# Supplementary Material (ESI) for Chemical Science
# This journal is (c) The Royal Society of Chemistry 2011
#==============================================================================

# 1. SUBMISSION DETAILS

_publ_contact_author_name         'Dr. Simona Galli'
_publ_contact_author_address
;
    Dipartimento di Scienze Chimiche e Ambientali,
    Università degli Studi dell'Insubria,
    Via Valleggio 11, 22100 Como - Italy.
;
_publ_contact_author_email        'simona.galli@uninsubria.it'
_publ_contact_author_fax          '+39-031-2386630'
_publ_contact_author_phone        '+39-031-2386627'

_publ_requested_journal           'Chemcial Science'
_publ_requested_category          ?

_publ_contact_letter
;  
;

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

# 2. PROCESSING SUMMARY (IUCr Office Use Only)

_journal_date_recd_electronic     ?
_journal_date_to_coeditor         ?
_journal_date_from_coeditor       ?
_journal_date_accepted            ?
_journal_date_printers_first      ?
_journal_date_printers_final      ?
_journal_date_proofs_out          ?
_journal_date_proofs_in           ?
_journal_coeditor_name            ?
_journal_coeditor_code            ?
_journal_coeditor_notes
; ?
;
_journal_techeditor_code          ?
_journal_paper_category           ?
_iucr_compatibility_tag           ?
_journal_techeditor_notes
; ?
;
_journal_coden_ASTM               ?
_journal_name_full                ?
_journal_year                     ? 
_journal_volume                   ?
_journal_issue                    ?
_journal_page_first               ? 
_journal_page_last                ?
_journal_suppl_publ_number        ?
_journal_suppl_publ_pages         ?

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

# 3. TITLE AND AUTHOR LIST

_publ_section_title
;
High Thermal and Chemical Stability
in Pyrazolate-Bridged Metal-Organic Frameworks with Exposed Metal Sites
;

# The loop structure below should contain the names and addresses of all
# authors, in the required order of publication. Repeat as necessary. 

loop_
    _publ_author_name
    _publ_author_address
   
    'Colombo, Valentina'
;   Dipartimento di Scienze Chimiche e Ambientali,
    Università degli Studi dell'Insubria,
    Via Valleggio 11, 22100 Como - Italy.
;
    'Galli, Simona'
;   Dipartimento di Scienze Chimiche e Ambientali,
    Università degli Studi dell'Insubria,
    Via Valleggio 11, 22100 Como - Italy.
;
    'Choi, Hye Jin'
;   Department of Chemistry
    University of California
    Berkeley, California 94720, USA
    and Materials Sciences Division
    Lawrence Berkeley National Laboratory
    Berkeley, California 94720, USA
;   
    'Han, Ggoch Ddeul'
;   Department of Chemistry
    University of California
    Berkeley, California 94720, USA
    and Materials Sciences Division
    Lawrence Berkeley National Laboratory
    Berkeley, California 94720, USA
;  
   'Maspero, Angelo'
;   Dipartimento di Scienze Chimiche e Ambientali,
    Università degli Studi dell'Insubria,
    Via Valleggio 11, 22100 Como - Italy.
;
   'Palmisano, Giovanni'
;   Dipartimento di Scienze Chimiche e Ambientali,
    Università degli Studi dell'Insubria,
    Via Valleggio 11, 22100 Como - Italy.
;
   'Masciocchi, Norberto'
;   Dipartimento di Scienze Chimiche e Ambientali,
    Università degli Studi dell'Insubria,
    Via Valleggio 11, 22100 Como - Italy.
;
   'Long, Jeffrey R.'
;   Department of Chemistry
    University of California
    Berkeley, California 94720, USA
    and Materials Sciences Division
    Lawrence Berkeley National Laboratory
    Berkeley, California 94720, USA
;
#==============================================================================

#data_Compound3

_chemical_name_systematic                           
;
?
;
_chemical_name_common             ? 
_chemical_formula_moiety          ?
_chemical_formula_structural      'Zn3 (C15 H9 N6)2 (C1 H4 O)4 (H2 O)2'
_chemical_formula_analytical      ?
_chemical_formula_iupac           ?
_chemical_formula_sum             'C34 H38 N12 O6 Zn3'
_chemical_formula_weight          906.9 
_chemical_melting_point           ?
_chemical_compound_source         'synthesis'

loop_
    _atom_type_symbol
    _atom_type_description
#   _atom_type_scat_dispersion_real
#   _atom_type_scat_dispersion_imag
    _atom_type_scat_source
    
    C  C  'International Tables for Crystallography (Vol. IV)'
    H  H  'International Tables for Crystallography (Vol. IV)'
    N  N  'International Tables for Crystallography (Vol. IV)'
    O  O  'International Tables for Crystallography (Vol. IV)'
    Zn Zn 'International Tables for Crystallography (Vol. IV)'
              
#==============================================================================

# 1.5. POWDER SPECIMEN AND CRYSTAL DATA

_space_group_crystal_system       tetragonal
_space_group_name_H-M_alt 	  'P42/ncm'
_space_group_name_Hall   	  ?

loop_
_symmetry_equiv_pos_as_xyz
	'-x, -y, -z'
	'-x, y+1/2, -z+1/2'
	'-x+1/2, -y+1/2, z'
	'-x+1/2, y, z+1/2'
	'-y, -x, -z'
	'-y, x+1/2, -z+1/2'
	'-y+1/2, -x+1/2, z'
	'-y+1/2, x, z+1/2'
	'y, -x+1/2, z+1/2'
	'y, x, z'
	'y+1/2, -x, -z+1/2'
	'y+1/2, x+1/2, -z'
	'x, -y+1/2, z+1/2'
	'x, y, z'
	'x+1/2, -y, -z+1/2'
	'x+1/2, y+1/2, -z'
	
_cell_length_a  15.55503(99)
_cell_length_b  15.55503(99)
_cell_length_c  20.0304(16)
_cell_angle_alpha 90
_cell_angle_beta  90
_cell_angle_gamma 90
_cell_volume 4846.54(73)
_cell_formula_units_Z     4                  
_cell_measurement_temperature     298(2)        

_pd_calibration_special_details      
; ?
;
_cell_special_details
; ?
;

_exptl_crystal_density_diffrn     1.20
_exptl_crystal_density_meas       ?
_exptl_crystal_density_method     'not measured'
_exptl_crystal_F_000              1856

# The next three fields give the specimen dimensions in mm.  The equatorial 
# plane contains the incident and diffracted beam.
_pd_spec_size_axial               15      # perpendicular to 
                                          # equatorial plane

_pd_spec_size_equat               13      # parallel to 
                                          # scattering vector 
                                          # in transmission

_pd_spec_size_thick               0.1     # parallel to 
                                          # scattering vector 
                                          # in reflection

# The next five fields are character fields that describe the specimen.

_pd_spec_mounting                          
;
packed powder pellet
;
_pd_spec_mount_mode         'reflection'  # options are 'reflection' 
                                          # or 'transmission'

_pd_spec_shape              'flat_sheet'  # options are 'cylinder',
                                          # 'flat_sheet' or 'irregular'

_pd_char_particle_morphology   ?
_pd_char_colour             'white'       # use ICDD colour descriptions



# The next four fields are normally only needed for transmission experiments.
_exptl_absorpt_coefficient_mu     ?
_exptl_absorpt_correction_type    ?        
_exptl_absorpt_correction_T_min   ?        
_exptl_absorpt_correction_T_max   ?        

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

# 1.6. EXPERIMENTAL DATA

_exptl_special_details
; ?
;

# This following item is used to identify the equipment used to record the
# powder pattern when the diffractogram was measured at a laboratory
# other than the authors' home institution, e.g. when neutron or synchrotron
# radiation is used.

_pd_instr_location
; ?
;

_diffrn_ambient_temperature      298(2)                    
_diffrn_source_target            Cu                                     
_diffrn_source_type              'sealed X-ray tube'
_diffrn_measurement_device_type  'Bruker AXS D8 Advance'       
_diffrn_detector_type            'Bruker Lynxeye position linear PSD'        
_pd_meas_scan_method             'step'         # options are 'step', 'cont',
                                                # 'tof', 'fixed' or
                                                # 'disp' (= dispersive)
_pd_meas_special_details
;  ?
;

# The following six items are used for angular dispersive measurements only.

loop_
    _diffrn_radiation_type  'Cu K\a'                 
    _diffrn_radiation_wavelength             
       CuK\a~1~ 1.54056
       CuK\a~2~ 1.54439
_diffrn_radiation_monochromator   'Nickel filter'                

# The following four items give details of the measured (not processed)
# powder pattern.  Angles are in degrees.

_pd_meas_number_of_points       5001                                     
_pd_meas_2theta_range_min          5                   
_pd_meas_2theta_range_max        105                   
_pd_meas_2theta_range_inc          0.02

# The following three items are used for time-of-flight measurements only.

_pd_instr_dist_src/spec           ?                    
_pd_instr_dist_spec/detc          ?                    
_pd_meas_2theta_fixed             ?                    

# The following fields are used to identify the programs used.

_computing_data_collection        'Bruker D8 Command'
_computing_cell_refinement        'Bruker TOPAS-R'
_computing_data_reduction         ?
_computing_structure_solution     'Bruker TOPAS-R'
_computing_structure_refinement   'Bruker TOPAS-R'
_computing_molecular_graphics     ?
_computing_publication_material   ?

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

# 1.7. REFINEMENT DATA

# Use the next field to give any special details about the fitting of the
# powder pattern.

_pd_proc_ls_special_details

; 
  
1) The use of a rigid body description for the organic ligand
   does not allow the derivation of statistically meaningful
   s.u.'s for its atoms.
  
   S.u.'s are available only for the center of mass (X, Y, Z),
   the rotation angles (RX, RZ, RZ) and the torsion (T)
   of the pyrazolate moiety
  
   X, Y, Z      0.4307(2), 0.5 - 0.4307(2), 0.1786(3)
   RY, RY, RZ 45, 45, 0
   RX, RY, RZ   5.62(5), 5.62(5), 0
   T            64.1(6)
  
   of the rigid body described by:
 
   z_matrix   H
   z_matrix   C1   H   =r1;
   z_matrix   C2   C1  =r1; H   60
   z_matrix   C3   C2  =r1; C1  120  H    0
   z_matrix   C4   C3  =r1; C2  120  C1   0
   z_matrix   H2   C2  =r2; C1  120  H  180
   z_matrix   H4   C4  =r2; C3  120  H  180
   z_matrix   C7   C1  =r3; C2  120  C3 180
   z_matrix   C8   C7  =r4; C1  126  C2   0
   z_matrix   H8   C8  =r2; C7  126  C1   0
   z_matrix   N1   C8  =r4; C7  108  C1 180
   z_matrix   C10  C3  =r3; C2  120  C1 180
   z_matrix   C11  C10 =r4; C3  126  C4   0
   z_matrix   H11  C11 =r2; C10 126  C4   0
   z_matrix   N3   C11 =r4; C10 108  C3 180
   z_matrix   C12  C10 =r4; C3  126  C2   0
   z_matrix   H12  C12 =r2; C10 126  C2   0
   z_matrix   N4   C12 =r4; C10 108  C3 180
  
   r1 = 1.39
   r2 = 0.95
   r3 = 1.45
   r4 = 1.36
   H = Dummy atom representing the centre of mass

2) The difference Fourier map calculated with the Fcs of the framework alone
   revealed that the solvent is highly disordered. Thus, its electronic
   density was modeled by allocating one dummy atom at the centre
   of the cavities, with a high isotropic thermal parameter.
   Its site occupancy factor was allowed to refine up to the total
   electron density of the solvent, as estimated from the elemental analysis.
   The fractional coordinates of the dummy atom are not provided.
;
 
# The next three items are given as text
_pd_proc_ls_profile_function      'fundamental parameters approach'  
_pd_proc_ls_background_function   'Chebychev polynomial'     
_pd_proc_ls_pref_orient_corr      ?
_pd_proc_ls_prof_R_factor         0.072         
_pd_proc_ls_prof_wR_factor        0.102         
_pd_proc_ls_prof_wR_expected      0.009        

_refine_special_details
; ?
;

_refine_ls_structure_factor_coef     Inet
_refine_ls_matrix_type               fullcycle
_refine_ls_weighting_scheme          '1/[Y~i~]'
_refine_ls_hydrogen_treatment        ?
_refine_ls_extinction_method         none        
_refine_ls_extinction_coef           ?           
_refine_ls_number_parameters         27
_refine_ls_number_restraints         ?
_refine_ls_number_constraints        ?
# The following item is 'CHI squared'
_refine_ls_goodness_of_fit_all       ?

_refine_ls_restrained_S_all          ?           
_refine_ls_restrained_S_obs          ?
_refine_ls_shift/su_max             .01
_refine_ls_shift/su_mean             ?


# The following four items apply to angular dispersive measurements.
# 2theta minimum, maximum and increment (in degrees) are for the 
# intensities used in the refinement.
_pd_proc_2theta_range_min          5             
_pd_proc_2theta_range_max        105             
_pd_proc_2theta_range_inc          0.02

loop_
      _pd_proc_wavelength       1.540562    1.544390   

_pd_block_diffractogram_id        ?            # The id used for the block
                                               # containing the powder 
                                               # pattern profile (section 11).

# Give appropriate details in the next two text fields.
_pd_proc_info_excluded_regions    ?             
_pd_proc_info_data_reduction      ?

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

# 1.8. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_symmetry_multiplicity
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_B_iso_or_equiv
Zn1 Zn   4  0.75         0.25        0          1    5.53(28)
Zn2 Zn   8  0.41694(27) -0.41694(27) 0          1    5.53(28)
C1   C  16  0.4394134    0.06054444  0.2473368  0.5  7.53(28)
C2   C  16  0.4900397    0.1193814   0.2129528  1    7.53(28)
C3   C  16  0.4813245    0.1281387   0.1442248  1    7.53(28)
C4   C  16  0.4219831    0.07805903  0.1098808  0.5  7.53(28)
H2   H  16  0.5305968    0.1536085   0.2364252  1    7.53(28)
H4   H  16  0.4160267    0.08404423  0.06290846 0.5  7.53(28)
C7   C  16  0.4485047    0.05140913  0.3190314  0.5  7.53(28)
C8   C  16  0.5037726    0.09614827  0.3585385  1    7.53(28)
H8   H  16  0.5432006    0.1388719   0.3440082  1    7.53(28)
N1   N  16  0.4926863    0.06898681  0.422499   1    7.53(28)
C10  C  16  0.5341361    0.1895154   0.1083565  1    7.53(28)
C11  C  16  0.5053206    0.2598714   0.07482912 1    7.53(28)
H11  H  16  0.4470575    0.2774334   0.07079728 1    7.53(28)
N3   N  16  0.5745574    0.300672    0.04808698 1    7.53(28)
C12  C  16  0.6211819    0.1868335   0.1023355  1    7.53(28)
H12  H  16  0.6580606    0.1444189   0.120891   1    7.53(28)
N4   N  16  0.6461637    0.255532    0.06508684 1    7.53(28)

