Isonicotinonitrile–4-methyl­benzoic acid (1/1)

Cai, X.-W.; Lu, H.-F.

doi:10.1107/S1600536811019799

organic compounds

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Volume 67| Part 6| June 2011| Page o1555

doi:10.1107/S1600536811019799

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Isonicotinonitrile–4-methylbenzoic acid (1/1)

Xing-Wei Cai ^a ^* and Hong-Fei Lu ^a

^aSchool of Biological and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang, Jiangsu 212003, People's Republic of China
^*Correspondence e-mail: cxwchem@yahoo.com.cn

(Received 16 May 2011; accepted 25 May 2011; online 28 May 2011)

The title structure, C₆H₄N₂·C₈H₈O₂, is built up from an assembly of isonicotinonitrile and 4-methylbenzoic acid molecules and may be regarded as a co-crystal. The two planar molecules [r.m.s. deviations of 0.002 (6) and 0.0028 (11) Å, respectively] are linked by O—H⋯N and C—H⋯O hydrogen bonds. They are nearly coplanar and only twisted from each other by a dihedral angle of 2.48 (6)°. In the crystal, the components are interconnected by slipped π–π stacking [centroid–centroid distance = 3.6797 (11), slippage = 1.304 Å] and intermolecular C—H⋯N interactions.

Related literature

For the structures of related derivatives, see: Fu et al. (2009 ); Aminabhavi et al. (1986 ); Dai & Fu (2008a ,b ). For the graph-set theory, see: Etter et al. (1990 ); Bernstein et al. (1995 ).

Experimental

Crystal data

C₆H₄N₂·C₈H₈O₂
M_r = 240.26
Monoclinic, C 2/c
a = 7.5368 (15) Å
b = 13.049 (3) Å
c = 24.749 (5) Å
β = 94.20 (3)°
V = 2427.5 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.40 × 0.30 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.89, T_max = 1.00
11659 measured reflections
2752 independent reflections
2416 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.124
S = 1.09
2752 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.87	2.6850 (15)	175
C1—H1A⋯O2	0.93	2.51	3.1858 (18)	130
C4—H4A⋯N2ⁱ	0.93	2.60	3.3700 (18)	141
Symmetry code: (i) $[-x, y, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811019799/dn2689sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811019799/dn2689Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811019799/dn2689Isup3.cml

checkCIF report

Comment top

The amino derivatives have found wide range of applications in material science, such as magnetic, fluorescent and dielectric behaviors. And there has been an increased interest in the preparation of amino co-crystal compounds (Aminabhavi et al., 1986; Dai & Fu 2008a; Dai & Fu 2008b; Fu, et al. 2009). As an extension on the structural characterization, we report here the crystal structure of the title compound isonicotinonitrile 4-methylbenzoic acid.

The asymmetric unit contains an organic isonicotinonitrile molecule and a 4-methylbenzoic acid organic molecule which are linked by a strong O—H···N and a weak C-H···O hydrogen bonds forming a C22(7) ring ( Etter et al., 1990; Bernstein et al., 1995)(Fig. 1). The benzene and pyridine rings are nearly coplanar and only twisted from each other by a dihedral angle of 2.48 (6)°. The geometric parameters of both the organic molecules are within the normal range.

There are intramolecular C-H···N hydrogen bonds and slippest π-π stacking which stabilize the packing (Tab.1 & 2).

Related literature top

For the structures of related derivatives, see: Fu et al. (2009); Aminabhavi et al. (1986); Dai & Fu (2008a,b). For the graph-set theory, see: Etter et al. (1990); Bernstein et al. (1995).

Experimental top

isonicotinonitrile and 4-methylbenzoic acid were obtained commercially from Alfa Aesar. The two organoc compounds were solved in the solution (ethanol/water). Colourless block-shaped crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol/water (2:1 v/v) solution.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A view of the asymmetric unit with the atomic numbering scheme. The displacement ellipsoids were drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii and the H bonds are shown as dashed lines.

Isonicotinonitrile–4-methylbenzoic acid (1/1) top

Crystal data top

C₆H₄N₂·C₈H₈O₂	F(000) = 1008
M_r = 240.26	D_x = 1.315 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3221 reflections
a = 7.5368 (15) Å	θ = 3.1–27.5°
b = 13.049 (3) Å	µ = 0.09 mm⁻¹
c = 24.749 (5) Å	T = 298 K
β = 94.20 (3)°	Block, colourless
V = 2427.5 (8) Å³	0.40 × 0.30 × 0.20 mm
Z = 8

Data collection top

Rigaku Mercury2 diffractometer	2752 independent reflections
Radiation source: fine-focus sealed tube	2416 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 1.7°
profile data from ϕ scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −16→16
T_min = 0.89, T_max = 1.00	l = −32→32
11659 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0713P)² + 0.8361P] where P = (F_o² + 2F_c²)/3
2752 reflections	(Δ/σ)_max = 0.001
165 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₆H₄N₂·C₈H₈O₂	V = 2427.5 (8) Å³
M_r = 240.26	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 7.5368 (15) Å	µ = 0.09 mm⁻¹
b = 13.049 (3) Å	T = 298 K
c = 24.749 (5) Å	0.40 × 0.30 × 0.20 mm
β = 94.20 (3)°

Data collection top

Rigaku Mercury2 diffractometer	2752 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2416 reflections with I > 2σ(I)
T_min = 0.89, T_max = 1.00	R_int = 0.033
11659 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.124	H-atom parameters constrained
S = 1.09	Δρ_max = 0.28 e Å⁻³
2752 reflections	Δρ_min = −0.18 e Å⁻³
165 parameters

Special details top

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 > 2sigma(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) top

	x	y	z	U_iso*/U_eq
N1	0.43937 (13)	0.09948 (8)	0.42051 (4)	0.0221 (2)
N2	−0.17678 (14)	0.10802 (9)	0.29801 (4)	0.0277 (3)
C1	0.28921 (16)	0.13083 (9)	0.44087 (5)	0.0230 (3)
H1A	0.2943	0.1523	0.4768	0.028*
C2	0.12616 (16)	0.13288 (9)	0.41101 (5)	0.0234 (3)
H2A	0.0238	0.1547	0.4264	0.028*
C3	0.12108 (15)	0.10120 (8)	0.35729 (5)	0.0197 (3)
C4	0.27629 (16)	0.06891 (10)	0.33537 (5)	0.0246 (3)
H4A	0.2754	0.0473	0.2995	0.030*
C5	0.43222 (16)	0.06995 (10)	0.36861 (5)	0.0256 (3)
H5A	0.5369	0.0491	0.3542	0.031*
C6	−0.04509 (16)	0.10367 (9)	0.32417 (5)	0.0224 (3)
O1	0.73800 (11)	0.10321 (7)	0.48667 (3)	0.0269 (2)
H1	0.6481	0.1058	0.4659	0.040*
O2	0.55361 (11)	0.16298 (7)	0.54594 (4)	0.0289 (2)
C7	1.30335 (18)	0.15462 (10)	0.69515 (5)	0.0299 (3)
H7A	1.4122	0.1618	0.6776	0.045*
H7B	1.3066	0.0923	0.7158	0.045*
H7C	1.2898	0.2118	0.7189	0.045*
C8	1.14836 (17)	0.15140 (9)	0.65291 (5)	0.0234 (3)
C9	1.16972 (16)	0.11425 (9)	0.60095 (5)	0.0244 (3)
H9A	1.2815	0.0926	0.5920	0.029*
C10	1.02690 (16)	0.10904 (9)	0.56240 (5)	0.0227 (3)
H10A	1.0432	0.0835	0.5280	0.027*
C11	0.85908 (15)	0.14193 (8)	0.57500 (5)	0.0195 (3)
C12	0.83696 (17)	0.17952 (9)	0.62657 (5)	0.0248 (3)
H12A	0.7254	0.2016	0.6354	0.030*
C13	0.98023 (18)	0.18425 (10)	0.66492 (5)	0.0272 (3)
H13A	0.9636	0.2098	0.6993	0.033*
C14	0.70140 (15)	0.13749 (9)	0.53480 (5)	0.0203 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0212 (5)	0.0233 (5)	0.0215 (5)	−0.0027 (4)	0.0000 (4)	0.0016 (4)
N2	0.0229 (5)	0.0348 (6)	0.0251 (5)	0.0010 (4)	−0.0008 (4)	−0.0017 (4)
C1	0.0243 (6)	0.0241 (6)	0.0205 (5)	−0.0011 (4)	0.0001 (4)	−0.0021 (4)
C2	0.0216 (6)	0.0256 (6)	0.0229 (6)	0.0004 (4)	0.0010 (4)	−0.0021 (4)
C3	0.0201 (6)	0.0174 (5)	0.0212 (6)	−0.0025 (4)	−0.0009 (4)	0.0014 (4)
C4	0.0252 (6)	0.0292 (6)	0.0194 (5)	0.0010 (5)	0.0008 (4)	−0.0019 (4)
C5	0.0205 (6)	0.0330 (7)	0.0234 (6)	0.0017 (5)	0.0027 (4)	0.0007 (5)
C6	0.0233 (6)	0.0231 (6)	0.0210 (5)	−0.0005 (4)	0.0020 (5)	−0.0015 (4)
O1	0.0188 (4)	0.0422 (5)	0.0194 (4)	0.0009 (4)	−0.0011 (3)	−0.0046 (4)
O2	0.0200 (5)	0.0370 (5)	0.0295 (5)	0.0029 (4)	0.0000 (3)	−0.0074 (4)
C7	0.0301 (7)	0.0302 (7)	0.0279 (6)	−0.0046 (5)	−0.0085 (5)	0.0007 (5)
C8	0.0263 (6)	0.0208 (6)	0.0223 (6)	−0.0048 (4)	−0.0037 (5)	0.0030 (4)
C9	0.0196 (6)	0.0288 (6)	0.0249 (6)	−0.0008 (4)	0.0015 (4)	0.0019 (5)
C10	0.0217 (6)	0.0275 (6)	0.0189 (5)	−0.0023 (5)	0.0019 (4)	−0.0001 (4)
C11	0.0208 (6)	0.0177 (5)	0.0198 (5)	−0.0027 (4)	0.0009 (4)	0.0010 (4)
C12	0.0234 (6)	0.0259 (6)	0.0253 (6)	0.0006 (5)	0.0024 (5)	−0.0032 (5)
C13	0.0320 (7)	0.0289 (6)	0.0205 (5)	−0.0012 (5)	−0.0002 (5)	−0.0044 (5)
C14	0.0205 (6)	0.0186 (5)	0.0220 (6)	−0.0024 (4)	0.0018 (4)	0.0003 (4)

Geometric parameters (Å, º) top

N1—C1	1.3362 (16)	C7—C8	1.5100 (17)
N1—C5	1.3384 (16)	C7—H7A	0.9600
N2—C6	1.1461 (16)	C7—H7B	0.9600
C1—C2	1.3871 (17)	C7—H7C	0.9600
C1—H1A	0.9300	C8—C13	1.3903 (18)
C2—C3	1.3903 (16)	C8—C9	1.3946 (17)
C2—H2A	0.9300	C9—C10	1.3866 (17)
C3—C4	1.3903 (17)	C9—H9A	0.9300
C3—C6	1.4459 (17)	C10—C11	1.3925 (17)
C4—C5	1.3844 (17)	C10—H10A	0.9300
C4—H4A	0.9300	C11—C12	1.3886 (16)
C5—H5A	0.9300	C11—C14	1.4942 (16)
O1—C14	1.3202 (14)	C12—C13	1.3858 (18)
O1—H1	0.8200	C12—H12A	0.9300
O2—C14	1.2134 (15)	C13—H13A	0.9300

C1—N1—C5	118.32 (10)	H7B—C7—H7C	109.5
N1—C1—C2	123.14 (11)	C13—C8—C9	118.23 (11)
N1—C1—H1A	118.4	C13—C8—C7	120.95 (11)
C2—C1—H1A	118.4	C9—C8—C7	120.82 (11)
C1—C2—C3	117.72 (11)	C10—C9—C8	121.01 (11)
C1—C2—H2A	121.1	C10—C9—H9A	119.5
C3—C2—H2A	121.1	C8—C9—H9A	119.5
C4—C3—C2	119.88 (11)	C9—C10—C11	120.19 (11)
C4—C3—C6	120.28 (10)	C9—C10—H10A	119.9
C2—C3—C6	119.83 (11)	C11—C10—H10A	119.9
C5—C4—C3	117.85 (11)	C12—C11—C10	119.13 (11)
C5—C4—H4A	121.1	C12—C11—C14	118.85 (11)
C3—C4—H4A	121.1	C10—C11—C14	122.01 (10)
N1—C5—C4	123.09 (11)	C13—C12—C11	120.35 (11)
N1—C5—H5A	118.5	C13—C12—H12A	119.8
C4—C5—H5A	118.5	C11—C12—H12A	119.8
N2—C6—C3	178.44 (13)	C12—C13—C8	121.09 (11)
C14—O1—H1	109.5	C12—C13—H13A	119.5
C8—C7—H7A	109.5	C8—C13—H13A	119.5
C8—C7—H7B	109.5	O2—C14—O1	123.63 (11)
H7A—C7—H7B	109.5	O2—C14—C11	122.45 (10)
C8—C7—H7C	109.5	O1—C14—C11	113.91 (10)
H7A—C7—H7C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.87	2.6850 (15)	175
C1—H1A···O2	0.93	2.51	3.1858 (18)	130
C4—H4A···N2ⁱ	0.93	2.60	3.3700 (18)	141

Symmetry code: (i) −x, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₆H₄N₂·C₈H₈O₂
M_r	240.26
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	7.5368 (15), 13.049 (3), 24.749 (5)
β (°)	94.20 (3)
V (Å³)	2427.5 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.89, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	11659, 2752, 2416
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.124, 1.09
No. of reflections	2752
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.18

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.87	2.6850 (15)	175
C1—H1A···O2	0.93	2.51	3.1858 (18)	130
C4—H4A···N2ⁱ	0.93	2.60	3.3700 (18)	141

Symmetry code: (i) −x, y, −z+1/2.

Table 2 π-π stacking interactions (Å,°) top

Cg1 is the centroid of the C8—C13 ring.

Cg2 is the centroid of the N1—C5 ring

CgI	CgJ	CgI···CgJ^a	CgI···P(J)^b	CgJ···P(I)^c	Slippage
Cg1	Cg2ⁱⁱ	3.6797 (11)	3.440	3.443	1.304

Symmetry codes: (ii)3/2-x,1/2-y,1-z Notes:

a : Distance between centroids

b : Perpendicular distance of CgI on ring plan J

c : Perpendicular distance of CgJ on ring plan I

Slippage = vertical displacement between ring centroids.

Acknowledgements

This work was supported by a start-up grant from Jiangsu University of Science and Technology, China.

References

Aminabhavi, T. M., Biradar, N. S. & Patil, S. B. (1986). Inorg. Chim. Acta, 125, 125–128. CrossRef CAS Web of Science Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Dai, W. & Fu, D.-W. (2008a). Acta Cryst. E64, m1016. Web of Science CSD CrossRef IUCr Journals Google Scholar
Dai, W. & Fu, D.-W. (2008b). Acta Cryst. E64, m1017. Web of Science CSD CrossRef IUCr Journals Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef CAS Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Fu, D.-W., Ge, J.-Z., Dai, J., Ye, H.-Y. & Qu, Z.-R. (2009). Inorg. Chem. Commun. 12, 994-997. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar