Schiff bases or glycosylamines: Crystal and molecular structures of four derivatives of D-mannose

Article abstract of DOI:10.1016/S0008-6215(00)00026-4

Crystal and molecular structures of four derivatives of D-mannose are described. Each could exist as either an open-chain Schiff base or as a glycosylamine in the solid state. The derivative formed upon reaction of D-mannose with hydroxylamine is an open-chain oxime, but those formed upon reaction with semicarbazide, aniline, and p-chloroaniline are glycosylamines. The oxime, which crystallizes as the syn-(E) isomer, has a fully extended carbon chain. The glycosylamines are all β-pyranoses. The packing arrangement of the oxime involves 'head-to-tail' hydrogen bonding. The semicarbazide derivative, which crystallizes as a dihydrate, features a hydrogen-bonded intramolecular bridge formed by the two water molecules and linking O-6 to the carbonyl oxygen atom. The packing arrangements of the aniline and p-chloroaniline derivatives differ from each other but are nevertheless closely related by similar hydrogen-bonding interactions. Copyright (C) 2000 Elsevier Science Ltd.

Full text of DOI:10.1016/S0008-6215(00)00026-4

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Carbohydrate Research 326 (2000) 104–112
Schiff bases or glycosylamines: crystal and molecular
structures of four derivatives of
D
-mannose
a,
b
b
William H. Ojala * , Joanne M. Ostman , Charles R. Ojala
a
Department of Chemistry, Uni6ersity of St. Thomas, St. Paul, MN 55105, USA
b
Department of Chemistry, Normandale Community College, Bloomington, MN 55431, USA
Received 13 October 1999; accepted 3 January 2000
Abstract
Crystal and molecular structures of four derivatives of
open-chain Schiff base or as a glycosylamine in the solid state. The derivative formed upon reaction of
D
-mannose are described. Each could exist as either an
-mannose
D
with hydroxylamine is an open-chain oxime, but those formed upon reaction with semicarbazide, aniline, and
p-chloroaniline are glycosylamines. The oxime, which crystallizes as the syn-(E) isomer, has a fully extended carbon
chain. The glycosylamines are all b-pyranoses. The packing arrangement of the oxime involves ‘head-to-tail’
hydrogen bonding. The semicarbazide derivative, which crystallizes as a dihydrate, features a hydrogen-bonded
intramolecular bridge formed by the two water molecules and linking O-6 to the carbonyl oxygen atom. The packing
arrangements of the aniline and p-chloroaniline derivatives differ from each other but are nevertheless closely related
by similar hydrogen-bonding interactions. © 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Schiff bases; Monosaccharide oximes; Monosaccharide semicarbazide derivatives; N-arylmannopyranosylamines; X-ray
crystallography
1
. Introduction
hydrazone [3], and oxime [4] of
been found to crystallize as cyclic structures,
as have the p-bromophenylhydrazone of
arabinose [1,5] and the tosylhydrazones of
-arabinose and -galactose [3]. In contrast,
the phenylhydrazone [6] and p-bromophenyl-
hydrazone [7] of -mannose, the p-bro-
mophenylhydrazone of -ribose [1,8], and the
oxime of -arabinose [4] have been shown to
assume acyclic structures in the solid state.
The factors that determine which form, Schiff
base or glycosylamine, will occur in the solid
state are not well known, but are clearly more
subtle than simply the chemical identity of the
monosaccharide, as is demonstrated by the
fact that crystalline arabinose derivatives oc-
cur in both acyclic and cyclic forms.
D
-glucose have
Monosaccharides react with ammonia
D
-
derivatives to form monosaccharide deriva-
tives that can exist as Schiff bases (open-chain
imino compounds) or as glycosylamines. Over
the years a variety of experimental techniques
have been used to determine which of the two
structures is assumed by a given monosacchar-
ide derivative in solution and in the solid
state. X-ray crystallography has been used to
determine the structures of several of these
compounds, and with respect to whether the
compound exists as an open chain or as a
ring, the results have been mixed. For exam-
ple, the p-bromophenylhydrazone [1,2], tosyl-
L
D
D
D
D
As part of a study of the solid-state struc-
tures of monosaccharide derivatives aimed at
*
Corresponding author. Fax: +1-651-962-5209.
E-mail address: whojala@stthomas.edu (W.H. Ojala)
0008-6215/00/$ - see front matter © 2000 Elsevier Science Ltd. All rights reserved.
PII: S0008-6215(00)00026-4

W.H. Ojala et al. / Carbohydrate Research 326 (2000) 104–112
105
a better understanding of the factors that de-
termine which structural type is formed, we
thus been proved conclusively to be the one
usually assumed in the normal crystalline state
by sugar anilides [12] was not accepted with-
out reservation [13,14]. Subsequent IR spec-
troscopic studies (samples in KBr discs)
support the cyclic structure in the solid state
for both the N-phenyl- and N-p-
chloropheny1mannosylamines examined here
have prepared several derivatives of
nose and have determined their crystal struc-
tures. We considered -mannose particularly
D-man-
D
interesting as a parent monosaccharide be-
cause its behavior when treated with hy-
drazine derivatives, forming crystalline
open-chain hydrazones, is different from that
[
15]. Recent crystallographic studies per-
of the other aldohexoses
D
-glucose and
D-
formed on acetylated ‘p-nitroanilides’ of
lyxose and arabinose, compounds of interest
as potential model systems for nucleosides,
have shown that these compounds assume
b-pyranose structures in the solid state as well
galactose, which when treated with these
reagents form crystalline glycosylamines. We
have examined the products of the reaction of
D-mannose with hydroxylamine, with semicar-
bazide, with aniline, and with p-chloroaniline.
Reaction with hydroxylamine could produce a
compound crystallizing as an open-chain
oxime or as a cyclic hydroxylamine, although
[
16]. On the other hand, given the fact that the
phenylhydrazone and p-bromophenylhydra-
zone of -mannose have been isolated in
D
Schiff base form, we considered the possibility
13
C NMR studies have shown that for -man-
D
of isolating an open-chain anilide or p-
nose the open-chain form of the derivative is
the one assumed in solution [9]. Reaction with
semicarbazide could produce a crystalline
open-chain semicarbazone or an N-mannopyr-
anosylsemicarbazide. Previous workers, ob-
taining an open-chain pentaacetate in solution
chloroanilide of -mannose to be worth inves-
D
tigating, so we prepared these compounds and
determined their crystal structures to establish
their molecular configurations conclusively.
We have found that, like the arabinose
derivatives, the mannose derivatives are not
confined to a single structural type (Scheme
(
structure determined by solution NMR) upon
acetylating -mannose semicarbazone, have
suggested that the predominant form of
D
1
). We have found the hydroxylamine deriva-
D-
tive 1 to be a true open-chain oxime, but the
derivatives formed on reaction with semicar-
bazide, aniline, and p-chloroaniline, com-
pounds 2–4, to be glycosylamines. The N-
mannopyranosylsemicarbazide 2 crystallizes
as a dihydrate. The N-phenylmannopyranosyl-
amine 3 in particular demonstrates the sensi-
tivity of the crystallizing compound to struc-
tural influences, the difference of only the
mannose semicarbazone in solution is there-
fore the open chain as well [10]. Reaction with
aniline or p-chloroaniline could yield the
open-chain Schiff base or the N-arylmannopyr-
anosylamine. Studies on acetylated derivatives
described in the older literature support the
glycosylamine structure for sugar ‘anilides’
[
11], but a subsequent claim that this form had
ꢀ
NHꢀ group between aniline and phenylhy-
drazine being sufficient to produce radically
different molecular structures in the corre-
sponding mannose derivatives.
2
. Results and discussion
Molecular geometry.—ORTEPII [17] draw-
ings showing the atom numbering scheme and
molecular conformation for each compound
are presented as Figs. 1–4. Torsional angles
for all four structures are listed in Table 1.
The
D
-mannose oxime 1 is found to possess
Scheme 1. Derivatives obtained.
a fully extended carbon chain. The compound

106
W.H. Ojala et al. / Carbohydrate Research 326 (2000) 104–112
H-2 being the least sterically demanding of the
substituents on C-2. It is interesting that this
particular conformation is also found in man-
nose phenylhydrazone and mannose p-bro-
mophenylhydrazone but not in arabinose
oxime, an ostensibly more closely related com-
pound. In the anti isomer of arabinose oxime,
the C-1ꢀN-1 bond is twisted away from the
C-2ꢀH-2 bond so that the C-1ꢀH-1 bond is
almost eclipsed by C-2ꢀO-2; in the syn isomer,
the C-1ꢀN-1 bond eclipses the C-2ꢀO-2 bond.
A similarity shared by 1 and both isomers of
arabinose oxime (and with the two arylhydra-
zones as well) is that the zig-zag of the chain
ends with the terminal carbon, the CꢀCꢀCꢀO
torsional angle involving the primary hydroxyl
assuming a value close to 60° in these
structures.
Comparison of relevant bond lengths in the
N-mannopyranosylsemicarbazide 2, the N-
phenylmannopyranosylamine 3, and the N-p-
chlorophenylmannopyranosylamine 4 indi-
cates that the aglycones do not differ greatly
in their degree of interaction with the
monosaccharide ring. The length of the C-
Fig. 1. ORTEPII [17] drawing of 1, showing atom numbering.
The ellipsoids are drawn at the 50% probability level.
1
ꢀN-1 bond in 2–4 is the same within experi-
mental uncertainty; in addition, although the
O-5ꢀC-1 bond length is greater than the O-
5
ꢀC-5 bond length in all three structures, the
differences in length between these bonds do
not vary significantly from structure to struc-
ture. Bond angles do differ, with the C-1ꢀN-
1
ꢀN-2 bond angle of 113.1(2)° in 2 becoming
a C-1ꢀN-1ꢀC-7 bond angle of 122.4(2)° in 3
and 123.2(2)° in 4. These latter two values are
comparable with the 122.0(3) and 123.8(2)°
values found in N-p-nitrophenyl-N-(2,3,4-tri-
Fig. 2. ORTEPII [17] drawing of 2, showing atom numbering.
The ellipsoids are drawn at the 50% probability level.
O-acetyl-b-
D
-lyxopyranosyl)amine and N-p-
-arabino-
nitrophenyl-N-(2,3,4-tri-O-acetyl-(a-
L
pyranosylamine, respectively [16], in which de-
localization of the nitrogen unshared electron
Fig. 3. ORTEPII [17] drawing of 3, showing atom numbering.
The ellipsoids are drawn at the 50% probability level.
is the syn-(E) isomer, the N-1ꢀO-1 bond ori-
ented syn with respect to the C-1ꢀH-1 bond.
The C-1ꢀN-1 bond eclipses the C-2ꢀH-2 bond,
Fig. 4. ORTEPII [17] drawing of 4, showing atom numbering.
The ellipsoids are drawn at the 50% probability level.

W.H. Ojala et al. / Carbohydrate Research 326 (2000) 104–112
107
Table 1
Selected torsional angles (°)
parameters DC [22] for the three rings (also
S
calculated using PLATON-94) are DC (C-1)=
S
DC (C-4)=4.9(3)°, DC (C-2)=DC (C-5)=
S
S
S
1
2
3
4
3
.9(3)°, DC (C-3)=DC (O-5)=1.3(3)° for 2;
S
S
N-1ꢀC-1ꢀO-5ꢀC-5
N-lꢀC-lꢀC-2ꢀC-3 −124.9(2) 177.4(2) 175.6(2) 174.5(2)
177.8(2) 176.8(2) 177.5(2)
DC (C-1)=DC (C-4)=7.4(2)°, DC (C-2)=
S
S
S
DC (C-5)=6.9(2)°, DC (C-3)=DC (O-5)=
S
S
S
N-2ꢀN-lꢀC-lꢀC-2
O-lꢀN-lꢀC-lꢀC-2
O-2ꢀC-2ꢀC-lꢀN-1 115.0(3)
O-2ꢀC-2ꢀC-1ꢀO-5
O-2ꢀC-2ꢀC-3ꢀO-3 180.0(2) −61.9(2) −53.6(3) −52.6(2)
O-2ꢀC-2ꢀC-3ꢀC-4 −56.4(3) 64.2(2) 67.9(3) 69.3(2)
O-3ꢀC-3ꢀC-2ꢀC-1
O-3ꢀC-3ꢀC-4ꢀO-4
O-3ꢀC-3ꢀC-4ꢀC-5 −52.4(3) −178.7(2) 172.6(2) 172.4(2)
O-4ꢀC-4ꢀC-3ꢀC-2 −55.1(3) 174.8(2) 171.0(2) 170.8(2)
O-4ꢀC-4ꢀC-5ꢀO-5−175.7(2) −179.6(2) −175.0(2) −175.3(2)
O-4ꢀC-4ꢀC-5ꢀC-6
O-5ꢀC-1ꢀN-1ꢀN-2
−178.8(2)
−178.0(2)
58.0(2)
0
.7(2)° for 3; and DC
(C-1)=DC
S
S
S
(
C-4)=8.0(2)°, DC (C-2)=DC (C-5)=
S
55.2(3)
53.5(2)
6
.9(2)°, DC (C-3)=DC (O-5)=1.2(2)° for 4.
−62.4(2) −65.8(3) −67.3(2)
S
S
Although comparison of selected bond lengths
(as noted above) would indicate that the agly-
60.1(2) 177.5(2) −173.0(2) −172.4(2)
67.4(2) −60.4(2) −67.8(2) −67.5(2)
cones do not differ greatly in their effect on
the monosaccharide rings, the puckering and
asymmetry parameters show an overall geo-
metric similarity between 3 and 4 that does
not extend to 2. In addition, torsional angles
of 3 and 4 resemble each other more closely
than those of either structure resemble those
of 2. Replacement of a semicarbazide with an
aniline (or substituted aniline) does cause a
corresponding adjustment in the monosacchar-
ide ring geometry [23]. On the basis of the
observed values of the torsional angles O-5ꢀC-
63.2(3)
60.9(2)
65.7(2)
65.1(2)
−58.6(2)
O-5ꢀC-1ꢀN-1ꢀC-7
O-5ꢀC-1ꢀC-2ꢀC-3
O-5ꢀC-5ꢀC-4ꢀC-3 −57.0(2) −58.8(2) −55.6(2) −55.6(2)
O-5ꢀC-5ꢀC-6ꢀO-6 −61.0(3) 63.1(2) 73.8(2) 73.6(2)
O-6ꢀC-6ꢀC-5ꢀC-4
C-lꢀN-lꢀN-2ꢀC-7
C-lꢀN-lꢀC-7ꢀC-8
C-1ꢀO-5ꢀC-5ꢀC-4
C-1ꢀO-5ꢀC-5ꢀC-6
C-1ꢀC-2ꢀC-3ꢀC-4 −176.2(2) −56.4(2) −51.4(3) −50.5(2)
C-2ꢀC-lꢀN-lꢀC-7
C-2ꢀC-1ꢀO-5ꢀC-5
C-2ꢀC-3ꢀC-4ꢀC-5 −174.8(2)
C-3ꢀC-4ꢀC-5ꢀC-6 −178.1(3) −178.3(2) −175.0(2) −175.2(2)
−72.1(3) −73.3(3)
54.6(3) 53.7(2)
57.0(2)
60.6(3) −175.8(2) −165.0(2) −165.0(2)
−115.3(2)
178.5(2) −178.7(2)
5
ꢀC-6ꢀO-6 and C-4ꢀC-5ꢀC-6ꢀO-6, the confor-
63.1(2)
61.6(2)
61.7(2)
−174.2(2) −175.6(2) −175.7(2)
mation of the C-6ꢀO-6 side chain in 2–4 can
be described as gt in all three structures [24].
The orientations of the aromatic rings in 3
and 4 (as defined by the torsional angles O-
166.7(2) 165.4(2)
−61.7(2) −61.1(2) −60.7(2)
56.5(2)
51.4(3)
50.7(2)
5
ꢀC-1ꢀN-1ꢀC-7 and C-1ꢀN-1ꢀC-7ꢀC-8) are
closely similar to each other.
Packing arrangements and intermolecular in-
teractions.—Details of the intermolecular hy-
drogen bonding for all four structures are
given in Table 2. The packing arrangements
assumed by 1–4 are shown in Figs. 5–8.
pair into the aromatic ring is suggested. On
the other hand, the N-1ꢀC(aryl) bonds in 3
and 4 are longer than those reported for the
nitrophenyl compounds (1.392(3) A
,
for both 3
,
for the lyxose
The packing arrangement assumed by
D
-
and 4 compared with 1.377(5) A
derivative and 1.383(3) A
,
for the arabinose
mannose oxime 1 (Fig. 5) is different from
that assumed by either isomer of arabinose
oxime. Both isomers of arabinose oxime crys-
tallize as ‘head-to-head’ dimers in which hy-
drogen-bonding interactions link pairs of
NꢀOH groups into six-membered rings, but
molecules of 1 are linked by a ‘head-to-tail’
interaction in which the NꢀOH group of each
molecule forms a hydrogen-bonded bridge
across the C-5 and C-6 hydroxyl groups of a
neighboring molecule, forming an eight-mem-
bered ring in which the O-6 and oxime hy-
droxyls are H-bond donors and the O-5
hydroxyl and oxime nitrogen are H-bond ac-
ceptors. The molecules are linked into chains
derivative), indicating that if delocalization
does occur in 3 and 4, it is of lesser impor-
tance in these structures than it is in the
structures with the powerfully electron-with-
drawing nitro substituent.
Compounds 2–4 all exist as the b anomer in
these solid-state structures, and all assume the
4
C conformation. Cremer–Pople puckering
1
parameters [18–20] (calculated using the pro-
gram PLATON-94 [21]) for the three pyranose
rings are Q=0.595(4) A
92.7(248)° for 2; Q=0.557(3) A
b=354.5(36)° for 3; and Q=0.556(3) A
=4.4(2)°, b=349.0(32)° for 4. Asymmetry
,
, [=0.0(4)°, b=
2
,
, [=3.8(2)°,
,
,
[

108
W.H. Ojala et al. / Carbohydrate Research 326 (2000) 104–112
by this interaction and are also linked side by
side by three H-bonding interactions along the
crystallographic a-axis and by one H-bonding
interaction along the crystallographic c-axis.
All of the hydroxyl groups serve as H-bond
donors; only O-4 does not also serve as a
H-bond acceptor.
The semicarbazide derivative 2 (packing
shown in Fig. 6) crystallizes as a dihydrate,
the water molecules forming a two-molecule
hydrogen-bonded bridge linking O-6 in-
tramolecularly to the carbonyl oxygen atom
O-1. With both water molecules engaging in
hydrogen bonding with O-1, there are no close
intermolecular contacts between O-1 and N-2
or between O-1 and N-3, and any hydrogen-
bonded interaction of the amide dimer type is
precluded. For their part, the NꢀH hydrogen
atoms do not engage in any particularly short
hydrogen-bonding interactions.
In the packing arrangement of aniline
derivative 3 (Fig. 7), hydrogen bonding be-
tween pyranose rings defines layers lying per-
pendicular to the b-axis. These alternate with
layers in which the phenyl rings are packed
together, the crystal thereby consisting of al-
ternating hydrophilic and hydrophobic layers.
Like the NꢀH hydrogen atoms in 2, the NꢀH
hydrogen atom in 3 does not engage in any
significant intermolecular interactions. On the
other hand, although the ring oxygen O-5
plays no role in the hydrogen bonding in 2, in
3 it acts as a hydrogen-bond acceptor.
The packing arrangement of the p-
chloroaniline derivative 4 (Fig. 8) is closely
related to that of 3, the hydrogen-bonding
schemes found in the two structures being
essentially the same. Both packing arrange-
Table 2
a
Hydrogen-bond parameters (A, °)
,
DꢀH···A
DꢀH
H···A
D···A
DꢀH···A
i
1
2
O-l-H-1OꢀO-5
0.74(3)
0.80(3)
0.72(3)
0.71(3)
0.76(3)
0.82(3)
0.91(4)
0.88(3)
0.82(3)
1.01(4)
0.86(3)
0.80(3)
0.79(3)
0.90(3)
0.88(3)
0.79(3)
0.79(3)
0.70(4)
0.79(3)
0.84(3)
0.82(3)
0.93(3)
0.89(3)
0.82(3)
0.85(3)
0.83(3)
0.90(3)
0.88(3)
1.95(3)
2.05(3)
2.07(3)
2.06(3)
2.01(3)
2.04(3)
1.90(4)
1.83(3)
2.07(4)
1.87(4)
1.86(3)
2.20(4)
1.92(3)
1.83(3)
2.08(3)
2.89(3)
2.92(3)
2.91(3)
2.27(3)
1.96(3)
1.90(3)
1.84(3)
2.27(3)
2.28(3)
1.96(3)
1.91(3)
1.89(3)
2.33(3)
2.654(2)
2.764(2)
2.738(2)
2.750(2)
2.734(3)
2.851(3)
2.794(2)
2.694(3)
2.880(3)
2.871(4)
2.709(2)
2.873(2)
2.657(2)
2.724(2)
2.951(3)
3.297(2)
3.241(2)
3.246(3)
2.953(3)
2.799(3)
2.709(3)
2.765(2)
3.104(3)
3.000(2)
2.808(2)
2.728(2)
2.773(2)
3.130(3)
158(4)
149(3)
156(4)
164(4)
160(4)
173(3)
168(3)
167(3)
170(3)
176(3)
172(3)
142(3)
155(3)
173(3)
169(3)
114(3)
107(3)
113(3)
145(3)
176(3)
172(3)
175(3)
155(3)
146(3)
176(3)
172(3)
166(3)
152(3)
ii
O-2ꢀH-2OꢀO-l
iii
O-3ꢀH-3OꢀO-2
O-4ꢀH-4OꢀO-3
ii
iv
O-5ꢀH-5OꢀO-6v
O-6ꢀH-6OꢀN-1
O-lWꢀH-lWꢀO-l
vi
vi
O-lWꢀH-2WꢀO-2W
vi
O-2WꢀH-3WꢀO-6
iv
O-2WꢀH-4WꢀO-l
vii
O-2ꢀH-2OꢀO-6
viii
O-3ꢀH-3OꢀO-1
viii
O-4ꢀH-4OꢀO-1W
ix
O-6ꢀH-6OꢀO-3
ii
N-lꢀH-1NꢀO-4
ix
O-4ꢀH-4OꢀO-6
iv
O-4ꢀH-4OꢀO-2
x
N-3ꢀH-31NꢀO-2
ii
3
4
O-2ꢀH-2OꢀO-4
iii
O-3ꢀH-3OꢀO-5
xi
O-4ꢀH-4OꢀO-3x
O-6ꢀH-6OꢀO-4
ii
N-lꢀH-1NꢀO-6
ix
O-2ꢀH-2OꢀO-4
iv
O-3ꢀH-3OꢀO-5
xii
O-4ꢀH-4OꢀO-3
ii
O-6ꢀH-6OꢀO-4
ix
N-lꢀH-1NꢀO-6
a
Symmetry codes: (i) −1+x, −1+y, z; (ii) 1+x, y, z; (iii) x, y, 1+z; (iv) −1+x, y, z; (v) 1+x, 1+y, z; (vi) x, y, z; (vii) 1+x,
1+y, z; (viii) x, −1+y, 1+z; (ix) x, 1+y, z; (x) x, y, −1+z; (xi) −1/2+x, 1/2−y, 1−z; (xii) −2−x, −1/2+y, −1−z.
−

W.H. Ojala et al. / Carbohydrate Research 326 (2000) 104–112
109
Fig. 5. Molecular packing in 1.
ments involve a side-by-side interaction in
which translationally related pyranosides are
linked by a pair of hydrogen bonds, O-3
None of the hydrogen-bonding interactions
found in 3 and 4 are found in 2, in which the
presence of the water molecules and their in-
(
donor) to O-5 (acceptor) and O-6 (donor) to
O-4 (acceptor). In both structures a hydrogen
bond links O-2 (donor) to O-4 (acceptor) of
another neighboring translationally related
molecule, and another hydrogen bond links
O-4 (donor) to O-3 (acceptor) of a neighbor-
ing molecule related by a screw axis. The close
relationship between the packing arrange-
ments of 3 and 4 can be seen by comparing
Figs. 7 and 8, the four-molecule motif shown
in Fig. 8 for 4 being embedded in the structure
of 3 shown in Fig. 7. The structure of 3
involves a stacking mode in which the motif
shown for 4 is turned over and stacked on top
of itself such that the phenyl groups define a
‘
herringbone’ pattern. Replacement of a
phenyl hydrogen atom by the chlorine atom
appears to disrupt this type of interaction
between phenyls in 3 and to replace it with a
parallel stacking of p-chlorophenyl rings in 4.
Fig. 6. Molecular packing in 2.

110
W.H. Ojala et al. / Carbohydrate Research 326 (2000) 104–112
teraction with the carbonyl oxygen produce
an entirely different hydrogen-bonding pat-
tern.
3
. Experimental
Preparation of
oxime 1 was prepared by combining
D
-mannose deri6ati6es.—The
-man-
nose (0.2 g), hydroxylamine hydrochloride
0.5 g), 10% aq NaOH (2 mL), and water (3
D
(
mL). Ethanol was added dropwise to clear
turbidity. The solution was heated for 15 min
and then refrigerated until needle-shaped crys-
tals appeared, mp 188–193 °C (lit. 176–
1
84 °C [25]). The semicarbazide derivative 2
was prepared by combining a solution of
D
-
mannose (0.5 g) in EtOH (5 mL) with a
solution of semicarbazide hydrochloride (0.5
g) and NaOAc (0.75 g) in water (5 mL). The
resulting solution was heated for 5 min. Crys-
tals of 2 were obtained by means of slow
diffusion of EtOH into the reaction mixture,
yielding prisms, mp 112 °C (lit. 108 °C [26]).
The anilides 3 and 4 were prepared by
combining
D-mannose (0.3 g) with aniline
(
0.15 g) and p-chloroaniline (0.25 g), respec-
tively, in EtOH (15 mL) and concentrating the
solution to a volume of ꢀ8 mL. Recrystal-
lization from EtOH of the powdery solid thus
obtained in each case yielded 3 as needles, mp
Fig. 7. Molecular packing in 3.
1
85–190 °C (lit. 180–181 °C [14]) and 4 as
needles, mp 188–192 °C (lit. 171–172 °C [27],
00 °C [15]). Inspection of crystals of 3 under
2
the microscope showed them to contain a
narrow channel of solvent extending length-
wise through every crystal examined. At-
tempts to trim these needles to a size suitable
for data collection caused the channel to
empty and leave the crystal hollow. An at-
tempt was made to choose the best available
untrimmed crystal for the structure determina-
tion, but it may have been the existence of a
solvent channel through the crystal ultimately
chosen that caused the relatively large value
for the final unweighted R factor for 3. No
such solvent channels were observed in crys-
tals of 4.
X-ray crystal structure determinations.—A
summary of the crystal data, data collection
parameters, and refinement results is given in
Fig. 8. Molecular packing in 4. Note the similarity between
this view and the bottom half of Fig. 7 (molecular packing in
3).

W.H. Ojala et al. / Carbohydrate Research 326 (2000) 104–112
111
Table 3
Crystal data, data collection parameters, and refinement results for 1–4
a
1
2
3
4
Formula
C H NO
C H N O
C H NO5
12 17
C H ClNO5
12 16
6
13
6
7
19
3
8
Formula weight
Crystal dimensions (mm )
Crystal system
195.17
273.24
255.27
289.72
3
0.24×0.13×0.10 0.52×0.24×0.12 0.42×0.06×0.05
triclinic
P1
0.48×0.10×0.08
monoclinic
P21
triclinic
P1
orthorhombic
Space group
P2 2 2
1
1 1
a (A
,
)
)
)
5.5968(8)
8.532(1)
4.9925(8)
94.71(1)
110.32(1)
102.02(1)
215.53(6)
1
7.0659(7)
7.3383(4)
6.7234(5)
91.500(6)
104.208(7)
67.458(5)
311.23(4)
1
6.766(2)
28.368(2)
6.449(2)
6.518(1)
6.878(1)
14.734(1)
b (A
,
c (A
,
h (°)
i (°)
k (°)
101.42(1)
3
V (A
,
)
1237.8(5)
4
1.37
647.6(1)
2
1.49
Z
−
3
D (g cm
)
1.50
1.46
c
F(000)
v (Cu K ) (cm
104
11.31
140.0
1693
765
0.013
1693
152
146
11.58
140.2
2384
1094
0.017
2384
215
544
9.02
140.2
2613
1308
0.035
2128
215
304
−
l
)
28.04
140.1
2728
1247
0.036
2283
a
2qmax (°)
No. of measured reflections
No. of unique reflections
Rint
No. of observed reflections (I\0.00|(I))
No. of variables
187
Trans. coefficients
Secondary extinction [28]
Min, max in final difference map (e A
R; wR
0.9452–1.0000
0.6928–1.0000
0.9575–1.0000
0.8977–1.0000
2.20998×10
−0.20, 0.29
0.042, 0.033
−
5
−4
−6
−5
5.88165×10
−0.19, 0.22
0.030, 0.027
1.66301×10
−0.23, 0.19
0.036, 0.043
1.79468×10
−0.31, 0.32
0.074, 0.032
−
3
,
)
a
For all four structures: T=298 K; diffractometer: Rigaku AFC6S; radiation: Cu K ; u=1.54178 A; cell determination: 25
,
a
reflections (23 for 3), 30°B2qB50°; data collection: MSC/AFC control software [29]; scan mode: ꢀ/2q; structure solution:
SHELXS86 [30]; structure refinement: teXsan software package [31]; decay correction: none for 1; 5.55% for 2; 2.46% for 3; 3.27%
2
2
obs
1/2
for 4; absorption correction: psi scans [32]; figures: ORTEPII [17]; R=ꢀꢁFobsꢂ−ꢂFcalcꢁ/ꢀꢂFobsꢂ; wR=[(ꢀw(ꢂFobsꢂ−ꢂFcalcꢂ) /ꢀwF
] ;
2
obs
2
2
obs
2
i
2
ij
2
i
w=4F /| (F ); Rint=ꢀꢀꢂBF \−F ꢂ/ꢀmBF \.
Table 3. For all four structures the non-hy-
drogen atoms were refined anisotropically.
For 1–3 the positional parameters of all the
hydrogen atoms were refined. An attempt to
do the same for 4 led to unreasonable bond
lengths for the methylene hydrogens, so in this
structure all the CꢀH hydrogen atoms were
placed in calculated positions, while the posi-
tional parameters of the O–H and NꢀH hy-
drogen atoms were refined.
1223-336408; fax: +44-1223-336033; e-mail:
deposit@ ccdc.cam.ac.uk).
Acknowledgements
The authors thank Dr William B. Gleason
of the Department of Laboratory Medicine
and Pathology of the University of Minnesota
for his assistance in this work and for making
the Department’s crystallographic facilities
available to us.
Supplementary material
Full crystallographic details have been de-
posited with the Cambridge Crystallographic
Data Centre. These data may be obtained, on
request, from The Director, CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK (Tel.: +44-
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