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Octa­kis(pyrazol-1-ylmeth­yl)­biphenyl­ene ethanol solvate, C44H40N16·C2H6O, has two independent centrosymmetric mol­ecules, one of which is hydrogen bonded to the solvent mol­ecule. One molecule adopts an arrangement with three arms up and one down in each benzene ring, whilst the other molecule has a conformation with two adjacent arms on the same side of the ring. In neither case is the expected fully alternating form observed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107022779/ga3053sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107022779/ga3053Isup2.hkl
Contains datablock I

CCDC reference: 655503

Comment top

We have long been involved in the synthesis and study of new N-heterocyclic ligands for use in coordination and metallosupramolecular chemistry (Steel, 2005). In particular we have prepared a large library of ligands that contain a central arene core to which are appended various heterocycles via flexible linker units (McMorran & Steel, 2002; McMorran et al., 2004). In the course of designing new ligands, we have employed the concept of `pre-organization' (Hennrich & Anslyn, 2002). This relies on the principle that six bulky substituents attached to a benzene ring will tend to arrange themselves on alternating faces of the ring in an ababab fashion [a and b being above and below the plane of the ring, as defined by MacNicol et al. (1985)]. For example, hexakis(pyrazol-1-ylmethyl)benzene adopts this conformation (Hartshorn & Steel, 1995). A common extension of this approach is to differentiate the two faces of the ring with differing 1,3,5- and 2,4,6-substituents, as for example in 1,3,5-triethyl-2,4,6-tris(pyrazol-1-ylmethyl)benzene (Hartshorn & Steel, 1997). We were interested to know whether this design concept could be extended to larger aromatic systems, such as biphenylenes. The X-ray crystal structure of octaethylbiphenylene revealed that this compound adopts an ababbaba conformation in the solid state rather than the fully alternating abababab conformation that was calculated to be the most stable (Taha et al., 2000; Marks et al., 2003). However, we previously prepared the new eight-armed ligand octakis(2-pyridylmethylsulfanyl)biphenylene and were encouraged to find that in the solid state it was preorganized into the fully alternating abababab conformation (McMorran & Steel, 2003). We now report the synthesis of octakis(pyrazol-1-ylmethyl)biphenylene and the X-ray crystal structure of its ethanol solvate, (I).

The new ligand octakis(pyrazol-1-ylmethyl)biphenylene was prepared by an eightfold phase-transfer catalysed alkylation of octakis(bromomethyl)biphenylene with pyrazole. It was purified by chromatography followed by recrystallization and was characterized by microanalysis, 1H NMR spectroscopy and electrospray mass spectrometry. In order to ascertain the conformation of this compound we sought to determine its X-ray structure. The analysis of (I) reveals that it crystallizes as the ethanol solvate, with two independent half molecules of the ligand in the asymmetric unit. The two independent molecules each lie on crystallographic centres of inversion. Fig. 1 shows a perspective view of the two molecules with unique and attached atoms labelled. The ethanol solvent molecule is hydrogen bonded to pyrazole atom N62 in one molecule of the ligand (Table 2). The planes of the pyrazole rings are inclined to the plane of the adjacent biphenylene unit at angles that range between 67.9 (2) and 112.8 (2)°. The duplicated pattern of bond lengths and angles within the biphenylene core (see Table 1) also parallels those observed in other structurally characterized octasubstituted biphenylenes (Hubig et al., 2000; Le Magueres et al., 2001a,b; Lu et al., 2002). These suggest that there is some bond delocalization in such molecules.

The two independent molecules have different arrangements of the arms with respect to the biphenylene plane. In the molecule in Fig. 1(a), the arms have an aababbab arrangement (C1–C4), whereas in the molecule in Fig. 1(b), the arms have an abbabaab arrangement (C1'–C4'). Thus, in neither case do the arms adopt the fully alternating form that might be expected to be energetically most favourable. Fig. 2 shows an overlay of the two independent molecules and serves to show that within each benzene ring two arms have very similar orientations, one shows a significant twisting in the orientation of the pyrazole ring and the fourth arm exists on opposite sides of the central plane.

Since all four octasubstituted biphenylenes have different relative orientations of the substituents it appears that the answer to the title question is that there is a much lower preference for the fully alternating conformation in these derivatives compared with the benzene analogues. We do not believe that the conformations of the two independent molecules are strongly influenced by crystal packing. The molecule with the unusual aababbab arrangement (see discussion below) is not involved in the hydrogen bond mentioned above. Apart from this hydrogen bond, the shortest intermolecular contact is between atoms N82 and H74 of adjacent molecules related by a centre of inversion. This distance is 2.453 (3) Å, which is not unusually short (Mascal, 1998). In order to gain more insight into the reasons for this, we carried out a search of the Cambridge Structural Database (CSD; Version 5.28, with updates of January 2007; Allen, 2002) to survey the conformations of octasubstituted naphthalenes that represent a closer analogy to the biphenylenes. Table 3 lists the conformational arrangements of substituents in octasubstituted biphenylenes and naphthalenes. From this it can be seen that octakis(bromomethyl)naphthalene is the only napthalene derivative that has the fully alternating arrangement. Table 3 also shows that in all but two examples each ring has two a arms and two b arms. Furthermore, in all cases the substituents in adjacent peri positions (analogous to C1 and C4 in Fig. 2, but conventionally labelled C1/C8 and C4/C5 for naphthalenes) are on opposite sides of the central plane. This is a well known effect that reduces syn peri steric effects (Marks et al., 2003). Such an effect is certain to be much less important in the biphenylenes than in the naphthalenes. We believe that an important reason for the scarcity of the fully alternating form in the octasubstituted biphenylenes and naphthalenes is that, unlike the hexasubstituted benzenes, this orientation is not centrosymmetric, a situation that minimizes dipole moments.

Related literature top

For related literature, see: Allen (2002); Hartshorn & Steel (1995, 1997); Hennrich & Anslyn (2002); Hubig et al. (2000); Le Magueres, Lindeman & Kochi (2001a, 2001b); Lu et al. (2002); MacNicol et al. (1985); Marks et al. (2003); Mascal (1998); McMorran & Steel (2002, 2003); McMorran et al. (2004); Steel (2005); Taha et al. (2000).

Experimental top

Octakis(bromomethyl)biphenylene (120 mg, 0.134 mmol), pyrazole (83 mg, 1.22 mmol), benzene (15 ml), 40% aqueous KOH (3 ml) and 40% aqueous Bu4NOH (2 drops) were refluxed together for 18 h. After cooling, water (10 ml) and ethyl acetate (20 ml) were added, the layers separated and the aqueous layer washed with ethyl acetate (2 × 20 ml). The combined organic fractions were washed with brine (10 ml) and dried over MgSO4. The solvents were evaporated to give a brown oil which was purified on a silica gel column [ethyl acetate/petroleum ether (50–70) 1:1]. Recrystallization from ethanol/petroleum ether (50–70) gave the product as yellow crystals (yield 54 mg, 51%).

Refinement top

Crystal decay was monitored by the measurement of duplicate reflections and was found to be negligible. The OH H atom was located in a difference Fourier synthesis and constrained to that position [Uiso(H) = 1.5Ueq(O)]. C-bound H atoms were placed in calculated positions, with C—H distances set at 0.95–0.99 Å, and refined as riding [Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C)]. Distinction between atoms N2 and C5 within the pyrazole rings was made on the basis of alternative refinements and the fact that the N1—N2 bonds are shorter than the N1—C5 bonds (Table 1).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Perspective views of the two independent centrosymmetric molecules. Displacement ellipsoids are drawn at the 50% probability level. Dotted lines represent hydrogen bonds. H atoms have been omitted, except for the solvent OH group.
[Figure 2] Fig. 2. Overlay of the two independent molecules, with selected labels to relate to Fig. 1. The darker (blue in the online version of the journal) single colour atoms represent the Fig. 1(a) (unprimed atoms) molecule.
Octakis(pyrazol-1-ylmethyl)biphenylene ethanol solvate top
Crystal data top
C44H40N16·C2H6OZ = 2
Mr = 838.99F(000) = 884
Triclinic, P1Dx = 1.349 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 12.937 (5) ÅCell parameters from 5034 reflections
b = 13.186 (5) Åθ = 2.8–26.3°
c = 13.815 (6) ŵ = 0.09 mm1
α = 87.300 (5)°T = 168 K
β = 70.756 (5)°Block, yellow
γ = 68.719 (5)°0.50 × 0.50 × 0.40 mm
V = 2066.2 (14) Å3
Data collection top
Siemens SMART CCD area-detector
diffractometer
7196 independent reflections
Radiation source: fine-focus sealed tube5180 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.045
phi and ω scansθmax = 25.1°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
h = 1515
Tmin = 0.870, Tmax = 0.967k = 158
24130 measured reflectionsl = 1616
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0576P)2 + 0.776P]
where P = (Fo2 + 2Fc2)/3
7196 reflections(Δ/σ)max < 0.001
569 parametersΔρmax = 0.27 e Å3
1 restraintΔρmin = 0.32 e Å3
Crystal data top
C44H40N16·C2H6Oγ = 68.719 (5)°
Mr = 838.99V = 2066.2 (14) Å3
Triclinic, P1Z = 2
a = 12.937 (5) ÅMo Kα radiation
b = 13.186 (5) ŵ = 0.09 mm1
c = 13.815 (6) ÅT = 168 K
α = 87.300 (5)°0.50 × 0.50 × 0.40 mm
β = 70.756 (5)°
Data collection top
Siemens SMART CCD area-detector
diffractometer
7196 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
5180 reflections with I > 2σ(I)
Tmin = 0.870, Tmax = 0.967Rint = 0.045
24130 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0501 restraint
wR(F2) = 0.126H-atom parameters constrained
S = 1.03Δρmax = 0.27 e Å3
7196 reflectionsΔρmin = 0.32 e Å3
569 parameters
Special details top

Experimental. M.p. 212–214° C. Analysis found: C 64.88, H 5.59, N 26.16%; C44H40N16·C2H6O·H2O requires: C 64.48, H 5.65, N 26.14%. ES—MS (CH3CN:HCO2H) 371.1 (100%) [M·2H]+, 793.1 [M·H]+. 1H NMR (CDCl3, 500 MHz, p.p.m.) δ 5.24 (s, 8H, CH2), 5.27 (s, 8H, CH2), 6.11 (t, 4H, H4), 6.16 (t, 4H, H4), 6.97 (d, 4H, H3), 7.32 (d, 4H, H3), 7.42 (d, 4H, H5), 7.45 (d, 4H H5).

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Four low angle reflections that suffered from background and beamstop screening effects were omitted from the refinement.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.82120 (18)0.47798 (17)0.01300 (15)0.0262 (5)
C20.74092 (18)0.57454 (17)0.01039 (15)0.0266 (5)
C30.76795 (18)0.66695 (18)0.03438 (16)0.0281 (5)
C40.87695 (18)0.67125 (17)0.03562 (15)0.0264 (5)
C50.95388 (18)0.57572 (17)0.01726 (15)0.0263 (5)
C60.92750 (18)0.48252 (17)0.00540 (15)0.0261 (5)
C110.79234 (19)0.37947 (17)0.04707 (16)0.0286 (5)
H11A0.84540.33640.08430.034*
H11B0.71060.40340.09600.034*
N110.80310 (15)0.30973 (14)0.03632 (13)0.0294 (4)
N120.91065 (16)0.25171 (17)0.10294 (15)0.0402 (5)
C130.8864 (2)0.2011 (2)0.16826 (19)0.0448 (6)
H13A0.94490.15260.22510.054*
C140.7675 (2)0.2259 (2)0.14515 (18)0.0382 (6)
H14A0.72950.20010.18120.046*
C150.71702 (19)0.29562 (19)0.05938 (18)0.0342 (5)
H15A0.63510.32840.02240.041*
C210.62601 (18)0.57506 (18)0.01314 (16)0.0309 (5)
H21A0.60470.51900.03030.037*
H21B0.56360.64710.01570.037*
N210.63219 (15)0.55300 (15)0.11802 (13)0.0302 (4)
N220.53212 (17)0.57667 (19)0.13801 (16)0.0479 (6)
C230.5671 (2)0.5377 (3)0.2348 (2)0.0553 (8)
H23A0.51500.54220.27120.066*
C240.6867 (2)0.4904 (2)0.2760 (2)0.0502 (7)
H24A0.73230.45730.34380.060*
C250.7262 (2)0.5009 (2)0.19932 (18)0.0443 (6)
H25A0.80610.47580.20270.053*
C310.68129 (19)0.76616 (18)0.06253 (17)0.0314 (5)
H31A0.72410.81140.10310.038*
H31B0.64640.74180.10650.038*
N310.58740 (16)0.83252 (15)0.02678 (14)0.0337 (5)
N320.61452 (18)0.86458 (17)0.10312 (16)0.0480 (6)
C330.5122 (2)0.9311 (2)0.1662 (2)0.0524 (7)
H33A0.50270.96680.22840.063*
C340.4212 (2)0.9423 (2)0.1308 (2)0.0511 (7)
H34A0.34010.98530.16240.061*
C350.4726 (2)0.8787 (2)0.0407 (2)0.0449 (6)
H35A0.43410.86900.00400.054*
C410.90167 (19)0.77323 (18)0.04874 (17)0.0316 (5)
H41A0.82660.83600.01980.038*
H41B0.95280.77230.00870.038*
N410.95824 (16)0.78954 (15)0.15491 (14)0.0335 (4)
N420.9228 (2)0.76652 (18)0.22940 (16)0.0472 (6)
C430.9832 (2)0.8000 (2)0.3134 (2)0.0505 (7)
H43A0.97720.79410.37950.061*
C441.0554 (2)0.8443 (2)0.2931 (2)0.0478 (7)
H44A1.10730.87370.34040.057*
C451.0366 (2)0.8370 (2)0.1906 (2)0.0434 (6)
H45A1.07270.86150.15170.052*
C1'0.67617 (18)0.90725 (17)0.36193 (15)0.0264 (5)
C2'0.67240 (19)0.81173 (17)0.32312 (15)0.0281 (5)
C3'0.57337 (19)0.78441 (17)0.36111 (16)0.0284 (5)
C4'0.47425 (18)0.84529 (17)0.44672 (16)0.0268 (5)
C5'0.48068 (18)0.93601 (17)0.48248 (16)0.0270 (5)
C6'0.57758 (18)0.96685 (16)0.44024 (16)0.0265 (5)
C510.77860 (19)0.94313 (18)0.31992 (16)0.0310 (5)
H51A0.78280.98490.37530.037*
H51B0.85230.87800.29630.037*
N510.76884 (15)1.01064 (15)0.23474 (14)0.0313 (4)
N520.67982 (17)1.10756 (16)0.25191 (15)0.0416 (5)
C530.6920 (2)1.1448 (2)0.15937 (19)0.0437 (6)
H53A0.64121.21300.14660.052*
C540.7872 (2)1.0728 (2)0.08397 (19)0.0415 (6)
H54A0.81381.08110.01230.050*
C550.8345 (2)0.98717 (19)0.13505 (17)0.0358 (6)
H55A0.90150.92290.10550.043*
C610.78111 (19)0.73744 (18)0.24071 (17)0.0338 (5)
H61A0.75730.69980.19640.041*
H61B0.82290.78190.19710.041*
N610.86065 (16)0.65634 (15)0.28458 (14)0.0334 (5)
N620.90219 (18)0.68707 (17)0.35111 (16)0.0466 (5)
C630.9745 (2)0.5942 (2)0.3704 (2)0.0524 (7)
H63A1.01710.58930.41600.063*
C640.9809 (2)0.5065 (2)0.3173 (2)0.0503 (7)
H64A1.02690.43180.31810.060*
C650.9069 (2)0.54931 (19)0.26273 (19)0.0410 (6)
H65A0.89120.50960.21720.049*
C710.5652 (2)0.69080 (17)0.31059 (17)0.0320 (5)
H71A0.48120.70090.32830.038*
H71B0.59840.69110.23500.038*
N710.62701 (16)0.58601 (14)0.34127 (14)0.0314 (4)
N720.66548 (17)0.49732 (15)0.27684 (16)0.0412 (5)
C730.7055 (2)0.4156 (2)0.3307 (2)0.0486 (7)
H73A0.73910.34100.30540.058*
C740.6929 (2)0.4510 (2)0.4275 (2)0.0483 (7)
H74A0.71540.40790.47950.058*
C750.6415 (2)0.56034 (19)0.43221 (18)0.0395 (6)
H75A0.61960.61020.48940.047*
C810.37507 (19)0.80724 (18)0.49795 (17)0.0312 (5)
H81A0.40750.72660.49710.037*
H81B0.33870.83720.57080.037*
N810.28383 (16)0.83850 (15)0.45078 (14)0.0316 (4)
N820.23706 (19)0.76575 (17)0.44085 (16)0.0440 (5)
C830.1496 (2)0.8207 (2)0.4078 (2)0.0517 (7)
H83A0.09940.79010.39370.062*
C840.1396 (2)0.9266 (2)0.3961 (2)0.0511 (7)
H84A0.08390.98180.37280.061*
C850.2264 (2)0.9362 (2)0.42496 (19)0.0440 (6)
H85A0.24321.00040.42650.053*
O900.8057 (2)0.81412 (17)0.54118 (16)0.0691 (6)
H90A0.82830.78960.47970.104*
C910.7532 (4)0.7452 (3)0.6080 (4)0.1064 (14)
H91A0.76040.68340.56510.128*
H91B0.79930.71440.65430.128*
C920.6375 (4)0.7951 (4)0.6671 (4)0.147 (2)
H92A0.62570.86520.69870.220*
H92B0.61590.74830.72120.220*
H92C0.58800.80750.62390.220*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0288 (11)0.0305 (12)0.0201 (11)0.0121 (9)0.0080 (9)0.0018 (9)
C20.0272 (11)0.0297 (12)0.0221 (11)0.0105 (9)0.0073 (9)0.0014 (9)
C30.0273 (11)0.0317 (12)0.0218 (11)0.0078 (9)0.0073 (9)0.0017 (9)
C40.0313 (12)0.0287 (12)0.0200 (11)0.0128 (9)0.0077 (9)0.0031 (9)
C50.0291 (11)0.0287 (12)0.0208 (11)0.0107 (9)0.0078 (9)0.0017 (9)
C60.0289 (12)0.0280 (12)0.0211 (11)0.0106 (9)0.0077 (9)0.0019 (9)
C110.0290 (12)0.0292 (12)0.0256 (11)0.0103 (9)0.0072 (10)0.0014 (9)
N110.0271 (10)0.0309 (10)0.0272 (10)0.0112 (8)0.0041 (8)0.0009 (8)
N120.0271 (10)0.0494 (13)0.0377 (11)0.0120 (9)0.0037 (9)0.0081 (10)
C130.0373 (14)0.0527 (16)0.0385 (14)0.0139 (12)0.0061 (12)0.0123 (12)
C140.0383 (14)0.0421 (14)0.0389 (14)0.0191 (11)0.0135 (11)0.0007 (11)
C150.0265 (12)0.0380 (14)0.0390 (13)0.0156 (10)0.0082 (10)0.0040 (11)
C210.0293 (12)0.0323 (12)0.0296 (12)0.0099 (10)0.0098 (10)0.0022 (10)
N210.0278 (10)0.0338 (11)0.0307 (10)0.0128 (8)0.0106 (8)0.0041 (8)
N220.0326 (11)0.0747 (16)0.0410 (13)0.0216 (11)0.0159 (10)0.0036 (11)
C230.0502 (17)0.088 (2)0.0415 (16)0.0344 (16)0.0233 (14)0.0046 (15)
C240.0529 (17)0.0592 (18)0.0331 (14)0.0148 (14)0.0132 (13)0.0019 (12)
C250.0318 (13)0.0545 (16)0.0335 (14)0.0055 (12)0.0056 (11)0.0014 (12)
C310.0300 (12)0.0305 (12)0.0331 (12)0.0096 (10)0.0120 (10)0.0058 (10)
N310.0313 (11)0.0281 (10)0.0375 (11)0.0064 (8)0.0119 (9)0.0065 (8)
N320.0473 (13)0.0453 (13)0.0394 (12)0.0024 (10)0.0202 (11)0.0032 (10)
C330.0586 (18)0.0370 (15)0.0396 (15)0.0045 (13)0.0134 (14)0.0016 (12)
C340.0384 (15)0.0335 (14)0.0599 (18)0.0036 (11)0.0007 (13)0.0066 (13)
C350.0323 (14)0.0381 (15)0.0605 (17)0.0105 (11)0.0141 (13)0.0054 (13)
C410.0333 (12)0.0329 (13)0.0312 (12)0.0130 (10)0.0135 (10)0.0042 (10)
N410.0382 (11)0.0329 (11)0.0347 (11)0.0185 (9)0.0138 (9)0.0081 (8)
N420.0619 (14)0.0599 (15)0.0338 (12)0.0380 (12)0.0167 (11)0.0084 (10)
C430.0625 (18)0.0561 (18)0.0364 (15)0.0316 (15)0.0113 (13)0.0122 (13)
C440.0397 (15)0.0447 (16)0.0541 (17)0.0179 (12)0.0094 (13)0.0227 (13)
C450.0414 (14)0.0393 (15)0.0574 (17)0.0218 (12)0.0199 (13)0.0135 (12)
C1'0.0282 (11)0.0255 (12)0.0223 (11)0.0070 (9)0.0082 (9)0.0051 (9)
C2'0.0323 (12)0.0245 (11)0.0216 (11)0.0037 (9)0.0092 (9)0.0023 (9)
C3'0.0361 (12)0.0230 (11)0.0246 (11)0.0083 (9)0.0116 (10)0.0034 (9)
C4'0.0304 (12)0.0230 (11)0.0260 (11)0.0081 (9)0.0106 (10)0.0050 (9)
C5'0.0293 (11)0.0230 (11)0.0250 (11)0.0068 (9)0.0079 (9)0.0039 (9)
C6'0.0284 (11)0.0223 (11)0.0254 (11)0.0072 (9)0.0074 (9)0.0033 (9)
C510.0304 (12)0.0299 (12)0.0289 (12)0.0093 (10)0.0077 (10)0.0049 (10)
N510.0305 (10)0.0296 (10)0.0287 (10)0.0103 (8)0.0047 (8)0.0058 (8)
N520.0370 (11)0.0362 (12)0.0389 (12)0.0052 (9)0.0070 (9)0.0083 (9)
C530.0476 (15)0.0423 (15)0.0440 (15)0.0176 (12)0.0193 (13)0.0169 (12)
C540.0535 (16)0.0453 (15)0.0320 (13)0.0256 (13)0.0150 (12)0.0106 (11)
C550.0391 (13)0.0365 (14)0.0290 (13)0.0173 (11)0.0037 (11)0.0002 (10)
C610.0357 (13)0.0308 (13)0.0268 (12)0.0070 (10)0.0058 (10)0.0005 (10)
N610.0317 (10)0.0304 (11)0.0295 (10)0.0059 (8)0.0054 (8)0.0016 (8)
N620.0495 (13)0.0406 (13)0.0481 (13)0.0083 (10)0.0231 (11)0.0011 (10)
C630.0446 (16)0.0492 (17)0.0590 (18)0.0062 (13)0.0248 (14)0.0065 (14)
C640.0367 (15)0.0350 (15)0.0652 (18)0.0028 (12)0.0113 (14)0.0045 (13)
C650.0336 (13)0.0313 (14)0.0447 (15)0.0066 (11)0.0015 (12)0.0044 (11)
C710.0395 (13)0.0250 (12)0.0309 (12)0.0100 (10)0.0129 (10)0.0019 (9)
N710.0374 (11)0.0229 (10)0.0323 (10)0.0093 (8)0.0113 (9)0.0006 (8)
N720.0456 (12)0.0271 (11)0.0461 (12)0.0079 (9)0.0139 (10)0.0085 (9)
C730.0526 (16)0.0234 (13)0.0700 (19)0.0094 (12)0.0257 (15)0.0016 (12)
C740.0542 (16)0.0367 (15)0.0579 (18)0.0170 (13)0.0253 (14)0.0183 (13)
C750.0491 (15)0.0337 (14)0.0356 (14)0.0135 (11)0.0166 (12)0.0071 (11)
C810.0348 (12)0.0284 (12)0.0306 (12)0.0128 (10)0.0106 (10)0.0049 (10)
N810.0333 (10)0.0278 (10)0.0330 (11)0.0118 (8)0.0095 (9)0.0036 (8)
N820.0536 (13)0.0462 (13)0.0492 (13)0.0313 (11)0.0260 (11)0.0185 (10)
C830.0494 (16)0.068 (2)0.0537 (17)0.0324 (15)0.0272 (14)0.0191 (14)
C840.0468 (16)0.0492 (17)0.0532 (17)0.0069 (13)0.0243 (14)0.0090 (13)
C850.0517 (16)0.0295 (14)0.0481 (15)0.0099 (12)0.0196 (13)0.0060 (11)
O900.0956 (17)0.0596 (14)0.0585 (13)0.0366 (12)0.0244 (13)0.0012 (11)
C910.093 (3)0.083 (3)0.115 (4)0.029 (2)0.001 (3)0.003 (3)
C920.102 (4)0.123 (4)0.141 (5)0.009 (3)0.010 (3)0.047 (3)
Geometric parameters (Å, º) top
C1—C61.367 (3)C2'—C611.511 (3)
C1—C21.424 (3)C3'—C4'1.425 (3)
C1—C111.492 (3)C3'—C711.499 (3)
C2—C31.383 (3)C4'—C5'1.355 (3)
C2—C211.497 (3)C4'—C811.495 (3)
C3—C41.426 (3)C5'—C6'1.394 (3)
C3—C311.515 (3)C5'—C6'ii1.499 (3)
C4—C51.367 (3)C6'—C5'ii1.499 (3)
C4—C411.481 (3)C51—N511.453 (3)
C5—C61.387 (3)C51—H51A0.9900
C5—C6i1.507 (3)C51—H51B0.9900
C6—C5i1.507 (3)N51—C551.339 (3)
C11—N111.447 (3)N51—N521.340 (3)
C11—H11A0.9900N52—C531.329 (3)
C11—H11B0.9900C53—C541.379 (4)
N11—C151.329 (3)C53—H53A0.9500
N11—N121.348 (2)C54—C551.362 (3)
N12—C131.324 (3)C54—H54A0.9500
C13—C141.377 (3)C55—H55A0.9500
C13—H13A0.9500C61—N611.456 (3)
C14—C151.353 (3)C61—H61A0.9900
C14—H14A0.9500C61—H61B0.9900
C15—H15A0.9500N61—C651.322 (3)
C21—N211.462 (3)N61—N621.348 (3)
C21—H21A0.9900N62—C631.322 (3)
C21—H21B0.9900C63—C641.362 (4)
N21—C251.333 (3)C63—H63A0.9500
N21—N221.336 (3)C64—C651.359 (4)
N22—C231.324 (3)C64—H64A0.9500
C23—C241.364 (4)C65—H65A0.9500
C23—H23A0.9500C71—N711.447 (3)
C24—C251.351 (3)C71—H71A0.9900
C24—H24A0.9500C71—H71B0.9900
C25—H25A0.9500N71—N721.338 (2)
C31—N311.451 (3)N71—C751.341 (3)
C31—H31A0.9900N72—C731.325 (3)
C31—H31B0.9900C73—C741.376 (4)
N31—C351.334 (3)C73—H73A0.9500
N31—N321.344 (3)C74—C751.345 (3)
N32—C331.323 (3)C74—H74A0.9500
C33—C341.376 (4)C75—H75A0.9500
C33—H33A0.9500C81—N811.455 (3)
C34—C351.357 (4)C81—H81A0.9900
C34—H34A0.9500C81—H81B0.9900
C35—H35A0.9500N81—C851.332 (3)
C41—N411.453 (3)N81—N821.339 (3)
C41—H41A0.9900N82—C831.315 (3)
C41—H41B0.9900C83—C841.362 (4)
N41—C451.328 (3)C83—H83A0.9500
N41—N421.343 (3)C84—C851.357 (4)
N42—C431.326 (3)C84—H84A0.9500
C43—C441.369 (4)C85—H85A0.9500
C43—H43A0.9500O90—C911.447 (5)
C44—C451.361 (4)O90—H90A0.8400
C44—H44A0.9500C91—C921.368 (5)
C45—H45A0.9500C91—H91A0.9900
C1'—C6'1.363 (3)C91—H91B0.9900
C1'—C2'1.415 (3)C92—H92A0.9800
C1'—C511.496 (3)C92—H92B0.9800
C2'—C3'1.386 (3)C92—H92C0.9800
C6—C1—C2115.0 (2)C2'—C3'—C71120.67 (19)
C6—C1—C11121.41 (19)C4'—C3'—C71117.3 (2)
C2—C1—C11123.56 (19)C5'—C4'—C3'114.9 (2)
C3—C2—C1121.74 (19)C5'—C4'—C81122.57 (19)
C3—C2—C21118.88 (19)C3'—C4'—C81122.33 (19)
C1—C2—C21119.3 (2)C4'—C5'—C6'122.8 (2)
C2—C3—C4121.86 (19)C4'—C5'—C6'ii147.1 (2)
C2—C3—C31119.65 (19)C6'—C5'—C6'ii90.11 (17)
C4—C3—C31118.5 (2)C1'—C6'—C5'123.5 (2)
C5—C4—C3114.8 (2)C1'—C6'—C5'ii146.4 (2)
C5—C4—C41122.50 (19)C5'—C6'—C5'ii89.89 (17)
C3—C4—C41122.57 (19)N51—C51—C1'111.67 (17)
C4—C5—C6123.3 (2)N51—C51—H51A109.3
C4—C5—C6i146.7 (2)C1'—C51—H51A109.3
C6—C5—C6i89.97 (17)N51—C51—H51B109.3
C1—C6—C5123.1 (2)C1'—C51—H51B109.3
C1—C6—C5i146.7 (2)H51A—C51—H51B107.9
C5—C6—C5i90.03 (17)C55—N51—N52112.08 (19)
N11—C11—C1113.84 (17)C55—N51—C51128.61 (19)
N11—C11—H11A108.8N52—N51—C51119.17 (18)
C1—C11—H11A108.8C53—N52—N51104.21 (19)
N11—C11—H11B108.8N52—C53—C54111.9 (2)
C1—C11—H11B108.8N52—C53—H53A124.0
H11A—C11—H11B107.7C54—C53—H53A124.0
C15—N11—N12112.56 (18)C55—C54—C53104.7 (2)
C15—N11—C11127.76 (18)C55—C54—H54A127.7
N12—N11—C11119.66 (17)C53—C54—H54A127.7
C13—N12—N11102.87 (18)N51—C55—C54107.1 (2)
N12—C13—C14113.0 (2)N51—C55—H55A126.4
N12—C13—H13A123.5C54—C55—H55A126.4
C14—C13—H13A123.5N61—C61—C2'111.80 (18)
C15—C14—C13104.2 (2)N61—C61—H61A109.3
C15—C14—H14A127.9C2'—C61—H61A109.3
C13—C14—H14A127.9N61—C61—H61B109.3
N11—C15—C14107.4 (2)C2'—C61—H61B109.3
N11—C15—H15A126.3H61A—C61—H61B107.9
C14—C15—H15A126.3C65—N61—N62111.6 (2)
N21—C21—C2111.45 (17)C65—N61—C61127.6 (2)
N21—C21—H21A109.3N62—N61—C61120.75 (19)
C2—C21—H21A109.3C63—N62—N61104.1 (2)
N21—C21—H21B109.3N62—C63—C64112.1 (2)
C2—C21—H21B109.3N62—C63—H63A124.0
H21A—C21—H21B108.0C64—C63—H63A124.0
C25—N21—N22111.65 (19)C65—C64—C63104.8 (2)
C25—N21—C21129.05 (19)C65—C64—H64A127.6
N22—N21—C21118.95 (17)C63—C64—H64A127.6
C23—N22—N21104.2 (2)N61—C65—C64107.5 (2)
N22—C23—C24112.0 (2)N61—C65—H65A126.3
N22—C23—H23A124.0C64—C65—H65A126.3
C24—C23—H23A124.0N71—C71—C3'112.84 (18)
C25—C24—C23104.9 (2)N71—C71—H71A109.0
C25—C24—H24A127.6C3'—C71—H71A109.0
C23—C24—H24A127.6N71—C71—H71B109.0
N21—C25—C24107.3 (2)C3'—C71—H71B109.0
N21—C25—H25A126.3H71A—C71—H71B107.8
C24—C25—H25A126.3N72—N71—C75112.06 (19)
N31—C31—C3112.86 (18)N72—N71—C71118.26 (18)
N31—C31—H31A109.0C75—N71—C71129.22 (18)
C3—C31—H31A109.0C73—N72—N71103.5 (2)
N31—C31—H31B109.0N72—C73—C74112.5 (2)
C3—C31—H31B109.0N72—C73—H73A123.8
H31A—C31—H31B107.8C74—C73—H73A123.8
C35—N31—N32112.0 (2)C75—C74—C73104.6 (2)
C35—N31—C31128.2 (2)C75—C74—H74A127.7
N32—N31—C31119.43 (18)C73—C74—H74A127.7
C33—N32—N31104.2 (2)N71—C75—C74107.4 (2)
N32—C33—C34111.9 (2)N71—C75—H75A126.3
N32—C33—H33A124.1C74—C75—H75A126.3
C34—C33—H33A124.1N81—C81—C4'114.43 (18)
C35—C34—C33104.9 (2)N81—C81—H81A108.7
C35—C34—H34A127.5C4'—C81—H81A108.7
C33—C34—H34A127.5N81—C81—H81B108.7
N31—C35—C34107.1 (2)C4'—C81—H81B108.7
N31—C35—H35A126.5H81A—C81—H81B107.6
C34—C35—H35A126.5C85—N81—N82111.3 (2)
N41—C41—C4114.09 (18)C85—N81—C81129.3 (2)
N41—C41—H41A108.7N82—N81—C81118.81 (18)
C4—C41—H41A108.7C83—N82—N81104.7 (2)
N41—C41—H41B108.7N82—C83—C84111.9 (2)
C4—C41—H41B108.7N82—C83—H83A124.0
H41A—C41—H41B107.6C84—C83—H83A124.0
C45—N41—N42111.6 (2)C85—C84—C83105.0 (2)
C45—N41—C41128.0 (2)C85—C84—H84A127.5
N42—N41—C41120.02 (18)C83—C84—H84A127.5
C43—N42—N41104.5 (2)N81—C85—C84107.1 (2)
N42—C43—C44111.6 (2)N81—C85—H85A126.5
N42—C43—H43A124.2C84—C85—H85A126.5
C44—C43—H43A124.2C91—O90—H90A109.5
C45—C44—C43105.0 (2)C92—C91—O90115.8 (4)
C45—C44—H44A127.5C92—C91—H91A108.3
C43—C44—H44A127.5O90—C91—H91A108.3
N41—C45—C44107.3 (2)C92—C91—H91B108.3
N41—C45—H45A126.3O90—C91—H91B108.3
C44—C45—H45A126.3H91A—C91—H91B107.4
C6'—C1'—C2'115.0 (2)C91—C92—H92A109.5
C6'—C1'—C51121.6 (2)C91—C92—H92B109.5
C2'—C1'—C51123.41 (19)H92A—C92—H92B109.5
C3'—C2'—C1'121.44 (19)C91—C92—H92C109.5
C3'—C2'—C61120.3 (2)H92A—C92—H92C109.5
C1'—C2'—C61118.3 (2)H92B—C92—H92C109.5
C2'—C3'—C4'122.03 (19)
C6—C1—C2—C32.7 (3)C6'—C1'—C2'—C3'1.9 (3)
C11—C1—C2—C3175.16 (19)C51—C1'—C2'—C3'176.83 (19)
C6—C1—C2—C21174.86 (18)C6'—C1'—C2'—C61176.27 (18)
C11—C1—C2—C217.2 (3)C51—C1'—C2'—C615.0 (3)
C1—C2—C3—C40.9 (3)C1'—C2'—C3'—C4'5.5 (3)
C21—C2—C3—C4178.53 (18)C61—C2'—C3'—C4'172.62 (19)
C1—C2—C3—C31177.75 (19)C1'—C2'—C3'—C71172.41 (19)
C21—C2—C3—C310.1 (3)C61—C2'—C3'—C719.5 (3)
C2—C3—C4—C53.6 (3)C2'—C3'—C4'—C5'4.9 (3)
C31—C3—C4—C5175.08 (18)C71—C3'—C4'—C5'173.06 (19)
C2—C3—C4—C41172.45 (19)C2'—C3'—C4'—C81170.69 (19)
C31—C3—C4—C418.9 (3)C71—C3'—C4'—C8111.3 (3)
C3—C4—C5—C62.7 (3)C3'—C4'—C5'—C6'1.1 (3)
C41—C4—C5—C6173.33 (19)C81—C4'—C5'—C6'174.50 (19)
C3—C4—C5—C6i179.2 (3)C3'—C4'—C5'—C6'ii179.9 (3)
C41—C4—C5—C6i3.1 (4)C81—C4'—C5'—C6'ii4.3 (5)
C2—C1—C6—C53.7 (3)C2'—C1'—C6'—C5'2.0 (3)
C11—C1—C6—C5174.23 (18)C51—C1'—C6'—C5'179.29 (19)
C2—C1—C6—C5i178.4 (3)C2'—C1'—C6'—C5'ii176.4 (3)
C11—C1—C6—C5i0.4 (4)C51—C1'—C6'—C5'ii4.8 (4)
C4—C5—C6—C11.0 (3)C4'—C5'—C6'—C1'2.4 (3)
C6i—C5—C6—C1177.1 (2)C6'ii—C5'—C6'—C1'176.9 (3)
C4—C5—C6—C5i178.1 (2)C4'—C5'—C6'—C5'ii179.3 (3)
C6i—C5—C6—C5i0.0C6'ii—C5'—C6'—C5'ii0.000 (1)
C6—C1—C11—N11101.5 (2)C6'—C1'—C51—N5191.0 (2)
C2—C1—C11—N1180.7 (2)C2'—C1'—C51—N5187.7 (2)
C1—C11—N11—C15108.2 (2)C1'—C51—N51—C55111.3 (2)
C1—C11—N11—N1270.1 (2)C1'—C51—N51—N5264.2 (3)
C15—N11—N12—C130.0 (3)C55—N51—N52—C530.3 (3)
C11—N11—N12—C13178.6 (2)C51—N51—N52—C53176.5 (2)
N11—N12—C13—C140.4 (3)N51—N52—C53—C540.2 (3)
N12—C13—C14—C150.6 (3)N52—C53—C54—C550.1 (3)
N12—N11—C15—C140.4 (3)N52—N51—C55—C540.4 (3)
C11—N11—C15—C14178.1 (2)C51—N51—C55—C54176.1 (2)
C13—C14—C15—N110.5 (3)C53—C54—C55—N510.3 (3)
C3—C2—C21—N2181.1 (2)C3'—C2'—C61—N6189.6 (2)
C1—C2—C21—N2196.6 (2)C1'—C2'—C61—N6188.6 (2)
C2—C21—N21—C2523.8 (3)C2'—C61—N61—C65128.1 (2)
C2—C21—N21—N22163.63 (19)C2'—C61—N61—N6256.4 (3)
C25—N21—N22—C230.2 (3)C65—N61—N62—C630.9 (3)
C21—N21—N22—C23174.0 (2)C61—N61—N62—C63177.1 (2)
N21—N22—C23—C240.1 (3)N61—N62—C63—C640.8 (3)
N22—C23—C24—C250.3 (4)N62—C63—C64—C650.4 (3)
N22—N21—C25—C240.4 (3)N62—N61—C65—C640.7 (3)
C21—N21—C25—C24173.4 (2)C61—N61—C65—C64176.5 (2)
C23—C24—C25—N210.4 (3)C63—C64—C65—N610.2 (3)
C2—C3—C31—N3181.1 (2)C2'—C3'—C71—N7181.1 (3)
C4—C3—C31—N31100.1 (2)C4'—C3'—C71—N71100.9 (2)
C3—C31—N31—C35136.9 (2)C3'—C71—N71—N72154.7 (2)
C3—C31—N31—N3251.3 (3)C3'—C71—N71—C7533.8 (3)
C35—N31—N32—C331.0 (3)C75—N71—N72—C730.6 (3)
C31—N31—N32—C33174.1 (2)C71—N71—N72—C73173.5 (2)
N31—N32—C33—C340.5 (3)N71—N72—C73—C740.1 (3)
N32—C33—C34—C350.2 (3)N72—C73—C74—C750.5 (3)
N32—N31—C35—C341.2 (3)N72—N71—C75—C740.9 (3)
C31—N31—C35—C34173.5 (2)C71—N71—C75—C74172.8 (2)
C33—C34—C35—N310.8 (3)C73—C74—C75—N710.8 (3)
C5—C4—C41—N4192.5 (2)C5'—C4'—C81—N8198.6 (2)
C3—C4—C41—N4191.8 (2)C3'—C4'—C81—N8186.2 (2)
C4—C41—N41—C45146.4 (2)C4'—C81—N81—C8549.9 (3)
C4—C41—N41—N4241.5 (3)C4'—C81—N81—N82139.1 (2)
C45—N41—N42—C430.9 (3)C85—N81—N82—C830.3 (3)
C41—N41—N42—C43174.1 (2)C81—N81—N82—C83172.9 (2)
N41—N42—C43—C440.4 (3)N81—N82—C83—C840.2 (3)
N42—C43—C44—C450.2 (3)N82—C83—C84—C850.5 (3)
N42—N41—C45—C441.0 (3)N82—N81—C85—C840.6 (3)
C41—N41—C45—C44173.6 (2)C81—N81—C85—C84172.2 (2)
C43—C44—C45—N410.7 (3)C83—C84—C85—N810.7 (3)
Symmetry codes: (i) x+2, y+1, z; (ii) x+1, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O90—H90A···N620.842.022.828 (3)162

Experimental details

Crystal data
Chemical formulaC44H40N16·C2H6O
Mr838.99
Crystal system, space groupTriclinic, P1
Temperature (K)168
a, b, c (Å)12.937 (5), 13.186 (5), 13.815 (6)
α, β, γ (°)87.300 (5), 70.756 (5), 68.719 (5)
V3)2066.2 (14)
Z2
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.50 × 0.50 × 0.40
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2002)
Tmin, Tmax0.870, 0.967
No. of measured, independent and
observed [I > 2σ(I)] reflections
24130, 7196, 5180
Rint0.045
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.126, 1.03
No. of reflections7196
No. of parameters569
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.27, 0.32

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

Selected geometric parameters (Å, º) top
C1—C61.367 (3)C1'—C6'1.363 (3)
C1—C21.424 (3)C1'—C2'1.415 (3)
C2—C31.383 (3)C2'—C3'1.386 (3)
C3—C41.426 (3)C3'—C4'1.425 (3)
C4—C51.367 (3)C4'—C5'1.355 (3)
C5—C61.387 (3)C5'—C6'1.394 (3)
C5—C6i1.507 (3)C5'—C6'ii1.499 (3)
N11—C151.329 (3)N51—C551.339 (3)
N11—N121.348 (2)N51—N521.340 (3)
N21—C251.333 (3)N61—C651.322 (3)
N21—N221.336 (3)N61—N621.348 (3)
N31—C351.334 (3)N71—N721.338 (2)
N31—N321.344 (3)N71—C751.341 (3)
N41—C451.328 (3)N81—C851.332 (3)
N41—N421.343 (3)N81—N821.339 (3)
C6—C1—C2115.0 (2)C6'—C1'—C2'115.0 (2)
C3—C2—C1121.74 (19)C3'—C2'—C1'121.44 (19)
C2—C3—C4121.86 (19)C2'—C3'—C4'122.03 (19)
C5—C4—C3114.8 (2)C5'—C4'—C3'114.9 (2)
C4—C5—C6123.3 (2)C4'—C5'—C6'122.8 (2)
C4—C5—C6i146.7 (2)C4'—C5'—C6'ii147.1 (2)
C6—C5—C6i89.97 (17)C6'—C5'—C6'ii90.11 (17)
C1—C6—C5123.1 (2)C1'—C6'—C5'123.5 (2)
Symmetry codes: (i) x+2, y+1, z; (ii) x+1, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O90—H90A···N620.842.022.828 (3)162.2
Conformational arrangements of substituents in octasubstituted biphenylenes and naphthalenes top
SubstituentCSD RefcodeConformation (MacNicol et al., 1985)
Biphenylenes
EthylaCEVDAXababbaba
2-PyridylsulfanylmethylbUKOZEZabababab
Pyrazol-1-ylmethylthis workaababbab
this workabbabaab
Naphthalenes
Phenylsulfanyl (Yellow form)cBOWWOZaabbaabb
Phenylsulfanyl (Red form)c,dBOWWOZ01aabbaabb
3-MethylphenylsulfanyleDEFCASaabbaabb
4-MethylphenylsulfanyleDEFCIAabbabaab
4-(2-Phenylprop-2-yl)phenylsulfanylfFAJDEZaaabaaab
3,5-DimethylphenylsulfanylgTELXENabababba
3,4-DimethylphenylsulfanylhTODMAAaabbaabb
CyclohexylsulfanyliKOLXAKabbabaab
PhenylselanyljJOTHIJabaababb
3-MethylphenoxykJEFDAZabbabaab
2-NaphthoxykJEFCUSababbaba
BromomethyllWUTRAEabababab
3,3-Dimethylbut-1-enylmFEWHIZabbabaab
Notes: (a) Taha et al. (2000); (b) McMorran & Steel (2003); (c) Barbour et al. (1983); (d) Suenaga et al. (2003); (e) MacNicol et al. (1985); (f) Downing et al. (1998); (g) Downing, MacNicol et al. (1996); (h) Downing, Frampton et al. (1996); (i) MacNicol et al. (1991); (j) MacNicol et al. (1992); (k) Freer et al. (1989); (l) Simaan et al. (2003); (m) Stulgies et al. (2005).
 

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