4-[2-(4-Cyanophenyl)ethenyl]-N-methylpyridinium tetraphenylborate

Article abstract of DOI:10.1107/S010827010503060X

In the title compound, C₁₅H₁₃N₂ ⁺·C₂₄H₂₀B^-, the pyridyl ring of the cation makes a dihedral angle of 1.6° with the benzene ring. Each is rotated in the same direction with respec

Full text of DOI:10.1107/S010827010503060X

organic compounds
the CÐBÐC bond angles are in the range 102.8 (4)±114.0 (2)ꢀ
(Table 1).
Acta Crystallographica Section C
Crystal Structure
Communications
The portioning scheme in the program OPEC (Gavezzotti,
1983) with largely improved parameters (Gavezzotti & Filip-
pini, 1994) was used to analyse the packing mode for the
cations and anions in the crystal structure of (I). Table 3 lists
the most important CÐHÁ Á Áꢀ interactions (type I; Umezawa
et al., 1998) in the title crystal. Table 4 lists the calculated
packing energy (PE) between the fundamental molecule (FM)
and its surrounding molecules (SMs) which most strongly
ISSN 0108-2701
4-[2-(4-Cyanophenyl)ethenyl]-N-
methylpyridinium tetraphenylborate
Dan Jin and De-Chun Zhang*
interact with the FM. Although the absolute total PE calcu-
1
lated is not very accurate (about 2 kcal mol 1; 1 kcal mol
=
Department of Chemistry, Suzhou University, Suzhou 215006, People's Republic of
4.184 kJ mol 1; Gavezzotti & Filippini, 1994), the relative
order after portioning into the contributions for individual
SMs is believed to be meaningful. According to Table 4, the
anion in the FM most strongly interacts with the ®rst eight
anions in the SMs, or in this sense, it is surrounded by these
eight anions. When comparing the SMs in both Tables 3 and 4,
one can see that the interactions between the FM and SMs,
particularly the anion±anion and cation±anion interactions,
are CÐHÁ Á Áꢀ type (type I; Umezawa et al., 1998). On the
other hand, the major cation±cation interaction is the
hydrogen bond (line 1 in Table 2) between the N atom in CN
and the CÐH group on the opposite side of the cation. This is
therefore in a head-to-tail mode and forms chains along [101].
The organic salt methodology principle (Marder et al., 1989)
suggests that the anion±cation interaction in organic salts
could override the dipole±dipole interaction, which provides a
strong driving force for centrosymmetric packing in dipolar
crystals. Compound (I) crystallized in the non-centrosym-
metric space group Cc, belonging to point group m, one of the
favourable groups for SHG, and is therefore a potential SHG
crystal. However, not all similar crystals are non-centrosym-
China
Correspondence e-mail: dczhang@suda.edu.cn
Received 21 July 2005
Accepted 26 September 2005
Online 22 October 2005
+
In the title compound, C15H13N2 ÁC24H20B , the pyridyl ring
of the cation makes a dihedral angle of 1.6ꢀ with the benzene
ring. Each is rotated in the same direction with respect to the
central ±CÐCH CHÐC± linkage, by 3.8 and 5.3ꢀ, respec-
tively. The anions have a slightly distorted tetrahedral
geometry. Molecular packing analysis was carried out using
the packing energy portioning scheme in the program OPEC.
Around each anion in the crystal structure there are eight
anions, which interact with the central anion through CÐ
HÁ Á Áꢀ interactions. The cations are hydrogen bonded in a
head-to-tail fashion, forming chains along [101].
Comment
Considerable effort has been made to investigate organic salts
with large second-order optical non-linearities (Chemla &
Zyss, 1987). Marder et al. (1994) have synthesized a number of
stilbazolium salts with large powder second harmonic
generation (SHG) ef®ciencies. According to the organic `salt
methodology' principle (Marder et al., 1989, 1994), Coulombic
interactions in organic salts could override dipole±dipole
interactions which are favoured for antiparallel centrosym-
metric packing. During our systematic search for organic non-
linear optical (NLO) materials, we isolated the title
compound, (I), and describe its crystal structure here.
Compound (I) consists of a 40-cyano-4-N-methylstilbaz-
olium cation and a BPh4 anion. In the cation, which is nearly
planar and in the trans form (Fig. 1), the pyridyl ring makes a
dihedral angle of 1.6ꢀ with the benzene ring. The rings are
rotated in the same direction with respect to the central
±CÐCH CHÐC± linkage, by 3.8 and 5.3ꢀ, respectively. The
anion adopts a slightly distorted tetrahedral geometry. The
Figure 1
A view of the molecular structure of the title compound, showing 30%
probability displacement ellipsoids and the atom-numbering scheme. H
atoms are shown as small spheres of arbitrary radii.
Ê
BÐC bond lengths are in the range 1.628 (6)±1.660 (6) A and
Acta Cryst. (2005). C61, o657±o659
DOI: 10.1107/S010827010503060X
# 2005 International Union of Crystallography o657

organic compounds
Crystal data
+
3
C15H13N2 ÁC24H20B
Dx = 1.198 Mg m
Mo Kꢄ radiation
Mr = 540.48
Monoclinic, Cc
Ê
a = 16.930 (3) A
Ê
b = 10.7694 (18) A
Cell parameters from 5327
re¯ections
ꢅ = 3.0±25.3ꢀ
1
Ê
c = 17.665 (3) A
ꢆ = 0.07 mm
T = 193 (2) K
ꢃ = 111.543 (5)ꢀ
3
Ê
V = 2995.8 (9) A
Z = 4
Block, yellow
0.50 Â 0.19 Â 0.11 mm
Data collection
Rigaku Mercury diffractometer
! scans
Absorption correction: multi-scan
(Jacobson, 1998)
Tmin = 0.966, Tmax = 0.993
14471 measured re¯ections
2726 independent re¯ections
2355 re¯ections with I > 2ꢇ(I)
Rint = 0.047
ꢅmax = 25.3ꢀ
h = 20 ! 20
k = 12 ! 12
l = 20 ! 21
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
Figure 2
A packing diagram for (I), viewed down the b axis. Key: L0 is C4Ð
H4Á Á ÁP4; L1 is C12ÐH12Á Á ÁP5(x; 1 y; z ‡ 12 ); L2 is C9Ð
H9Á Á ÁP5(x ‡ 12; 21 y; z ‡ 21 ); L3 is C1ÐH1Á Á ÁP4(x ‡ 21; y ‡ 12; z); for
detailed geometric data, see Table 3.
N1ÐC5
N1ÐC1
N1ÐC14
N2ÐC15
C3ÐC6
C6ÐC7
1.339 (6)
1.344 (6)
1.479 (6)
1.148 (6)
1.451 (6)
1.328 (5)
C7ÐC8
1.464 (6)
C11ÐC15
C16ÐB1
C22ÐB1
C28ÐB1
C34ÐB1
1.443 (6)
1.643 (6)
1.628 (6)
1.660 (6)
1.635 (6)
metric. A search was carried out of the Cambridge Structural
Database (CSD, Version 5.26; Allen, 2002) for stilbazolium
tetraphenylborates and resulted in three structures. In order
to estimate the relative contributions of the cation±cation,
anion±anion and anion±cation interactions, packing energies
were calculated on these three structures and (I) using the
program OPEC. The results are listed in Table 5. Although the
data are very limited and the calculated absolute total PE
value is not very accurate, we could tentatively state that the
non-centrosymmetric packing of the title crystal is possibly
due to the much stronger anion±cation interaction.
C5ÐN1ÐC1
C5ÐN1ÐC14
C1ÐN1ÐC14
C4ÐC3ÐC2
C4ÐC3ÐC6
C2ÐC3ÐC6
C7ÐC6ÐC3
C6ÐC7ÐC8
120.0 (4)
120.0 (4)
120.0 (4)
116.8 (4)
119.6 (4)
123.6 (4)
126.3 (3)
125.7 (3)
C13ÐC8ÐC9
C13ÐC8ÐC7
C9ÐC8ÐC7
C10ÐC11ÐC12
C10ÐC11ÐC15
C12ÐC11ÐC15
N2ÐC15ÐC11
118.8 (4)
121.5 (4)
119.6 (4)
120.6 (4)
121.1 (4)
118.3 (4)
177.7 (5)
Table 2
Hydrogen-bond geometry (A, ).
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
C14iÐH14AiÁ Á ÁN2
0.98
0.95
2.54
2.65
3.463 (7)
3.359 (8)
157
131
C35iiÐH35iiÁ Á ÁN2
Experimental
Symmetry codes: (i) x ‡ 12; y ‡ 21; z 21; (ii) x; y; z
.
1
2
1,4-Dimethylpyridinium iodide (7.05 g, 30 mmol) (prepared from
CH3I and 1-methylpyridine), 4-cyanobenzaldehyde (6.42 g, 49 mmol)
and piperidine (0.2 ml) in methanol (40 ml) were heated at 353 K
with stirring for 8 h (Okada et al., 1990). The product was recrys-
tallized twice from ethanol±water (2:1 v/v), dissolved in water (0.70 g
in 100 ml) and treated with a saturated solution of sodium tetra-
phenylborate. The title compound was separated and recrystallized
twice from ethanol±water (4:1). Yellow crystals of (I) (m.p. 489±
490 K) were grown by slow evaporation at ambient temperature from
N,N-dimethylformamide over a period of 18 d. Elemental analysis
(Perkin±Elmer 240C elemental analyser): calculated for
Table 3
ꢀ
Ê
CÐHÁ Á Áꢀ interactions (A, ) in (I).
C
H
Plane²
dHP
³
ꢈ§
Molecule}
C4
H4
P4
P5
P5
P4
P4
P6
P7
P6
P2
P7
P5
P7
P1
2.88
2.46
2.91
2.53
2.13
2.27
2.60
2.51
2.66
2.27
2.09
2.27
2.79
13.3
20.9
12.5
16.6
23.4
30.9
23.8
30.5
17.0
20.7
24.0
29.5
15.5
FM
3
5
7
1
1
2
3
4
4
7
7
8
C12
C9
H12
H9
C1
H1
C37
C37
C5
H37
H37
H5
+
C15H13N2 ÁBPh4 : C 86.67, H 6.11, N 5.19%; found: C 87.09, H 6.27,
C18
C29
C26
C31
C31
C39
H18
H29
H26
H31
H31
H39
N 4.85%. IR (FT±IR spectrometer with KBr pellets, ꢁ, cm 1): 3050
(Ar-H), 2995 (±CÐH), 2227 (cyano), 1644 (±CH CH±), 1627
(±CH N±), 1519 (Ph), 1478 (Ph), 1427 (Ph), 1334 (±CH3), 1188
(±CH CÐH), 1151 (±CH CÐH), 1031 (Ar-H), 972 (Ar-H), 955
(Ar-H), 848 (Ar-H), 733 (Ar-H), 711 (Ar-H); 1H NMR (Bruker
AV-400 NMR spectrometer, DMSO, 399.97 MHz, ambient tem-
perature): ꢂ 8.91 (d, 2H, pyridyl ring), 8.25 (d, 2H, pyridyl ring),
8.03 (d, 1H, ±CH CH±), 7.97 (d, 2H, Ph), 7.91 (d, 2H, Ph), 7.32
(d, 1H, ±CH CH±), 7.18 (s, 8H, Ph), 6.94±6.90 (m, 8H, Ph), 6.80±6.77
(m, 4H, Ph), 2.50 (s, 3H, ±CH3).
² The planes P1 (C1±C5/N1), P2 (C8±C13), P3 (C3/C6±C8), P4 (C16±C21), P5 (C22±
C27), P6 (C28±C33) and P7 (C34±C39) in the fundamental molecule (FM). The CÐH
group is in a particular surrounding molecule (SM), speci®ed by the code in the last
column. ³ dHP is the distance of the H atom from the plane. § ꢈ is the angle formed
by the vectors of CÐH and the perpendicular line passing through the H atom to the
plane. } The SMs which interact most strongly with the FM, numbered as in Table 4.
The ®rst four interactions are indicated in Fig. 2 by bold dashed lines and labelled L0±L3.
+
ꢁ
o658 Jin and Zhang C15H13N2 ÁC24H20
B
Acta Cryst. (2005). C61, o657±o659

organic compounds
Table 4
Table 5
Packing energies² of some stilbazolium tetraphenylborates (kcal mol 1).
The packing energy (PE) portioning in (I) (kcal mol 1).
Molecule² PE³
c±c§
5.9
a±a}
2.6
c±a²²
3.6
dBÁ Á ÁB³³
Symmetry code
CSD refcode Total PE Space (a±a)%³ (c±a)%§ ꢆ}
group
Substituent
1
12.1
10.03 (x 12, y + 12, z)
10.03 (x + 12, y 21, z)
8.84 (x, y + 1, z + 12)
8.84 (x, y + 1, z
11.00 (x + 12, y + 21, z + 12)
2
3
4
5
6
7
12.1
10.2
10.2
10.0
10.0
7.2
5.9
0.4
0.4
0.9
0.9
0.3
0.3
0.4
0.4
2.6
4.4
4.4
0.7
0.7
2.6
2.6
3.6
5.4
5.4
8.4
8.4
4.3
4.3
3.7
3.7
1.9
1.9
1.9
1.9
81.1
QOBDEQa
WOCRAHb
BOQKEXc
(I)d
235.73
257.22
264.73
258.74
P21/c
P21/c
Cc
22.63
23.29
16.35
20.97
53.16
58.42
68.51
65.51
15.61 4-N(OCH3)2
14.63 4-OCH3
18.34 3,4-OCH3
18.85 4-CN
1
2
)
Cc
1
2
1
2
11.00 (x
,
y + 12, z
)
)
² Packing energies calculated using the program OPEC (Gavezzotti, 1983). ³ (a±a)%
is the percentage for the anion±anion interaction in the total PE. § (c±a)% is the
percentage for the cation±anion interaction in the total PE. } The dipole moment of
the cation (Debye), calculated by the program MOPAC (Dewar et al., 1985) using the
dipole moment summation method (Kurtz et al., 1990). References: (a) Li et al. (2000a);
(b) Li et al. (2000b); (c) Zhang et al. (1999); (d) this study.
10.03 (x + 12, y + 21, z)
10.03 (x 12, y 12, z)
8
9
7.2
4.1
(x, y, z + 12)
1
2
10
11
12
13
14
Total
4.1
3.5
3.5
2.6
2.6
123.7
(x, y, z
1
)
1
2
1.6
1.6
0.7
0.7
(x
,
y + 32, z
2
(x + 12, y + 23, z + 12)
(x, y 1, z)
(x, y + 1, z)
16.7
25.9
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SF1010). Services for accessing these data are
described at the back of the journal.
² Taking one molecule in the crystal as the fundamental molecule (FM), then all
surrounding molecules (SMs) interact with the FM, each of which may correspond to a
certain symmetry operator when the asymmetric unit consists of one or less than one
molecule. ³ The packing energies, calculated using the program OPEC (Gavezzotti,
1983) with the improved set of parameters (Gavezzotti & Filippini, 1994). Value omitted
if it is less than 1% of the total PE in the column. § The PE between the cation in the
FM and that in the SM indicated by the symmetry code in the last column. } The PE
between the anion in the FM and that in the SM indicated by the symmetry code in the
last column. ²² The PE between the cation in the FM and the anion in the SM
indicated by the symmetry code in the last column. ³³ The distance between the
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Ê
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Re®nement
Re®nement on F2
R[F2 > 2ꢇ(F2)] = 0.051
wR(F2) = 0.121
S = 1.11
2726 re¯ections
w = 1/[ꢇ2(Fo2) + (0.0568P)2
+ 0.9638P]
where P = (Fo2 + 2Fc2)/3
(Á/ꢇ)max < 0.001
3
Ê
Áꢉmax = 0.15 e A
3
Ê
0.18 e A
381 parameters
H-atom parameters constrained
Áꢉmin
=
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distances for Car and Csp were set at 0.95 A, and for Csp were set at
3
Ê
0.98 A; Uiso(H) = 1.2Ueq(C) for Car and Csp2, and 1.5Ueq(C) for Csp3.
Ê
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È
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This work was supported by the Key Subject Programme of
Jiangsu Province (grant No. S1109001).
+
ꢁ
Acta Cryst. (2005). C61, o657±o659
Jin and Zhang
C15H13N2 ÁC24H20
B
o659