Metal and Organic Templates Together Control the Size of Covalent Macrocycles and Cages

Covalent macrocycles and three-dimensional cages were prepared by the self-assembly of di- or tritopic anilines and 2,6-diformylpyridine subcomponents around palladium(II) templates. The resulting 2,6-bis(imino)pyridyl-PdII motif contains a tridentate ligand, leaving a free coordination site on the PdII centers, which points inward. The binding of ligands to the free coordination sites in these assemblies was found to alter the product stability, and multitopic ligands could be used to control product size. Multitopic ligands also bridged metallomacrocycles to form higher-order supramolecular assemblies, which were characterized via NMR spectroscopy, mass spectrometry, and X-ray crystallography. An efficient method was developed to reduce the imine bonds to secondary amines, leading to fully organic covalent macrocycles and cages that were inaccessible through other means.


Experimental Section
The reactions were not performed under inert atmosphere or anhydrous conditions unless otherwise stated. Commercial HPLC grade MeOH and MeCN and reagent grade dioxane were used as solvents. CH2Cl2 was distilled prior to use. Silica gel 60 (0.040-0.063 mm) was used for flash chromatography. Preparative layer chromatography (PLC) were performed with Silica gel 60 F254, 1 mm thick plates from Merck. The starting compounds 1, 2, 4, 11, 14a-g, T2, [Pd(MeCN)4](BF4)2, BH3•THF and ethylenediamine were commercial. S1 1 and T3 2 were prepared according to reported procedures. Complexes 15a-f were not isolated but directly used from crude solution. [Pd(MeCN)4](BF4)2 was stored under inert atmosphere. Caution: benzidine 2 is a known carcinogen and should be handled with extra care.
Useful information regarding syntheses: -Concentration and order of addition of subcomponents was observed to have a significant effect on the outcome of the self-assemblies (e.g. attempts to synthesize cages 12 and 13 with [Pd 2+ ] = 60 mM led to polymeric precipitate; mixing polyanilines with Pd(II) without aldehyde can lead to precipitate). Therefore, most self-assemblies were performed at [Pd 2+ ] = 2-4 mM and adding either Pd(II) or the polyaniline last. NMR spectra were recorded at either 9.4 Tesla (Bruker Avance III HD 400 equipped with a Smart Probe) or 11.7 Tesla (Bruker Avance III HD 500 equipped with a Smart Probe or Bruker Avance 500 equipped with a TCI CryoProbe or Bruker Avance 500 equipped with a DCH CryoProbe). Solvent signals were used for chemical shift referencing: 1  DOSY NMR experiments were performed on a Bruker Avance 500 NMR spectrometer equipped with a TCI CryoProbe or a Smart Probe. Maximum gradient strength was 5.35 G/mm at 10 A. DOSY measurements were performed using the standard Bruker pulse program, ledbpgp2s, employing a stimulated echo and longitudinal eddy-current delay (LED) using a gradient ramp from 5% to 95%. Relaxation delay was set to 10 s. Diffusion delay Δ (d20) and diffusion gradient length δ (2 × p30) were optimized for individual experiments. Individual rows of the quasi-2D diffusion databases were phased and baseline corrected. Raw DOSY data were processed using the Bayesian DOSY transform program in MestReNova 9.0.1-13254 or the peak height fit in MestReNova 11.0.5-18998.
Reactions under microwave irradiation were performed on a CEM Discover SP microwave synthesizer.      (11.7 Tesla, CD3CN, 298 K). The unusual shape of the correlation spot for the N=CH is most likely caused by a 1 J coupling constant value out of the usual range covered by standard HSQC parameters. Figure S5. 1 H-13 C HMBC spectrum of 3•(CD3CN)4 (11.7 Tesla, CD3CN, 298 K). The 1 J coupling artifacts are caused by 1 J coupling constant values out of the range filtered by standard HMBC parameters. Figure S6A. Gradual formation of 3•S14 upon addition of S1 in a solution of 3•(CD3CN)4 in CD3CN monitored by 1 H NMR spectroscopy (500 MHz, CD3CN, 298 K). The minor species in the bottom spectrum correspond to partial degradation of 3. Further additions of 4 did not increase the amount of 3•S14 as shown by the bottom spectrum. 3•S14 remained stable over days in solution at r.t. Note that addition of pyridine, nBu4N + Clor nBu4N + Brin place of S1 led to complete degradation of 3. Figure S6B. 1 H DOSY spectrum of 3•S14 (500 MHz, CD3CN, 298 K, diffusion delay Δ = 100 ms, diffusion gradient length δ = 2200 µs). The DOSY was processed by peak height fit on selected peaks (3•S14, S1, H2O and CHD2CN). Figure S7. ESI-LRMS of 3•S14. The loss of SiMe3 is suspected to originate from ESI-MS conditions. Weaker peaks corresponding to adducts with additional S1 are also observed. S8
Spectral data are in accordance with the literature. 3 (11.7 Tesla, CD3CN, 298 K). The unusual shape of the correlation spot for the N=CH is most likely caused by a 1 J coupling constant value out of the usual range covered by standard HSQC parameters. S12 Figure S13. 1 H-13 C HMBC spectrum of 5•T1 (11.7 Tesla, CD3CN, 298 K).        The brown mixture was stirred at 60°C for 20 h. The solution was cooled down to r.t., concentrated to a volume of ca. 3 mL with a rotary evaporator and slowly poured into 10 mL of iPr2O. The mixture was shaken and left to rest 10 minutes for complete precipitation then the precipitate was collected by centrifugation, washed with 5 mL Et2O and dried under vacuum affording 6•T2(BF4)8 as a brown solid (68.2 mg, 0.0232 mmol, FW = 2936.15 g/mol). Yield: 92%. 1 H NMR (500 MHz, CD3CN, 298 K, two conformers) δ (ppm) = 9.82 (dd, J = 5.9, 0.9 Hz, 1H, partial-cone), 9.71 (d, J = 2.0 Hz, 2H, partial-cone), 9.67 (dd, J = 6.0, 1.3 Hz, 4H, 1,2-alternate), 9.57 (d, J = 5.7 Hz, 2H, partial-cone), 9.40 (d, J = 2.0 Hz, 4H, 1,2-alternate), 9.33 (d, J = 2.0 Hz, 1H, partial-cone), 9.31 (dd, J = 6.0, 1.4 Hz, 1H, partial-cone), 9.29   . Numerous overlapping signals prevented complete assignment. The C2h symmetric conformer was identified by the presence of one set of 1 H NMR signals for the pyridyl moieties of the porphyrin template T2 and two sets for the imines and aromatic protons of the macrocycle 6; indeed, only one set of signals would have been expected for the highly symmetric cone (C4v) and 1,3-alternate (D2d) conformers.        The orange mixture was stirred at 60°C for 20 h. 1,3,5-tris(3-pyridyl)benzene T1 (23.1 mg, 0.0672 mmol) was added and the mixture was stirred at 60°C for 2 h. The solution was cooled down to r.t. under stirring and 10 mL MeOH were added. After 10 minutes, BH3•THF (1M) was added stepwise (10 additions of 100 µL, one every 10 min., total 1.00 mmol) and the reaction was monitored by ESI-MS (see Figure S27). The mixture was concentrated to a volume of ca. 5 mL with a rotary evaporator, filtered and slowly poured into 30 mL of Et2O. The precipitate was collected by centrifugation, washed with 5 mL Et2O and dried under vacuum affording 7•T1(BF4)6 as a yellowish grey solid (142 mg, purity and yield undetermined at this stage, FW = 2059.55 g/mol).      4+ . No change was observed between 8 and 10 additions, therefore the reaction was stopped even if the peak after 10 additions does not match perfectly the simulated spectrum of the product.   The brown mixture was stirred at 60°C for 20 h. The solution was cooled down to r.t. under stirring and 10 mL MeOH were added. After 10 minutes, BH3•THF (1M) was added stepwise (8 additions of 100 µL, one every 10 min., total 0.800 mmol) and the reaction was monitored by ESI-MS (see Figure S31). The mixture was concentrated to a volume of ca. 5 mL with a rotary evaporator, filtered and slowly poured into 30 mL of Et2O. The precipitate was collected by centrifugation, washed with 10 mL Et2O and dried under vacuum affording 8•T2(BF4)8 as a brown solid (153 mg, purity and yield undetermined at this stage, FW = 2952.27 g/mol).      To a stirred solution of 7•T1 (crude, 64.0 mg, ≤30 µmol) in 6 mL MeCN/CH2Cl2, 1:1, was added ethylenediamine (12.0 µL, d = 0.897 g/mL, 179 µmol). The mixture was stirred at r.t. for 10 min., filtered to remove insoluble material and the solvents were evaporated under vacuum. The resulting solid was dissolved in 3 mL CH2Cl2, filtered and subjected to preparative layer chromatography (PLC) (SiO2, CH2Cl2/MeOH, 85:15). The first band was separated in three sections: the central section contained pure 9 while the top and bottom sections contained 9 and impurities. The second band contained pure T1 (8.7 mg, 28 µmol). The impure fractions of 9 were combined and subjected to as second PLC (SiO2, CH2Cl2/acetone, 1:1). The main central band contained pure 9. Pure fractions of 9 from both PLCs were combined and dried under vacuum affording a slightly yellow solid (11.0 mg, 12.1 µmol, FW = 910.10 g/mol). Yield over 4 steps (from 4): 40%.        . 1 H NMR spectra (500 MHz, CDCl3, 298 K) of 9 (A) as crude material after demetallation, and (B) isolated by PLC. s: residual solvents, *impurity from PLC silica binder. This comparison shows that the crude material contains mainly 9 and the free template T1 as proof of the good selectivity of the synthesis method despite the relatively low isolated yield resulting from tedious purification process to remove the minor impurities.

S55
The theoretical radii for a sphere containing 12 and a spheroid containing 13 would be 13.4 Å and 14.7 Å, respectively, based on the crystal structure of 12•Cl6 and a PM3 model of 13•Cl9 (see Figure S61B). The Stokes-Einstein equation can generally be used to determine the effective radius of a spherical particle moving through a fluid by thermal motion (or diffusion): , where r is the effective radius (in m), kB the Boltzmann constant (in J . K -1 ), T the temperature (in K), η the fluid viscosity (in Pa . s), and D the diffusion coefficient of the particle (in m 2. s -1 ).
Following the Stokes-Einstein equation and with a CD3CN viscosity of 3.41 × 10 -4 Pa . s, 5 the diffusion coefficients calculated following the DOSY experiment of Figure S61A correspond to solvodynamic radii of 9.8 Å and 12.2 Å for Pd6[4+6] 12•(MeCN)6 and Pd9[6+9] 13•(MeCN)9, respectively (assuming perfect sphere behavior). These calculated solvodynamic radii are smaller than the corresponding particle radii which we infer is due to the shape of cages 12•(MeCN)6 and 13•(MeCN)9. Indeed, these cages are hollow with open faces, which leads to a smaller contact surface area compared to the corresponding closed spheres. Therefore, such open cage structures are expected to diffuse more rapidly than the corresponding closed spheres.
The radius values obtained with the Stokes-Einstein equation hold limited physical meaning for particles that deviate strongly from the behavior of a closed spherical particle. As we are not aware of a suitable theoretical model to correlate the diffusion coefficients with the radii of such open cage structures, we interpret the diffusion coefficients qualitatively, noting that larger assembly 13 diffuses more slowly than smaller assembly 12. . nBu4N + NTf2 -(523 mg, 1.00 mmol) was added and the mixture was concentrated to a volume of ca. 5 mL with a rotary evaporator and slowly poured into 30 mL of Et2O. The mixture was shaken and left to rest 10 minutes to complete precipitation. The precipitate was collected by centrifugation, washed with 5 mL Et2O and dissolved in a minimum amount of MeCN without drying. Two more cycles of nBu4N + NTf2addition, concentration, precipitation, washing and dissolution were performed. The final precipitate was dried under vacuum affording a poorly soluble black solid containing a mixture of 12•Cl6(NTf2)6 and 13•Cl9(NTf2)9. Repeated extractions of the solid with 5 mL MeCN were performed, regularly replacing the MeCN (initially after one hour and gradually increasing the extraction time up to one month) and isolating each extract fraction. The extract fractions were gently dried by blowing N2 affording solids of <10 mg each. 1 H NMR analysis in CD3CN showed enrichment in 12•Cl6(NTf2)6 for the early fractions and 13•Cl9(NTf2)9 for the late fractions. The amount of material dissolved over time decreased exponentially, thus the solid was never fully dissolved but some product could continuously be extracted (over 10 extractions for 3 months). Sonication and heating to 60 °C over periods of less than an hour did not show significant effect on the kinetics of dissolution. The synthesis of 13•T3•Cl3 was attempted under stirring at r.t. or at 60°C (oil bath) for 24 h but the yield of 13•T3•Cl3 was in the range 8-10% according to NMR analysis (see Table S1). The synthesis of 13•T3•Cl3 was also attempted through aniline exchange without improving the yield (see Figure S80).       The reduction and demetallation of cages 12•Cl6 and 13•Cl9 was performed. ESI-MS monitoring of the reduction step shows that the reaction proceeds smoothly, similarly to the reduction of macrocycles 5•T1 and 6•T2 (see Figures S66 and S67). The demetallation occurs swiftly upon addition of ethylenediamine as shown by NMR monitoring (see Figure S68). Unfortunately, the numerous stereoisomers of reduced cages S2•Cl6 and S3•Cl9 prevented NMR characterization and purity assessment and the low solubility of the final demetallated cages S4 and S5 after precipitation prevented further characterization and purity assessment. Therefore, no yield could be determined.

Procedure:
To a stirred solution of 12•(MeCN)6(BF4)12 and 13•(MeCN)9(BF4)18 (124 mg, 0.202 mmol in Pd) in 50 mL MeCN at r.t. was added a solution of nBu4N + Clin MeCN (0.10 M, 2.00 mL, 0.200 mmol). After 5 min. 10 mL MeOH was added to the mixture. After 10 minutes, BH3•THF (1M) was added stepwise (8 additions of 100 µL, one every 10 min., total 0.80 mmol) and the reaction was monitored by ESI-MS (see Figures S66 and S67). The mixture was filtered and slowly poured into 60 mL of Et2O. The precipitate was collected by centrifugation, washed with 5 mL Et2O without drying. The solid was dissolved in 10 mL MeCN by sonication. The solution was slowly poured into 30 mL Et2O, left to rest for 30 min. and the precipitate was collected by centrifugation then washed with 5 mL Et2O and dried under vacuum affording a black solid (87.2 mg, presumably mixture of S2•Cl6 and S3•Cl9).
Note: the two precipitations were performed to remove nBu4N + BF4byproduct.
To a solution of the mixture of S2•Cl6 and S3•Cl9 (2.0 mg, expected 3.8 µmol in Pd) in 0.5 mL DMSO-d6 at r.t. was added ethylenediamine (7.6 µmol, stock solution in DMSO-d6) under 1 H NMR spectroscopy monitoring (see Figure S68). The mixture was poured into 5 mL H2O and the precipitate was collected by centrifugation. The solid material obtained could not be dissolved despite a wide range of solvents tested under heating and sonication: DMSO, DMF, pyridine, toluene, chlorobenzene, CH2Cl2, CHCl3, CH2ClCH2Cl, CHCl2CHCl2, CCl2=CCl2, THF, MeOH, EtOH, MeCN, AcOEt, acetone, hexane. The solvent did not show coloration and spots deposited on TLC plates did not show the presence of product after drying.       Figure S73. 1 H NMR spectra (500 MHz, CD3CN, 298 K) of products from assembly of rigid tris-anilines with 1 and Pd(II). Sharp peaks are extremely small and only stand out because of the extreme broadening of signals for the main oligomeric products. Despite careful stoichiometry balance for the subcomponents, free 1 was observed in some cases which is suspected to originate from noncondensed anilines in the oligomeric species. For comparison purpose, the peaks of remaining 1 integrate for less than 10% of the original value (recorded before addition of Pd(II) and heating). *traces of solvents.

Potential cage formation from tetrakis-aniline building blocks
With a 90° divalent building block such as the bis(imino)pyridyl-Pd(II) studied herein and a planar tetravalent building block (90° between linkers), two symmetrical structures can be predicted (i.e. structures where all building blocks of the same type have the same role). These structures are either a [6+12] cuboctahedral cage or a linear planar polymer ( Figure S81). The cage should be entropically favorable but the linear polymer can be favored if it is more favorable for the divalent and tetravalent building blocks to be in a same plane rather than perpendicular (which is the case in the cage structure).
We tested the assembly of 1, Pd(II) and the tetrakis(4-aminophenyl)porphyrin subcomponent S10 under typical assembly conditions (i.e. CD3CN, 2 mM in Pd, 60°C) but 1 H NMR analysis only revealed extremely broadened signals likely corresponding to polymeric species and nothing was observed by ESI-MS analysis. This result suggests that polymeric species are favored. Figure S81. Potential symmetric structures resulting from the assembly of a divalent 90° bent and a tetravalent planar 90° building blocks.
The fact that polymeric species are favored from the self-assembly of 1 and S10 building blocks can be put in parallel with the absence of report for the corresponding "classical" Pd(II)12 coordination cage expected for the tetrakis-pyridyl ligand tetrakis(4-pyridyl)porphyrin while the capped linear oligomers, so-called "porphyrin tapes", were reported. 6 Indeed, aromatic rings stemming from porphyrin cores have a preferential out-of-plane orientation in regard to the porphyrin plane due to steric hindrance and such an orientation is expected to favor the linear polymer over the desired cage (see geometrical details in Figure S82). Other tetrakis-aniline compounds with different geometrical properties might lead to the expected Pd12 cage with bis(imino)pyridyl-Pd(II) building block but were not explored in the present study.

X-ray Crystallography
Data were collected at Beamline I19 of Diamond Light Source employing silicon double crystal monochromated synchrotron radiation (0.6889 Å) with ω and ψ scans at 100(2) K. 7 Data integration and reduction were undertaken with Xia2. 8 Subsequent computations were carried out using the WinGX-32 graphical user interface. 9 Multi-scan empirical absorption corrections were applied to the data using the AIMLESS 10 tool in the CCP4 suite. 11 The structures were solved by dual-space methods using SHELXT 12 then refined and extended with SHELXL. 13 In general, non-hydrogen atoms with occupancies greater than 0.5 were refined anisotropically. Carbon-bound hydrogen atoms were included in idealized positions and refined using a riding model. Disorder was modelled using standard crystallographic methods including constraints, restraints and rigid bodies where necessary. Crystallographic data along with specific details pertaining to the refinement follow. Crystallographic data have been deposited with the CCDC (1903235, 1903236 and 1903237

Specific refinement details:
The crystals of [3]·8AsF6·4MeCN·2H2O were grown by diffusion at r.t. of iPr2O into an acetonitrile solution of [3·(MeCN)4]·8BF4 (0.5 mM) containing excess K + AsF6 -(ca. 20 mM). The crystals employed immediately lost solvent after removal from the mother liquor and rapid handling prior to flash cooling in the cryostream was required to collect data. Despite these measures and the use of synchrotron radiation few reflections at greater than 0.97 Å resolution were observed. The asymmetric unit was found to contain one half of a 3·(MeCN)4 assembly and associated counterions and solvent molecules. The hydrogen atoms of the half occupancy water molecules could not be located in the electron density map and were not included in the model.
The anions within the structure show evidence of significant disorder. The four anions (per asymmetric unit) were modelled as disordered over five lattice sites, one of which shows additional disorder of the fluorine atoms. Bond length and thermal parameter restraints were applied to facilitate a reasonable refinement of the disordered AsF6 − anions. Even with these restraints some thermal parameters remain larger than ideal as a consequence of the high level of thermal motion or minor unresolved disorder of the anions and solvent molecules.
CheckCIF gives three A and fifteen B level alerts. These alerts (both A and B level) result from the limited data resolution, water molecules for which hydrogens were not modelled and thermal motion and/or unresolved disorder of some anions and solvent molecules as described above.  . 20 mM). The crystals employed immediately lost solvent after removal from the mother liquor and rapid handling prior to flash cooling in the cryostream was required to collect data. Data were obtained to 0.84 Å resolution. The asymmetric unit was found to contain one complete 52·T33 assembly and associated counterions and solvent molecules. The structure shows evidence of a significant amount of thermal motion throughout. Therefore, bond lengths and angles within pairs of chemically identical organic ligands were restrained to be similar to each other and thermal parameter restraints (SIMU, RIGU) were applied to all atoms except for palladium and antimony.
The anions and solvent molecules within the structure show evidence of substantial disorder. The 11 SbF6 − anions were modelled as disordered over 14 lattice sites. Nine of these lattice sites were further disordered over two or three positions. The occupancies of the disordered anions were allowed to refine freely and then fixed at the obtained values. Some additional minor occupancy positions of the anions could not be located in the electron density map and were not included in the model resulting in a discrepancy of 0.85 counterions per 52·T33 assembly which were included as SbF6 − in the formula. Some lower occupancy disordered atoms were modelled with isotropic thermal parameters and bond length and thermal parameter restraints were applied to facilitate realistic modelling of the disordered SbF6 − anions. The content of the cavity was modelled as one BF4 − anion disordered over three locations and one disordered water molecule. The disordered BF4 − anion was restrained to have an idealized tetrahedral geometry and modelled with isotropic thermal parameters. Most acetonitrile solvent molecules were also modelled as disordered over two or more locations with bond length and thermal parameter restraints applied to ensure a reasonable refinement. Benzene solvent molecules were modelled as rigid groups (AFIX 66). The hydrogen atoms of the disordered water and acetonitrile molecules could not be located in the electron density map and were not included in the model.
The SQUEEZE 14 function of PLATON 15 was employed to account for a small quantity of highly disordered solvent, which gave a potential solvent accessible void of 401 Å 3 per unit cell (a total of approximately 116 electrons). Since the identity of these diffuse solvent molecules could not be assigned conclusively they were not included in the formula. Consequently, the molecular weight and density given above are likely to be slightly underestimated.
CheckCIF gives sixteen B level alerts. These alerts all result from thermal motion and/or unresolved disorder, especially of the anions and solvent molecules as described above. . The crystals employed immediately lost solvent after removal from the mother liquor and rapid handling prior to flash cooling in the cryostream was required to collect data. The diffraction pattern was extremely broad and diffuse and few reflections were observed at better than 1.15 Å resolution despite the use of synchrotron radiation. As a result of the poorly diffracting ability of the crystals, the quality of the integration was also poor. Despite these limitations the quality of the data is more than sufficient to establish the connectivity of the structure. The asymmetric unit was found to contain one fourth of a 12·Cl6 assembly and associated counterions and solvent molecules.
Due to the less than ideal resolution, extensive thermal parameter and bond length restraints were required to facilitate realistic modelling for the organic parts of the structure. The GRADE program 16 was employed using the GRADE Web Server 17 to generate a full set of bond distance and angle restraints (DFIX, DANG, FLAT) for the organic ligands. Two ligand phenyl rings were modelled as disordered over two equal occupancy locations and the remaining phenyl rings were all disordered around special positions by symmetry. The disordered atoms were modelled with isotropic thermal parameters. One benzene solvent molecule was modelled as a rigid group (AFIX 66) with partial occupancy. Thermal parameter restraints (SIMU, RIGU) were applied to all atoms except for palladium, arsenic and chlorine. Even with these restraints some thermal parameters remain larger than ideal as a consequence of the high level of thermal motion or minor unresolved disorder present throughout the structure.
The anions within the structure show evidence of significant disorder. One AsF6 − anion was modelled as disordered over two locations and another anion was modelled with partial occupancy. The occupancies of the disordered anions were freely refined and then fixed at the obtained values. Some lower occupancy disordered atoms were modelled with isotropic thermal parameters and bond length and thermal parameter restraints were applied to facilitate realistic modelling of the disordered AsF6 − anions. Further reflecting the solvent loss and poor diffraction properties there is a significant amount of void volume in the lattice containing smeared electron density from disordered solvent. Consequently the SQUEEZE 14 function of PLATON 15 was employed to remove the contribution of the electron density associated with this highly disordered solvent. This gave a potential solvent accessible void of 5668.6 Å 3 per unit cell (a total of approximately 853 electrons). Since the identity of the diffuse solvent molecules could not be assigned conclusively to acetonitrile or benzene, they were not included in the formula. Consequently, the molecular weight and density given above are likely to be slightly underestimated.

S80
CheckCIF gives one A and five B level alerts. These alerts (both A and B level) all result from the limited data resolution, and thermal motion and/or unresolved disorder of some anions and solvent molecules as described above.

Calculation of angle α
The angle α defined in Figure S83 and referred in the manuscript is calculated (in degrees °) through formula (1) where x, y and z are the Cartesian coordinates of atoms a, b, c and d.

Modelling
Geometry optimized structures were modelled with semi-empirical methods using PM3 or PM6 models on SCIGRESS software (Fujitsu Limited, Tokyo, Japan, 2013) version FJ 2.6 (EU 3.1.9) Build 5996.8255.20141202. The Cartesian coordinates given below can be pasted in a text file with .xyz extension.