# Supplementary Material (ESI) for Dalton Transactions
# This journal is (c) The Royal Society of Chemistry 2009

data_global
_journal_name_full               'Dalton Trans.'

_journal_coden_Cambridge         0222
_journal_volume                  ?
_journal_page_first              ?
_journal_year                    ?

_publ_contact_author_name        'Prof M. Weller '
_publ_contact_author_email       MTW@SOTON.AC.UK

_publ_section_title              
;
[NH4]12[(MoO2)2O(HPO4)2]4[PO4]X , X = Cl, Br - new
porous layer molybdenophosphates with embedded multiple anionic and
cationic guests
;
loop_
_publ_author_name
'M. Weller'
'Eleni Kotsapa'

# Attachment '[NH4]12[_MoO2_2O_HPO4_2]4[PO4]Cl_singlecrystal_X-ray.CIF'

data_h0032
_database_code_depnum_ccdc_archive 'CCDC 695315'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'Cl H56 Mo8 N12 O56 P9 '
_chemical_formula_weight         2202.27

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
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'
Mo Mo -1.6832 0.6857 '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'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 '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 -4'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, z'
'y, -x, -z'
'-y, x, -z'

_cell_length_a                   9.71480(10)
_cell_length_b                   9.71480(10)
_cell_length_c                   14.5615(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1374.28(3)
_cell_formula_units_Z            1
_cell_measurement_temperature    120(2)
_cell_measurement_reflns_used    7230
_cell_measurement_theta_min      2.91
_cell_measurement_theta_max      27.48

_exptl_crystal_description       plate
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.02
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.661
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1076
_exptl_absorpt_coefficient_mu    2.216
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.797
_exptl_absorpt_correction_T_max  0.957
_exptl_absorpt_process_details   'SADABS 2007/2 (Sheldrick, G.M., 2007)'

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      120(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'Bruker-Nonius FR591 rotating anode'
_diffrn_radiation_monochromator  '10cm confocal mirrors'
_diffrn_measurement_device_type  
'Bruker-Nonius APEX II CCD camera on \k-goniostat'
_diffrn_measurement_method       '\f & \w scans'
#_diffrn_detector_area_resol_mean '4096x4096pixels / 62x62mm'
_diffrn_reflns_number            10374
_diffrn_reflns_av_R_equivalents  0.0359
_diffrn_reflns_av_sigmaI/netI    0.0393
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         3.28
_diffrn_reflns_theta_max         27.49
_reflns_number_total             3113
_reflns_number_gt                3090
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'COLLECT (Hooft, R.W.W., 1998)'
_computing_cell_refinement       
'DENZO (Otwinowski & Minor, 1997) & COLLECT (Hooft, R.W.W., 1998)'
#Although determined using DirAx, the cell is refined in the HKL
#package during data reduction
_computing_data_reduction        
'DENZO (Otwinowski & Minor, 1997) & COLLECT (Hooft, R.W.W., 1998)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ 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/[\s^2^(Fo^2^)+(0.0000P)^2^+4.7505P] where P=(Fo^2^+2Fc^2^)/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     SHELXL
_refine_ls_extinction_coef       0.0019(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.07(4)
_refine_ls_number_reflns         3113
_refine_ls_number_parameters     241
_refine_ls_number_restraints     28
_refine_ls_R_factor_all          0.0267
_refine_ls_R_factor_gt           0.0264
_refine_ls_wR_factor_ref         0.0628
_refine_ls_wR_factor_gt          0.0627
_refine_ls_goodness_of_fit_ref   1.133
_refine_ls_restrained_S_all      1.130
_refine_ls_shift/su_max          0.000
_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
Mo1 Mo 0.12187(4) 0.35248(4) 0.19335(2) 0.01016(10) Uani 1 1 d . . .
Mo2 Mo 0.62884(4) 0.14217(4) 0.16153(2) 0.00907(10) Uani 1 1 d . . .
P1 P 0.65095(11) 0.86025(11) 0.29970(7) 0.0083(2) Uani 1 1 d . . .
P2 P 0.82013(11) 0.35279(12) 0.30624(8) 0.0101(2) Uani 1 1 d . . .
P3 P 0.5000 0.5000 0.5000 0.0146(5) Uani 1 4 d S . .
Cl Cl 0.0000 0.0000 0.5000 0.0365(7) Uani 1 4 d S . .
O1 O 0.5000 0.0000 0.1258(3) 0.0115(9) Uani 1 2 d S . .
O2 O 0.0000 0.5000 0.1611(3) 0.0115(9) Uani 1 2 d S . .
O3 O 0.5783(4) 0.2581(4) 0.0800(3) 0.0194(8) Uani 1 1 d . . .
O4 O 0.2648(3) 0.3997(4) 0.1324(2) 0.0173(7) Uani 1 1 d . . .
O5 O 0.7738(4) 0.0726(4) 0.1129(3) 0.0223(8) Uani 1 1 d . . .
O6 O 0.0529(4) 0.2301(4) 0.1229(3) 0.0214(8) Uani 1 1 d . . .
O7 O 0.4663(4) 0.2084(3) 0.2483(2) 0.0147(7) Uani 1 1 d . . .
O8 O 0.6662(3) 0.0135(3) 0.2829(2) 0.0160(7) Uani 1 1 d . . .
O9 O 0.7857(3) 0.7855(4) 0.2774(3) 0.0169(8) Uani 1 1 d . . .
O10 O 0.1881(3) 0.4915(3) 0.3031(2) 0.0144(7) Uani 1 1 d . . .
O11 O 0.9668(3) 0.3004(3) 0.2980(3) 0.0147(7) Uani 1 1 d . . .
O12 O 0.7286(4) 0.2921(4) 0.2299(3) 0.0182(7) Uani 1 1 d . . .
O13 O 0.5231(4) 0.3718(5) 0.4408(3) 0.0350(11) Uani 1 1 d . . .
O14 O 0.6275(4) 0.8446(4) 0.4054(2) 0.0188(7) Uani 1 1 d D . .
H14 H 0.587(7) 0.774(6) 0.413(5) 0.028 Uiso 1 1 d D . .
O15 O 0.7660(4) 0.3027(4) 0.4004(3) 0.0204(8) Uani 1 1 d D . .
H15 H 0.724(7) 0.347(7) 0.437(4) 0.031 Uiso 1 1 d D . .
N1 N 0.0000 0.0000 0.2561(7) 0.0320(19) Uani 1 2 d SD . .
H1A H 0.074(5) 0.006(7) 0.224(4) 0.038 Uiso 1 1 d D . .
H1B H 0.006(6) 0.060(5) 0.299(3) 0.038 Uiso 1 1 d D . .
N2 N 0.5000 0.5000 0.2369(5) 0.0135(11) Uani 1 2 d SD . .
H2A H 0.514(5) 0.453(5) 0.285(2) 0.016 Uiso 1 1 d D . .
H2B H 0.571(4) 0.498(6) 0.203(3) 0.016 Uiso 1 1 d D . .
N3 N 0.6825(5) 0.0868(5) 0.5224(3) 0.0241(10) Uani 1 1 d D . .
H3A H 0.647(5) 0.028(4) 0.486(3) 0.029 Uiso 1 1 d D . .
H3B H 0.760(3) 0.112(5) 0.502(3) 0.029 Uiso 1 1 d D . .
H3C H 0.628(4) 0.157(4) 0.526(3) 0.029 Uiso 1 1 d D . .
H3D H 0.691(5) 0.051(5) 0.575(2) 0.029 Uiso 1 1 d D . .
N4 N 0.8348(5) 0.3249(6) 0.9993(3) 0.0319(13) Uani 1 1 d D . .
H4A H 0.872(5) 0.256(4) 1.021(3) 0.038 Uiso 1 1 d D . .
H4B H 0.838(6) 0.390(4) 1.042(3) 0.038 Uiso 1 1 d D . .
H4C H 0.882(4) 0.359(5) 0.955(3) 0.038 Uiso 1 1 d D . .
H4D H 0.753(3) 0.318(5) 0.983(3) 0.038 Uiso 1 1 d D . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Mo1 0.00908(19) 0.00955(19) 0.01185(17) -0.00065(15) -0.00014(15) 0.00296(14)
Mo2 0.0086(2) 0.00833(19) 0.01028(17) 0.00014(14) 0.00089(14) -0.00195(14)
P1 0.0073(5) 0.0069(5) 0.0106(4) 0.0012(5) 0.0009(4) 0.0007(4)
P2 0.0100(5) 0.0097(5) 0.0106(5) 0.0005(5) 0.0001(4) -0.0031(4)
P3 0.0170(7) 0.0170(7) 0.0097(11) 0.000 0.000 0.000
Cl 0.0240(8) 0.0240(8) 0.062(2) 0.000 0.000 0.000
O1 0.015(2) 0.012(2) 0.008(2) 0.000 0.000 -0.0021(18)
O2 0.014(2) 0.011(2) 0.010(2) 0.000 0.000 0.0020(17)
O3 0.0207(18) 0.0154(17) 0.0221(18) 0.0052(15) -0.0044(15) -0.0037(14)
O4 0.0104(16) 0.0244(19) 0.0172(17) -0.0006(14) 0.0022(14) 0.0026(13)
O5 0.0135(18) 0.0175(18) 0.036(2) -0.0053(16) 0.0114(16) -0.0028(14)
O6 0.027(2) 0.0130(17) 0.0241(19) -0.0049(15) -0.0071(16) 0.0061(14)
O7 0.0144(17) 0.0104(16) 0.0194(18) -0.0011(14) 0.0077(14) -0.0005(13)
O8 0.0178(17) 0.0098(15) 0.0203(19) 0.0007(13) -0.0038(14) -0.0003(13)
O9 0.0107(16) 0.0145(17) 0.0254(19) -0.0026(14) 0.0035(14) 0.0036(13)
O10 0.0149(16) 0.0131(16) 0.0151(16) -0.0015(14) -0.0021(14) 0.0014(12)
O11 0.0106(16) 0.0107(15) 0.0228(18) 0.0051(14) 0.0001(15) -0.0011(12)
O12 0.0157(17) 0.0174(18) 0.0214(18) 0.0004(15) -0.0057(15) -0.0073(14)
O13 0.018(2) 0.048(3) 0.039(2) -0.030(2) 0.0118(18) -0.0122(19)
O14 0.032(2) 0.0156(19) 0.0090(14) 0.0028(14) 0.0016(15) 0.0009(17)
O15 0.028(2) 0.0153(18) 0.0183(18) 0.0017(14) 0.0047(16) -0.0022(15)
N1 0.018(4) 0.009(3) 0.068(6) 0.000 0.000 -0.002(3)
N2 0.007(3) 0.011(3) 0.022(3) 0.000 0.000 0.001(2)
N3 0.030(3) 0.021(2) 0.021(2) 0.004(2) -0.003(2) -0.0035(18)
N4 0.019(2) 0.053(3) 0.023(2) 0.015(2) -0.002(2) -0.014(2)

_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
Mo1 O6 1.707(4) . ?
Mo1 O4 1.711(3) . ?
Mo1 O2 1.9172(12) . ?
Mo1 O9 2.025(3) 2_665 ?
Mo1 O10 2.189(3) . ?
Mo1 O11 2.202(3) 1_455 ?
Mo2 O3 1.709(3) . ?
Mo2 O5 1.715(3) . ?
Mo2 O1 1.9353(13) . ?
Mo2 O12 2.013(3) . ?
Mo2 O7 2.123(3) . ?
Mo2 O8 2.195(3) . ?
P1 O8 1.516(4) 1_565 ?
P1 O7 1.517(4) 2_665 ?
P1 O9 1.532(3) . ?
P1 O14 1.564(3) . ?
P2 O10 1.516(3) 2_665 ?
P2 O11 1.518(3) . ?
P2 O12 1.540(4) . ?
P2 O15 1.547(4) . ?
P3 O13 1.531(4) 4_656 ?
P3 O13 1.531(4) 3_566 ?
P3 O13 1.531(4) . ?
P3 O13 1.531(4) 2_665 ?
O1 Mo2 1.9353(13) 2_655 ?
O2 Mo1 1.9172(12) 2_565 ?
O7 P1 1.517(3) 2_665 ?
O8 P1 1.516(4) 1_545 ?
O9 Mo1 2.025(3) 2_665 ?
O10 P2 1.516(3) 2_665 ?
O11 Mo1 2.202(3) 1_655 ?
O14 H14 0.80(5) . ?
O15 H15 0.80(5) . ?
N1 H1A 0.86(2) . ?
N1 H1B 0.86(2) . ?
N2 H2A 0.84(2) . ?
N2 H2B 0.85(2) . ?
N3 H3A 0.85(2) . ?
N3 H3B 0.84(2) . ?
N3 H3C 0.87(2) . ?
N3 H3D 0.85(2) . ?
N4 H4A 0.83(2) . ?
N4 H4B 0.89(2) . ?
N4 H4C 0.86(2) . ?
N4 H4D 0.83(2) . ?

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 Mo1 O4 101.15(18) . . ?
O6 Mo1 O2 97.54(15) . . ?
O4 Mo1 O2 100.02(14) . . ?
O6 Mo1 O9 94.38(16) . 2_665 ?
O4 Mo1 O9 97.51(16) . 2_665 ?
O2 Mo1 O9 156.43(17) . 2_665 ?
O6 Mo1 O10 169.62(17) . . ?
O4 Mo1 O10 88.56(15) . . ?
O2 Mo1 O10 84.20(14) . . ?
O9 Mo1 O10 80.61(13) 2_665 . ?
O6 Mo1 O11 89.27(17) . 1_455 ?
O4 Mo1 O11 167.45(15) . 1_455 ?
O2 Mo1 O11 85.35(13) . 1_455 ?
O9 Mo1 O11 74.51(13) 2_665 1_455 ?
O10 Mo1 O11 80.65(13) . 1_455 ?
O3 Mo2 O5 102.05(19) . . ?
O3 Mo2 O1 95.58(15) . . ?
O5 Mo2 O1 97.98(13) . . ?
O3 Mo2 O12 90.32(16) . . ?
O5 Mo2 O12 95.39(16) . . ?
O1 Mo2 O12 163.91(15) . . ?
O3 Mo2 O7 90.00(16) . . ?
O5 Mo2 O7 167.49(17) . . ?
O1 Mo2 O7 83.99(13) . . ?
O12 Mo2 O7 81.04(15) . . ?
O3 Mo2 O8 169.24(16) . . ?
O5 Mo2 O8 88.42(17) . . ?
O1 Mo2 O8 85.26(14) . . ?
O12 Mo2 O8 86.21(14) . . ?
O7 Mo2 O8 79.40(13) . . ?
O8 P1 O7 115.20(19) 1_565 2_665 ?
O8 P1 O9 110.4(2) 1_565 . ?
O7 P1 O9 109.2(2) 2_665 . ?
O8 P1 O14 105.6(2) 1_565 . ?
O7 P1 O14 109.5(2) 2_665 . ?
O9 P1 O14 106.7(2) . . ?
O10 P2 O11 112.45(18) 2_665 . ?
O10 P2 O12 109.3(2) 2_665 . ?
O11 P2 O12 110.9(2) . . ?
O10 P2 O15 108.8(2) 2_665 . ?
O11 P2 O15 106.5(2) . . ?
O12 P2 O15 108.8(2) . . ?
O13 P3 O13 111.5(4) 4_656 3_566 ?
O13 P3 O13 108.48(19) 4_656 . ?
O13 P3 O13 108.48(19) 3_566 . ?
O13 P3 O13 108.48(19) 4_656 2_665 ?
O13 P3 O13 108.48(19) 3_566 2_665 ?
O13 P3 O13 111.5(4) . 2_665 ?
Mo2 O1 Mo2 148.8(3) 2_655 . ?
Mo1 O2 Mo1 151.7(3) 2_565 . ?
P1 O7 Mo2 136.0(2) 2_665 . ?
P1 O8 Mo2 132.3(2) 1_545 . ?
P1 O9 Mo1 145.2(2) . 2_665 ?
P2 O10 Mo1 128.5(2) 2_665 . ?
P2 O11 Mo1 128.3(2) . 1_655 ?
P2 O12 Mo2 155.7(2) . . ?
P1 O14 H14 107(5) . . ?
P2 O15 H15 127(5) . . ?
H1A N1 H1B 107(3) . . ?
H2A N2 H2B 110(3) . . ?
H3A N3 H3B 109(3) . . ?
H3A N3 H3C 109(3) . . ?
H3B N3 H3C 110(3) . . ?
H3A N3 H3D 109(3) . . ?
H3B N3 H3D 111(3) . . ?
H3C N3 H3D 109(3) . . ?
H4A N4 H4B 107(3) . . ?
H4A N4 H4C 112(3) . . ?
H4B N4 H4C 103(3) . . ?
H4A N4 H4D 117(3) . . ?
H4B N4 H4D 107(3) . . ?
H4C N4 H4D 109(3) . . ?

_diffrn_measured_fraction_theta_max 0.996
_diffrn_reflns_theta_full        27.49
_diffrn_measured_fraction_theta_full 0.996
_refine_diff_density_max         1.406
_refine_diff_density_min         -0.661
_refine_diff_density_rms         0.129