Isonicotinonitrile–benzoic acid (1/1)

Cui, L.-J.; Chen, X.-Y.

doi:10.1107/S1600536810003442

organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o722

doi:10.1107/S1600536810003442

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Isonicotinonitrile–benzoic acid (1/1)

Li-Jing Cui ^a ^* and Xin-Yuan Chen ^a

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: fudavid88@yahoo.com.cn

(Received 21 January 2010; accepted 28 January 2010; online 27 February 2010)

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 R₂²(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 ); Fu et al. (2008 ). For hydrogen-bonding motifs, see: Bernstein et al. (1995 ); Etter et al. (1990 ).

Experimental

Crystal data

C₆H₄N₂·C₇H₆O₂
M_r = 226.23
Triclinic, $[P \overline 1]$
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 ) 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[F² > 2σ(F²)] = 0.059
wR(F²) = 0.154
S = 0.96
2646 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.14 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	0.90	1.83	2.726 (2)	176
C8—H8⋯O2	0.93	2.53	3.222 (3)	131

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	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.

Isonicotinonitrile–benzoic acid (1/1) top

Crystal data top

C₆H₄N₂·C₇H₆O₂	Z = 2
M_r = 226.23	F(000) = 236
Triclinic, P1	D_x = 1.296 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4274 (15) Å	Cell parameters from 1346 reflections
b = 7.7389 (15) Å	θ = 3.2–27.5°
c = 11.668 (2) Å	µ = 0.09 mm⁻¹
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 top

Rigaku Mercury2 diffractometer	2646 independent reflections
Radiation source: fine-focus sealed tube	1346 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ω scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
T_min = 0.881, T_max = 0.940	l = −15→15
6025 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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.154	H-atom parameters constrained
S = 0.96	w = 1/[σ²(F_o²) + (0.0699P)²] where P = (F_o² + 2F_c²)/3
2646 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₆H₄N₂·C₇H₆O₂	γ = 62.79 (2)°
M_r = 226.23	V = 579.6 (2) Å³
Triclinic, P1	Z = 2
a = 7.4274 (15) Å	Mo Kα radiation
b = 7.7389 (15) Å	µ = 0.09 mm⁻¹
c = 11.668 (2) Å	T = 298 K
α = 85.26 (3)°	0.4 × 0.35 × 0.2 mm
β = 76.44 (3)°

Data collection top

Rigaku Mercury2 diffractometer	2646 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1346 reflections with I > 2σ(I)
T_min = 0.881, T_max = 0.940	R_int = 0.042
6025 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.154	H-atom parameters constrained
S = 0.96	Δρ_max = 0.14 e Å⁻³
2646 reflections	Δρ_min = −0.18 e Å⁻³
154 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 > 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) top

	x	y	z	U_iso*/U_eq
O1	0.3710 (2)	0.8106 (2)	0.47118 (13)	0.0701 (5)
H1	0.4865	0.8033	0.4202	0.105*
O2	0.5897 (2)	0.6595 (2)	0.58797 (14)	0.0824 (5)
N1	0.7138 (3)	0.8082 (2)	0.32068 (15)	0.0578 (5)
C1	0.2396 (3)	0.7201 (3)	0.65759 (17)	0.0491 (5)
C7	0.4176 (3)	0.7263 (3)	0.56976 (18)	0.0529 (5)
C9	1.0739 (3)	0.7156 (3)	0.29472 (19)	0.0615 (6)
H9	1.1922	0.6611	0.3257	0.074*
C6	0.0455 (3)	0.7920 (3)	0.63365 (19)	0.0595 (6)
H6	0.0224	0.8473	0.5614	0.071*
C11	0.9010 (3)	0.8656 (3)	0.13992 (18)	0.0584 (6)
H11	0.9012	0.9140	0.0643	0.070*
C8	0.8875 (3)	0.7304 (3)	0.35995 (18)	0.0610 (6)
H8	0.8827	0.6831	0.4359	0.073*
C10	1.0797 (3)	0.7841 (3)	0.18209 (18)	0.0503 (5)
C2	0.2716 (3)	0.6398 (3)	0.76576 (18)	0.0616 (6)
H2	0.4022	0.5920	0.7825	0.074*
C12	0.7228 (3)	0.8737 (3)	0.21192 (19)	0.0612 (6)
H12	0.6022	0.9278	0.1832	0.073*
C13	1.2710 (3)	0.7712 (3)	0.1076 (2)	0.0642 (6)
C5	−0.1155 (4)	0.7817 (3)	0.7179 (2)	0.0717 (7)
H5	−0.2463	0.8285	0.7015	0.086*
N2	1.4213 (3)	0.7615 (3)	0.04740 (19)	0.0934 (8)
C4	−0.0823 (4)	0.7023 (3)	0.8254 (2)	0.0762 (7)
H4	−0.1913	0.6979	0.8821	0.091*
C3	0.1099 (4)	0.6302 (3)	0.8492 (2)	0.0719 (7)
H3	0.1325	0.5747	0.9215	0.086*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0597 (9)	0.0992 (12)	0.0555 (10)	−0.0427 (9)	−0.0132 (7)	0.0230 (8)
O2	0.0527 (10)	0.1130 (13)	0.0769 (12)	−0.0362 (9)	−0.0181 (8)	0.0305 (10)
N1	0.0573 (11)	0.0652 (11)	0.0517 (11)	−0.0313 (9)	−0.0058 (9)	0.0008 (9)
C1	0.0536 (13)	0.0467 (12)	0.0467 (12)	−0.0242 (10)	−0.0075 (10)	0.0021 (9)
C7	0.0512 (13)	0.0548 (13)	0.0512 (13)	−0.0243 (11)	−0.0099 (10)	0.0070 (10)
C9	0.0539 (13)	0.0739 (15)	0.0575 (14)	−0.0289 (11)	−0.0175 (10)	0.0124 (11)
C6	0.0581 (14)	0.0697 (14)	0.0572 (14)	−0.0346 (12)	−0.0131 (11)	0.0046 (11)
C11	0.0569 (13)	0.0664 (14)	0.0519 (13)	−0.0292 (11)	−0.0132 (11)	0.0130 (11)
C8	0.0659 (15)	0.0683 (14)	0.0488 (13)	−0.0324 (12)	−0.0110 (11)	0.0088 (11)
C10	0.0488 (12)	0.0512 (12)	0.0515 (12)	−0.0253 (10)	−0.0071 (9)	0.0027 (9)
C2	0.0623 (14)	0.0644 (14)	0.0547 (14)	−0.0273 (11)	−0.0117 (11)	0.0074 (11)
C12	0.0519 (12)	0.0753 (15)	0.0570 (14)	−0.0292 (11)	−0.0147 (10)	0.0096 (11)
C13	0.0540 (14)	0.0720 (15)	0.0629 (15)	−0.0271 (12)	−0.0123 (12)	0.0101 (11)
C5	0.0562 (14)	0.0832 (17)	0.0800 (18)	−0.0386 (13)	−0.0056 (13)	−0.0037 (13)
N2	0.0625 (13)	0.126 (2)	0.0867 (17)	−0.0462 (14)	−0.0044 (12)	0.0156 (14)
C4	0.0825 (18)	0.0744 (16)	0.0691 (17)	−0.0466 (15)	0.0151 (14)	−0.0085 (13)
C3	0.0852 (18)	0.0718 (16)	0.0497 (14)	−0.0353 (14)	−0.0008 (13)	0.0068 (11)

Geometric parameters (Å, º) top

O1—C7	1.313 (2)	C11—C10	1.376 (3)
O1—H1	0.9025	C11—H11	0.9300
O2—C7	1.205 (2)	C8—H8	0.9300
N1—C12	1.325 (3)	C10—C13	1.446 (3)
N1—C8	1.326 (3)	C2—C3	1.384 (3)
C1—C6	1.377 (3)	C2—H2	0.9300
C1—C2	1.383 (3)	C12—H12	0.9300
C1—C7	1.488 (3)	C13—N2	1.144 (3)
C9—C8	1.373 (3)	C5—C4	1.375 (3)
C9—C10	1.375 (3)	C5—H5	0.9300
C9—H9	0.9300	C4—C3	1.363 (3)
C6—C5	1.388 (3)	C4—H4	0.9300
C6—H6	0.9300	C3—H3	0.9300
C11—C12	1.368 (3)

C7—O1—H1	110.0	C9—C10—C11	119.40 (19)
C12—N1—C8	117.62 (18)	C9—C10—C13	120.88 (19)
C6—C1—C2	119.62 (19)	C11—C10—C13	119.72 (19)
C6—C1—C7	121.69 (18)	C1—C2—C3	120.2 (2)
C2—C1—C7	118.69 (18)	C1—C2—H2	119.9
O2—C7—O1	123.03 (18)	C3—C2—H2	119.9
O2—C7—C1	122.61 (18)	N1—C12—C11	123.1 (2)
O1—C7—C1	114.36 (18)	N1—C12—H12	118.4
C8—C9—C10	117.7 (2)	C11—C12—H12	118.4
C8—C9—H9	121.2	N2—C13—C10	179.1 (3)
C10—C9—H9	121.2	C4—C5—C6	120.2 (2)
C1—C6—C5	119.7 (2)	C4—C5—H5	119.9
C1—C6—H6	120.2	C6—C5—H5	119.9
C5—C6—H6	120.2	C3—C4—C5	120.2 (2)
C12—C11—C10	118.44 (19)	C3—C4—H4	119.9
C12—C11—H11	120.8	C5—C4—H4	119.9
C10—C11—H11	120.8	C4—C3—C2	120.0 (2)
N1—C8—C9	123.7 (2)	C4—C3—H3	120.0
N1—C8—H8	118.2	C2—C3—H3	120.0
C9—C8—H8	118.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.90	1.83	2.726 (2)	176
C8—H8···O2	0.93	2.53	3.222 (3)	131

Experimental details

Crystal data
Chemical formula	C₆H₄N₂·C₇H₆O₂
M_r	226.23
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.4274 (15), 7.7389 (15), 11.668 (2)
α, β, γ (°)	85.26 (3), 76.44 (3), 62.79 (2)
V (Å³)	579.6 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.4 × 0.35 × 0.2

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.881, 0.940
No. of measured, independent and observed [I > 2σ(I)] reflections	6025, 2646, 1346
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.154, 0.96
No. of reflections	2646
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.18

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.90	1.83	2.726 (2)	175.5
C8—H8···O2	0.93	2.53	3.222 (3)	131.0

π–π interactions (Å, °) top

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

	Centroid–centroid	Plane–plane	Offset
Cg1—- Cg2ⁱ	3.83	3.52	23.2
Cg1—-Cg2ⁱⁱ	3.91	3.59	23.3

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

Acknowledgements

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

References

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