# Electronic Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2012


data_global
_journal_name_full               Chem.Commun.
#TrackingRef '- DUT-51(revision).cif'
_journal_coden_Cambridge         0182
_publ_section_title              
;
Zr(IV) and Hf(IV) Metal-Organic Frameworks with
reo-topology
;
_publ_section_abstract           
;
Zr- and Hf-based MOFs with enhanced pore accessibility
for large molecules and good hydrothermal stability were obtained
using a bent dithienothiophene dicarboxylate and Zr4+ or Hf4+ source.
A modulator facilitates formation of an eight-connecting cluster leading
to a new framework which adopts reo topology.
;
_publ_contact_author_name        'Irena Senkovska'
_publ_contact_author_address     
;Department of Inorganic Chemistry
Dresden University of Technology
Bergstr. 66, 01069 Dresden (Germany)
;

_publ_contact_author_email       irena.senkovska@chemie.tu-dresden.de
_publ_contact_author_phone       (+49)351-4633-22564
_publ_contact_author_fax         '(+49)351-4633-7287 '
loop_
_publ_author_name
_publ_author_address
'Volodymyr Bon'
;Department of Inorganic Chemistry
Dresden University of Technology
Bergstr. 66, 01069 Dresden (Germany)
;
'Volodymyr Senkovskyy'
;Leibniz-Institut f r Polymerforschung Dresden e. V.,
Hohestr. 66, 01069 Dresden (Germany)
;
'Irena Senkovska'
;Department of Inorganic Chemistry
Dresden University of Technology
Bergstr. 66, 01069 Dresden (Germany)
;
'Stefan Kaskel'
;Department of Inorganic Chemistry
Dresden University of Technology
Bergstr. 66, 01069 Dresden (Germany)
;

data_DUT-51(Zr)
_database_code_depnum_ccdc_archive 'CCDC 872966'
#TrackingRef '- DUT-51(revision).cif'

# start Validation Reply Form
_vrf_PLAT213_DUT-51Zr            
;
PROBLEM: Atom S1 has ADP max/min Ratio ..... 5.1 prola
RESPONSE: The disorder of linker molecule can't be resolved with
better ADP paramerters
;
_vrf_PLAT241_DUT-51Zr            
;
PROBLEM: Check High Ueq as Compared to Neighbors for O1
RESPONSE: The large difference between Ueq of O1 and neighboring Zr atoms
can be explained by disorder
;
_vrf_PLAT213_DUT-51Hf            
;
PROBLEM: Atom S1 has ADP max/min Ratio ..... 5.1 prola
RESPONSE: The disorder of linker molecule can't be resolved properly with
better ADP paramerters
;
_vrf_CHEMW03_DUT-51Zr            
;
PROBLEM: ALERT: The ratio of given/expected molecular weight as
RESPONSE: The composition, involving SQUEEZEd lattice solvent molecules,
is used at the final refinement stage
;
_vrf_PLAT043_DUT-51Zr            
;
PROBLEM: Check Reported Molecular Weight ................ 3706.77
RESPONSE: The composition, involving SQUEEZEd lattice solvent molecules,
is used at the final refinement stage
;
_vrf_PLAT044_DUT-51Zr            
;
PROBLEM: Calculated and Reported Dx Differ .............. ?
RESPONSE: The composition, involving SQUEEZEd lattice solvent molecules,
is used at the final refinement stage
;
_vrf_CHEMW03_DUT-51Hf            
;
PROBLEM: ALERT: The ratio of given/expected molecular weight as
RESPONSE: The composition, involving SQUEEZEd lattice solvent molecules,
is used at the final refinement stage
;
_vrf_PLAT043_DUT-51Hf            
;
PROBLEM: Check Reported Molecular Weight ................ 3906.10
RESPONSE: The composition, involving SQUEEZEd lattice solvent molecules,
is used at the final refinement stage
;
_vrf_PLAT044_DUT-51Hf            
;
PROBLEM: Calculated and Reported Dx Differ .............. ?
RESPONSE: The composition, involving SQUEEZEd lattice solvent molecules,
is used at the final refinement stage
;
# end Validation Reply Form

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            DUT-51(Zr)
_chemical_melting_point          'not measured'
_chemical_formula_moiety         
;
Zr6O6(OH)2(C10H2O4S3)4(C6H5CO2)2(H2O)19(C3H7NO)18
;
_chemical_formula_sum            'C108 H184 N18 O65 S12 Zr6'
_chemical_formula_weight         3706.77

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0060 0.0030 '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 0.0180 0.0100 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1740 0.1930 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Zr Zr -1.2060 0.8400 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Cubic
_symmetry_space_group_name_H-M   Fm-3m

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

_cell_length_a                   49.964(6)
_cell_length_b                   49.964(6)
_cell_length_c                   49.964(6)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     124726(25)
_cell_formula_units_Z            24
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    2158
_cell_measurement_theta_min      2.58
_cell_measurement_theta_max      31.23

_exptl_crystal_description       octahedr
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.184
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             45840
_exptl_absorpt_coefficient_mu    0.482
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9857
_exptl_absorpt_correction_T_max  0.9857
_exptl_absorpt_process_details   Scala

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      296(2)
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.88561
_diffrn_source                   synchrotron
_diffrn_source_type              'BESSY BL MX-14.2'
_diffrn_radiation_monochromator  'Si 111'
_diffrn_measurement_device_type  'MX-225 CCD'
_diffrn_measurement_method       '\D\f scans'
_diffrn_reflns_number            11457
_diffrn_reflns_av_R_equivalents  0.0141
_diffrn_reflns_av_sigmaI/netI    0.0284
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_k_min       2
_diffrn_reflns_limit_k_max       63
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_limit_l_max       63
_diffrn_reflns_theta_min         3.21
_diffrn_reflns_theta_max         34.11
_reflns_number_total             6283
_reflns_number_gt                5878
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'marCCD 1994-2002'
_computing_cell_refinement       'mosflm 1.0.5'
_computing_data_reduction        scala
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Diamond 3.1'
_computing_publication_material  WinGX

_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^)+(0.0706P)^2^+565.7514P] 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    constr
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.000013(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_number_reflns         6283
_refine_ls_number_parameters     114
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0483
_refine_ls_R_factor_gt           0.0467
_refine_ls_wR_factor_ref         0.1334
_refine_ls_wR_factor_gt          0.1317
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_restrained_S_all      1.096
_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
Zr1 Zr 0.215130(5) 0.5000 0.215130(5) 0.01766(13) Uani 1 4 d S . .
Zr2 Zr 0.225027(4) 0.464601(6) 0.274973(4) 0.02849(13) Uani 1 2 d S . .
S1 S 0.08942(5) 0.41058(5) 0.18539(5) 0.1814(16) Uani 1 2 d S . .
S2 S 0.14130(2) 0.41380(2) 0.25053(2) 0.0975(5) Uani 1 1 d . . .
O1 O 0.23314(5) 0.46509(9) 0.23314(5) 0.0789(13) Uani 1 2 d S . .
O2 O 0.18004(3) 0.47321(3) 0.21779(4) 0.0355(4) Uani 1 1 d . . .
O3 O 0.22713(7) 0.42122(6) 0.27287(7) 0.0779(12) Uani 1 2 d S . .
O4 O 0.24391(5) 0.45032(5) 0.31375(5) 0.0689(8) Uani 1 1 d . . .
O5 O 0.24211(6) 0.5000 0.29206(9) 0.0673(11) Uani 1 2 d S . .
O6 O 0.19427(5) 0.46647(11) 0.30573(5) 0.0869(14) Uani 1 2 d S . .
C1 C 0.15054(7) 0.43881(7) 0.22825(8) 0.0737(13) Uani 1 1 d . . .
C2 C 0.13521(9) 0.43954(9) 0.20610(9) 0.108(2) Uani 1 1 d . . .
H2A H 0.1377 0.4514 0.1920 0.129 Uiso 1 1 calc R . .
C3 C 0.11485(10) 0.41999(10) 0.20716(10) 0.119(2) Uani 1 1 d . . .
C4 C 0.17418(6) 0.45547(6) 0.23456(6) 0.0502(7) Uani 1 1 d . . .
C5 C 0.11563(8) 0.40450(8) 0.22992(9) 0.0920(17) Uani 1 1 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
Zr1 0.02110(15) 0.01079(17) 0.02110(15) 0.000 -0.00238(12) 0.000
Zr2 0.02933(14) 0.02682(17) 0.02933(14) 0.01157(7) -0.00572(10) -0.01157(7)
S1 0.1917(18) 0.1917(18) 0.1606(18) 0.1438(17) -0.1438(17) -0.173(2)
S2 0.0960(7) 0.1018(7) 0.0946(7) 0.0652(6) -0.0643(6) -0.0814(6)
O1 0.0545(12) 0.128(3) 0.0545(12) 0.0587(17) 0.0177(15) 0.0587(17)
O2 0.0317(8) 0.0293(8) 0.0456(9) 0.0103(7) -0.0087(7) -0.0147(7)
O3 0.1015(19) 0.0306(15) 0.1015(19) 0.0218(13) -0.031(2) -0.0218(13)
O4 0.0645(14) 0.0764(15) 0.0658(14) 0.0541(13) -0.0315(11) -0.0393(12)
O5 0.0421(16) 0.0212(12) 0.139(3) 0.000 -0.0503(19) 0.000
O6 0.0496(12) 0.162(4) 0.0496(12) 0.0333(15) 0.0092(15) -0.0333(15)
C1 0.067(2) 0.069(2) 0.084(2) 0.0440(19) -0.0400(19) -0.0514(19)
C2 0.109(3) 0.105(3) 0.110(3) 0.076(3) -0.070(3) -0.090(3)
C3 0.126(4) 0.115(4) 0.116(4) 0.079(3) -0.090(3) -0.103(3)
C4 0.0478(15) 0.0467(15) 0.0560(17) 0.0173(13) -0.0201(13) -0.0301(13)
C5 0.088(3) 0.087(3) 0.101(3) 0.057(2) -0.059(2) -0.069(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
Zr1 O1 2.159(3) 99_565 ?
Zr1 O1 2.159(3) . ?
Zr1 O5 2.166(3) 145_565 ?
Zr1 O5 2.166(3) 166 ?
Zr1 O2 2.2097(15) 120 ?
Zr1 O2 2.2097(15) 22_565 ?
Zr1 O2 2.2097(15) 99_565 ?
Zr1 O2 2.2099(15) . ?
Zr2 O1 2.129(2) 51 ?
Zr2 O1 2.129(2) . ?
Zr2 O5 2.1414(17) . ?
Zr2 O5 2.1415(17) 166 ?
Zr2 O3 2.173(3) . ?
Zr2 O6 2.175(3) . ?
Zr2 O4 2.2697(19) 166 ?
Zr2 O4 2.2698(19) . ?
S1 C3 1.737(3) . ?
S1 C3 1.737(3) 181 ?
S2 C5 1.709(3) . ?
S2 C1 1.736(3) . ?
O1 Zr2 2.129(2) 51 ?
O2 C4 1.254(3) . ?
O4 C4 1.260(3) 166 ?
O5 Zr2 2.1415(17) 99_565 ?
O5 Zr1 2.166(3) 145_565 ?
C1 C2 1.346(5) . ?
C1 C4 1.479(4) . ?
C2 C3 1.411(4) . ?
C2 H2A 0.9300 . ?
C3 C5 1.376(5) . ?
C4 O4 1.260(3) 166 ?
C5 C5 1.422(6) 181 ?

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 Zr1 O1 107.8(3) 99_565 . ?
O1 Zr1 O5 70.01(9) 99_565 145_565 ?
O1 Zr1 O5 70.01(9) . 145_565 ?
O1 Zr1 O5 70.01(9) 99_565 166 ?
O1 Zr1 O5 70.01(9) . 166 ?
O5 Zr1 O5 109.1(2) 145_565 166 ?
O1 Zr1 O2 142.64(5) 99_565 120 ?
O1 Zr1 O2 79.41(11) . 120 ?
O5 Zr1 O2 78.98(10) 145_565 120 ?
O5 Zr1 O2 142.41(5) 166 120 ?
O1 Zr1 O2 79.41(11) 99_565 22_565 ?
O1 Zr1 O2 142.64(5) . 22_565 ?
O5 Zr1 O2 78.98(10) 145_565 22_565 ?
O5 Zr1 O2 142.41(5) 166 22_565 ?
O2 Zr1 O2 74.56(10) 120 22_565 ?
O1 Zr1 O2 79.41(11) 99_565 99_565 ?
O1 Zr1 O2 142.64(5) . 99_565 ?
O5 Zr1 O2 142.41(5) 145_565 99_565 ?
O5 Zr1 O2 78.98(10) 166 99_565 ?
O2 Zr1 O2 117.55(9) 120 99_565 ?
O2 Zr1 O2 74.26(10) 22_565 99_565 ?
O1 Zr1 O2 142.64(5) 99_565 . ?
O1 Zr1 O2 79.41(11) . . ?
O5 Zr1 O2 142.41(5) 145_565 . ?
O5 Zr1 O2 78.99(10) 166 . ?
O2 Zr1 O2 74.26(10) 120 . ?
O2 Zr1 O2 117.55(9) 22_565 . ?
O2 Zr1 O2 74.56(10) 99_565 . ?
O1 Zr2 O1 68.04(17) 51 . ?
O1 Zr2 O5 71.05(13) 51 . ?
O1 Zr2 O5 107.83(18) . . ?
O1 Zr2 O5 107.82(18) 51 166 ?
O1 Zr2 O5 71.05(13) . 166 ?
O5 Zr2 O5 68.64(13) . 166 ?
O1 Zr2 O3 87.40(15) 51 . ?
O1 Zr2 O3 87.40(15) . . ?
O5 Zr2 O3 145.48(6) . . ?
O5 Zr2 O3 145.48(6) 166 . ?
O1 Zr2 O6 145.84(8) 51 . ?
O1 Zr2 O6 145.84(8) . . ?
O5 Zr2 O6 87.96(16) . . ?
O5 Zr2 O6 87.96(16) 166 . ?
O3 Zr2 O6 96.39(18) . . ?
O1 Zr2 O4 139.67(10) 51 166 ?
O1 Zr2 O4 76.00(12) . 166 ?
O5 Zr2 O4 139.96(10) . 166 ?
O5 Zr2 O4 75.74(11) 166 166 ?
O3 Zr2 O4 72.99(8) . 166 ?
O6 Zr2 O4 72.79(9) . 166 ?
O1 Zr2 O4 76.01(12) 51 . ?
O1 Zr2 O4 139.67(10) . . ?
O5 Zr2 O4 75.74(11) . . ?
O5 Zr2 O4 139.96(10) 166 . ?
O3 Zr2 O4 73.00(8) . . ?
O6 Zr2 O4 72.79(9) . . ?
O4 Zr2 O4 127.63(10) 166 . ?
C3 S1 C3 90.2(2) . 181 ?
C5 S2 C1 90.51(15) . . ?
Zr2 O1 Zr2 111.94(16) 51 . ?
Zr2 O1 Zr1 109.81(13) 51 . ?
Zr2 O1 Zr1 109.81(13) . . ?
C4 O2 Zr1 130.81(16) . . ?
C4 O4 Zr2 134.36(17) 166 . ?
Zr2 O5 Zr2 111.36(13) . 99_565 ?
Zr2 O5 Zr1 109.08(13) . 145_565 ?
Zr2 O5 Zr1 109.07(13) 99_565 145_565 ?
C2 C1 C4 127.9(3) . . ?
C2 C1 S2 113.3(2) . . ?
C4 C1 S2 118.7(2) . . ?
C1 C2 C3 111.1(3) . . ?
C5 C3 C2 113.6(3) . . ?
C5 C3 S1 112.7(2) . . ?
C2 C3 S1 133.7(3) . . ?
O2 C4 O4 127.1(2) . 166 ?
O2 C4 C1 116.2(2) . . ?
O4 C4 C1 116.7(2) 166 . ?
C3 C5 C5 112.20(18) . 181 ?
C3 C5 S2 111.5(2) . . ?
C5 C5 S2 136.28(11) 181 . ?
C1 C2 H2A 124.4 . . ?
C3 C2 H2A 124.4 . . ?

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
O1 Zr2 O1 Zr2 1.4(3) 51 . . 51 ?
O5 Zr2 O1 Zr2 120.6(2) 166 . . 51 ?
O5 Zr2 O1 Zr2 61.6(2) . . . 51 ?
O6 Zr2 O1 Zr2 175.6(2) . . . 51 ?
O3 Zr2 O1 Zr2 -86.83(19) . . . 51 ?
O4 Zr2 O1 Zr2 -27.2(3) . . . 51 ?
O4 Zr2 O1 Zr2 -160.0(2) 166 . . 51 ?
O1 Zr2 O1 Zr1 -120.83(11) 51 . . . ?
O5 Zr2 O1 Zr1 -1.66(16) 166 . . . ?
O5 Zr2 O1 Zr1 -60.66(19) . . . . ?
O6 Zr2 O1 Zr1 53.4(4) . . . . ?
O3 Zr2 O1 Zr1 150.93(18) . . . . ?
O4 Zr2 O1 Zr1 -149.46(10) . . . . ?
O4 Zr2 O1 Zr1 77.81(17) 166 . . . ?
O1 Zr1 O1 Zr2 61.75(17) 99_565 . . . ?
O5 Zr1 O1 Zr2 121.8(2) 145_565 . . . ?
O5 Zr1 O1 Zr2 1.65(16) 166 . . . ?
O2 Zr1 O1 Zr2 -156.14(19) 120 . . . ?
O2 Zr1 O1 Zr2 157.61(7) 22_565 . . . ?
O2 Zr1 O1 Zr2 -34.1(4) 99_565 . . . ?
O2 Zr1 O1 Zr2 -80.37(16) . . . . ?
O1 Zr1 O1 Zr2 -61.75(17) 99_565 . . 51 ?
O5 Zr1 O1 Zr2 -1.65(16) 145_565 . . 51 ?
O5 Zr1 O1 Zr2 -121.8(2) 166 . . 51 ?
O2 Zr1 O1 Zr2 80.37(16) 120 . . 51 ?
O2 Zr1 O1 Zr2 34.1(4) 22_565 . . 51 ?
O2 Zr1 O1 Zr2 -157.61(7) 99_565 . . 51 ?
O2 Zr1 O1 Zr2 156.14(19) . . . 51 ?
O1 Zr1 O2 C4 31.9(3) . . . . ?
O1 Zr1 O2 C4 -73.6(4) 99_565 . . . ?
O5 Zr1 O2 C4 67.5(3) 145_565 . . . ?
O5 Zr1 O2 C4 -39.6(3) 166 . . . ?
O2 Zr1 O2 C4 113.7(3) 120 . . . ?
O2 Zr1 O2 C4 176.4(3) 22_565 . . . ?
O2 Zr1 O2 C4 -121.1(3) 99_565 . . . ?
O1 Zr2 O4 C4 33.2(4) 51 . . 166 ?
O1 Zr2 O4 C4 60.5(5) . . . 166 ?
O5 Zr2 O4 C4 -68.0(5) 166 . . 166 ?
O5 Zr2 O4 C4 -40.4(4) . . . 166 ?
O6 Zr2 O4 C4 -132.7(4) . . . 166 ?
O3 Zr2 O4 C4 124.8(4) . . . 166 ?
O4 Zr2 O4 C4 176.3(3) 166 . . 166 ?
O1 Zr2 O5 Zr2 118.8(2) 51 . . 99_565 ?
O1 Zr2 O5 Zr2 60.50(19) . . . 99_565 ?
O5 Zr2 O5 Zr2 0.0(3) 166 . . 99_565 ?
O6 Zr2 O5 Zr2 -88.63(19) . . . 99_565 ?
O3 Zr2 O5 Zr2 173.0(2) . . . 99_565 ?
O4 Zr2 O5 Zr2 -161.4(2) . . . 99_565 ?
O4 Zr2 O5 Zr2 -28.8(3) 166 . . 99_565 ?
O1 Zr2 O5 Zr1 -1.65(16) 51 . . 145_565 ?
O1 Zr2 O5 Zr1 -59.93(15) . . . 145_565 ?
O5 Zr2 O5 Zr1 -120.46(8) 166 . . 145_565 ?
O6 Zr2 O5 Zr1 150.94(16) . . . 145_565 ?
O3 Zr2 O5 Zr1 52.6(4) . . . 145_565 ?
O4 Zr2 O5 Zr1 78.18(14) . . . 145_565 ?
O4 Zr2 O5 Zr1 -149.24(10) 166 . . 145_565 ?
C5 S2 C1 C2 -1.3(5) . . . . ?
C5 S2 C1 C4 -178.4(4) . . . . ?
C4 C1 C2 C3 178.4(5) . . . . ?
S2 C1 C2 C3 1.7(7) . . . . ?
C1 C2 C3 C5 -1.4(9) . . . . ?
C1 C2 C3 S1 -179.2(6) . . . . ?
C3 S1 C3 C5 -0.7(8) 181 . . . ?
C3 S1 C3 C2 177.2(6) 181 . . . ?
Zr1 O2 C4 O4 7.6(6) . . . 166 ?
Zr1 O2 C4 C1 -172.3(3) . . . . ?
C2 C1 C4 O2 3.3(7) . . . . ?
S2 C1 C4 O2 179.9(3) . . . . ?
C2 C1 C4 O4 -176.6(5) . . . 166 ?
S2 C1 C4 O4 0.0(6) . . . 166 ?
C2 C3 C5 C5 -177.8(5) . . . 181 ?
S1 C3 C5 C5 0.5(6) . . . 181 ?
C2 C3 C5 S2 0.4(8) . . . . ?
S1 C3 C5 S2 178.7(4) . . . . ?
C1 S2 C5 C3 0.5(5) . . . . ?
C1 S2 C5 C5 178.1(3) . . . 181 ?

_diffrn_measured_fraction_theta_max 0.994
_diffrn_reflns_theta_full        34.11
_diffrn_measured_fraction_theta_full 0.994
_refine_diff_density_max         0.942
_refine_diff_density_min         -0.787
_refine_diff_density_rms         0.068

# SQUEEZE RESULTS (APPEND TO CIF)
# Note: Data are Listed for all Voids in the P1 Unit Cell
# i.e. Centre of Gravity, Solvent Accessible Volume,
# Recovered number of Electrons in the Void and
# Details about the Squeezed Material
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.003 -0.014 -0.003 97916 11681 ' '
_platon_squeeze_details          
;
;

#===END

data_DUT-51(Hf)
_database_code_depnum_ccdc_archive 'CCDC 872967'
#TrackingRef '- DUT-51(revision).cif'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            DUT-51(Hf)
_chemical_melting_point          ?
_chemical_formula_moiety         
;
Hf6O6(OH)2(C10H2O4S3)4(C6H5COO)2(C3H7NO)18(H2O)
;
_chemical_formula_sum            'C108 H148 Hf6 N18 O47 S12'
_chemical_formula_weight         3906.10

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0060 0.0030 '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'
Hf Hf -1.6680 8.8820 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0180 0.0100 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1740 0.1930 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Cubic
_symmetry_space_group_name_H-M   Fm-3m

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

_cell_length_a                   49.840(6)
_cell_length_b                   49.840(6)
_cell_length_c                   49.840(6)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     123804(26)
_cell_formula_units_Z            24
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    2154
_cell_measurement_theta_min      2.64
_cell_measurement_theta_max      31.52

_exptl_crystal_description       octahedral
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.257
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             46128
_exptl_absorpt_coefficient_mu    3.185
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9105
_exptl_absorpt_correction_T_max  0.9105
_exptl_absorpt_process_details   Scala

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.88561
_diffrn_source                   synchrotron
_diffrn_source_type              'BESSY BL MX-14.2'
_diffrn_radiation_monochromator  'Si 111'
_diffrn_measurement_device_type  'MX-225 CCD'
_diffrn_measurement_method       '\D\f scans'
_diffrn_reflns_number            11374
_diffrn_reflns_av_R_equivalents  0.0178
_diffrn_reflns_av_sigmaI/netI    0.0308
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_k_min       2
_diffrn_reflns_limit_k_max       63
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_limit_l_max       63
_diffrn_reflns_theta_min         3.22
_diffrn_reflns_theta_max         34.13
_reflns_number_total             6239
_reflns_number_gt                5971
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'marCCD 1994-2002'
_computing_cell_refinement       mosflm
_computing_data_reduction        scala
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Diamond 3.1'
_computing_publication_material  WinGX

_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^)+(0.0494P)^2^+1403.3625P] 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    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         6239
_refine_ls_number_parameters     113
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0365
_refine_ls_R_factor_gt           0.0355
_refine_ls_wR_factor_ref         0.1046
_refine_ls_wR_factor_gt          0.1034
_refine_ls_goodness_of_fit_ref   1.100
_refine_ls_restrained_S_all      1.100
_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
Hf1 Hf 0.215213(4) 0.5000 0.215213(4) 0.01895(9) Uani 1 4 d S . .
Hf2 Hf 0.225069(3) 0.464689(4) 0.274931(3) 0.02965(9) Uani 1 2 d S . .
S1 S 0.08896(7) 0.41104(7) 0.18539(7) 0.172(2) Uani 1 2 d S . .
S2 S 0.14141(3) 0.41380(4) 0.25047(4) 0.0944(7) Uani 1 1 d . . .
O1 O 0.23303(8) 0.46503(14) 0.23303(8) 0.073(2) Uani 1 2 d S . .
O2 O 0.18025(5) 0.47340(5) 0.21769(5) 0.0327(6) Uani 1 1 d . . .
O3 O 0.22690(10) 0.42154(9) 0.27310(10) 0.0710(18) Uani 1 2 d S . .
O4 O 0.24399(7) 0.45045(8) 0.31364(7) 0.0665(12) Uani 1 1 d . . .
O5 O 0.24245(9) 0.5000 0.29158(13) 0.0624(16) Uani 1 2 d S . .
O6 O 0.19434(7) 0.46658(16) 0.30566(7) 0.083(2) Uani 1 2 d S . .
C1 C 0.15074(12) 0.43874(12) 0.22801(13) 0.075(2) Uani 1 1 d . . .
C2 C 0.13430(14) 0.44060(13) 0.20691(14) 0.099(3) Uani 1 1 d . . .
H2A H 0.1359 0.4535 0.1935 0.119 Uiso 1 1 calc R . .
C3 C 0.11419(16) 0.42050(15) 0.20759(15) 0.108(3) Uani 1 1 d . . .
C4 C 0.17426(9) 0.45565(9) 0.23446(10) 0.0490(12) Uani 1 1 d . . .
C5 C 0.11570(13) 0.40462(13) 0.22956(14) 0.090(3) Uani 1 1 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
Hf1 0.02245(10) 0.01196(12) 0.02245(10) 0.000 -0.00273(9) 0.000
Hf2 0.03060(10) 0.02777(12) 0.03060(10) 0.01189(6) -0.00599(8) -0.01189(6)
S1 0.177(3) 0.177(3) 0.162(3) 0.138(3) -0.138(3) -0.159(3)
S2 0.0900(11) 0.0969(11) 0.0964(11) 0.0648(10) -0.0635(9) -0.0781(10)
O1 0.0466(17) 0.126(5) 0.0466(17) 0.054(2) 0.013(2) 0.054(2)
O2 0.0312(13) 0.0259(12) 0.0411(14) 0.0091(11) -0.0099(11) -0.0160(10)
O3 0.096(3) 0.021(2) 0.096(3) 0.0202(18) -0.028(3) -0.0202(18)
O4 0.062(2) 0.075(2) 0.062(2) 0.0529(19) -0.0301(17) -0.0411(19)
O5 0.040(2) 0.0213(18) 0.126(5) 0.000 -0.050(3) 0.000
O6 0.0449(17) 0.160(6) 0.0449(17) 0.035(2) 0.009(2) -0.035(2)
C1 0.068(3) 0.066(3) 0.090(4) 0.047(3) -0.042(3) -0.053(3)
C2 0.097(5) 0.092(5) 0.109(5) 0.069(4) -0.066(4) -0.077(4)
C3 0.112(5) 0.100(5) 0.111(5) 0.070(4) -0.079(5) -0.085(5)
C4 0.045(2) 0.039(2) 0.063(3) 0.017(2) -0.021(2) -0.0263(19)
C5 0.087(4) 0.083(4) 0.100(5) 0.060(4) -0.060(4) -0.071(4)

_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
Hf1 O5 2.137(5) 66_565 ?
Hf1 O5 2.137(5) 145_565 ?
Hf1 O1 2.148(5) 103_565 ?
Hf1 O1 2.148(4) . ?
Hf1 O2 2.193(2) . ?
Hf1 O2 2.193(2) 114 ?
Hf1 O2 2.193(2) 103_565 ?
Hf1 O2 2.193(2) 21_565 ?
Hf2 O1 2.126(3) . ?
Hf2 O1 2.126(3) 55 ?
Hf2 O5 2.130(2) . ?
Hf2 O5 2.130(2) 66_565 ?
Hf2 O3 2.154(5) . ?
Hf2 O6 2.168(5) . ?
Hf2 O4 2.262(3) . ?
Hf2 O4 2.262(3) 165 ?
S1 C3 1.740(6) . ?
S1 C3 1.740(5) 174 ?
S2 C5 1.714(5) . ?
S2 C1 1.736(5) . ?
O1 Hf2 2.126(3) 55 ?
O2 C4 1.253(5) . ?
O4 C4 1.259(5) 165 ?
O5 Hf2 2.130(2) 103_565 ?
O5 Hf1 2.137(5) 145_565 ?
C1 C2 1.336(7) . ?
C1 C4 1.479(6) . ?
C2 C3 1.418(6) . ?
C2 H2A 0.9300 . ?
C3 C5 1.353(7) . ?
C4 O4 1.259(5) 165 ?
C5 C5 1.432(8) 174 ?

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 Hf1 O5 108.2(3) 66_565 145_565 ?
O5 Hf1 O1 69.96(13) 66_565 103_565 ?
O5 Hf1 O1 69.96(13) 145_565 103_565 ?
O5 Hf1 O1 69.96(13) 66_565 . ?
O5 Hf1 O1 69.96(13) 145_565 . ?
O1 Hf1 O1 108.5(4) 103_565 . ?
O5 Hf1 O2 79.55(15) 66_565 . ?
O5 Hf1 O2 142.52(8) 145_565 . ?
O1 Hf1 O2 142.71(8) 103_565 . ?
O1 Hf1 O2 79.32(17) . . ?
O5 Hf1 O2 142.52(8) 66_565 114 ?
O5 Hf1 O2 79.55(15) 145_565 114 ?
O1 Hf1 O2 142.71(8) 103_565 114 ?
O1 Hf1 O2 79.32(17) . 114 ?
O2 Hf1 O2 73.99(15) . 114 ?
O5 Hf1 O2 79.55(15) 66_565 103_565 ?
O5 Hf1 O2 142.52(8) 145_565 103_565 ?
O1 Hf1 O2 79.32(17) 103_565 103_565 ?
O1 Hf1 O2 142.71(8) . 103_565 ?
O2 Hf1 O2 74.38(15) . 103_565 ?
O2 Hf1 O2 117.06(13) 114 103_565 ?
O5 Hf1 O2 142.52(8) 66_565 21_565 ?
O5 Hf1 O2 79.55(15) 145_565 21_565 ?
O1 Hf1 O2 79.32(17) 103_565 21_565 ?
O1 Hf1 O2 142.71(8) . 21_565 ?
O2 Hf1 O2 117.06(13) . 21_565 ?
O2 Hf1 O2 74.38(15) 114 21_565 ?
O2 Hf1 O2 73.99(15) 103_565 21_565 ?
O1 Hf2 O1 68.5(2) . 55 ?
O1 Hf2 O5 107.5(3) . . ?
O1 Hf2 O5 70.5(2) 55 . ?
O1 Hf2 O5 70.5(2) . 66_565 ?
O1 Hf2 O5 107.5(3) 55 66_565 ?
O5 Hf2 O5 68.5(2) . 66_565 ?
O1 Hf2 O3 87.6(2) . . ?
O1 Hf2 O3 87.6(2) 55 . ?
O5 Hf2 O3 145.50(9) . . ?
O5 Hf2 O3 145.50(9) 66_565 . ?
O1 Hf2 O6 145.64(11) . . ?
O1 Hf2 O6 145.64(11) 55 . ?
O5 Hf2 O6 88.6(2) . . ?
O5 Hf2 O6 88.6(2) 66_565 . ?
O3 Hf2 O6 95.9(3) . . ?
O1 Hf2 O4 139.71(15) . . ?
O1 Hf2 O4 75.65(19) 55 . ?
O5 Hf2 O4 75.97(16) . . ?
O5 Hf2 O4 140.24(15) 66_565 . ?
O3 Hf2 O4 72.86(12) . . ?
O6 Hf2 O4 72.87(13) . . ?
O1 Hf2 O4 75.65(19) . 165 ?
O1 Hf2 O4 139.71(15) 55 165 ?
O5 Hf2 O4 140.23(15) . 165 ?
O5 Hf2 O4 75.96(16) 66_565 165 ?
O3 Hf2 O4 72.86(12) . 165 ?
O6 Hf2 O4 72.87(13) . 165 ?
O4 Hf2 O4 127.79(15) . 165 ?
C3 S1 C3 89.3(4) . 174 ?
C5 S2 C1 90.0(2) . . ?
Hf2 O1 Hf2 111.5(2) . 55 ?
Hf2 O1 Hf1 109.6(2) . . ?
Hf2 O1 Hf1 109.6(2) 55 . ?
C4 O2 Hf1 130.8(3) . . ?
C4 O4 Hf2 134.4(3) 165 . ?
Hf2 O5 Hf2 111.45(19) 103_565 . ?
Hf2 O5 Hf1 109.9(2) 103_565 145_565 ?
Hf2 O5 Hf1 109.9(2) . 145_565 ?
C2 C1 C4 128.1(4) . . ?
C2 C1 S2 113.1(3) . . ?
C4 C1 S2 118.7(4) . . ?
C1 C2 C3 111.4(5) . . ?
C1 C2 H2A 124.3 . . ?
C3 C2 H2A 124.3 . . ?
C5 C3 C2 113.2(5) . . ?
C5 C3 S1 113.3(4) . . ?
C2 C3 S1 133.4(5) . . ?
O2 C4 O4 126.9(4) . 165 ?
O2 C4 C1 116.5(4) . . ?
O4 C4 C1 116.6(4) 165 . ?
C3 C5 C5 112.0(3) . 174 ?
C3 C5 S2 112.2(3) . . ?
C5 C5 S2 135.85(16) 174 . ?

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
O1 Hf2 O1 Hf2 1.0(4) 55 . . 55 ?
O5 Hf2 O1 Hf2 61.0(3) . . . 55 ?
O5 Hf2 O1 Hf2 119.8(4) 66_565 . . 55 ?
O3 Hf2 O1 Hf2 -87.4(3) . . . 55 ?
O6 Hf2 O1 Hf2 175.6(4) . . . 55 ?
O4 Hf2 O1 Hf2 -27.8(5) . . . 55 ?
O4 Hf2 O1 Hf2 -160.3(3) 165 . . 55 ?
O1 Hf2 O1 Hf1 -120.55(15) 55 . . . ?
O5 Hf2 O1 Hf1 -60.5(3) . . . . ?
O5 Hf2 O1 Hf1 -1.8(2) 66_565 . . . ?
O3 Hf2 O1 Hf1 151.1(3) . . . . ?
O6 Hf2 O1 Hf1 54.1(6) . . . . ?
O4 Hf2 O1 Hf1 -149.28(15) . . . . ?
O4 Hf2 O1 Hf1 78.2(2) 165 . . . ?
O5 Hf1 O1 Hf2 1.8(2) 66_565 . . . ?
O5 Hf1 O1 Hf2 120.9(4) 145_565 . . . ?
O1 Hf1 O1 Hf2 61.3(3) 103_565 . . . ?
O2 Hf1 O1 Hf2 -80.9(2) . . . . ?
O2 Hf1 O1 Hf2 -156.4(3) 114 . . . ?
O2 Hf1 O1 Hf2 -35.3(5) 103_565 . . . ?
O2 Hf1 O1 Hf2 158.00(11) 21_565 . . . ?
O5 Hf1 O1 Hf2 -120.9(4) 66_565 . . 55 ?
O5 Hf1 O1 Hf2 -1.8(2) 145_565 . . 55 ?
O1 Hf1 O1 Hf2 -61.3(3) 103_565 . . 55 ?
O2 Hf1 O1 Hf2 156.4(3) . . . 55 ?
O2 Hf1 O1 Hf2 80.9(2) 114 . . 55 ?
O2 Hf1 O1 Hf2 -158.00(11) 103_565 . . 55 ?
O2 Hf1 O1 Hf2 35.3(5) 21_565 . . 55 ?
O5 Hf1 O2 C4 -39.1(4) 66_565 . . . ?
O5 Hf1 O2 C4 67.3(5) 145_565 . . . ?
O1 Hf1 O2 C4 -74.3(6) 103_565 . . . ?
O1 Hf1 O2 C4 32.2(4) . . . . ?
O2 Hf1 O2 C4 114.1(4) 114 . . . ?
O2 Hf1 O2 C4 -121.1(4) 103_565 . . . ?
O2 Hf1 O2 C4 176.6(5) 21_565 . . . ?
O1 Hf2 O4 C4 61.0(7) . . . 165 ?
O1 Hf2 O4 C4 33.5(6) 55 . . 165 ?
O5 Hf2 O4 C4 -39.6(6) . . . 165 ?
O5 Hf2 O4 C4 -66.7(7) 66_565 . . 165 ?
O3 Hf2 O4 C4 125.4(6) . . . 165 ?
O6 Hf2 O4 C4 -132.5(6) . . . 165 ?
O4 Hf2 O4 C4 176.4(4) 165 . . 165 ?
O1 Hf2 O5 Hf2 61.5(3) . . . 103_565 ?
O1 Hf2 O5 Hf2 120.3(4) 55 . . 103_565 ?
O5 Hf2 O5 Hf2 1.5(4) 66_565 . . 103_565 ?
O3 Hf2 O5 Hf2 173.9(3) . . . 103_565 ?
O6 Hf2 O5 Hf2 -87.6(3) . . . 103_565 ?
O4 Hf2 O5 Hf2 -160.2(3) . . . 103_565 ?
O4 Hf2 O5 Hf2 -26.9(5) 165 . . 103_565 ?
O1 Hf2 O5 Hf1 -60.5(2) . . . 145_565 ?
O1 Hf2 O5 Hf1 -1.8(2) 55 . . 145_565 ?
O5 Hf2 O5 Hf1 -120.53(12) 66_565 . . 145_565 ?
O3 Hf2 O5 Hf1 51.9(6) . . . 145_565 ?
O6 Hf2 O5 Hf1 150.4(2) . . . 145_565 ?
O4 Hf2 O5 Hf1 77.7(2) . . . 145_565 ?
O4 Hf2 O5 Hf1 -148.89(16) 165 . . 145_565 ?
C5 S2 C1 C2 3.2(8) . . . . ?
C5 S2 C1 C4 -179.1(6) . . . . ?
C4 C1 C2 C3 179.3(8) . . . . ?
S2 C1 C2 C3 -3.4(11) . . . . ?
C1 C2 C3 C5 1.7(13) . . . . ?
C1 C2 C3 S1 -174.8(9) . . . . ?
C3 S1 C3 C5 2.6(11) 174 . . . ?
C3 S1 C3 C2 179.1(8) 174 . . . ?
Hf1 O2 C4 O4 7.2(9) . . . 165 ?
Hf1 O2 C4 C1 -171.8(4) . . . . ?
C2 C1 C4 O2 -2.7(12) . . . . ?
S2 C1 C4 O2 -179.9(5) . . . . ?
C2 C1 C4 O4 178.2(8) . . . 165 ?
S2 C1 C4 O4 1.0(9) . . . 165 ?
C2 C3 C5 C5 -179.3(7) . . . 174 ?
S1 C3 C5 C5 -2.0(9) . . . 174 ?
C2 C3 C5 S2 0.8(12) . . . . ?
S1 C3 C5 S2 178.0(6) . . . . ?
C1 S2 C5 C3 -2.2(8) . . . . ?
C1 S2 C5 C5 177.8(4) . . . 174 ?

_diffrn_measured_fraction_theta_max 0.994
_diffrn_reflns_theta_full        34.13
_diffrn_measured_fraction_theta_full 0.994
_refine_diff_density_max         1.162
_refine_diff_density_min         -0.864
_refine_diff_density_rms         0.102

# SQUEEZE RESULTS (APPEND TO CIF)
# Note: Data are Listed for all Voids in the P1 Unit Cell
# i.e. Centre of Gravity, Solvent Accessible Volume,
# Recovered number of Electrons in the Void and
# Details about the Squeezed Material
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.003 -0.014 -0.004 96985 14164 ' '
_platon_squeeze_details          
;
;