4-Nitro­phthalo­nitrile

Abstract

In the title compound, C₈H₃N₃O₂ (systematic name: 4-nitro­benzene-1,2-dicarbo­nitrile), the nitro group is twisted out of the plane of the benzene ring to which it is attached [O—N—C_ring—C_ring torsion angle = 9.80 (13)°]. In the crystal packing, supra­molecular layers with a zigzag topology in the ac plane are sustained by C—H⋯N inter­actions.

Related literature  

For background to the synthesis of functional phthalocyanines, see: Chin et al. (2012 ▶). For a related structure, see: Lin et al. (2006 ▶). For the synthesis, see: Rasmussen et al. (1978 ▶).

Experimental  

Crystal data  

• C₈H₃N₃O₂

• M _r = 173.13

• Orthorhombic,

• a = 12.8642 (3) Å

• b = 9.2013 (2) Å

• c = 13.2578 (3) Å

• V = 1569.29 (6) ų

• Z = 8

• Cu Kα radiation

• μ = 0.94 mm⁻¹

• T = 100 K

• 0.35 × 0.30 × 0.25 mm

Data collection  

• Agilent SuperNova Dual diffractometer with an Atlas detector

• Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ▶) T _min = 0.626, T _max = 1.000

• 7104 measured reflections

• 1638 independent reflections

• 1556 reflections with I > 2σ(I)

• R _int = 0.016

Refinement  

• R[F ² > 2σ(F ²)] = 0.030

• wR(F ²) = 0.088

• S = 1.10

• 1638 reflections

• 130 parameters

• All H-atom parameters refined

• Δρ_max = 0.21 e Å⁻³

• Δρ_min = −0.24 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2013 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

CCDC reference: 987296

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯N3i	0.962 (14)	2.621 (14)	3.3880 (13)	136.9 (11)
C3—H3⋯N2ii	0.950 (14)	2.554 (14)	3.3955 (13)	147.8 (10)
C6—H6⋯N3iii	0.943 (13)	2.457 (13)	3.3412 (13)	156.1 (10)

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

1. Chemical context

As part of our on-going study of functional phthalocyanines, we have previously reported the synthesis and structure of 4-(prop-2-yn-1-yl­oxy)benzene-1,2-dicarbo­nitrile prepared from 4-nitro­phthalo­nitrile (Chin et al., 2012). We now report the structure of the latter.

2. Structural commentary

In the title compound (Fig. 1), the nitro group is slightly twisted out of the plane of the benzene ring to which it is attached as seen in the value of the O1—N1—C1—C6 torsion angle of 9.80 (13)°. A similar small twist was found in the structure of the most closely related compound in the literature, i.e. 4-bromo-5-nitro­phthalo­nitrile (Lin et al., 2006).

3. Supra­molecular features

Supra­molecular layers (Fig. 2) sustained by C—H···N inter­actions which form 22-membered {···NC₄N···HC₂H···NC₃H···NC₅H} synthons (Table 1) features in the crystal packing. The layers have a zigzag topolgy and extend parallel to the ac plane and stack along the b axis (Fig. 3).

5. Synthesis and crystallization

The title compound was prepared by a literature procedure (Rasmussen et al., 1978). Thio­nyl chloride (4.3 ml, 0.56 mmol) was added drop wise with stiring over 5 minutes to 4-nitro­phthalamide (2.83 g, 13.5 mmol) in dry DMF (10.4 ml, 0.20 mmol) at 263 to 258 K (salt-ice bath). After 4 h, the homogenous yellow solution was poured onto excess ice-water with vigorous stirring. The precipitate was vacuum filtered, washed with cold water and dried. Crystals for the X-ray study were grown from slow evaporation from its methanol solution. Yield = 1.92 g (68 %), M.pt: 408–413 K (lit. 413–415 K). IR (KBr) ν/cm^-1: 2924, 2241, 1610, 1587, 1538, 1463, 1356, 1297, 1076, 931, 855, 802, 745, 718.

6. Refinement

All hydrogen atoms were refined freely.

Figures

Fig. 1.

The molecular structure of the title compound showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level.

Fig. 2.

A view of the supramolecular layer in the title compound, sustained by C—H···N interactions shown as orange dashed lines.

Fig. 3.

A view of the unit-cell contents of the title compound in projection down the a axis. The C—H···N interactions are shown as orange dashed lines.

Crystal data

C8H3N3O2	F(000) = 704
Mr = 173.13	Dx = 1.466 Mg m−3
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4240 reflections
a = 12.8642 (3) Å	θ = 3.3–76.1°
b = 9.2013 (2) Å	µ = 0.94 mm−1
c = 13.2578 (3) Å	T = 100 K
V = 1569.29 (6) Å3	Prism, colourless
Z = 8	0.35 × 0.30 × 0.25 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector	1638 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	1556 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.016
Detector resolution: 10.4041 pixels mm-1	θmax = 76.3°, θmin = 6.7°
ω scan	h = −8→16
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −10→11
Tmin = 0.626, Tmax = 1.000	l = −16→16
7104 measured reflections

Refinement

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.088	All H-atom parameters refined
S = 1.10	w = 1/[σ2(Fo2) + (0.0522P)2 + 0.3777P] where P = (Fo2 + 2Fc2)/3
1638 reflections	(Δ/σ)max < 0.001
130 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.24 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	0.55783 (6)	0.56540 (8)	0.23140 (6)	0.0224 (2)
O2	0.41285 (6)	0.62811 (9)	0.16017 (6)	0.0284 (2)
N1	0.46305 (7)	0.56035 (9)	0.22296 (6)	0.0185 (2)
N2	0.49465 (7)	0.20831 (10)	0.59515 (7)	0.0245 (2)
N3	0.20184 (7)	0.10850 (10)	0.54001 (7)	0.0214 (2)
C1	0.40488 (7)	0.46610 (10)	0.29308 (7)	0.0159 (2)
C2	0.30038 (8)	0.44112 (11)	0.27448 (7)	0.0185 (2)
C3	0.24639 (7)	0.34933 (11)	0.33907 (7)	0.0183 (2)
C4	0.29752 (7)	0.28688 (10)	0.42094 (7)	0.0158 (2)
C5	0.40307 (7)	0.31687 (10)	0.43884 (7)	0.0152 (2)
C6	0.45807 (7)	0.40675 (10)	0.37365 (7)	0.0156 (2)
C7	0.45469 (7)	0.25464 (10)	0.52497 (7)	0.0176 (2)
C8	0.24319 (7)	0.18890 (10)	0.48760 (7)	0.0173 (2)
H2	0.2670 (11)	0.4827 (16)	0.2163 (10)	0.027 (3)*
H3	0.1745 (11)	0.3317 (13)	0.3282 (9)	0.020 (3)*
H6	0.5294 (10)	0.4254 (13)	0.3839 (9)	0.017 (3)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0156 (4)	0.0246 (4)	0.0271 (4)	−0.0022 (3)	0.0032 (3)	0.0031 (3)
O2	0.0248 (4)	0.0300 (4)	0.0304 (4)	−0.0019 (3)	−0.0029 (3)	0.0151 (3)
N1	0.0177 (4)	0.0174 (4)	0.0204 (4)	−0.0004 (3)	0.0013 (3)	0.0015 (3)
N2	0.0198 (4)	0.0303 (5)	0.0235 (5)	0.0001 (3)	−0.0016 (3)	0.0064 (4)
N3	0.0183 (4)	0.0241 (4)	0.0217 (4)	−0.0026 (3)	0.0008 (3)	0.0014 (3)
C1	0.0166 (5)	0.0145 (4)	0.0167 (5)	0.0002 (3)	0.0030 (3)	−0.0003 (3)
C2	0.0176 (5)	0.0204 (5)	0.0174 (5)	0.0014 (3)	−0.0017 (3)	0.0002 (4)
C3	0.0132 (5)	0.0219 (5)	0.0199 (5)	−0.0009 (3)	−0.0010 (3)	−0.0005 (4)
C4	0.0155 (4)	0.0152 (4)	0.0166 (4)	−0.0002 (3)	0.0021 (3)	−0.0022 (3)
C5	0.0152 (4)	0.0144 (4)	0.0159 (4)	0.0021 (3)	−0.0001 (3)	−0.0020 (3)
C6	0.0125 (4)	0.0153 (4)	0.0190 (5)	0.0005 (3)	0.0006 (3)	−0.0021 (4)
C7	0.0135 (4)	0.0185 (5)	0.0208 (5)	−0.0015 (3)	0.0019 (3)	0.0000 (4)
C8	0.0139 (4)	0.0196 (5)	0.0184 (4)	0.0002 (3)	−0.0014 (3)	−0.0023 (4)

Geometric parameters (Å, º)

O1—N1	1.2252 (12)	C2—H2	0.962 (14)
O2—N1	1.2243 (11)	C3—C4	1.3932 (13)
N1—C1	1.4752 (12)	C3—H3	0.949 (13)
N2—C7	1.1453 (13)	C4—C5	1.4057 (13)
N3—C8	1.1459 (13)	C4—C8	1.4431 (13)
C1—C6	1.3811 (14)	C5—C6	1.3898 (13)
C1—C2	1.3859 (14)	C5—C7	1.4397 (13)
C2—C3	1.3889 (14)	C6—H6	0.943 (13)
O2—N1—O1	124.59 (8)	C3—C4—C5	120.44 (9)
O2—N1—C1	117.40 (8)	C3—C4—C8	120.41 (8)
O1—N1—C1	118.01 (8)	C5—C4—C8	119.15 (8)
C6—C1—C2	123.54 (9)	C6—C5—C4	120.23 (9)
C6—C1—N1	117.94 (8)	C6—C5—C7	119.68 (8)
C2—C1—N1	118.52 (9)	C4—C5—C7	120.09 (8)
C1—C2—C3	118.44 (9)	C1—C6—C5	117.66 (9)
C1—C2—H2	120.7 (8)	C1—C6—H6	121.4 (8)
C3—C2—H2	120.8 (8)	C5—C6—H6	120.9 (8)
C2—C3—C4	119.67 (9)	N2—C7—C5	178.04 (11)
C2—C3—H3	119.8 (8)	N3—C8—C4	178.30 (10)
C4—C3—H3	120.5 (8)
O2—N1—C1—C6	−170.25 (9)	C3—C4—C5—C7	178.52 (9)
O1—N1—C1—C6	9.80 (13)	C8—C4—C5—C7	−2.37 (13)
O2—N1—C1—C2	10.12 (13)	C2—C1—C6—C5	0.25 (14)
O1—N1—C1—C2	−169.82 (9)	N1—C1—C6—C5	−179.36 (8)
C6—C1—C2—C3	−1.26 (15)	C4—C5—C6—C1	1.09 (14)
N1—C1—C2—C3	178.34 (8)	C7—C5—C6—C1	−178.85 (8)
C1—C2—C3—C4	0.91 (15)	C6—C5—C7—N2	96 (3)
C2—C3—C4—C5	0.38 (14)	C4—C5—C7—N2	−84 (3)
C2—C3—C4—C8	−178.71 (9)	C3—C4—C8—N3	122 (3)
C3—C4—C5—C6	−1.41 (14)	C5—C4—C8—N3	−57 (4)
C8—C4—C5—C6	177.69 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N3i	0.962 (14)	2.621 (14)	3.3880 (13)	136.9 (11)
C3—H3···N2ii	0.950 (14)	2.554 (14)	3.3955 (13)	147.8 (10)
C6—H6···N3iii	0.943 (13)	2.457 (13)	3.3412 (13)	156.1 (10)

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x−1/2, −y+1/2, −z+1; (iii) x+1/2, −y+1/2, −z+1.