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access1,4-Bis(4-nitrostyryl)benzene
aDepartment of Chemistry, Penn State Worthington Scranton, 120 Ridge View Drive, Dumore, Pennsylvania 18512, USA
*Correspondence e-mail: ptp2@psu.edu
The complete molecule of the title compound, C22H16N2O4, is generated by a crystallographic centre of inversion. The plane of the central aromatic ring is tilted by 11.85 (4)° with respect to the outer aromatic ring. The crystal packing is determined by van der Waals interactions, with stair-like stacking between adjacent aromatic rings. The stacks are staggered and each layer is approximately 3.8 Å from the next. The closest intermolecular contact (approximately 2.42 Å) is between an O atom and a vinyl H atom.
Related literature
For background information on photonic materials, see: He et al. (2008![[He, T., Wang, C., Pan, X., Yang, H. & Lu, G. (2008). Dyes Pigm. 82, 47-52.]](../../../../../../logos/arrows/e_arr.gif "He, T., Wang, C., Pan, X., Yang, H. & Lu, G. (2008). Dyes Pigm. 82, 47-52.")
). For stilbenes, see: Moreno-Fuquen et al. (2008, 2009). For the synthesis, see: Borsche (1912); Nakatsuji et al. (1991). For a related structure, see: Bazan et al. (2000).
![[Scheme 1]](ng2592scheme1.gif)
Experimental
Crystal data
|
Data collection: SMART (Bruker, 2001); cell SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2009).
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536809024751/ng2592sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536809024751/ng2592Isup2.hkl
Synthesis was carried out following literature procedures (Nakatsuj) by standard Wittig synthesis. To a mixture of p-phenylenedimethylene- bis(tripheny1phosphonium chloride) (1.00 g, 1.43 mmol) and p-nitrobenzaldehyde (0.432 g 2.86 mmol) in EtOH (10 ml) was added 0.2 mol/L EtOLi(20 ml, 4.0 mmol) and the mixture was stirred overnight. The resulting reaction mixture was poured into water to give a yellow precipitate (0.4 g, 75%) which was filtered off, washed with EtOH, dried under reduced pressure, m.p. 289–290. Crystallization attempts from various solvents yielded only powders. Yellowish orange crystals however were grown by sublimation.
All hydrogen atoms were placed in ideal positions and refined as riding atoms with relative isotropic displacement parameters.
Data collection: SMART (Bruker, 2001); cell SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2009).
![[Figure 1]](./ng2592fig1thm.gif) | Fig. 1. The molecular structure of 1,4-di(4-nitrostyryl)benzene with atom lables. |
![[Figure 2]](./ng2592fig2thm.gif) | Fig. 2. Crystal packing viewed along the a axis. |
| C22H16N2O4 | F(000) = 388 |
| Mr = 372.37 | Dx = 1.424 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 851 reflections |
| a = 7.4689 (12) Å | θ = 2.5–27.5° |
| b = 16.615 (3) Å | µ = 0.10 mm−1 |
| c = 7.3917 (12) Å | T = 173 K |
| β = 108.824 (3)° | Needle, yellow |
| V = 868.2 (2) Å3 | 0.40 × 0.18 × 0.12 mm |
| Z = 2 |
| Bruker SMART Platform CCD diffractometer | 1486 reflections with I > 2σ(I) |
| Radiation source: normal-focus sealed tube | Rint = 0.041 |
| Graphite monochromator | θmax = 27.5°, θmin = 2.5° |
| ω scans | h = −9→9 |
| 10088 measured reflections | k = −21→21 |
| 2001 independent reflections | l = −9→9 |
| 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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.116 | All H-atom parameters refined |
| S = 1.02 | w = 1/[σ2(Fo2) + (0.0595P)2 + 0.1981P] where P = (Fo2 + 2Fc2)/3 |
| 2001 reflections | (Δ/σ)max < 0.001 |
| 159 parameters | Δρmax = 0.30 e Å−3 |
| 0 restraints | Δρmin = −0.18 e Å−3 |
| C22H16N2O4 | V = 868.2 (2) Å3 |
| Mr = 372.37 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 7.4689 (12) Å | µ = 0.10 mm−1 |
| b = 16.615 (3) Å | T = 173 K |
| c = 7.3917 (12) Å | 0.40 × 0.18 × 0.12 mm |
| β = 108.824 (3)° |
| Bruker SMART Platform CCD diffractometer | 1486 reflections with I > 2σ(I) |
| 10088 measured reflections | Rint = 0.041 |
| 2001 independent reflections |
| R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
| wR(F2) = 0.116 | All H-atom parameters refined |
| S = 1.02 | Δρmax = 0.30 e Å−3 |
| 2001 reflections | Δρmin = −0.18 e Å−3 |
| 159 parameters |
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. |
| x | y | z | Uiso*/Ueq | ||
| N1 | −0.18351 (16) | 0.18081 (7) | −0.31257 (17) | 0.0314 (3) | |
| O1 | −0.31485 (14) | 0.14204 (7) | −0.29133 (16) | 0.0424 (3) | |
| O2 | −0.20374 (14) | 0.23244 (7) | −0.43745 (15) | 0.0415 (3) | |
| C1 | 0.00888 (18) | 0.16483 (8) | −0.18509 (19) | 0.0268 (3) | |
| C2 | 0.03516 (19) | 0.10424 (8) | −0.0511 (2) | 0.0293 (3) | |
| H2 | −0.068 (2) | 0.0758 (9) | −0.037 (2) | 0.034 (4)* | |
| C3 | 0.2169 (2) | 0.08605 (8) | 0.0623 (2) | 0.0299 (3) | |
| H3 | 0.234 (2) | 0.0439 (10) | 0.154 (2) | 0.036 (4)* | |
| C4 | 0.37281 (19) | 0.12795 (8) | 0.04412 (18) | 0.0274 (3) | |
| C5 | 0.3394 (2) | 0.19080 (9) | −0.0888 (2) | 0.0309 (3) | |
| H5 | 0.440 (2) | 0.2209 (9) | −0.102 (2) | 0.032 (4)* | |
| C6 | 0.1573 (2) | 0.20926 (9) | −0.2043 (2) | 0.0302 (3) | |
| H6 | 0.137 (2) | 0.2519 (10) | −0.294 (2) | 0.037 (4)* | |
| C7 | 0.56766 (19) | 0.10807 (9) | 0.1593 (2) | 0.0304 (3) | |
| H7 | 0.659 (2) | 0.1468 (9) | 0.145 (2) | 0.036 (4)* | |
| C8 | 0.62118 (19) | 0.04369 (9) | 0.27155 (19) | 0.0296 (3) | |
| H8 | 0.530 (2) | 0.0058 (9) | 0.282 (2) | 0.027 (4)* | |
| C9 | 0.81506 (18) | 0.02312 (8) | 0.38677 (18) | 0.0270 (3) | |
| C10 | 0.9717 (2) | 0.07130 (9) | 0.39725 (19) | 0.0291 (3) | |
| H10 | 0.959 (2) | 0.1202 (10) | 0.333 (2) | 0.040 (4)* | |
| C11 | 0.8479 (2) | −0.04871 (9) | 0.49188 (19) | 0.0295 (3) | |
| H11 | 0.740 (2) | −0.0827 (10) | 0.482 (2) | 0.039 (4)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0255 (6) | 0.0340 (7) | 0.0330 (6) | 0.0040 (5) | 0.0072 (5) | −0.0046 (5) |
| O1 | 0.0245 (5) | 0.0545 (7) | 0.0467 (7) | −0.0036 (5) | 0.0091 (5) | −0.0009 (5) |
| O2 | 0.0348 (6) | 0.0417 (6) | 0.0426 (6) | 0.0100 (5) | 0.0050 (5) | 0.0105 (5) |
| C1 | 0.0224 (6) | 0.0296 (7) | 0.0267 (7) | 0.0041 (5) | 0.0054 (5) | −0.0038 (5) |
| C2 | 0.0261 (7) | 0.0292 (7) | 0.0330 (7) | −0.0030 (5) | 0.0103 (6) | −0.0011 (6) |
| C3 | 0.0309 (7) | 0.0280 (7) | 0.0299 (7) | −0.0001 (5) | 0.0087 (6) | 0.0026 (6) |
| C4 | 0.0267 (7) | 0.0279 (7) | 0.0260 (7) | 0.0015 (5) | 0.0064 (5) | −0.0017 (5) |
| C5 | 0.0246 (7) | 0.0322 (7) | 0.0355 (8) | −0.0021 (5) | 0.0093 (6) | 0.0031 (6) |
| C6 | 0.0295 (7) | 0.0293 (7) | 0.0312 (7) | 0.0027 (5) | 0.0089 (6) | 0.0056 (6) |
| C7 | 0.0244 (7) | 0.0331 (8) | 0.0314 (7) | −0.0010 (6) | 0.0059 (6) | −0.0005 (6) |
| C8 | 0.0260 (7) | 0.0312 (7) | 0.0300 (7) | 0.0002 (6) | 0.0071 (5) | −0.0017 (6) |
| C9 | 0.0278 (7) | 0.0301 (7) | 0.0221 (6) | 0.0037 (5) | 0.0066 (5) | −0.0032 (5) |
| C10 | 0.0313 (7) | 0.0283 (7) | 0.0268 (7) | 0.0034 (5) | 0.0082 (5) | 0.0026 (5) |
| C11 | 0.0270 (7) | 0.0313 (7) | 0.0294 (7) | −0.0008 (5) | 0.0082 (5) | −0.0011 (6) |
| N1—O1 | 1.2253 (16) | C5—H5 | 0.932 (16) |
| N1—O2 | 1.2332 (15) | C6—H6 | 0.950 (16) |
| N1—C1 | 1.4661 (17) | C7—C8 | 1.334 (2) |
| C1—C6 | 1.3765 (19) | C7—H7 | 0.969 (16) |
| C1—C2 | 1.381 (2) | C8—C9 | 1.4640 (19) |
| C2—C3 | 1.379 (2) | C8—H8 | 0.951 (15) |
| C2—H2 | 0.940 (16) | C9—C10 | 1.399 (2) |
| C3—C4 | 1.4001 (19) | C9—C11 | 1.4020 (19) |
| C3—H3 | 0.953 (16) | C10—C11i | 1.384 (2) |
| C4—C5 | 1.3999 (19) | C10—H10 | 0.930 (17) |
| C4—C7 | 1.4670 (19) | C11—C10i | 1.384 (2) |
| C5—C6 | 1.3868 (19) | C11—H11 | 0.968 (17) |
| O1—N1—O2 | 123.49 (12) | C1—C6—C5 | 118.71 (13) |
| O1—N1—C1 | 118.79 (12) | C1—C6—H6 | 121.2 (10) |
| O2—N1—C1 | 117.71 (11) | C5—C6—H6 | 120.1 (10) |
| C6—C1—C2 | 122.13 (12) | C8—C7—C4 | 125.71 (13) |
| C6—C1—N1 | 119.44 (12) | C8—C7—H7 | 121.2 (9) |
| C2—C1—N1 | 118.42 (12) | C4—C7—H7 | 113.1 (9) |
| C3—C2—C1 | 118.68 (13) | C7—C8—C9 | 126.21 (14) |
| C3—C2—H2 | 120.4 (9) | C7—C8—H8 | 120.2 (9) |
| C1—C2—H2 | 120.9 (9) | C9—C8—H8 | 113.6 (9) |
| C2—C3—C4 | 121.26 (13) | C10—C9—C11 | 117.57 (12) |
| C2—C3—H3 | 118.2 (9) | C10—C9—C8 | 123.46 (13) |
| C4—C3—H3 | 120.6 (9) | C11—C9—C8 | 118.97 (13) |
| C5—C4—C3 | 118.20 (12) | C11i—C10—C9 | 120.98 (13) |
| C5—C4—C7 | 119.61 (13) | C11i—C10—H10 | 117.5 (10) |
| C3—C4—C7 | 122.18 (13) | C9—C10—H10 | 121.5 (10) |
| C6—C5—C4 | 120.96 (13) | C10i—C11—C9 | 121.45 (13) |
| C6—C5—H5 | 118.6 (9) | C10i—C11—H11 | 121.0 (9) |
| C4—C5—H5 | 120.5 (9) | C9—C11—H11 | 117.6 (9) |
| O1—N1—C1—C6 | −178.44 (12) | N1—C1—C6—C5 | −176.92 (12) |
| O2—N1—C1—C6 | 2.28 (19) | C4—C5—C6—C1 | 0.4 (2) |
| O1—N1—C1—C2 | 2.67 (19) | C5—C4—C7—C8 | −170.57 (14) |
| O2—N1—C1—C2 | −176.61 (12) | C3—C4—C7—C8 | 9.5 (2) |
| C6—C1—C2—C3 | −2.3 (2) | C4—C7—C8—C9 | 179.87 (13) |
| N1—C1—C2—C3 | 176.57 (12) | C7—C8—C9—C10 | 1.9 (2) |
| C1—C2—C3—C4 | 0.3 (2) | C7—C8—C9—C11 | −177.62 (13) |
| C2—C3—C4—C5 | 1.9 (2) | C11—C9—C10—C11i | −0.2 (2) |
| C2—C3—C4—C7 | −178.18 (13) | C8—C9—C10—C11i | −179.77 (13) |
| C3—C4—C5—C6 | −2.3 (2) | C10—C9—C11—C10i | 0.2 (2) |
| C7—C4—C5—C6 | 177.80 (13) | C8—C9—C11—C10i | 179.80 (13) |
| C2—C1—C6—C5 | 1.9 (2) |
| Symmetry code: (i) −x+2, −y, −z+1. |
Experimental details
| Crystal data | |
| Chemical formula | C22H16N2O4 |
| Mr | 372.37 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 173 |
| a, b, c (Å) | 7.4689 (12), 16.615 (3), 7.3917 (12) |
| β (°) | 108.824 (3) |
| V (Å3) | 868.2 (2) |
| Z | 2 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.10 |
| Crystal size (mm) | 0.40 × 0.18 × 0.12 |
| Data collection | |
| Diffractometer | Bruker SMART Platform CCD diffractometer |
| Absorption correction | – |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 10088, 2001, 1486 |
| Rint | 0.041 |
| (sin θ/λ)max (Å−1) | 0.650 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.116, 1.02 |
| No. of reflections | 2001 |
| No. of parameters | 159 |
| H-atom treatment | All H-atom parameters refined |
| Δρmax, Δρmin (e Å−3) | 0.30, −0.18 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2009).
Acknowledgements
This work was supported in part by Research Development Grants from the Pennsylvania State University. The author also acknowledges Benjamin E. Kucera, Victor G. Young Jr, and the X-Ray Crystallographic Laboratory at the University of Minnesota.
References
Bazan, G., Bartholomew, G., Bu, X. & Lachicotte, R. (2000). Chem. Mater. 12, 1422–1430. Google Scholar
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Distyrylbenzene derivatives have been studied as laser dyes, components of organic light-emitting diodes, and as model compounds for the study of conductivity and molecular properties in substituted p-phenylenevinylene (PPV) polymers. For background information on photonic materials, see: He et al. (2008). For related systems of stilbene, see: Moreno-Fuquen et al. (2008, 2009). For literature related to the synthesis, see: Borsche (1912).