Supramolecular structures of substituted α,α′-trehalose derivatives

Article abstract of DOI:10.1107/S0108768104010912

The structures of five substituted α,α′-trehalose trehalose derivatives have been determined, and these are compared with those of four previously published analogues. In 2,2′,3,3′,4,4′- hexaacetato-6,6′-bis-O-methylsulfonyl-α,α′-trehalose, C₂₆

Full text of DOI:10.1107/S0108768104010912

research papers
Acta Crystallographica Section B
Structural
0
Supramolecular structures of substituted a,a -treha-
Science
lose derivatives
ISSN 0108-7681
a
0
Received 19 April 2004
Thomas C. Baddeley, Iain G.
The structures of ®ve substituted ꢀ,ꢀ -trehalose trehalose
derivatives have been determined, and these are compared
b
Accepted 4 May 2004
Davidson, Christopher
c
a
with those of four previously published analogues. In
0
Glidewell, * John N. Low,
0
0
0
0
a
2,2 ,3,3 ,4,4 -hexaacetato-6,6 -bis-O-methylsulfonyl-ꢀ,ꢀ -treha-
lose, C H O S , where the molecules lie across twofold
Janet M. S. Skakle and James L.
a
2
6
38 21 2
Wardell ³
rotation axes in the space group C2, a single CÐHÁ Á ÁO
S
hydrogen bond links the molecules into sheets. 2,2 ,3,3 ,4,-
0
0
a
0
0
0
Department of Chemistry, University of
4
C H O S , crystallizes with Z = 2 in the space group
-Hexaacetato-6,6 -bis-O-(4-toluenesulfonyl)-ꢀ,ꢀ -trehalose,
Aberdeen, Meston Walk, Old Aberdeen AB24
0
b
38 46 21 2
3
UE, Scotland, Quadrant Drug Delivery Ltd, 1
P2 2 2 and a combination of three CÐHÁ Á ÁO hydrogen
1
1 1
Mere Way, Ruddington, Nottingham NG11 6JS,
c
bonds, each having a carbonyl O atom as an acceptor, and a
England, and School of Chemistry, University
of St Andrews, St Andrews, Fife KY16 9ST,
Scotland
CÐHÁ Á Áꢁ(arene) hydrogen bond link the molecules into a
0
0
0
0
three-dimensional framework. 2,2 ,3,3 ,4,4 -Hexaacetato-6,6 -
0
diazido-ꢀ,ꢀ -trehalose, C H N O , crystallizes as a partial
2
4
32
6
15
ethanol solvate and three CÐHÁ Á ÁO hydrogen bonds link the
³
Present address: Instituto de Qu Âõ mica,
substituted trehalose molecules into a three-dimensional
0
Departamento de Qu Âõ mica Inorg aà nica, Univer-
sidade Federal do Rio de Janeiro, 21945-970 Rio
de Janeiro-RJ, Brazil.
0
0
framework. In 2,2 ,3,3 -tetraacetato-6,6 -bis(N-acetylamino)-
0
ꢀ
trehalose molecules lie across twofold rotation axes in the
,ꢀ -trehalose dihydrate, C H N O Á2H O, the substituted
2
4
36
2
15
2
space group P2 2 2 and a three-dimensional framework is
1
1
Correspondence e-mail: cg@st-andrews.ac.uk
generated by the combination of OÐHÁ Á ÁO and NÐHÁ Á ÁO
0
hydrogen bonds. The diaminotrehalose molecules in 6,6 -
0
diamino-ꢀ,ꢀ -trehalose dihydrate, C H N O .2(H O), lie
1
2
24
2
9
2
across twofold rotation axes in the space group P4 2 2: a
3
1
single OÐHÁ Á ÁN hydrogen bond links the trehalose molecules
into sheets, which are linked into a three-dimensional
framework by OÐHÁ Á ÁO hydrogen bonds.
1
. Introduction
Recent reports on the structures of the multiply substituted
0
ꢀ
,ꢀ -trehalose derivatives (1) [see (I)], which crystallizes as an
ethyl acetate monosolvate (Baddeley et al., 2001), (2), which
crystallizes as a partial (0.7 mol) hydrate (Clow et al., 2001), (3)
(Baddeley et al., 2002) and (4) (Baddeley et al., 2003) indicate
that, despite the wide variation of the substituents, particularly
0
those at the 6 and 6 positions, the pyranose rings all adopt
very similar chair conformations, as judged by the ring-puck-
ering parameters (Cremer & Pople, 1975).
In (1)±(3) there are no direction-speci®c interactions
between the molecules, but in (4) a single OÐHÁ Á ÁO hydrogen
bond links the molecules into helical C12 (Bernstein et al.,
1
995) chains, which are weakly reinforced by a CÐHÁ Á ÁO
C
hydrogen bond. Two further CÐHÁ Á ÁO contacts were
reported in (4), but both of these involve methyl CÐH bonds.
Since it is now well established (Riddell & Rogerson, 1996,
1997) that in the solid state methyl groups, H CÐX, generally
3
undergo very rapid rotation about their CÐX bonds, even at
#
2004 International Union of Crystallography
Printed in Great Britain ± all rights reserved
Acta Cryst. (2004). B60, 461±471
DOI: 10.1107/S0108768104010912 461

research papers
very low temperatures, such that the H-atom sites identi®ed
from diffraction data generally represent the minima in the
corresponding rotational potential functions, rather than
statically occupied sites, it is unlikely that contacts involving
methyl CÐH bonds such as those reported will, or can, have
any structural signi®cance.
collected, washed with water, dried in vacuo at 330 K and
recrystallized from ethanol; yield 10.4 g (92%), m.p. 441 K, lit.
m.p. 441±442 K; (Birch & Richardson, 1968); [ꢀ] (CHCl3)
D
ꢀ
ꢀ
146.2 , lit. [ꢀ] (CHCl ) 143 (Birch & Richardson, 1968).
D
3
1
NMR (CDCl ): ꢂ( H) 2.01 (s, 3H, Me), 2.05 (s, 3H, Me), 2.08
3
(3, 3H, Me), 3.01 (s, 3H, Me), 4.11 (td, 1H, J = 2.14, 6.22, H-5),
0
4
.14 (dd, 1H, J = 2.14, 11.10, H-6 ), 4.22 (dd, 1H, J = 6.22, 11.10,
H-6), 4.98 (t, 1H, J = ca 9), 5.01 (dd, 1H, J = 3.85, 10.37, H-2),
1
3
5
2
.28 (d, 1H, J = 3.85, H-1), 5.46 (t, 1H, J = 10.37, H-3): ꢂ( C)
0.6, 37.7, 66.5, 68.2, 68.4, 69.6, 69.7, 92.6, 169.6, 169.8, 169.9.
�
1
IR (KBr, cm ): 2972, 2932, 1760, 1743, 1357, 1219, 1178, 1143,
1
037, 1018, 989, 955, 811.
Compound (6): A solution of 2,2 ,3,3 ,4,4 -hexa-O-acetyl-
0
0
0
0
ꢀ
chloride (9.6 g, 50.5 mmol) in acetonitrile (30 cm ) and pyri-
,ꢀ -trehalose (10 g, 16.8 mmol) and 4-toluenesulfonyl
3
3
dine (10 cm ) was stirred for 24 h and DMAP (ca 10 mg)
added. After stirring for a further 5 h, the solution was
evaporated to a syrupy residue, which was poured into water
with vigorous stirring. The off-white precipitate was ®ltered
off, washed with water and air dried. The resulting solid was
washed with boiling ethanol, dried at 330 K in vacuum and
recrystallized from ethanol; yield 11.4 g (90.4%), m.p. 431±
4
34 K, lit. m.p. 443±445 K (Birch & Richardson, 1968). NMR
1
(CDCl ): ꢂ( H) 1.98 (s, 3H, Me), 2.01 (s, 3H, Me), 2.06 (s, 3H,
3
Me), 2.43 (s, 3H, Me), 4.02 (m, 2H), 4.10 (m, 1H), 4.90 (m, 3H),
1
3
5
2
1
1
6
4
.38 (m, 1H), 7.32 (d, 2H, J = 7.95), 7.72 (d, 2H, J = 8.35): ꢂ( C)
0.6, 21.6, 67.6, 68.2, 68.6, 69.2, 69.8, 92.8, 128.0, 129.9, 132.4,
�
1
45.3, 169.5, 169.6, 169.9. IR (KBr, cm ): 2963, 1754, 1371,
+
221, 1178, 1081, 1039, 979, (810, 669, 554). MS (ES , MeCN):
67.4 [100%], 796.4 [30%], 925.5 [20%, M + Na], 458.4 [18%],
17.4 [15%], 771.5 [10%, M � CH C H SO + Na].
3
6
4
2
0
0
0
Compound (7): To a solution of 2,2 ,3,3 ,4,4 -hexa-O-acetyl-
0 0
6
,6 -di-O-methanesulfonyl-ꢀ,ꢀ -trehalose (10.0 g, 14.9 mmol)
3
in DMSO (60 cm ) was added sodium azide (3.0 g, 46 mmol)
and the solution heated to 350 K. After 1 h, TLC with ethyl
acetate:light petroleum (boiling range 313±333 K) (2:1 v/v) as
eluent showed complete reaction. The solution was poured
into water (200 cm ) and the solid was collected, dried and
recrystallized from ethanol as a partial solvate; yield 8.5 g
In this paper, we report the molecular and supramolecular
0
structures of further examples of substituted ꢀ,ꢀ -trehalose
3
derivatives, (5)±(9) [see (I)], where the substituents were
selected to afford the possibility of other types of direction-
speci®c intermolecular interactions: for example, (5) and (6)
both offer the possibility of CÐHÁ Á ÁO S hydrogen bonds,
while both CÐHÁ Á Áꢁ(arene) hydrogen bonds and aromatic
(
1
94%), m.p. 413 K, lit. m.p. 387±389 K (Birch & Richardson,
968), 392±393 K (Kurita et al., 1994), 394±398 K (Liav &
ꢀ
ꢀ
Goren, 1980); [ꢀ] (CHCl ) 127 , lit. [ꢀ] (CHCl ) 134 (Birch
&
D
3
D
3
ꢀ
Richardson, 1968), (CHCl ) 138 (Kurita et al., 1994). NMR
3
ꢁ
Á Á Áꢁ stacking interactions could occur in (6); CÐHÁ Á ÁN
1
(CDCl ): ꢂ( H) 2.02 (s, 3H, Me), 2.05 (s, 3H, Me), 2.11 (s, 3H,
3
hydrogen bonds could in principle occur in (7); OÐHÁ Á ÁO and
NÐHÁ Á ÁO hydrogen bonds could both occur in (8); and OÐ
HÁ Á ÁO, NÐHÁ Á ÁO, and OÐHÁ Á ÁN hydrogen bonds are all
possible in (9).
0
Me), 3.16 (dd, 1H, J = 2.44, 13.32, H-6 ), 3.36 (dd, 1H, J = 7.39,
1
9
3
6
1
1
3.32, H-6), 4.08 (m, 1H, J = 2.44, 7.39, 9.1, H-5), 4.98 (dd, 1H,
.4, 9.9, H-4), 5.07 (dd, 1H, J = 3.82, 10.31, H-2), 5.31 (d, 1H, J =
1
3
.82, H-1), 5.45 (dd, 1H, J = 9.4, 10.31, H-3): ꢂ( C) 20.7, 51.0,
�
1
7.7, 69.8, 69.9, 92.7, 169.6, 170.0. IR (KBr, cm ): 2101, 1740,
+
211, 1033, 1014. MS (ES , MeCN): 667.2 [100%, M + Na],
2
. Experimental
05.1 [50%], 642.2 [20%].
Compound (8): To a solution of 2,2 ,3,3 ,4,4 -hexa-O-acetyl-
2
.1. Syntheses
0
0
0
3
0
0
0
0
0
3
Compound (5): A solution of 2,2 ,3,3 ,4,4 -hexa-O-acetyl-
0
6,6 -di-O-azido-ꢀ,ꢀ -trehalose (10.0 g, 16.4 cm ) in thf (80 cm )
was added triphenylphosphine (9.0 g, 34.4 mmol) and water
3
(2 cm ). After stirring for 1 h, TLC, using ethyl acetate: light
ꢀ
(
(
,ꢀ -trehalose (10 g, 16.8 mmol) and methanesulfonyl chloride
3
5.8 g, 4 cm , 50.5 mmol) in acetonitrile (30 cm ) and pyridine
3
3
10 cm ) was stirred for 3 h, and rotary evaporated to leave an
petroleum (2:1 v/v) as eluent, indicated the consumption of the
starting material. The suspension was ®ltered and the solid
oily solid. After shaking the residue with water, a solid was
ꢁ
0
462 Thomas C. Baddeley et al.
Substituted ꢀ,ꢀ -trehalose derivatives
Acta Cryst. (2004). B60, 461±471

research papers
Table 1
Experimental details.
(5)
(6)
(7)
(8)
(9)
Crystal data
Chemical formula
C
26
H
38
750.68
O
21
S
2
C
38
H
46
O
21
S
2
C
24 32
H
660.68
N
6
O
15Á0.35C
2
H
6
O
C
24 36
H
628.58
N
2
O
15Á2H
2
O
C
12
H
24
N
2
O
9
Á2H
2
O
M
r
902.89
Orthorhombic, P2
376.36
Tetragonal, P4
Cell setting,
space group
Ê
a, b, c (A)
Monoclinic, C2
1
2
1
2
1
Orthorhombic, P2
1
2
1
2
1
Orthorhombic, P2
1
2
1
2
3
2
1
2
21.3279 (8), 8.9299 (4),
8
99.4537 (17)
1660.43 (12)
2
1.501
Mo Kꢀ
3048
18.1484 (9), 21.1046 (9), 12.2281 (4), 15.5803 (6), 8.8385 (2), 21.8363 (8),
23.4224 (14) 18.1066 (8) 8.0831 (2)
90.00 90.00 90.00
8971.1 (8)
8
1.337
8.6093 (2), 8.6093 (2),
22.1566 (8)
90.00
1642.25 (8)
4
1.522
.8382 (4)
ꢀ
ꢃ ( )
Ê
3
V (A )
3449.6 (2)
4
1.272
Mo Kꢀ
4368
1560.04 (8)
2
1.338
Mo Kꢀ
2067
Z
�
3
D )
Radiation type
x
(Mg m
Mo Kꢀ
14 269
Mo Kꢀ
1163
No. of re¯ections
for cell parameters
ꢀ
ꢄ range ( )
ꢅ (mm
3.3±27.5
0.25
3.0±24.4
0.20
3.1±27.5
0.11
2.5±27.5
0.11
3.0±27.5
0.13
�
1
)
Temperature (K)
Crystal form, colour
Crystal size (mm)
120 (2)
Block, colourless
0.30 Â 0.25 Â 0.15
120 (2)
Lath, colourless
0.30 Â 0.10 Â 0.02
150 (2)
Block, colourless
0.50 Â 0.30 Â 0.25
120 (2)
Block, colourless
0.30 Â 0.20 Â 0.15
120 (2)
Block, colourless
0.15 Â 0.15 Â 0.10
Data collection
Diffractometer
Data collection
method
Kappa-CCD
' scans, and ! scans
with ꢆ offsets
Multi-scan
Kappa-CCD
' scans, and ! scans
with ꢆ offsets
Multi-scan
Kappa-CCD
' scans, and ! scans
with ꢆ offsets
Multi-scan
Kappa-CCD
' scans, and ! scans
with ꢆ offsets
Multi-scan
Kappa-CCD
' scans, and ! scans
with ꢆ offsets
Multi-scan
Absorption correction
T
T
min
0.934
0.964
6104, 3048, 2781
0.949
0.996
34 701, 14 269, 8221
0.942
0.974
17 686, 4368, 2580
0.960
0.983
13 388, 2067, 1658
0.972
0.987
8561, 1163, 951
max
No. of measured,
independent and
observed re¯ections
Criterion for observed
re¯ections
I > 2ꢇ(I)
I > 2ꢇ(I)
I > 2ꢇ(I)
I > 2ꢇ(I)
I > 2ꢇ(I)
R
int
0.059
27.5
0.110
25.0
� 20 ) h ) 20
� 24 ) k ) 24
� 26 ) l ) 26
0.104
27.5
� 12 ) h ) 15
� 18 ) k ) 20
� 23 ) l ) 23
0.091
27.5
� 11 ) h ) 11
� 28 ) k ) 27
� 9 ) l ) 10
0.055
27.5
� 9 ) h ) 11
� 11 ) k ) 11
� 20 ) l ) 28
ꢀ
ꢄmax ( )
Range of h, k, l
� 27 ) h ) 26
�
�
10 ) k ) 11
11 ) l ) 11
Re®nement
Re®nement on
R[F > 2ꢇ(F )], wR(F ), S 0.051, 0.145, 1.05
No. of re¯ections
No. of parameters
H-atom treatment
2
2
2
2
2
F
F
F
F
F
2
2
2
0.060, 0.136, 0.96
14 269
1113
Constrained to
parent site
0.070, 0.191, 0.99
4368
439
Constrained to
parent site
0.055, 0.148, 1.12
2067
215
Constrained to
parent site
0.043, 0.126, 0.98
1163
115
Constrained to
parent site
3048
227
Constrained to
parent site
2
2
2
2
2
2
2
2
2
2
Weighting scheme
w = 1/[ꢇ (F ) +
w = 1/[ꢇ (F ) +
w = 1/[ꢇ (F ) +
w = 1/[ꢇ (F ) +
w = 1/[ꢇ (F ) +
o
o
o
o
o
2
0.1014P) ], where
2
(0.0479P) ], where
2
(0.1153P) ], where
2
2
(
P = (F + 2F )/3
(0.0967P)
+ 0.0109P], where
(0.0747P)
+ 0.9377P], where
P = (F + 2F )/3
o c
2
2
c
2
2
c
2
2
c
P = (F + 2F )/3
P = (F + 2F )/3
o
o
o
2
2
c
2
2
P = (F + 2F )/3
<0.0001
0.47, � 0.41
o
(Á/ꢇ)max
<0.0001
0.001
0.86, � 0.28
<0.0001
0.43, � 0.43
<0.0001
0.24, � 0.35
Ê
� 3
)
Áꢈmax, Áꢈmin (e A
Extinction method
Extinction coef®cient
Absolute structure
0.48, � 0.62
SHELXL
0.0065 (18)
Flack (1983), 1018
Friedel pairs
0.16 (10)
None
±
None
None
None
±
±
±
±
±
±
Flack (1983), 6179
Friedel pairs
� 0.02 (8)
Flack parameter
±
±
±
Computer programs used: Kappa-CCD server software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN and SHELXS97 (Sheldrick, 1997b), SHELXL97
(
Sheldrick, 1997a), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).
0
0
0
0
0
0
+
22.8, 40.8, 71.7, 72.0, 72.1, 72.4, 73.4, 94.4, 175.5. MS (ES ):
2
halose was washed with dichloromethane and dried; yield 4.9 g
,2 ,3,3 ,4,4 -hexa-O-acetyl-6,6 -diamino-6,6 -dideoxy-ꢀ,ꢀ -tre-
579.0 [100%], 301.0 [80%], 615.1 [45%, M + Na].
A solution of the foregoing 2,2 ,3,3 ,4,4 -hexa-O-acetyl-6,6 -
1
0 0 0 0
(
51%), m.p. 418±428 K. NMR (CDCl ): ꢂ( H) 1.95 (s, 3H, Me),
2.05 (s, 3H, Me), 2.07 (s, 3H, Me), 3.14 (dd, 1H, J = 7.59, 14.15,
H-6), 3.42 (t, 1H, J = 9.57, H-4), 3.68 (m, 1H, H-5), 3.81 (dd,
3
0
0
diamino-6,6 -dideoxy-ꢀ,ꢀ -trehalose (0.5 g) in pyridine
3
(10 cm ) was allowed to stand overnight. Diethyl ether was
0
1
(
H, J = 2.61, 14.15, H-6 ), 4.85 (dd, 1H, J = 3.58, 10.3, H-2), 5.33
1
d, 1H, J = 3.58, H-1), 5.34 (m, 1H, J = 10.3, H-3): ꢂ( C) 21.3,
added to precipitate the rearranged product, (8), which was
recrystallized from aqueous ethanol as the dihydrate, m.p.
3
ꢁ
0
Acta Cryst. (2004). B60, 461±471
Thomas C. Baddeley et al.
Substituted ꢀ,ꢀ -trehalose derivatives 463

research papers
4
77 K; lit. m.p. (from ethanol/ether) 470±473 K (Liav &
ꢀ
Table 2
Ring-puckering parameters for pyranose rings (A, ).
Ê
o
Goren, 1980); [ꢀ]D (MeOH) 123.2 , lit. [ꢀ]D (MeOH/water,
ꢀ
1
3
3
3
6
3
6
2
:1) 130 (Liav & Goren, 1980). NMR (CDCl ): ꢂ( H) 1.80 (s,
Ring-puckering parameters are for the atom sequence (O5, C1, C2, C3, C4,
C5).
3
H, Me), 1.98 (s, 3H, Me), 2.02 (s, 3H, Me), 2.91 (m, 1H, H-6),
.38 (t, 1H, J = 9.15, H-4), 3.54 (m, 1H, H-5), 3.70 (m, 1H, H-
0
Ê
Q (A)
ꢀ
ꢀ
ꢄ ( )
' ( )
), 4.79 (dd, 1H, J = 3.66, 10.37, H-2), 5.18 (m, 2H, H-1 and H-
1
(
(
1)
2)
0.549 (2)
0.563 (2)
4.5 (3)
4.3 (3)
14 (3)
106 (4)
3
), 7.81 (t, J = 4.28, NHCOCH ): ꢂ( C) 20.3, 20.8, 22.4, 69.0,
3
�
1
9.8, 71.4, 71.7, 90.6, 169.7, 169.9. IR (KBr, cm ): 3615±3096,
0.56 (1)
0.57 (1)
9 (1)
3 (1)
94 (7)
322 (21)
867, 1739, 1643, 1571, 1437, 1378, 1236, 1141, 1047, 1017. MS
+
(
ES ): 615.3 [100%, M + Na], 573.3 [6%, M � Ac + Na], 1207.7
[2%, 2M + Na], 531.3 [1%, M � 2Ac + Na].
(3)
0.592 (2)
4.5 (2)
246 (2)
0
0
0
Compound (9): A suspension of 2,2 ,3,3 ,4,4 -hexa-O-acetyl-
0 0
(
4)
0.571 (5)
0.568 (5)
4.5 (5)
5.5 (5)
319 (5)
317 (5)
6
,6 -di-O-azido-ꢀ,ꢀ -trehalose (5.0 g, 7.8 mmol) and sodium
3
methoxide (42.2 mg, 0.78 mmol) in methanol (40 cm ) was
stirred for 4.5 h. The colourless solution was neutralized with
DOWEX 50 W X-8 resin and the resin ®ltered off. The resin
was washed with methanol, and the ®ltrates and washings were
(
(
5)
6)
0.579 (3)
4.9 (3)
122 (4)
0.553 (5)
0.544 (5)
0.554 (5)
3.9 (5)
5.5 (5)
6.3 (5)
4.4 (5)
11 (7)
354 (5)
357 (5)
308 (7)
0
combined and evaporated to leave a white product, 6,6 -
0
0.569 (5)
0
diazido-6,6 -dideoxy-ꢀ,ꢀ -trehalose, which was crystallized
from ethanol; yield 2.05 g (67%), m. p. 474±476 K; [ꢀ] (water)
(7)
(8)
0.558 (4)
0.546 (5)
8.7 (4)
5.1 (5)
332 (3)
347 (6)
D
ꢀ
1
4
53 ; lit. m.p. 482±484 K (Birch & Richardson, 1968), 463±
ꢀ
65 K (Kurita et al., 1994), lit. [ꢀ]D (water) 158 (Birch &
1
0.567 (3)
0.580 (3)
8.4 (3)
4.3 (3)
75 (2)
Richardson, 1968). NMR (CDCl ): ꢂ( H) 3.29(t, 1H, J = 9.23,
3
(
9)
245 (4)
H-3/4), 3.39 (dd, 1H, J = 6.16, 13.68, H-6), 3.51 (m, 2H, J = 2.39,
0
1
2
7
2
1
4
3.68, H-6 , H-2), 3.66 (t, 1H, J= 9.23, H-3/4), 3.81 (ddd, 1H, J=
1
3
.39, 5.81, 9.92, H-5), 5.03 (d, 1H, J = 3.76, H-1): ꢂ( C) 51.9,
For (5) the systematic absences permitted C2 and Cm as
�
1
1.5, 71.9, 72.1, 73.3, 94.8. IR (KBr, cm ): 3537±3263, 2947,
918, 2200, 2106, 1601, 1446, 1415, 1344, 1288, 1147, 1105, 1070,
043, 984, 930, 584, 567. MS (ES+): 415.1 ([100%, M + Na],
possible space groups: in view of the enantiopure nature of the
chiral compound, the space group C2 was selected and
con®rmed by the analysis. For each of (6) and (7) the space
55.3 [32%], 432.9 [25%, M + Na + H O].
2
group P2 2 2 was uniquely assigned from the systematic
1 1 1
0
0
0
The foregoing 6,6 -diazido-6,6 -dideoxy-ꢀ,ꢀ -trehalose
0.5 g, 1.27 mmol) and triphenylphosphine (1.34 g, 5.10 mmol)
absences: similarly P2 2 2 was uniquely assigned for (8). For
1
1
(
(9) the systematic absences permitted one of the enantiomeric
pair P4 2 2 and P4 2 2: space group P4 2 2 was selected by
3
were dissolved in DMF (10 cm ). After 2 h when efferves-
cence had ceased, ammonium hydroxide solution (30%,
1
1
3 1
3 1
reference to the known absolute con®guration of the
compound. The structures were all solved by direct methods
2
and re®ned with all data on F . A weighting scheme based
3
cm ) was added and a precipitate formed. Ethanol (50 cm )
3
4
was added and the reaction mixture was heated at 330 K for
0
2
o
2
c
2
6
h to ensure complete dissolution. Crystals of 6,6 -diamino-
0
upon P ˆ ‰F ‡ 2F Š=3 was employed in order to reduce the
0
,6 -dideoxy-ꢀ,ꢀ -trehalose dihydrate were obtained on
statistical bias (Wilson, 1976). In (5), (8) and (9) the disac-
charide unit lies across a twofold rotation axis, while in (6)
there are two independent disaccharide molecules in the
asymmetric unit. In (7) there is a partially occupied ethanol:
when the C and O atoms of this unit were re®ned isotropically,
the site-occupancy factor re®ned to 0.35 (2). Thereafter this
occupancy was ®xed at 0.35, while the C and O atoms were
re®ned anisotropically. In all the compounds the absolute
structure was set from the known absolute con®guration of the
cooling; 260 mg (60%); m.p. 498±500 K; lit. m.p. 473 K (Kurita
1
et al., 1994). NMR (CDCl ): ꢂ( H) 2.70 (dd, 1H, J = 7.63, 13.73,
3
0
H-6), 2.95 (dd, 1H, J = 2.44, 13.73, H-6 ), 3.29 (t, 1H, J = 9.77,
H-3/4), 3.62 (dd, 1H, J = 3.36, 10.07, H-2), 3.71 (m, 1H, H-5),
1
3
3
4
2
9
.80 (t, 1H, J = 9.77, H-3/4), 5.17 (d, 1H, J = 3.36, H-1)): ꢂ( C)
�
1
4.0, 73.6, 73.8, 74.9, 75.0, 95.4. IR (KBr, cm ): 3544±3315,
930, 2904, 1638, 1615, 1382, 1155, 1105, 1087, 1038, 1016, 986,
39.
0
enantiopure chiral ꢀ,ꢀ -trehalose starting material: in the case
of (5) and (6) this was con®rmed by the values of the Flack
parameter (Flack, 1983), 0.16 (10) and � 0.02 (8), respectively.
For (7)±(9) the absence of any signi®cant anomalous scatterers
meant that the Flack parameters for these compounds [values
4.1 (18), � 0.1 (17) and 0 (3), respectively] were inconclusive
(Flack & Bernardinelli, 2000): hence the Friedel-equivalent
re¯ections were merged prior to the ®nal re®nements of (7)±
(9). All H atoms were located in difference maps and in (5)±
(8) they were fully ordered. The H atoms bonded to C atoms
2
.2. Data collection, structure solution and refinement
Diffraction data for (5)±(9) were collected at 120 (2) K
using a Nonius Kappa-CCD diffractometer, using graphite-
monochromated Mo Kꢀ radiation (ꢉ = 0.71073 A). Other
details of cell data, data collection and re®nement are
summarized in Table 1, together with details of the software
employed (Ferguson, 1999; Nonius, 1997; Otwinowski &
Minor, 1997; Sheldrick, 1997a,b; Spek, 2003).
Ê
Ê
were all treated as riding atoms with distances 0.95 A
ꢁ
0
464 Thomas C. Baddeley et al.
Substituted ꢀ,ꢀ -trehalose derivatives
Acta Cryst. (2004). B60, 461±471

research papers
Ê
aromatic), 0.98 A (CH ), 0.99 A (CH ) or 1.00 A (aliphatic
Ê
Ê
(
CH). The H atoms bonded to N or O in (8) were allowed to
Similar distortions of the chair conformation towards the
boat form are also evident in (1), (3) and (4), although in (2)
the uncertainties associated with the ' values preclude any
analysis of the nature of the ring distortion in this compound.
3
2
ride on their parent atoms at the positions found from the
Ê
Ê
difference maps, with distances NÐH 0.81 A; OÐH 0.82 A (in
Ê
the trehalose component) and 0.96 and 0.98 A in the water
molecule. In (9) the H atoms bonded to O2 and O4 in the
trehalose component were both modelled as riding atoms
3.2. Supramolecular structures
Where amino or hydroxyl groups are available, as in (8) and
(9), the supramolecular aggregation is dominated by hard
Braga et al., 1995; Desiraju & Steiner, 1999) hydrogen bonds
using two sites with 0.50 occupancy and OÐH distances of
Ê
0
.84 A; the H atoms bonded to N were allowed to ride at the
positions found from the difference maps with NÐH distances
(
Ê
.95 and 1.00 A; the H atoms of the water molecule were
of OÐHÁ Á ÁO, OÐHÁ Á ÁN and NÐHÁ Á ÁO types, and where
these are present, the supramolecular structures are three
dimensional. In derivatives where hard hydrogen bonds are
not possible, soft hydrogen bonds of CÐHÁ Á ÁO type become
dominant, giving a two-dimensional structure in (5) or three-
dimensional structures as in (6) and (7). The structures of most
of the compounds described here exhibit a substantial number
0
likewise allowed to ride at the positions found from the
Ê
difference maps with OÐH distances 0.94 and 0.99 A.
Examination of the re®ned structures using PLATON (Spek,
2
3
003) showed small voids in (6), each of volume ca 37 A ;
Ê
however, these contained no signi®cant electron density as
they are probably too small to accommodate even a water
molecule.
Supramolecular analyses were made and the diagrams were
prepared with the aid of PLATON. The pyranose ring-puck-
ering parameters are given in Table 2 and parameters for
1
selected hydrogen bonds are given in Table 3. Figs. 1±15 show
the molecular aggregates, with the atom-labelling schemes,
and aspects of the supramolecular structures.
3. Results and discussion
3
.1. Pyranose ring conformations
For each of (5)±(9) the ring-puckering parameters for the
pyranose rings, corresponding to the atom sequence (O5, C1,
C2, C3, C4, C5) for each independent ring, are collected in
Table 2, along with those for the previously published struc-
tures of (1)±(4) by way of comparison. It is clear that the gross
conformations of these rings are largely independent both of
the degree of substitution and of the steric bulk of the
substituents. In every case the value of the parameter ꢄ is less
Figure 1
ꢀ
The molecule of (5) showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level. The atoms marked `a'
are at the symmetry position (1 � x; y; 1 � z). For the sake of clarity the
H atoms have been omitted.
than 10 , indicating only a small distortion of the ring shape
from the expected chair conformation; a regular chair
ꢀ
conformer of exact D (3m) symmetry has a ꢄ value of zero
3
d
(
Boeyens, 1978).
Consistent with this deduction, the total puckering ampli-
Ê
tude Q lies in the range 0.54±0.58 A for (5)±(9), only a little
Ê
less than the Q value of 0.63 A calculated for the chair
conformer of cyclohexane. However, the ' values in (5)±(9)
ꢀ
are all close to N Â 60 , where N takes the values N = 2 in (5),
N = 0, 5 or 6 in (6), N = 6 in (7), N = 1 in (8) and N = 4 in (9),
indicating that the distortions from the chair conformation are
all towards the boat conformation. Thus, the rings are slightly
¯attened, allowing the ring angle CÐOÐC to increase
somewhat beyond the tetrahedral angle: in fact, in (5)±(9) the
ꢀ
ring CÐOÐC angles lie in the range 113.0 (3) for ring A in
ꢀ
(
1
7) to 114.9 (4) for ring D of (6), with a mean value of ca
ꢀ
13.7 .
Figure 2
Stereoview of part of the crystal structure of (5) showing the formation of
1
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: NA5016). Services for accessing these data are described
at the back of the journal.
4
a (001) sheet of R ꢂ36† rings. For the sake of clarity, the H atoms bonded
4
to C atoms but not taking part in the motif shown are omitted.
ꢁ
0
Acta Cryst. (2004). B60, 461±471
Thomas C. Baddeley et al.
Substituted ꢀ,ꢀ -trehalose derivatives 465

research papers
of CÐHÁ Á ÁO contacts in which the HÁ Á ÁO distances are close
to the sum of their van der Waals radii. In general, we have
considered only CÐHÁ Á ÁO interactions where the HÁ Á ÁO
Table 3
Selected hydrogen-bond parameters (A, ).
Ê
ꢀ
DÐHÁ Á ÁA
5)
C6ÐH6AÁ Á ÁO61
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
Ê
distance is less than 2.55 A and where the CÐHÁ Á ÁO angle
(
ꢀ
exceeds 135 ; however, contacts involving methyl groups have
i
2.43
3.221 (4)
136
been discounted because of the rotational properties of these
groups. Furthermore, because of the large numbers of contacts
present, we have considered only the minimum numbers of the
strongest interactions which suf®ce to de®ne the dimension-
ality of the supramolecular structures.
(
6)
ii
C4CÐH4CÁ Á ÁO41D
2.46
2.49
2.41
2.66
3.365 (7)
3.272 (6)
3.313 (7)
3.418 (7)
150
136
160
137
ii
C6CÐH6FÁ Á ÁO41D
iii
C55CÐH55CÁ Á ÁO31B
iv
C53DÐH53DÁ Á ÁCg1 ²
3.2.1. Compound (5). Molecules of (5) (Fig. 1) lie across the
rotation axes in the space group C2 and the reference mole-
(
7)
v
C6AÐH6BÁ Á ÁO41B
2.32
2.48
2.52
3.268 (6)
3.363 (8)
3.400 (7)
160
149
148
vi
C6BÐH6CÁ Á ÁO31A
vii
C6BÐH6DÁ Á ÁO41A
(
8)
N1ÐH1AÁ Á ÁO6W
2.05
1.81
2.21
1.93
2.835 (4)
2.606 (3)
3.009 (4)
2.865 (3)
165
162
137
164
vi
O4ÐH4AÁ Á ÁO61
viii
O6WÐH6CÁ Á ÁO31
ix
O6WÐH6DÁ Á ÁO4
(
9)
iii
x
O3ÐH3AÁ Á ÁN1
1.88
2.01
1.74
1.75
2.711 (3)
2.833 (3)
2.667 (3)
2.733 (5)
168
165
155
165
O4ÐH4BÁ Á ÁO4
O6WÐH6CÁ Á ÁO3
x
O6WÐH6DÁ Á ÁO6W
1
1
2
1
2
3
2
Symmetry codes: (i) � x; ‡ y; 1 � z; (ii) � ‡ x; � y; � z; (iii) x; 1 ‡ y; z; (iv)
2
(v)
(viii)
1
2
1
2
3
2
1
2
1
2
1
2
�
�
x; 2 � y; ‡ z;
� x; 1 � y; � ‡ z;
(vi)
�
‡ x; � y; 1 � z;
(vii)
(x)
3
1
x; 1 � y; ‡ z;
1 � x; 1 � y; � 1 ‡ z;
(ix)
x; y; � 1 ‡ z;
2
2
1
1
� y; 1 � x; � z. ² Cg1 is the centroid of the ring C51C±C56C.
2
1
1
cule was selected as that across the axis along ( , y, ). A single
2
2
CÐHÁ Á ÁO S hydrogen bond (Table 3) links the molecules
into sheets in which each molecule acts as a double donor and
as a double acceptor of hydrogen bonds, such that each
molecule is linked to four others. Atom C6 at (x; y; z), which is
adjacent to the very electronegative sulfonyl unit, and which
1
1
forms part of the molecule across the axis along ( , y, ), acts as
1
2
2
1
a hydrogen-bond donor, via H6A, to sulfonyl O61 at ( � x, +
2
2
y, 1 � z), which forms part of the molecule whose central atom
1
1
O1 is at (0, 2 + y, ). Similarly, O61 at (x; y; z) accepts a
2
1
1
hydrogen bond from C6 at ( � x, � + y, 1 � z), part of the
2
2
Figure 3
Figure 4
Stereoview of part of the crystal structure of (6), showing the formation of
The two independent molecules of (6) showing the atom-labelling
scheme: (a) molecule A; (b) molecule B. Displacement ellipsoids are
drawn at the 30% probability level. For the sake of clarity the H atoms
have been omitted.
1
a C(13)C(13)[R ꢂ6†] chain of rings along [100]. For the sake of clarity, the
2
H atoms bonded to C atoms but not taking part in the motif shown are
omitted.
ꢁ
0
466 Thomas C. Baddeley et al.
Substituted ꢀ,ꢀ -trehalose derivatives
Acta Cryst. (2004). B60, 461±471

research papers
1
1
molecule whose O1 atom is at (0, � + y, ). Propagation of this
2
2
hydrogen bond by rotation then generates a deeply puckered
001) sheet in the form of a (4,4) net (Batten & Robson, 1998)
(
4
built from a single type of R ꢂ36† (Bernstein et al., 1995) ring
4
(
Fig. 2).
There are no direction-speci®c interactions between adja-
cent sheets, but there is one rather short non-bonded contact,
probably attractive, within the sheet. The atoms O31 at
(
2
x; y; z) and C61 at (1 � x; 1 ‡ y; 1 � z) are separated by only
Ê
.973 (4) A, rather less than the sum of the van der Waals
Ê
radii, 3.22 A (Bondi, 1964): since O31 is a carbonyl O, while
methyl C61 is bonded to a sulfonyl group, these two atoms will
Figure 5
Stereoview of part of the crystal structure of (6) showing the formation of
a chain along [001] generated by the CÐHÁ Á Áꢁ(arene) hydrogen bond.
For the sake of clarity, the H atoms bonded to C atoms but not taking part
in the motif shown are omitted.
ꢂ�
ꢂ+
be polarized as O and C . Since the methyl group is almost
certainly undergoing rapid rotation about the CÐS bond, the
sa isgs no ic®i ac at en dt .CÐHÁ Á ÁO interaction is unlikely to be structurally
3.2.2. Compound (6). Although (6) is very similar in
chemical type to (5), both its crystallization behaviour and its
supramolecular structure are rather different. Compound (6)
Figure 6
The trehalose molecule of (7) showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 30% probability level. For the
sake of clarity, the partial ethanol solvate molecule is omitted.
Figure 8
Stereoview of part of the crystal structure of (7) showing the formation of
a chain of rings along [001]. For the sake of clarity the ethanol molecule is
omitted and the H atoms bonded to C atoms but not taking part in the
motif shown are omitted.
Figure 7
Figure 9
Stereoview of part of the crystal structure of (7) showing the formation of
a C(12) helical chain along [100]. For the sake of clarity the ethanol
molecule is omitted and the H atoms bonded to C atoms but not taking
part in the motif shown are omitted.
Stereoview of part of the crystal structure of (7) showing the formation of
a chain along [010]. For the sake of clarity the ethanol molecule is omitted
and the H atoms bonded to C atoms but not taking part in the motif
shown are omitted.
ꢁ
0
Acta Cryst. (2004). B60, 461±471
Thomas C. Baddeley et al.
Substituted ꢀ,ꢀ -trehalose derivatives 467

research papers
0
0
(
0
Fig. 3) crystallizes with Z = 2 in space group P2 2 2 [cf. Z =
1
The CÐHÁ Á Áꢁ(arene) hydrogen bond also involves only the
type B molecules and it gives rise to a chain parallel to [001].
The phenyl atom C53D in the type B molecule at (x; y; z) acts
as a hydrogen-bond donor to the phenyl ring C51CÐC56C in
1 1
.5 in C2 for (5)] and its supramolecular structure is based on a
combination of three CÐHÁ Á ÁO hydrogen bonds, with
carbonyl O, rather than sulfonyl O, as the acceptor in each,
together with a CÐHÁ Á Áꢁ(arene) hydrogen bond (Table 3).
On the other hand, aromatic ꢁÁ Á Áꢁ stacking interactions are
absent from the structure of (6).
1
1
the type B molecule at ( � x; 2 � y; ‡ z), giving a chain
2
2
1
4
generated by the 2 screw axis along ( , 1, z) (Fig. 5). The
1
combination of the [100] and [001] chains, when propagated by
the space group generates a continuous three-dimensional
framework of type B molecules, to which the type A molecules
are linked via a third CÐHÁ Á ÁO hydrogen bond. The phenyl
atom C55C in the type B molecule at (x; y; z) acts as a
hydrogen-bond donor to the carbonyl O31B atom in the type
A molecule at (x; 1 ‡ y; z): had the asymmetric unit been
selected so that the two independent molecules were linked
within it by this CÐHÁ Á ÁO hydrogen bond, one of the mole-
cules would necessarily have fallen entirely outside the unit
cell.
The molecules of type B, with O1B as the central atom,
form a single three-dimensional framework from which the
type A molecules, having O1A as the central atom, are
pendent. The formation of the framework structure is most
readily analysed in terms of the one-dimensional sub-struc-
tures (Gregson et al., 2000) generated by the CÐHÁ Á ÁO and
CÐHÁ Á Áꢁ(arene) hydrogen bonds in turn.
In the type B molecule at (x; y; z), atoms C4C and C6C both
act as hydrogen-bond donors, via H4C and H6F, respectively,
1
3
2
to carbonyl atom O41D in the type B molecule at (� + x, �
2
1
2
y, � z), so producing a C(13)C(13)[R ꢂ6†] chain of rings
3.2.3. Compound (7). Compound (7) crystallizes as a partial
ethanol solvate in the space group P2 2 2 (Fig. 6): because of
running parallel to the [100] direction and generated by the 2
3
1
1 1 1
screw axis along (x, , 0) (Fig. 4). A second, antiparallel chain
the low occupancy, 0.35, of the ethanol sites, only the inter-
actions between disaccharide molecules will be discussed. The
supramolecular aggregation is dominated by three CÐHÁ Á ÁO
hydrogen bonds (Table 3), all involving ring CÐH bonds as
donors and carbonyl O as acceptors; together they link the
molecules into a continuous three-dimensional framework.
Atom C6B in the molecule at (x; y; z) acts as a hydrogen-
bond donor, via H6C, to the carbonyl atom O31A in the
4
1 1
4 2
of this type is generated by the 2 axis along (� x, , ). The
1
[100] chain is modestly reinforced by a dipolar interaction
between nearly antiparallel carbonyl groups. The carbonyl
group C21CÐO21C in the type B molecule at (x; y; z) and the
1
2
carbonyl group C21DÐO21D in the type B molecule at (� +
3
x, � y, � z) lie in the same [100] chain of rings: the
2
i
i
O21CÁ Á ÁC21D and C21CÁ Á ÁO21D distances [symmetry code:
1
2
3
2
Ê
1
1
(
a nearly rhomboidal type II (Allen et al., 1998) interaction.
i) � ‡ x; � y; � z] are 2.958 (7) and 3.221 (7) A, so forming
molecule at (� ‡ x; � y; 1 � z), so forming a simple C(12)
2
2
chain running parallel to the [100] direction, and generated by
1 1
4 2
the 2 screw axis along (x, , ) (Fig. 7). A second chain of this
1
type, antiparallel to the ®rst, is generated by the 2 axis along
1
3
4
(
� x, , 0).
In a more complex motif, atoms C6A and C6B in the
molecule at (x; y; z) act as hydrogen-bond donors, via H6B
and H6D, respectively, to the carbonyl O atoms O41B in the
Figure 10
Figure 11
Stereoview of part of the crystal structure of (8) showing the formation of
The molecule of (8), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level. The atoms marked `a'
are at the symmetry position (1 � x; 1 � y; z).
4
a (001) sheet of R ꢂ44† rings. For the sake of clarity the water molecule is
4
omitted, as are the H atoms bonded to C atoms.
ꢁ
0
468 Thomas C. Baddeley et al.
Substituted ꢀ,ꢀ -trehalose derivatives
Acta Cryst. (2004). B60, 461±471

research papers
3
2
1
2
molecule at ( � x; 1 � y; � ‡ z) and O41A in the molecule
(4,4) net (Batten & Robson, 1998) built from a single type of
4
3
2
1
2
2
2
at ( � x; 1 � y; ‡ z) so forming a C(13)C(13)[R ꢂ14†] chain
R ꢂ44† ring (Fig. 11).
4
of rings running parallel to the [001] direction and which is
The (001) sheets are formed solely by the disaccharide
components and they are linked into a three-dimensional
framework by the water molecules. The water atom O6W at
(x; y; z) acts as a hydrogen-bond donor, via H6D, to the
3 1
4 2
generated by the 2 screw axis along ( , , z) (Fig. 8). A second
1
chain of this type, antiparallel to the ®rst, is generated by the
1
21
axis along ( , 0, � z).
4
The [100] and [001] chains are each generated by the
hydroxyl atom O4 at (x; y; � 1 ‡ z), so generating by transla-
2
2
repetition of just one of the interactions described above: the
combination of the two interactions together generates a chain
running parallel to the [010] direction (Fig. 9), and the
combination of the [100], [010] and [001] chains generates the
three-dimensional framework structure.
.2.4. Compound (8). In (8) the substituted trehalose
molecules lie across a twofold rotation axis in the space group
P2 2 2, selected for the reference molecule as that along ( , ,
tion a C ꢂ8† chain parallel to the [001] direction, and the action
of the twofold rotation axis converts this chain into a mole-
2
cular ladder, in which parallel C ꢂ8† chains act as the uprights
2
and the disaccharide molecules as the rungs (Fig. 12). The
combination of the [001] chains with the (001) sheets is
suf®cient to produce a three-dimensional structure, but this is
further reinforced by a third OÐHÁ Á ÁO hydrogen bond. The
water atom O6W at (x; y; z), which lies in the reference (001)
sheet, acts as a hydrogen-bond donor via H6C to the acetato
atom O31 at (1 � x; 1 � y; � 1 ‡ z), which lies in the adjacent
sheet along [001], again linking adjacent sheets.
3
1 1
2 2
1
1
z), while the water molecule lies in a general position. In the
selected asymmetric unit the water molecule is linked to the
disaccharide by means of an NÐHÁ Á ÁO hydrogen bond (Table
3
), so forming a compact three-molecule aggregate (Fig. 10).
3.2.5. Compound (9). The diaminotrehalose molecules in
(9) lie across twofold rotation axes in the space group P4 2 2,
selected for the reference molecule as that having z = 0, x = y;
The supramolecular aggregation is then determined by the six
hydroxyl or water OÐH bonds available in each three-
molecule aggregate for external hydrogen-bond formation.
The construction of the resulting three-dimensional frame-
work structure can then most readily be analysed in terms of
the effect of each distinct hydrogen bond in turn.
3
1
The hydroxyl O4 atoms at (x; y; z) and (1 � x; 1 � y; z)
both lie in the reference disaccharide molecule whose central
1
1
atom O1 lies at ( , , z). These two hydroxyl atoms act as
1
2
2
hydrogen-bond donors, respectively, to atoms O61 at (� + x,
2
1
2
3
2
1
2
�
y, 1 � z) and at ( � x, + y, 1 � z), which themselves lie in
molecules whose central atoms are at (0, 0, 1 � z) and (1, 1,
� z), respectively. Similarly, the two atoms of type O61 in the
reference molecule across ( , , z) accept hydrogen bonds from
1
1
2
1
2
1
2
1
2
1
2
1
2
the O4 atoms at ( + x, � y, 1 � z) and ( � x, + y, 1 � z),
which lie, respectively, in molecules where the O1 atoms are at
(
1, 0, 1 � z) and (0, 1, 1 � z). In this manner, a single OÐ
HÁ Á ÁO hydrogen bond generates a (001) sheet in the form of a
Figure 13
The independent molecular components of compound (9) showing the
atom-labelling scheme. Displacement ellipsoids are drawn at the 30%
probability level. The atoms marked `a' are at the symmetry position
(
y; x; � z).
Figure 12
Figure 14
Stereoview of part of the crystal structure of (9) showing the formation of
Stereoview of part of the crystal structure of (8) showing the formation of
a molecular ladder along [001]. For the sake of clarity, the H atoms
bonded to C atoms are omitted.
4
a (001) sheet of R ꢂ44† rings. For the sake of clarity the water molecule is
4
omitted, as are the H atoms bonded to C atoms.
ꢁ
0
Acta Cryst. (2004). B60, 461±471
Thomas C. Baddeley et al.
Substituted ꢀ,ꢀ -trehalose derivatives 469

research papers
there is also a water molecule lying in a general position and in
the selected asymmetric unit (Fig. 13) this water molecule is
linked to the disaccharide via an OÐHÁ Á ÁO hydrogen bond
H4B sites in any sheet will be available to form this hydrogen
bond. In an entirely similar way, the water atom O6W, which is
linked to the z = 0 sheet via O3 (Table 3), acts as a hydrogen-
1
(
Table 3). With no acyl substituents present, there is an
bond donor, via H6D, to O6W at (1 � y; 1 � x; � z), which is
2
1
2
extensive series of hydrogen bonds present in the structure,
encompassing OÐHÁ Á ÁO, OÐHÁ Á ÁN and NÐHÁ Á ÁO types.
However, the three-dimensional nature of the supramolecular
structure can be readily established in terms of just two
hydrogen bonds, in addition to that within the asymmetric
unit; one of these hydrogen bonds generates sheets and the
second links the sheets into a three-dimensional framework.
The other hydrogen bonds can be regarded as reinforcing
elaborations.
linked to the sheet at z = . Propagation of these interactions
by rotation and translation then links each (001) sheet to the
two adjacent sheets, forming a chain of rings along the [001]
direction (Fig. 15).
4
. Concluding comments
It is striking how little the conformations of the pyranose rings
0
in substituted ꢀ,ꢀ -trehalose molecules are affected either by
The hydroxyl atom O3 at (x; y; z) acts as a hydrogen-bond
donor to the amino atom N1 at (x; 1 ‡ y; z), so generating by
translation a C(7) chain running parallel to the [010] direction:
the action of the twofold axes through the molecules generates
a similar chain running parallel to the [100] direction and the
combination of these two chain motifs generates a (001) sheet
the extent of the substitution or by the steric bulk of the
substituents: this is clearly illustrated at the extremes of the
range of substitution considered here by (3) and (9) [see (I)],
where the ring-puckering behaviour is essentially identical for
the two compounds. On the other hand, the direction-speci®c
intermolecular forces are very strongly in¯uenced by the
substitution pattern, with (4)±(9) forming a supramolecular
structure (4) in one dimension, (5) in two dimensions and (6)±
(9) three dimensions, while (1)±(3) contain effectively isolated
molecules.
in the form of a (4,4) net (Batten & Robson, 1998) built from a
4
single type of R ꢂ44† ring and involving only a single OÐ
4
HÁ Á ÁN hydrogen bond (Fig. 14). It may be noted here that
although the gross topology of the (001) sheets in (8) and (9) is
the same, the sheet in (8) is generated by a combination of
twofold rotation and screw axes, whereas that in (9) is
generated by a combination of translation and twofold rota-
tion axes.
X-ray data were collected at the EPSRC X-ray Crystal-
lographic Service, University of Southampton, UK, using a
Nonius Kappa-CCD diffractometer. The authors thank the
staff for all their help and advice. JNL thanks NCR Self
Service Dundee for grants which have provided computing
facilities for this work.
There are two interactions which link the (001) sheets into a
continuous framework. Atom O4 at (x; y; z) lies in the (001)
sheet whose twofold rotation axes are at z = 0; this atom acts
as
a
hydrogen-bond donor, via H4B, to O4 at
1
(
1 � y; 1 � x; � z), which lies in the sheet with its axes at z =
2
1
2
.
Although the occupancy of the H4B site is only 0.5, there is
no necessary correlation between the occupancy of the H4A
and H4B sites throughout a given sheet and hence 50% of the
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