# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.
# This journal is © The Royal Society of Chemistry 2017

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_2
_database_code_depnum_ccdc_archive 'CCDC 1515264'
_audit_update_record             
;
2016-11-07 deposited with the CCDC.
2017-07-26 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C16 H8 Cu10 N24 O40 P W12'
_chemical_formula_sum            'C16 H8 Cu10 N24 O40 P W12'
_chemical_formula_weight         4049.01

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'
P P 0.1023 0.0942 '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'
W W -0.8490 6.8722 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      tetragonal
_space_group_IT_number           141
_space_group_name_H-M_alt        'I 41/a m d'
_space_group_name_Hall           '-I 4bd 2'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y+1/2, z'
'x, -y, -z'
'-x, y+1/2, -z'
'-y+1/4, -x+1/4, -z+3/4'
'y+1/4, x+3/4, -z+1/4'
'y+1/4, -x+1/4, z+3/4'
'-y+1/4, x+3/4, z+1/4'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1, z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'-x+1/2, y+1, -z+1/2'
'-y+3/4, -x+3/4, -z+5/4'
'y+3/4, x+5/4, -z+3/4'
'y+3/4, -x+3/4, z+5/4'
'-y+3/4, x+5/4, z+3/4'
'-x, -y, -z'
'x, y-1/2, -z'
'-x, y, z'
'x, -y-1/2, z'
'y-1/4, x-1/4, z-3/4'
'-y-1/4, -x-3/4, z-1/4'
'-y-1/4, x-1/4, -z-3/4'
'y-1/4, -x-3/4, -z-1/4'
'-x+1/2, -y+1/2, -z+1/2'
'x+1/2, y, -z+1/2'
'-x+1/2, y+1/2, z+1/2'
'x+1/2, -y, z+1/2'
'y+1/4, x+1/4, z-1/4'
'-y+1/4, -x-1/4, z+1/4'
'-y+1/4, x+1/4, -z-1/4'
'y+1/4, -x-1/4, -z+1/4'

_cell_length_a                   21.0740(19)
_cell_length_b                   21.0740(19)
_cell_length_c                   12.766(2)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     5669.4(12)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    13238
_cell_measurement_theta_min      1.87
_cell_measurement_theta_max      25.00

_exptl_crystal_description       block
_exptl_crystal_colour            black
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    4.744
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             7140.0
_exptl_absorpt_coefficient_mu    28.035
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker P4'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            13238
_diffrn_reflns_av_R_equivalents  0.0636
_diffrn_reflns_av_sigmaI/netI    0.0333
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         1.87
_diffrn_reflns_theta_max         25.00
_reflns_number_total             1334
_reflns_number_gt                1170
_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)+(0.0582P)²+599.3580P] 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         1334
_refine_ls_number_parameters     95
_refine_ls_number_restraints     24
_refine_ls_R_factor_all          0.0501
_refine_ls_R_factor_gt           0.0414
_refine_ls_wR_factor_ref         0.1176
_refine_ls_wR_factor_gt          0.1070
_refine_ls_goodness_of_fit_ref   1.116
_refine_ls_restrained_S_all      1.105
_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
C2 C 0.2460(5) -0.0760(5) 0.1232(7) 0.013(3) Uani 1 1 d U . .
H2 H 0.2662 -0.1152 0.1214 0.015 Uiso 1 1 calc R . .
C1 C 0.4479(5) 0.0252(5) 0.1236(7) 0.015 Uiso 1 1 d R . .
N1 N 0.2748(5) -0.0209(5) 0.1244(9) 0.010(2) Uani 1 1 d . . .
N2 N 0.4688(7) 0.0869(6) 0.1321(11) 0.026(3) Uani 1 1 d . . .
N3 N 0.1828(5) -0.0672(5) 0.1250 0.0083(16) Uani 1 2 d SU . .
N4 N 0.5000 -0.0084(10) 0.1180(15) 0.024(4) Uani 1 2 d S . .
O2 O 0.5635(4) 0.0872(4) 0.5076(7) 0.0046(17) Uani 1 1 d U . .
O3 O 0.5627(4) 0.1123(4) 0.7135(7) 0.0061(18) Uani 1 1 d U . .
O5 O 0.6326(3) 0.1336(3) 0.3352(4) 0.0085(19) Uani 1 1 d . . .
O6 O 0.5000(3) 0.1517(3) 0.3611(4) 0.010 Uiso 1 2 d SR . .
O7 O 0.5000(3) 0.1902(3) 0.5548(4) 0.010 Uiso 1 2 d SR . .
P1 P 0.5000(3) 0.2500(3) 0.6250(4) 0.010 Uiso 1 8 d SR . .
O1 O 0.5000(3) 0.0027(3) 0.6416(4) 0.010 Uiso 1 2 d SR . .
O4 O 0.5778(3) 0.2500(3) 0.3922(4) 0.010 Uiso 1 2 d SR . .
Cu1 Cu 0.4015(2) 0.1515(2) 0.1250 0.0255(13) Uani 0.50 2 d SP . .
Cu2 Cu 0.36299(8) -0.00256(9) 0.11751(15) 0.0184(4) Uani 1 1 d . . .
W1 W 0.5000 0.08129(4) 0.61659(6) 0.0101(2) Uani 1 2 d S . .
W2 W 0.58064(2) 0.16208(2) 0.42758(4) 0.0084(2) Uani 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
C2 N1 1.310(15) . ?
C2 N3 1.346(14) . ?
C2 H2 0.9300 . ?
C1 N4 1.309(15) . ?
C1 N2 1.375(17) . ?
C1 Cu2 1.885(10) . ?
N1 N1 1.36(2) 6_545 ?
N1 Cu2 1.901(11) . ?
N2 N2 1.32(3) 19_655 ?
N2 Cu1 1.968(14) . ?
N3 C2 1.346(14) 6_545 ?
N4 C1 1.309(15) 19_655 ?
O2 W2 1.914(8) . ?
O2 W1 1.934(8) . ?
O3 W2 1.914(8) 13 ?
O3 W1 1.924(8) . ?
O5 W2 1.718(6) . ?
O6 W2 1.912(7) 19_655 ?
O6 W2 1.912(7) . ?
O7 P1 1.5460 . ?
O7 W2 2.424(6) 19_655 ?
O7 W2 2.424(6) . ?
O7 W1 2.428(6) . ?
P1 O7 1.546(10) 6_546 ?
P1 O7 1.546(9) 2_655 ?
P1 O7 1.546(10) 13 ?
O1 W1 1.687(6) . ?
O4 W2 1.908(6) 20_565 ?
O4 W2 1.908(6) . ?
Cu1 N2 1.968(14) 6_545 ?
Cu2 Cu2 3.002(4) 3 ?
W1 O3 1.924(8) 19_655 ?
W1 O2 1.934(8) 19_655 ?
W2 O3 1.914(8) 13 ?

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
N1 C2 N3 109.6(10) . . ?
N1 C2 H2 125.2 . . ?
N3 C2 H2 125.2 . . ?
N4 C1 N2 104.4(12) . . ?
N4 C1 Cu2 128.7(10) . . ?
N2 C1 Cu2 126.9(9) . . ?
C2 N1 N1 107.4(7) . 6_545 ?
C2 N1 Cu2 129.2(9) . . ?
N1 N1 Cu2 123.2(3) 6_545 . ?
N2 N2 C1 108.6(7) 19_655 . ?
N2 N2 Cu1 136.1(5) 19_655 . ?
C1 N2 Cu1 114.8(10) . . ?
C2 N3 C2 105.8(14) 6_545 . ?
C1 N4 C1 114.0(18) 19_655 . ?
W2 O2 W1 124.6(4) . . ?
W2 O3 W1 150.6(5) 13 . ?
W2 O6 W2 125.4(3) 19_655 . ?
P1 O7 W2 126.01(15) . 19_655 ?
P1 O7 W2 126.01(15) . . ?
W2 O7 W2 89.02(18) 19_655 . ?
P1 O7 W1 125.58(13) . . ?
W2 O7 W1 89.2(2) 19_655 . ?
W2 O7 W1 89.2(2) . . ?
O7 P1 O7 109.7(9) 6_546 2_655 ?
O7 P1 O7 109.7(3) 6_546 . ?
O7 P1 O7 109.1(2) 2_655 . ?
O7 P1 O7 109.1(7) 6_546 13 ?
O7 P1 O7 109.7(9) 2_655 13 ?
O7 P1 O7 109.7(3) . 13 ?
W2 O4 W2 152.4(3) 20_565 . ?
N2 Cu1 N2 177.7(9) 6_545 . ?
C1 Cu2 N1 171.9(5) . . ?
C1 Cu2 Cu2 91.7(3) . 3 ?
N1 Cu2 Cu2 93.1(4) . 3 ?
O1 W1 O3 102.2(3) . . ?
O1 W1 O3 102.2(3) . 19_655 ?
O3 W1 O3 86.7(5) . 19_655 ?
O1 W1 O2 101.5(3) . 19_655 ?
O3 W1 O2 156.3(4) . 19_655 ?
O3 W1 O2 88.0(4) 19_655 19_655 ?
O1 W1 O2 101.5(3) . . ?
O3 W1 O2 88.0(4) . . ?
O3 W1 O2 156.3(4) 19_655 . ?
O2 W1 O2 87.6(5) 19_655 . ?
O1 W1 O7 172.0(3) . . ?
O3 W1 O7 83.6(3) . . ?
O3 W1 O7 83.6(3) 19_655 . ?
O2 W1 O7 72.9(3) 19_655 . ?
O2 W1 O7 72.9(3) . . ?
O5 W2 O4 101.3(3) . . ?
O5 W2 O6 102.8(3) . . ?
O4 W2 O6 88.7(3) . . ?
O5 W2 O3 101.3(3) . 13 ?
O4 W2 O3 85.5(3) . 13 ?
O6 W2 O3 155.9(3) . 13 ?
O5 W2 O2 101.5(3) . . ?
O4 W2 O2 157.0(3) . . ?
O6 W2 O2 88.6(3) . . ?
O3 W2 O2 87.7(4) 13 . ?
O5 W2 O7 173.0(4) . . ?
O4 W2 O7 84.2(2) . . ?
O6 W2 O7 72.7(2) . . ?
O3 W2 O7 83.4(3) 13 . ?
O2 W2 O7 73.2(3) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
N3 C2 N1 N1 -0.8(15) . . . 6_545 ?
N3 C2 N1 Cu2 -177.3(7) . . . . ?
N4 C1 N2 N2 -0.6(11) . . . 19_655 ?
Cu2 C1 N2 N2 -178.9(6) . . . 19_655 ?
N4 C1 N2 Cu1 172.9(11) . . . . ?
Cu2 C1 N2 Cu1 -5.4(15) . . . . ?
N1 C2 N3 C2 0.3(6) . . . 6_545 ?
N2 C1 N4 C1 1(2) . . . 19_655 ?
Cu2 C1 N4 C1 179.3(6) . . . 19_655 ?
W2 O7 P1 O7 60.0(5) 19_655 . . 6_546 ?
W2 O7 P1 O7 -179.8(6) . . . 6_546 ?
W1 O7 P1 O7 -59.9(4) . . . 6_546 ?
W2 O7 P1 O7 -60.1(5) 19_655 . . 2_655 ?
W2 O7 P1 O7 60.1(5) . . . 2_655 ?
W1 O7 P1 O7 180.0(8) . . . 2_655 ?
W2 O7 P1 O7 179.8(6) 19_655 . . 13 ?
W2 O7 P1 O7 -60.0(5) . . . 13 ?
W1 O7 P1 O7 59.9(4) . . . 13 ?
N2 N2 Cu1 N2 -2.7(4) 19_655 . . 6_545 ?
C1 N2 Cu1 N2 -173.8(10) . . . 6_545 ?
N4 C1 Cu2 N1 148(3) . . . . ?
N2 C1 Cu2 N1 -34(4) . . . . ?
N4 C1 Cu2 Cu2 -86.0(13) . . . 3 ?
N2 C1 Cu2 Cu2 91.9(10) . . . 3 ?
C2 N1 Cu2 C1 -145(3) . . . . ?
N1 N1 Cu2 C1 39(4) 6_545 . . . ?
C2 N1 Cu2 Cu2 89.0(11) . . . 3 ?
N1 N1 Cu2 Cu2 -87.0(14) 6_545 . . 3 ?
W2 O3 W1 O1 -128.0(10) 13 . . . ?
W2 O3 W1 O3 -26.2(12) 13 . . 19_655 ?
W2 O3 W1 O2 51.2(15) 13 . . 19_655 ?
W2 O3 W1 O2 130.6(10) 13 . . . ?
W2 O3 W1 O7 57.7(10) 13 . . . ?
W2 O2 W1 O1 171.2(5) . . . . ?
W2 O2 W1 O3 -86.7(5) . . . . ?
W2 O2 W1 O3 -9.6(12) . . . 19_655 ?
W2 O2 W1 O2 69.9(6) . . . 19_655 ?
W2 O2 W1 O7 -2.9(4) . . . . ?
P1 O7 W1 O1 180(100) . . . . ?
W2 O7 W1 O1 44(3) 19_655 . . . ?
W2 O7 W1 O1 -45(3) . . . . ?
P1 O7 W1 O3 -43.7(3) . . . . ?
W2 O7 W1 O3 -179.2(3) 19_655 . . . ?
W2 O7 W1 O3 91.8(3) . . . . ?
P1 O7 W1 O3 43.7(3) . . . 19_655 ?
W2 O7 W1 O3 -91.8(3) 19_655 . . 19_655 ?
W2 O7 W1 O3 179.2(3) . . . 19_655 ?
P1 O7 W1 O2 133.6(3) . . . 19_655 ?
W2 O7 W1 O2 -1.9(3) 19_655 . . 19_655 ?
W2 O7 W1 O2 -90.9(3) . . . 19_655 ?
P1 O7 W1 O2 -133.6(3) . . . . ?
W2 O7 W1 O2 90.9(3) 19_655 . . . ?
W2 O7 W1 O2 1.9(3) . . . . ?
W2 O4 W2 O5 -132.5(7) 20_565 . . . ?
W2 O4 W2 O6 124.6(8) 20_565 . . . ?
W2 O4 W2 O3 -32.0(9) 20_565 . . 13 ?
W2 O4 W2 O2 41.3(15) 20_565 . . . ?
W2 O4 W2 O7 51.9(10) 20_565 . . . ?
W2 O6 W2 O5 170.16(11) 19_655 . . . ?
W2 O6 W2 O4 -88.5(4) 19_655 . . . ?
W2 O6 W2 O3 -12.5(9) 19_655 . . 13 ?
W2 O6 W2 O2 68.7(4) 19_655 . . . ?
W2 O6 W2 O7 -4.2(4) 19_655 . . . ?
W1 O2 W2 O5 -172.3(5) . . . . ?
W1 O2 W2 O4 13.9(12) . . . . ?
W1 O2 W2 O6 -69.5(5) . . . . ?
W1 O2 W2 O3 86.7(5) . . . 13 ?
W1 O2 W2 O7 2.9(4) . . . . ?
P1 O7 W2 O5 176(3) . . . . ?
W2 O7 W2 O5 -48(3) 19_655 . . . ?
W1 O7 W2 O5 41(3) . . . . ?
P1 O7 W2 O4 -42.4(3) . . . . ?
W2 O7 W2 O4 93.2(2) 19_655 . . . ?
W1 O7 W2 O4 -177.58(3) . . . . ?
P1 O7 W2 O6 -132.90(11) . . . . ?
W2 O7 W2 O6 2.7(3) 19_655 . . . ?
W1 O7 W2 O6 91.9(2) . . . . ?
P1 O7 W2 O3 43.7(3) . . . 13 ?
W2 O7 W2 O3 179.3(3) 19_655 . . 13 ?
W1 O7 W2 O3 -91.5(3) . . . 13 ?
P1 O7 W2 O2 133.3(3) . . . . ?
W2 O7 W2 O2 -91.1(3) 19_655 . . . ?
W1 O7 W2 O2 -1.9(3) . . . . ?

_diffrn_measured_fraction_theta_max 1.000
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 1.000
_refine_diff_density_max         12.801
_refine_diff_density_min         -2.354
_refine_diff_density_rms         0.487


####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_3
_database_code_depnum_ccdc_archive 'CCDC 1515265'
_audit_update_record             
;
2016-11-07 deposited with the CCDC.
2017-07-26 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C16 H8 Cu10 N24 O40 Si W12'
_chemical_formula_sum            'C16 H8 Cu10 N24 O40 Si W12'
_chemical_formula_weight         4046.13

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'
Si Si 0.0817 0.0704 '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'
W W -0.8490 6.8722 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      tetragonal
_space_group_IT_number           141
_space_group_name_H-M_alt        'I 41/a m d'
_space_group_name_Hall           '-I 4bd 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+1/2, z'
'x, -y, -z'
'-x, y+1/2, -z'
'-y+1/4, -x+1/4, -z+3/4'
'y+1/4, x+3/4, -z+1/4'
'y+1/4, -x+1/4, z+3/4'
'-y+1/4, x+3/4, z+1/4'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1, z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'-x+1/2, y+1, -z+1/2'
'-y+3/4, -x+3/4, -z+5/4'
'y+3/4, x+5/4, -z+3/4'
'y+3/4, -x+3/4, z+5/4'
'-y+3/4, x+5/4, z+3/4'
'-x, -y, -z'
'x, y-1/2, -z'
'-x, y, z'
'x, -y-1/2, z'
'y-1/4, x-1/4, z-3/4'
'-y-1/4, -x-3/4, z-1/4'
'-y-1/4, x-1/4, -z-3/4'
'y-1/4, -x-3/4, -z-1/4'
'-x+1/2, -y+1/2, -z+1/2'
'x+1/2, y, -z+1/2'
'-x+1/2, y+1/2, z+1/2'
'x+1/2, -y, z+1/2'
'y+1/4, x+1/4, z-1/4'
'-y+1/4, -x-1/4, z+1/4'
'-y+1/4, x+1/4, -z-1/4'
'y+1/4, -x-1/4, -z+1/4'

_cell_length_a                   21.0434(8)
_cell_length_b                   21.0434(8)
_cell_length_c                   12.7594(9)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     5650.2(6)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    13568
_cell_measurement_theta_min      1.867
_cell_measurement_theta_max      25.000

_exptl_crystal_description       block
_exptl_crystal_colour            black
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    4.756
_exptl_crystal_F_000             7136.0
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_absorpt_coefficient_mu    28.124
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker P4'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            13568
_diffrn_reflns_av_unetI/netI     0.0182
_diffrn_reflns_av_R_equivalents  0.0356
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         1.867
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_full        25.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             1327
_reflns_number_gt                1277
_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.
 
 _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       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_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)+(0.0238P)²+170.6789P] 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         1327
_refine_ls_number_parameters     131
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0235
_refine_ls_R_factor_gt           0.0221
_refine_ls_wR_factor_ref         0.0581
_refine_ls_wR_factor_gt          0.0575
_refine_ls_goodness_of_fit_ref   1.162
_refine_ls_restrained_S_all      1.162
_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
C1 C 0.0522(3) 0.5257(3) 0.1228(5) 0.0096(15) Uani 1 1 d . . . . .
C2 C 0.2537(4) 0.4241(4) 0.1240(6) 0.0185(17) Uani 1 1 d . . . . .
H2 H 0.2337 0.3847 0.1234 0.022 Uiso 1 1 calc R U . . .
N1 N 0.2248(3) 0.4787(3) 0.1239(6) 0.0156(15) Uani 1 1 d . . . . .
N2 N 0.3167(3) 0.4333(3) 0.1250 0.022(2) Uani 1 2 d S T P . .
N3 N 0.0000 0.5098(5) -0.1195(9) 0.030(3) Uani 1 2 d S T P . .
N4 N 0.0320(4) 0.4141(4) -0.1313(7) 0.036(2) Uani 1 1 d . . . . .
O2 O 0.0000 0.3262(3) 0.1429(5) 0.0070(14) Uani 1 2 d S T P . .
O3 O 0.2464(4) 0.2500 0.3947(6) 0.0148(16) Uani 1 2 d S T P . .
O4 O 0.1646(2) 0.3148(2) 0.2569(4) 0.0090(10) Uani 1 1 d . . . . .
O5 O 0.0628(3) 0.2500 0.3004(5) 0.0072(14) Uani 1 2 d S T P . .
O6 O 0.0625(2) 0.3863(2) 0.2874(4) 0.0096(10) Uani 1 1 d . . . . .
O7 O 0.1164(2) 0.3820(2) 0.0873(4) 0.0139(11) Uani 1 1 d . . . . .
O10 O 0.0997(3) 0.2500 0.1083(5) 0.0091(15) Uani 1 2 d S T P . .
Si1 Si 0.0000 0.2500 0.3750 0.0058(11) Uani 1 8 d S T P . .
Cu1 Cu 0.13693(5) 0.49697(6) 0.11731(9) 0.0269(3) Uani 1 1 d . . . . .
Cu2 Cu 0.09933(12) 0.34933(12) -0.1250 0.0313(8) Uani 0.5 2 d S T P . .
W1 W 0.08798(2) 0.32927(2) 0.17868(2) 0.01039(12) Uani 1 1 d . . . . .
W2 W 0.16765(2) 0.2500 0.36477(3) 0.01070(13) 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
C1 N3 1.330(10) 17_565 ?
C1 N4 1.342(11) 3_565 ?
C1 Cu1 1.883(7) . ?
C2 N1 1.300(11) . ?
C2 N2 1.340(10) . ?
C2 H2 0.9300 . ?
N1 N1 1.385(13) 13_554 ?
N1 Cu1 1.890(6) . ?
N2 C2 1.340(10) 13_554 ?
N3 C1 1.330(10) 17_565 ?
N3 C1 1.330(10) 3_565 ?
N4 C1 1.342(11) 3_565 ?
N4 N4 1.346(18) 19 ?
N4 Cu2 1.967(9) . ?
O2 W1 1.9081(17) 19 ?
O2 W1 1.9081(17) . ?
O3 W2 1.701(8) . ?
O4 W1 1.921(5) . ?
O4 W2 1.939(5) . ?
O5 Si1 1.629(7) . ?
O5 W1 2.340(5) . ?
O5 W1 2.340(5) 20_565 ?
O5 W2 2.354(7) . ?
O6 W1 1.911(5) . ?
O6 W2 1.929(5) 14_445 ?
O7 W1 1.717(5) . ?
O10 W1 1.910(3) . ?
O10 W1 1.910(3) 20_565 ?
Si1 O5 1.629(7) 14_445 ?
Si1 O5 1.629(7) 2 ?
Si1 O5 1.629(7) 5 ?
Cu1 Cu1 2.996(2) 3_565 ?
Cu2 N4 1.967(9) 14_444 ?
W2 O6 1.929(5) 14_445 ?
W2 O6 1.929(5) 24_566 ?
W2 O4 1.939(5) 20_565 ?

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
N3 C1 N4 105.7(8) 17_565 3_565 ?
N3 C1 Cu1 126.9(7) 17_565 . ?
N4 C1 Cu1 127.4(6) 3_565 . ?
N1 C2 N2 109.6(7) . . ?
N1 C2 H2 125.2 . . ?
N2 C2 H2 125.2 . . ?
C2 N1 N1 107.1(5) . 13_554 ?
C2 N1 Cu1 129.7(6) . . ?
N1 N1 Cu1 123.3(2) 13_554 . ?
C2 N2 C2 106.6(10) 13_554 . ?
C1 N3 C1 111.5(11) 17_565 3_565 ?
C1 N4 N4 108.5(5) 3_565 19 ?
C1 N4 Cu2 114.9(6) 3_565 . ?
N4 N4 Cu2 136.1(3) 19 . ?
W1 O2 W1 152.0(4) 19 . ?
W1 O4 W2 120.5(2) . . ?
Si1 O5 W1 124.8(2) . . ?
Si1 O5 W1 124.8(2) . 20_565 ?
W1 O5 W1 90.9(2) . 20_565 ?
Si1 O5 W2 123.9(4) . . ?
W1 O5 W2 91.1(2) . . ?
W1 O5 W2 91.1(2) 20_565 . ?
W1 O6 W2 151.2(3) . 14_445 ?
W1 O10 W1 121.7(4) . 20_565 ?
O5 Si1 O5 109.9(2) . 14_445 ?
O5 Si1 O5 108.5(5) . 2 ?
O5 Si1 O5 109.9(2) 14_445 2 ?
O5 Si1 O5 109.9(2) . 5 ?
O5 Si1 O5 108.5(5) 14_445 5 ?
O5 Si1 O5 109.9(2) 2 5 ?
C1 Cu1 N1 171.6(3) . . ?
C1 Cu1 Cu1 91.4(2) . 3_565 ?
N1 Cu1 Cu1 93.1(2) . 3_565 ?
N4 Cu2 N4 177.7(5) . 14_444 ?
O7 W1 O2 101.4(3) . . ?
O7 W1 O10 101.6(3) . . ?
O2 W1 O10 89.0(3) . . ?
O7 W1 O6 100.7(2) . . ?
O2 W1 O6 85.6(2) . . ?
O10 W1 O6 157.7(2) . . ?
O7 W1 O4 99.4(2) . . ?
O2 W1 O4 159.0(3) . . ?
O10 W1 O4 89.9(3) . . ?
O6 W1 O4 87.6(2) . . ?
O7 W1 O5 172.0(2) . . ?
O2 W1 O5 85.1(3) . . ?
O10 W1 O5 73.7(2) . . ?
O6 W1 O5 84.36(19) . . ?
O4 W1 O5 74.5(2) . . ?
O3 W2 O6 100.9(2) . 14_445 ?
O3 W2 O6 100.9(2) . 24_566 ?
O6 W2 O6 85.9(3) 14_445 24_566 ?
O3 W2 O4 101.0(2) . . ?
O6 W2 O4 88.2(2) 14_445 . ?
O6 W2 O4 158.0(2) 24_566 . ?
O3 W2 O4 101.0(2) . 20_565 ?
O6 W2 O4 158.0(2) 14_445 20_565 ?
O6 W2 O4 88.2(2) 24_566 20_565 ?
O4 W2 O4 89.4(3) . 20_565 ?
O3 W2 O5 172.6(3) . . ?
O6 W2 O5 84.52(19) 14_445 . ?
O6 W2 O5 84.52(19) 24_566 . ?
O4 W2 O5 73.83(17) . . ?
O4 W2 O5 73.83(17) 20_565 . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
N2 C2 N1 N1 -0.6(10) . . . 13_554 ?
N2 C2 N1 Cu1 177.3(5) . . . . ?
N1 C2 N2 C2 0.3(4) . . . 13_554 ?
W1 O5 Si1 O5 -60.00(18) . . . 14_445 ?
W1 O5 Si1 O5 179.4(5) 20_565 . . 14_445 ?
W2 O5 Si1 O5 59.71(15) . . . 14_445 ?
W1 O5 Si1 O5 60.3(3) . . . 2 ?
W1 O5 Si1 O5 -60.3(3) 20_565 . . 2 ?
W2 O5 Si1 O5 180.000(0) . . . 2 ?
W1 O5 Si1 O5 -179.4(5) . . . 5 ?
W1 O5 Si1 O5 60.00(18) 20_565 . . 5 ?
W2 O5 Si1 O5 -59.71(15) . . . 5 ?
N3 C1 Cu1 Cu1 88.4(8) 17_565 . . 3_565 ?
N4 C1 Cu1 Cu1 -91.9(7) 3_565 . . 3_565 ?
C2 N1 Cu1 Cu1 -90.3(8) . . . 3_565 ?
N1 N1 Cu1 Cu1 87.3(8) 13_554 . . 3_565 ?

_refine_diff_density_max         3.386
_refine_diff_density_min         -1.167
_refine_diff_density_rms         0.250



