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

Article abstract of DOI:10.1107/S0108270100007538

In the cation of the title compound, C₁₅H₁₆NO⁺·C₂₄H₂₀B^-, the pyridyl ring makes a dihedral angle of 14.03° with the phenyl ring. The anion has a slightly distorted tetrahedral geometry and

Full text of DOI:10.1107/S0108270100007538

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
ISSN 0108-2701
4
-[2-(4-Methoxyphenyl)ethenyl]-N-
methylpyridinium tetraphenylborate
a
a
a
Shu-Jin Li, De-Chun Zhang, * Zhong-Lin Huang,
a
b
Yan-Qiu Zhang and Kai-Bei Yu
a
Department of Chemistry, Suzhou University, Suzhou 215006, People's Republic of
b
China, and Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences,
Chengdu 610041, People's Republic of China
Correspondence e-mail: dczhang@suda.edu.cn
Received 6 December 1999
Accepted 22 May 2000
+
�
24 20
In the cation of the title compound, C H NO ÁC H B , the
1
5
16
ꢁ
pyridyl ring makes a dihedral angle of 14.03 with the phenyl
ring. The anion has a slightly distorted tetrahedral geometry
and forms honeycomb-like sheets which extend along the b
axis, forming channels containing the cations. A comparison of
packing energies reveals a difference between the title
compound and a similar material which has non-linear optical
properties.
Figure 1
The molecular structure of (I) showing the atom-numbering scheme and
50% probability displacement ellipsoids. H atoms have been omitted for
clarity.
0
system, i.e. 4 -methoxy-N-methyl-4-stilbazolium tosylate
Marder et al., 1994), have corresponding packing energies of
Comment
(
�
1
Considerable efforts have been made to investigate organic
non-linear optical (NLO) materials (Chemla & Zyss, 1987).
Marder et al. (1994) have successfully synthesized a number of
crystals exhibiting second-harmonic generation (SHG) using
their `salt methodology', which suggests that the anion±cation
interaction in organic salts can override the dipole±dipole
interaction which favours antiparallel centrosymmetric
packing. During our systematic search for organic NLO
compounds following this line of thought, we synthesized the
title compound, (I).
� 20.6, � 76.1 and � 126.6 kJ mol , respectively. The centro-
symmetric packing in the crystal of (I) is likely to be due to its
+
Compound (I) is a salt consisting of a C H NO cation
1
5
16
�
and a BPh4 anion. In the cation, the pyridyl ring makes a
ꢁ
dihedral angle of 14.03 with the phenyl ring and both of these
rings are essentially planar. The anion has a slightly distorted
tetrahedral geometry (Table 1).
The crystals of (I) failed to crystallize in a non-centrosym-
metric space group and therefore show no SHG effect. To
analyse the reason for this, the molecular packing in the crystal
was studied by calculating packing energies using the OPEC
program (Gavezzotti, 1983); the results are listed in Table 2.
The total packing energies for anion±anion, cation±cation
and anion±cation interactions are � 65.7, � 47.0 and
Figure 2
The packing diagram for (I) viewed down the b axis.
�
1
�
124.6 kJ mol , respectively. Crystals of a well known SHG
1
122 # 2000 International Union of Crystallography ꢀ Printed in Great Britain ± all rights reserved
Acta Cryst. (2000). C56, 1122±1123

organic compounds
much stronger anion±anion interaction.
The anions form inversion-related pairs through ꢀÁ Á Áꢀ
Table 1
Selected geometric parameters (A, ).
Ê
ꢁ
interactions. The planes de®ned by the phenyl ring made up of
atoms C28±C33 and its closest symmetry-related partner (1 � x,
OÐC12
OÐC15
NÐC2
NÐC6
1.3642 (19)
1.4221 (19)
1.340 (2)
NÐC1
1.468 (2)
1.449 (2)
1.325 (2)
1.453 (2)
C4ÐC7
C7ÐC8
C8ÐC9
Ê
�
1 � y, 1 � z) are separated by 2.2 A; the centres of these two
1.3443 (19)
Ê
rings are 5.91 A apart. The next closest anion±anion interac-
1
3
tion occurs through the operation (1 � x, � y, 2 � z), and
2
C12ÐOÐC15
C2ÐNÐC6
C2ÐNÐC1
C6ÐNÐC1
C22ÐBÐC28
C22ÐBÐC34
118.24 (14)
119.41 (15)
119.98 (15)
120.56 (14)
109.87 (12)
105.98 (12)
C28ÐBÐC34
C22ÐBÐC16
C28ÐBÐC16
C34ÐBÐC16
C8ÐC7ÐC4
C7ÐC8ÐC9
113.07 (12)
113.01 (12)
105.12 (11)
109.94 (11)
126.42 (16)
126.94 (15)
these three anions and their inversion-related counterparts
form a distorted hexahedron-shaped channel along the b
direction, similar in appearance to a honeycomb. Two inver-
sion-related strands of cations run along these channels. This
kind of three-dimensional structure probably contributes to
the macroscopic morphology of the crystals, which grow as
distinct granules, and might contribute to their application in a
C3ÐC4ÐC7ÐC8
C4ÐC7ÐC8ÐC9
C7ÐC8ÐC9ÐC10
168.18 (16)
� 175.97 (15)
� 3.9 (3)
C7ÐC8ÐC9ÐC14
C15ÐOÐC12ÐC11
C15ÐOÐC12ÐC13
176.17 (16)
� 5.8 (2)
175.51 (14)
®eld other than SHG.
Experimental
Table 2
Ion-packing energies (PE) (kJ mol ).
�
1
1,4-Dimethylpyridinium iodide (7.05 g, 30 mmol, prepared from
CH and 1-methylpyridine), 4-methoxybenzaldehyde (6.67 g,
3
I
9 mmol) and piperidine (0.2 ml) in methanol (40 ml) were heated at
Interaction
PE
Interaction
PE
4
3
i
viii
53 K with stirring for 11 h (Okada et al., 1990). The product was
anion±anion
anion±anion
anion±anion
anion±anion
anion±anion
� 12.1
� 10.0
� 10.0
� 7.1
cation±cation
i
anion±cation
anion±cation
anion±cation
anion±cation
anion±cation
anion±cation
� 12.6
� 23.6
� 25.7
� 25.7
� 6.9
ii
iii
iv
v
recrystallized twice from ethanol±water (2:1), dissolved in water
0.70 g in 100 ml) and treated with a saturated solution of sodium
ii
(
ii
vii
tetraphenylborate. Compound (I) was separated and recrystallized
twice from ethanol±water (4:1), and yellow±green crystals (m.p. 509±
� 7.1
vi
viii
cation±cation
cation±cation
� 15.3
� 6.9
vii
vi
� 12.6
� 0.2
510 K) were grown from a solution in N,N-dimethylformamide. IR
spectroscopic analysis, cm : 706, 976, 1142, 1173, 1304, 1335, 1424,
�
1
1
2
3
2
1 3
2 2
Symmetry codes: (i) 1 � x, � y � 1, 1 � z; (ii) 1 � x, y �
,
� z; (iii) 1 � x, y + , � z;
1
2
3
2
1 3
2 2
(iv) 2 � x, y �
y + 1, z.
,
� z; (v) 2 � x, y + , � z; (vi) � x, � y, 1 � z; (vii) x, y � 1, z; (viii) x,
1
2
516, 1598, 1647, 3052; elemental analysis, found: C 86.28, H 6.57, N
�
+
.49%; C15
H
16NO ÁBPh
4
requires: C 85.86, H 6.65, N 2.57%.
Crystal data
+
C
�
� 3
15
H16NO ÁC24
H
20
B
x
D = 1.202 Mg m
Data collection and cell re®nement: XSCANS (Siemens, 1994);
data reduction: SHELXTL (Sheldrick, 1995); program(s) used to
solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to
re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics
and software used to prepare material for publication: SHELXTL.
M
r
= 545.50
Mo Kꢂ radiation
Cell parameters from 26
re¯ections
Monoclinic, P2 =c
1
Ê
Ê
a = 13.029 (2) A
ꢁ
� 1
b = 10.819 (2) A
ꢃ = 3.81±17.23
Ê
c = 21.660 (3) A
= 99.160 (10)
V = 3014.3 (8) A
Z = 4
ꢄ = 0.070 mm
T = 296 (2) K
ꢁ
Ê
ꢁ
3
Granular, yellow±green
0.60 Â 0.56 Â 0.52 mm
This work was supported by the Provincial Natural Science
Foundation of Jiangsu Province, People's Republic of China.
Data collection
Siemens P4 diffractometer
scans
502 measured re¯ections
318 independent re¯ections
204 re¯ections with I> 2ꢅ(I)
h = 0 ! 15
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: DA1127). Services for accessing these data are
described at the back of the journal.
!
k = � 1 ! 12
6
5
3
l = � 25 ! 25
3 standard re¯ections
every 97 re¯ections
intensity decay: 2.74%
R
int = 0.010
References
ꢁ
ꢃ
max = 25.01
Chemla, D. S. & Zyss, J. (1987). Editors. Nonlinear Optical Properties of
Organic Molecules and Crystals, Vol. 1, pp. 23±187. Orlando: Academic
Press.
Gavezzotti, A. (1983). J. Am. Chem. Soc. 105, 5520±5525.
Marder, S. R., Perry, J. M. & Yakymyshyn, C. P. (1994). Chem. Mater. 6, 1137±
1147.
Okada, S., Masaki, A., Matsudo, H., Kato, M. & Muramatsu, R. (1990). Jpn J.
Appl. Phys. 29, 1112±1115.
Sheldrick, G. M. (1995). SHELXTL. Version 5.0. Siemens Analytical X-ray
Instruments Inc., Madison, Wisconsin, USA.
Re®nement
2
2
2
2
Re®nement on F
2
w = 1/[ꢅ (F
where P = (F
(Á/ꢅ)max < 0.001
o
) + (0.047P) ]
2
2 2
R[F > 2ꢅ(F )] = 0.036
wR(F ) = 0.088
S = 0.868
o c
+ 2F )/3
2
Ê
� 3
Áꢆmax = 0.13 e A
Ê
� 3
5
3
318 re¯ections
82 parameters
Áꢆmin = � 0.11 e A
Extinction correction: SHELXL97
Extinction coef®cient: 0.0103 (7)
H-atom parameters constrained
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of G oÈ tt-
ingen, Germany.
Siemens (1994). XSCANS Users Manual. Version 2.1. Siemens Analytical
X-ray Instruments Inc., Madison, Wisconsin, USA.
H atoms were placed theoretically according to standard geom-
Ê
etries, with all CÐH distances being 0.93 A, except for those invol-
Ê
ving C1 and C15 which were 0.96 A.
+
�
Acta Cryst. (2000). C56, 1122±1123
Shu-Jin Li et al. ꢀ
C
15
H
16NO ÁC24
20
H B
1123