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Crystal Structure of 2 4-Hexadiynediol.

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assignment is given in Figure 3. The zero-field parameter
0=128 MHz was determined from the distance of H z 2
and Hzl.
Apart from the high-field part of the spectrum considered
with (Am= 1)-transitions, a half-field transition (Am =2) of
lower intensity is also observed at 1637 G. In agreement
with theory" its absorption maximum lies exactly at
Radical ( 1 ) is the first organic three-spin system for which
a quartet ground state has been proved.
Received: August 5,1971 [Z 509 IE]
German version: Angew. Chem. 83, 1015 (1971)
A Novel Phosphorus Heterocycle:
By Marianne Baudler, Jiirgen Vesper, Peter Junkes,
and Harald Sandmann[*l
Several carbon heterocycles containing one or two phosphorus atoms are already known and have been reportedC2].
We have been able to synthesize 1,2,3,4-tetraphenyl1,2,3,4-tetraphospholane (1) as the first phosphorus
heterocycle of the type (PR'),- ,CRi ("cyclocarbaphosphanes") derived from the cyclophosphanes (PR),.
Compound ( I ) is formed in the reaction of methylene
chloride with triphenylcyclotriphosphanedipotassium
(2)"' or 1,2,3,4-tetraphenyltetraphosphane-1,4-dipotassium (3)c4'.
( 3 ) ,n = 4
The title compound can be prepared batchwise in 73%
yield by reaction of pentaphenylcyclopentaphosphane,
(PC6Hs)5,in tetrahydrofuran with the requisite stoichiometric amount of potassium for formation of (2) or (?)
and subsequent treatment of the potassium salt with an
equimolar amount of methylene chloride. Compound ( I )
crystallizes from acetonitrile as colorless needles, m. p.
134-138 "C, which are readily soluble in benzene, toluene,
and tetrahydrofuran. In the solid state, ( I ) is stable towards atmospheric oxygen for a short while but is rapidly
oxidized in the presence of solvents. It could be characterized by complete elemental analysis, osmometric molecular
weight determinations, and IR,UV, 'H-NMR, 31P-NMR,
and MS spectro~copy[~l.
R spectrum closely resembles that of pentaphenylThe I
cyclopentaphosphane; however, a few characteristic differences are observable in the range 520-300 cm- (ringvibration region) and additional absorptions of the CH,
group occur at 2924 and 2880cm-' and in the region of
the C-Haliph bending vibrations. The UV spectrum [Amax
= 215 nm ( E = 37600) in n-hexane] exhibits increased extinction, so additional interactions probably occur between
the P atoms via d-hybrid functions.
The NMR spectra (solution in CS,, 24°C) provide unequivocal evidence of the symmetry of the ring. The
Prof. Dr. M. Baudler, Dipl.-Chem. J. Vesper, Dr. P. Junkes,
and Dip].-Chem. H. Sandmann
Institut fur Anorganische Chemie der Universitat
5 Koln 1, Ziilpicher Strasse 47 (Germany)
'H-NMR spectrum shows two groups of signals in the
intensity ratio 1O:l which can be assigned to aromatic
and methylene protons. On decoupling of the 31Pnucleus,
the multiplet of the methylene protons degenerates to a
sharp line at s=6.970 ppm, so there is obviously equivalence. The 31P-NMR spectrum consists-with simultaneous proton decoupling-of one AA'BB' system centered at
6 = - 34.6 ppm (against 85% H3P04,external). These findings are compatible only with C, symmetry of the ring.
Detailed analysis of the AA'BB' system and X-ray structural
investigations are presently being carried out.
The mass spectrum (15 eV) contains a very strong signal
due to the molecular ion (rn/e=446) alongside one for the
fragment C6Hl. With increasing electronic energy and
heating, additional signals of the following transformation
products occur: (C6HS),P, (m/e= 370), (C,H,P), (324),
(C6H513PCH z (2761, (C,H 513P (262), (C& 42PCH3 (1991,
(C6Hs),PH (I%), and C6H,P,H3 (142).
A solution of pentaphenylcyclopentaphosphane (12.5 g,
0.023 mol) in dry tetrahydrofuran (150 ml) is heated under
reflux with potassium (3.0 g, 0.077 g atom) for several hours
in the absence of air. The reaction mixture is vigorously
stirred and reaction allowed to proceed until a clear, dark
red solution of (2) is formed. A solution of methylene
chloride (3.28 g, 0.039 mol) in tetrahydrofuran (20 ml) is
then added at 0°C over a period of 2 hours and the resulting
mixture stirred for a further 10 hours. After complete
removal of the solvent at reduced pressure, the residue is
taken up in carbon disulfide (100 ml), filtered to remove
insoluble material, and finally re-evaporated to dryness.
Recrystallization of the final residue from acetonitrile
(400 ml) affords ( 1 ) in 73% yield [9.4 g; mol. wt. (osmometric in CS,, 25 "C) : 4361.
Received: August 10,1971 [Z 511 IE]
German version: Angew. Chem. 83, 1019 (1971)
[I] Contributions to the chemistry of phosphorus, Part 42.- Part 41 :
M . Baudler and A . Zarkadas, Chem. Ber., in press.
121 Cf. K . D.Berlin and D.M . Hdlwege, Top. Phosphorus Chem. 6, 1
[3] K . Issleib and E. Fluck,Angew. Chem. 78,597(1966);Angew. Chem.
internat. Edit. 5, 587 (1966).
[4] K. Issleib and K . Krech, Chem. Ber. 99, 1310 (1966).
[S] We thank Dr. K. Glinka for recording the mass spectra.
Crystal Structure of 2,4-Hexadiynediolr1'
By Erich Hadicke, Klaus Penzien, and Hans W Schnellc'l
Numerous derivatives of diacetylene can be polymerized
in the crystalline state by heat or high-energy radiation.
The main contribution to the understanding of these topochemically controlled reactions"] has hitherto been the
structure determination of polymeric 2,4-hexadiynylenebi~(phenylurethane)['*~].We therefore tried to find an explanation for the ready polymerizability of 2,4-hexadiynediol by an X-ray structure analysis of the monomer. The
monomeric crystals of 2,4-hexadiynediol, unlike those of
2,4-hexadiynylenebis(phenylurethane), are stable under
the employed conditions for an X-ray structure analysis.
[*] Dr. E. Hadicke, Dr. K. Penzien, and Dr. W. Schnell
Badische Anilin- & Soda-Fabrik AG
67 Ludwigshafen (Germany)
Angew. Chem. internat. Edit. / Vol. 10 (1971) / No. 12
The three-dimensional X-ray structure analysis of 2,4hexadiynediol was carried out with monoclinic platelets
obtained by crystallization from watp. Crystallographic
data: a=4.08,, b=15.99,, c=4.76, A ; p=106.5,"; dexp
=1.22 g c m - 3 ; space group P2,/c. The asymmetric unit
contains '/* molecule C6H,0, (dCale=
1.22 g cm-3): The
individual molecule has a center of symmetry. Owing to
their sensitivity to X-rays a number of crystals had to be
used in succession for intensity measurements. These
measurements on our single-crystal diffractometer (9/23scan, 5-point measurement) were carried out with one
crystal as long as periodically repeated measurements on
reference reflections showed a statistically significant
decrease in intensity. The quality of this crystal was then
checked by photography. We recorded 382 reflections of
8 crystals (Cu,, radiation, 3 < 50"); 10 of these reflections
could not be observed ( I < 2 IS,).
Using triple product methods with symbolic addition['I,
96 signs could be determined for the 99 strongest reflections
( E 2 1.0). An &Fourier synthesis based on these data
afforded the positions of all atoms (R=50.4%). By leastsquares isotropic refinement (full matrix) with a scaling
factor an R factor of only 25.3% could be obtained. However, simultaneous refinement of the scaling factors from
the sets of data obtained from the eight crystals and of the
anisotropic temperature factors lowered the R value to
9.4%. The structure of the planar single molecule is shown
in Figure 1. The standard deviations of the bond lengths
are 0.01 A, those of the bond angles 0.7". All bond lengths
are in agreement with values given in the literature for
similar compoundsL6.'I.
It is found that the distance between the C atoms to be
bound is 3.94 and 3.52 A, respectively. We therefore assume
c - CXlS
Fig. 2. Possible modes of polymerization of 2,4-hexadiynediol.
that polymerization is possible in both planes; this in turn
would account for the largely amorphous character of
polymeric 2,4-hexadiynediol.
Received:August 18,1971 [Z 513 IE]
German version: Angew. Chem. 83, 1024 (1971)
Fig. 1. Monomeric 2,4-hexadiynediol. Bond lengths
angles (").
and bond
If the product in this reaction too (cf. ref. 14]) is a poly-en-yne
formed by 1,Clinkage of neighboring monomer units
(Fig. 2c), the carbon atoms to be bonded should not be
farther apart than about 4 .&[2,81. The experimentally obtained intermolecular distances reveal that the monomers
can polymerize either along the c axis or along the a/c
diagonal. Figures 2 a and 2 b show the planes fixed by
these two directions and the molecular axis.
Angew. Chem. internat. Edit.J Vol. 10 (1971) J No. I2
[l] Dr. A . W Hanson, Biochemistry Laboratory, National Research
Council of Canada, Ottawa 7, has informed us that he has independently
solved the same structure.
[2] G . M . J . Schmidt in: Reactivity of the Photoexcited Organic Molecule. Wiley, New York 1967, p. 227.
131 G . Wegner, 2. Naturforsch. 24b, 824 (1969).
[4] E. Hadicke, H . C . Mez, C . H . Krauch, G. Wegner, and J . Kaiser,
Angew. Chem. 83, 253 (1971); Angew. Chem. internat. Edit. 10, 266
[S] J . Karle and I . L. Karle, Acta Crystallogr. 21, 849 (1966).
[6] J. D. Dunitz and J . M . Robertson, J. Chem. SOC. 1947, 1145.
[7] G. A . Heath, L. F . Thomas, E . I. Sherrard, and J . Sheridan, Discuss.
Faraday SOC.19,38 (1955).
[8] A. M . Sladkou and Y. P . Kudryantseu, Russian Chem. Rev. 32, 229
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crystals, structure, hexadiynediol
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