# Electronic Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2011


data_global
_journal_name_full               Chem.Commun.
_journal_coden_cambridge         0182
_journal_year                    ?
_journal_volume                  ?
_journal_page_first              ?
_publ_contact_author_email       'eric.breynaert@biw.kuleuven.be   '
_publ_contact_author_name        'Breynaert, Eric'
loop_
_publ_author_name
'Danilo Mustafa'
'Eric Breynaert'
'Sneha Bajpe'
'Johan Martens'
'Christine Kirschhock'

data_EMPTYCUBTC_publ
_database_code_depnum_ccdc_archive 'CCDC 827934'
#TrackingRef '- JM-ART-03-2011-010947 - HKUST-1.cif'

_audit_creation_method           'from EXP file using GSAS2CIF'
_audit_creation_date             2011-05-21T12:32
_audit_author_name               ceak
_audit_update_record             
;
2011-05-21T12:32 Initial CIF as created by GSAS2CIF
;

#=============================================================================
# This information describes the refinement of Cu3(Btc)2 powder pattern kept #
# at room temperature. #
# reported in : "Stability improvement of Cu3(BTC)2 metal-organic frame- #
# work under steaming conditions by encapsulation of Keggin polyoxometalate" #
# with as authors Danilo Mustafa, Eric Breynaert, Sneha R Bajpe, Johan A #
# Martens and Christine E A Kirschhock #
#=============================================================================

_publ_section_abstract           
;
Cu3(BTC)2 with incorporated Keggin polyoxometalate was demonstrated to
be stable under steaming conditions up to 483K, while the isostructural
HKUST-1 degrades and transforms into [Cu2OH(BTC)(H2O)]n.2nH2O from 343K
onwards.
;

_publ_section_exptl_refinement   
;
Refinement strategy: Background and profile were refined in a Le Baile fit
before the atomic positions were Rietveld refined. Occupation numbers of
framework atoms were kept at 100%. Occupation numbers of atomsof Keggin ions
were refined together and constrained to account for the chemical compos
ition of the HPA. Initially, the organic linker was inserted as rigid body
whereof the position and orientation was freely refined. In a next step the
observed and difference electron density maps were inspected for residual
intensity. The latter was throughout assumed as water molecules,which were
added successively to the coordinate lists. Positions and occupation of
water were freely refined. After reasonably good fits were obtained the
rigid body of the organic linker was replaced by individual atoms and the
isotropic temperature factorswere refined together with the positions of all
atoms. Several occupation numbers of water molecules approached unity and
were fixed. This strategy resulted in both cases in reasonable structures,
sensible temperature factors and acceptable profile fits. The occupation
factor of Keggin ions in HPA@ Cu2Btc3 refined to a value very close to
unity, strongly indicating 100% occupation of one of the two types of large
cavities in the framework.
;

#==============================================================================

# Phase information from GSAS

_pd_phase_name                   'Cu3(Btc)2 rt'
_cell_length_a                   26.36053(7)
_cell_length_b                   26.36053
_cell_length_c                   26.36053
_cell_angle_alpha                90.0
_cell_angle_beta                 90.0
_cell_angle_gamma                90.0
_cell_volume                     18317.33(14)
_symmetry_cell_setting           cubic
_symmetry_space_group_name_H-M   'F m -3 m'

_refine_ls_shift/su_max          0.10
_refine_ls_shift/su_mean         0.00
_computing_structure_refinement  GSAS
_refine_ls_number_parameters     58
_refine_ls_goodness_of_fit_all   1.64
_refine_ls_number_restraints     0
_refine_ls_matrix_type           full
_pd_proc_ls_prof_R_factor        0.0238
_pd_proc_ls_prof_wR_factor       0.0334
_pd_proc_ls_prof_wR_expected     0.0205
_refine_ls_R_Fsqd_factor         0.0757

_chemical_formula_sum            'C72 Cu12 O133.98'
_chemical_formula_weight         3771.36
_cell_formula_units_Z            4
_diffrn_ambient_temperature      295
_diffrn_ambient_pressure         1013
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a~1~'
_diffrn_radiation_wavelength     1.54056
_diffrn_source                   'sealed X-ray tube'
_diffrn_measurement_device_type  'Stoe Stadi MP'

# ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS

loop_
_atom_site_type_symbol
_atom_site_label
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_thermal_displace_type
_atom_site_U_iso_or_equiv
_atom_site_symmetry_multiplicity
Cu Cu1 0.28592(4) 0.0 0.21408(4) 1.0 Uiso 0.0106(4) 48
C C1 0.20142(16) 0.06830(20) 0.20142(16) 1.0 Uiso 0.0333(27) 96
C C2 0.17813(16) 0.11626(21) 0.17813(16) 1.0 Uiso 0.0181(19) 96
C C3 0.13255(18) 0.13255(18) 0.19895(21) 1.0 Uiso 0.0119(23) 96
O Obtc 0.24365(9) 0.05261(8) 0.18245(9) 1.0 Uiso 0.0231(11) 192
O Ow 0.36053(16) 0.13953(16) 0.13953(16) 0.993(7) Uiso 0.125(5) 32
O Ow3 -0.16190(29) 0.0 0.0 1.0 Uiso 0.091(4) 24
O Ow4 -0.06949(14) -0.06949(14) -0.06949(14) 0.938(9) Uiso 0.102(4) 32
O Ow5 0.37846(11) 0.0 0.37846(11) 1.0 Uiso 0.0452(24) 48
O ow6 0.07597(35) 0.5 0.0 1.0 Uiso 0.109(6) 24
O ow7 0.54555(20) 0.54555(20) 0.36706(33) 0.547(5) Uiso 0.101(6) 96
O O32 0.34297(13) -0.15703(13) 0.0 1.0 Uiso 0.0207(21) 48
O ow8 0.26835(16) -0.04718(13) 0.0 0.892(4) Uiso 0.0756(27) 96

loop_
_atom_type_symbol
_atom_type_number_in_cell
Cu 48.0
C 288.0
O 536.034

#--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--#

# Attachment '- JM-ART-03-2011-010947 - HPA@Cu3Btc2.cif'

data_KEGGIN_publ
_database_code_depnum_ccdc_archive 'CCDC 827935'
#TrackingRef '- JM-ART-03-2011-010947 - HPA@Cu3Btc2.cif'

_audit_creation_method           'from EXP file using GSAS2CIF'
_audit_creation_date             2011-05-20T10:11
_audit_author_name               ceak
_audit_update_record             
;
2011-05-20T10:11 Initial CIF as created by GSAS2CIF
;

#=============================================================================
# This information describes the refinement of HPA@Cu3(Btc)2 kept at room #
# temperature #
# reported in : "Stability improvement of Cu3(BTC)2 metal-organic frame- #
# work under steaming conditions by encapsulation of Keggin polyoxometalate" #
# with as authors Danilo Mustafa, Eric Breynaert, Sneha R Bajpe, Johan A #
# Martens and Christine E A Kirschhock #
#=============================================================================

_publ_section_abstract           
;
Cu3(BTC)2 with incorporated Keggin polyoxometalate was demonstrated to
be stable under steaming conditions up to 483K, while the isostructural
HKUST-1 degrades and transforms into [Cu2OH(BTC)(H2O)]n.2nH2O from 343K
onwards.
;

_publ_section_exptl_refinement   
;
Refinement strategy: Background and profile were refined in a Le Baile fit
before the atomic positions were Rietveld refined. Occupation numbers of
framework atoms were kept at 100%. Occupation numbers of atomsof Keggin ions
were refined together and constrained to account for the chemical compos
ition of the HPA. Initially, the organic linker was inserted as rigid body
whereof the position and orientation was freely refined. In a next step the
observed and difference electron density maps were inspected for residual
intensity. The latter was throughout assumed as water molecules,which were
added successively to the coordinate lists. Positions and occupation of
water were freely refined. After reasonably good fits were obtained the
rigid body of the organic linker was replaced by individual atoms and the
isotropic temperature factorswere refined together with the positions of all
atoms. Several occupation numbers of water molecules approached unity and
were fixed. This strategy resulted in both cases in reasonable structures,
sensible temperature factors and acceptable profile fits. The occupation
factor of Keggin ions in HPA@Cu2Btc3 refined to a value very close to
unity, strongly indicating 100% occupation of one of the two types of large
cavities in the framework.
;

_pd_block_id                     2011-05-20T10:11|KEGGIN_phase1|ceak||

#==============================================================================

# Phase information from GSAS

_pd_phase_name                   'HPA@Cu3(Btc)2 rt'
_cell_length_a                   26.34577
_cell_length_b                   26.34577
_cell_length_c                   h
_cell_angle_alpha                90.0
_cell_angle_beta                 90.0
_cell_angle_gamma                90.0
_cell_volume                     18286.58008
_symmetry_cell_setting           cubic
_symmetry_space_group_name_H-M   'F m -3 m'
_symmetry_int_tables_number      225
_chemical_absolute_configuration ?

_refine_ls_shift/su_max          0.03
_refine_ls_shift/su_mean         0.01
_computing_structure_refinement  GSAS
_refine_ls_number_parameters     62
_refine_ls_goodness_of_fit_all   1.59
_refine_ls_number_restraints     0
_refine_ls_matrix_type           full
_pd_proc_ls_prof_R_factor        0.0325
_pd_proc_ls_prof_wR_factor       0.0461
_pd_proc_ls_prof_wR_expected     0.0291
_refine_ls_R_Fsqd_factor         0.0963

_chemical_name_common            HPA@Cu3Btc2
_chemical_formula_sum            'C72 Cu12 O148.58 P W12'
_chemical_properties_physical    hygroscopic
_chemical_formula_weight         6241.64
_cell_formula_units_Z            4
_diffrn_ambient_temperature      295
_diffrn_ambient_pressure         1013
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a~1~'
_diffrn_radiation_wavelength     1.54056
_diffrn_source                   'sealed X-ray tube'
_diffrn_measurement_device_type  'Stoe Stadi MP'

_pd_char_colour                  blue
_pd_spec_mounting                capillary
_pd_spec_mount_mode              reflection

# ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS

loop_
_atom_site_type_symbol
_atom_site_label
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_thermal_displace_type
_atom_site_U_iso_or_equiv
_atom_site_symmetry_multiplicity
Cu Cu1 0.28556(6) 0.0 0.21444(6) 1.0 Uiso 0.0137(11) 48
C C1 0.2000(4) 0.0692(5) 0.2000(4) 1.0 Uiso 0.027(6) 96
C C2 0.1772(4) 0.1155(6) 0.1772(4) 1.0 Uiso 0.023(6) 96
C C3 0.1337(4) 0.1337(4) 0.1990(5) 1.0 Uiso 0.030(6) 96
O Obtc 0.24313(18) 0.05362(17) 0.18280(18) 1.0 Uiso 0.0023(23) 192
P P1 0.5 1.0 0.5 0.971(11) Uiso 0.016(7) 4
W W 0.40461(2) 1.0 0.59537(2) 0.971(11) Uiso 0.00177(31) 48
O O1 0.5318(4) 0.0318(4) 0.5318(4) 0.485(6) Uiso 0.011(13) 32
O O2b 0.37903(27) 0.94657(18) 0.55343(18) 0.971(11) Uiso 0.0152(34) 96
O O3 0.1412(4) 0.0 0.1412(4) 0.971(11) Uiso 0.027(5) 48
O ow1 0.8989(11) 0.5 0.0 0.734(17) Uiso 0.125(15) 24
O ow 0.62837(25) 0.62837(25) 0.56118(35) 0.841(10) Uiso 0.092(7) 96
O O32 0.34255(29) -0.15744(29) 0.0 1.0 Uiso 0.003(5) 48
O ow5 0.2526(4) -0.07467(31) 0.0 1.0 Uiso 0.078(5) 96

loop_
_atom_type_symbol
_atom_type_number_in_cell
P 4.0
Cu 48.0
C 288.0
O 594.319
W 48.0

#--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--#