3-(2-Nitro­phen­oxy)phthalonitrile

Zhang, X.-F.; Jia, D.; Song, A.; Liu, Q.

doi:10.1107/S1600536807067797

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o356

doi:10.1107/S1600536807067797

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3-(2-Nitrophenoxy)phthalonitrile

Xian-Fu Zhang,^a ^* Dandan Jia,^a Aijun Song ^a and Qiang Liu ^b

^aDepartment of Chemistry, Hebei Normal University of Science and Technology, Qinhuangdao, Hebei Province 066004, People's Republic of China, and ^bDepartment of Chemistry, Tsinghua University, Beijing 100084, People's Republic of China
^*Correspondence e-mail: zhangxianfu@tsinghua.org.cn

(Received 1 December 2007; accepted 19 December 2007; online 4 January 2008)

In the title compound, C₁₄H₇N₃O₃, the dihedral angle between the two arene units is 62.57 (12)°.

Related literature

For related literature, see: Atalay et al. (2003 , 2004 ); Cave et al. (1986 ); Köysal et al. (2004 ); Leznoff & Lever (1989–1996 ); McKeown (1998 ); Ocak Ískeleli (2007 ); Ocak et al. (2003 ), Sharman & van Lier(2003 ).

Experimental

Crystal data

C₁₄H₇N₃O₃
M_r = 265.23
Monoclinic, P 2₁ /n
a = 8.0814 (17) Å
b = 7.9899 (12) Å
c = 19.068 (3) Å
β = 95.944 (15)°
V = 1224.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 295 (2) K
0.4 × 0.4 × 0.1 mm

Data collection

Bruker P4 diffractometer
Absorption correction: none
3018 measured reflections
2155 independent reflections
1252 reflections with I > 2σ(I)
R_int = 0.092
3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.145
S = 1.03
2155 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: XSCANS (Bruker, 1997 ); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067797/gd2031sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807067797/gd2031Isup2.hkl

checkCIF report

Comment top

Phthalonitriles are among the most important precursors of phthalocyanine materials (Leznoff, 1989–1996). Monophneoxyphthalonitriles have been used for preparing symmetrical phthalocyanines which have been applied in many areas, such as laser printing, photocopying, optical data storage, and catalysis (McKeown, 1998).

In the title compound, (I), (Fig. 1) the triple bond lengths between C and N, 1.136 (5) Å and 1.129 (5) Å, agree with literature values (Ocak et al., 2003). The geometry around the O atoms is in good agreement with the literature (Atalay et al., 2003, 2004; Köysal et al., 2004). The dihedral angle between the two intramolecular arene moieties is 62.57 (12)°.

Related literature top

For related literature, see: Atalay et al. (2003, 2004); Cave et al. (1986); Köysal et al. (2004); Leznoff & Lever (1989–1996); McKeown (1998); Ocak Ískeleli (2007); Ocak et al. (2003), Sharman et al. (2003).

Experimental top

o-nitrophenol (1.39 g, 10.0 mmol) and 3-nitrophthalonitrile (1.73. g, 10.0 mmol) were dissolved in dry DMF (15 ml) with stirring under N₂. Dry fine-powdered potassium carbonate (2.5 g, 18.1 mmol) was added over the course 1 h in equal portions every 10 min. The reaction mixture was stirred for 48 h at room temperature and poured into iced water (150 g). The product was filtered off and washed with(10% w/w) NaOH solution and water until the filtrate was neutral. Recrystallization from ethanol gave a white product (yield 1.72 g, 65%). Single crystals were obtained from absolute ethanol at room temperature via slow evaporation (m.p. 397–400 K). IR data (ν _max/cm^-1): 3050(Ar—H), 1591(NO₂), 2230(CN). NMR δ(H) 7.34–7.39(1H, m), 7.53–7.63(2H,m), 7.81–7.93(3H,m), 8.19–8.26(1H,m).

Computing details top

Data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS (Bruker, 1997); data reduction: XSCANS (Bruker, 1997); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL (Bruker, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures top

Fig. 1. The molecular structure of C₁₄H7N₃O₃ with 35% probability ellipsoids, showing the atom numbering scheme.

3-(2-Nitrophenoxy)phthalonitrile top

Crystal data top

C₁₄H₇N₃O₃	F(000) = 544
M_r = 265.23	D_x = 1.439 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 51 reflections
a = 8.0814 (17) Å	θ = 5.0–12.5°
b = 7.9899 (12) Å	µ = 0.11 mm⁻¹
c = 19.068 (3) Å	T = 295 K
β = 95.944 (15)°	Plate, colorless
V = 1224.6 (4) Å³	0.4 × 0.4 × 0.1 mm
Z = 4

Data collection top

Bruker P4 diffractometer	R_int = 0.092
Radiation source: fine-focus sealed tube	θ_max = 25.0°, θ_min = 2.2°
Graphite monochromator	h = −1→9
ω scans	k = −9→1
3018 measured reflections	l = −22→22
2155 independent reflections	3 standard reflections every 97 reflections
1252 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.001P)² + 1.2P] where P = (F_o² + 2F_c²)/3
2155 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₄H₇N₃O₃	V = 1224.6 (4) Å³
M_r = 265.23	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.0814 (17) Å	µ = 0.11 mm⁻¹
b = 7.9899 (12) Å	T = 295 K
c = 19.068 (3) Å	0.4 × 0.4 × 0.1 mm
β = 95.944 (15)°

Data collection top

Bruker P4 diffractometer	R_int = 0.092
3018 measured reflections	3 standard reflections every 97 reflections
2155 independent reflections	intensity decay: none
1252 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.067	0 restraints
wR(F²) = 0.146	H-atom parameters constrained
S = 1.03	Δρ_max = 0.20 e Å⁻³
2155 reflections	Δρ_min = −0.27 e Å⁻³
181 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	0.4115 (3)	0.5913 (3)	0.63769 (12)	0.0683 (8)
O2	0.5975 (4)	0.8586 (4)	0.66974 (15)	0.0806 (9)
O3	0.7869 (4)	0.8009 (4)	0.75304 (16)	0.0932 (11)
N1	0.0726 (6)	0.4464 (5)	0.36401 (19)	0.0967 (14)
N2	0.1821 (5)	0.7972 (5)	0.50408 (18)	0.0822 (11)
N3	0.6493 (4)	0.7811 (4)	0.72224 (17)	0.0609 (9)
C1	0.1511 (5)	0.4108 (5)	0.4142 (2)	0.0651 (11)
C2	0.2279 (5)	0.6648 (6)	0.51586 (18)	0.0566 (10)
C3	0.2487 (5)	0.3691 (5)	0.47972 (18)	0.0534 (9)
C4	0.2840 (4)	0.4955 (5)	0.53013 (17)	0.0492 (9)
C5	0.3749 (4)	0.4568 (5)	0.59366 (18)	0.0524 (9)
C6	0.4322 (5)	0.2954 (5)	0.6072 (2)	0.0623 (10)
H6A	0.4952	0.2702	0.6495	0.075*
C7	0.3950 (5)	0.1729 (5)	0.5576 (2)	0.0657 (11)
H7A	0.4328	0.0644	0.5667	0.079*
C8	0.3024 (5)	0.2082 (5)	0.49420 (19)	0.0620 (10)
H8A	0.2765	0.1234	0.4615	0.074*
C9	0.4213 (4)	0.5689 (5)	0.71071 (17)	0.0523 (9)
C10	0.5397 (4)	0.6628 (4)	0.75215 (18)	0.0480 (9)
C11	0.5535 (5)	0.6431 (5)	0.82497 (18)	0.0584 (10)
H11A	0.6334	0.7036	0.8530	0.070*
C12	0.4516 (5)	0.5362 (5)	0.85555 (19)	0.0603 (10)
H12A	0.4628	0.5220	0.9042	0.072*
C14	0.3162 (5)	0.4646 (5)	0.7422 (2)	0.0626 (11)
H14A	0.2348	0.4043	0.7148	0.075*
C13	0.3319 (5)	0.4496 (5)	0.8141 (2)	0.0643 (11)
H13A	0.2599	0.3792	0.8352	0.077*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.090 (2)	0.0637 (18)	0.0462 (14)	−0.0149 (15)	−0.0149 (13)	−0.0003 (13)
O2	0.090 (2)	0.082 (2)	0.0670 (18)	−0.0169 (17)	−0.0075 (16)	0.0199 (16)
O3	0.0672 (19)	0.119 (3)	0.088 (2)	−0.0375 (19)	−0.0167 (17)	0.0071 (19)
N1	0.128 (4)	0.087 (3)	0.065 (2)	0.014 (3)	−0.036 (2)	−0.007 (2)
N2	0.113 (3)	0.067 (3)	0.063 (2)	0.008 (2)	−0.005 (2)	0.0033 (19)
N3	0.064 (2)	0.062 (2)	0.0549 (19)	−0.0103 (18)	−0.0035 (17)	−0.0013 (17)
C1	0.082 (3)	0.056 (2)	0.054 (2)	−0.005 (2)	−0.009 (2)	−0.0072 (19)
C2	0.065 (3)	0.062 (3)	0.0408 (19)	−0.002 (2)	−0.0030 (18)	−0.0008 (19)
C3	0.060 (2)	0.056 (2)	0.0429 (19)	−0.005 (2)	−0.0001 (17)	0.0012 (18)
C4	0.049 (2)	0.053 (2)	0.0451 (19)	−0.0043 (18)	0.0015 (15)	−0.0005 (17)
C5	0.056 (2)	0.056 (2)	0.0438 (19)	−0.006 (2)	0.0004 (17)	−0.0018 (18)
C6	0.064 (2)	0.068 (3)	0.053 (2)	0.001 (2)	−0.0055 (19)	0.006 (2)
C7	0.080 (3)	0.057 (2)	0.059 (2)	0.007 (2)	0.002 (2)	0.006 (2)
C8	0.076 (3)	0.057 (3)	0.053 (2)	0.000 (2)	0.004 (2)	−0.0059 (19)
C9	0.056 (2)	0.053 (2)	0.045 (2)	0.0009 (19)	−0.0076 (17)	0.0009 (17)
C10	0.049 (2)	0.043 (2)	0.050 (2)	0.0003 (17)	−0.0030 (16)	−0.0021 (16)
C11	0.062 (2)	0.059 (2)	0.051 (2)	−0.002 (2)	−0.0103 (19)	−0.0059 (18)
C12	0.065 (3)	0.068 (3)	0.047 (2)	−0.001 (2)	0.0039 (19)	−0.0027 (19)
C14	0.059 (2)	0.065 (3)	0.061 (2)	−0.016 (2)	−0.007 (2)	0.001 (2)
C13	0.066 (3)	0.065 (3)	0.062 (2)	−0.011 (2)	0.010 (2)	0.002 (2)

Geometric parameters (Å, º) top

O1—C5	1.377 (4)	C6—H6A	0.9300
O1—C9	1.398 (4)	C7—C8	1.383 (5)
O2—N3	1.214 (4)	C7—H7A	0.9300
O3—N3	1.213 (4)	C8—H8A	0.9300
N1—C1	1.129 (5)	C9—C14	1.372 (5)
N2—C2	1.136 (5)	C9—C10	1.395 (5)
N3—C10	1.452 (5)	C10—C11	1.390 (5)
C1—C3	1.445 (5)	C11—C12	1.359 (5)
C2—C4	1.443 (6)	C11—H11A	0.9300
C3—C8	1.376 (5)	C12—C13	1.372 (5)
C3—C4	1.403 (5)	C12—H12A	0.9300
C4—C5	1.385 (5)	C14—C13	1.369 (5)
C5—C6	1.385 (5)	C14—H14A	0.9300
C6—C7	1.372 (5)	C13—H13A	0.9300

C5—O1—C9	119.6 (3)	C3—C8—C7	119.8 (3)
O3—N3—O2	123.6 (4)	C3—C8—H8A	120.1
O3—N3—C10	117.4 (3)	C7—C8—H8A	120.1
O2—N3—C10	119.0 (3)	C14—C9—C10	119.9 (3)
N1—C1—C3	178.2 (5)	C14—C9—O1	122.7 (3)
N2—C2—C4	179.1 (4)	C10—C9—O1	117.4 (3)
C8—C3—C4	119.8 (3)	C11—C10—C9	119.0 (4)
C8—C3—C1	121.4 (3)	C11—C10—N3	118.5 (3)
C4—C3—C1	118.7 (3)	C9—C10—N3	122.5 (3)
C5—C4—C3	119.3 (3)	C12—C11—C10	120.6 (3)
C5—C4—C2	120.1 (3)	C12—C11—H11A	119.7
C3—C4—C2	120.5 (3)	C10—C11—H11A	119.7
O1—C5—C4	114.8 (3)	C11—C12—C13	119.5 (4)
O1—C5—C6	124.5 (3)	C11—C12—H12A	120.3
C4—C5—C6	120.5 (3)	C13—C12—H12A	120.3
C7—C6—C5	119.4 (3)	C13—C14—C9	119.6 (4)
C7—C6—H6A	120.3	C13—C14—H14A	120.2
C5—C6—H6A	120.3	C9—C14—H14A	120.2
C6—C7—C8	121.1 (4)	C14—C13—C12	121.3 (4)
C6—C7—H7A	119.4	C14—C13—H13A	119.3
C8—C7—H7A	119.4	C12—C13—H13A	119.3

Experimental details

Crystal data
Chemical formula	C₁₄H₇N₃O₃
M_r	265.23
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	8.0814 (17), 7.9899 (12), 19.068 (3)
β (°)	95.944 (15)
V (Å³)	1224.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.4 × 0.4 × 0.1

Data collection
Diffractometer	Bruker P4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3018, 2155, 1252
R_int	0.092
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.146, 1.03
No. of reflections	2155
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.27

Computer programs: XSCANS (Bruker, 1997), SHELXTL (Bruker, 1997).

Acknowledgements

The authors thank the HBUST for financial support.

References

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