13_466 ?
O6 Cu1 Cu1 83.31(13) 13_466 13_466 ?
O4 Cu1 Cu1 173.90(17) . 13_466 ?
O7 Cu2 O7 89.0(3) 3_556 12 ?
O7 Cu2 O7 89.7(3) 3_556 10_557 ?
O7 Cu2 O7 167.9(2) 12 10_557 ?
O7 Cu2 O7 167.9(2) 3_556 . ?
O7 Cu2 O7 89.7(3) 12 . ?
O7 Cu2 O7 89.0(3) 10_557 . ?
O7 Cu2 O9 96.03(12) 3_556 . ?
O7 Cu2 O9 96.03(12) 12 . ?
O7 Cu2 O9 96.03(12) 10_557 . ?
O7 Cu2 O9 96.03(12) . . ?
O7 Cu2 Cu3 83.97(12) 3_556 . ?
O7 Cu2 Cu3 83.97(12) 12 . ?
O7 Cu2 Cu3 83.97(12) 10_557 . ?
O7 Cu2 Cu3 83.97(12) . . ?
O9 Cu2 Cu3 180.0 . . ?
O8 Cu3 O8 88.6(2) 3_556 12 ?
O8 Cu3 O8 90.1(2) 3_556 10_557 ?
O8 Cu3 O8 167.7(2) 12 10_557 ?
O8 Cu3 O8 167.7(2) 3_556 . ?
O8 Cu3 O8 90.1(2) 12 . ?
O8 Cu3 O8 88.6(2) 10_557 . ?
O8 Cu3 O10 96.13(10) 3_556 . ?
O8 Cu3 O10 96.13(10) 12 . ?
O8 Cu3 O10 96.13(10) 10_557 . ?
O8 Cu3 O10 96.13(10) . . ?
O8 Cu3 Cu2 83.87(10) 3_556 . ?
O8 Cu3 Cu2 83.87(10) 12 . ?
O8 Cu3 Cu2 83.87(10) 10_557 . ?
O8 Cu3 Cu2 83.87(10) . . ?
O10 Cu3 Cu2 180.0 . . ?
C1 O1 Cu1 123.2(4) . . ?
C1 O2 Cu1 121.9(4) . 13_466 ?
C21 O5 Cu1 122.6(4) . . ?
C21 O6 Cu1 122.9(3) . 13_466 ?
C28 O7 Cu2 123.9(4) . . ?
C28 O8 Cu3 122.8(4) . . ?
O2 C1 O1 126.8(6) . . ?
O2 C1 C2 116.7(6) . . ?
O1 C1 C2 116.4(6) . . ?
C3 C2 C4 117.2(7) . . ?
C3 C2 C1 121.5(6) . . ?
C4 C2 C1 121.2(6) . . ?
C2 C3 C2 122.2(8) . 10_556 ?
C5 C4 C2 123.9(7) . . ?
C4 C5 C4 115.6(9) 10_556 . ?
C4 C5 C6 122.2(4) 10_556 . ?
C4 C5 C6 122.2(4) . . ?
C7 C6 C5 125.0(10) . . ?
C7 C6 C8 109.7(8) . 10_556 ?
C5 C6 C8 113.1(8) . 10_556 ?
C7 C6 C8 109.7(8) . . ?
C5 C6 C8 113.1(8) . . ?
C8 C6 C8 75.6(12) 10_556 . ?
C6 C7 C6 130.1(13) 3 . ?
C9 C8 C6 121.3(14) . . ?
C9 C8 C8 106.1(15) . 10_556 ?
C6 C8 C8 52.2(6) . 10_556 ?
C8 C9 C8 117(2) . 12 ?
C8 C9 C10 121.7(10) . . ?
C8 C9 C10 121.7(10) 12 . ?
O3 C10 O3 125(3) . 12 ?
O3 C10 C9 115.0(15) . . ?
O3 C10 C9 115.0(15) 12 . ?
O5 C21 O6 126.4(5) . . ?
O5 C21 C22 117.8(6) . . ?
O6 C21 C22 115.8(5) . . ?
C27 C22 C23 119.5(5) . . ?
C27 C22 C21 119.6(5) . . ?
C23 C22 C21 120.8(6) . . ?
C24 C23 C22 121.6(5) . . ?
C23 C24 C25 117.3(5) . . ?
C23 C24 C29 120.7(5) . . ?
C25 C24 C29 121.9(5) . . ?
C24 C25 C26 122.6(5) . . ?
C25 C26 C27 118.4(6) . . ?
C25 C26 C28 121.8(5) . . ?
C27 C26 C28 119.7(5) . . ?
C22 C27 C26 120.6(5) . . ?
O8 C28 O7 125.3(6) . . ?
O8 C28 C26 119.5(5) . . ?
O7 C28 C26 115.2(5) . . ?
C30 C29 C31 117.1(6) . . ?
C30 C29 C24 121.1(6) . . ?
C31 C29 C24 121.8(5) . . ?
C29 C30 C29 122.4(8) . 4_576 ?
C32 C31 C29 120.9(7) . . ?
C31 C32 C31 121.6(10) . 4_576 ?
C31 C32 C33 119.2(5) . . ?
C31 C32 C33 119.2(5) 4_576 . ?
O17 C33 O17 121.4(14) . 4_576 ?
O17 C33 C32 119.3(7) . . ?
O17 C33 C32 119.3(7) 4_576 . ?

_refine_diff_density_max         0.812
_refine_diff_density_min         -0.324
_refine_diff_density_rms         0.080

_shelxl_version_number           2013-4




_database_code_depnum_ccdc_archive 'CCDC 1014323'
