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Acta Crystallogr Sect E Struct Rep Online. 2010 March 1; 66(Pt 3): o722.
Published online 2010 February 27. doi:  10.1107/S1600536810003442
PMCID: PMC2983705

Isonicotinonitrile–benzoic acid (1/1)

Abstract

In the title 1:1 adduct, C6H4N2·C7H6O2, the carboxyl group and its attached phenyl ring are essentially coplanar, being twisted from each other by a dihedral angle of only 2.05 (3)°. In the crystal, the mol­ecules are connected via O—H(...)N and C—H(...)O hydrogen bonds, building an R 2 2(7) ring. Mol­ecules are further linked through π–π inter­actions [centroid–centroid distance of 3.8431 (8) and 3.9094 (8) Å], leading to a one-dimensional chain parallel to the b axis.

Related literature

For related structures, see: Chen et al. (2009 [triangle]); Fu et al. (2008 [triangle]). For hydrogen-bonding motifs, see: Bernstein et al. (1995 [triangle]); Etter et al. (1990 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o722-scheme1.jpg

Experimental

Crystal data

  • C6H4N2·C7H6O2
  • M r = 226.23
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o722-efi1.jpg
  • a = 7.4274 (15) Å
  • b = 7.7389 (15) Å
  • c = 11.668 (2) Å
  • α = 85.26 (3)°
  • β = 76.44 (3)°
  • γ = 62.79 (2)°
  • V = 579.6 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 298 K
  • 0.4 × 0.35 × 0.2 mm

Data collection

  • Rigaku Mercury2 diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.881, T max = 0.940
  • 6025 measured reflections
  • 2646 independent reflections
  • 1346 reflections with I > 2σ(I)
  • R int = 0.042

Refinement

  • R[F 2 > 2σ(F 2)] = 0.059
  • wR(F 2) = 0.154
  • S = 0.96
  • 2646 reflections
  • 154 parameters
  • H-atom parameters constrained
  • Δρmax = 0.14 e Å−3
  • Δρmin = −0.18 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810003442/dn2532sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810003442/dn2532Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by a start-up grant from SEU.

supplementary crystallographic information

Comment

Cocrystal attracted more and more attention in recent years for its wide range of applation, for example phase transition dielectric materials and pharmaceutical(Chen, et al. 2009; Fu, et al. 2008). With the purpose of obtaining cocrystals of isonicotinonitrile, its interaction with various acids has been studied and we have elaborated a serie of new materials with this organic molecule. In this paper, we describe the crystal structure of the title compound, isonicotinonitrile benzoate.

The asymmetric unit is composed of a discrete isonicotinonitrile and benzoic acid molecules (Fig.1). The carboxyl and its parent phenyl ring are essentially coplanar, and only twisted from each other by a dihedral angles of 2.05 (3)°. The two molecules are nearly planar and are only slightly twisted by a dihedral angle of 1.87 (7)° . The molecules were connected via O—H···N and C-H···O hydrogen bonds building a R22(7) ring (Etter et al., 1990; Bernstein et al., 1995) which play an important role in stabilizing the structural conformation. The molecules units are further linked by weak offset π···π interactions leading to a one-dimensional chain parallel to the b axis (Table 2 and Fig. 2).

Experimental

The commercial isonicotinonitrile and benzoic acid (1/1 mol rate) were dissolved in water/methanol (5:3 v/v) solution. The solvent was slowly evaporated in air affording colourless block-shaped crystals of the title compound suitable for X-ray analysis.

While the permittivity measurement shows that there is no phase transition within the temperature range (from 100 K to 400 K), and the permittivity is 5.9 at 1 MHz at room temperature.

Refinement

All H atoms attached to C atoms were positioned geometrically and treated as riding, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) and the H atoms of carboxyl O located in difference Fourier maps and freely refined. In the last stage of refinement they were treated as riding on the O atom, with Uĩso(H) = 1.5Ueq(O).

Figures

Fig. 1.
A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.
Fig. 2.
The crystal packing of the title compound, showing the 1D chain. H atoms not involved in hydrogen bonding (dashed line) have been omitted for clarity.

Crystal data

C6H4N2·C7H6O2Z = 2
Mr = 226.23F(000) = 236
Triclinic, P1Dx = 1.296 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.4274 (15) ÅCell parameters from 1346 reflections
b = 7.7389 (15) Åθ = 3.2–27.5°
c = 11.668 (2) ŵ = 0.09 mm1
α = 85.26 (3)°T = 298 K
β = 76.44 (3)°Block, colourless
γ = 62.79 (2)°0.4 × 0.35 × 0.2 mm
V = 579.6 (2) Å3

Data collection

Rigaku Mercury2 diffractometer2646 independent reflections
Radiation source: fine-focus sealed tube1346 reflections with I > 2σ(I)
graphiteRint = 0.042
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.2°
ω scansh = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −10→10
Tmin = 0.881, Tmax = 0.940l = −15→15
6025 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.154H-atom parameters constrained
S = 0.96w = 1/[σ2(Fo2) + (0.0699P)2] where P = (Fo2 + 2Fc2)/3
2646 reflections(Δ/σ)max < 0.001
154 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = −0.18 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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, conventional 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)

xyzUiso*/Ueq
O10.3710 (2)0.8106 (2)0.47118 (13)0.0701 (5)
H10.48650.80330.42020.105*
O20.5897 (2)0.6595 (2)0.58797 (14)0.0824 (5)
N10.7138 (3)0.8082 (2)0.32068 (15)0.0578 (5)
C10.2396 (3)0.7201 (3)0.65759 (17)0.0491 (5)
C70.4176 (3)0.7263 (3)0.56976 (18)0.0529 (5)
C91.0739 (3)0.7156 (3)0.29472 (19)0.0615 (6)
H91.19220.66110.32570.074*
C60.0455 (3)0.7920 (3)0.63365 (19)0.0595 (6)
H60.02240.84730.56140.071*
C110.9010 (3)0.8656 (3)0.13992 (18)0.0584 (6)
H110.90120.91400.06430.070*
C80.8875 (3)0.7304 (3)0.35995 (18)0.0610 (6)
H80.88270.68310.43590.073*
C101.0797 (3)0.7841 (3)0.18209 (18)0.0503 (5)
C20.2716 (3)0.6398 (3)0.76576 (18)0.0616 (6)
H20.40220.59200.78250.074*
C120.7228 (3)0.8737 (3)0.21192 (19)0.0612 (6)
H120.60220.92780.18320.073*
C131.2710 (3)0.7712 (3)0.1076 (2)0.0642 (6)
C5−0.1155 (4)0.7817 (3)0.7179 (2)0.0717 (7)
H5−0.24630.82850.70150.086*
N21.4213 (3)0.7615 (3)0.04740 (19)0.0934 (8)
C4−0.0823 (4)0.7023 (3)0.8254 (2)0.0762 (7)
H4−0.19130.69790.88210.091*
C30.1099 (4)0.6302 (3)0.8492 (2)0.0719 (7)
H30.13250.57470.92150.086*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0597 (9)0.0992 (12)0.0555 (10)−0.0427 (9)−0.0132 (7)0.0230 (8)
O20.0527 (10)0.1130 (13)0.0769 (12)−0.0362 (9)−0.0181 (8)0.0305 (10)
N10.0573 (11)0.0652 (11)0.0517 (11)−0.0313 (9)−0.0058 (9)0.0008 (9)
C10.0536 (13)0.0467 (12)0.0467 (12)−0.0242 (10)−0.0075 (10)0.0021 (9)
C70.0512 (13)0.0548 (13)0.0512 (13)−0.0243 (11)−0.0099 (10)0.0070 (10)
C90.0539 (13)0.0739 (15)0.0575 (14)−0.0289 (11)−0.0175 (10)0.0124 (11)
C60.0581 (14)0.0697 (14)0.0572 (14)−0.0346 (12)−0.0131 (11)0.0046 (11)
C110.0569 (13)0.0664 (14)0.0519 (13)−0.0292 (11)−0.0132 (11)0.0130 (11)
C80.0659 (15)0.0683 (14)0.0488 (13)−0.0324 (12)−0.0110 (11)0.0088 (11)
C100.0488 (12)0.0512 (12)0.0515 (12)−0.0253 (10)−0.0071 (9)0.0027 (9)
C20.0623 (14)0.0644 (14)0.0547 (14)−0.0273 (11)−0.0117 (11)0.0074 (11)
C120.0519 (12)0.0753 (15)0.0570 (14)−0.0292 (11)−0.0147 (10)0.0096 (11)
C130.0540 (14)0.0720 (15)0.0629 (15)−0.0271 (12)−0.0123 (12)0.0101 (11)
C50.0562 (14)0.0832 (17)0.0800 (18)−0.0386 (13)−0.0056 (13)−0.0037 (13)
N20.0625 (13)0.126 (2)0.0867 (17)−0.0462 (14)−0.0044 (12)0.0156 (14)
C40.0825 (18)0.0744 (16)0.0691 (17)−0.0466 (15)0.0151 (14)−0.0085 (13)
C30.0852 (18)0.0718 (16)0.0497 (14)−0.0353 (14)−0.0008 (13)0.0068 (11)

Geometric parameters (Å, °)

O1—C71.313 (2)C11—C101.376 (3)
O1—H10.9025C11—H110.9300
O2—C71.205 (2)C8—H80.9300
N1—C121.325 (3)C10—C131.446 (3)
N1—C81.326 (3)C2—C31.384 (3)
C1—C61.377 (3)C2—H20.9300
C1—C21.383 (3)C12—H120.9300
C1—C71.488 (3)C13—N21.144 (3)
C9—C81.373 (3)C5—C41.375 (3)
C9—C101.375 (3)C5—H50.9300
C9—H90.9300C4—C31.363 (3)
C6—C51.388 (3)C4—H40.9300
C6—H60.9300C3—H30.9300
C11—C121.368 (3)
C7—O1—H1110.0C9—C10—C11119.40 (19)
C12—N1—C8117.62 (18)C9—C10—C13120.88 (19)
C6—C1—C2119.62 (19)C11—C10—C13119.72 (19)
C6—C1—C7121.69 (18)C1—C2—C3120.2 (2)
C2—C1—C7118.69 (18)C1—C2—H2119.9
O2—C7—O1123.03 (18)C3—C2—H2119.9
O2—C7—C1122.61 (18)N1—C12—C11123.1 (2)
O1—C7—C1114.36 (18)N1—C12—H12118.4
C8—C9—C10117.7 (2)C11—C12—H12118.4
C8—C9—H9121.2N2—C13—C10179.1 (3)
C10—C9—H9121.2C4—C5—C6120.2 (2)
C1—C6—C5119.7 (2)C4—C5—H5119.9
C1—C6—H6120.2C6—C5—H5119.9
C5—C6—H6120.2C3—C4—C5120.2 (2)
C12—C11—C10118.44 (19)C3—C4—H4119.9
C12—C11—H11120.8C5—C4—H4119.9
C10—C11—H11120.8C4—C3—C2120.0 (2)
N1—C8—C9123.7 (2)C4—C3—H3120.0
N1—C8—H8118.2C2—C3—H3120.0
C9—C8—H8118.2

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···N10.901.832.726 (2)176
C8—H8···O20.932.533.222 (3)131

Table 2 π–π interactions (Å, °)

Cg1 is the centroid of C1–C6 and Cg2 is the centroid of N1–C12.

Centroid–centroidPlane–planeOffset
Cg1—- Cg2i3.833.5223.2
Cg1—-Cg2ii3.913.5923.3

Symmetry codes: (i) 1-x, 1-y, 1-z; (ii) 1-x, 2-y, 1-z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DN2532).

References

  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl.34, 1555–1573.
  • Chen, L. Z., Zhao, H., Ge, J. Z., Xiong, R. G. & Hu, H. W. (2009). Cryst. Growth Des.9, 3828–3831.
  • Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. [PubMed]
  • Fu, D.-W. & Xiong, R.-G. (2008). Dalton Trans.30, pp. 3946–3948. [PubMed]
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography