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Crystal Structure of Violet Phosphorus.

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and
A New Method for the Preparation of
Alkaline Earth Hydroxometalates
possible to obtain the isocyanate (2) in a pure state because
of the very similar boiling points [36-3SoC/1 mm for ( I )
and 42 OCiO.7 mm for the azeotropic mixture of ( I ) and (2)].
CCI3SOR, R =
M(0H)x
+ y OH-
-+
[M(OH)x + y l y - .
vco (cm-9
VNCO (Cm-l)
Received: October 17th, 1966
[Z 349 IE]
German version: Angew. Chem. 78, 1102 (1966)
C1 [ I ]
1190
vSO(cm-l)
The preparation is thus complicated, and the attainable purity
of the products, particularly of alkalihydroxometalates, is not
satisfactory.
The new method of preparation, consisting in direct, quantitative reaction of a finely powdered, almost stoichiometric
mixture of the two hydroxide components at a relatively low
temperature, is remarkably simple and affords mucn purer
substances. In this way compounds of the type Na2[M(OH)41
are obtained for M = Mn, Co, Ni, Cu, Zn, Cd, or Mg with
at most 15 hours' heating between 50 OC (for Zn) and 140 "C
(for Ni) under highly purified N2. Similarly, hydrated Fez03
with NaOH at 80°C affords Nas[Fe(OH)s], and with
partially dehydrated Ba(0H)z.S H20 at 90 "C Ba3[Fe(OH)&.
It is surprising that an oxide MO can be used in place of the
metal(r1) hydroxide for preparation of compounds of the
type Naz[M(OH)4] if the reaction is carried out under H20saturated Nz at 50-100 "C (M = Cu, Zn, Cd, or Mg; not Ni).
The purity of the hydroxometalates obtained by the thermal
method is illustrated by the observed ratios MO :Nan0 :HzO=
1:1.00-1.02:2.03-2.05 (total oxides [21 > 99 %). The products
give very good X-ray powder diagrams.
Depending on the temperature of preparation (65 or 100 "C),
Naz[Mg(OH)4] is obtained in one of two modifications which
have different X-ray diffraction patterns.
It has not yet been possible to obtain potassium hydroxometalates; however, preliminary thermal experiments with
Ca(0H)z and NaOH in the range 3.5-4.5 N a 0 H : l Ca(0H)Z
gave a new phase consisting of a ternary hydroxide which,
according to the X-ray powder diagram, has the NaCl
structure.
I I
1
I
NCO
1190
I
NHCONHz
NHC02C2H5
1110
1680-1700
1110
1740
I
NHC~HS
[I1
1085-1095
2250
Received: October 6th and 17th, 1966 [Z 350 IEI
German version: Angew. Chem. 78, 1 1 0 0 (1966)
[l] (I. Schollkopf and P . Hilbert, Angew. Chem. 74, 431 (1962);
Angew. Chem. internat. Edit. I , 401 (1962); cf. A . Senning,
Chem. Reviews 65, 385 (1965).
[2] Cf. G. Kemmner, G. Nonnenmacher, W. Wucherpfennig, and
G . Kresze, 8th European Congress of Molecular Spectroscopy,
Copenhagen, 1965.
Crystal Structure of Violet Phosphorus
By H. Thurn and Prof. H. Krebs
Laboratorium fur Anorganische Chemie,
Technische Hochschule Stuttgart (Germany)
Violet (Hittorf) phosphorus crystallizes in the monoclinic form, with space group P2/c, a = 9.21, b = 9.15,
c = 22.59 A, p = 106.1 O, and 84 atoms in the unit cell.
The structure is based on two units: a PS group in which the
atoms are arranged as in AsqS4[11, and a P9 group. These
units are linked, each through two further phosphorus
atoms, to form infinite, tube-like structures of pentagonal
cross-section (Fig. l), which are bent somewhat "downwards" at the sites of the Pg groups. This kind of linkage
results in two planar, zigzag chains of phosphorus atoms
being formed on two sides of'the tubes (in Fig. 1 the atoms 1
t o 8 and 9 to 16). This is the type of structure was previously
assumed for violet phosphorus [21 and a similar structure
was found for HgPbP14 [31.
[l] R . Scholder and C. Keller, Z . anorg. allg. Chem. 317, 113
(1962).
121 I.e., Yo MO + % NaO % H20.
+
Trichloromethanesulfinyl Isocyanate
By A. Senning
Chemical Institute, Aarhus University (Denmark)
"
021'
In contrast to other aliphatic sulfinyl chlorides, trichlorois converted by silver cymethanesulfinyl chloiide ( I )
anate in boiling benzene into the corresponding isocyanate
(2), the first sulfinyl isocyanate reported. After filtration of
the solution the benzene is distilled off and the residue is at
once treated further. It contains about equal amounts of
compounds ( I ) and (2), as well as by-products. It was not
CCI3SOCI + AgOCN + CCISSONCO+ AgCl
(1)
A n g e w . C h e m . internat. Edit.
(2)
/ Vol. 5
(1966)
No. 12
Fig. 1. Section of a "tube" of violet phosphorus. Above: parallel
perspective. Below: projection parallel to the tube axis (end view).
1047
The tubes are packed parallel to one another to form layers.
Pairs of layers (e.g. aAaA and bBbB in Fig. 2) are connected
via atoms 21 of the P9 groups so that the axes of the tubes
in the two layers form a n angle of almost exactly 90". As
shown in Fig. 2, the tubes marked a and A of one layer are
joined to the tubes marked b and B, respectively, in the
second layer. Thus a double layer consists of two interlocking
systems that, however, are not linked by chemical bonds.
These double layers are stacked in the direction of the c-axis
so that each tube is above a gap between two tubes of the
layer below; they are held together by van der Waals forces.
la), X
=
H
(b),X
=
lr), X
=
CI
Br
id), X
i
NO2
Oil
102-103
106- I08
208-210
90 (crude)
53
55
66
CS21. Compounds (2a)-(2c) are stable for several months
at -15 "C but decompose, with development of a blue color,
within 2 to 6 weeks at room temperature, the anilines ( l a ) to
( I c ) being identified among the decomposition products.
Compound (2d) is stable at room temperature. When
compounds (2a)-(2c) are heated in an excess of boiling
dimethylbutadiene for 6 hr, the 2-aryl-3,6-dihydro-4,5-dimethyl-l,2-thiazines (3u)-(3c)
can be isolated by subsequent column chromatography and distillation. We assume
that the hitherto unknown thioanilines (4a)-(#c) are intermediates in this reaction.
Fig. 2. Schematic representation of the structure of violet phosphorus.
The "tubes" are represented by pentagonal prisms; in parts of the
upper layer only one edge is drawn to show the linkage of the two
halves of a double layer via atoms 21 and 21'.
(4)
The mean bond length is 2.219 A, the mean bond angle
100.9 '. The values diverging most from the mean are:
Bond 21-21'
19-20
2.178 4,
2.298 A
Angle 5-6-7
13-14-15
17-21-18
84.5
86.5 '
115.9'
The R-value is 5.8 %.
The relatively complicated structure of violet phosphorus
probably is due to the difficulty of satisfying all three pyramidal phosphorus valences with retention of the normal
valence angle of somewhat over 100 '. The complexity of the
structure explains why glasses are first formed when white
phosphorus is heated and the infinite crystal structure is
formed only on long annealing.
Received: September 28th, 1966; revised October 26th, 1966 [Z 351 1El
German version: Angew. Chem. 78, 1101 (1966)
[l] T. Ito, N . Morimoto, and R . Sadanaga, Acta crystallogr. 5,
775 (1952).
[2] I. Pakulla, Dissertation, Universitiit Bonn, 1953; H . Krebs,
K . H . Miiller, I. Pakulla, and G . Ziirn, Angew. Chem. 67, 524
(1955).
[3] H . Krebs and Th. Ludwig, Z. anorg. allg. Chem. 294, 257
(1958).
N-Thioaniline, C&sN=S, as Intermediate in the
Decomposition of N,N -Thiodianiline
By Dr. P. Tavs
Shell Grundlagenforschung-Gesellschaft,
SchloR Birlinghoven/Siegkreis (Germany)
The N,N'-thiodianilines (2a)-(2d)
were obtained by dropwise addition of piperidine-1-sulfenyl chloride [I] to a solution
of the anilines ( l a ) - ( I d ) in anhydrous ether at -20 ' C .
Compounds (2b)-(2d) were characterized by composition,
IR spectra (VN-H = 3400-3420 cm-I), and N M R spectra
[tetramethylsilane as internal standard, AB spectrum unchanged from those of (1b)-(Id), N H proton at T = 4.1 in
1048
(3)
~
(a), X - H
( b ) ,X
(c), X
=
=
CI
Br
79-80
(lit. [31 79-80)
53
103-105
22
150-151
157-158
46
58
117-120
138-142
32
41
Compounds (3a)-(Sc)
were characterized by elemental
analysis, I R spectra (no N - H stretching vibration, v c = c =
1650-1670 cm-1, very weak), and N M R spectra [signals of
the aromatic portion unchanged in comparison with those
of (I) and (2), ring methylene protons at T = 6.2 and 1.2,
C-CH3 at T = 8.3 (broad singlet), ratio of areas 2:2:6].
Compounds (#a)-(4c)
were converted into 2-aryl-3,6-dihydro-4,5-dimethyl-l,2-thiazine1-oxides with perphthalic
acid. These products were the same as those obtained from
the corresponding thionylanilines and dimethylbutadiene [2,31
(m.p., mixed m.p., I R spectra).
Experimental:
( I c ) -+ (2c). 34.4 g (0.2 mole) of p-bromoaniline in 300 ml
of anhydrous ether at -2OOC was treated dropwise with
15.1 g (0.1 mole) of piperidine-1-sulfenyl chloride. As soon
as the temperature had risen to 0 O C the piperidinium chloride
was filtered off and the ether distilled off at room temperature.
The 34.5 g of yellow-brown residue crystallized when
scratched and after two recrystallizations from methylene
chloride afforded 20.1 g.
(2a) + (3a). 18.0 g of crude product prepared as above from
aniline and piperidine-1-sulfenyl chloride was warmed with
20 ml of dimethylbutadiene for 6 hr at 70 to 80OC. The
Angew. Chem. internat. Edit. 1 Vol. 5 (1966) 1 No. 12
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