# Electronic Supplementary Material (ESI) for RSC Advances.
# This journal is © The Royal Society of Chemistry 2016

####################################################################### 
# 
# 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. 
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data_1216-x19_sq
_database_code_depnum_ccdc_archive 'CCDC 1473396'
_audit_update_record             
;
2016-07-24 deposited with the CCDC.
2016-11-11 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         
'(C2H8N) (PW12O40) (Cu2(C26H18N4)2) (C3H7NO)4 (H2O)6'
_chemical_formula_sum            'C66 H84 Cu2 N13 O50 P W12'
_chemical_formula_weight         4223.71

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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 -1.9646 0.5888 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
P P 0.2955 0.4335 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
W W -5.4734 5.5774 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      tetragonal
_space_group_IT_number           142
_space_group_name_H-M_alt        'I 41/a c d'
_space_group_name_Hall           '-I 4bd 2c'

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

_cell_length_a                   26.9629(3)
_cell_length_b                   26.9629(3)
_cell_length_c                   27.5365(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     20018.9(5)
_cell_formula_units_Z            8
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    15326
_cell_measurement_theta_min      3.9660
_cell_measurement_theta_max      71.1970

_exptl_crystal_description       block
_exptl_crystal_colour            brown
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.803
_exptl_crystal_F_000             15456
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_exptl_absorpt_coefficient_mu    26.130
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.14443
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            34410
_diffrn_reflns_av_unetI/netI     0.0175
_diffrn_reflns_av_R_equivalents  0.0371
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_theta_min         6.105
_diffrn_reflns_theta_max         71.240
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measured_fraction_theta_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_point_group_measured_fraction_full 0.996
_reflns_number_total             4809
_reflns_number_gt                4190
_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.
The contribution of disordered solvent molecules was treated as diffuse 
using the SQUEEZE procedure implemented in PLATON, 
subsequently a set of solvent-free diffraction intensities was produced. 
The final formula was figured out based on 
the SQUEEZE results, elemental analysis data and TGA data.
The masked entities were calculated from the squeeze results
 combined with elemental analyses and TGA data, showing that
 there are 4 DMF, 6 H2O and 1 (CH3)2NH2+ per formula.
;

_computing_data_collection       'SMART (Bruker AXS, 2000)'
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_refine_special_details          ', SQUEEZE'
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0525P)²+460.8347P] 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         4809
_refine_ls_number_parameters     273
_refine_ls_number_restraints     3
_refine_ls_R_factor_all          0.0480
_refine_ls_R_factor_gt           0.0407
_refine_ls_wR_factor_ref         0.1146
_refine_ls_wR_factor_gt          0.1065
_refine_ls_goodness_of_fit_ref   1.144
_refine_ls_restrained_S_all      1.154
_refine_ls_shift/su_max          0.002
_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
W1 W 0.59143(2) 0.26973(2) 0.53347(2) 0.03016(13) Uani 1 1 d . . . . .
W2 W 0.61303(2) 0.18220(2) 0.62211(2) 0.02918(13) Uani 1 1 d . . . . .
W3 W 0.58979(2) 0.27557(2) 0.71660(2) 0.02870(13) Uani 1 1 d . . . . .
P1 P 0.5000 0.2500 0.6250 0.0178(7) Uani 1 4 d DS T P . .
Cu1 Cu 0.7500 0.37085(6) 0.5000 0.0245(3) Uani 1 2 d S T P . .
O1 O 0.6659(2) 0.1499(2) 0.6310(3) 0.0429(16) Uani 1 1 d . . . . .
O2 O 0.5829(2) 0.1438(2) 0.5714(3) 0.0364(14) Uani 1 1 d . . . . .
O3 O 0.5683(2) 0.1532(2) 0.6670(2) 0.0356(14) Uani 1 1 d . . . . .
O4 O 0.6335(2) 0.2274(2) 0.5713(2) 0.0372(14) Uani 1 1 d . . . . .
O5 O 0.6313(2) 0.2895(2) 0.4900(3) 0.0438(16) Uani 1 1 d . . . . .
O6 O 0.5312(2) 0.3020(2) 0.5169(2) 0.0374(14) Uani 1 1 d . . . . .
O7 O 0.54029(19) 0.22562(19) 0.5923(2) 0.0298(12) Uani 1 1 d D . . . .
O8 O 0.6177(2) 0.2354(2) 0.6669(2) 0.0339(13) Uani 1 1 d . . . . .
O9 O 0.6345(2) 0.2769(2) 0.7598(3) 0.0417(15) Uani 1 1 d . . . . .
O10 O 0.5398(2) 0.3159(2) 0.7464(3) 0.0404(15) Uani 1 1 d . . . . .
N1 N 0.4185(2) 0.4877(2) 0.6897(2) 0.0259(13) Uani 1 1 d . . . . .
N2 N 0.6919(2) 0.4166(2) 0.4855(2) 0.0270(14) Uani 1 1 d . . . . .
C1 C 0.3957(3) 0.4670(3) 0.6510(3) 0.0264(16) Uani 1 1 d . . . . .
H1 H 0.3663 0.4497 0.6562 0.032 Uiso 1 1 calc R U . . .
C2 C 0.4139(3) 0.4701(3) 0.6044(3) 0.0293(17) Uani 1 1 d . . . . .
H2 H 0.3969 0.4556 0.5786 0.035 Uiso 1 1 calc R U . . .
C3 C 0.4585(3) 0.4955(3) 0.5965(3) 0.0241(15) Uani 1 1 d . . . . .
C4 C 0.4832(3) 0.5143(3) 0.6364(3) 0.0322(18) Uani 1 1 d . . . . .
H4 H 0.5140 0.5294 0.6328 0.039 Uiso 1 1 calc R U . . .
C5 C 0.4615(3) 0.5104(3) 0.6820(3) 0.0304(17) Uani 1 1 d . . . . .
H5 H 0.4779 0.5243 0.7084 0.037 Uiso 1 1 calc R U . . .
C6 C 0.4797(3) 0.4994(3) 0.5474(3) 0.0229(15) Uani 1 1 d . . . . .
C7 C 0.5286(3) 0.4853(3) 0.5390(3) 0.0253(15) Uani 1 1 d . . . . .
H7 H 0.5480 0.4758 0.5653 0.030 Uiso 1 1 calc R U . . .
C8 C 0.5494(3) 0.4849(3) 0.4932(3) 0.0246(15) Uani 1 1 d . . . . .
C9 C 0.5996(3) 0.4635(3) 0.4880(3) 0.0239(15) Uani 1 1 d . . . . .
C10 C 0.6383(3) 0.4797(3) 0.5171(3) 0.0295(17) Uani 1 1 d . . . . .
H10 H 0.6340 0.5066 0.5378 0.035 Uiso 1 1 calc R U . . .
C11 C 0.6836(3) 0.4554(3) 0.5148(3) 0.0281(16) Uani 1 1 d . . . . .
H11 H 0.7094 0.4666 0.5345 0.034 Uiso 1 1 calc R U . . .
C12 C 0.6550(3) 0.4020(3) 0.4568(3) 0.0275(16) Uani 1 1 d . . . . .
H12 H 0.6608 0.3759 0.4354 0.033 Uiso 1 1 calc R U . . .
C13 C 0.6083(3) 0.4237(3) 0.4571(3) 0.0276(16) Uani 1 1 d . . . . .
H13 H 0.5833 0.4118 0.4370 0.033 Uiso 1 1 calc R U . . .
C50 C 0.7108(12) 0.3108(13) 1.0066(12) 0.033(7) Uiso 0.25 1 d D . P . .
H50A H 0.7435 0.3045 0.9942 0.049 Uiso 0.25 1 calc R U P . .
H50B H 0.6955 0.2800 1.0157 0.049 Uiso 0.25 1 calc R U P . .
H50C H 0.7131 0.3320 1.0345 0.049 Uiso 0.25 1 calc R U P . .
C51 C 0.692(3) 0.367(3) 0.928(2) 0.11(2) Uiso 0.25 1 d D . P . .
H51A H 0.7220 0.3565 0.9130 0.163 Uiso 0.25 1 calc R U P . .
H51B H 0.6948 0.4004 0.9391 0.163 Uiso 0.25 1 calc R U P . .
H51C H 0.6649 0.3645 0.9053 0.163 Uiso 0.25 1 calc R U P . .
N5 N 0.681(2) 0.335(2) 0.9695(17) 0.100 Uiso 0.25 1 d D U P . .
H5A H 0.6592 0.3520 0.9866 0.120 Uiso 0.25 1 calc R U P . .
H5B H 0.6643 0.3098 0.9565 0.120 Uiso 0.25 1 calc R U 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 O5 1.695(6) . ?
W1 O3 1.897(6) 20_657 ?
W1 O6 1.898(6) . ?
W1 O4 1.916(6) . ?
W1 O10 1.931(6) 26_566 ?
W1 O7 2.437(5) . ?
W2 O1 1.689(6) . ?
W2 O3 1.895(6) . ?
W2 O8 1.896(6) . ?
W2 O2 1.919(6) . ?
W2 O4 1.936(6) . ?
W2 O7 2.427(5) . ?
W3 O9 1.694(6) . ?
W3 O6 1.894(6) 26_566 ?
W3 O8 1.901(6) . ?
W3 O10 1.916(6) . ?
W3 O2 1.919(6) 20_657 ?
W3 O7 2.429(6) 20_657 ?
P1 O7 1.556(5) 20_657 ?
P1 O7 1.556(5) 3_655 ?
P1 O7 1.556(5) 26_566 ?
P1 O7 1.557(5) . ?
Cu1 N1 1.999(7) 23_765 ?
Cu1 N1 1.999(7) 26_566 ?
Cu1 N2 2.033(7) . ?
Cu1 N2 2.033(7) 6_656 ?
O2 W3 1.919(6) 26_566 ?
O3 W1 1.898(6) 26_566 ?
O6 W3 1.894(6) 20_657 ?
O7 W3 2.429(6) 26_566 ?
O10 W1 1.931(6) 20_657 ?
N1 C5 1.329(10) . ?
N1 C1 1.349(10) . ?
N1 Cu1 1.999(7) 20_657 ?
N2 C12 1.331(10) . ?
N2 C11 1.341(11) . ?
C1 C2 1.377(12) . ?
C2 C3 1.402(11) . ?
C3 C4 1.379(12) . ?
C3 C6 1.474(10) . ?
C4 C5 1.388(12) . ?
C6 C7 1.389(10) . ?
C6 C8 1.429(11) 17_666 ?
C7 C8 1.380(11) . ?
C8 C6 1.429(11) 17_666 ?
C8 C9 1.480(10) . ?
C9 C10 1.387(11) . ?
C9 C13 1.389(11) . ?
C10 C11 1.387(11) . ?
C12 C13 1.390(10) . ?
C50 N5 1.445(10) . ?
C51 N5 1.455(10) . ?

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
O5 W1 O3 104.0(3) . 20_657 ?
O5 W1 O6 103.2(3) . . ?
O3 W1 O6 85.5(3) 20_657 . ?
O5 W1 O4 101.3(3) . . ?
O3 W1 O4 88.6(3) 20_657 . ?
O6 W1 O4 155.5(3) . . ?
O5 W1 O10 100.8(3) . 26_566 ?
O3 W1 O10 155.2(3) 20_657 26_566 ?
O6 W1 O10 88.5(3) . 26_566 ?
O4 W1 O10 87.0(3) . 26_566 ?
O5 W1 O7 169.1(3) . . ?
O3 W1 O7 84.4(2) 20_657 . ?
O6 W1 O7 84.2(2) . . ?
O4 W1 O7 71.5(2) . . ?
O10 W1 O7 71.1(2) 26_566 . ?
O1 W2 O3 103.3(3) . . ?
O1 W2 O8 103.9(3) . . ?
O3 W2 O8 86.0(3) . . ?
O1 W2 O2 100.6(3) . . ?
O3 W2 O2 89.0(3) . . ?
O8 W2 O2 155.5(3) . . ?
O1 W2 O4 100.9(3) . . ?
O3 W2 O4 155.8(3) . . ?
O8 W2 O4 88.5(3) . . ?
O2 W2 O4 86.2(3) . . ?
O1 W2 O7 168.5(3) . . ?
O3 W2 O7 84.6(2) . . ?
O8 W2 O7 84.8(2) . . ?
O2 W2 O7 70.9(2) . . ?
O4 W2 O7 71.5(2) . . ?
O9 W3 O6 103.3(3) . 26_566 ?
O9 W3 O8 103.6(3) . . ?
O6 W3 O8 85.7(3) 26_566 . ?
O9 W3 O10 100.8(3) . . ?
O6 W3 O10 88.7(3) 26_566 . ?
O8 W3 O10 155.6(3) . . ?
O9 W3 O2 101.6(3) . 20_657 ?
O6 W3 O2 155.0(3) 26_566 20_657 ?
O8 W3 O2 88.6(3) . 20_657 ?
O10 W3 O2 86.4(3) . 20_657 ?
O9 W3 O7 169.2(3) . 20_657 ?
O6 W3 O7 84.4(2) 26_566 20_657 ?
O8 W3 O7 84.2(2) . 20_657 ?
O10 W3 O7 71.5(2) . 20_657 ?
O2 W3 O7 70.8(2) 20_657 20_657 ?
O7 P1 O7 109.5(2) 20_657 3_655 ?
O7 P1 O7 109.3(4) 20_657 26_566 ?
O7 P1 O7 109.5(2) 3_655 26_566 ?
O7 P1 O7 109.5(2) 20_657 . ?
O7 P1 O7 109.3(4) 3_655 . ?
O7 P1 O7 109.5(2) 26_566 . ?
N1 Cu1 N1 115.9(4) 23_765 26_566 ?
N1 Cu1 N2 106.6(3) 23_765 . ?
N1 Cu1 N2 111.0(3) 26_566 . ?
N1 Cu1 N2 111.0(3) 23_765 6_656 ?
N1 Cu1 N2 106.6(3) 26_566 6_656 ?
N2 Cu1 N2 105.3(4) . 6_656 ?
W3 O2 W2 127.8(3) 26_566 . ?
W2 O3 W1 151.3(3) . 26_566 ?
W1 O4 W2 126.8(3) . . ?
W3 O6 W1 151.7(4) 20_657 . ?
P1 O7 W2 124.9(3) . . ?
P1 O7 W3 125.4(3) . 26_566 ?
W2 O7 W3 90.44(17) . 26_566 ?
P1 O7 W1 125.0(3) . . ?
W2 O7 W1 90.17(17) . . ?
W3 O7 W1 90.16(19) 26_566 . ?
W2 O8 W3 150.8(3) . . ?
W3 O10 W1 127.2(4) . 20_657 ?
C5 N1 C1 117.6(7) . . ?
C5 N1 Cu1 121.3(6) . 20_657 ?
C1 N1 Cu1 118.9(5) . 20_657 ?
C12 N2 C11 117.7(7) . . ?
C12 N2 Cu1 120.8(5) . . ?
C11 N2 Cu1 119.0(5) . . ?
N1 C1 C2 123.3(7) . . ?
C1 C2 C3 118.6(8) . . ?
C4 C3 C2 118.1(7) . . ?
C4 C3 C6 121.2(7) . . ?
C2 C3 C6 120.6(7) . . ?
C3 C4 C5 119.3(7) . . ?
N1 C5 C4 123.0(8) . . ?
C7 C6 C8 118.1(7) . 17_666 ?
C7 C6 C3 120.1(7) . . ?
C8 C6 C3 121.8(7) 17_666 . ?
C8 C7 C6 122.6(7) . . ?
C7 C8 C6 119.3(7) . 17_666 ?
C7 C8 C9 117.7(7) . . ?
C6 C8 C9 122.8(7) 17_666 . ?
C10 C9 C13 118.0(7) . . ?
C10 C9 C8 120.7(7) . . ?
C13 C9 C8 121.0(7) . . ?
C11 C10 C9 119.2(8) . . ?
N2 C11 C10 122.8(7) . . ?
N2 C12 C13 123.3(7) . . ?
C9 C13 C12 118.9(7) . . ?
C50 N5 C51 135(6) . . ?

_refine_diff_density_max         1.402
_refine_diff_density_min         -1.885
_refine_diff_density_rms         0.214


