Polymorphism and solvolysis of 2-cyano-3-[4-(N,N-diethylamino)-phenyl]prop- 2-enethioamide

Article abstract of DOI:10.1107/S010827010402150X

Two new polymorph forms, (Ia) and (Ib), of the title compound, C ₁₄H₁₇N₃S, and its solvate with acetonitrile, C₁₄H₁₇N₃S-0.25C₂H₃N, (Ic), have been investigated. Crystals of the two polymorphs were grown from different solvents, viz. ethanol and N,N-dimethylformamide, respectively. The polymorphs have different orientations of the thioamide group relative to the CN substituent, with s-cis and s-trans geometry of the C=C-C=S diene fragment, respectively. Compound (Ic) contains two independent molecules, A and B, with s-cis geometry, and the solvate molecule lies on a twofold axis. The core of each molecule is slightly non-planar; the dihedral angles between the conjugated C=C-CN linkage and the phenyl ring, and between this linkage and the thioamide group are 13.4 (2) and 12.0 (2)° in (Ia), 14.0 (2) and 18.2 (2)° in (Ib), 2.3 (3) and 12.7 (4)° in molecule A of (Ic), and 23.2 (3) and 8.1 (4)° in molecule B of (Ic). As a result of strong conjugation between donor and acceptor parts, the substituted phenyl rings have noticeable quinoid character. In (Ib), there exists a very strong intramolecular steric interaction (H...H = 1.95 A) between the bridging and thioamide parts of the molecule, which makes such a form less stable. In the crystal structure of (Ia), intermolecular N-H...N and N-H...S hydrogen bonds link molecules into infinite tapes along the [110] direction. In (Ib), such intermolecular hydrogen bonds link molecules into infinite (101) planes. In (Ic), intermolecular N-H...N hydrogen bonds link molecules A and B into dimers, which are connected via N-H...S hydrogen bonds and form infinite chains along the c direction.

Full text of DOI:10.1107/S010827010402150X

organic compounds
Acta Crystallographica Section C
Crystal Structure
®nd applications in non-linear optical materials (Zyss, 1994;
Kuzyk & Dirk, 1998) and in the syntheses of hetero-
Communications
ISSN 0108-2701
Polymorphism and solvolysis of
2
-cyano-3-[4-(N,N-diethylamino)-
phenyl]prop-2-enethioamide
a
a,b
Vladimir N. Nesterov * and Volodymyr V. Nesterov
a
Department of Natural Sciences, New Mexico Highlands University, Las Vegas,
b
NM 87701, USA, and Department of Chemistry and Biochemistry, The University
of Texas at Austin, TX 78712-0165, USA
cyclic compounds (Brunskill et al., 1984; Nesterov et al., 2002).
Moreover, related compounds have found applications as
potential antitumor drugs (Hutchinson et al., 2001; Thacher et
al., 2001; Wermuth, 2004). During thorough and systematic
work, we have found many compounds that crystallize in
different space groups and reveal polymorphism (Timofeeva
et al., 2000; Timofeeva, Nesterov et al., 2003; Timofeeva, Kuhn
et al., 2003; Wang et al., 2001). Thus, cocrystallization of such
compounds with chiral molecules can build non-centrosym-
metric crystalline structures or polymorphs (Timofeeva et al.,
Correspondence e-mail: vnesterov@nmhu.edu
Received 20 July 2004
Accepted 1 September 2004
Online 9 October 2004
Two new polymorph forms, (Ia) and (Ib), of the title
compound, C H N S, and its solvate with acetonitrile,
1
4
17
3
C H N SÁ0.25C H N, (Ic), have been investigated. Crystals
1
4
17
3
2
3
of the two polymorphs were grown from different solvents,
viz. ethanol and N,N-dimethylformamide, respectively. The
polymorphs have different orientations of the thioamide
group relative to the CN substituent, with s-cis and s-trans
geometry of the C CÐC S diene fragment, respectively.
Compound (Ic) contains two independent molecules, A and B,
with s-cis geometry, and the solvate molecule lies on a twofold
axis. The core of each molecule is slightly non-planar; the
dihedral angles between the conjugated C CÐCN linkage
and the phenyl ring, and between this linkage and the
2
000), and polymorphism is a very important phenomenon in
ꢀ
thioamide group are 13.4 (2) and 12.0 (2) in (Ia), 14.0 (2) and
ꢀ
ꢀ
1
8.2 (2) in (Ib), 2.3 (3) and 12.7 (4) in molecule A of (Ic),
ꢀ
and 23.2 (3) and 8.1 (4) in molecule B of (Ic). As a result of
strong conjugation between donor and acceptor parts, the
substituted phenyl rings have noticeable quinoid character. In
(
Ib), there exists a very strong intramolecular steric interac-
Ê
tion (HÁ Á ÁH = 1.95 A) between the bridging and thioamide
parts of the molecule, which makes such a form less stable. In
the crystal structure of (Ia), intermolecular NÐHÁ Á ÁN and
NÐHÁ Á ÁS hydrogen bonds link molecules into in®nite tapes
along the [110] direction. In (Ib), such intermolecular
hydrogen bonds link molecules into in®nite (101) planes. In
Figure 1
A view of polymorph (Ia), showing the atom numbering used. Non-H
atoms in Figs. 1±3 are shown with displacement ellipsoids drawn at the
50% probability level.
(
Ic), intermolecular NÐHÁ Á ÁN hydrogen bonds link molecules
A and B into dimers, which are connected via NÐHÁ Á ÁS
hydrogen bonds and form in®nite chains along the c direction.
Comment
The present investigation is a continuation of a project that
includes syntheses and structural studies of polar conjugated
organic compounds that crystallize in non-centrosymmetric
space groups (Antipin et al., 1998; Nesterov et al., 1998, 2000;
Nesterov, Antipin, Nesterov, Moore et al., 2004; Nesterov,
Antipin, Nesterov, Penn et al., 2004). These compounds may
Figure 2
A view of polymorph (Ib), showing the atom numbering used.
Acta Cryst. (2004). C60, o781±o785
DOI: 10.1107/S010827010402150X
# 2004 International Union of Crystallography o781

organic compounds
Figure 3
A view of adduct (Ic), showing the atom numbering used. The dashed line represents the intermolecular NÐHÁ Á ÁS hydrogen bond.
tural investigations have been carried out for two polymorphs,
viz. orange triclinic (Ia) and red monoclinic (Ib) (Figs. 1 and
2
), and for a complex, (Ic) (Fig. 3), of (I) with acetonitrile. In
an attempt to ®nd other crystalline forms, crystals of (I) have
been grown from several solvents, including ethanol, propan-
2
-ol, acetonitrile, toluene, chloroform, and their mixtures. In
almost all cases, we obtained crystals of (Ia), and only from
acetonitrile did we obtain complex (Ic). Starting with (I), we
have synthesized several thiazole derivatives using dimethyl-
formamide (DMF) as a solvent. In one case, crystals with
different shapes were separated from the reaction mixture,
viz. red prisms (several crystals) and orange plates. The former
were another monoclinic form, (Ib), of the starting material,
while the latter crystals were the thiazole product. According
to the Cambridge Structural Database (CSD; Allen, 2002), the
structure of another monoclinic modi®cation, (Id), of (I) has
been investigated (Brunskill et al., 1984). All our attempts to
obtain complexes of (I) with l-proline and l-tartaric acid,
using different solvents and different crystallization condi-
tions, gave only good crystals of polymorph (Ia).
Figure 4
A projection of the crystal packing of (Ia) along the b axis. Dashed lines
represent intermolecular NÐHÁ Á ÁN and NÐHÁ Á ÁS hydrogen bonds.
As can be seen in Figs. 1 and 2, the main distinction between
Ia) and (Ib) is the different orientation of the thioamide
(
group relative to the CN substituent (two rotamers). In
accordance with the results of Brunskill et al. (1984), in these
cases we obtained two forms, with s-cis and s-trans geometry of
the C CÐC S fragment. Although conformer (Id) has a
structure similar to that of (Ib), the values of the C7ÐC8Ð
ꢀ
C10ÐS1 torsion angles are different [159.37 (13) in (Ib) and
ꢀ
�
158.5 in (Id)]. In both independent molecules, A and B, of
Ic), the orientation of this substituent is similar to that in (Ia)
Fig. 3), but compounds (Ic) and (Ia) also have different
(
(
dihedral angles (see below). The rotation of the thioamide
group about the C8ÐC10 single bond is a possible reason for
the existence of the three forms.
Figure 5
A projection of the crystal packing of (Ib) along the a axis. Dashed lines
represent intermolecular NÐHÁ Á ÁN and NÐHÁ Á ÁS hydrogen bonds.
Most of the geometric parameters in the investigated mol-
ecules (Ia)±(Ic) are very similar. The molecular skeleton of
each molecule is slightly non-planar; the dihedral angles
between the conjugated linkage (C CÐCN) and the phenyl
ring, and between this linkage and the thioamide group are
the pharmaceutical industry (Davey et al., 1997; Bernstein,
2
002).
In this paper, we present interesting results that were
obtained working with the title compound, (I). X-Ray struc-
ꢀ
ꢀ
13.4 (2) and 12.0 (2) in (Ia), 14.0 (2) and 18.2 (2) in (Ib),
ꢁ
o782 Nesterov and Nesterov
C H N S and C14H N
14 17 3 17 3
2 3
SÁ0.25C H N
Acta Cryst. (2004). C60, o781±o785

organic compounds
ꢀ
Ê
Ê
Ê
2
8
.3 (3) and 12.7 (4) in molecule A of (Ic), and 23.2 (3) and
ꢀ
2.38 A and H2AÁ Á ÁC9 = 2.28 A in (Ia), H6AÁ Á ÁC9 = 2.52 A
Ê Ê
and H7AÁ Á ÁH2A = 1.95 A in (Ib), H6AAÁ Á ÁC9A = 2.44 A and
.1 (4) in molecule B of (Ic). Such slight non-planarity is not
Ê
suf®cient to preclude conjugation between aryl and CN groups
via a C C-bridged fragment. Because of the strong conju-
gation between donor and acceptor parts in these molecules,
the substituted phenyl rings have a noticeably quinoid char-
acter (Tables 1, 3 and 5). Moreover, the dihedral angles
between the trigonal diethylamine substituent [in all struc-
tures, the sum of the bond angles around the N atom is
H2AAÁ Á ÁC9A = 2.25 A in molecule A of (Ic), and
Ê
Ê
H6BAÁ Á ÁC9B = 2.48 A and H2BAÁ Á ÁC9B = 2.33 A in mol-
ecule B of (Ic)]. In (Ib), there exists a very strong steric HÁ Á ÁH
interaction between the bridging and thioamide parts of the
molecule. The same short steric contact is also found in the
Ê
monoclinic form (Id) at 2.04 A. Probably, the presence of such
short contacts indicates that polymorphs (Ib) and (Id) are
energetically less stable than (Ia). This is perhaps the reason
that we were unable to obtain polymorphs (Ib) and (Id) again
in our work. Such intramolecular interactions are the reason
for the elongation of the C8ÐC10 bond lengths.
The crystal packings of (Ia) and (Ib) are different. In (Ia),
intermolecular NÐHÁ Á ÁN and NÐHÁ Á ÁS hydrogen bonds link
molecules in two centrosymmetric dimers to build in®nite
tapes along the [110] direction (Fig. 4 and Table 2). However,
in (Ib), such hydrogen bonds link molecules into in®nite (101)
planes (Fig. 5 and Table 4). In the case of (Ic), intermolecular
NÐHÁ Á ÁN hydrogen bonds link molecules A and B into
dimers, which are connected via NÐHÁ Á ÁS hydrogen bonds
and form in®nite chains along the c direction (Fig. 6 and
ꢀ
ꢀ
3
1
59.5 (2) ] and the phenyl ring are small [5.6 (2) in (Ia),
ꢀ
ꢀ
0.7 (2) in (Ib), and 10.6 (4) and 10.4 (4) in molecules A and
B of (Ic)]. In all compounds, the N3ÐC4 bond length [range
Ê
.351 (4)±1.369 (4) A] is comparable to the average conju-
1
gated CÐN single bond (1.370 A) and is distinctly shorter
Ê
Ê
than the average non-conjugated CÐN single bond (1.430 A)
found in the CSD. Furthermore, the C1ÐC7 and C7 C8
bond lengths also have noticeable differences in comparison
with standard distances (Allen et al., 1987).
As can be seen in Tables 1, 3 and 5, all of the molecules
possess a strong conjugation in the thioamide fragment. The
C
S bond lengths are distinctly elongated, while the CÐN
bonds have a partial double-bond character. In our previous
work (Nesterov et al., 1986), we have analyzed such conjuga-
tion in the thioamide fragments. As mentioned above, the
deviations of the thioamide groups in (Ia)±(Ic) from the
bridged plane are not signi®cant, but the C8ÐC10 bond
lengths are equal or slightly elongated compared with the
Table 6). In molecule B, one atom of the NH group (H2BB)
2
does not participate in hydrogen bonding. The intermolecular
distance between atoms H2BB and S1A of molecules A and B
Ê
(3.05 A) is greater than the sum of the van der Waals radii of
these atoms (Rowland & Taylor, 1996).
Ê
conjugated CÐC bond (1.470 A; Allen et al., 1987).
The planarity of the molecules leads to the existence of
According to the foregoing results, previously studied
compounds (Nesterov et al., 2003) having 4-diethylamino
substituents that occupy different positions relative to the
shortened HÁ Á ÁCH intramolecular contacts [H6AÁ Á ÁC9 =
phenyl ring (two CH groups above a plane or disordered)
3
might also yield polymorphic forms.
Experimental
Compound (I) was synthesized by the reaction of 4-(diethylamino)-
benzaldehyde with 2-cyanothioacetamide in the presence of a cata-
lytic amount of morpholine in ethanol at room temperature. The
precipitate was separated from the solution, and the structure and
purity were investigated by NMR (m.p. 421±425 K, yield 83%). The
large melting interval is probably a result of the mixture of isomers
present. After recrystallization from ethanol, only crystals of (Ia)
(m.p. 424±425 K) were found. Crystals of (Ic) were obtained by slow
isothermal evaporation from an acetonitrile solution of (I).
Compound (I) was used to synthesize a 2,4-disubstituted thiazole
derivative, using DMF as solvent. From one such reaction mixture
were extracted two types of crystals with different shapes. X-Ray
analysis revealed that one of these forms was the thiazole derivative
and the other was a monoclinic polymorph, (Ib). All attempts to re-
obtain polymorph (Ib), complex (Ic) and the literature polymorph
(
Id), using exactly the same conditions and variations of them, gave
1
only (Ia). Polymorph (Ia) is probably the most stable energetically. H
NMR (CDCl , 300 MHz): ꢀ 8.65 (s, 1H, C7H), 7.96 (d, 2H, J = 9.2 Hz,
C2, C6), 7.57 (br s, 1H, NH), 7.36 (br s, 1H, NH), 6.69 (d, 2H, J =
3
9
.2 Hz, C3, C5), 3.47 (q, 4H, J = 7.1 Hz, 2CH ), 1.24 (t, 6H, J = 7.2 Hz,
2
13
2
CH ). C NMR (CDCl , 75 MHz): ꢀ 193.6 (C S), 158.1 (C7), 152.0
3 3
Figure 6
A projection of the crystal packing of (Ic) along the b axis. Dashed lines
represent intermolecular NÐHÁ Á ÁN and NÐHÁ Á ÁS hydrogen bonds.
(C4), 134.9 (C2, C6), 119.3 (C1), 118.3 (C9), 111.3 (C3, C5), 98.7 (C8),
44.8 (2CH
2
3
), 12.5 (2CH ).
ꢁ
Acta Cryst. (2004). C60, o781±o785
Nesterov and Nesterov
C H N S and C14H
14 17 3 17
3 2 3
N SÁ0.25C H N
o783

organic compounds
Polymorph (Ia)
Data collection
Enraf±Nonius CAD-4
diffractometer
ꢄ/2ꢄ scans
3307 measured re¯ections
3114 independent re¯ections
2316 re¯ections with I > 2ꢆ(I)
h = 0 ! 11
Crystal data
k = 0 ! 16
C
14
17
H N
3
S
Z = 2
= 1.220 Mg m
Mo Kꢁ radiation
l = � 15 ! 15
�
3
M
r
= 259.38
Triclinic, P1
D
x
3 standard re¯ections
every 97 re¯ections
intensity decay: 3%
Ê
a = 8.753 (3) A
Cell parameters from 24
re¯ections
Ê
b = 8.890 (3) A
Rint = 0.027
Ê
c = 10.830 (4) A
ꢀ
ꢀ
ꢄ = 11±12
ꢄ
max = 27.0
ꢀ
� 1
ꢁ
= 85.44 (3)
ꢅ = 0.22 mm
T = 298 (2) K
ꢀ
ꢀ
Re®nement
ꢂ = 69.76 (2)
ꢃ = 63.65 (3)
Plate, orange
0.50 Â 0.40 Â 0.20 mm
2
2
2
o
2
Re®nement on F
2
w = 1/[ꢆ (F ) + (0.06P)
Ê
V = 705.8 (5) A
3
2
R[F > 2ꢆ(F )] = 0.038
wR(F ) = 0.113
+ 0.25P]
where P = (Fo + 2F )/3
2
2
2
c
Data collection
S = 1.03
3114 re¯ections
165 parameters
H-atom parameters constrained
(Á/ꢆ)max < 0.001
ꢀ
Ê
� 3
Áꢇmax = 0.21 e A
Enraf±Nonius CAD-4
diffractometer
ꢄ/2ꢄ scans
ꢄ
max = 25.1
Áꢇmin = � 0.15 e AÊ
� 3
h = 0 ! 10
k = � 9 ! 10
2
2
1
639 measured re¯ections
465 independent re¯ections
811 re¯ections with I > 2ꢆ(I)
l = � 12 ! 12
3 standard re¯ections
every 97 re¯ections
intensity decay: 3%
Table 3
Selected geometric parameters (A, ) for polymorph (Ib).
Rint = 0.016
Ê
ꢀ
Re®nement
2
S1ÐC10
N1ÐC9
N2ÐC10
N3ÐC4
1.6723 (15)
1.137 (2)
1.3270 (19)
1.362 (2)
C7ÐC8
C8ÐC9
C8ÐC10
1.366 (2)
1.433 (2)
1.467 (2)
Re®nement on F
2
H-atom parameters constrained
2
2
2
2
R[F > 2ꢆ(F )] = 0.035
wR(F ) = 0.098
S = 1.00
w = 1/[ꢆ (F ) + (0.06P) ]
o
2
2
2
c
where P = (Fo + 2F )/3
(Á/ꢆ)max < 0.001
Ê
� 3
Áꢇmax = 0.15 e A
2
1
465 re¯ections
65 parameters
Áꢇmin = � 0.18 e AÊ
� 3
C8ÐC7ÐC1
132.68 (14)
N1ÐC9ÐC8
178.70 (18)
C2ÐC1ÐC7ÐC8
C1ÐC7ÐC8ÐC10
170.58 (19)
� 179.09 (17)
C9ÐC8ÐC10ÐN2
C7ÐC8ÐC10ÐS1
164.83 (16)
159.37 (13)
Table 1
Selected geometric parameters (A, ) for polymorph (Ia).
Ê
ꢀ
S1ÐC10
N1ÐC9
N2ÐC10
N3ÐC4
1.669 (2)
1.145 (2)
1.330 (2)
1.361 (2)
C7ÐC8
C8ÐC9
C8ÐC10
1.358 (2)
1.428 (3)
1.476 (2)
Table 4
Hydrogen-bonding geometry (A, ) for polymorph (Ib).
Ê
ꢀ
C8ÐC7ÐC1
131.08 (16)
N1ÐC9ÐC8
177.31 (18)
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
iii
N2ÐH2AÁ Á ÁN1
0.86
0.86
2.20
2.58
2.989 (2)
3.421 (2)
152
167
C2ÐC1ÐC7ÐC8
C1ÐC7ÐC8ÐC10
167.98 (17)
� 177.86 (16)
C9ÐC8ÐC10ÐN2
C7ÐC8ÐC10ÐS1
� 10.0 (2)
� 13.1 (2)
iv
N2ÐH2BÁ Á ÁS1
1
1
3
Symmetry codes: (iii) � x; ‡ y; � z; (iv) � x; 1 � y; 2 � z.
2
2
2
Table 2
Hydrogen-bonding geometry (A, ) for polymorph (Ia).
Ê
ꢀ
Compound (Ic)
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
Crystal data
i
C
M = 269.64
14
H
17
N
3
SÁ0:25C
2
H
3
N
Mo Kꢁ radiation
Cell parameters from 24
re¯ections
N2ÐH2AÁ Á ÁN1
0.86
0.86
2.35
2.66
3.069 (2)
3.481 (2)
141
160
ii
N2ÐH2BÁ Á ÁS1
r
Monoclinic, C2=c
Ê
a = 39.370 (8) A
ꢀ
Symmetry codes: (i) 2 � x; 1 � y; � z; (ii) 3 � x; � y; � z.
ꢄ = 10±11
ꢅ = 0.21 mm
T = 298 (2) K
Ê
b = 8.8800 (18) A
� 1
Ê
c = 17.056 (3) A
ꢀ
ꢂ = 101.19 (3)
Plate, orange
0.50 Â 0.40 Â 0.20 mm
V = 5850 (2) AÊ
Z = 16
D = 1.225 Mg m
3
Polymorph (Ib)
�
3
Crystal data
x
C
14
H
17
N
3
S
Mo Kꢁ radiation
Cell parameters from 24
re¯ections
Data collection
r
M = 259.38
Monoclinic, P2 =n
Ê
a = 9.1670 (18) A
b = 13.023 (3) A
Ê
c = 12.172 (2) A
ꢂ = 93.97 (3)
V = 1449.6 (5) A
Z = 4
Enraf±Nonius CAD-4
diffractometer
ꢄ/2ꢄ scans
5506 measured re¯ections
5423 independent re¯ections
h = 0 ! 47
1
ꢀ
ꢄ = 11±12
ꢅ = 0.21 mm
T = 295 (2) K
k = 0 ! 10
Ê
� 1
l = � 20 ! 20
3 standard re¯ections
every 97 re¯ections
intensity decay: 3%
ꢀ
Prism, red
0.50 Â 0.35 Â 0.25 mm
Ê
3
2754 re¯ections with I > 2ꢆ(I)
Rint = 0.050
�
3
ꢀ
D
x
= 1.189 Mg m
ꢄ
max = 25.5
ꢁ
o784 Nesterov and Nesterov
C H N S and C14H N
14 17 3 17 3
2 3
SÁ0.25C H N
Acta Cryst. (2004). C60, o781±o785

organic compounds
Re®nement
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SQ1169). Services for accessing these data are
described at the back of the journal.
2
Re®nement on F
2
H-atom parameters constrained
2 2
2
2
R[F > 2ꢆ(F )] = 0.050
wR(F ) = 0.149
S = 0.99
w = 1/[ꢆ (F ) + (0.075P) ]
o
2
2
2
c
where P = (Fo + 2F )/3
(Á/ꢆ)max < 0.001
Ê
� 3
Áꢇmax = 0.38 e A
5
3
423 re¯ections
44 parameters
Áꢇmin = � 0.24 e AÊ
� 3
References
Allen, F. H. (2002). Acta Cryst. B58, 380±388.
Table 5
Selected geometric parameters (A, ) for (Ic).
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor,
R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1±19.
Antipin, M. Yu., Timofeeva, T. V., Clark, R. D., Nesterov, V. N., Sanghadasa,
M., Barr, T. A., Penn, B., Romero, L. & Romero, M. (1998). J. Phys. Chem.
A, 102, 7222±7232.
Bernstein, J. (2002). Polymorphism in Molecular Crystals, p. 424. Oxford
University Press.
Brunskill, J. S. A., De, A., Ewing, D. F. & Welch, A. J. (1984). Acta Cryst. C40,
493±495.
Davey, R. J., Blagden, N., Potts, G. D. & Docherty, R. (1997). J. Am. Chem. Soc.
Ê
ꢀ
S1AÐC10A
N1AÐC9A
N2AÐC10A
N3AÐC4A
C7AÐC8A
C8AÐC9A
C8AÐC10A
1.671 (3)
1.148 (4)
1.320 (4)
1.369 (4)
1.355 (4)
1.422 (4)
1.484 (4)
S1BÐC10B
N1BÐC9B
N2BÐC10B
N3BÐC4B
C7BÐC8B
C8BÐC9B
C8BÐC10B
1.662 (3)
1.144 (4)
1.328 (4)
1.351 (4)
1.363 (4)
1.422 (4)
1.473 (4)
199, 1767±1772.
Enraf±Nonius (1989). CAD-4 Software. Version 5.0. Enraf±Nonius, Delft, The
Netherlands.
Hutchinson, I., Chua, M. S., Browne, H. L., Trapani, V., Bradshaw,
T. D., Westwell, A. D. & Stevens, M. F. G. (2001). J. Med. Chem. 44,
1446±1455.
Kuzyk, M. C. & Dirk, C. W. (1998). In Characterization Techniques and
Tabulations for Organic Nonlinear Optical Materials. New York/Basel/
Hong Kong: Marcel Dekker Inc.
Nesterov, V. N., Antipin, M. Yu., Timofeeva, T. V. & Clark, R. D. (2000). Acta
Cryst. C56, 88±89.
C8AÐC7AÐC1A
N1AÐC9AÐC8A
132.1 (3)
175.4 (3)
C8BÐC7BÐC1B
N1BÐC9BÐC8B
131.4 (3)
176.8 (4)
C2AÐC1AÐC7AÐC8A
176.7 (3)
C2BÐC1BÐC7BÐC8B
C1BÐC7BÐC8BÐC10B
C9BÐC8BÐC10BÐN2B
C7BÐC8BÐC10BÐS1B
165.7 (3)
177.1 (3)
7.9 (4)
C1AÐC7AÐC8AÐC10A � 178.3 (3)
C9AÐC8AÐC10AÐN2A � 12.4 (4)
C7AÐC8AÐC10AÐS1A � 13.0 (4)
2.0 (4)
Nesterov, V. N., Montoya, N. G., Antipin, M. Yu., Sanghadasa, M., Clark, R. D.
& Timofeeva, T. V. (2002). Acta Cryst. C58, o72±o75.
Nesterov, V. N., Sharanin, Yu. A., Litvinov, V. P., Shklover, V. E., Struchkov,
Yu. T., Promonenkov, V. K., Mortikov, V. Yu. & Shestopalov, A. M. (1986).
Izv. Akad. Nauk SSSR Ser. Khim. pp. 1378±1383.
Nesterov, V. N., Timofeeva, T. V., Duerksen, G. & Clark, R. D. (1998). J. Mol.
Struct. 444, 135±146.
Nesterov, V. N., Timofeeva, T. V., Sarkisov, S. S., Leyderman, A., Lee, C. Y.-C.
Table 6
Hydrogen-bonding geometry (A, ) for (Ic).
Ê
ꢀ
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
v
N2AÐH2AAÁ Á ÁN1B
N2AÐH2ABÁ Á ÁS1B
0.86
0.86
0.86
2.26
2.48
2.43
2.990 (4)
3.293 (4)
3.133 (4)
143
158
139
vi
N2BÐH2BAÁ Á ÁN1A
&
Antipin, M. Yu. (2003). Acta Cryst. C59, o605±o608.
Nesterov, V. V., Antipin, M. Yu., Nesterov, V. N., Moore, C. E., Cardelino, B. H.
Timofeeva, T. V. (2004). J. Phys. Chem. B, 108, 8531±8539.
1
1
Symmetry codes: (v) x; 1 � y; z � ; (vi) x; 1 � y; ‡ z.
2
2
&
Nesterov, V. V., Antipin, M. Yu., Nesterov, V. N., Penn, B. G., Frazier, D. O. &
Timofeeva, T. V. (2004). Cryst. Growth Des. 4, 521±531.
Rowland, R. S. & Taylor, R. (1996). J. Phys. Chem. 100, 7384±7391.
Sheldrick, G. M. (1990). Acta Cryst. A46, 467±473.
Sheldrick, G. M. (1994). SHELXTL-Plus. PC Version 5.02. Siemens Analytical
X-ray Instruments Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (1997). SHELXL97. University of Gottingen, Germany.
È
Thacher, S. M., Vasudevan, J., Tsang, K.-Y., Nagpal, S. & Chandraratna, A. S.
For all molecules of (Ia)±(Ic), H atoms were placed in calculated
positions and included in the re®nement using a riding model, with
Ê
CÐH or NÐH distances of 0.93 A for aromatic H atoms, 0.97 A for
Ê
Ê
atoms and 0.86 A for NH
Ê
with CÐH distances of 0.96 A for CH
CH
2
2
atoms [Uiso(H) = 1.2Ueq(C,N)], and
groups [Uiso(H) = 1.5Ueq(C)].
3
The H atoms in the disordered acetonitrile molecule (which lies on a
twofold axis) were found from a difference Fourier map and included
using an AFIX 33 command (SHELXL97; Sheldrick, 1997), with an
(
2001). J. Med. Chem. 44, 281±297.
Timofeeva, T. V., Kuhn, G. H., Nesterov, V. V., Nesterov, V. N., Frazier,
D. O., Penn, B. G. & Antipin, M. Yu. (2003). Cryst. Growth Des. 3, 383±
391.
Ê
occupancy of 0.5 and with CÐH = 0.96 A and Uiso(H) values of
Timofeeva, T. V., Nesterov, V. N., Clark, R. D., Penn, B., Frazier, D. O. &
Antipin, M. Yu. (2003). J. Mol. Struct. 647, 181±202.
Timofeeva, T. V., Nesterov, V. N., Dolgushin, F. M., Zubavichus, Y. V.,
Goldshtein, J. T., Sammeth, D. M., Clark, R. D., Penn, B. & Antipin, M. Yu.
(2000). Cryst. Eng. 3, 263±288.
Wang, Z., Nesterov, V. N., Borbulevych, O. Ya., Clark, R. D., Antipin, M. Yu. &
Timofeeva, T. V. (2001). Acta Cryst. C57, 1343±1348.
Wermuth, C. G. (2004). J. Med. Chem. 47, 1303±1314.
Zyss, J. (1994). Molecular Nonlinear Optics: Materials, Physics and Devices,
p. 479. New York: Academic Press/Harcourt Brace and Jovanovich.
1
.5Ueq(C).
For all determinations, data collection: CAD-4 Software (Enraf±
Nonius, 1989); cell re®nement: CAD-4 Software; data reduction:
SHELXTL-Plus (Sheldrick, 1994); program(s) used to solve-
structure: SHELXS97 (Sheldrick, 1990); program(s) used to re®ne
structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
SHELXTL-Plus; software used to prepare material for publication:
SHELXL97.
ꢁ
Acta Cryst. (2004). C60, o781±o785
Nesterov and Nesterov
C H N S and C14H
14 17 3 17
3 2 3
N SÁ0.25C H N
o785