Benzene-1,3-dicarb-oxy-lic acid-1,2-bis-(4-pyrid-yl)ethene (1/1).

Abstract

In the title compound, C(12)H(10)N(2)·C(8)H(6)O(4), the asymmetric unit contains two halves of 1,2-bis-(4-pyrid-yl)ethene (bpe) mol-ecules and one benzene-1,3-dicarb-oxy-lic acid (1,3-H(2)BDC) mol-ecule. These bpe and 1,3-H(2)BDC mol-ecules are linked by classical O-H⋯N hydrogen bonds, forming an extended one-dimensional zigzag chain. Each chain is further linked with neighboring ones by π-π inter-actions between the pyridine and aromatic rings [centroid-centroid distances = 3.9306 (15) Å] and the pyridine rings of pairs of symmetry-related mol-ecules [centroid-centroid distances = 3.5751 (15), 3.7350 (15) and 3.6882 (15) Å], with the formation of a three-dimensional supra-molecular framework.

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Benzene-1,3-dicarboxylic acid–1,2-bis(4-
pyridyl)ethene (1/1)
Dong Liu* and Ni-Ya Li
College of Chemistry and Materials Science, Huaibei Normal University, Huaibei
235000, Anhui, People’s Republic of China
Correspondence e-mail: dongliu@chnu.edu.cn
Received 4 October 2011; accepted 19 October 2011
Key indicators: single-crystal X-ray study; T = 223 K; mean ?(C–C) = 0.003 A ˚;
R factor = 0.051; wR factor = 0.137; data-to-parameter ratio = 12.8.
In the title compound, C12H10N2?C8H6O4, the asymmetric unit
contains two halves of 1,2-bis(4-pyridyl)ethene (bpe) mol-
ecules and one benzene-1,3-dicarboxylic acid (1,3-H2BDC)
molecule. These bpe and 1,3-H2BDC molecules are linked by
classical O—H???N hydrogen bonds, forming an extended
one-dimensional zigzag chain. Each chain is further linked
with neighboring ones by ?–? interactions between the
pyridine and aromatic rings [centroid–centroid distances =
3.9306 (15) A˚] and the pyridine rings of pairs of symmetry-
related molecules [centroid–centroid distances = 3.5751 (15),
3.7350 (15) and 3.6882 (15) A˚], with the formation of a three-
dimensional supramolecular framework.
Related literature
For structures and properties of self-assembled supramole-
cular compounds, see: Lehn (1990). For hydrogen-bonding
interactionsand
?–?
interactions
compounds, see: Biradha (2003); Shan & Jones (2003); Weyna
et al. (2009).
in supramolecular
Experimental
Crystal data
C12H10N2?C8H6O4
Mr= 348.35
Triclinic, P1
a = 6.8331 (14) A˚
b = 6.8804 (14) A˚
c = 18.618 (4) A˚
? = 99.47 (3)?
? = 93.87 (3)?
? = 102.69 (3)?
V = 837.4 (3) A˚3
Z = 2
Mo K? radiation
? = 0.10 mm?1
T = 223 K
0.40 ? 0.40 ? 0.35 mm
Data collection
Rigaku Mercury CCD
diffractometer
Absorption correction: multi-scan
(REQAB; Jacobson, 1998)
Tmin= 0.962, Tmax= 0.967
8280 measured reflections
3054 independent reflections
2153 reflections with I > 2?(I)
Rint= 0.037
Refinement
R[F2> 2?(F2)] = 0.051
wR(F2) = 0.137
S = 1.06
3054 reflections
238 parameters
H-atom parameters constrained
??max= 0.23 e A˚?3
??min= ?0.19 e A˚?3
Table 1
Hydrogen-bond geometry (A˚,?).
D—H???A
O1—H1???N1i
O3—H3???N2
Symmetry code: (i) x ? 1;y;z.
D—HH???AD???AD—H???A
0.83
0.83
1.77
1.79
2.597 (2)
2.618 (2)
176
176
Data collection: CrystalClear (Rigaku, 2001); cell refinement:
CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004);
program(s) used to solve structure: SHELXTL (Sheldrick, 2008);
program(s) used to refine structure: SHELXTL; molecular graphics:
SHELXTL; software used to prepare material for publication:
SHELXTL and PLATON (Spek, 2009).
This work was supported by the Research Start-Up Fund
for New Staff of Huaibei Normal University (grant No.
600581).
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: RK2306).
References
Biradha, K. (2003). CrystEngComm, 5, 374–384.
Jacobson, R. (1998). REQAB. Private communication to the Rigaku
Corporation, Tokyo, Japan.
Lehn, M. L. (1990). Angew. Chem. Int. Ed. 29, 1304-1319.
Rigaku (2001). CrystalClear. Rigaku Corporation, Tokyo, Japan.
Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC, The Woodlands, Texas,
USA.
Shan, N. & Jones, W. (2003). Tetrahedron Lett. 44, 3687–3689.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
Weyna, D., Shattock, R. T., Vishweshwar, P. & Zaworotko, M. J. (2009). Cryst.
Growth Des. 9, 1106-1123.
organic compounds
Acta Cryst. (2011). E67, o3039doi:10.1107/S1600536811043418 Liu and Li
o3039
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

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Acta Cryst. (2011). E67, o3039 [ doi:10.1107/S1600536811043418 ]
Benzene-1,3-dicarboxylic acid-1,2-bis(4-pyridyl)ethene (1/1)
D. Liu and N.-Y. Li
Comment
In the past decades, the supramolecular synthesis of multicomponent organic materials has attracted considerable attention
due to their functional properties (Lehn, 1990). The facile way of synthesizing these co-crystals is to employ the components
containing complementary functional groups such as pyridine and carboxylic acid. Owing to the hydrogen-bonds and π–π
stacking between these types of groups, several multicomponent cocrystals containing various network geometries were
prepared using these two functional groups (Biradha, 2003; Shan & Jones, 2003; Weyna et al., 2009).
The hydrothermal reaction of 1,2-bis(4-pyridyl)ethene (bpe) with benzene-1,3-dicarboxylic acid (1,3-H2BDC) resulted
in the cocrystals of C12H10N2.C8H6O4, I. In I, the asymmetric unit is formed by two halves of bpe molecules and one 1,3-
H2BDC molecule (Fig. 1). These molecular units are linked by classical O–H···N hydrogen-bonds (O1–H1···N1iii, O1···N1iii
= 2.597 (2)Å; O3–H3···N2, O3···N2 = 2.618 (2)Å) forming an extended one-dimensional zigzag chain (Table 1, Fig. 2).
Furthermore, the adjacent one-dimensional chains are interconnected each other through π–π interactions between pairs of
molecules [Cg1···Cg1iv = 3.5751 (15)Å; Cg1···Cg3 = 3.9306 (15)Å; Cg2···Cg2v = 3.7350 (15)Å; Cg2···Cg2vi = 3.7350 (15)Å
form a three-dimensional framework (Fig. 3). The Cg1, Cg2 and Cg3, are the centroids of the rings N1/C9-C13, N2/C15-
C19 and C1-C6. Symmetry codes: (iii) -x+1, y, z; (iv) -x+1, -y+1, -z+2; (v) -x+1, -y+1, -z+1; (vi) -x+2, -y+1, -z+1 .
Experimental
To a 10 mL Pyrex glass tube was loaded 1,2-bis(4-pyridyl)ethene (18 mg, 0.1 mmol), benzene-1,3-dicarboxylic acid (17
mg, 0.1 mmol) and 3 ml of H2O. The tube was sealed and heated in an oven to 423 K for three days, and then cooled to
ambient temperature at the rate of 5 K h-1 to form yellow crystals.
Refinement
All H atoms were placed in geometrically idealized positions (C–H = 0.94Å for phenyl, pyridyl and vinyl groups, O–H =
0.83Å for OH group) and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C) and Uiso(H) = 1.5Ueq(O).
Figures
Fig. 1. The structure of the title compound, showing the atom-numbering scheme. Displace-
ment ellipsoids are presented at the 30% probability level. Symmetry codes: (i) -x+2, -y+2, -
z+1; (ii): -x, -y+1, -z+2; (iii) x+1, y, z.
Fig. 2. The one-dimensional zigzag chain linked by hydrogen-bonding interactions. The blue
dashed lines represent the hydrogen-bonds.

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Fig. 3. The three-dimensional supramolecular framework linked by hydrogen-bonding inter-
actions and π–π interactions. The blue and cyan dashed lines represent the hydrogen-bonds
and π–π interactions, respectively.
Benzene-1,3-dicarboxylic acid111,2-bis(4-pyridyl)ethene (1/1)
Crystal data
C12H10N2·C8H6O4
Mr = 348.35
Z = 2
F(000) = 364
Dx = 1.382 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 2779 reflections
θ = 3.1–25.4°
µ = 0.10 mm−1
T = 223 K
Block, yellow
0.40 × 0.40 × 0.35 mm
Triclinic, P1
Hall symbol: -P 1
a = 6.8331 (14) Å
b = 6.8804 (14) Å
c = 18.618 (4) Å
α = 99.47 (3)°
β = 93.87 (3)°
γ = 102.69 (3)°
V = 837.4 (3) Å3
Data collection
Rigaku Mercury CCD
diffractometer
Radiation source: fine-focus sealed tube
graphite
φ and ω scans
Absorption correction: multi-scan
(REQAB; Jacobson, 1998)
Tmin = 0.962, Tmax = 0.967
8280 measured reflections
3054 independent reflections
2153 reflections with I > 2σ(I)
Rint = 0.037
θmax = 25.3°, θmin = 3.1°
h = −8→8
k = −7→8
l = −22→21
Refinement
Refinement on F2
Secondary atom site location: difference Fourier map
Least-squares matrix: full
Hydrogen site location: inferred from neighbouring
sites
R[F2 > 2σ(F2)] = 0.051
H-atom parameters constrained
wR(F2) = 0.137
w = 1/[σ2(Fo2) + (0.0616P)2 + 0.1982P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.23 e Å−3
Δρmin = −0.19 e Å−3
Extinction correction: SHELXTL (Sheldrick, 2008),
Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
S = 1.06
3054 reflections
238 parameters
0 restraints

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Primary atom site location: structure-invariant direct
methods
Extinction coefficient: 0.028 (4)
Special details
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The
cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between
s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is
used for estimating s.u.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, convention-
al R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-
factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large
as those based on F, and R-factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
−0.1898 (3)
−0.2835
−0.2446 (3)
0.5207 (2)
0.5796
0.4236 (3)
0.5203 (3)
0.6910 (3)
0.0121 (3)
0.1342 (3)
0.1109
0.2909 (3)
0.3240 (3)
0.4293
0.2028 (4)
0.2260
0.0478 (4)
−0.0337
−0.1539 (3)
0.4193 (3)
0.4644 (3)
0.5339
0.3099 (3)
0.2752
0.2046 (3)
0.2643 (3)
0.1989
0.4199 (3)
0.4568
0.0399 (3)
−0.0139
y
0.1743 (2)
0.1999
−0.0994 (3)
0.0878 (2)
0.1779
0.3460 (2)
0.2721 (3)
0.3812 (3)
−0.0583 (3)
0.0735 (3)
0.2030
0.0166 (3)
−0.1741 (3)
−0.2141
−0.3062 (3)
−0.4357
−0.2489 (3)
−0.3389
0.0031 (3)
0.1663 (3)
0.4451 (4)
0.5335
0.4988 (3)
0.6216
0.3725 (3)
0.1941 (4)
0.1041
0.1495 (4)
0.0270
0.4214 (4)
0.3314
z
0.81468 (9)
0.8378
0.86694 (10)
0.62885 (9)
0.6079
0.69323 (9)
0.88516 (10)
0.56392 (10)
0.78717 (11)
0.75112 (11)
0.7507
0.71557 (11)
0.71652 (11)
0.6925
0.75262 (12)
0.7530
0.78806 (12)
0.8128
0.82700 (12)
0.67866 (11)
0.88158 (12)
0.8533
0.91739 (12)
0.9132
0.95979 (11)
0.96377 (12)
0.9923
0.92569 (12)
0.9284
1.00081 (13)
1.0313
Uiso*/Ueq
0.0437 (5)
0.065*
0.0528 (5)
0.0417 (4)
0.063*
0.0495 (5)
0.0348 (5)
0.0353 (5)
0.0306 (5)
0.0292 (5)
0.035*
0.0283 (5)
0.0346 (5)
0.041*
0.0403 (6)
0.048*
0.0369 (6)
0.044*
0.0347 (5)
0.0327 (5)
0.0380 (6)
0.046*
0.0372 (6)
0.045*
0.0334 (5)
0.0390 (6)
0.047*
0.0379 (6)
0.046*
0.0391 (6)
0.047*
O1
H1
O2
O3
H3
O4
N1
N2
C1
C2
H2
C3
C4
H4
C5
H5
C6
H6
C7
C8
C9
H9
C10
H10
C11
C12
H12
C13
H13
C14
H14