# Electronic Supplementary Material (ESI) for Chemical Science.
# This journal is © The Royal Society of Chemistry 2020

####################################################################### 
# 
# 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_PCN-224'
_database_code_depnum_ccdc_archive 'CCDC 1992907'
loop_
_audit_author_name
_audit_author_address
'David Zee'
;Northwestern University
United States of America
;
_audit_update_record             
;
2020-03-26 deposited with the CCDC.	2020-05-07 downloaded from the CCDC.
;

# start Validation Reply Form
_vrf_PLAT213_PCN-224'            
;
PROBLEM: Atom O2              has ADP max/min Ratio .....        6.0 prolat
RESPONSE: The thermal ellipsoids of atoms in the Zr6 cluster (Zr1, O1, O2, O2A) 
are each prolate in shape. The long axes of these ellipsoids are perpendicular 
to the porphyrin linkers coordinated to the Zr6 cluster. Thus the elongated
ellipsoids of the Zr6 cluster are consistent with vibrations or breathing
behavior of the entire cluster perpendicular to the rigid/restrained direction.
elongated ellipsoids are attributed to vibration/breathing modes of the entire 
cluster within the evacuated crystal.

The atoms in the porphyrin linkers (N1, O3, C1>C8) display prolate ellipsoids 
pointing in the same direction to each other, and perpendicular to the MOF 
structural building unit (the Zr6 clusters). These features the porphyrin 
linkers vibrating in the evacuated crystal. 

The atoms in the acetate ligands coordinated to the Zr6 cluster (O4, O4A, C9,
C9A, C10, C10A, H10A>H10F) exhibit elongated thermal ellipsoids in the same
direction as the atoms in the Zr6 cluster. This phenomenon is consistent with
their coupled, coincident vibrational motion. The ellipsoids of atoms O4, C9, 
and C10 are further elongated due to wagging in the acetate ligands.
;
_vrf_PLAT602_PCN-224'            
;
PROBLEM: VERY LARGE Solvent Accessible VOID(S) in Structure        ! Info  
RESPONSE: The crystal is of an evacuated, porous metal-organic framework. The 
large, solvent accessible void space is expected, normal, and consistent with 
the experimentally measured surface area.
;
_vrf_PLAT049_PCN-224'            
;
PROBLEM: Calculated Density Less Than 1.0 gcm-3 .........     0.5085 Check 
RESPONSE: The crystal is of an evacuated, porous metal-organic framework. The 
low density is expected and normal.
;
_vrf_PLAT250_PCN-224'            
;
PROBLEM: Large U3/U1 Ratio for Average U(i,j) Tensor ....        4.2 Note  
RESPONSE: The atoms in the Zr6 clusters (Zr1, O1, O2) display elongated 
ellipsoids pointing in the same direction to each other, and perpendicular to 
the coordinated porphyrin linkers. The atoms in the porphyrin linkers 
(N1, O3, C1>C8) display elongated ellipsoids pointing in the same direction to 
each other, and perpendicular to the MOF structural building unit. These 
features are consistent with vibrational behavior in the cluster and linkers 
that occur within an evacuated crystal.
;

# end Validation Reply Form

_audit_creation_date             2020-02-24
_audit_creation_method           
;
Olex2 1.3
(compiled 2019.11.21 svn.r41b79517 for OlexSys, GUI svn.r6003)
;
_shelx_SHELXL_version_number     2018/3

_chemical_name_common            PCN-224'
_chemical_name_systematic        '[H2TCPP]3[Zr6O4(OH)4(CH3CO2)6]2'
_chemical_formula_moiety         'C168 H114 N12 O64 Zr12'
_chemical_formula_sum            'C168 H114 N12 O64 Zr12'
_chemical_formula_weight         4419.35
_chemical_melting_point          'not measured'

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Zr Zr -0.1862 2.2449 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      cubic
_space_group_IT_number           229
_space_group_name_H-M_alt        'I m -3 m'
_space_group_name_Hall           '-I 4 2 3'

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

_cell_length_a                   38.649(4)
_cell_length_b                   38.649(4)
_cell_length_c                   38.649(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     57731(19)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    9717
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      68.11
_cell_measurement_theta_min      3.62
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    1.942
_exptl_absorpt_correction_T_max  0.7530
_exptl_absorpt_correction_T_min  0.6926
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016) was used for absorption correction.
wR2(int) was 0.0528 before and 0.0466 after correction.
The Ratio of minimum to maximum transmission is 0.9198.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear dark violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    0.508
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       cuboctahedral
_exptl_crystal_F_000             8792
_exptl_crystal_preparation       
;
Single crystals were directly synthesized via solvothermal methods from ZrCl4,
DMF, benzoic acid, acetic acid, and tetrakis(carboxyphenyl)porphyrin.
;
_exptl_crystal_recrystallization_method 'See preparation details.'
_exptl_crystal_size_max          0.344
_exptl_crystal_size_mid          0.303
_exptl_crystal_size_min          0.264
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0364
_diffrn_reflns_av_unetI/netI     0.0106
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       45
_diffrn_reflns_limit_h_min       -46
_diffrn_reflns_limit_k_max       43
_diffrn_reflns_limit_k_min       -45
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            240641
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        66.566
_diffrn_reflns_theta_max         66.566
_diffrn_reflns_theta_min         1.616
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       'ω and φ scans'
_diffrn_radiation_monochromator  'Quazar optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_source                   microsource
_diffrn_source_current           0.64
_diffrn_source_power             0.0286272
_diffrn_source_voltage           44.73
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                4422
_reflns_number_total             4767
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'SAINT V8.34A (Bruker, 2017)'
_computing_data_collection       'APEX2 V2017.3 (Bruker, 2017)'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_refine_diff_density_max         1.248
_refine_diff_density_min         -0.574
_refine_diff_density_rms         0.076
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.132
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     139
_refine_ls_number_reflns         4767
_refine_ls_number_restraints     217
_refine_ls_R_factor_all          0.0610
_refine_ls_R_factor_gt           0.0563
_refine_ls_restrained_S_all      1.115
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0616P)²+175.0492P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1399
_refine_ls_wR_factor_ref         0.1450
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O4-C9 \\sim O4A-C9A
 with sigma of 0.02
 C9-C10 \\sim C9A-C10A
 with sigma of 0.02
 O4-C10 \\sim O4A-C10A
 with sigma of 0.04
3. Restrained planarity
 O4, O4_$2, C9, C10
 with sigma of 0.1
 O4A_$2, O4A_$8, C9A_$8, C10A_$8
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 O3, N1, C1, C2, C3, C4, C5, C6, C7, C8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Zr1, O1, O3, O2, O4, C9, C10, O4A, C9A, C10A, O2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(O4A)=1-FVAR(1)
 Sof(C9A)=Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=0.5*(1-FVAR(2))
 Sof(C9)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=0.5*FVAR(2)
 Sof(O4)=FVAR(1)
 Sof(O2A)=0.5*(1-FVAR(3))
 Sof(O2)=0.5*FVAR(3)
 Fixed Sof: H1(0.25)
7.a Aromatic/amide H refined with riding coordinates:
 N1(H1), C3(H3), C4(H4), C8(H8)
7.b Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C10A(H10D,H10E,H10F)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   ?
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
Zr1 Zr 0.27153(2) 0.20724(2) 0.20724(2) 0.04840(18) Uani 1 2 d S TU P . .
O1 O 0.21838(9) 0.21838(9) 0.21838(9) 0.0382(12) Uani 1 6 d S T P . .
O3 O 0.31440(5) 0.17244(5) 0.22232(6) 0.0522(6) Uani 1 1 d . U . . .
N1 N 0.44686(7) 0.000000 0.24967(12) 0.0523(11) Uani 1 2 d S TU P . .
H1 H 0.469605 0.000001 0.248524 0.063 Uiso 0.5 2 calc R U P . .
C1 C 0.33133(7) 0.16867(7) 0.250000 0.0494(11) Uani 1 2 d S TU P . .
C2 C 0.35884(6) 0.14116(6) 0.250000 0.0464(10) Uani 1 2 d S TU P . .
C3 C 0.36484(8) 0.12196(8) 0.22075(11) 0.0570(9) Uani 1 1 d . U . . .
H3 H 0.351674 0.126138 0.200417 0.068 Uiso 1 1 calc R U . . .
C4 C 0.39017(8) 0.09641(8) 0.22080(12) 0.0608(9) Uani 1 1 d . U . . .
H4 H 0.394091 0.083008 0.200573 0.073 Uiso 1 1 calc R U . . .
C5 C 0.40954(6) 0.09046(6) 0.250000 0.0519(12) Uani 1 2 d S TU P . .
C6 C 0.43701(6) 0.06299(6) 0.250000 0.0528(13) Uani 1 2 d S TU P . .
C7 C 0.42597(6) 0.02857(6) 0.25073(11) 0.0535(9) Uani 1 1 d . U . . .
C8 C 0.39058(6) 0.01737(7) 0.25256(12) 0.0623(11) Uani 1 1 d . U . . .
H8 H 0.370781 0.031901 0.253584 0.075 Uiso 1 1 calc R U . . .
O2 O 0.2906(3) 0.23681(17) 0.23681(17) 0.054(2) Uani 0.509(17) 2 d S TU P . 1
O4 O 0.24834(12) 0.15615(12) 0.20645(14) 0.0673(14) Uani 0.756(8) 1 d D U P . 1
C9 C 0.2244(2) 0.14201(19) 0.2244(2) 0.104(4) Uani 0.756(8) 2 d DS TU P . 1
C10 C 0.2174(4) 0.1050(2) 0.2174(4) 0.230(12) Uani 0.756(8) 2 d DS TU P . 1
H10A H 0.238988 0.091783 0.219504 0.345 Uiso 0.378(4) 1 calc R U P . 1
H10B H 0.208152 0.102347 0.193966 0.345 Uiso 0.378(4) 1 calc R U P . 1
H10C H 0.200535 0.096234 0.234205 0.345 Uiso 0.378(4) 1 calc R U P . 1
O4A O 0.2522(4) 0.1501(4) 0.1919(4) 0.074(4) Uani 0.244(8) 1 d D U P . 2
C9A C 0.2441(5) 0.1613(4) 0.1613(4) 0.085(6) Uani 0.244(8) 2 d DS TU P . 2
C10A C 0.2249(12) 0.1379(6) 0.1379(6) 0.169(17) Uani 0.244(8) 2 d DS TU P . 2
H10D H 0.225505 0.114267 0.147145 0.253 Uiso 0.122(4) 1 calc R U P . 2
H10E H 0.235704 0.138168 0.114908 0.253 Uiso 0.122(4) 1 calc R U P . 2
H10F H 0.200840 0.145595 0.135977 0.253 Uiso 0.122(4) 1 calc R U P . 2
O2A O 0.25849(11) 0.1878(3) 0.25849(11) 0.035(3) Uani 0.491(17) 2 d S T P . 2


_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
Zr1 O1 2.1426(19) . ?
Zr1 O3 2.2121(19) . ?
Zr1 O3 2.2121(19) 67 ?
Zr1 O2 2.188(6) 38 ?
Zr1 O2 2.188(6) 48 ?
Zr1 O2 1.776(11) . ?
Zr1 O2 2.188(6) 81 ?
Zr1 O2 2.188(6) 77 ?
Zr1 O4 2.168(5) . ?
Zr1 O4 2.168(5) 67 ?
Zr1 O4A 2.404(17) . ?
Zr1 O4A 2.404(17) 67 ?
O3 C1 1.263(3) . ?
N1 H1 0.8800 . ?
N1 C7 1.369(3) 51 ?
N1 C7 1.369(3) . ?
C1 C2 1.504(5) . ?
C2 C3 1.372(4) 38 ?
C2 C3 1.372(4) . ?
C3 H3 0.9500 . ?
C3 C4 1.391(4) . ?
C4 H4 0.9500 . ?
C4 C5 1.373(4) . ?
C5 C6 1.502(5) . ?
C6 C7 1.397(3) 38 ?
C6 C7 1.397(3) . ?
C7 C8 1.436(3) . ?
C8 C8 1.343(5) 51 ?
C8 H8 0.9500 . ?
O2 O2 0.00(4) 67 ?
O4 C9 1.279(6) . ?
C9 C10 1.482(13) . ?
C10 H10A 0.98(15) 72 ?
C10 H10A 0.9800 . ?
C10 H10B 0.9800 . ?
C10 H10B 0.98(7) 72 ?
C10 H10C 0.980(17) 72 ?
C10 H10C 0.9800 . ?
O4A C9A 1.297(15) . ?
C9A C10A 1.48(2) . ?
C10A H10D 0.98(19) 67 ?
C10A H10D 0.9800 . ?
C10A H10E 0.9800 . ?
C10A H10E 0.98(3) 67 ?
C10A H10F 1.0(3) 67 ?
C10A H10F 0.9800 . ?
O2A O2A 0.00(3) 72 ?

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 Zr1 O3 141.94(5) . 67 ?
O1 Zr1 O3 141.94(5) . . ?
O1 Zr1 O2 69.7(2) . 48 ?
O1 Zr1 O2 69.7(2) . 38 ?
O1 Zr1 O2 69.7(2) . 77 ?
O1 Zr1 O2 69.7(2) . 81 ?
O1 Zr1 O4 77.84(15) . 67 ?
O1 Zr1 O4 77.85(15) . . ?
O1 Zr1 O4A 86.3(4) . 67 ?
O1 Zr1 O4A 86.3(4) . . ?
O3 Zr1 O3 76.08(10) . 67 ?
O3 Zr1 O4A 108.9(4) 67 . ?
O3 Zr1 O4A 74.9(3) 67 67 ?
O3 Zr1 O4A 108.9(4) . 67 ?
O3 Zr1 O4A 74.9(3) . . ?
O2 Zr1 O1 98.0(3) . . ?
O2 Zr1 O3 134.5(3) 81 . ?
O2 Zr1 O3 82.72(17) 38 . ?
O2 Zr1 O3 134.5(3) 77 67 ?
O2 Zr1 O3 134.5(3) 38 67 ?
O2 Zr1 O3 84.9(2) . . ?
O2 Zr1 O3 82.72(17) 81 67 ?
O2 Zr1 O3 84.9(2) . 67 ?
O2 Zr1 O3 134.5(3) 48 . ?
O2 Zr1 O3 82.72(17) 77 . ?
O2 Zr1 O3 82.72(17) 48 67 ?
O2 Zr1 O2 84.4(5) 77 81 ?
O2 Zr1 O2 53.1(4) . 81 ?
O2 Zr1 O2 0.0(5) 48 81 ?
O2 Zr1 O2 53.1(4) . 77 ?
O2 Zr1 O2 84.4(5) 77 48 ?
O2 Zr1 O2 53.1(4) . 48 ?
O2 Zr1 O2 84.4(5) 38 48 ?
O2 Zr1 O2 53.1(4) . 38 ?
O2 Zr1 O2 0.0(3) 77 38 ?
O2 Zr1 O2 84.4(5) 38 81 ?
O2 Zr1 O4 140.01(15) . . ?
O2 Zr1 O4 140.02(15) . 67 ?
O2 Zr1 O4A 151.4(4) . 67 ?
O2 Zr1 O4A 103.5(5) 48 67 ?
O2 Zr1 O4A 150.6(4) 77 67 ?
O2 Zr1 O4A 150.6(4) 38 67 ?
O2 Zr1 O4A 103.5(5) 81 67 ?
O4 Zr1 O3 76.10(14) . . ?
O4 Zr1 O3 122.75(13) . 67 ?
O4 Zr1 O3 76.10(14) 67 67 ?
O4 Zr1 O3 122.76(13) 67 . ?
O4 Zr1 O2 89.3(3) 67 81 ?
O4 Zr1 O2 147.1(2) 67 77 ?
O4 Zr1 O2 147.1(2) . 81 ?
O4 Zr1 O2 147.1(2) . 48 ?
O4 Zr1 O2 89.3(3) 67 48 ?
O4 Zr1 O2 147.1(2) 67 38 ?
O4 Zr1 O2 89.3(3) . 77 ?
O4 Zr1 O2 89.3(3) . 38 ?
O4 Zr1 O4 78.7(3) . 67 ?
O4 Zr1 O4A 14.6(3) 67 67 ?
O4 Zr1 O4A 68.6(4) . 67 ?
O4A Zr1 O4A 56.7(7) . 67 ?
Zr1 O1 Zr1 110.18(14) 5 . ?
Zr1 O1 Zr1 110.18(14) 5 72 ?
Zr1 O1 Zr1 110.18(14) . 72 ?
C1 O3 Zr1 133.0(2) . . ?
C7 N1 H1 126.2 51 . ?
C7 N1 H1 126.2 . . ?
C7 N1 C7 107.6(3) . 51 ?
O3 C1 O3 126.7(3) 38 . ?
O3 C1 C2 116.64(17) 38 . ?
O3 C1 C2 116.64(17) . . ?
C3 C2 C1 120.12(18) 38 . ?
C3 C2 C1 120.12(18) . . ?
C3 C2 C3 119.8(4) 38 . ?
C2 C3 H3 119.9 . . ?
C2 C3 C4 120.1(4) . . ?
C4 C3 H3 119.9 . . ?
C3 C4 H4 119.9 . . ?
C5 C4 C3 120.2(4) . . ?
C5 C4 H4 119.9 . . ?
C4 C5 C4 119.5(4) . 38 ?
C4 C5 C6 120.24(19) 38 . ?
C4 C5 C6 120.24(19) . . ?
C7 C6 C5 117.21(16) . . ?
C7 C6 C5 117.21(16) 38 . ?
C7 C6 C7 125.6(3) 38 . ?
N1 C7 C6 126.0(2) . . ?
N1 C7 C8 108.7(2) . . ?
C6 C7 C8 125.4(2) . . ?
C7 C8 H8 126.2 . . ?
C8 C8 C7 107.54(14) 51 . ?
C8 C8 H8 126.2 51 . ?
Zr1 O2 Zr1 106.8(4) 38 48 ?
Zr1 O2 Zr1 0.000(18) 38 77 ?
Zr1 O2 Zr1 123.9(3) . 38 ?
Zr1 O2 Zr1 123.9(3) . 77 ?
Zr1 O2 Zr1 123.9(3) . 48 ?
Zr1 O2 Zr1 106.8(4) 77 48 ?
O2 O2 Zr1 0(8) 67 77 ?
O2 O2 Zr1 0(5) 67 . ?
O2 O2 Zr1 0(8) 67 38 ?
O2 O2 Zr1 0(2) 67 48 ?
C9 O4 Zr1 132.9(5) . . ?
O4 C9 O4 127.0(8) . 72 ?
O4 C9 C10 116.5(4) 72 . ?
O4 C9 C10 116.5(4) . . ?
C9 C10 H10A 109(5) . 72 ?
C9 C10 H10A 109.5 . . ?
C9 C10 H10B 109.5 . . ?
C9 C10 H10B 109.5(12) . 72 ?
C9 C10 H10C 109.5 . . ?
C9 C10 H10C 109.5(5) . 72 ?
H10A C10 H10A 65.8 . 72 ?
H10A C10 H10B 109.5 . . ?
H10A C10 H10B 139.7 . 72 ?
H10A C10 H10B 109.5 72 72 ?
H10A C10 H10C 109.5 . . ?
H10A C10 H10C 46.6 . 72 ?
H10A C10 H10C 109.5 72 72 ?
H10B C10 H10A 139.7 . 72 ?
H10B C10 H10B 46.6 . 72 ?
H10B C10 H10C 109.5 72 72 ?
H10B C10 H10C 65.8 . 72 ?
H10B C10 H10C 109.5 . . ?
H10C C10 H10A 46.6 . 72 ?
H10C C10 H10B 65.8 . 72 ?
H10C C10 H10C 139.7 . 72 ?
C9A O4A Zr1 89.7(13) . . ?
O4A C9A O4A 123(2) . 67 ?
O4A C9A C10A 118.4(12) 67 . ?
O4A C9A C10A 118.4(12) . . ?
C9A C10A H10D 109.5 . . ?
C9A C10A H10D 109(4) . 67 ?
C9A C10A H10E 109(10) . 67 ?
C9A C10A H10E 109.5 . . ?
C9A C10A H10F 109(10) . 67 ?
C9A C10A H10F 109.5 . . ?
H10D C10A H10D 132.9 . 67 ?
H10D C10A H10E 31.1 . 67 ?
H10D C10A H10E 109.5 . . ?
H10D C10A H10E 109.5 67 67 ?
H10D C10A H10F 80.9 . 67 ?
H10D C10A H10F 109.5 . . ?
H10D C10A H10F 109.5 67 67 ?
H10E C10A H10D 31.1 . 67 ?
H10E C10A H10E 80.9 . 67 ?
H10E C10A H10F 109.5 67 67 ?
H10E C10A H10F 132.9 . 67 ?
H10E C10A H10F 109.5 . . ?
H10F C10A H10D 80.9 . 67 ?
H10F C10A H10E 132.9 . 67 ?
H10F C10A H10F 31.1 . 67 ?
Zr1 O2A Zr1 98.4(4) 72 38 ?
Zr1 O2A Zr1 98.4(4) 72 77 ?
Zr1 O2A Zr1 0.00(3) 77 38 ?
O2A O2A Zr1 0.0(15) 72 77 ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Zr1 O3 C1 O3 -0.84(12) . . . 38 ?
Zr1 O3 C1 C2 179.17(12) . . . . ?
Zr1 O4 C9 O4 2.0(16) . . . 72 ?
Zr1 O4 C9 C10 -175.8(10) . . . . ?
Zr1 O4A C9A O4A 8.7(19) . . . 67 ?
Zr1 O4A C9A C10A -172(2) . . . . ?
O1 Zr1 O2 Zr1 -75.2(4) . . . 48 ?
O1 Zr1 O2 Zr1 75.2(4) . . . 77 ?
O1 Zr1 O2 Zr1 75.2(4) . . . 38 ?
O1 Zr1 O2 O2 0.00(3) . . . 67 ?
O3 Zr1 O2 Zr1 -143.0(4) 67 . . 38 ?
O3 Zr1 O2 Zr1 -66.5(4) . . . 77 ?
O3 Zr1 O2 Zr1 66.5(4) 67 . . 48 ?
O3 Zr1 O2 Zr1 -143.0(4) 67 . . 77 ?
O3 Zr1 O2 Zr1 143.0(4) . . . 48 ?
O3 Zr1 O2 Zr1 -66.5(4) . . . 38 ?
O3 Zr1 O2 O2 0.000(19) 67 . . 67 ?
O3 Zr1 O2 O2 0.00(5) . . . 67 ?
O3 C1 C2 C3 -179.10(19) . . . 38 ?
O3 C1 C2 C3 -179.11(19) 38 . . . ?
O3 C1 C2 C3 0.90(19) 38 . . 38 ?
O3 C1 C2 C3 0.89(19) . . . . ?
N1 C7 C8 C8 0.0(4) . . . 51 ?
C1 C2 C3 C4 -179.7(2) . . . . ?
C2 C3 C4 C5 -0.6(5) . . . . ?
C3 C2 C3 C4 0.3(2) 38 . . . ?
C3 C4 C5 C4 0.3(2) . . . 38 ?
C3 C4 C5 C6 -179.7(2) . . . . ?
C4 C5 C6 C7 -73.3(2) 38 . . 38 ?
C4 C5 C6 C7 106.7(2) 38 . . . ?
C4 C5 C6 C7 -73.3(2) . . . . ?
C4 C5 C6 C7 106.7(2) . . . 38 ?
C5 C6 C7 N1 177.6(4) . . . . ?
C5 C6 C7 C8 -2.0(5) . . . . ?
C6 C7 C8 C8 179.7(3) . . . 51 ?
C7 N1 C7 C6 -179.67(16) 51 . . . ?
C7 N1 C7 C8 0.1(6) 51 . . . ?
C7 C6 C7 N1 -2.4(4) 38 . . . ?
C7 C6 C7 C8 178.0(5) 38 . . . ?
O2 Zr1 O2 Zr1 -132.3(4) 38 . . 48 ?
O2 Zr1 O2 Zr1 132.3(4) 48 . . 38 ?
O2 Zr1 O2 Zr1 18.2(4) 38 . . 77 ?
O2 Zr1 O2 Zr1 132.3(4) 81 . . 77 ?
O2 Zr1 O2 Zr1 18.2(4) 77 . . 38 ?
O2 Zr1 O2 Zr1 18.2(4) 77 . . 77 ?
O2 Zr1 O2 Zr1 -18.2(4) 48 . . 48 ?
O2 Zr1 O2 Zr1 -132.3(4) 77 . . 48 ?
O2 Zr1 O2 Zr1 18.2(4) 38 . . 38 ?
O2 Zr1 O2 Zr1 132.3(4) 48 . . 77 ?
O2 Zr1 O2 Zr1 -18.2(4) 81 . . 48 ?
O2 Zr1 O2 Zr1 132.3(4) 81 . . 38 ?
O2 Zr1 O2 O2 0.0(2) 38 . . 67 ?
O2 Zr1 O2 O2 0.00(13) 81 . . 67 ?
O2 Zr1 O2 O2 0.0(2) 77 . . 67 ?
O2 Zr1 O2 O2 0.00(13) 48 . . 67 ?
O4 Zr1 O2 Zr1 155.8(2) 67 . . 38 ?
O4 Zr1 O2 Zr1 -5.3(7) . . . 77 ?
O4 Zr1 O2 Zr1 155.8(2) 67 . . 77 ?
O4 Zr1 O2 Zr1 -5.3(7) . . . 38 ?
O4 Zr1 O2 Zr1 5.3(7) 67 . . 48 ?
O4 Zr1 O2 Zr1 -155.8(2) . . . 48 ?
O4 Zr1 O2 O2 0.0(3) 67 . . 67 ?
O4 Zr1 O2 O2 0.0(3) . . . 67 ?

_olex2_exptl_crystal_mounting_method 
;
In a solvent-free, dinitrogen-filled glovebox, activated crystals were coated 
with Paratone-N oil. The crystals were removed from the glovebox. A suitable 
single crystal was mounted on a MiTeGen loop, and cooled under a stream of N2 
at 100 K for collection.
;
_olex2_submission_original_sample_id PCN-224'
_olex2_submission_special_instructions 'No special instructions were received'
####################################################################### 
# 
# 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_PCN-224'FeCl
_database_code_depnum_ccdc_archive 'CCDC 1992908'
loop_
_audit_author_name
_audit_author_address
'David Zee'
;Northwestern University
United States of America
;
_audit_update_record             
;
2020-03-26 deposited with the CCDC.	2020-05-07 downloaded from the CCDC.
;

# start Validation Reply Form
_vrf_PLAT213_PCN-224'FeCl        
;
PROBLEM: Atom C6              has ADP max/min Ratio .....        5.4 prolat
RESPONSE: The atoms in the heme linkers (Fe1, N1, O3, C1>C8) display prolate 
ellipsoids pointing in the same direction to each other. This phenomenon is due
to two reasons: 1) The heme ligand vibrates in the direction perpendicular to
the MOF structural building unit (the Zr6 clusters); 2) the ferric heme 
exhibits "doming" that is typical of high-spin Fe3+ porphyrins, but that 
disorder could not be adequately modeled because of the proximity between the
heme and the crystallographic mirror plane. 

The thermal ellipsoids of atoms in the Zr6 cluster (Zr1, O1, O2, O2A) 
are each prolate in shape. The long axes of these ellipsoids are perpendicular 
to the porphyrin linkers coordinated to the Zr6 cluster. Thus the elongated
ellipsoids of the Zr6 cluster are consistent with vibrations or breathing
behavior of the entire cluster perpendicular to the rigid/restrained direction.
elongated ellipsoids are attributed to vibration/breathing modes of the entire 
cluster within the evacuated crystal.

The atoms in the acetate ligands coordinated to the Zr6 cluster (O4, O4A, C9,
C9A, C10, C10A, H10A>H10F) exhibit elongated thermal ellipsoids in the same
direction as the atoms in the Zr6 cluster. This phenomenon is consistent with
their coupled, coincident vibrational motion. The ellipsoids of atoms O4, C9, 
and C10 are further elongated due to wagging in the acetate ligands.

;
_vrf_PLAT215_PCN-224'FeCl        
;
PROBLEM: Disordered Fe1       has ADP max/min Ratio .....        5.4 Note  
RESPONSE: The Fe1 atom in the heme linkers is modeled as disordered over two
positions, either side of the porphyrin ligand. This is consistent with doming
that is commonly observed in axially ligated 5-coordinate ferric hemes. 
display prolate 
ellipsoids pointing in the same direction to each other. This phenomenon is due
to two reasons: 1) The heme ligand vibrates in the direction perpendicular to
the MOF structural building unit (the Zr6 clusters); 2) the ferric heme 
exhibits "doming" that is typical of high-spin Fe3+ porphyrins, but that 
disorder could not be adequately modeled because of the proximity between the
heme and the crystallographic mirror plane.
;
_vrf_PLAT602_PCN-224'FeCl        
;
PROBLEM: VERY LARGE Solvent Accessible VOID(S) in Structure        ! Info  
RESPONSE: The crystal is of an evacuated, porous metal-organic framework. The 
large, solvent accessible void space is expected, normal, and consistent with 
the experimentally measured surface area.
;
_vrf_PLAT049_PCN-224'FeCl        
;
PROBLEM: Calculated Density Less Than 1.0 gcm-3 .........     0.5460 Check 
RESPONSE: The crystal is of an evacuated, porous metal-organic framework. The 
low density is expected and normal.
;
_vrf_PLAT250_PCN-224'FeCl        
;
PROBLEM: Large U3/U1 Ratio for Average U(i,j) Tensor ....        5.8 Note  
RESPONSE: Visual inspection of the thermal ellipsoid plot shows rigidly bonded
atoms have their major axes pointing in the same direction. Thus the large 
U3/U1 parameter likely reflects thermal motion in the evacuated structure, and
not errors in the data or model. 
;
# end Validation Reply Form

_audit_creation_date             2020-02-24
_audit_creation_method           
;
Olex2 1.3
(compiled 2019.11.21 svn.r41b79517 for OlexSys, GUI svn.r6003)
;
_shelx_SHELXL_version_number     2018/3

_chemical_name_common            PCN-224'FeCl
_chemical_name_systematic        '[FeCl(TCPP)]3[ZrO4(OH)4(CH3CO2)6]2'
_chemical_formula_moiety         'C168 H108 Cl3 Fe3 N12 O64 Zr12'
_chemical_formula_sum            'C168 H108 Cl3 Fe3 N12 O64 Zr12'
_chemical_formula_weight         4687.20
_chemical_melting_point          'not measured'

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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'
Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Fe Fe -1.1336 3.1974 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Zr Zr -0.1862 2.2449 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      cubic
_space_group_IT_number           229
_space_group_name_H-M_alt        'I m -3 m'
_space_group_name_Hall           '-I 4 2 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x, z'
'-x, -y, z'
'y, -x, z'
'x, -z, y'
'x, -y, -z'
'x, z, -y'
'z, y, -x'
'-x, y, -z'
'-z, y, x'
'z, x, y'
'y, z, x'
'-y, -z, x'
'z, -x, -y'
'-y, z, -x'
'-z, -x, y'
'-z, x, -y'
'y, -z, -x'
'y, x, -z'
'-y, -x, -z'
'-x, z, y'
'-x, -z, -y'
'z, -y, x'
'-z, -y, -x'
'x+1/2, y+1/2, z+1/2'
'-y+1/2, x+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'y+1/2, -x+1/2, z+1/2'
'x+1/2, -z+1/2, y+1/2'
'x+1/2, -y+1/2, -z+1/2'
'x+1/2, z+1/2, -y+1/2'
'z+1/2, y+1/2, -x+1/2'
'-x+1/2, y+1/2, -z+1/2'
'-z+1/2, y+1/2, x+1/2'
'z+1/2, x+1/2, y+1/2'
'y+1/2, z+1/2, x+1/2'
'-y+1/2, -z+1/2, x+1/2'
'z+1/2, -x+1/2, -y+1/2'
'-y+1/2, z+1/2, -x+1/2'
'-z+1/2, -x+1/2, y+1/2'
'-z+1/2, x+1/2, -y+1/2'
'y+1/2, -z+1/2, -x+1/2'
'y+1/2, x+1/2, -z+1/2'
'-y+1/2, -x+1/2, -z+1/2'
'-x+1/2, z+1/2, y+1/2'
'-x+1/2, -z+1/2, -y+1/2'
'z+1/2, -y+1/2, x+1/2'
'-z+1/2, -y+1/2, -x+1/2'
'-x, -y, -z'
'y, -x, -z'
'x, y, -z'
'-y, x, -z'
'-x, z, -y'
'-x, y, z'
'-x, -z, y'
'-z, -y, x'
'x, -y, z'
'z, -y, -x'
'-z, -x, -y'
'-y, -z, -x'
'y, z, -x'
'-z, x, y'
'y, -z, x'
'z, x, -y'
'z, -x, y'
'-y, z, x'
'-y, -x, z'
'y, x, z'
'x, -z, -y'
'x, z, y'
'-z, y, -x'
'z, y, x'
'-x+1/2, -y+1/2, -z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'x+1/2, y+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'-x+1/2, z+1/2, -y+1/2'
'-x+1/2, y+1/2, z+1/2'
'-x+1/2, -z+1/2, y+1/2'
'-z+1/2, -y+1/2, x+1/2'
'x+1/2, -y+1/2, z+1/2'
'z+1/2, -y+1/2, -x+1/2'
'-z+1/2, -x+1/2, -y+1/2'
'-y+1/2, -z+1/2, -x+1/2'
'y+1/2, z+1/2, -x+1/2'
'-z+1/2, x+1/2, y+1/2'
'y+1/2, -z+1/2, x+1/2'
'z+1/2, x+1/2, -y+1/2'
'z+1/2, -x+1/2, y+1/2'
'-y+1/2, z+1/2, x+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, x+1/2, z+1/2'
'x+1/2, -z+1/2, -y+1/2'
'x+1/2, z+1/2, y+1/2'
'-z+1/2, y+1/2, -x+1/2'
'z+1/2, y+1/2, x+1/2'

_cell_length_a                   38.4891(9)
_cell_length_b                   38.4891(9)
_cell_length_c                   38.4891(9)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     57018(4)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    9484
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      63.721
_cell_measurement_theta_min      3.631
_shelx_estimated_absorpt_T_max   0.591
_shelx_estimated_absorpt_T_min   0.555
_exptl_absorpt_coefficient_mu    2.687
_exptl_absorpt_correction_T_max  0.7524
_exptl_absorpt_correction_T_min  0.6566
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016) was used for absorption correction.
wR2(int) was 0.0422 before and 0.0334 after correction.
The Ratio of minimum to maximum transmission is 0.8727.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear dark violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    0.546
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       cuboctahedral
_exptl_crystal_F_000             9284
_exptl_crystal_preparation       ?
_exptl_crystal_recrystallization_method 
'See Experimental Section in Supporting Information'
_exptl_crystal_size_max          0.248
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.219
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0524
_diffrn_reflns_av_unetI/netI     0.0168
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       44
_diffrn_reflns_limit_h_min       -42
_diffrn_reflns_limit_k_max       44
_diffrn_reflns_limit_k_min       -44
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            167138
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        63.832
_diffrn_reflns_theta_max         63.832
_diffrn_reflns_theta_min         3.248
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       'ω and φ scans'
_diffrn_radiation_monochromator  'Quazar optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_source                   microsource
_diffrn_source_current           0.64
_diffrn_source_power             0.0286336
_diffrn_source_voltage           44.74
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                3868
_reflns_number_total             4417
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'SAINT V8.34A (Bruker, 2017)'
_computing_data_collection       'APEX2 V2017.3 (Bruker, 2017)'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_refine_diff_density_max         0.937
_refine_diff_density_min         -0.489
_refine_diff_density_rms         0.099
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.191
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     145
_refine_ls_number_reflns         4417
_refine_ls_number_restraints     128
_refine_ls_R_factor_all          0.0844
_refine_ls_R_factor_gt           0.0733
_refine_ls_restrained_S_all      1.180
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1299P)²+126.4133P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2249
_refine_ls_wR_factor_ref         0.2456
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C10-C9 \\sim C10A-C9A
 with sigma of 0.02
 C10A-O4 \\sim O4A-C10
 with sigma of 0.04
 C9-O4 \\sim O4A-C9A
 with sigma of 0.02
3. Restrained planarity
 O4, O4_$2, C9, C10
 with sigma of 0.1
 O4A_$1, O4A, C9A, C10A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 0.9A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 0.9A
Uanis(C10) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
5. Rigid body (RIGU) restrains
 Zr1, O1, O2, O4, C9, C10, O2A, O4A, C9A, C10A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Fe1, Cl1, O3, N1, C1, C2, C3, C4, C5, C6, C7, C8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(O4A)=1-FVAR(1)
 Sof(C9A)=Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=0.5*(1-FVAR(2))
 Sof(C9)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=0.5*FVAR(2)
 Sof(O4)=FVAR(1)
 Sof(O2A)=0.5*(1-FVAR(3))
 Sof(O2)=0.5*FVAR(3)
 Fixed Sof: Fe1(0.125) Cl1(0.125)
7.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C8(H8)
7.b Idealised Me refined with riding coordinates:
 C10(H10A,H10B,H10C), C10A(H10D,H10E,H10F)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   ?
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
Zr1 Zr 0.29310(2) 0.29310(2) 0.22862(2) 0.1322(7) Uani 1 2 d S T P . .
Fe1 Fe 0.26494(19) 0.500000 0.000000 0.139(5) Uani 0.5 4 d S T P . .
Cl1 Cl 0.3228(5) 0.500000 0.000000 0.191(6) Uani 0.5 4 d S T P . .
O1 O 0.28189(19) 0.28189(19) 0.28189(19) 0.095(3) Uani 1 6 d S T P . .
O3 O 0.27801(13) 0.32775(11) 0.18577(12) 0.135(2) Uani 1 1 d . . . . .
N1 N 0.2501(3) 0.500000 0.05212(12) 0.145(4) Uani 1 2 d S T P . .
C1 C 0.250000 0.33107(12) 0.16893(12) 0.123(3) Uani 1 2 d S T P . .
C2 C 0.250000 0.35894(11) 0.14106(11) 0.112(3) Uani 1 2 d S T P . .
C3 C 0.2797(2) 0.37781(14) 0.13533(14) 0.126(3) Uani 1 1 d . . . . .
H3 H 0.300047 0.373313 0.148550 0.151 Uiso 1 1 calc R U . . .
C4 C 0.2797(3) 0.40377(14) 0.10982(14) 0.140(3) Uani 1 1 d . . . . .
H4 H 0.299941 0.417351 0.105788 0.167 Uiso 1 1 calc R U . . .
C5 C 0.250000 0.40931(12) 0.09069(12) 0.130(4) Uani 1 2 d S T P . .
C6 C 0.250000 0.43705(9) 0.06295(9) 0.147(5) Uani 1 2 d S T P . .
C7 C 0.2492(3) 0.47165(11) 0.07362(10) 0.146(4) Uani 1 1 d . . . . .
C8 C 0.2471(3) 0.48256(11) 0.10913(10) 0.159(4) Uani 1 1 d . . . . .
H8 H 0.245962 0.467890 0.128944 0.191 Uiso 1 1 calc R U . . .
O2 O 0.2636(3) 0.2636(3) 0.2098(5) 0.105(5) Uani 0.56(3) 2 d S T P . 1
O4 O 0.3431(4) 0.2918(4) 0.2493(4) 0.151(5) Uani 0.608(15) 1 d D U P . 1
C9 C 0.3571(5) 0.2740(5) 0.2740(5) 0.239(16) Uani 0.608(15) 2 d DS T P . 1
C10 C 0.3936(6) 0.2821(12) 0.2821(12) 0.45(4) Uani 0.608(15) 2 d DS TU P . 1
H10A H 0.408671 0.272239 0.264131 0.674 Uiso 0.304(7) 1 calc R U P . 1
H10B H 0.399668 0.272120 0.304724 0.674 Uiso 0.304(7) 1 calc R U P . 1
H10C H 0.396689 0.307368 0.282871 0.674 Uiso 0.304(7) 1 calc R U P . 1
O2A O 0.2442(3) 0.3158(5) 0.2442(3) 0.088(7) Uani 0.44(3) 2 d S T P . 2
O4A O 0.3524(6) 0.3107(7) 0.2539(7) 0.178(9) Uani 0.392(15) 1 d D U P . 2
C9A C 0.3429(7) 0.3429(7) 0.2606(8) 0.179(14) Uani 0.392(15) 2 d DS T P . 2
C10A C 0.3681(8) 0.3681(8) 0.2756(16) 0.32(3) Uani 0.392(15) 2 d DS T P . 2
H10D H 0.391360 0.363201 0.266566 0.479 Uiso 0.196(7) 1 calc R U P . 2
H10E H 0.368173 0.365831 0.300978 0.479 Uiso 0.392(15) 2 calc R U P . 2
H10F H 0.361241 0.391742 0.269208 0.479 Uiso 0.196(7) 1 calc R U P . 2


_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
Zr1 O1 2.139(4) . ?
Zr1 O3 2.199(4) 68 ?
Zr1 O3 2.199(4) . ?
Zr1 O2 1.76(2) . ?
Zr1 O2 2.205(11) 84 ?
Zr1 O2 2.205(11) 83 ?
Zr1 O4 2.083(16) . ?
Zr1 O4 2.083(16) 68 ?
Zr1 O2A 2.160(6) 12 ?
Zr1 O2A 2.160(6) . ?
Zr1 O4A 2.57(3) . ?
Zr1 O4A 2.57(3) 68 ?
Fe1 Fe1 1.150(14) 77 ?
Fe1 Cl1 2.23(2) . ?
Fe1 N1 2.089(6) 77 ?
Fe1 N1 2.085(6) 51 ?
Fe1 N1 2.089(6) 79_554 ?
Fe1 N1 2.085(6) . ?
O3 C1 1.264(6) . ?
N1 C7 1.370(5) . ?
N1 C7 1.370(5) 57_565 ?
C1 C2 1.517(8) . ?
C2 C3 1.372(8) 46 ?
C2 C3 1.372(9) . ?
C3 H3 0.9500 . ?
C3 C4 1.401(7) . ?
C4 H4 0.9500 . ?
C4 C5 1.377(9) . ?
C5 C6 1.510(8) . ?
C6 C7 1.394(5) 46 ?
C6 C7 1.394(5) . ?
C7 C8 1.432(5) . ?
C8 C8 1.342(9) 57_565 ?
C8 H8 0.9500 . ?
O2 O2 1.79(2) 84 ?
O2 O2 1.79(2) 83 ?
O4 C9 1.289(15) . ?
C9 C10 1.47(3) . ?
C10 H10A 0.9800 70 ?
C10 H10A 0.9800 . ?
C10 H10B 0.9802 70 ?
C10 H10B 0.9800 . ?
C10 H10C 0.9801 70 ?
C10 H10C 0.9800 . ?
O4A C9A 1.31(2) 68 ?
O4A C9A 1.31(2) . ?
C9A C9A 0.00(15) 68 ?
C9A C10A 1.49(4) . ?
C10A H10D 0.9799 68 ?
C10A H10D 0.9800 . ?
C10A H10E 0.9801 68 ?
C10A H10E 0.9800 . ?
C10A H10F 0.9800 . ?
C10A H10F 0.9800 68 ?

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 Zr1 O3 141.99(9) . . ?
O1 Zr1 O3 141.99(9) . 68 ?
O1 Zr1 O2 70.1(4) . 84 ?
O1 Zr1 O2 70.1(4) . 83 ?
O1 Zr1 O2A 68.9(2) . . ?
O1 Zr1 O2A 68.9(2) . 12 ?
O1 Zr1 O4A 82.5(6) . . ?
O1 Zr1 O4A 82.5(6) . 68 ?
O3 Zr1 O3 75.99(17) . 68 ?
O3 Zr1 O2 82.6(3) . 84 ?
O3 Zr1 O2 133.5(5) . 83 ?
O3 Zr1 O2 82.6(3) 68 83 ?
O3 Zr1 O2 133.5(5) 68 84 ?
O3 Zr1 O4A 79.4(5) 68 . ?
O3 Zr1 O4A 111.0(6) 68 68 ?
O3 Zr1 O4A 79.4(5) . 68 ?
O3 Zr1 O4A 111.0(6) . . ?
O2 Zr1 O1 97.7(6) . . ?
O2 Zr1 O3 85.0(4) . 68 ?
O2 Zr1 O3 85.0(4) . . ?
O2 Zr1 O2 52.1(8) . 84 ?
O2 Zr1 O2 83.2(9) 83 84 ?
O2 Zr1 O2 52.1(8) . 83 ?
O2 Zr1 O4 137.4(5) . . ?
O2 Zr1 O4 137.4(5) . 68 ?
O2 Zr1 O2A 79.2(8) . 12 ?
O2 Zr1 O4A 153.8(5) . 68 ?
O2 Zr1 O4A 147.1(7) 83 68 ?
O2 Zr1 O4A 104.7(8) 84 68 ?
O4 Zr1 O1 79.4(4) 68 . ?
O4 Zr1 O1 79.4(4) . . ?
O4 Zr1 O3 73.7(4) . 68 ?
O4 Zr1 O3 123.0(3) 68 68 ?
O4 Zr1 O3 123.0(3) . . ?
O4 Zr1 O3 73.7(4) 68 . ?
O4 Zr1 O2 149.4(4) . 84 ?
O4 Zr1 O2 149.4(4) 68 83 ?
O4 Zr1 O2 88.3(7) . 83 ?
O4 Zr1 O2 88.3(7) 68 84 ?
O4 Zr1 O4 84.2(9) 68 . ?
O4 Zr1 O2A 59.9(8) . 12 ?
O4 Zr1 O2A 135.2(7) 68 12 ?
O4 Zr1 O4A 68.5(8) . 68 ?
O4 Zr1 O4A 16.7(6) 68 68 ?
O2A Zr1 O3 147.5(3) . 68 ?
O2A Zr1 O3 147.5(3) 12 . ?
O2A Zr1 O3 74.5(2) 12 68 ?
O2A Zr1 O3 74.5(2) . . ?
O2A Zr1 O2 28.4(5) . 84 ?
O2A Zr1 O2 108.6(9) 12 84 ?
O2A Zr1 O2 28.4(5) 12 83 ?
O2A Zr1 O2 108.6(9) . 83 ?
O2A Zr1 O2A 128.9(7) . 12 ?
O2A Zr1 O4A 124.1(8) . . ?
O2A Zr1 O4A 76.5(9) . 68 ?
O2A Zr1 O4A 124.1(8) 12 68 ?
O2A Zr1 O4A 76.5(9) 12 . ?
O4A Zr1 O4A 52.3(11) . 68 ?
Fe1 Fe1 Cl1 180.0 77 . ?
Fe1 Fe1 N1 73.8(4) 77 79_554 ?
Fe1 Fe1 N1 74.2(4) 77 . ?
Fe1 Fe1 N1 74.2(4) 77 51 ?
Fe1 Fe1 N1 73.8(4) 77 77 ?
N1 Fe1 Cl1 105.8(4) . . ?
N1 Fe1 Cl1 106.2(4) 79_554 . ?
N1 Fe1 Cl1 105.8(4) 51 . ?
N1 Fe1 Cl1 106.2(4) 77 . ?
N1 Fe1 N1 147.7(7) 79_554 77 ?
N1 Fe1 N1 85.64(10) . 77 ?
N1 Fe1 N1 85.64(10) 51 77 ?
N1 Fe1 N1 85.64(10) . 79_554 ?
N1 Fe1 N1 85.64(10) 51 79_554 ?
N1 Fe1 N1 148.3(7) . 51 ?
Zr1 O1 Zr1 110.2(3) 12 . ?
Zr1 O1 Zr1 110.2(3) 12 11 ?
Zr1 O1 Zr1 110.2(3) 11 . ?
C1 O3 Zr1 132.1(4) . . ?
Fe1 N1 Fe1 32.0(4) . 77 ?
C7 N1 Fe1 125.0(4) . 77 ?
C7 N1 Fe1 125.0(4) 57_565 77 ?
C7 N1 Fe1 126.0(3) . . ?
C7 N1 Fe1 126.0(3) 57_565 . ?
C7 N1 C7 105.6(5) . 57_565 ?
O3 C1 O3 128.6(6) 46 . ?
O3 C1 C2 115.7(3) 46 . ?
O3 C1 C2 115.7(3) . . ?
C3 C2 C1 119.2(3) 46 . ?
C3 C2 C1 119.2(3) . . ?
C3 C2 C3 121.6(7) . 46 ?
C2 C3 H3 120.3 . . ?
C2 C3 C4 119.4(8) . . ?
C4 C3 H3 120.3 . . ?
C3 C4 H4 120.5 . . ?
C5 C4 C3 119.0(8) . . ?
C5 C4 H4 120.5 . . ?
C4 C5 C4 121.6(7) . 46 ?
C4 C5 C6 119.2(4) 46 . ?
C4 C5 C6 119.2(4) . . ?
C7 C6 C5 117.9(2) . . ?
C7 C6 C5 117.9(2) 46 . ?
C7 C6 C7 124.3(5) . 46 ?
N1 C7 C6 125.6(4) . . ?
N1 C7 C8 110.2(4) . . ?
C6 C7 C8 124.2(4) . . ?
C7 C8 H8 126.5 . . ?
C8 C8 C7 107.1(2) 57_565 . ?
C8 C8 H8 126.5 57_565 . ?
Zr1 O2 Zr1 105.5(7) 84 83 ?
Zr1 O2 Zr1 124.8(6) . 83 ?
Zr1 O2 Zr1 124.8(6) . 84 ?
Zr1 O2 O2 76.8(14) . 83 ?
Zr1 O2 O2 76.8(14) . 84 ?
O2 O2 Zr1 51.1(8) 84 84 ?
O2 O2 Zr1 132.6(6) 83 84 ?
O2 O2 Zr1 132.6(6) 84 83 ?
O2 O2 Zr1 51.1(8) 83 83 ?
O2 O2 O2 110.0(13) 84 83 ?
C9 O4 Zr1 132.8(12) . . ?
O4 C9 O4 128(2) 70 . ?
O4 C9 C10 116.2(11) 70 . ?
O4 C9 C10 116.2(11) . . ?
C9 C10 H10A 109.5 . . ?
C9 C10 H10A 109(2) . 70 ?
C9 C10 H10B 109.5(6) . 70 ?
C9 C10 H10B 109.5 . . ?
C9 C10 H10C 109.5(14) . 70 ?
C9 C10 H10C 109.5 . . ?
H10A C10 H10A 26.0 . 70 ?
H10A C10 H10B 109.5 . . ?
H10A C10 H10B 85.7 . 70 ?
H10A C10 H10B 109.5 70 70 ?
H10A C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 70 70 ?
H10A C10 H10C 129.8 . 70 ?
H10B C10 H10A 85.7 . 70 ?
H10B C10 H10B 129.8 . 70 ?
H10B C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 70 70 ?
H10B C10 H10C 26.0 . 70 ?
H10C C10 H10A 129.8 . 70 ?
H10C C10 H10B 26.0 . 70 ?
H10C C10 H10C 85.7 . 70 ?
Zr1 O2A Zr1 93.5(7) 11 84 ?
Zr1 O2A Zr1 108.7(4) 11 . ?
Zr1 O2A Zr1 93.5(7) . 84 ?
C9A O4A Zr1 94(2) . . ?
C9A O4A Zr1 94(2) 68 . ?
C9A O4A C9A 0(2) 68 . ?
O4A C9A O4A 119(4) . 68 ?
O4A C9A C10A 120.4(18) . . ?
O4A C9A C10A 120.4(18) 68 . ?
C9A C9A O4A 0(10) 68 68 ?
C9A C9A O4A 0(10) 68 . ?
C9A C9A C10A 0(10) 68 . ?
C9A C10A C9A 0(5) 68 . ?
C9A C10A H10D 109.5(11) 68 68 ?
C9A C10A H10D 109.5(11) . 68 ?
C9A C10A H10D 109.5 68 . ?
C9A C10A H10D 109.5 . . ?
C9A C10A H10E 109.5 68 . ?
C9A C10A H10E 109.5 . . ?
C9A C10A H10E 109(2) 68 68 ?
C9A C10A H10E 109(2) . 68 ?
C9A C10A H10F 109.5 68 . ?
C9A C10A H10F 109.5(9) 68 68 ?
C9A C10A H10F 109.5(9) . 68 ?
C9A C10A H10F 109.5 . . ?
H10D C10A H10D 102.9 . 68 ?
H10D C10A H10E 109.5 68 68 ?
H10D C10A H10E 109.5 . . ?
H10D C10A H10E 115.8 . 68 ?
H10D C10A H10F 109.5 68 68 ?
H10D C10A H10F 7.5 . 68 ?
H10D C10A H10F 109.5 . . ?
H10E C10A H10D 115.8 . 68 ?
H10E C10A H10E 7.5 . 68 ?
H10E C10A H10F 109.5 68 68 ?
H10E C10A H10F 109.5 . . ?
H10E C10A H10F 102.9 . 68 ?
H10F C10A H10D 7.4 . 68 ?
H10F C10A H10E 102.9 . 68 ?
H10F C10A H10F 115.8 . 68 ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Zr1 O3 C1 O3 -0.8(2) . . . 46 ?
Zr1 O3 C1 C2 179.2(2) . . . . ?
Zr1 O4 C9 O4 5(3) . . . 70 ?
Zr1 O4 C9 C10 -177(3) . . . . ?
Zr1 O4A C9A O4A 2(2) . . . 68 ?
Zr1 O4A C9A C9A 0.0(4) . . . 68 ?
Zr1 O4A C9A C10A -178(2) . . . . ?
Fe1 N1 C7 C6 23.6(15) 77 . . . ?
Fe1 N1 C7 C6 -16.0(15) . . . . ?
Fe1 N1 C7 C8 164.3(8) . . . . ?
Fe1 N1 C7 C8 -156.2(8) 77 . . . ?
O1 Zr1 O2 Zr1 -75.8(8) . . . 83 ?
O1 Zr1 O2 Zr1 75.8(8) . . . 84 ?
O1 Zr1 O2 O2 57.29(19) . . . 84 ?
O1 Zr1 O2 O2 -57.29(19) . . . 83 ?
O3 Zr1 O2 Zr1 142.4(8) . . . 83 ?
O3 Zr1 O2 Zr1 66.1(8) 68 . . 83 ?
O3 Zr1 O2 Zr1 -142.4(8) 68 . . 84 ?
O3 Zr1 O2 Zr1 -66.1(8) . . . 84 ?
O3 Zr1 O2 O2 -84.5(2) . . . 84 ?
O3 Zr1 O2 O2 160.9(2) . . . 83 ?
O3 Zr1 O2 O2 -160.9(2) 68 . . 84 ?
O3 Zr1 O2 O2 84.5(2) 68 . . 83 ?
O3 C1 C2 C3 1.5(3) 46 . . 46 ?
O3 C1 C2 C3 -178.5(3) 46 . . . ?
O3 C1 C2 C3 1.5(3) . . . . ?
O3 C1 C2 C3 -178.5(3) . . . 46 ?
N1 C7 C8 C8 -0.6(9) . . . 57_565 ?
C1 C2 C3 C4 -179.5(4) . . . . ?
C2 C3 C4 C5 -1.1(8) . . . . ?
C3 C2 C3 C4 0.5(4) 46 . . . ?
C3 C4 C5 C4 0.5(4) . . . 46 ?
C3 C4 C5 C6 -179.5(4) . . . . ?
C4 C5 C6 C7 106.5(5) 46 . . . ?
C4 C5 C6 C7 -73.5(5) 46 . . 46 ?
C4 C5 C6 C7 -73.5(5) . . . . ?
C4 C5 C6 C7 106.5(5) . . . 46 ?
C5 C6 C7 N1 177.9(8) . . . . ?
C5 C6 C7 C8 -2.4(11) . . . . ?
C6 C7 C8 C8 179.7(7) . . . 57_565 ?
C7 N1 C7 C6 -179.4(4) 57_565 . . . ?
C7 N1 C7 C8 0.9(15) 57_565 . . . ?
C7 C6 C7 N1 -2.1(8) 46 . . . ?
C7 C6 C7 C8 177.6(11) 46 . . . ?
O2 Zr1 O2 Zr1 133.0(8) 83 . . 84 ?
O2 Zr1 O2 Zr1 -18.5(8) 83 . . 83 ?
O2 Zr1 O2 Zr1 -133.0(8) 84 . . 83 ?
O2 Zr1 O2 Zr1 18.5(8) 84 . . 84 ?
O2 Zr1 O2 O2 114.6(4) 83 . . 84 ?
O2 Zr1 O2 O2 -114.6(4) 84 . . 83 ?
O4 Zr1 O2 Zr1 6.9(14) . . . 83 ?
O4 Zr1 O2 Zr1 -158.4(5) 68 . . 83 ?
O4 Zr1 O2 Zr1 -6.9(14) 68 . . 84 ?
O4 Zr1 O2 Zr1 158.4(5) . . . 84 ?
O4 Zr1 O2 O2 -25.4(7) 68 . . 84 ?
O4 Zr1 O2 O2 25.4(7) . . . 83 ?
O4 Zr1 O2 O2 -140.0(7) 68 . . 83 ?
O4 Zr1 O2 O2 140.0(7) . . . 84 ?
O4A C9A C10A C9A 0(100) 68 . . 68 ?
O4A C9A C10A C9A 0(100) . . . 68 ?
C9A O4A C9A O4A 0(88) 68 . . 68 ?
C9A O4A C9A C10A 0(100) 68 . . . ?

_olex2_exptl_crystal_mounting_method 
; 
In a solvent-free, dinitrogen-filled glovebox, activated crystals were coated 
with Paratone-N oil. The crystals were removed from the glovebox. A suitable 
single crystal was mounted on a MiTeGen loop, and cooled under a stream of N2 
at 100 K for collection.
;
_olex2_submission_original_sample_id PCN-224'FeCl
_olex2_submission_special_instructions 'No special instructions were received'
####################################################################### 
# 
# 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_PCN-224
_database_code_depnum_ccdc_archive 'CCDC 1992909'
loop_
_audit_author_name
_audit_author_address
'David Zee'
;Northwestern University
United States of America
;
_audit_update_record             
;
2020-03-26 deposited with the CCDC.	2020-05-07 downloaded from the CCDC.
;

# start Validation Reply Form
_vrf_PLAT420_PCN-224             
;
PROBLEM: D-H Without Acceptor       O4       --H4A      .     Please Check 
RESPONSE: The atoms O4 and H4A correspond to the terminal hydroxide ligands
at the Zr6 cluster. The H atom H4A points into the pore of the evacuated
MOF framework, where there is largely void space.
;
# end Validation Reply Form

_audit_creation_date             2020-02-24
_audit_creation_method           
;
Olex2 1.3
(compiled 2019.11.21 svn.r41b79517 for OlexSys, GUI svn.r6003)
;
_shelx_SHELXL_version_number     2018/3

_chemical_name_common            PCN-224
_chemical_name_systematic        '[H2TCPP]3[Zr6O4(mu-OH)4(OH)6]2'
_chemical_formula_moiety         'C144 H90 N12 O52 Zr12'
_chemical_formula_sum            'C144 H90 N12 O52 Zr12'
_chemical_formula_weight         3914.91
_chemical_melting_point          'not measured'
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'
Zr Zr -2.9673 0.5597 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      cubic
_space_group_IT_number           229
_space_group_name_H-M_alt        'I m -3 m'
_space_group_name_Hall           '-I 4 2 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, -z'
'-y, -x, -z'
'y, -x, z'
'-y, x, z'
'x, z, -y'
'-x, z, y'
'-x, -z, -y'
'x, -z, y'
'z, y, -x'
'z, -y, x'
'-z, y, x'
'-z, -y, -x'
'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+1/2'
'x+1/2, -y+1/2, -z+1/2'
'z+1/2, 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+1/2, x+1/2, -y+1/2'
'y+1/2, z+1/2, 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+1/2, x+1/2'
'y+1/2, x+1/2, -z+1/2'
'-y+1/2, -x+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, z+1/2, -y+1/2'
'-x+1/2, z+1/2, y+1/2'
'-x+1/2, -z+1/2, -y+1/2'
'x+1/2, -z+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, y+1/2, x+1/2'
'-z+1/2, -y+1/2, -x+1/2'
'-x, -y, -z'
'x, y, -z'
'x, -y, z'
'-x, y, z'
'-z, -x, -y'
'-z, x, y'
'z, x, -y'
'z, -x, y'
'-y, -z, -x'
'y, -z, x'
'-y, z, x'
'y, z, -x'
'-y, -x, z'
'y, x, z'
'-y, x, -z'
'y, -x, -z'
'-x, -z, y'
'x, -z, -y'
'x, z, y'
'-x, z, -y'
'-z, -y, x'
'-z, y, -x'
'z, -y, -x'
'z, y, x'
'-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+1/2'
'-x+1/2, y+1/2, z+1/2'
'-z+1/2, -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+1/2, -x+1/2, y+1/2'
'-y+1/2, -z+1/2, -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+1/2, -x+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, x+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, -z+1/2, y+1/2'
'x+1/2, -z+1/2, -y+1/2'
'x+1/2, z+1/2, y+1/2'
'-x+1/2, z+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, -y+1/2, -x+1/2'
'z+1/2, y+1/2, x+1/2'

_cell_length_a                   38.8372(12)
_cell_length_b                   38.8372(12)
_cell_length_c                   38.8372(12)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     58579(5)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    9504
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.366
_cell_measurement_theta_min      2.225
_shelx_estimated_absorpt_T_max   0.890
_shelx_estimated_absorpt_T_min   0.856
_exptl_absorpt_coefficient_mu    0.227
_exptl_absorpt_correction_T_max  0.7459
_exptl_absorpt_correction_T_min  0.6945
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016) was used for absorption correction.
wR2(int) was 0.1177 before and 0.0500 after correction.
The Ratio of minimum to maximum transmission is 0.9311.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear dark violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    0.444
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       cuboctahedral
_exptl_crystal_F_000             7736
_exptl_crystal_preparation       ?
_exptl_crystal_recrystallization_method 
'See Experimental Section in Supporting Information.'
_exptl_crystal_size_max          0.706
_exptl_crystal_size_mid          0.592
_exptl_crystal_size_min          0.524
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0698
_diffrn_reflns_av_unetI/netI     0.0157
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       53
_diffrn_reflns_limit_h_min       -52
_diffrn_reflns_limit_k_max       52
_diffrn_reflns_limit_k_min       -52
_diffrn_reflns_limit_l_max       53
_diffrn_reflns_limit_l_min       -53
_diffrn_reflns_number            370650
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.128
_diffrn_reflns_theta_min         0.741
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       'ω and φ scans'
_diffrn_radiation_monochromator  'MX optics'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   microsource
_diffrn_source_current           0.99
_diffrn_source_power             0.0495
_diffrn_source_voltage           50.0
_diffrn_special_details          ?
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                5613
_reflns_number_total             7260
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'SAINT V8.34A (Bruker, 2017)'
_computing_data_collection       'APEX2 V2017.3 (Bruker, 2017)'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_refine_diff_density_max         1.798
_refine_diff_density_min         -1.543
_refine_diff_density_rms         0.071
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     94
_refine_ls_number_reflns         7260
_refine_ls_number_restraints     80
_refine_ls_R_factor_all          0.0845
_refine_ls_R_factor_gt           0.0696
_refine_ls_restrained_S_all      1.036
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1139P)²+170.4568P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2005
_refine_ls_wR_factor_ref         0.2246
_refine_special_details          'A solvent mask was applied.'
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All O(H) groups
2. Uiso/Uaniso restraints and constraints
O4: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Zr1: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
O2: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
3. Rigid body (RIGU) restrains
 N1, C7, C8, C6, C5, C4, C3, C2, C1, O3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O3, O2, Zr1, O4, O1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Fixed Sof: H1(0.25) H4A(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 N1(H1), C4(H4), C3(H3), C8(H8)
5.b Idealised tetrahedral OH refined as rotating group:
 O4(H4A)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   ?
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
Zr1 Zr 0.29128(2) 0.29128(2) 0.22438(2) 0.04422(17) Uani 1 2 d S T P . .
C5 C 0.250000 0.41012(6) 0.08988(6) 0.0472(10) Uani 1 2 d S T P . .
N1 N 0.24941(11) 0.44736(7) 0.000000 0.0475(9) Uani 1 2 d S T P . .
H1 H 0.248558 0.469999 -0.000001 0.057 Uiso 0.5 2 calc R U P . .
C7 C 0.25020(10) 0.42634(6) 0.02843(6) 0.0477(8) Uani 1 1 d . . . . .
C6 C 0.250000 0.43739(6) 0.06261(6) 0.0470(11) Uani 1 2 d S T P . .
C4 C 0.27937(11) 0.40350(9) 0.10842(9) 0.0632(10) Uani 1 1 d . . . . .
H4 H 0.299727 0.416324 0.103980 0.076 Uiso 1 1 calc R U . . .
C2 C 0.250000 0.35963(6) 0.14037(6) 0.0448(9) Uani 1 2 d S T P . .
C3 C 0.27944(11) 0.37781(9) 0.13395(8) 0.0600(9) Uani 1 1 d . . . . .
H3 H 0.299820 0.373130 0.146650 0.072 Uiso 1 1 calc R U . . .
O3 O 0.27717(6) 0.32797(6) 0.18399(5) 0.0543(6) Uani 1 1 d . . . . .
C1 C 0.250000 0.33248(6) 0.16752(6) 0.0498(11) Uani 1 2 d S T P . .
C8 C 0.25185(10) 0.39101(6) 0.01729(7) 0.0539(9) Uani 1 1 d . . . . .
H8 H 0.252769 0.371311 0.031760 0.065 Uiso 1 1 calc R U . . .
O2 O 0.25628(7) 0.25628(7) 0.19731(8) 0.0566(9) Uani 1 2 d S T P . .
O1 O 0.2820(2) 0.2820(2) 0.2820(2) 0.115(3) Uani 1 6 d S T P . .
O4 O 0.32193(12) 0.32193(12) 0.24757(17) 0.1147(19) Uani 1 2 d S T P . .
H4A H 0.311481 0.331660 0.263817 0.172 Uiso 0.5 1 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
Zr1 Zr1 3.3197(8) 77 ?
Zr1 Zr1 3.6746(6) 5 ?
Zr1 Zr1 3.6746(6) 9 ?
Zr1 Zr1 3.3197(8) 81 ?
Zr1 O3 2.1887(19) 62 ?
Zr1 O3 2.1887(19) . ?
Zr1 O2 2.0427(14) 81 ?
Zr1 O2 2.0427(14) 77 ?
Zr1 O2 2.191(4) . ?
Zr1 O1 2.296(5) . ?
Zr1 O4 1.910(6) . ?
Zr1 H4A 2.33(6) 62 ?
C5 C6 1.498(5) . ?
C5 C4 1.373(4) . ?
C5 C4 1.373(4) 43 ?
N1 H1 0.8800 . ?
N1 C7 1.373(3) . ?
N1 C7 1.373(3) 50 ?
C7 C6 1.395(3) . ?
C7 C8 1.440(3) . ?
C4 H4 0.9500 . ?
C4 C3 1.407(4) . ?
C2 C3 1.367(4) . ?
C2 C3 1.367(4) 43 ?
C2 C1 1.491(5) . ?
C3 H3 0.9500 . ?
O3 C1 1.246(3) . ?
C8 C8 1.343(5) 50 ?
C8 H8 0.9500 . ?
O4 H4A 0.8400 . ?
O4 H4A 0.84(8) 62 ?

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
Zr1 Zr1 Zr1 60.0 5 9 ?
Zr1 Zr1 Zr1 67.21(2) 77 81 ?
Zr1 Zr1 Zr1 56.398(10) 77 9 ?
Zr1 Zr1 Zr1 56.398(10) 81 5 ?
Zr1 Zr1 Zr1 90.0 77 5 ?
Zr1 Zr1 Zr1 90.0 81 9 ?
Zr1 Zr1 H4A 125(3) 77 62 ?
Zr1 Zr1 H4A 77(5) 9 62 ?
Zr1 Zr1 H4A 91(4) 5 62 ?
Zr1 Zr1 H4A 146(3) 81 62 ?
O3 Zr1 Zr1 109.25(5) . 5 ?
O3 Zr1 Zr1 109.25(5) 62 9 ?
O3 Zr1 Zr1 75.30(6) 62 77 ?
O3 Zr1 Zr1 165.25(6) . 9 ?
O3 Zr1 Zr1 116.85(7) 62 81 ?
O3 Zr1 Zr1 75.30(6) . 81 ?
O3 Zr1 Zr1 165.25(6) 62 5 ?
O3 Zr1 Zr1 116.85(7) . 77 ?
O3 Zr1 O3 79.19(10) . 62 ?
O3 Zr1 O2 84.53(9) . . ?
O3 Zr1 O2 84.53(9) 62 . ?
O3 Zr1 O1 139.60(8) 62 . ?
O3 Zr1 O1 139.60(8) . . ?
O3 Zr1 H4A 115(4) . 62 ?
O3 Zr1 H4A 97(3) 62 62 ?
O2 Zr1 Zr1 83.88(7) 81 9 ?
O2 Zr1 Zr1 96.39(10) 77 81 ?
O2 Zr1 Zr1 84.30(6) . 9 ?
O2 Zr1 Zr1 25.92(8) 81 5 ?
O2 Zr1 Zr1 83.88(7) 77 5 ?
O2 Zr1 Zr1 39.97(12) 81 81 ?
O2 Zr1 Zr1 39.97(12) 77 77 ?
O2 Zr1 Zr1 36.80(3) . 77 ?
O2 Zr1 Zr1 25.91(8) 77 9 ?
O2 Zr1 Zr1 36.80(3) . 81 ?
O2 Zr1 Zr1 96.39(10) 81 77 ?
O2 Zr1 Zr1 84.30(6) . 5 ?
O2 Zr1 O3 84.03(9) 81 . ?
O2 Zr1 O3 155.03(13) 77 . ?
O2 Zr1 O3 84.02(9) 77 62 ?
O2 Zr1 O3 155.03(13) 81 62 ?
O2 Zr1 O2 75.52(13) 81 . ?
O2 Zr1 O2 75.52(13) 77 . ?
O2 Zr1 O2 104.90(15) 81 77 ?
O2 Zr1 O1 105.9(3) . . ?
O2 Zr1 O1 62.21(16) 81 . ?
O2 Zr1 O1 62.21(16) 77 . ?
O2 Zr1 H4A 160(4) . 62 ?
O2 Zr1 H4A 85(3) 77 62 ?
O2 Zr1 H4A 107(3) 81 62 ?
O1 Zr1 Zr1 89.9(3) . 77 ?
O1 Zr1 Zr1 36.84(17) . 9 ?
O1 Zr1 Zr1 89.9(3) . 81 ?
O1 Zr1 Zr1 36.84(17) . 5 ?
O1 Zr1 H4A 61(5) . 62 ?
O4 Zr1 Zr1 96.16(18) . 5 ?
O4 Zr1 Zr1 143.40(8) . 77 ?
O4 Zr1 Zr1 143.40(8) . 81 ?
O4 Zr1 Zr1 96.16(18) . 9 ?
O4 Zr1 O3 95.06(17) . . ?
O4 Zr1 O3 95.06(17) . 62 ?
O4 Zr1 O2 104.78(16) . 81 ?
O4 Zr1 O2 104.78(16) . 77 ?
O4 Zr1 O2 179.5(2) . . ?
O4 Zr1 O1 74.7(4) . . ?
O4 Zr1 H4A 20(4) . 62 ?
C4 C5 C6 120.20(18) 43 . ?
C4 C5 C6 120.21(18) . . ?
C4 C5 C4 119.6(4) . 43 ?
C7 N1 H1 126.5 50 . ?
C7 N1 H1 126.5 . . ?
C7 N1 C7 107.0(3) 50 . ?
N1 C7 C6 125.6(2) . . ?
N1 C7 C8 109.0(2) . . ?
C6 C7 C8 125.4(2) . . ?
C7 C6 C5 117.08(15) . . ?
C7 C6 C5 117.08(15) 43 . ?
C7 C6 C7 125.8(3) . 43 ?
C5 C4 H4 119.9 . . ?
C5 C4 C3 120.3(4) . . ?
C3 C4 H4 119.9 . . ?
C3 C2 C3 120.8(4) . 43 ?
C3 C2 C1 119.62(18) 43 . ?
C3 C2 C1 119.62(18) . . ?
C4 C3 H3 120.2 . . ?
C2 C3 C4 119.6(4) . . ?
C2 C3 H3 120.2 . . ?
C1 O3 Zr1 132.2(2) . . ?
O3 C1 C2 117.53(17) . . ?
O3 C1 C2 117.53(17) 43 . ?
O3 C1 O3 124.9(3) 43 . ?
C7 C8 H8 126.3 . . ?
C8 C8 C7 107.48(14) 50 . ?
C8 C8 H8 126.3 50 . ?
Zr1 O2 Zr1 128.17(17) 81 77 ?
Zr1 O2 Zr1 103.23(12) 81 . ?
Zr1 O2 Zr1 103.23(12) 77 . ?
Zr1 O1 Zr1 106.3(3) . 9 ?
Zr1 O1 Zr1 106.3(3) 5 9 ?
Zr1 O1 Zr1 106.3(3) . 5 ?
Zr1 O4 H4A 109.5 . . ?
Zr1 O4 H4A 109(10) . 62 ?
H4A O4 H4A 82.6 . 62 ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Zr1 O3 C1 C2 -177.67(12) . . . . ?
Zr1 O3 C1 O3 2.32(12) . . . 43 ?
C5 C4 C3 C2 -0.5(5) . . . . ?
N1 C7 C6 C5 178.4(3) . . . . ?
N1 C7 C6 C7 -1.6(3) . . . 43 ?
N1 C7 C8 C8 -0.3(4) . . . 50 ?
C7 N1 C7 C6 179.58(14) 50 . . . ?
C7 N1 C7 C8 0.5(6) 50 . . . ?
C6 C5 C4 C3 -179.8(3) . . . . ?
C6 C7 C8 C8 -179.4(3) . . . 50 ?
C4 C5 C6 C7 105.7(3) . . . . ?
C4 C5 C6 C7 -74.3(3) . . . 43 ?
C4 C5 C6 C7 -74.3(3) 43 . . . ?
C4 C5 C6 C7 105.7(3) 43 . . 43 ?
C4 C5 C4 C3 0.2(3) 43 . . . ?
C3 C2 C3 C4 0.2(2) 43 . . . ?
C3 C2 C1 O3 1.5(2) 43 . . 43 ?
C3 C2 C1 O3 1.5(2) . . . . ?
C3 C2 C1 O3 -178.5(2) 43 . . . ?
C3 C2 C1 O3 -178.5(2) . . . 43 ?
C1 C2 C3 C4 -179.8(3) . . . . ?
C8 C7 C6 C5 -2.7(4) . . . . ?
C8 C7 C6 C7 177.3(4) . . . 43 ?

_smtbx_masks_special_details     ?
loop_
_smtbx_masks_void_nr
_smtbx_masks_void_average_x
_smtbx_masks_void_average_y
_smtbx_masks_void_average_z
_smtbx_masks_void_volume
_smtbx_masks_void_count_electrons
_smtbx_masks_void_content
1 -0.789 -0.665 -0.607 48182.0 9325.6 ?

_olex2_exptl_crystal_mounting_method 
;
In a solvent-free, dinitrogen-filled glovebox, activated crystals were coated 
with Paratone-N oil. The crystals were removed from the glovebox. A suitable 
single crystal was mounted on a MiTeGen loop, and cooled under a stream of N2 
at 100 K for collection.
;
_olex2_submission_original_sample_id PCN-224
_olex2_submission_special_instructions 'No special instructions were received'

#===END





