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# This journal is © The Royal Society of Chemistry 2014

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#                                CCDC 
# 
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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 retrieval see:
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data_2013_hzg_xxl_02_0m

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'Cu4 H23 N0 Na2 O76 Sb2 W18'
_chemical_formula_weight         5068.94

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'
Sb Sb -0.5866 1.5461 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
W W -0.8490 6.8722 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Na Na 0.0362 0.0249 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Tetragonal
_symmetry_space_group_name_H-M   'P-42(1)m '

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

_cell_length_a                   16.466(4)
_cell_length_b                   16.466(4)
_cell_length_c                   14.115(6)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     3827(2)
_cell_formula_units_Z            2
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    8023
_cell_measurement_theta_min      2.27
_cell_measurement_theta_max      29.23

_exptl_crystal_description       block
_exptl_crystal_colour            blue
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.13
_exptl_crystal_density_meas      none
_exptl_crystal_density_diffrn    4.399
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             4360
_exptl_absorpt_coefficient_mu    28.820
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.010
_exptl_absorpt_correction_T_max  0.024
_exptl_absorpt_process_details   sadabs

_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  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            18926
_diffrn_reflns_av_R_equivalents  0.0393
_diffrn_reflns_av_sigmaI/netI    0.0320
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         1.90
_diffrn_reflns_theta_max         25.01
_reflns_number_total             3552
_reflns_number_gt                3315
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_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)+(0.0346P)²+29.2877P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   ?
_refine_ls_hydrogen_treatment    ?
_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   0.006(14)
_refine_ls_number_reflns         3552
_refine_ls_number_parameters     259
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0302
_refine_ls_R_factor_gt           0.0265
_refine_ls_wR_factor_ref         0.0674
_refine_ls_wR_factor_gt          0.0651
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_restrained_S_all      1.045
_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
W1 W 0.32899(3) 0.33031(3) 0.72883(4) 0.03032(14) Uani 1 1 d . . .
W2 W 0.21022(4) 0.44760(4) 0.59234(4) 0.03460(14) Uani 1 1 d . . .
W3 W 0.28295(3) 0.52000(3) 0.79537(5) 0.03346(14) Uani 1 1 d . . .
W4 W 0.20286(3) 0.44001(3) 1.02150(4) 0.02515(12) Uani 1 1 d . . .
W5 W 0.24927(3) 0.25073(3) 0.95558(5) 0.02581(17) Uani 1 2 d S . .
Sb1 Sb 0.10340(4) 0.39660(4) 0.80397(9) 0.0206(2) Uani 1 2 d S . .
Cu1 Cu 0.0000 0.5000 1.0372(3) 0.0326(7) Uani 1 4 d S . .
Cu2 Cu 0.10437(9) 0.60437(9) 0.90149(18) 0.0290(5) Uani 1 2 d S . .
Cu3 Cu 0.0000 0.5000 0.6068(2) 0.0289(7) Uani 1 4 d S . .
Na1 Na 0.1306(4) 0.6306(4) 0.6927(6) 0.043(2) Uani 1 2 d S . .
O1 O 0.3515(6) 0.5956(6) 0.8152(8) 0.045(3) Uani 1 1 d . . .
O2 O 0.2710(5) 0.4755(5) 0.9192(7) 0.031(2) Uani 1 1 d . . .
O3 O 0.2127(5) 0.4104(5) 0.7471(6) 0.0252(19) Uani 1 1 d . . .
O4 O 0.3641(5) 0.4327(6) 0.7731(7) 0.034(2) Uani 1 1 d . . .
O5 O 0.2560(5) 0.2440(5) 0.7009(9) 0.041(3) Uani 1 2 d S . .
O6 O 0.4204(6) 0.2860(7) 0.7040(8) 0.047(3) Uani 1 1 d . . .
O7 O 0.1521(5) 0.3479(5) 0.9165(8) 0.019(2) Uani 1 2 d S . .
O8 O 0.0000 0.5000 0.4488(15) 0.071(8) Uani 1 4 d S . .
O9 O 0.1491(5) 0.3509(5) 0.5699(8) 0.032(3) Uani 1 2 d S . .
O10 O 0.1171(6) 0.5029(7) 0.6198(9) 0.049(3) Uani 1 1 d . . .
O13 O 0.1186(6) 0.5057(5) 0.9738(7) 0.035(2) Uani 1 1 d . . .
O14 O 0.2421(6) 0.4916(7) 1.1153(7) 0.044(3) Uani 1 1 d . . .
O15 O 0.3065(5) 0.3774(6) 0.6083(7) 0.040(2) Uani 1 1 d . . .
O16 O 0.2751(5) 0.5286(6) 0.6611(6) 0.032(2) Uani 1 1 d . . .
O17 O 0.2335(7) 0.4785(8) 0.4788(8) 0.058(3) Uani 1 1 d . . .
O18 O 0.1861(6) 0.5697(6) 0.8119(7) 0.038(2) Uani 1 1 d . . .
O19 O 0.1196(6) 0.3804(6) 1.0918(10) 0.036(3) Uani 1 2 d S . .
O20 O 0.3158(5) 0.1842(5) 1.0071(10) 0.037(3) Uani 1 2 d S . .
O21 O 0.2718(5) 0.3436(5) 1.0329(6) 0.0270(19) Uani 1 1 d . . .
O22 O 0.3137(5) 0.2974(6) 0.8579(7) 0.035(2) Uani 1 1 d . . .
O1W O 0.2431(19) 0.2569(19) 0.224(3) 0.090(13) Uani 0.50 2 d SP . .
O2W O 0.8917(9) 0.3917(9) 0.1850(17) 0.085(6) Uani 1 2 d S . .
O3W O 0.4324(11) 0.4115(13) 0.9765(17) 0.130(8) Uani 1 1 d . . .
O4W O 0.258(3) 0.4053(18) 0.292(2) 0.110(12) Uani 0.50 1 d 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
W1 O6 1.709(9) . ?
W1 O4 1.889(10) . ?
W1 O5 1.903(3) . ?
W1 O15 1.905(10) . ?
W1 O22 1.918(10) . ?
W1 O3 2.339(8) . ?
W2 O17 1.725(11) . ?
W2 O10 1.825(10) . ?
W2 O9 1.910(3) . ?
W2 O16 1.965(9) . ?
W2 O15 1.975(9) . ?
W2 O3 2.269(9) . ?
W3 O1 1.703(9) . ?
W3 O18 1.808(9) . ?
W3 O2 1.905(10) . ?
W3 O16 1.905(9) . ?
W3 O4 1.988(8) . ?
W3 O3 2.249(9) . ?
W4 O14 1.701(10) . ?
W4 O13 1.884(9) . ?
W4 O2 1.920(9) . ?
W4 O19 1.956(7) . ?
W4 O21 1.958(8) . ?
W4 O7 2.280(8) . ?
W5 O20 1.711(12) . ?
W5 O22 1.901(10) 6 ?
W5 O22 1.902(10) . ?
W5 O21 1.916(9) . ?
W5 O21 1.916(9) 6 ?
W5 O7 2.329(11) . ?
Sb1 O7 1.951(11) . ?
Sb1 O3 1.983(8) . ?
Sb1 O3 1.983(8) 6 ?
Cu1 O13 2.149(9) 8_455 ?
Cu1 O13 2.149(9) 6 ?
Cu1 O13 2.149(9) . ?
Cu1 O13 2.149(9) 3_565 ?
Cu2 O18 1.933(9) 8_455 ?
Cu2 O18 1.933(9) . ?
Cu2 O13 1.933(9) 8_455 ?
Cu2 O13 1.933(9) . ?
Cu2 O20 2.263(13) 2_567 ?
Cu3 O10 1.937(10) 3_565 ?
Cu3 O10 1.937(10) . ?
Cu3 O10 1.937(10) 8_455 ?
Cu3 O10 1.937(10) 6 ?
Cu3 O8 2.23(2) . ?
Cu3 Na1 3.275(10) 3_565 ?
Na1 O18 2.161(12) . ?
Na1 O18 2.161(12) 8_455 ?
Na1 O10 2.352(14) . ?
Na1 O10 2.352(14) 8_455 ?
Na1 O16 2.946(9) 8_455 ?
Na1 O16 2.946(9) . ?
Na1 W3 3.422(4) 8_455 ?
Na1 W2 3.579(5) 8_455 ?
O5 W1 1.903(3) 6 ?
O7 W4 2.280(8) 6 ?
O9 W2 1.910(3) 6 ?
O19 W4 1.956(7) 6 ?
O20 Cu2 2.263(13) 4_657 ?

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
O6 W1 O4 100.3(4) . . ?
O6 W1 O5 101.2(5) . . ?
O4 W1 O5 158.3(4) . . ?
O6 W1 O15 99.3(5) . . ?
O4 W1 O15 89.5(4) . . ?
O5 W1 O15 89.8(5) . . ?
O6 W1 O22 100.9(5) . . ?
O4 W1 O22 88.8(4) . . ?
O5 W1 O22 84.4(5) . . ?
O15 W1 O22 159.6(4) . . ?
O6 W1 O3 169.8(4) . . ?
O4 W1 O3 73.2(3) . . ?
O5 W1 O3 85.8(4) . . ?
O15 W1 O3 73.1(3) . . ?
O22 W1 O3 87.0(3) . . ?
O17 W2 O10 103.7(6) . . ?
O17 W2 O9 102.1(6) . . ?
O10 W2 O9 90.5(5) . . ?
O17 W2 O16 97.9(5) . . ?
O10 W2 O16 90.8(5) . . ?
O9 W2 O16 159.1(5) . . ?
O17 W2 O15 95.8(5) . . ?
O10 W2 O15 160.4(4) . . ?
O9 W2 O15 87.3(5) . . ?
O16 W2 O15 84.5(4) . . ?
O17 W2 O3 166.0(5) . . ?
O10 W2 O3 86.9(4) . . ?
O9 W2 O3 86.8(4) . . ?
O16 W2 O3 72.4(3) . . ?
O15 W2 O3 73.6(3) . . ?
O1 W3 O18 103.5(4) . . ?
O1 W3 O2 101.5(5) . . ?
O18 W3 O2 88.0(4) . . ?
O1 W3 O16 98.9(5) . . ?
O18 W3 O16 92.0(4) . . ?
O2 W3 O16 159.1(4) . . ?
O1 W3 O4 96.2(4) . . ?
O18 W3 O4 160.2(4) . . ?
O2 W3 O4 86.4(4) . . ?
O16 W3 O4 86.7(4) . . ?
O1 W3 O3 167.6(4) . . ?
O18 W3 O3 87.0(4) . . ?
O2 W3 O3 85.2(3) . . ?
O16 W3 O3 73.9(3) . . ?
O4 W3 O3 73.6(3) . . ?
O14 W4 O13 105.7(5) . . ?
O14 W4 O2 102.2(5) . . ?
O13 W4 O2 89.3(4) . . ?
O14 W4 O19 97.0(5) . . ?
O13 W4 O19 87.3(5) . . ?
O2 W4 O19 160.7(4) . . ?
O14 W4 O21 96.9(4) . . ?
O13 W4 O21 157.2(4) . . ?
O2 W4 O21 88.3(4) . . ?
O19 W4 O21 87.6(5) . . ?
O14 W4 O7 168.0(4) . . ?
O13 W4 O7 83.1(4) . . ?
O2 W4 O7 85.9(3) . . ?
O19 W4 O7 74.9(4) . . ?
O21 W4 O7 74.2(4) . . ?
O20 W5 O22 102.1(4) . 6 ?
O20 W5 O22 102.1(4) . . ?
O22 W5 O22 85.7(6) 6 . ?
O20 W5 O21 98.3(4) . . ?
O22 W5 O21 159.5(4) 6 . ?
O22 W5 O21 89.0(4) . . ?
O20 W5 O21 98.3(4) . 6 ?
O22 W5 O21 89.0(4) 6 6 ?
O22 W5 O21 159.5(4) . 6 ?
O21 W5 O21 89.1(5) . 6 ?
O20 W5 O7 168.6(5) . . ?
O22 W5 O7 86.2(3) 6 . ?
O22 W5 O7 86.2(3) . . ?
O21 W5 O7 73.7(3) . . ?
O21 W5 O7 73.7(3) 6 . ?
O7 Sb1 O3 90.2(3) . . ?
O7 Sb1 O3 90.2(3) . 6 ?
O3 Sb1 O3 92.5(5) . 6 ?
O13 Cu1 O13 130.8(6) 8_455 6 ?
O13 Cu1 O13 75.4(5) 8_455 . ?
O13 Cu1 O13 84.6(5) 6 . ?
O13 Cu1 O13 84.6(5) 8_455 3_565 ?
O13 Cu1 O13 75.4(5) 6 3_565 ?
O13 Cu1 O13 130.8(6) . 3_565 ?
O18 Cu2 O18 89.1(6) 8_455 . ?
O18 Cu2 O13 90.7(4) 8_455 8_455 ?
O18 Cu2 O13 165.1(4) . 8_455 ?
O18 Cu2 O13 165.1(4) 8_455 . ?
O18 Cu2 O13 90.7(4) . . ?
O13 Cu2 O13 85.7(5) 8_455 . ?
O18 Cu2 O20 98.1(4) 8_455 2_567 ?
O18 Cu2 O20 98.1(4) . 2_567 ?
O13 Cu2 O20 96.7(4) 8_455 2_567 ?
O13 Cu2 O20 96.7(4) . 2_567 ?
O10 Cu3 O10 169.2(8) 3_565 . ?
O10 Cu3 O10 92.3(7) 3_565 8_455 ?
O10 Cu3 O10 86.7(7) . 8_455 ?
O10 Cu3 O10 86.7(7) 3_565 6 ?
O10 Cu3 O10 92.3(7) . 6 ?
O10 Cu3 O10 169.2(8) 8_455 6 ?
O10 Cu3 O8 95.4(4) 3_565 . ?
O10 Cu3 O8 95.4(4) . . ?
O10 Cu3 O8 95.4(4) 8_455 . ?
O10 Cu3 O8 95.4(4) 6 . ?
O10 Cu3 Na1 45.2(3) 3_565 3_565 ?
O10 Cu3 Na1 129.4(4) . 3_565 ?
O10 Cu3 Na1 129.4(4) 8_455 3_565 ?
O10 Cu3 Na1 45.2(3) 6 3_565 ?
O8 Cu3 Na1 111.72(15) . 3_565 ?
O18 Na1 O18 77.7(6) . 8_455 ?
O18 Na1 O10 88.0(4) . . ?
O18 Na1 O10 132.4(5) 8_455 . ?
O18 Na1 O10 132.4(5) . 8_455 ?
O18 Na1 O10 88.0(4) 8_455 8_455 ?
O10 Na1 O10 68.8(6) . 8_455 ?
O18 Na1 O16 137.2(5) . 8_455 ?
O18 Na1 O16 60.8(3) 8_455 8_455 ?
O10 Na1 O16 127.0(5) . 8_455 ?
O10 Na1 O16 60.0(3) 8_455 8_455 ?
O18 Na1 O16 60.8(3) . . ?
O18 Na1 O16 137.2(5) 8_455 . ?
O10 Na1 O16 60.0(3) . . ?
O10 Na1 O16 127.0(5) 8_455 . ?
O16 Na1 O16 153.9(4) 8_455 . ?
O18 Na1 W3 103.6(4) . 8_455 ?
O18 Na1 W3 27.6(2) 8_455 8_455 ?
O10 Na1 W3 142.2(4) . 8_455 ?
O10 Na1 W3 77.2(3) 8_455 8_455 ?
O16 Na1 W3 33.78(18) 8_455 8_455 ?
O16 Na1 W3 155.8(4) . 8_455 ?
O18 Na1 W2 146.5(4) . 8_455 ?
O18 Na1 W2 76.3(3) 8_455 8_455 ?
O10 Na1 W2 94.3(4) . 8_455 ?
O10 Na1 W2 26.9(2) 8_455 8_455 ?
O16 Na1 W2 33.29(19) 8_455 8_455 ?
O16 Na1 W2 146.0(4) . 8_455 ?
W3 Na1 W2 56.70(3) 8_455 8_455 ?
W3 O2 W4 150.2(5) . . ?
Sb1 O3 W3 115.9(4) . . ?
Sb1 O3 W2 113.8(4) . . ?
W3 O3 W2 94.8(3) . . ?
Sb1 O3 W1 136.3(4) . . ?
W3 O3 W1 93.7(3) . . ?
W2 O3 W1 93.5(3) . . ?
W1 O4 W3 119.4(4) . . ?
W1 O5 W1 154.2(8) 6 . ?
Sb1 O7 W4 114.0(4) . . ?
Sb1 O7 W4 114.0(4) . 6 ?
W4 O7 W4 93.7(4) . 6 ?
Sb1 O7 W5 139.2(6) . . ?
W4 O7 W5 92.9(3) . . ?
W4 O7 W5 92.9(3) 6 . ?
W2 O9 W2 148.3(7) 6 . ?
W2 O10 Cu3 143.5(7) . . ?
W2 O10 Na1 117.4(5) . . ?
Cu3 O10 Na1 99.1(5) . . ?
W4 O13 Cu2 139.5(5) . . ?
W4 O13 Cu1 119.7(4) . . ?
Cu2 O13 Cu1 98.4(4) . . ?
W1 O15 W2 119.8(4) . . ?
W3 O16 W2 118.6(4) . . ?
W3 O16 Na1 86.9(4) . . ?
W2 O16 Na1 91.3(4) . . ?
W3 O18 Cu2 146.4(6) . . ?
W3 O18 Na1 118.8(5) . . ?
Cu2 O18 Na1 94.5(4) . . ?
W4 O19 W4 116.5(7) 6 . ?
W5 O20 Cu2 170.4(8) . 4_657 ?
W5 O21 W4 119.2(4) . . ?
W5 O22 W1 151.2(5) . . ?

_diffrn_measured_fraction_theta_max 0.996
_diffrn_reflns_theta_full        25.01
_diffrn_measured_fraction_theta_full 0.996
_refine_diff_density_max         2.453
_refine_diff_density_min         -2.284
_refine_diff_density_rms         0.247
_database_code_depnum_ccdc_archive 'CCDC 1017979'
