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Acta Cryst. (1984). C40, 1570-1572
2,5,8,11,14,17,20-Heptaoxahenicosane-Barium Isothiocyanate, C14H30OT.Ba(NCS)*
BY GABRIELA WEBER, FUMITOSHI HIRAYAMA AND WOLFRAM SAENGER
Institut ffir Kristallographie der Freien Universitfit, Takustrasse 6, D-1000 Berlin 33, Federal Republic of
Germany
AND GEORGE M. SHELDRICK
lnstitut ffir Anorganische Chemie der Universitfit, Tammannstrasse 4, D-3400 Gd'ttingen, Federal Republic of
Germany
(Received 9 March 1984; accepted 30 May 1984)
Abstract. M r= 563.89, triclinic, P1, a = 7.859 (3),
b=ll.010(4), c=14.299(4)A, a=89.65(2), fl=
78.39 (3), 7= 78.50 (3) °, V= 1186.9 (7) A 3, Z = 2,
D x = 1.578 (1) Mg m -a, 2(Mo Kc0 = 0.71069 A, ~ =
1.87 mm -1, F(000) = 568, T= 291 K, final R = 0.025
for 3979 observed reflections. The open-chain
oligoether approximates to one turn of a helix, thus
facilitating a sevenfold coordination of the cation to all
the ether O atoms (mean 2.91 A) and additional
interactions with the two anions (mean Ba2÷...N -
distance = 2.83 A). No linkages between the complex
units were observed.
Introduction. Linear oligoethers containing (--CH 2-
CH2--O--)n units are well established ligands for alkali
and alkaline-earth metal ions (V6gtle & Weber, 1979;
Hilgenfeld & Saenger, 1982). Terminal donor groups
such as aromatic bases (e.g. V6gtle & Sieger, 1977;
Saenger, Suh & Weber, 1979), -OH or -COEH
(capable of additional hydrogen bonding) (e.g. Hughes
& Wingfield, 1978; Hughes, Mortimer & Truter, 1978;
Yamaguchi, Miki, Yasuoka & Kasai, 1982) or, at least,
terminal aromatic nuclei (e.g. Sieger & V6gtle, 1978;
Hilgenfeld et al., 1984) seemed essential for the stability
of the complexes formed (e.g. Tiimmler, Maass, V6gtle,
Sieger, Heimann & Weber, 1979; Parsons, Truter &
Wingfield, 1981). Complexes with unsubstituted
oligoglymes could be obtained (Sieger & V6gtle, 1978)
but X-ray investigations have been reported only for
complexes with mercuric salts (Iwamoto, 1973), CdCI 2
*Structures of Polyether Complexes. XXI. Part XX: Suh,
Namgung, Ku Yoon, Saenger & V6gfle (1984).
(Iwamoto & Wakano, 1976) and for a compound in
which potassium accepts additional n-interactions
(Hodgson & Raymond, 1972). We report here the first
structure determination of a complex between an
alkaline-earth metal cation and an unsubstituted
oligoglyme.
Experimental. Sample kindly provided by Professor F.
V6gtle, University of D-5300 Bonn (FRG), crystal ca
0.7 x 0.3 x 0.1 mm, grown from ethyl acetate/
petroleum ether; Stoe-Siemens four-circle diffrac-
tometer, cell dimensions from 20 angles for 24
reflections (20 _< 20 <_ 25°); 5261 profile-fitted (Clegg,
1981) data up to 20= 50 °, -9 < h < 1,
-13 < k < -13, -17 _< l _< 17; no significant decline in
intensities of three standard reflections; empirical
absorption correction based on ~, scans, max./min.
transmission 0.63/0.53; 4169 reflections unique (Rl, t
=0.012), 3982 with F> 3a(F), three suppressed
(machine fault); Ba 2+ position from an E x F Patterson
map, positions of remaining non-H atoms from a
subsequent difference Fourier synthesis; structure
refined anisotropically by blocked-cascade least squares
on F, C(3)-C(4) restrained to 1.4800 _+0-0003 A
because of slight conformational (irresolvable) disorder;
H atoms included in idealized positions [C-H=
0.96A; U(Hi)= 1.2Ueq(Ct)], methylene H atoms
treated as 'riding atoms', methyl groups as 'rigid
groups'; 259 LS parameters, R = 0.025, wR --0.027,
w-l= tr2(F) + 0.0004F 2, S = 1.25, slope of normal
probability plot 1.15, max. A/a=0.06 [rotation of
methyl group C(1)], mean 0.004, largest peak
0.66 e A -3 (close to Ba2+), largest hole 0.35 e A -3 in
0108-2701/84/091570-03501.50 © 1984 International Union of Crystallography