# Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2004


data_global

_journal_coden_Cambridge         182

loop_
_publ_author_name
'Didier Riou'
'K. Barthelet'
'Gerard Ferey'
'Jerome Marrot'

_publ_contact_author_name        'Prof Didier Riou'
_publ_contact_author_address     
;
University of Versailles
IREM UMR CNRS8637
45 Avenue des Etats-Unis
Versailles
78035
FRANCE
;

_publ_contact_author_email       RIOU@CHIMIE.UVSQ.FR

_publ_requested_journal          'Chemical Communications'

_publ_section_title              
;
VIII(OH){O2C-C6H4-CO2}.(HO2C-C6H4-CO2H)x(DMF)y(H2O)z (or MIL-68), a new
vanadocarboxylate with a large pores hybrid topology : reticular
synthesis with infinite inorganic building blocks ?
;

data_63fil
_database_code_depnum_ccdc_archive 'CCDC 222072'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C16 H8 O10 V2'
_chemical_formula_weight         462.10

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
V V 0.3005 0.5294 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   Cmcm

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

_cell_length_a                   21.2105(18)
_cell_length_b                   36.721(4)
_cell_length_c                   6.8606(6)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     5343.5(9)
_cell_formula_units_Z            6
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       ?
_exptl_crystal_colour            ?
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.01
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    0.862
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1380
_exptl_absorpt_coefficient_mu    0.552
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9783
_exptl_absorpt_correction_T_max  0.9945
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  ?
_diffrn_measurement_method       '\w scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            7810
_diffrn_reflns_av_R_equivalents  0.1131
_diffrn_reflns_av_sigmaI/netI    0.1474
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_theta_min         1.11
_diffrn_reflns_theta_max         23.27
_reflns_number_total             2133
_reflns_number_gt                969
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Siemens XSCANS'
_computing_cell_refinement       'Siemens XSCANS'
_computing_data_reduction        'Siemens SHELXTL'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Siemens SHELXTL'
_computing_publication_material  'Siemens SHELXTL'

_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^)+(0.1655P)^2^+0.0000P] 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     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         2133
_refine_ls_number_parameters     111
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1662
_refine_ls_R_factor_gt           0.0975
_refine_ls_wR_factor_ref         0.2867
_refine_ls_wR_factor_gt          0.2635
_refine_ls_goodness_of_fit_ref   0.948
_refine_ls_restrained_S_all      0.948
_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
V1 V 0.0000 0.0000 0.5000 0.0398(3) Uani 1 4 d S . .
V2 V 0.2500 0.2500 0.5000 0.0429(2) Uani 1 2 d S . .
O1 O 0.33667(7) 0.23833(5) 0.5904(2) 0.0343(5) Uani 1 1 d . . .
O2 O 0.06257(9) 0.03720(4) 0.5841(2) 0.0477(6) Uani 1 1 d . . .
O3 O 0.22314(9) 0.20075(5) 0.5849(2) 0.0421(6) Uani 1 1 d . . .
O4 O 0.0000 0.01756(13) 0.2500 0.127(3) Uani 1 4 d S . .
O5 O 0.27004(16) 0.22866(9) 0.2500 0.0774(13) Uani 1 2 d S . .
C1 C 0.43577(16) 0.23267(9) 0.7500 0.0245(10) Uani 1 2 d S . .
C2 C 0.46885(12) 0.23184(8) 0.5786(4) 0.0470(9) Uani 1 1 d . . .
H2 H 0.4472 0.2313 0.4607 0.056 Uiso 1 1 calc R . .
C3 C 0.20721(18) 0.18816(11) 0.7500 0.0397(13) Uani 1 2 d S . .
C4 C 0.36013(17) 0.23763(9) 0.7500 0.0213(10) Uani 1 2 d S . .
C5 C 0.16879(14) 0.13181(7) 0.9208(4) 0.0441(9) Uani 1 1 d . . .
H5 H 0.1809 0.1425 1.0378 0.053 Uiso 1 1 calc R . .
C6 C 0.18335(19) 0.14837(9) 0.7500 0.0383(13) Uani 1 2 d S . .
C7 C 0.08027(19) 0.04964(9) 0.7500 0.0371(13) Uani 1 2 d S . .
C8 C 0.12093(19) 0.08481(9) 0.7500 0.0391(13) Uani 1 2 d S . .
C9 C 0.13690(14) 0.09988(7) 0.9233(4) 0.0498(10) Uani 1 1 d . . .
H9 H 0.1263 0.0886 1.0402 0.060 Uiso 1 1 calc R . .

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
V1 0.0472(5) 0.0145(4) 0.0576(6) -0.0066(5) 0.000 0.000
V2 0.0250(3) 0.0393(3) 0.0644(4) 0.0238(4) -0.0080(4) -0.0140(3)
O1 0.0191(8) 0.0625(10) 0.0215(9) 0.0085(9) -0.0142(8) -0.0021(9)
O2 0.0725(12) 0.0343(9) 0.0364(10) 0.0057(9) -0.0026(11) -0.0299(9)
O3 0.0508(10) 0.0396(9) 0.0359(11) 0.0135(9) -0.0095(10) -0.0172(9)
O4 0.303(8) 0.070(3) 0.009(2) 0.000 0.000 0.000
O5 0.078(2) 0.105(2) 0.0489(19) 0.000 0.000 -0.031(2)
C1 0.0147(18) 0.0406(19) 0.0181(18) 0.000 0.000 -0.0156(17)
C2 0.0242(13) 0.095(2) 0.0215(14) -0.0114(16) 0.0037(12) 0.0022(16)
C3 0.046(3) 0.057(2) 0.016(2) 0.000 0.000 -0.021(2)
C4 0.037(2) 0.0252(17) 0.0019(15) 0.000 0.000 -0.0133(17)
C5 0.067(2) 0.0372(14) 0.0281(15) -0.0009(14) -0.0043(16) -0.0227(15)
C6 0.038(2) 0.033(2) 0.043(2) 0.000 0.000 -0.008(2)
C7 0.048(3) 0.0238(18) 0.039(2) 0.000 0.000 0.0071(19)
C8 0.050(3) 0.0258(19) 0.041(2) 0.000 0.000 -0.010(2)
C9 0.068(2) 0.0488(16) 0.0320(16) -0.0043(14) -0.0100(16) -0.0292(15)

_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
V1 O4 1.8323(17) 9_556 ?
V1 O4 1.8323(17) . ?
V1 O2 1.9900(18) . ?
V1 O2 1.9900(18) 9_556 ?
V1 O2 1.9900(18) 4_556 ?
V1 O2 1.9900(18) 12 ?
V2 O5 1.9329(16) 13_556 ?
V2 O5 1.9329(16) . ?
V2 O3 1.9837(17) 13_556 ?
V2 O3 1.9837(17) . ?
V2 O1 1.9868(16) 13_556 ?
V2 O1 1.9868(16) . ?
O1 C4 1.203(2) . ?
O2 C7 1.282(2) . ?
O3 C3 1.269(2) . ?
O4 V1 1.8323(17) 2_554 ?
O5 V2 1.9329(16) 6_554 ?
C1 C2 1.370(3) 10_557 ?
C1 C2 1.370(3) . ?
C1 C4 1.615(5) . ?
C2 C2 1.321(5) 12_655 ?
C2 H2 0.9300 . ?
C3 O3 1.269(2) 10_557 ?
C3 C6 1.546(5) . ?
C4 O1 1.203(2) 10_557 ?
C5 C9 1.354(4) . ?
C5 C6 1.356(3) . ?
C5 H5 0.9300 . ?
C6 C5 1.356(3) 10_557 ?
C7 O2 1.282(2) 10_557 ?
C7 C8 1.553(5) . ?
C8 C9 1.354(3) . ?
C8 C9 1.354(3) 10_557 ?
C9 H9 0.9300 . ?

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
O4 V1 O4 180.0(3) 9_556 . ?
O4 V1 O2 88.28(11) 9_556 . ?
O4 V1 O2 91.72(11) . . ?
O4 V1 O2 91.72(11) 9_556 9_556 ?
O4 V1 O2 88.28(11) . 9_556 ?
O2 V1 O2 180.00(11) . 9_556 ?
O4 V1 O2 91.72(11) 9_556 4_556 ?
O4 V1 O2 88.28(11) . 4_556 ?
O2 V1 O2 96.34(11) . 4_556 ?
O2 V1 O2 83.66(11) 9_556 4_556 ?
O4 V1 O2 88.28(11) 9_556 12 ?
O4 V1 O2 91.72(11) . 12 ?
O2 V1 O2 83.66(11) . 12 ?
O2 V1 O2 96.34(11) 9_556 12 ?
O2 V1 O2 180.00(11) 4_556 12 ?
O5 V2 O5 180.00(18) 13_556 . ?
O5 V2 O3 87.38(11) 13_556 13_556 ?
O5 V2 O3 92.62(11) . 13_556 ?
O5 V2 O3 92.62(11) 13_556 . ?
O5 V2 O3 87.38(11) . . ?
O3 V2 O3 180.00(4) 13_556 . ?
O5 V2 O1 89.20(11) 13_556 13_556 ?
O5 V2 O1 90.80(11) . 13_556 ?
O3 V2 O1 88.70(7) 13_556 13_556 ?
O3 V2 O1 91.30(7) . 13_556 ?
O5 V2 O1 90.80(11) 13_556 . ?
O5 V2 O1 89.20(11) . . ?
O3 V2 O1 91.30(7) 13_556 . ?
O3 V2 O1 88.70(7) . . ?
O1 V2 O1 180.00(10) 13_556 . ?
C4 O1 V2 132.18(19) . . ?
C7 O2 V1 134.19(19) . . ?
C3 O3 V2 132.1(2) . . ?
V1 O4 V1 138.8(3) 2_554 . ?
V2 O5 V2 125.08(18) . 6_554 ?
C2 C1 C2 118.3(3) 10_557 . ?
C2 C1 C4 120.76(16) 10_557 . ?
C2 C1 C4 120.76(16) . . ?
C2 C2 C1 120.81(16) 12_655 . ?
C2 C2 H2 119.6 12_655 . ?
C1 C2 H2 119.6 . . ?
O3 C3 O3 126.4(4) . 10_557 ?
O3 C3 C6 115.55(18) . . ?
O3 C3 C6 115.55(18) 10_557 . ?
O1 C4 O1 131.1(3) . 10_557 ?
O1 C4 C1 114.42(17) . . ?
O1 C4 C1 114.42(17) 10_557 . ?
C9 C5 C6 120.9(3) . . ?
C9 C5 H5 119.6 . . ?
C6 C5 H5 119.6 . . ?
C5 C6 C5 119.6(3) 10_557 . ?
C5 C6 C3 119.88(17) 10_557 . ?
C5 C6 C3 119.88(17) . . ?
O2 C7 O2 125.1(3) . 10_557 ?
O2 C7 C8 117.31(16) . . ?
O2 C7 C8 117.31(16) 10_557 . ?
C9 C8 C9 122.7(4) . 10_557 ?
C9 C8 C7 118.60(18) . . ?
C9 C8 C7 118.60(18) 10_557 . ?
C5 C9 C8 117.9(3) . . ?
C5 C9 H9 121.0 . . ?
C8 C9 H9 121.0 . . ?

_diffrn_measured_fraction_theta_max 0.974
_diffrn_reflns_theta_full        23.27
_diffrn_measured_fraction_theta_full 0.974
_refine_diff_density_max         1.227
_refine_diff_density_min         -1.025
_refine_diff_density_rms         0.125