# Electronic Supplementary Material (ESI) for Chemical Science.
# 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_PCN224MnO2
_database_code_depnum_ccdc_archive 'CCDC 1570584'
_audit_update_record             
;
2017-08-23 deposited with the CCDC.
2017-12-14 downloaded from the CCDC.
;
_audit_creation_date             2017-06-19
_audit_creation_method           
;
Olex2 1.2
(compiled Mar 28 2017 19:26:29 for OlexSys, GUI svn.r5337)
;
_shelx_SHELXL_version_number     2014/7
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         '0.25(C576 H288 Mn12 N48 O280 Zr48)'
_chemical_formula_sum            'C144 H72 Mn3 N12 O70 Zr12'
_chemical_formula_weight         4349.59
_chemical_melting_point          ?
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'
Mn Mn -0.5299 2.8052 '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                   38.4015(12)
_cell_length_b                   38.4015(12)
_cell_length_c                   38.4015(12)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     56630(5)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    9862
_cell_measurement_temperature    100
_cell_measurement_theta_max      67.963
_cell_measurement_theta_min      2.818
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    2.499
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6220
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2014/5 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.0931 before and 0.0773 after correction.
The Ratio of minimum to maximum transmission is 0.8259.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'dark violet'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    0.510
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             8540
_exptl_crystal_size_max          0.213
_exptl_crystal_size_mid          0.196
_exptl_crystal_size_min          0.156
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0723
_diffrn_reflns_av_unetI/netI     0.0293
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       46
_diffrn_reflns_limit_h_min       -46
_diffrn_reflns_limit_k_max       46
_diffrn_reflns_limit_k_min       -44
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            148036
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.292
_diffrn_reflns_theta_min         1.627
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_source                   ?
_diffrn_special_details          
;
# start Validation Reply Form
#_vrf_PLAT084_PCN224MnO2
#;
#PROBLEM: High wR2 Value (i.e. > 0.25) ...................       0.44 Report
#RESPONSE: The large wR2 is reflective of the disorder present in the structure.
#;
#_vrf_PLAT213_PCN224MnO2
#;
#PROBLEM: Atom N3              has ADP max/min Ratio .....        4.3 prolat
#RESPONSE: This elongated parameter arising from the disorder intrinsic to the system, elongating atoms out of the plane of the porphyrin.
#;
#_vrf_PLAT215_PCN224MnO2
#;
#PROBLEM: Disordered Mn1       has ADP max/min Ratio .....        4.6 Note  
#RESPONSE: This elongated parameter arising from the disorder intrinsic to the system, elongating atoms out of the plane of the porphyrin.
#;
#_vrf_PLAT241_PCN224MnO2
#;
#PROBLEM: High   'MainMol' Ueq as Compared to Neighbors of         O3 Check 
#RESPONSE: The high equivalent for this atom is due to the disorder intrinsic to the structure that creates larger thermal factors for the atoms in the porphyrin unit.
#;
#_vrf_PLAT250_PCN224MnO2
#;
#PROBLEM: Large U3/U1 Ratio for Average U(i,j) Tensor ....        4.9 Note  
#RESPONSE: This elongated parameter arising from the disorder intrinsic to the system, elongating atoms out of the plane of the porphyrin.
#;
# end Validation Reply Form
;
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                4033
_reflns_number_total             4843
_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 v8.37A (Bruker, 2015)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    ?
_refine_diff_density_max         2.576
_refine_diff_density_min         -1.034
_refine_diff_density_rms         0.143
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   2.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     121
_refine_ls_number_reflns         4843
_refine_ls_number_restraints     232
_refine_ls_R_factor_all          0.1566
_refine_ls_R_factor_gt           0.1445
_refine_ls_restrained_S_all      2.278
_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)+(0.2000P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4146
_refine_ls_wR_factor_ref         0.4351
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 O2-O2_$1
 1.49 with sigma of 0.02
 O1_$1-O1
 1.49 with sigma of 0.02
 Mn1-N3_$2
 2.18955 with sigma of 0.02
 Mn1-O1 = Mn1-O2
 1.70024 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
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
Uanis(O6) \\sim Ueq, Uanis(Zr1) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(O5) \\sim
Ueq, Uanis(O3) \\sim Ueq, Uanis(Zr2) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C7)
\\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C4) \\sim Ueq,
Uanis(C3) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(N3) \\sim Ueq, Uanis(C1) \\sim
Ueq, Uanis(O2) \\sim Ueq, Uanis(O1) \\sim Ueq: with sigma of 0.03 and sigma for
terminal atoms of 0.06
Uanis(Mn1) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.05
5. Others
 Sof(Zr2)=0.5*(1-FVAR(2))
 Sof(Zr1)=0.5*FVAR(2)
 Fixed Sof: Mn1(0.125) O2(0.125) O1(0.125)
6.a Aromatic/amide H refined with riding coordinates:
 C6(H6), C5(H5), C1(H1)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     ?
_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 0.30155(9) 0.30155(9) 0.23688(9) 0.0845(14) Uani 0.451(6) 2 d S TU P . .
Zr2 Zr 0.21547(9) 0.28011(9) 0.21547(9) 0.0961(13) Uani 0.549(6) 2 d S TU P . .
C4 C 0.40937(19) 0.2500 0.09063(19) 0.151(4) Uani 1 2 d S TU P . .
C3 C 0.43625(16) 0.2500 0.06375(16) 0.167(5) Uani 1 2 d S TU P . .
C7 C 0.35923(18) 0.2500 0.14077(18) 0.149(4) Uani 1 2 d S TU P . .
C6 C 0.3650(2) 0.2179(4) 0.1239(2) 0.166(4) Uani 1 1 d . U . . .
H6 H 0.3522 0.1973 0.1286 0.199 Uiso 1 1 calc R U . . .
C5 C 0.3923(3) 0.2202(5) 0.0992(3) 0.182(5) Uani 1 1 d . U . . .
H5 H 0.3991 0.1993 0.0877 0.218 Uiso 1 1 calc R U . . .
O5 O 0.2834(2) 0.2834(2) 0.2834(2) 0.080(3) Uani 1 6 d S TU P . .
O4 O 0.3147(3) 0.3413(3) 0.2498(3) 0.211(4) Uani 1 1 d . U . . .
O3 O 0.3267(2) 0.2755(3) 0.1845(2) 0.190(4) Uani 1 1 d . U . . 2
C8 C 0.3318(2) 0.2500 0.1682(2) 0.150(4) Uani 1 2 d S TU P . .
O6 O 0.24935(18) 0.3201(3) 0.24935(18) 0.135(3) Uani 1 2 d S TU P . 2
Mn1 Mn 0.5000 0.2708(2) 0.0000 0.153(3) Uani 0.5 4 d DS TU P . .
O2 O 0.5000 0.3106(12) 0.0191(3) 0.212(8) Uani 0.25 2 d DS TU P . .
N3 N 0.5000 0.2517(4) 0.05240(16) 0.166(4) Uani 1 2 d DS TU P . .
C2 C 0.47191(15) 0.2480(4) 0.07374(15) 0.178(4) Uani 1 1 d . U . . .
C1 C 0.48288(16) 0.2495(4) 0.10931(15) 0.184(5) Uani 1 1 d . U . . .
H1 H 0.4682 0.2503 0.1292 0.221 Uiso 1 1 calc R U . . .
O1 O 0.5191(3) 0.3109(12) 0.0000 0.203(9) Uani 0.25 2 d DS TU 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 3.512(2) 12 ?
Zr1 Zr1 3.512(2) 11 ?
Zr1 Zr2 3.504(9) 12 ?
Zr1 Zr2 3.504(9) . ?
Zr1 Zr2 1.131(3) 83 ?
Zr1 O5 2.040(2) . ?
Zr1 O4 1.684(14) . ?
Zr1 O4 1.684(14) 68 ?
Zr1 O3 2.446(9) 68 ?
Zr1 O3 2.446(9) . ?
Zr1 O6 2.180(5) . ?
Zr1 O6 2.180(5) 12 ?
Zr2 Zr1 1.131(3) 84 ?
Zr2 Zr1 3.504(9) 11 ?
Zr2 Zr2 2.663(7) 84 ?
Zr2 Zr2 3.510(2) 11 ?
Zr2 Zr2 2.663(7) 83 ?
Zr2 O5 2.438(8) 73 ?
Zr2 O3 2.142(6) 84 ?
Zr2 O3 2.142(6) 46 ?
Zr2 O6 2.396(14) . ?
Zr2 O6 2.229(7) 84 ?
Zr2 O6 2.229(7) 83 ?
C4 C3 1.460(13) . ?
C4 C5 1.360(17) . ?
C4 C5 1.360(17) 48 ?
C3 C2 1.424(7) . ?
C3 C2 1.424(7) 48 ?
C7 C6 1.409(14) . ?
C7 C6 1.409(14) 48 ?
C7 C8 1.487(14) . ?
C6 C5 1.417(13) . ?
O5 Zr1 2.040(2) 12 ?
O5 Zr1 2.040(2) 11 ?
O5 Zr2 2.439(8) 84 ?
O5 Zr2 2.439(8) 83 ?
O5 Zr2 2.439(8) 73 ?
O4 O4 1.45(2) 68 ?
O3 Zr2 2.142(6) 83 ?
O3 C8 1.179(11) . ?
C8 O3 1.179(11) 48 ?
O6 Zr1 2.180(5) 11 ?
O6 Zr2 2.229(7) 84 ?
O6 Zr2 2.229(7) 83 ?
Mn1 Mn1 1.596(16) 80_554 ?
Mn1 O2 1.69(4) . ?
Mn1 O2 1.69(4) 9_655 ?
Mn1 N3 2.141(9) . ?
Mn1 N3 2.190(9) 48 ?
Mn1 N3 2.190(9) 82 ?
Mn1 N3 2.141(9) 51 ?
Mn1 O1 1.71(4) 9_655 ?
Mn1 O1 1.71(4) . ?
O2 O2 1.47(2) 9_655 ?
O2 O1 1.037(10) . ?
O2 O1 1.037(10) 9_655 ?
N3 Mn1 2.190(9) 80_554 ?
N3 C2 1.362(7) . ?
N3 C2 1.363(7) 54_655 ?
C2 C1 1.431(8) . ?
C1 C1 1.314(12) 54_655 ?
O1 O2 1.037(10) 9_655 ?
O1 O1 1.46(2) 9_655 ?

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 11 12 ?
Zr2 Zr1 Zr1 59.93(9) . 11 ?
Zr2 Zr1 Zr1 89.96(9) 83 12 ?
Zr2 Zr1 Zr1 89.99(3) . 12 ?
Zr2 Zr1 Zr1 59.93(9) 12 12 ?
Zr2 Zr1 Zr1 89.96(9) 83 11 ?
Zr2 Zr1 Zr1 89.99(3) 12 11 ?
Zr2 Zr1 Zr2 35.32(11) 83 12 ?
Zr2 Zr1 Zr2 60.11(17) 12 . ?
Zr2 Zr1 Zr2 35.32(11) 83 . ?
Zr2 Zr1 O5 96.3(4) 83 . ?
Zr2 Zr1 O4 150.1(4) 83 . ?
Zr2 Zr1 O4 150.1(4) 83 68 ?
Zr2 Zr1 O3 61.1(3) 83 68 ?
Zr2 Zr1 O3 61.1(3) 83 . ?
Zr2 Zr1 O6 77.5(4) 83 . ?
Zr2 Zr1 O6 77.5(4) 83 12 ?
O5 Zr1 Zr1 30.60(8) . 12 ?
O5 Zr1 Zr1 30.60(8) . 11 ?
O5 Zr1 Zr2 78.6(3) . . ?
O5 Zr1 Zr2 78.6(3) . 12 ?
O5 Zr1 O3 135.6(3) . . ?
O5 Zr1 O3 135.6(3) . 68 ?
O5 Zr1 O6 66.7(2) . 12 ?
O5 Zr1 O6 66.7(2) . . ?
O4 Zr1 Zr1 90.2(4) 68 12 ?
O4 Zr1 Zr1 115.7(4) 68 11 ?
O4 Zr1 Zr1 90.2(4) . 11 ?
O4 Zr1 Zr1 115.7(4) . 12 ?
O4 Zr1 Zr2 124.4(4) 68 12 ?
O4 Zr1 Zr2 174.5(5) 68 . ?
O4 Zr1 Zr2 174.5(5) . 12 ?
O4 Zr1 Zr2 124.4(4) . . ?
O4 Zr1 O5 98.9(5) . . ?
O4 Zr1 O5 98.9(5) 68 . ?
O4 Zr1 O4 50.9(8) 68 . ?
O4 Zr1 O3 90.4(5) . 68 ?
O4 Zr1 O3 119.8(4) 68 68 ?
O4 Zr1 O3 119.7(4) . . ?
O4 Zr1 O3 90.4(5) 68 . ?
O4 Zr1 O6 85.1(5) . . ?
O4 Zr1 O6 85.1(5) 68 12 ?
O4 Zr1 O6 132.2(6) 68 . ?
O4 Zr1 O6 132.2(6) . 12 ?
O3 Zr1 Zr1 149.4(3) . 11 ?
O3 Zr1 Zr1 149.4(3) 68 12 ?
O3 Zr1 Zr1 106.99(17) 68 11 ?
O3 Zr1 Zr1 106.99(17) . 12 ?
O3 Zr1 Zr2 60.9(3) 68 . ?
O3 Zr1 Zr2 94.7(3) . . ?
O3 Zr1 Zr2 94.7(3) 68 12 ?
O3 Zr1 Zr2 60.9(3) . 12 ?
O3 Zr1 O3 69.3(4) . 68 ?
O6 Zr1 Zr1 94.3(2) . 12 ?
O6 Zr1 Zr1 36.35(18) 12 12 ?
O6 Zr1 Zr1 94.3(2) 12 11 ?
O6 Zr1 Zr1 36.35(18) . 11 ?
O6 Zr1 Zr2 42.4(4) 12 12 ?
O6 Zr1 Zr2 42.4(4) . . ?
O6 Zr1 Zr2 98.2(4) 12 . ?
O6 Zr1 Zr2 98.3(4) . 12 ?
O6 Zr1 O3 71.1(3) . 68 ?
O6 Zr1 O3 71.1(3) 12 . ?
O6 Zr1 O3 132.6(4) 12 68 ?
O6 Zr1 O3 132.6(4) . . ?
O6 Zr1 O6 123.5(6) 12 . ?
Zr1 Zr2 Zr1 60.15(17) . 11 ?
Zr1 Zr2 Zr1 144.68(11) 84 . ?
Zr1 Zr2 Zr1 144.68(11) 84 11 ?
Zr1 Zr2 Zr2 90.05(9) 84 11 ?
Zr1 Zr2 Zr2 90.01(3) . 11 ?
Zr1 Zr2 Zr2 59.94(9) 11 11 ?
Zr1 Zr2 Zr2 130.46(19) 84 84 ?
Zr1 Zr2 Zr2 130.46(19) 84 83 ?
Zr1 Zr2 O5 56.3(3) 84 73 ?
Zr1 Zr2 O3 91.3(4) 84 84 ?
Zr1 Zr2 O3 91.3(4) 84 46 ?
Zr1 Zr2 O6 175.4(2) 84 . ?
Zr1 Zr2 O6 72.8(3) 84 83 ?
Zr1 Zr2 O6 72.8(3) 84 84 ?
Zr2 Zr2 Zr1 72.0(2) 84 . ?
Zr2 Zr2 Zr1 14.22(9) 84 11 ?
Zr2 Zr2 Zr1 72.0(2) 83 11 ?
Zr2 Zr2 Zr1 14.22(9) 83 . ?
Zr2 Zr2 Zr2 82.5(3) 83 84 ?
Zr2 Zr2 Zr2 48.76(14) 84 11 ?
Zr2 Zr2 Zr2 90.0 83 11 ?
O5 Zr2 Zr1 102.3(2) 73 11 ?
O5 Zr2 Zr1 102.3(2) 73 . ?
O5 Zr2 Zr2 92.5(2) 73 84 ?
O5 Zr2 Zr2 44.0(2) 73 11 ?
O5 Zr2 Zr2 92.5(2) 73 83 ?
O3 Zr2 Zr1 121.7(4) 46 . ?
O3 Zr2 Zr1 82.8(3) 84 . ?
O3 Zr2 Zr1 121.7(4) 84 11 ?
O3 Zr2 Zr1 82.8(3) 46 11 ?
O3 Zr2 Zr2 109.51(19) 46 11 ?
O3 Zr2 Zr2 134.5(4) 46 83 ?
O3 Zr2 Zr2 134.5(4) 84 84 ?
O3 Zr2 Zr2 169.4(2) 84 11 ?
O3 Zr2 Zr2 81.1(3) 46 84 ?
O3 Zr2 Zr2 81.1(3) 84 83 ?
O3 Zr2 O5 130.2(3) 46 73 ?
O3 Zr2 O5 130.2(3) 84 73 ?
O3 Zr2 O3 80.9(4) 46 84 ?
O3 Zr2 O6 85.1(4) 84 . ?
O3 Zr2 O6 85.1(4) 46 . ?
O3 Zr2 O6 76.2(3) 46 84 ?
O3 Zr2 O6 76.2(3) 84 83 ?
O3 Zr2 O6 151.6(4) 84 84 ?
O3 Zr2 O6 151.6(4) 46 83 ?
O6 Zr2 Zr1 37.81(16) . . ?
O6 Zr2 Zr1 72.0(3) 83 . ?
O6 Zr2 Zr1 123.7(3) 84 . ?
O6 Zr2 Zr1 72.0(3) 84 11 ?
O6 Zr2 Zr1 123.7(3) 83 11 ?
O6 Zr2 Zr1 37.81(16) . 11 ?
O6 Zr2 Zr2 52.0(2) . 83 ?
O6 Zr2 Zr2 38.1(2) 84 11 ?
O6 Zr2 Zr2 52.0(2) . 84 ?
O6 Zr2 Zr2 127.1(3) 83 84 ?
O6 Zr2 Zr2 93.96(18) . 11 ?
O6 Zr2 Zr2 57.8(3) 84 84 ?
O6 Zr2 Zr2 127.1(3) 84 83 ?
O6 Zr2 Zr2 94.26(19) 83 11 ?
O6 Zr2 Zr2 57.8(3) 83 83 ?
O6 Zr2 O5 59.5(2) 83 73 ?
O6 Zr2 O5 128.4(4) . 73 ?
O6 Zr2 O5 59.5(2) 84 73 ?
O6 Zr2 O6 119.0(4) 83 84 ?
O6 Zr2 O6 109.2(4) 83 . ?
O6 Zr2 O6 109.2(3) 84 . ?
C5 C4 C3 120.7(6) 48 . ?
C5 C4 C3 120.7(6) . . ?
C5 C4 C5 118.5(13) . 48 ?
C2 C3 C4 119.3(4) 48 . ?
C2 C3 C4 119.3(4) . . ?
C2 C3 C2 121.4(8) 48 . ?
C6 C7 C6 128.2(11) . 48 ?
C6 C7 C8 115.9(5) 48 . ?
C6 C7 C8 115.9(5) . . ?
C7 C6 C5 111.8(13) . . ?
C4 C5 C6 124.7(14) . . ?
Zr1 O5 Zr1 118.80(15) . 11 ?
Zr1 O5 Zr1 118.80(15) . 12 ?
Zr1 O5 Zr1 118.80(15) 12 11 ?
Zr1 O5 Zr2 110.6(4) . 84 ?
Zr1 O5 Zr2 110.6(4) 12 83 ?
Zr1 O5 Zr2 27.46(14) 12 73 ?
Zr1 O5 Zr2 110.6(4) 12 84 ?
Zr1 O5 Zr2 110.6(4) 11 83 ?
Zr1 O5 Zr2 27.46(14) 11 84 ?
Zr1 O5 Zr2 110.6(4) 11 73 ?
Zr1 O5 Zr2 27.46(14) . 83 ?
Zr1 O5 Zr2 110.6(4) . 73 ?
Zr2 O5 Zr2 92.1(4) 84 73 ?
Zr2 O5 Zr2 92.1(4) 84 83 ?
Zr2 O5 Zr2 92.1(4) 83 73 ?
O4 O4 Zr1 64.5(4) 68 . ?
Zr2 O3 Zr1 27.54(13) 83 . ?
C8 O3 Zr1 147.6(7) . . ?
C8 O3 Zr2 126.9(9) . 83 ?
O3 C8 C7 119.7(6) . . ?
O3 C8 C7 119.7(6) 48 . ?
O3 C8 O3 120.6(12) 48 . ?
Zr1 O6 Zr1 107.3(4) . 11 ?
Zr1 O6 Zr2 99.8(4) 11 . ?
Zr1 O6 Zr2 113.6(4) 11 83 ?
Zr1 O6 Zr2 99.8(4) . . ?
Zr1 O6 Zr2 29.71(11) . 83 ?
Zr1 O6 Zr2 113.6(4) . 84 ?
Zr1 O6 Zr2 29.71(11) 11 84 ?
Zr2 O6 Zr2 103.9(5) 84 83 ?
Zr2 O6 Zr2 70.2(4) 84 . ?
Zr2 O6 Zr2 70.2(4) 83 . ?
Mn1 Mn1 O2 154.3(8) 80_554 . ?
Mn1 Mn1 O2 154.3(8) 80_554 9_655 ?
Mn1 Mn1 N3 70.0(5) 80_554 51 ?
Mn1 Mn1 N3 66.8(4) 80_554 48 ?
Mn1 Mn1 N3 66.8(4) 80_554 82 ?
Mn1 Mn1 N3 70.0(5) 80_554 . ?
Mn1 Mn1 O1 154.6(7) 80_554 9_655 ?
Mn1 Mn1 O1 154.6(7) 80_554 . ?
O2 Mn1 O2 51.3(15) . 9_655 ?
O2 Mn1 N3 135.7(9) 9_655 . ?
O2 Mn1 N3 110.8(4) . 82 ?
O2 Mn1 N3 135.7(9) . 51 ?
O2 Mn1 N3 110.8(4) . 48 ?
O2 Mn1 N3 110.8(4) 9_655 48 ?
O2 Mn1 N3 84.3(9) . . ?
O2 Mn1 N3 110.8(4) 9_655 82 ?
O2 Mn1 N3 84.3(9) 9_655 51 ?
O2 Mn1 O1 35.5(9) 9_655 9_655 ?
O2 Mn1 O1 35.5(9) 9_655 . ?
O2 Mn1 O1 35.5(9) . 9_655 ?
O2 Mn1 O1 35.5(9) . . ?
N3 Mn1 N3 82.25(14) . 48 ?
N3 Mn1 N3 82.25(14) . 82 ?
N3 Mn1 N3 82.25(14) 51 48 ?
N3 Mn1 N3 82.25(14) 51 82 ?
N3 Mn1 N3 133.5(9) 48 82 ?
N3 Mn1 N3 140.0(9) . 51 ?
O1 Mn1 N3 108.0(4) . 51 ?
O1 Mn1 N3 138.7(9) . 48 ?
O1 Mn1 N3 87.8(9) . 82 ?
O1 Mn1 N3 108.0(4) . . ?
O1 Mn1 N3 108.0(4) 9_655 . ?
O1 Mn1 N3 108.0(4) 9_655 51 ?
O1 Mn1 N3 138.7(9) 9_655 82 ?
O1 Mn1 N3 87.8(8) 9_655 48 ?
O1 Mn1 O1 50.8(15) . 9_655 ?
O2 O2 Mn1 64.3(8) 9_655 . ?
O1 O2 Mn1 72.8(15) 9_655 . ?
O1 O2 Mn1 72.8(15) . . ?
O1 O2 O2 44.9(6) . 9_655 ?
O1 O2 O2 44.9(6) 9_655 9_655 ?
O1 O2 O1 89.8(11) 9_655 . ?
Mn1 N3 Mn1 43.2(4) . 80_554 ?
C2 N3 Mn1 120.7(7) . 80_554 ?
C2 N3 Mn1 127.0(5) 54_655 . ?
C2 N3 Mn1 127.0(5) . . ?
C2 N3 Mn1 120.7(7) 54_655 80_554 ?
C2 N3 C2 104.7(7) . 54_655 ?
N3 C2 C3 126.4(6) . . ?
N3 C2 C1 109.7(6) . . ?
C1 C2 C3 122.6(6) . . ?
C1 C1 C2 107.1(4) 54_655 . ?
O2 O1 Mn1 71.7(15) . . ?
O2 O1 Mn1 71.7(15) 9_655 . ?
O2 O1 O2 90.1(11) 9_655 . ?
O2 O1 O1 45.1(6) . 9_655 ?
O2 O1 O1 45.1(6) 9_655 9_655 ?
O1 O1 Mn1 64.6(7) 9_655 . ?

_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 -0.324 -0.443 -0.816 44380.7 7304.5 ?

_olex2_submission_original_sample_id PCN224MnO2
_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_PCN224Mn
_database_code_depnum_ccdc_archive 'CCDC 1570585'
_audit_update_record             
;
2017-08-23 deposited with the CCDC.
2017-12-14 downloaded from the CCDC.
;
_audit_creation_date             2017-06-20
_audit_creation_method           
;
Olex2 1.2
(compiled Mar 28 2017 19:26:29 for OlexSys, GUI svn.r5337)
;
_shelx_SHELXL_version_number     2014/7
_chemical_name_common            ?
_chemical_name_systematic        PCN224Mn
_chemical_formula_moiety         '0.25(C576 H288 Mn12 N48 O208 Zr48)'
_chemical_formula_sum            'C144 H72 Mn3 N12 O52 Zr12'
_chemical_formula_weight         4061.59
_chemical_melting_point          ?
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'
Mn Mn -0.5299 2.8052 '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                   38.6720(10)
_cell_length_b                   38.6720(10)
_cell_length_c                   38.6720(10)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     57835(4)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    9863
_cell_measurement_temperature    100
_cell_measurement_theta_max      64.91
_cell_measurement_theta_min      2.28
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    2.409
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6302
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2014/5 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.0825 before and 0.0713 after correction.
The Ratio of minimum to maximum transmission is 0.8368.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'dark violet'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    0.466
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       Cube
_exptl_crystal_F_000             7964
_exptl_crystal_size_max          0.204
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0934
_diffrn_reflns_av_unetI/netI     0.0392
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       44
_diffrn_reflns_limit_h_min       -46
_diffrn_reflns_limit_k_max       46
_diffrn_reflns_limit_k_min       -42
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            154240
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.349
_diffrn_reflns_theta_min         2.285
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_source                   ?
_diffrn_special_details          
;
# start Validation Reply Form
#_vrf_PLAT430_PCN224Mn
#;
#PROBLEM: Short Inter D...A Contact  O3     ..  O4      ..       2.25 Ang.  
#RESPONSE: The short distance is a result of disorder in the Z6O8 cluster.
#;
#_vrf_PLAT213_PCN224Mn
#;
#PROBLEM: Atom Mn1             has ADP max/min Ratio .....        4.8 prolat
#RESPONSE: This elongated parameter arises from the disorder intrinsic to the system, in which atoms of the porphyrin are elongated out-of the plane
#;
#_vrf_PLAT241_PCN224Mn
#;
#PROBLEM: High   'MainMol' Ueq as Compared to Neighbors of         O2 Check 
#RESPONSE: The high equivalent for this atom is due to the disorder intrinsic to the structure that creates larger thermal factors for the atoms in the porphyrin unit.
#;
#_vrf_PLAT250_PCN224Mn
#;
#PROBLEM: Large U3/U1 Ratio for Average U(i,j) Tensor ....        5.8 Note  
#RESPONSE: This elongated parameter arising from the disorder intrinsic to the system, elongating atoms out of the plane of the porphyrin.
#;
# end Validation Reply Form
;
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                4013
_reflns_number_total             4950
_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 v8.37A (Bruker, 2015)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    ?
_refine_diff_density_max         1.489
_refine_diff_density_min         -0.737
_refine_diff_density_rms         0.092
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     102
_refine_ls_number_reflns         4950
_refine_ls_number_restraints     211
_refine_ls_R_factor_all          0.0949
_refine_ls_R_factor_gt           0.0844
_refine_ls_restrained_S_all      1.237
_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)+(0.1790P)²+83.5939P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2432
_refine_ls_wR_factor_ref         0.2639
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. 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
Uanis(O2) \\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(Zr1) \\sim
Ueq, Uanis(Zr2) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(O4)
\\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C4) \\sim Ueq,
Uanis(C3) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(N17) \\sim
Ueq, : with sigma of 0.03 and sigma for terminal atoms of 0.06
Uanis(Mn1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(Zr1)=0.5*(1-FVAR(2))
 Sof(Zr2)=0.5*FVAR(2)
5.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C5(H5), C6(H6)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     ?
_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 0.28505(17) 0.28505(17) 0.22263(9) 0.0678(10) Uani 0.489(16) 2 d S TU P
. .
Zr2 Zr 0.29594(16) 0.29594(16) 0.22688(9) 0.0659(10) Uani 0.511(16) 2 d S TU P
. .
O1 O 0.32830(10) 0.27724(11) 0.18443(10) 0.1166(16) Uani 1 1 d . U . . .
O2 O 0.32327(16) 0.32327(16) 0.2479(2) 0.158(3) Uani 1 2 d S TU P . .
O3 O 0.25698(12) 0.25698(12) 0.19646(12) 0.0971(14) Uani 1 2 d S TU P . .
O4 O 0.28091(13) 0.28091(13) 0.28091(13) 0.0718(18) Uani 1 6 d S TU P . .
N17 N 0.5000 0.2502(3) 0.05168(12) 0.138(3) Uani 1 2 d S TU P . .
C1 C 0.48251(11) 0.2483(2) 0.10864(9) 0.138(3) Uani 1 1 d . U . . .
H1 H 0.4678 0.2476 0.1283 0.166 Uiso 1 1 calc R U . . .
C2 C 0.47199(10) 0.2496(2) 0.07330(10) 0.129(3) Uani 1 1 d . U . . .
C3 C 0.43735(9) 0.2500 0.06265(9) 0.120(3) Uani 1 2 d S TU P . .
C4 C 0.41012(10) 0.2500 0.08988(10) 0.109(3) Uani 1 2 d S TU P . .
C5 C 0.39228(13) 0.2206(2) 0.09665(14) 0.120(2) Uani 1 1 d . U . . .
H5 H 0.3974 0.2002 0.0840 0.144 Uiso 1 1 calc R U . . .
C6 C 0.36606(13) 0.21999(19) 0.12235(13) 0.1048(19) Uani 1 1 d . U . . .
H6 H 0.3533 0.1995 0.1270 0.126 Uiso 1 1 calc R U . . .
C7 C 0.35977(10) 0.2500 0.14023(10) 0.091(2) Uani 1 2 d S TU P . .
C8 C 0.33213(11) 0.2500 0.16787(11) 0.094(2) Uani 1 2 d S TU P . .
Mn1 Mn 0.5000 0.2500 0.0000 0.193(2) Uani 1 8 d S TU P A 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 Zr1 2.743(15) 84 ?
Zr1 Zr1 2.743(15) 83 ?
Zr1 Zr2 3.246(15) 84 ?
Zr1 Zr2 3.246(15) 83 ?
Zr1 Zr2 0.618(3) . ?
Zr1 O1 2.252(4) . ?
Zr1 O1 2.252(4) 68 ?
Zr1 O2 2.308(14) . ?
Zr1 O3 1.943(3) 84 ?
Zr1 O3 1.839(12) . ?
Zr1 O3 1.943(3) 83 ?
Zr1 O4 2.265(6) . ?
Zr2 Zr1 3.246(15) 84 ?
Zr2 Zr1 3.246(15) 83 ?
Zr2 Zr1 3.643(5) 12 ?
Zr2 Zr1 3.643(5) 11 ?
Zr2 O1 2.187(4) 68 ?
Zr2 O1 2.187(4) . ?
Zr2 O2 1.702(14) . ?
Zr2 O3 2.160(5) 83 ?
Zr2 O3 2.434(12) . ?
Zr2 O3 2.160(5) 84 ?
Zr2 O4 2.246(3) . ?
O1 C8 1.242(5) . ?
O3 Zr1 1.943(3) 83 ?
O3 Zr1 1.943(3) 84 ?
O3 Zr2 2.160(5) 83 ?
O3 Zr2 2.160(5) 84 ?
O4 Zr1 2.265(6) 11 ?
O4 Zr1 2.265(6) 12 ?
O4 Zr2 2.245(3) 12 ?
O4 Zr2 2.245(3) 11 ?
N17 C2 1.369(5) . ?
N17 C2 1.369(5) 54_655 ?
N17 Mn1 1.998(5) . ?
C1 C1 1.353(9) 54_655 ?
C1 C2 1.427(5) . ?
C2 C3 1.402(4) . ?
C3 C2 1.402(4) 48 ?
C3 C4 1.489(7) . ?
C4 C5 1.354(8) 48 ?
C4 C5 1.354(8) . ?
C5 C6 1.420(6) . ?
C6 C7 1.373(7) . ?
C7 C6 1.373(7) 48 ?
C7 C8 1.512(7) . ?
C8 O1 1.242(5) 48 ?
Mn1 N17 1.999(5) 82 ?
Mn1 N17 1.999(5) 80_554 ?
Mn1 N17 1.999(5) 51 ?

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 77.0(4) 83 84 ?
Zr1 Zr1 Zr2 74.4(3) 84 83 ?
Zr1 Zr1 Zr2 74.4(3) 83 84 ?
Zr1 Zr1 Zr2 6.89(8) 84 84 ?
Zr1 Zr1 Zr2 6.89(8) 83 83 ?
Zr2 Zr1 Zr1 140.9(2) . 83 ?
Zr2 Zr1 Zr1 140.9(2) . 84 ?
Zr2 Zr1 Zr2 144.42(15) . 83 ?
Zr2 Zr1 Zr2 144.42(15) . 84 ?
Zr2 Zr1 Zr2 71.1(3) 84 83 ?
Zr2 Zr1 O1 76.1(4) . 68 ?
Zr2 Zr1 O1 76.1(4) . . ?
Zr2 Zr1 O2 9.7(4) . . ?
Zr2 Zr1 O3 162.0(5) . . ?
Zr2 Zr1 O3 102.2(4) . 83 ?
Zr2 Zr1 O3 102.2(4) . 84 ?
Zr2 Zr1 O4 80.3(5) . . ?
O1 Zr1 Zr1 82.9(2) . 83 ?
O1 Zr1 Zr1 130.4(4) 68 83 ?
O1 Zr1 Zr1 82.9(2) 68 84 ?
O1 Zr1 Zr1 130.4(4) . 84 ?
O1 Zr1 Zr2 123.5(4) . 84 ?
O1 Zr1 Zr2 80.3(2) 68 84 ?
O1 Zr1 Zr2 80.3(2) . 83 ?
O1 Zr1 Zr2 123.5(4) 68 83 ?
O1 Zr1 O1 76.6(2) 68 . ?
O1 Zr1 O2 83.6(3) . . ?
O1 Zr1 O2 83.6(3) 68 . ?
O1 Zr1 O4 134.1(3) . . ?
O1 Zr1 O4 134.1(3) 68 . ?
O2 Zr1 Zr1 138.4(2) . 84 ?
O2 Zr1 Zr1 138.4(2) . 83 ?
O2 Zr1 Zr2 143.39(15) . 83 ?
O2 Zr1 Zr2 143.39(15) . 84 ?
O3 Zr1 Zr1 108.5(4) 84 83 ?
O3 Zr1 Zr1 42.0(2) 83 83 ?
O3 Zr1 Zr1 45.0(3) . 84 ?
O3 Zr1 Zr1 108.5(4) 83 84 ?
O3 Zr1 Zr1 45.0(3) . 83 ?
O3 Zr1 Zr1 42.0(2) 84 84 ?
O3 Zr1 Zr2 48.3(2) 84 84 ?
O3 Zr1 Zr2 109.0(4) 84 83 ?
O3 Zr1 Zr2 39.2(2) . 84 ?
O3 Zr1 Zr2 39.2(2) . 83 ?
O3 Zr1 Zr2 109.0(4) 83 84 ?
O3 Zr1 Zr2 48.3(2) 83 83 ?
O3 Zr1 O1 159.53(18) 84 . ?
O3 Zr1 O1 83.14(14) 83 . ?
O3 Zr1 O1 89.9(3) . . ?
O3 Zr1 O1 83.14(14) 84 68 ?
O3 Zr1 O1 89.9(3) . 68 ?
O3 Zr1 O1 159.53(18) 83 68 ?
O3 Zr1 O2 97.4(3) 83 . ?
O3 Zr1 O2 171.7(3) . . ?
O3 Zr1 O2 97.4(3) 84 . ?
O3 Zr1 O3 116.8(3) 84 83 ?
O3 Zr1 O3 87.0(4) . 84 ?
O3 Zr1 O3 87.0(4) . 83 ?
O3 Zr1 O4 64.11(19) 84 . ?
O3 Zr1 O4 117.7(4) . . ?
O3 Zr1 O4 64.11(19) 83 . ?
O4 Zr1 Zr1 91.74(17) . 84 ?
O4 Zr1 Zr1 91.74(17) . 83 ?
O4 Zr1 Zr2 98.2(2) . 84 ?
O4 Zr1 Zr2 98.2(2) . 83 ?
O4 Zr1 O2 70.7(4) . . ?
Zr1 Zr2 Zr1 63.6(3) . 12 ?
Zr1 Zr2 Zr1 46.48(15) 84 11 ?
Zr1 Zr2 Zr1 32.19(16) . 84 ?
Zr1 Zr2 Zr1 32.19(16) . 83 ?
Zr1 Zr2 Zr1 55.86(5) 11 12 ?
Zr1 Zr2 Zr1 63.6(3) . 11 ?
Zr1 Zr2 Zr1 46.48(15) 83 12 ?
Zr1 Zr2 Zr1 78.69(6) 83 11 ?
Zr1 Zr2 Zr1 63.4(2) 84 83 ?
Zr1 Zr2 Zr1 78.69(6) 84 12 ?
Zr1 Zr2 O1 88.0(5) . . ?
Zr1 Zr2 O1 88.0(5) . 68 ?
Zr1 Zr2 O2 166.8(6) . . ?
Zr1 Zr2 O3 61.5(3) . 83 ?
Zr1 Zr2 O3 61.5(3) . 84 ?
Zr1 Zr2 O3 13.5(4) . . ?
Zr1 Zr2 O4 83.9(5) . . ?
O1 Zr2 Zr1 72.6(3) 68 84 ?
O1 Zr2 Zr1 105.80(14) 68 11 ?
O1 Zr2 Zr1 105.80(14) . 12 ?
O1 Zr2 Zr1 111.9(4) 68 83 ?
O1 Zr2 Zr1 111.9(4) . 84 ?
O1 Zr2 Zr1 72.6(3) . 83 ?
O1 Zr2 Zr1 150.5(3) 68 12 ?
O1 Zr2 Zr1 150.5(3) . 11 ?
O1 Zr2 O1 79.34(19) 68 . ?
O1 Zr2 O3 77.7(3) . . ?
O1 Zr2 O3 77.7(3) 68 . ?
O1 Zr2 O4 139.55(13) 68 . ?
O1 Zr2 O4 139.55(13) . . ?
O2 Zr2 Zr1 105.1(3) . 11 ?
O2 Zr2 Zr1 143.57(18) . 84 ?
O2 Zr2 Zr1 105.1(3) . 12 ?
O2 Zr2 Zr1 143.57(19) . 83 ?
O2 Zr2 O1 102.1(4) . . ?
O2 Zr2 O1 102.1(4) . 68 ?
O2 Zr2 O3 111.5(3) . 83 ?
O2 Zr2 O3 111.5(3) . 84 ?
O2 Zr2 O3 179.7(5) . . ?
O2 Zr2 O4 82.9(4) . . ?
O3 Zr2 Zr1 36.59(18) . 83 ?
O3 Zr2 Zr1 32.53(19) 83 83 ?
O3 Zr2 Zr1 75.24(9) . 11 ?
O3 Zr2 Zr1 25.84(12) 84 11 ?
O3 Zr2 Zr1 79.51(13) 84 12 ?
O3 Zr2 Zr1 79.51(13) 83 11 ?
O3 Zr2 Zr1 25.84(12) 83 12 ?
O3 Zr2 Zr1 36.59(18) . 84 ?
O3 Zr2 Zr1 75.24(9) . 12 ?
O3 Zr2 Zr1 87.9(3) 84 83 ?
O3 Zr2 Zr1 87.9(3) 83 84 ?
O3 Zr2 Zr1 32.53(19) 84 84 ?
O3 Zr2 O1 143.5(4) 84 . ?
O3 Zr2 O1 79.96(18) 83 . ?
O3 Zr2 O1 143.5(4) 83 68 ?
O3 Zr2 O1 79.96(18) 84 68 ?
O3 Zr2 O3 68.7(3) 83 . ?
O3 Zr2 O3 68.7(3) 84 . ?
O3 Zr2 O3 100.1(3) 84 83 ?
O3 Zr2 O4 61.4(2) 83 . ?
O3 Zr2 O4 61.4(2) 84 . ?
O4 Zr2 Zr1 36.3(2) . 12 ?
O4 Zr2 Zr1 36.3(2) . 11 ?
O4 Zr2 Zr1 79.9(2) . 83 ?
O4 Zr2 Zr1 79.9(2) . 84 ?
O4 Zr2 O3 97.4(4) . . ?
Zr2 O1 Zr1 15.92(8) . . ?
C8 O1 Zr1 122.7(4) . . ?
C8 O1 Zr2 137.4(4) . . ?
Zr2 O2 Zr1 3.49(15) . . ?
Zr1 O3 Zr1 93.0(4) . 83 ?
Zr1 O3 Zr1 122.9(3) 84 83 ?
Zr1 O3 Zr1 93.0(4) . 84 ?
Zr1 O3 Zr2 95.1(3) 84 . ?
Zr1 O3 Zr2 108.3(3) . 84 ?
Zr1 O3 Zr2 16.24(11) 83 83 ?
Zr1 O3 Zr2 16.24(11) 84 84 ?
Zr1 O3 Zr2 125.2(3) 83 84 ?
Zr1 O3 Zr2 108.3(3) . 83 ?
Zr1 O3 Zr2 125.2(3) 84 83 ?
Zr1 O3 Zr2 95.1(3) 83 . ?
Zr1 O3 Zr2 4.50(13) . . ?
Zr2 O3 Zr2 110.0(3) 83 . ?
Zr2 O3 Zr2 110.0(3) 84 . ?
Zr2 O3 Zr2 121.9(3) 83 84 ?
Zr1 O4 Zr1 97.8(4) 11 . ?
Zr1 O4 Zr1 97.8(4) 11 12 ?
Zr1 O4 Zr1 97.8(4) 12 . ?
Zr2 O4 Zr1 107.8(3) 12 11 ?
Zr2 O4 Zr1 15.74(7) 12 12 ?
Zr2 O4 Zr1 107.8(3) 11 . ?
Zr2 O4 Zr1 107.8(3) . 11 ?
Zr2 O4 Zr1 15.74(7) 11 11 ?
Zr2 O4 Zr1 107.8(3) . 12 ?
Zr2 O4 Zr1 15.74(7) . . ?
Zr2 O4 Zr1 107.8(3) 11 12 ?
Zr2 O4 Zr1 107.8(3) 12 . ?
Zr2 O4 Zr2 114.5(2) 12 11 ?
Zr2 O4 Zr2 114.5(2) 12 . ?
Zr2 O4 Zr2 114.5(2) 11 . ?
C2 N17 C2 104.6(5) . 54_655 ?
C2 N17 Mn1 127.7(2) 54_655 . ?
C2 N17 Mn1 127.7(2) . . ?
C1 C1 C2 106.6(2) 54_655 . ?
N17 C2 C1 111.1(3) . . ?
N17 C2 C3 125.2(4) . . ?
C3 C2 C1 123.7(4) . . ?
C2 C3 C2 124.2(5) . 48 ?
C2 C3 C4 117.9(2) . . ?
C2 C3 C4 117.9(2) 48 . ?
C5 C4 C3 119.8(3) 48 . ?
C5 C4 C3 119.8(3) . . ?
C5 C4 C5 120.4(6) . 48 ?
C4 C5 C6 120.9(7) . . ?
C7 C6 C5 117.6(7) . . ?
C6 C7 C6 122.5(6) . 48 ?
C6 C7 C8 118.8(3) . . ?
C6 C7 C8 118.8(3) 48 . ?
O1 C8 O1 126.6(6) 48 . ?
O1 C8 C7 116.7(3) . . ?
O1 C8 C7 116.7(3) 48 . ?
N17 Mn1 N17 90.001(3) . 82 ?
N17 Mn1 N17 90.001(3) . 80_554 ?
N17 Mn1 N17 179.5(6) 82 80_554 ?
N17 Mn1 N17 90.001(3) 51 80_554 ?
N17 Mn1 N17 179.5(6) . 51 ?
N17 Mn1 N17 90.001(3) 82 51 ?

_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 -0.100 -0.461 -0.268 47302.4 1784.5 ?

_olex2_submission_original_sample_id PCN224Mn
_olex2_submission_special_instructions 'No special instructions were received'

