4-Nitro­phthalo­nitrile

Jan, C.Y.; Shamsudin, N.B.H.; Tan, A.L.; Young, D.J.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536814003468

organic compounds

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Volume 70| Part 3| March 2014| Page o323

doi:10.1107/S1600536814003468

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4-Nitrophthalonitrile

Chin Yee Jan,^a Norzianah Binti Haji Shamsudin,^a Ai Ling Tan,^a David J. Young,^a ‡ Seik Weng Ng ^b,^c and Edward R. T. Tiekink ^b ^*

^aFaculty of Science, Universiti Brunei Darussalam, Jalan Tungku Link BE 1410, Negara Brunei Darussalam, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 13 February 2014; accepted 17 February 2014; online 22 February 2014)

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.

CCDC reference: 987296

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, P b c a
a = 12.8642 (3) Å
b = 9.2013 (2) Å
c = 13.2578 (3) Å
V = 1569.29 (6) Å³
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[F² > 2σ(F²)] = 0.030
wR(F²) = 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

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) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

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 ).

Supporting information

CCDC reference: 987296

Crystal structure: contains datablocks general, I. DOI: 10.1107/S1600536814003468/wm5005sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814003468/wm5005Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814003468/wm5005Isup3.cml

checkCIF report

Chemical context top

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.

Structural commentary top

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).

Supramolecular features top

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).

Synthesis and crystallization top

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.

Refinement top

All hydrogen atoms were refined freely.

Related literature top

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).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); 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).

Figures top

	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.

4-Nitrobenzene-1,2-dicarbonitrile top

Crystal data top

C₈H₃N₃O₂	F(000) = 704
M_r = 173.13	D_x = 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 top

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	R_int = 0.016
Detector resolution: 10.4041 pixels mm^-1	θ_max = 76.3°, θ_min = 6.7°
ω scan	h = −8→16
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −10→11
T_min = 0.626, T_max = 1.000	l = −16→16
7104 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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	All H-atom parameters refined
S = 1.10	w = 1/[σ²(F_o²) + (0.0522P)² + 0.3777P] where P = (F_o² + 2F_c²)/3
1638 reflections	(Δ/σ)_max < 0.001
130 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₈H₃N₃O₂	V = 1569.29 (6) Å³
M_r = 173.13	Z = 8
Orthorhombic, Pbca	Cu Kα radiation
a = 12.8642 (3) Å	µ = 0.94 mm⁻¹
b = 9.2013 (2) Å	T = 100 K
c = 13.2578 (3) Å	0.35 × 0.30 × 0.25 mm

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	1638 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	1556 reflections with I > 2σ(I)
T_min = 0.626, T_max = 1.000	R_int = 0.016
7104 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.088	All H-atom parameters refined
S = 1.10	Δρ_max = 0.21 e Å⁻³
1638 reflections	Δρ_min = −0.24 e Å⁻³
130 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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) top

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) top

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.

Hydrogen-bond geometry (Å, º) top

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.

Footnotes

‡Additional correspondence author, e-mail: david.young@ubd.edu.bn.

Acknowledgements

We gratefully acknowledge funding from the Brunei Research Council, and thank the Ministry of Higher Education (Malaysia) and the University of Malaya for funding structural studies through the High-Impact Research scheme (UM.C/HIR-MOHE/SC/03).

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 3| March 2014| Page o323

doi:10.1107/S1600536814003468

Open

access