# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.
# This journal is © The Royal Society of Chemistry 2014

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

# 1. SUBMISSION DETAILS

 _publ_contact_author_name         'Dr. Simona Galli'
 _publ_contact_author_address
;
       Dipartimento di Scienza e Alta Tecnologia,
       Universita' 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        '+39-958-2386627'
 
 _publ_requested_journal           'Journal of Materials Chemistry'
 _publ_requested_category          'FA'
 
 _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
;
When long bis(pyrazolates) meet late transition metals:
structure, stability and adsorption of
MOFs featuring large parallel channels

;
 
 # 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

     'Galli, Simona'
;    Dipartimento di Scienza e Alta Tecnologia,
     Universita' degli Studi dell'Insubria,
     Via Valleggio 11, 22100 Como - Italy.
;
     'Maspero, Angelo'
;    Dipartimento di Scienza e Alta Tecnologia,
     Universita' degli Studi dell'Insubria,
     Via Valleggio 11, 22100 Como - Italy.   
;
     'Giacobbe, Carlotta'
;    Dipartimento di Scienza e Alta Tecnologia,
     Universita' degli Studi dell'Insubria,
     Via Valleggio 11, 22100 Como - Italy.
; 
     'Palmisano Giovanni'
;    Dipartimento di Scienza e Alta Tecnologia,
     Universita' degli Studi dell'Insubria,
     Via Valleggio 11, 22100 Como - Italy.
;
     'Nardo, Luca'
;    Dipartimento di Scienze della Salute, 
     Universita' di Milano Bicocca,
     Via Cadore 48, 20900 Monza - Italy.
;
     'Angiolina, Comotti'
;    Dipartimento di Scienza dei Materiali,
     Universita' di Milano Bicocca,
     Via Cozzi 55, 20100 Milano - Italy
;
     'Bassanetti, Irene'
;    Dipartimento di Scienza dei Materiali,
     Universita' di Milano Bicocca,
     Via Cozzi 55, 20100 Milano - Italy
;
    'Sozzani, Piero'
;   Dipartimento di Scienza dei Materiali,
    Universita' di Milano Bicocca,
    Via Cozzi 55, 20100 Milano - Italy
;
     'Masciocchi, Norberto'
;    Dipartimento di Scienza e Alta Tecnologia,
     Universita' degli Studi dell'Insubria,
     Via Valleggio 11, 22100 Como - Italy.
;

 #==============================================================================
 
data_Compound_Fe2BPEB3

_chemical_name_systematic        
;
 tris(1,4-bis(1H-pyrazol-4-ylethynyl)benzene)-bis(fe(iii))
;
_chemical_name_common            ?
_chemical_formula_moiety         'C48 H24 Fe2 N12'
_chemical_formula_structural     'Fe2 (C16 H8 N4)3'
_chemical_formula_analytical     ?
_chemical_formula_iupac          ?
_chemical_formula_sum            'C48 H24 Fe2 N12'
_chemical_formula_weight         880.5
_chemical_melting_point          ?
_chemical_compound_source        ?

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)'
Fe Fe 'International Tables for Crystallography (Vol. IV)'

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

_space_group_crystal_system      'orthorhombic'
_space_group_name_H-M_alt        Fddd
_space_group_name_Hall           ?

loop_
_symmetry_equiv_pos_as_xyz
'-x, -y, -z'
'-x, -y+1/2, -z+1/2'
'-x, y+1/4, z+1/4'
'-x, y-1/4, z-1/4'
'-x+1/4, -y+1/4, z'
'-x+1/4, -y-1/4, z+1/2'
'-x+1/4, y, -z+1/4'
'-x+1/4, y+1/2, -z-1/4'
'-x+1/2, -y, -z+1/2'
'-x+1/2, -y+1/2, -z'
'-x+1/2, y+1/4, z-1/4'
'-x+1/2, y-1/4, z+1/4'
'-x-1/4, -y+1/4, z+1/2'
'-x-1/4, -y-1/4, z'
'-x-1/4, y, -z-1/4'
'-x-1/4, y+1/2, -z+1/4'
'x, -y+1/4, -z+1/4'
'x, -y-1/4, -z-1/4'
'x, y, z'
'x, y+1/2, z+1/2'
'x+1/4, -y, z+1/4'
'x+1/4, -y+1/2, z-1/4'
'x+1/4, y+1/4, -z'
'x+1/4, y-1/4, -z+1/2'
'x+1/2, -y+1/4, -z-1/4'
'x+1/2, -y-1/4, -z+1/4'
'x+1/2, y, z+1/2'
'x+1/2, y+1/2, z'
'x-1/4, -y, z-1/4'
'x-1/4, -y+1/2, z+1/4'
'x-1/4, y+1/4, -z+1/2'
'x-1/4, y-1/4, -z'

_cell_length_a  7.3968(53)
_cell_length_b  36.3567(25)
_cell_length_c  63.4375(97)
_cell_angle_alpha 90
_cell_angle_beta  90
_cell_angle_gamma 90
_cell_volume 17060(13)
_cell_formula_units_Z            8
_cell_measurement_temperature    298

_pd_calibration_special_details  
; ?
;
_cell_special_details            
; ?
;

_exptl_crystal_density_diffrn    0.69
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             3584

# The next three fields give the specimen dimensions in mm.  The equatorial 
# plane contains the incident and diffracted beam.
_pd_spec_size_axial              10 	# perpendicular to 
					# equatorial plane

_pd_spec_size_equat              15 	# parallel to 
					# scattering vector 
					# in transmission

_pd_spec_size_thick              0.2 	# 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                  'black'	# use ICDD colour descriptions



# The next four fields are normally only needed for transmission experiments.
_exptl_absorpt_coefficient_mu    29.27
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?

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

_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
_diffrn_source_target            Cu
_diffrn_source_type              'sealed X-ray tube'
_diffrn_measurement_device_type  'Bruker AXS D8 Advance'
_diffrn_detector_type            'Bruker Lynxeye 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     1.5418  # 1.5406, 1.5443 
_diffrn_radiation_monochromator  'Ni filter'

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

_pd_meas_number_of_points        5051
_pd_meas_2theta_range_min        4
_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 AXS Commander'
_computing_cell_refinement      'TOPAS-R (Bruker AXS, V 3.0, 2005, Germany)'
_computing_data_reduction       ?
_computing_structure_solution   'TOPAS-R (Bruker AXS, V 3.0, 2005, Germany)'
_computing_structure_refinement 'TOPAS-R (Bruker AXS, V 3.0, 2005, Germany)'
_computing_molecular_graphics   'Schakal99 (E.Keller Chem.Uns.Zeit, 1980,14,56)'
_computing_publication_material
;
TOPAS-R (Bruker AXS, V 3.0, 2005, Germany)
Schakal99 (E.Keller Chem.Uns.Zeit, 1980,14,56)
;

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

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

_pd_proc_ls_special_details      
; 
   The crystallographically independent portions of the two organic ligands
   were described, through the Topas-R z-matrix formalism,
   by the following rigid body:
   
     	z_matrix   Du
	z_matrix   C1  Du    =r1;
	z_matrix   C2  C1    =r1;   Du   60
	z_matrix   H2  C2    =r2;   C1  120  Du    180
	z_matrix   C3  C1    =r5;   C2  120  Du    180 
	z_matrix   C4  C3    =r4;   Du  180  C2    180 
	z_matrix   C5  C4    =r5;   C3  180  C1      0
	z_matrix   C6  C5    =r3;   C4  126  C2      0
	z_matrix   H6  C6    =r2;   C5  120  H2      0
	z_matrix   N1  C6    =r3;   C5  108  C4    180
	'six-membered ring disorder
 	z_matrix   C2a  C1  =r1;    C2  120  C3    180
 	z_matrix   H2a  C2a =r2;    C1  120  C2    180
 	z_matrix   C2b  C2a =r1;    C1  120  C2      0
 	z_matrix   H2b  C2b =r2;    C2a 120  C1    180
 	z_matrix   C2c  C2  =r1;    C1  120  C2a     0
 	z_matrix   H2c  C2c =r2;    C2  120  C1    180
   
        r1 = 1.39
        r2 = 0.95
        r3 = 1.36
        r4 = 1.24
        r5 = 1.54
        Du = centre of mass (Dummy atom)
        
Rotations of the rigid body about the crystallographic axes a, b, c: -90, 0, 0
Position of the center of mass translation: 0.125, 0.125, 0.125
Out of plane rotation (disorder) of the six-membered ring about C1-C3: 99(7)

      	z_matrix   Ha
	z_matrix   C11   Ha  =r1;
	z_matrix   C12   C11  =r1;   Ha    60
	z_matrix   H12   C12  =r2;   C11  120  Ha    180
	z_matrix   C13   C11  =r5;   C12  120  Ha    180 
	z_matrix   C14   C13  =r4;   Ha   180  C12   180 
	z_matrix   C15   C14  =r5;   C13  180  C11     0
	z_matrix   C16   C15  =r3;   C14  126  C12     0
	z_matrix   H16   C16  =r2;   C15  120  H12     0
	z_matrix   N11   C16  =r3;   C15  108  C14   180
	z_matrix   C17   C11  =r1;   C12  120  H12   180
	z_matrix   H17   C17  =r2;   C11  120  C13     0
	z_matrix   C19   C15  =r3;   C14  126  H17     0
	z_matrix   H19   C19  =r2;   C15  120  H16   180
 	z_matrix   N12   C19  =r3;   C15  108  C16     0
	'six-membered ring disorder
 	z_matrix   C12a  C12  =r1;   C11  120  C13   180
 	z_matrix   H12a  C12a =r2;   C12  120  C11   180
 	z_matrix   C17a  C17  =r1;   C11  120  C13   180
 	z_matrix   H17a  C17a =r2;   C17  120  C11   180
        
        r1 = 1.39
        r2 = 0.95
        r3 = 1.36
        r4 = 1.24
        r5 = 1.54
        Ha = centre of mass (Dummy atom)

Rotations of the rigid body about the crystallographic axes a, b, c: -90, 0, 0
Position of the center of mass translation: -151.4(1), 13.8(4), 0 
Out of plane rotation (disorder) of the six-membered ring about C11-C13: -42(1)
	
;

# 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        0.020
_pd_proc_ls_prof_wR_factor       0.026
_pd_proc_ls_prof_wR_expected     0.010

_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     56
_refine_ls_number_restraints     0
_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        4
_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     ?

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

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
Fe   Fe 16  0.375       0.375       0.12114(41)     1    4.11(83)
C1   C  16  0.125       0.1632323   0.125           1    6.11(83)
C2   C  32  0.09872158  0.1441162   0.1437268       0.25 6.11(83)
H2   H  32  0.08076152  0.1571812   0.1565256       0.25 6.11(83)
C3   C  16  0.125       0.2055904   0.125           1    6.11(83)
C4   C  16  0.125       0.2396969   0.125           1    6.11(83)
C5   C  16  0.125       0.282055    0.125           1    6.11(83)
C6   C  32  0.2737485   0.3040424   0.125           1    6.11(83)
H6   H  32  0.3910787   0.2934144   0.125           1    6.11(83)
N1   N  32  0.2169316   0.3396187   0.125           1    6.11(83)
C2a  C  32  0.1512784   0.1441162   0.1062732       0.25 6.11(83)
H2a  H  32  0.1692385   0.1571812   0.09347438      0.25 6.11(83)
C2b  C  32  0.1512784   0.1058838   0.1062732       0.25 6.11(83)
H2b  H  32  0.1692385   0.09281884  0.09347438      0.25 6.11(83)
C2c  C  32  0.09872158  0.1058838   0.1437268       0.25 6.11(83)
H2c  H  32  0.08076152  0.09281884  0.1565256       0.25 6.11(83)
C11  C  32 -0.03937797  0.5183263  -0.01867383      1    6.11(83)
C12  C  32  0.08601323  0.4898504  -0.01859266      0.5  6.11(83)
H12  H  32  0.1447992   0.4829135  -0.03129988      0.5  6.11(83)
C13  C  32 -0.08300536  0.5386303  -0.03936281      1    6.11(83)
C14  C  32 -0.1181339   0.554979   -0.05602148      1    6.11(83)
C15  C  32 -0.1617613   0.575283   -0.07671046      1    6.11(83)
C16  C  32 -0.03996123  0.5858224  -0.09159093      1    6.11(83)
H16  H  32  0.08492197  0.580728   -0.08966635      1    6.11(83)
N11  N  32 -0.1317772   0.6028756  -0.1073857       1    6.11(83)
C17  C  32 -0.1253912   0.528476    0               0.5  6.11(83)
H17  H  32 -0.2110902   0.547938   -0.0001366345    0.5  6.11(83)
C19  C  32 -0.3288538   0.5858224  -0.08330861      1    6.11(83)
H19  H  32 -0.431844    0.580728   -0.07485108      1    6.11(83)
N12  N  32 -0.3103226   0.6028756  -0.1022669       1    6.11(83)
C12a C  32  0.1253912   0.471524    0               0.5  6.11(83)
H12a H  32  0.2110902   0.452062    0.0001366345    0.5  6.11(83)
C17a C  32 -0.08601323  0.5101496   0.01859266      0.5  6.11(83)
H17a H  32 -0.1447992   0.5170865   0.03129988      0.5  6.11(83)

