Water Superstructures within Organic Arrays
FULL PAPER
paper. These data can be obtained free of charge from the Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
All of the single-crystal structures were solved by direct methods using
13.20; found:
).
Hydrate qd·2H
2 3 2
0.311 g, 1.92 mmol) and Na CO (0.755 g, 7.13 mmol) in H O (60 cm )
C 67.82, H 3.70, N 12.91; MS (EI+) m/z: 212.0
(C12
8 2 2
H N O
2
O: A solution of 1,4-dihydroquinoxaline-2,3-dione (qd)
3
[
32]
[33]
SHELXS-97, except for Phqd·3H
2
O which was solved using SIR92,
(
and all non-hydrogen atoms were located using subsequent difference-
was heated to boiling and the solution was allowed to slowly cool to
room temperature. After being left at room temperature for 24 h, the so-
[
34]
Fourier methods. In all cases, hydrogen atoms were placed in calculat-
ed positions and thereafter allowed to ride on their parent atoms, except
for water hydrogen atoms which were located from the difference Fouri-
er map. The water hydrogen atoms were refined with suitable OÀH and
lution was filtered, producing a white microcrystalline solid, qd·2H O
2
(213 mg, 56%). Single crystals were prepared by heating to boiling a so-
lution of qd (0.151 g, 0.93 mmol) and Na CO (0.301 g, 2.84 mmol) in
2
3
3
H···H distance restraints. Analysis of extended hydrogen-bonded struc-
H O (40 cm ) and allowing the solution to slowly cool to room tempera-
2
tures was performed and several of the figures were produced using
ture. IR (KBr): n˜ =3436 (w), 3157 (m), 3049 (m), 2967 (m), 2883 (m),
[
35]
OLEX.
Synthesis
,4-Dihydroquinoxaline-2,3-dione (qd): 1,4-Dihydroquinoxaline-2,3-dione
2778 (m), 1695 (vs), 1392 (m), 1248 (m), 865 (m), 855 (m), 760 (m),
À1
7
05 cm (m). We were unable to obtain accurate CHN elemental analy-
sis due to the concomitant precipitation/crystallisation of nonhydrated
1
qd.
[
36]
(qd) was prepared as previously described. A solution of o-phenylene-
diamine (1.204 g, 0.011 mol) and oxalic acid (1.480 g, 0.016 mol) in HCl
1
Hydrate mqd· =
2
H
2
O: A solution of 6-methyl-1,4-dihydroquinoxaline-2,3-
3
3
2
dione (mqd) (0.852 g, 4.83 mmol) in DMF/H O (1:1, 50 cm ) was heated
(
4m, 40 cm ) was refluxed for 8 h. The resulting solution was cooled to
to boiling and the solution was allowed to slowly cool to room tempera-
room temperature, filtered and the filtrate washed with cold water
3
1
ture. After being left at room temperature for 24 h, the solution was fil-
(
50 cm ). Yield: 1.602 g, 88%; H NMR ([D
6
]DMSO): d=7.09 (m, 2H;
1
tered, producing a brown microcrystalline solid, mqd· =
2
H
2
O (752 mg,
H5A, H8A), 7.09 (m, 2H; H6A, H7A), 11.92 ppm (s, 2H; H1A, H4A);
1
3
84%). Single crystals were prepared by slowly cooling a solution of mqd
6
C NMR ([D ]DMSO): d=115.5 (C5, C8), 123.3 (C6, C7), 125.9 (C9,
3
(
(
(
2
13.6 mg, 0.077 mmol) in DMF/H O (1:1, 15 cm ). IR (KBr): n˜ =3470
C10), 155.5 ppm (C2, C3); IR (KBr): n˜ =3048 (m), 2969 (m), 2882 (m),
w), 3171 (m), 3061 (m), 2950 (m), 2849 (m), 2770 (m), 1693 (vs), 1626
s), 1387 (m), 808 (m), 689 cm (m); elemental analysis calcd (%) for
À1
1
681 (vs), 1629 (m), 1614 (m), 1392 (m), 855 (m), 753 cm (m); elemen-
À1
tal analysis calcd (%) for C
5
8
H
6
N
2
O
2
: C 59.26, H 3.73, N 17.28; found: C
8.95, H 3.77, N 17.30; MS (EI+) m/z: 162.0 (C ).
-Methyl-1,4-dihydroquinoxaline-2,3-dione (mqd): 6-Methyl-1,4-dihydro-
C
9
H
9
N
2
O
2.5: C 58.37, H 4.90, N 15.13; found: C 59.56, H 4.75, N 15.43.
8 6 2 2
H N O
1
Hydrate dmqd· =
3
H
2
O: A solution of 6,7-dimethyl-1,4-dihydroquinoxa-
6
3
2
line-2,3-dione (dmqd) (0.385 g, 2.02 mmol) in DMF/H O (1:1, 50 cm )
quinoxaline-2,3-dione (mqd) was prepared in an analogous way to that
described for qd. A solution of 3,4-diaminotoluene (3.446 g, 0.028 mol)
was heated to boiling and the solution was allowed to slowly cool to
room temperature. After being left at room temperature for 24 h, the so-
3
and oxalic acid (4.876 g, 0.054 mol) in HCl (4m, 50 cm ) was refluxed for
1
lution was filtered, producing a white microcrystalline solid, dmqd· =
3
H
2
O
8
h. The resulting solution was cooled to room temperature, filtered and
(
320 mg, 80%). Single crystals were prepared by slowly cooling a solution
3
1
the filtrate washed with cold water (50 cm ). Yield: 4.822 g, 97%;
NMR ([D
8
H
=
3
2
of dmqd (14.8 mg, 0.078 mmol) in DMF/H O (1:1, 15 cm ). IR (KBr): n˜ =
3
6
]DMSO): d=2.16 (s, 3H; H11A, H11B, H11C), 6.76 (d, JH,H
3
1
436 (w), 3160 (m), 3073 (m), 2946 (m), 2920 (m), 1686 (vs), 1628 (s),
397 (m), 687 cm (m). We were unable to obtain accurate CHN ele-
3
.15 Hz, 1H; H8A), 6.82 (s, 1H; H5A), 6.91 (d,
J
H,H =8.15 Hz, 1H;
À1
1
3
H7A) 11.86 (s, 1H; H1A/H4A), 11.88 ppm (s, 1H; H4A/H1A); C NMR
mental analysis due to the concomitant precipitation/crystallisation of
nonhydrated dmqd and other hydrates of dmqd.
(
(
(
6
[D ]DMSO): d=20.8 (C11), 115.3 (C7), 115.5 (C5), 123.5 (C8), 124.1
C9), 125.7 (C10), 132.6 (C6), 155.3, (C2/C3), 155.6 ppm (C3/C2); IR
+
À
Hydrates dmqd·6H
2 2
O and [Na dmqd ]dmqd·H O: A solution of 6,7-di-
KBr): n˜ =3468 (m), 3060 (m), 2918 (m), 2854 (m), 1697 (vs), 1533 (m),
methyl-1,4-dihydroquinoxaline-2,3-dione (dmqd) (0.334 g, 1.76 mmol)
À1
1
393 (m), 872 (m), 807 (m), 690 cm (m); elemental analysis calcd (%)
3
2 3 2
and Na CO (1.169 g, 11.03 mmol) in H O (50 cm ) was heated to boiling
for C
(
9
H
8
N
2
O
2
: C 61.36, H 4.58, N 15.90; C 61.32, H 4.49, N 16.04; MS
EI+) m/z: 176.3 (C ).
,7-Dimethyl-1,4-dihydroquinoxaline-2,3-dione (dmqd): 6,7-Dimethyl-1,4-
and the solution was allowed to slowly cool to room temperature. After
being left at room temperature for 24 h, the solution was filtered, produc-
ing a white microcrystalline solid (344 mg, 66%). Single crystals of
9 8 2 2
H N O
6
dihydroquinoxaline-2,3-dione (dmqd) was prepared in an analogous way
to that described for qd. A solution of 4,5-dimethyl,-1,2-phenylenedi-
dmqd·6H O were prepared by heating a solution of dmqd (0.151 g,
2
3
0.79 mmol) and Na CO (0.248 g, 2.36 mmol) in water (30 cm ) to boiling
2
3
amine (1.352 g, 4.75 mmol) and oxalic acid (1.352 g, 15.0 mmol) in HCl
and allowing the solution to slowly cool to room temperature. Single
3
+
À
(
4m, 50 cm ) was refluxed for 8 h. The resulting solution was cooled to
crystals of [Na dmqd ]dmqd·H O were prepared by heating to boiling a
2
room temperature, filtered and the filtrate washed with cold water
solution of dmqd (0.124 g, 0.59 mmol) and Na CO (0.227 g, 2.13 mmol)
in water (30 cm ) and allowing the solution to slowly cool to room tem-
2
3
3
1
3
(
50 cm ). Yield 0.656 g, 72%; H NMR ([D
6
]DMSO): d=2.14 (s, 6H;
H11A, H11B, H11C, H12A, H12B, H12C), 6.84 (s, 2H; H5A, H8A)
perature. IR (KBr): n˜ =3527 (w), 3436 (m br), 3166 (m), 3067 (m), 2929
(m), 1678 (vs), 1387 (m), 688 cm (m). We were unable to obtain accu-
1
3
À1
1
1.79 ppm (s, 2H; H1A, H4A); C NMR ([D
6
]DMSO): d=19.3 (C11,
C12), 116.0 (C5, C8), 123.7 (C9, C10), 131.4 (C6, C7), 155.5 ppm
rate CHN elemental analysis due to the concomitant precipitation/crys-
tallisation of dmqd·6H O, [Na dmqd ]dmqd·H O and nonhydrated
2 2
dmqd.
+
À
(
C2,C3); IR (KBr): n˜ =3156 (m), 2945 (m), 2920 (m), 1689 (vs), 1628
À1
(
m), 1397 (m), 687 cm
(m); elemental analysis calcd (%) for
C
(
10
H
10
N
2
O
2
: C 63.15, H 5.30, N 14.73; C 63.22, H 5.34, N 14.60; MS
EI+) m/z: 190.2 (C10 ).
,4-Dihydrobenzo[g]quinoxaline-2,3-dione (Phqd): 1,4-Dihydrobenzo[g]-
quinoxaline-2,3-dione (Phqd) was prepared in an analogous way to that
described for qd. solution of 2,3-diaminonaphthalene (0.120 g,
.76 mmol) and oxalic acid (0.125 g, 1.39 mmol) in 4m HCl (20 cm ) was
Hydrate Phqd·3H O: A solution of 1,4-dihydrobenzo[g]quinoxaline-2,3-
dione (Phqd) (0.206 g, 0.97 mmol) in DMF/H O (1:1, 50 cm ) was heated
to boiling and then allowed to slowly cool to room temperature. After
being left at room temperature for 24 h, the solution was filtered, produc-
2
3
2
H
10
N
2
O
2
1
ing a brown microcrystalline solid, Phqd·3H
2
O (0.170 g, 62%). Single
A
3
crystals were prepared by heating to boiling a solution of Phqd (4.0 mg,
0
3
0
2
.002 mmol) in DMF/H O (1:1, 10 cm ) and allowing the solution to
refluxed for 8 h. The resulting solution was cooled to room temperature,
filtered and the filtrate washed with cold water (50 cm ). Yield 0.132 g,
3
slowly cool to room temperature. IR (KBr): n˜ =3515 (s), 3455 (m), 3223
À1
1
(w), 3055 (w), 2946 (w), 1690 (vs), 1643 (s), 1398 (s), 879 cm (s). We
8
2%; H NMR ([D
6
]DMSO): d=7.37 (m, 2H; H12A, H13A), 7.52 (s,
were unable to obtain accurate CHN elemental analysis due to the con-
comitant precipitation/crystallisation of nonhydrated Phqd.
2
H; H5A, H8A), 7.81 (m, 2H; H11A, H14A), 12.11 ppm (s, 2H; H1A,
1
3
H4A); C NMR ([D
6
]DMSO): d=111.2 (C5, C8), 125.4 (C12, C13),
1
1
26.6 (C11, C14/C6, C7), 127.1 (C6, C7/C11, C14), 129.6 (C9, C10)
55.5 ppm (C2, C3); IR (KBr): n˜ =3241 (m), 3048 (m), 2944 (m), 2909
À1
(m), 2862 (w), 1691 (vs), 1641 (m), 1399 (m), 866 (m), 737 (m), 560 cm
m); elemental analysis calcd (%) for C12
(
H
8
N
2
O
2
: C 67.92, H 3.80, N
Chem. Eur. J. 2005, 11, 4643 – 4654
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4653