# Electronic Supplementary Material (ESI) for Chemical Communications.
# This journal is © The Royal Society of Chemistry 2017

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_MIL-173_Zr
_database_code_depnum_ccdc_archive 'CCDC 1544198'
_audit_update_record             
;
2017-04-15 deposited with the CCDC.
2017-06-14 downloaded from the CCDC.
;

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

# POWDER SPECIMEN AND CRYSTAL DATA

_chemical_formula_moiety         '(Zr4+)2, (N4C44H18O12 8-)(C2H7N)5 (H2O)4.7 '
_chemical_formula_sum            'C54 N9 H62.4 O16.7 Zr2'
_chemical_formula_weight         1287.17
_exptl_crystal_colour            red


_cell_length_a                   28.4436(6)
_cell_length_b                   28.4436(6)
_cell_length_c                   14.9962(9)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     12132.5(9)



_cell_formula_units_Z            8
_diffrn_ambient_temperature      293
_cell_measurement_temperature    293
_pd_spec_mounting                'glass capillary'
_pd_spec_mount_mode              transmission
_pd_spec_shape                   cylinder


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

#  EXPERIMENTAL DATA

_diffrn_source                   'Sealed tube'
_diffrn_radiation_type           CuKa1

_diffrn_radiation_monochromator  Ge(111)


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

#_pd_meas_number_of_points         8504
_pd_meas_2theta_range_min        4.000
_pd_meas_2theta_range_max        90.00
_pd_meas_2theta_range_inc        0.010113

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

#  REFINEMENT DATA


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


# The next three items are given as text.

_pd_proc_ls_profile_function     
'Thomson Cox Hasting pseudo-Voigt function + Stephens model'
_pd_proc_ls_background_function  'Chebychev polynomial and one additional peak'



#  The following profile R-factors are NOT CORRECTED for background
#  The sum is extended to all non-excluded points.
#  These are the current CIF standard

_pd_proc_ls_prof_R_factor        0.049
_pd_proc_ls_prof_wR_factor       0.076

#  Items related to LS refinement

_refine_ls_R_I_factor            0.034
_refine_ls_goodness_of_fit_all   10.4
_refine_ls_number_reflns         1316
_refine_ls_number_structural_parameters 3
_refine_ls_number_profile_parameters 30
_refine_ls_number_restraints     4

# 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        4.000
_pd_proc_2theta_range_max        90.000
_pd_proc_2theta_range_inc        0.010113
_diffrn_radiation_wavelength     1.5406

_computing_structure_solution    'SIR97 and TOPAS'
_computing_structure_refinement  TOPAS
_computing_molecular_graphics    DIAMOND

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


_symmetry_space_group_name_H-M   I41/amd:2
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z '
'-x, y, z '
'-x+1/2, -y, z+1/2 '
'-x+1/2, y, -z+1/2 '
'-y+1/4, -x+1/4, -z-1/4 '
'-y+1/4, x-1/4, z+1/4 '
'-y-1/4, -x+1/4, z-1/4 '
'-y-1/4, x-1/4, -z+1/4 '
'y+1/4, -x+1/4, z-1/4 '
'y+1/4, x-1/4, -z+1/4 '
'y-1/4, -x+1/4, -z-1/4 '
'y-1/4, x-1/4, z+1/4 '
'x, -y, -z '
'-x, -y, -z '
'x+1/2, -y, z+1/2 '
'x+1/2, y, -z+1/2 '
'x+1/2, y+1/2, z+1/2 '
'-x+1/2, y+1/2, z+1/2 '
'-x, -y+1/2, z '
'-x, y+1/2, -z '
'-y-1/4, -x-1/4, -z+1/4 '
'-y-1/4, x+1/4, z-1/4 '
'-y+1/4, -x-1/4, z+1/4 '
'-y+1/4, x+1/4, -z-1/4 '
'y-1/4, -x-1/4, z+1/4 '
'y-1/4, x+1/4, -z-1/4 '
'y+1/4, -x-1/4, -z+1/4 '
'y+1/4, x+1/4, z-1/4 '
'x+1/2, -y+1/2, -z+1/2 '
'-x+1/2, -y+1/2, -z+1/2 '
'x, -y+1/2, z '
'x, y+1/2, -z '
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
Zr1 Zr 16 0.2524(5) 0.5 0.5 1 3.00(13)
O1 O 32 0.195578 0.5587521 0.2212508 1 3.00(13)
O2 O 32 0.2277339 0.5272655 0.375 1 3.00(13)
O3 O 32 0.195504 0.5586764 0.5287492 1 3.00(13)
N1 N 16 1.170042e-016 0.6775759 0.375 1 3.00(13)
N2 N 16 0.07242407 0.75 0.375 1 3.00(13)
C1 C 32 0.03820709 0.6494175 0.375 1 3.00(13)
C2 C 32 0.02446119 0.6039749 0.375 1 3.00(13)
C3 C 32 0.1041676 0.713026 0.375 1 3.00(13)
C4 C 32 0.1500792 0.7251135 0.375 1 3.00(13)
C5 C 32 0.08830501 0.6634711 0.375 1 3.00(13)
C6 C 32 0.1248746 0.6277469 0.375 1 3.00(13)
C7 C 32 0.1421207 0.6109376 0.295883 1 3.00(13)
C8 C 32 0.1765748 0.57728 0.295883 1 3.00(13)
C9 C 32 0.1937828 0.5604318 0.375 1 3.00(13)
C10 C 32 0.1765368 0.5772411 0.454117 1 3.00(13)
C11 C 32 0.1420827 0.6108987 0.454117 1 3.00(13)
H7 H 32 0.1304393 0.6223747 0.2421758 1 4
H11 H 32 0.1303755 0.6223094 0.5078242 1 4
X1 H 8 9.860761e-032 0.75 0.375 0 4
H4 H 32 0.1750341 0.7039876 0.375 1 4
H2 H 32 0.0446674 0.5782697 0.375 1 4
N20 N 32 0.92913 0.96843 0.17093 1 3
C21 C 32 0.38822 0.04263 0.6251 0.6667 3
C22 C 32 0.73258 0.16874 0.49124 0.6667 3
C23 C 32 0.02558 0.52528 0.12851 0.6667 3
C31 C 32 0.41134 0.71564 0.88983 0.5 3
N30 N 16 0.54033 0.70967 0.875 0.5 3
Ow1 O 32 0.93616 0.98008 0.55735 0.5 3
Ow2 O 16 0.30438 0.75 0.9031 1 3
Ow3 O 32 0.69154 0.36705 0.12533 0.1745 3
_chemical_name_systematic        Zr2(PorphGal)
_chemical_name_common            MIL-173
_exptl_crystal_recrystallization_method 'solvotherml synthesis'
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_shelx
_database_code_depnum_ccdc_archive 'CCDC 1544211'
_audit_update_record             
;
2017-04-15 deposited with the CCDC.
2017-06-14 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        MIL-173(La)
_chemical_name_common            La2(H6PorphGal)
_chemical_melting_point          ?
_chemical_formula_moiety         La2C44H24N4O12
_chemical_formula_sum            'C22 H12 La N2 O6'
_chemical_formula_weight         539.25

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'
N N 0.0061 0.0033 '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'
La La -0.2871 2.4523 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      tetragonal
_space_group_IT_number           139
_space_group_name_H-M_alt        'I 4/m m m'
_space_group_name_Hall           '-I 4 2'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

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

_cell_length_a                   20.6040(6)
_cell_length_b                   20.6040(6)
_cell_length_c                   8.5110(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3613.1(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    2829
_cell_measurement_theta_min      3.233
_cell_measurement_theta_max      29.203


_exptl_crystal_description       needle
_exptl_crystal_colour            red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    0.991
_exptl_crystal_F_000             1052
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_exptl_absorpt_coefficient_mu    1.206
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.75299
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'Enhance (Mo) X-ray Source'
_diffrn_measurement_device_type  'Xcalibur, Onyx'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean 8.2634
_diffrn_reflns_number            6428
_diffrn_reflns_av_unetI/netI     0.0241
_diffrn_reflns_av_R_equivalents  0.0308
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         2.589
_diffrn_reflns_theta_max         29.400
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.897
_diffrn_measured_fraction_theta_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.897
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.897
_diffrn_reflns_point_group_measured_fraction_full 0.997
_reflns_number_total             1299
_reflns_number_gt                1059
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_structure_solution    SHELXS-97
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          ', SQUEEZE'
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0456P)²+9.1343P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         1299
_refine_ls_number_parameters     55
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0427
_refine_ls_R_factor_gt           0.0371
_refine_ls_wR_factor_ref         0.1004
_refine_ls_wR_factor_gt          0.0983
_refine_ls_goodness_of_fit_ref   1.121
_refine_ls_restrained_S_all      1.120
_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_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
La1 La 0.500000 0.000000 0.250000 0.02907(16) Uani 1 8 d S T P . .
O1 O 0.500000 -0.06112(18) 0.500000 0.0370(10) Uani 1 4 d S T P . .
C1 C 0.500000 -0.1258(3) 0.500000 0.0361(13) Uani 1 4 d S T P . .
C4 C 0.500000 -0.2601(2) 0.500000 0.0363(14) Uani 1 4 d S T P . .
C2 C 0.500000 -0.1595(2) 0.6388(6) 0.0579(15) Uani 1 2 d S T P . .
C5 C 0.500000 -0.3329(3) 0.500000 0.0357(15) Uani 1 4 d S T P . .
C3 C 0.500000 -0.2280(2) 0.6374(7) 0.0607(16) Uani 1 2 d DS T P . .
H3 H 0.500000 -0.250884 0.731621 0.073 Uiso 1 2 calc R U P . .
O2 O 0.500000 -0.1234(2) 0.7713(4) 0.122(3) Uani 1 2 d DS T P . .
H2 H 0.500000 -0.1451(11) 0.852(2) 0.146 Uiso 0.75 2 d DS U P . .
N1 N 0.57066(16) -0.42934(16) 0.500000 0.0399(13) Uani 1 4 d S T P . .
H1 H 0.541149 -0.458853 0.500000 0.048 Uiso 0.5 4 calc R U P . .
C6 C 0.55932(19) -0.36410(19) 0.500000 0.0406(11) Uani 1 2 d S T P . .
C7 C 0.6214(2) -0.3330(2) 0.500000 0.0637(17) Uani 1 2 d S T P . .
H7 H 0.628626 -0.288428 0.500000 0.076 Uiso 1 2 calc R U P . .


_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
La1 O1 2.4725(19) . ?
La1 O1 2.4726(19) 27 ?
La1 O1 2.4726(19) 17_656 ?
La1 O1 2.4726(19) 11_544 ?
La1 O2 2.549(4) 11_544 ?
La1 O2 2.549(4) 18_556 ?
La1 O2 2.549(4) 12_554 ?
La1 O2 2.549(4) 17_656 ?
O1 C1 1.332(6) . ?
C1 C2 1.370(6) 18_556 ?
C1 C2 1.370(6) . ?
C4 C3 1.344(6) 18_556 ?
C4 C3 1.344(6) . ?
C4 C5 1.498(7) . ?
C2 O2 1.351(6) . ?
C2 C3 1.411(6) . ?
C5 C6 1.381(5) . ?
C5 C6 1.381(5) 5_656 ?
C3 H3 0.9300 . ?
O2 H2 0.82(2) . ?
N1 C6 1.364(5) . ?
N1 C6 1.364(5) 7_646 ?
N1 H1 0.8600 . ?
C6 C7 1.431(6) . ?
C7 C7 1.329(10) 7_646 ?
C7 H7 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
O1 La1 O1 137.78(10) . 27 ?
O1 La1 O1 61.24(15) . 17_656 ?
O1 La1 O1 137.78(10) 27 17_656 ?
O1 La1 O1 137.78(10) . 11_544 ?
O1 La1 O1 61.25(15) 27 11_544 ?
O1 La1 O1 137.78(10) 17_656 11_544 ?
O1 La1 O2 86.50(7) . 11_544 ?
O1 La1 O2 124.69(11) 27 11_544 ?
O1 La1 O2 86.50(7) 17_656 11_544 ?
O1 La1 O2 63.45(11) 11_544 11_544 ?
O1 La1 O2 63.45(11) . 18_556 ?
O1 La1 O2 86.50(7) 27 18_556 ?
O1 La1 O2 124.69(11) 17_656 18_556 ?
O1 La1 O2 86.50(7) 11_544 18_556 ?
O2 La1 O2 90.289(12) 11_544 18_556 ?
O1 La1 O2 86.50(7) . 12_554 ?
O1 La1 O2 63.45(11) 27 12_554 ?
O1 La1 O2 86.50(7) 17_656 12_554 ?
O1 La1 O2 124.69(11) 11_544 12_554 ?
O2 La1 O2 171.86(17) 11_544 12_554 ?
O2 La1 O2 90.289(12) 18_556 12_554 ?
O1 La1 O2 124.69(11) . 17_656 ?
O1 La1 O2 86.50(7) 27 17_656 ?
O1 La1 O2 63.45(11) 17_656 17_656 ?
O1 La1 O2 86.50(7) 11_544 17_656 ?
O2 La1 O2 90.289(12) 11_544 17_656 ?
O2 La1 O2 171.86(17) 18_556 17_656 ?
O2 La1 O2 90.289(12) 12_554 17_656 ?
C1 O1 La1 120.62(7) . 17_656 ?
C1 O1 La1 120.62(7) . . ?
La1 O1 La1 118.76(15) 17_656 . ?
O1 C1 C2 120.5(3) . 18_556 ?
O1 C1 C2 120.5(3) . . ?
C2 C1 C2 119.1(5) 18_556 . ?
C3 C4 C3 121.0(5) 18_556 . ?
C3 C4 C5 119.5(3) 18_556 . ?
C3 C4 C5 119.5(3) . . ?
O2 C2 C1 116.1(4) . . ?
O2 C2 C3 123.9(5) . . ?
C1 C2 C3 120.0(5) . . ?
C6 C5 C6 124.4(5) . 5_656 ?
C6 C5 C4 117.8(2) . . ?
C6 C5 C4 117.8(2) 5_656 . ?
C4 C3 C2 120.0(5) . . ?
C4 C3 H3 120.0 . . ?
C2 C3 H3 120.0 . . ?
C2 O2 La1 119.4(3) . 17_656 ?
C2 O2 H2 113.4(16) . . ?
La1 O2 H2 127.3(16) 17_656 . ?
C6 N1 C6 109.7(5) . 7_646 ?
C6 N1 H1 125.1 . . ?
C6 N1 H1 125.1 7_646 . ?
N1 C6 C5 127.6(4) . . ?
N1 C6 C7 106.7(4) . . ?
C5 C6 C7 125.6(4) . . ?
C7 C7 C6 108.4(2) 7_646 . ?
C7 C7 H7 125.8 7_646 . ?
C6 C7 H7 125.8 . . ?

_refine_diff_density_max         0.593
_refine_diff_density_min         -0.729
_refine_diff_density_rms         0.078



_exptl_crystal_recrystallization_method 'solvothermal synthesis'
