Polysulfonylamine, XCVI [1]. Homokonjugate aus Di(organosulfonyl)aminen und ihren konjugierten Anionen: Vier Kristallstrukturen mit asymmetrischen [N -H ··· N ]^--Wasserstoffbrücken / Polysulfonylamines, XCVI [1]. Homoconjugates Formed from Di(organosulfonyl)amines and their Conjugate Anions: Four Crystal Structures Featuring A symmetric [ N - H ··· N ]^- Hydrogen Bonds

Abstract

Polysulfonylamine, XCVI [1] Homokonjugate aus Di(organosulfonyl)aminen und ihren konjugierten Anionen: Vier Kristallstrukturen mit asymmetrischen [N -H -N ]--WasserstoffbrückenPolysulfonylam ines, X C V I [1] H om oconjugates Form ed from D i(organosulfonyl)am ines and their C onjugate A n ions: Four C rystal Structures F eatu rin g A sym m etric [ N -H -N ]-H ydrogen Bonds K arna W ijaya, D ag m ar H enschel, O liver M oers, A rm and Blaschette*, P eter G. Jones* Institut für A n organ isch e und A n alytisch e C h em ie der Technischen U niversität, Postfach 3329, D -38023 B raunsch w eig Z. N aturforsch. 52b, 1 2 1 9 -1 2 2 8 (1997); ein gegan gen am 30. Juli 1997 [ N -H --N ] " H om ocon ju gate, [ 0 -H -0 ] + H om ocon jugate, H ydrogen -bis[di(organosu lfon yl)am id e], H yd rogen -b is(l,3 -d im eth y lu rea ), Crystal Structure The follow in g com p ou n d s w ere prepared by cocrystallization o f their com p on en ts from M 0.5 M eC N (5, m onoclin ic, P 2!/n). The four structures exhibit [ ( R S 0 2)2N -H -N ( S 0 2R )2]~ anion s as rare exam ples o f interm olecular [ N -H -N ] -h o m o conjugates. The N -N distan ces o f the asym m etric hydrogen bonds are, in order, 266.9(6), 276.0(3), 291.3(4) and 279.4(2) pm , the correspon ding N -H -N angles am ounting to 137(10), 176(3), 177(4) and 177(2)°. The asym m etry o f the hydrogen bonds is clearly reflected in the geom etry o f the N S 2 groups (am ine m oieties: N -S 1 6 2 .3 -1 6 5 .2 pm, S -N -S 124 .5 -1 2 7 .1°; am ide m oieties: N -S 1 5 9 .7 -1 6 1 .8 pm , S -N -S 1 1 9 .1 -1 2 2 .6°). The dihedral angles form ed by the N S 2 plan es vary from 51.8° in 4 to 87.6° in 5. The crystal lattices o f 2 and 4 consist o f discrete ions, san dw ich-typ e [N a(12-crow n -4)2]+ com p lexes acting as the counter-ions. In 3, N a + is coord in ated in an ou t-of-cavity pattern by the five polyether oxygen atom s and further accepts tw o N a -O bonds from the am ide m oiety o f the com plex anion [N a -O (c r o w n ) 2 4 1 .5 (2 )-2 4 9 .9 (2 ), N a -O ( a n io n ) 235.0(2) and 263.9(2) pm]. The surprising structure o f 5 contains h om ocon ju gated 1,3-dim ethylurea cations [(M e N H )2C -0 -H -0 = C ( N H M e ) 2]+, which are form ed via a very strong asym m etric [ O -H -0 ] + hydrogen bond [ 0 -0 247.7(2) pm, O -H -O 172(3)°] and are associated with the am ide m o ieties o f the anions through a set o f N -H -O bon ds to form infinite chains; the M eC N m olecu les occupy lattice cavities. * Sonderdruckanforderungen an Prof. A . B laschette oder Prof. P. G. Jones.