Abstract
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,
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[F 2 > 2σ(F 2)] = 0.067
wR(F 2) = 0.145
S = 1.03
2155 reflections
181 parameters
H-atom parameters constrained
Δρmax = 0.20 e Å−3
Δρmin = −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.
Supplementary Material
Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067797/gd2031sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S1600536807067797/gd2031Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors thank the HBUST for financial support.
supplementary crystallographic information
Comment
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)°.
Experimental
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).
Refinement
H atoms were included as riding atoms in geometrically idealized positions with C—H distances 0.93 Å and Uiso(H) = 1.2Ueq(C).
Figures
Fig. 1.
The molecular structure of C14H7N3O3 with 35% probability ellipsoids, showing the atom numbering scheme.
Crystal data
| C14H7N3O3 | F000 = 544 |
| Mr = 265.23 | Dx = 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 = 5.0–12.5º |
| b = 7.9899 (12) Å | µ = 0.11 mm−1 |
| c = 19.068 (3) Å | T = 295 (2) K |
| β = 95.944 (15)º | Plate, colorless |
| V = 1224.6 (4) Å3 | 0.4 × 0.4 × 0.1 mm |
| Z = 4 |
Data collection
| Bruker P4 diffractometer | Rint = 0.092 |
| Radiation source: fine-focus sealed tube | θmax = 25.0º |
| Monochromator: graphite | θmin = 2.2º |
| T = 295(2) K | h = −1→9 |
| ω scans | k = −9→1 |
| Absorption correction: none | l = −22→22 |
| 3018 measured reflections | 3 standard reflections |
| 2155 independent reflections | every 97 reflections |
| 1252 reflections with I > 2σ(I) | intensity decay: none |
Refinement
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.067 | H-atom parameters constrained |
| wR(F2) = 0.146 | w = 1/[σ2(Fo2) + (0.001P)2 + 1.2P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.03 | (Δ/σ)max < 0.001 |
| 2155 reflections | Δρmax = 0.20 e Å−3 |
| 181 parameters | Δρmin = −0.27 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
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 (Å2)
| x | y | z | Uiso*/Ueq | ||
| 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)
| 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, °)
| 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 |
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GD2031).
References
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- Cave, R. J., Siders, P. & Marcus, R. A. (1986). J. Phys. Chem.90, 1436–1439.
- Köysal, Y., Işık, Ş., Akdemir, N., Ağar, E. & Kantar, C. (2004). Acta Cryst. E60, o930–o931.
- Leznoff, C. C. & Lever, A. B. P. (1989–1996). Phthalocyanines: Properties and Applications , Vols. 1-4. Weinheim/New York: VHC Publishers Inc.
- McKeown, N. B. (1998). Phthalocyanine Materials: Synthesis, Structure and Function Cambridge University Press.
- Ocak, N., Ağar, A., Akdemir, N., Ağar, E., García-Granda, S. & Erdönmez, A. (2003). Acta Cryst. E59, o1000–o1001.
- Ocak Ískeleli, N. (2007). Acta Cryst. E63, o997–o998.
- Sharman, W. M. & van Lier, J. E. (2003). The Porphyrin Handbook, Vol. 15, edited by K. M. Kadish, K. M. Smith & G. Guilard, pp. 1–60. New York: Academic Press.
Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067797/gd2031sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S1600536807067797/gd2031Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report