3-(2-Oxo-2H-pyridin-1-yl)phthalonitrile

In the title compound, C₁₃H₇N₃O, the dihedral angle between the pyridine and the benzene ring is 65.94 (7)°. In the crystal structure, mol­ecules are linked by a pair of C—H...N hydrogen bonds into a centrosymmetric dimer.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.040
• wR factor = 0.100
• Data-to-parameter ratio = 15.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) .        600 Ang.
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C8     -   C13     ..       5.99 su
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C7     -   C12    ...       1.44 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C8     -   C13    ...       1.44 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Substituted phthalonitriles have been used as starting materials for phthalocyanines. Phthalocyanines and metallophthalocyanines have been investigated for many years because of their wide range of applications, including use in chemical sensors, electrochromism, batteries, semiconductor materials,liquid crystals, Langmuir- Blodgett films and non-linear optics (Leznoff & Lever, 1989–1996; Huang et al., 2005; Huang et al., 2006). We report here the crystal structure of the title compound, (I).

The molecular structure of (I) is shown in Fig. 1. The benzene ring of the phthalonitrile group and the pyridinone ring make a dihedral angle of 65.94 (7)°. The C≡N bond distances [N2≡C12 = 1.1380 (12) Å and N3≡ C13 = 1.1352 (19) Å] compare well with values reported in the literature (Subbiah Pandi et al., 2002; Yu et al., 2005, 2006). As expected, the N≡C—C angles [N2≡C12—C7 176.84 (16)° and N3≡ C13—C8 179.40 (17)°] are linear.

In the crystal structure, the molecules are linked by a pair of C—H···N hydrogen bonds into a centrosymmetric dimer (Table 1).

Related literature

For related literature, see: Leznoff & Lever (1989–1996); Subbiah Pandi et al. (2002); Yu et al. (2006).

S2. Experimental

3-Nitrophthalonitrile (0.87 g, 5 mmol) and 2-pyridone (0.42 g, 5 mmol) were heated at 353 K in dry DMSO (10 ml) under argon atmosphere. After stirring for about 20 min, dry fine-powderd potassium carbonate (1.4 g, 10 mmol) was added portionwise over 2 h with vigorous stirring. The reaction was stirred for 6 h at 353 K, and ffter cooling, poured into ice-water (100 g). The reaction mixture was filtered off and washed with water until the filtrate was neutral. Recrystallization from ethanol gave a light yellow product (yield 10%). Single crystals of (I) were obtained from absolute ethanol at room temperature by slow evaporation (m.p.503–504 K).

S3. Refinement

H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: TEXRAY (Molecular Structure Corporation, 1999); cell refinement: TEXRAY; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2004); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level

3-(2-Oxo-2H-pyridin-1-yl)phthalonitrile

Crystal data

C13H7N3O	F(000) = 456
Mr = 221.22	Dx = 1.382 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3144 reflections
a = 8.132 (6) Å	θ = 12–27.5°
b = 11.739 (6) Å	µ = 0.09 mm^−1
c = 11.224 (6) Å	T = 173 K
β = 97.21 (3)°	Plate, colourless
V = 1063.0 (11) Å^3	0.50 × 0.10 × 0.05 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	1736 reflections with I > 2σ(I)
Radiation source: rotor target	Rint = 0.040
Graphite monochromator	θmax = 27.5°, θmin = 3.1°
ω scans	h = −10→10
10183 measured reflections	k = −15→15
2438 independent reflections	l = −14→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.039P)^2 + 0.0958P] where P = (Fo^2 + 2Fc^2)/3
2438 reflections	(Δ/σ)max = 0.001
154 parameters	Δρmax = 0.17 e Å^−3
0 restraints	Δρmin = −0.16 e Å^−3

Special details

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

	x	y	z	Uiso*/Ueq
O1	0.31247 (16)	0.12379 (10)	0.34925 (9)	0.0625 (4)
N1	0.49154 (14)	0.27336 (9)	0.37337 (9)	0.0351 (3)
N2	0.71257 (19)	0.03731 (12)	0.26652 (12)	0.0597 (4)
N3	0.64943 (19)	0.07514 (12)	−0.08270 (12)	0.0636 (4)
C1	0.40276 (18)	0.18427 (11)	0.41863 (12)	0.0415 (3)
C2	0.4276 (2)	0.17428 (13)	0.54678 (12)	0.0494 (4)
H2A	0.3771	0.1130	0.5838	0.059*
C3	0.5210 (2)	0.24964 (15)	0.61644 (12)	0.0518 (4)
H3A	0.5337	0.2407	0.7012	0.062*
C4	0.5996 (2)	0.34088 (13)	0.56606 (13)	0.0495 (4)
H4A	0.6630	0.3946	0.6158	0.059*
C5	0.58317 (18)	0.35060 (12)	0.44602 (12)	0.0426 (3)
H5A	0.6358	0.4120	0.4106	0.051*
C6	0.47567 (16)	0.28870 (10)	0.24546 (11)	0.0340 (3)
C7	0.54359 (16)	0.20828 (10)	0.17489 (11)	0.0334 (3)
C8	0.52876 (16)	0.22445 (11)	0.05010 (11)	0.0363 (3)
C9	0.45006 (18)	0.32051 (12)	−0.00116 (12)	0.0437 (3)
H9A	0.4418	0.3321	−0.0855	0.052*
C10	0.38409 (19)	0.39884 (12)	0.07032 (13)	0.0459 (4)
H10A	0.3298	0.4645	0.0349	0.055*
C11	0.39565 (18)	0.38340 (11)	0.19317 (12)	0.0410 (3)
H11A	0.3486	0.4379	0.2416	0.049*
C12	0.63438 (18)	0.11190 (11)	0.22724 (11)	0.0396 (3)
C13	0.59691 (19)	0.14098 (12)	−0.02375 (12)	0.0426 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0785 (9)	0.0619 (7)	0.0466 (6)	−0.0349 (6)	0.0061 (6)	−0.0005 (5)
N1	0.0397 (7)	0.0339 (5)	0.0324 (5)	−0.0030 (5)	0.0072 (4)	−0.0011 (5)
N2	0.0674 (10)	0.0559 (8)	0.0550 (8)	0.0180 (7)	0.0040 (7)	0.0084 (7)
N3	0.0749 (11)	0.0649 (9)	0.0555 (8)	0.0055 (8)	0.0254 (7)	−0.0114 (7)
C1	0.0472 (9)	0.0402 (7)	0.0379 (7)	−0.0059 (6)	0.0087 (6)	0.0024 (6)
C2	0.0562 (10)	0.0537 (9)	0.0397 (7)	−0.0022 (7)	0.0110 (7)	0.0098 (7)
C3	0.0536 (10)	0.0686 (10)	0.0327 (6)	0.0110 (8)	0.0041 (6)	0.0010 (7)
C4	0.0503 (10)	0.0533 (9)	0.0433 (8)	0.0001 (7)	−0.0001 (6)	−0.0125 (7)
C5	0.0423 (8)	0.0381 (7)	0.0474 (8)	−0.0035 (6)	0.0058 (6)	−0.0064 (6)
C6	0.0360 (7)	0.0336 (7)	0.0331 (6)	−0.0043 (5)	0.0074 (5)	0.0013 (5)
C7	0.0330 (7)	0.0336 (6)	0.0340 (6)	−0.0019 (5)	0.0055 (5)	0.0026 (5)
C8	0.0346 (7)	0.0402 (7)	0.0353 (6)	−0.0014 (5)	0.0090 (5)	0.0005 (6)
C9	0.0473 (9)	0.0492 (8)	0.0354 (7)	0.0027 (7)	0.0086 (6)	0.0099 (6)
C10	0.0500 (9)	0.0405 (7)	0.0483 (8)	0.0078 (6)	0.0102 (6)	0.0127 (6)
C11	0.0451 (9)	0.0343 (7)	0.0458 (7)	0.0028 (6)	0.0137 (6)	0.0016 (6)
C12	0.0442 (9)	0.0402 (7)	0.0347 (7)	0.0033 (6)	0.0056 (6)	−0.0012 (6)
C13	0.0462 (9)	0.0494 (8)	0.0337 (7)	−0.0003 (7)	0.0108 (6)	0.0024 (6)

Geometric parameters (Å, º)

O1—C1	1.2272 (17)	C5—H5A	0.95
N1—C5	1.3747 (17)	C6—C11	1.3813 (19)
N1—C1	1.4019 (18)	C6—C7	1.3905 (18)
N1—C6	1.4366 (17)	C7—C8	1.4036 (18)
N2—C12	1.1380 (18)	C7—C12	1.4358 (19)
N3—C13	1.1352 (19)	C8—C9	1.386 (2)
C1—C2	1.432 (2)	C8—C13	1.439 (2)
C2—C3	1.350 (2)	C9—C10	1.373 (2)
C2—H2A	0.95	C9—H9A	0.95
C3—C4	1.402 (2)	C10—C11	1.382 (2)
C3—H3A	0.95	C10—H10A	0.95
C4—C5	1.342 (2)	C11—H11A	0.95
C4—H4A	0.95
C5—N1—C1	122.86 (11)	C11—C6—N1	120.26 (11)
C5—N1—C6	118.96 (11)	C7—C6—N1	119.47 (11)
C1—N1—C6	118.03 (10)	C6—C7—C8	119.09 (12)
O1—C1—N1	119.74 (12)	C6—C7—C12	121.50 (11)
O1—C1—C2	126.01 (13)	C8—C7—C12	119.37 (11)
N1—C1—C2	114.25 (12)	C9—C8—C7	120.12 (12)
C3—C2—C1	121.78 (14)	C9—C8—C13	120.41 (12)
C3—C2—H2A	119.1	C7—C8—C13	119.46 (12)
C1—C2—H2A	119.1	C10—C9—C8	119.76 (13)
C2—C3—C4	121.25 (13)	C10—C9—H9A	120.1
C2—C3—H3A	119.4	C8—C9—H9A	120.1
C4—C3—H3A	119.4	C9—C10—C11	120.83 (13)
C5—C4—C3	118.48 (14)	C9—C10—H10A	119.6
C5—C4—H4A	120.8	C11—C10—H10A	119.6
C3—C4—H4A	120.8	C6—C11—C10	119.92 (13)
C4—C5—N1	121.18 (14)	C6—C11—H11A	120.0
C4—C5—H5A	119.4	C10—C11—H11A	120.0
N1—C5—H5A	119.4	N2—C12—C7	176.84 (16)
C11—C6—C7	120.26 (12)	N3—C13—C8	179.40 (17)
C5—N1—C1—O1	174.04 (14)	C11—C6—C7—C8	−0.36 (19)
C6—N1—C1—O1	−1.4 (2)	N1—C6—C7—C8	−179.45 (11)
C5—N1—C1—C2	−5.38 (19)	C11—C6—C7—C12	176.94 (13)
C6—N1—C1—C2	179.18 (12)	N1—C6—C7—C12	−2.14 (19)
O1—C1—C2—C3	−175.48 (16)	C6—C7—C8—C9	1.18 (19)
N1—C1—C2—C3	3.9 (2)	C12—C7—C8—C9	−176.18 (13)
C1—C2—C3—C4	−0.7 (2)	C6—C7—C8—C13	−179.26 (12)
C2—C3—C4—C5	−1.5 (2)	C12—C7—C8—C13	3.38 (19)
C3—C4—C5—N1	0.1 (2)	C7—C8—C9—C10	−1.1 (2)
C1—N1—C5—C4	3.6 (2)	C13—C8—C9—C10	179.32 (14)
C6—N1—C5—C4	179.00 (13)	C8—C9—C10—C11	0.2 (2)
C5—N1—C6—C11	−63.99 (18)	C7—C6—C11—C10	−0.5 (2)
C1—N1—C6—C11	111.63 (15)	N1—C6—C11—C10	178.57 (12)
C5—N1—C6—C7	115.10 (14)	C9—C10—C11—C6	0.6 (2)
C1—N1—C6—C7	−69.28 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···N2^i	0.95	2.60	3.530 (3)	165

Symmetry code: (i) −x+1, −y, −z+1.