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CsNa2(OH)3 ╖ 6H2O Structural Differentiation in the Hydrate of a Ternary Alkali-Metal Hydroxide.

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pentacyclo[*.113. ‘6]eicosa-4,6.8(20)-triene(IUPAC name), pentacyclo[ 1.7.13-7.13,7.1 14]eicosane-10,12,14(20)-triene(nodal
nomenclature[l3]), [13~7.13~9.15~7][ll]metacyclophane
(usual phane
nomenclature[l4]), [2.2](1,3jadamantanometacyclophane (“araliphane”
name). For this reason, corresponding names of compounds (e.g.,
triquinacenophane[l5], cyclooctatetraenophane[16]) have already been
coined in the literature. I t seems reasonable to classify uraliphatic compounds such as I , 3, and 4 as “uraliphanes” and completely uliphatic phane
analogues as “uliphanes” (from uliphatic).
[5] Spectroscopic data for 1 (numbering shown in formula: ‘H NMR
(200 MHz, CD,CI,, TMS): 6 =7.75 ( s , 1 H ; 20-Hj; 7.20 (t, 3 J = 7 . 4 Hz,
1 H; 17-H); 6.96 (d, ’J=7.4 Hz, 2 H ; 16,18-H); 3.14, 2.65 (AB,
’J = 13.6 Hz, ’ J = 12.113.6 Hz, 4 H , 1-H,,,,,. 14-Hsx,eq),2.53, 1.29 (AB,
’J= 12.0 Hz,4H;4,6-H,,,4,6-H,);2.23(m,
1H;S-H); 1.98(m. 1H;9-H);
1.65 (tt. ’J= 3.2Hz, 4 J =1.0 Hz, 2H; 12-H); 1.41, 0.87 (AB,
’3 = 12.6 Hz, ’J = 12.013.6 Hz, 4 H ; 2-H.,,,,, 13-Hax!eq);
1.36 (m, 4 H ; 8H, 10-H); 0.06 (dt, ’J = 16.6 Hz, ‘J = 3.0 Hz, 1 H ; ll-HGq);- 0.10 (d,
’J = 16.6 Hz, 1 H; ll-HaJ. ”C NMR (50.32 MHz, CDCI ): 6 = 145 7
(C-15, C-19); 140.5 (C-20): 130.0 (C-17); 127.4 (C-18, C-12); 50.6 (C-8,
C-l0);42.6(C-2. C-13);41.1 (C-11); 39.2(C-l2); 37.3 (C-6.C-4); 32.3 (C-1,
C-14); 32.2 (C-9), 31.4 (C-3. C-7); 29.0 (C-5). The assignment was made by
H,H- and C,H-COSY, spin-echo, and IH{ ‘H) NOE difference NMR spectroscopy. MS (70 eV): mjr 266.2027 ( M a , 100%) (calcd 266.2028).
161 S . Hirano, H. Hara, T. Hiyama, S. Fujita, H. Nozaki, Tetrahedron 31
(1975) 2219.
[7] Crystal structure analysis of 1: monoclinic, space group P2Jc (No.
14); a = 1149.6(1). h = 1558.7(2), c = 916.7(1)pm, B = 112.30(1).; Y =
1519.713)~1 0 6 p m 3 ; Z= 4 ; ~= ~
~ , ~ ~
Mo,,(1 = 0.70930A);
p = 0.06 mm-’; F&)
= 584; T = 296 k 1 K , crystal dimensions,
0.20 x 0.18 x 0.24 mm; CAD4 diffractometer (Enraf-Nonius); corrections:
Lorentz polarization, linear 5 % decrease (corrected with factors 1.000 to
1.024011I); 2 8 = 4 - 50.; hklrange: h = - 13-12, k = - 1 8 4 , I = 0-10:
2179 measured, unique reflections, 1417 with I > 3.0 01. The structure was
solved using MULTAN (least-squares Fourier method). Refinement:
R = 0.045, R, = 0.055, non-hydrogen atoms refined anisotropically, H
atoms determined using the AF map and refined with fixed, isotropic
temperature factors (SDP and PLUTO programs). Further details of the
crystal structure investigations are available on request from the Director
of the Cambridge Crystallographic Data Centre. University Chemical
Laboratory, Lensfield Road, Cambridge CB2 1EW (UK), on quoting the
full journal citation.
(81 The dithiaphane 3 was also characterized by X-ray structure analysis: cf.
[9] a) S. C. Swen-Walstra, G. J. Visser, Chem. Commun. 197f, 82; b) R. A.
Alden, J. Kraut, T. G. Traylor, J Am. Chem. Soc. 90 (1968) 74: c) 0.
Ermer,ibid. 110(1988)3747;d)O.Ermer,C.-D.Bodecker,Chem.
Ber. 114
(1981) 652; e) M. A. Flamm-ter Meer, H.-D. Beckhaus, K. Peters, H.-G.
von Schnering, C. Ruchardt, ihid. ff8 (1985) 4665.
[lo] MM2(85)/MMP2 calculations (on an HP 9000/825S SRX) gave a 0 strain
energy of 217 kJ mol-’ for 1 and 85.5 kJ mol-’ for 2; semiempirical
calculations using AM1 (on a CONVEX C 220) gave an SCF standard
enthalpy of formation of 50.9 kJ mol-’ for 1 and 182 kJ mol-’ for 2. We
thank DipLChem. P.M . Windschef for the calculations. For strain energies of other small cyclophanes cf. F. Bickelhaupt, Pure Appl. Chem. 62
(1990) 373.
[ I l l This was further substantiated by our synthesis of macrocycles of type 6 ,
formally obtained by replacement of two benzene rings by adamantane
6 : R = H, C H j , CH2COOEt
units in hexa-m-phenylene[17]. The poor solubility of hexa-m-phenylene
was still exhibited even after incorporation of the adamantane framework.
The following macrocycles were identified by mass spectrometry: 6
(R = H): EI-MS, m/z calcd 636.3228, found 636.3259 (M”); 6 (R = CH,):
EI-MS, m/z 692 (M”); 6 (R=CH,COOC,H,): EI-MS, m/z 980 (M”).
[12] Unstrained macrocyclic polyethers containing an adamantane unit. A. A.
Chaikovskaya, T. N. Kudrya, A. M. Pinchuk, Zh. Org: Khim. 25 (1989)
[13] N. Lozac’h, A. L. Goodson, Angew. Chem. 96 (1984) 1; Angew. Chem. Int.
Ed. Engl. 23 (1984) 1.
[14] F. Vogtle, P. Neumann, Tetrahedron 26 (1970) 5847.
1151 W. P. Roberts, G. Shoham, Tetrahedron Lett. 22 (1981) 4895.
[16] L. A. Paquette, M. A. Kesselmayer, J Am. Chern. SOC.1 f 2 (1990) 1258.
117) H. A. Staab, F. Binning. Chem. Ber. 100 (1967) 293.
Verlugsgesdlschuff mbH, 0-6940 Weinheim, 1990
CsNa,(OH), * 6 H,O : Structural Differentiation
in the Hydrate of a Ternary Alkali-Metal
Hydroxide **
By Dietrich Mootz* and Heinz Riitter
Dedicated to Professor Dietrich Babel on the occasion
of his 60th birthday
The structures of most hydrates of the lighter alkali-metal
hydroxides were determined some time ago.[’*21 More recently, structural characterizations have also been carried
out for such compounds of the heavy alkali
as well
as for anhydrous ternary alkali hydroxides.[41 Hydrates,
however, of ternary alkali hydroxides, to our knowledge,
have so far not been subjected to crystal structure analysis.
Only one phase of this kind, to which the composition
CsOH . 2 NaOH .4H,O has been assigned, can be found in
the literature.[’] Our structure determinationt6] unmistakably shows that the compound in question, melting congruently at 46.5 “C, is a hexahydrate dominated in a characteristic way by differentiation between the cations of unequal size
as well as between the H,O molecules and the OH@ions.[71
In the crystal structure of CsNa,(OH), .6H,O the Nae
ions are coordinated by the six H,O molecules to form distorted octahedra (Na-0 distances between 2.275(3) and
2.688(3) A). The octahedra are linked by common faces to
form columns parallel to the crystallographic b axis. These
are arranged according to the pattern of closest packing of
cylindrical rods[’’ and connected with each other by a complex system of hydrogen bonds with the H,O molecules as
twofold proton donors and the OHe ions as fourfold
proton acceptors (0..‘ 0 distances between 2.633(4) and
2.798(4) A). Thus, each OHe ion bridges two octahedron
edges in adjacent columns. Each column, together with two
further ones and the associated OH@ ions, encloses in a
Fig. 1. Perspective drawing of the structure of CsNa,(OH), . 6H,O, projected
down the h axis (atomic thermal-vibration ellipsoids at the 25% probability
level, ORTEP plot[lO]). Ellipsoids without equators, OHe ions; ellipsoid with
equator, Cse ion; bold lines, hydrogen bonds. One sees the pseudotrigonal
arrangement of three columns of the face-linked Na(H,O), octahedra and,
between them and the bridging OHe ions, the large cavities containing the Cse
ions. For completion of the three small cavities another column each (not
shown in the figure) has to be added.
[*] Prof. Dr. D. Mootz, DipLChem. H. Rutter
Institut fur Anorganische Chemie und Strukturchemie der Universitat
Universitatsstrasse 1, D-4000 Dusseldorf (FRG)
This work was supported by the Minister fur Wissenschaft und Forschung
des Landes Nordrhein-Westfalen, the Fonds der Chemischen Industrie,
and the Dr. Jost Henkel-Stiftung. It is part of the doctoral dissertation in
progress of H. Riitfer, Universitdt Dusseldorf.
0570-0833/90j0808-0904$3.50+ .25/0
Angew. Chem. Int. Ed. Engl. 29 (1990) N o . 8
pseudotrigonal arrangement a total of three small and three
large cavities, of which the latter type is highlighted in Figure 1. The H atoms of the OHe ions probably project into
the small cavities. In agreement with the generally low proton-donor strength of the OHQion, they do not participarte
in hydrogen bonds.['' The large cavities enclose the Cs@ions
and may be considered as cuboctahedra consisting of nine
H,O molecules and the three OHe groups, compressed
along the pseudo-threefold axis (Fig. 2). The corresponding
ther details of the crystal structure determination can be obtained o n
request from the Fachinformationszentrum Karlsruhe, Gesellschaft fur
wissenschdftlich-technische Information mbH, D-7514 Eggenstein-Leopoldshafen 2 (FRG), on quoting the depository number CSD-54521. the
names of the authors, and the journal citation.
[7] Even without definitely determined H-atom positions the assignment of
H,O and OHe as made for the subsequent description of the structure is
practically inevitable.
[8] M. OKeeffe, S. Anderson, Acta. Crystallogr. Sect. A 33 (1977) 914.
[9] Due to difficulties in the preparation of samples an IR spectrum of the
substance suitable for a check of this result could so far not be obtained.
However, apart from the O . - - Odistances already assigned as hydrogen
bonds (see text), there are no further distances with OH" ions smaller than
3.385(5) .& in the structure.
[lo] C. K . Johnson, ORTEP 11, Report ORNL-5138. Oak Ridge National
Laboratory, Oak Ridge, TN, 1976.
C 4 0 , (1,2,3-Butatriene-l,Cdione), the First Dioxide
of Carbon with an Even Number of C Atoms
By Giinther Maier,* Hans Peter Reisenauer, Heinz Balli,
Wilty Brandt, and Rudoy Janoschek
Fig. 2. Stereoscopic drawing of two cuboctahedra containing the Cs@ ions,
succeeding each other along the pseudo-threefold axis, and their connection by
hydrogen bonds; same way of representation as in Figure 1.
twelve Cs-0 distances of 3.287(3) to 3.981(3)A are the
shortest ones; the next shortest distance, however, is already
4.113(3) A.
In the higher hydrates of NaOH the OHQions are also not
coordinated to the small, hard Na@ ions.['] This generally
has to do with the lowered charge density of the OHe ions
due to multiple proton-acceptor function in hydrogen
bonds. Conversely, in the title compound the coordination
of two of the OHeions to the large, softer Cse ion is reflected in the shortest Cs-0 distances (3.287(3) and 3.296(3) A),
and also the third OHe ion, following after five H,O
molecules, i s still rather tightly bound at 3.542(3) A.
Received: September 28, 1989;
supplemented: April 9, 1990 [Z 3567 IE]
Publication delayed at authors' request
German version: Angew. Chem. 102 (1990) 949
CAS Registry number.
CsNa2(OH),.6H,0. 128112-95-8
P. A. Agron, W R. Busing, H. A. Levy, Winter Meet. f 9 7 2 Crystallogr.
Assoc.. Albuquerque, N M , Collect. Abstr., p. 52; 1. A. Wunderlich, Bull,
Soc. Fr. Mineral. Cristallogr. 81 (1958) 287; G. Beurskens, G. A. Jeffrey,
J Chem. Phys. 4 f (1964) 924; P. Hemily, C . R. Hebd. Seances Acad. Sci.
236 (1953) 1579.
R. Seidel. Dissertation, Universitat Dusseldorf 1988.
H. Jacobs, T. Tacke, J. Kockelkorn, 2. Anorg. Allg. Chem. 516 (1984) 67;
H. Jacobs, A. Schardey, zbid. 565 (1988) 34; H. Jacobs, B. Harbrecht, P.
Muller. W Bronger, ihid. 491 (1982) 154.
H. Jacobs, A. Schardey, 8. Harbrecht, Z . Anorg. A&. Chem. 555 (1987)
L A . Sadokhina, V. V. Otdel'nov, G. V. Zimina, S. B. Stepina, R u n . J
Inorg. Chem. (Engl. Transl.) 25 (1980) 1266.
Large. colorless columns of the title compound were obtained by slow
evaporation of the solvent water; space group Pca2, (No. 29), a =
13.951(3). b = 6.089(1), e = 12.508(3) A, V = 1062.6 A3, 2 = 4, SiemensStoe AEDZ, Mo,. radiation, graphite monochromator, measuring range
3" < 20 < 70", 2430 measured symmetry-independent reflections, of
which 2202 with F > 4 4 6 , absorption correction with $-scan, R = 0.026,
R, = 0 040. Due to the strongly scattering Cs atoms the H atoms could not
be localized unambiguously; a neutron diffraction study is planned. FurAngen.. Chem. Int. Ed. EngI. 29 (1990) No. 8
Dedicated to Professor Wolfgang Kirmse on the occasion of
his 60th birthday
The long known dioxides of carbon, CO, 1 and C,O, 3, as
well as that recently prepared by us, C,O, 5:11 have an odd
number of carbon atoms. Analogues with an even number of
carbon atoms-C,O,
2 or C40, &have so far defied experimental detection.[', 31
Theoretically, the compounds 2 and 4 should-in contrast
to 1 , 3 and S h a v e a triplet ground
as also indicated
by simple MO considerations: the electronic situation compares with that in the 0, molecule. The .rc-molecular orbitals
of 1-5, with a linear geometry (D-,,), are pairwise degenerate
(x and y directions indistinguishable). This leads, with an
even number of C atoms, to two electrons being available for
the highest occupied pair of molecular orbitals instead of the
four electrons required for a closed shell. According to
Hund's rule this situation should lead to a triplet ground
Motivated by the simple synthetic entry to 5 by photolytic
or thermal decomposition of trisdiazocyclohexanetrione [I1
we have prepared the structurally similar cyclic diazoketones
615'-8 by diazo-group transfer in the hope of finding an
entry to 2 or 4.
[*] Prof. Dr. G. Maier, Dr. H. P. Reisenauer
Institut fur Organische Chemie der Universitat
Heinrich-Buff-Ring 58, D-6300 Giessen (FRG)
Prof. Dr. H. Balli, DipLChem. W. Brandt
Institut fur Farbenchemie der Universitat
St. Johannsvorstadt 10, CH-4056 Basel (Switzerland)
Prof. Dr. R. Janoschek
Institut fur Theoretische Chemie der Universitdt
Mozartgasse 14, A-8010 Graz (Austria)
Verlagsgesellschaft mbH. D-6940 Weinherm, 1990
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csna2, structure, ternary, metali, differentiation, alkali, hydroxide, 6h2o, hydrates
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