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organic compounds
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access1,5-Dicyanoanthraquinone
aDepartment of Chemistry, General Campus, Shahid Beheshti University, Tehran 1983963113, Iran, and bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my
The complete molecule of the title compound, C16H6N2O2, which is generated by a crystallographic inversion centre, is almost planar (r.m.s. deviation = 0.04 Å). In the crystal, adjacent molecules are stacked along the a axis, with a shortest centroid–centroid separation of 3.826 (2) Å.
Related literature
For the synthesis, see: Casey et al. (1999![[Casey, J. L., Deady, L. W., Hughes, A. B., Klonis, N., Quazi, N. H. & Tilley, L. M. (1999). PCT Int. Appl. Patent No. WO 99-AU14419990311.]](../../../../../../logos/arrows/e_arr.gif "Casey, J. L., Deady, L. W., Hughes, A. B., Klonis, N., Quazi, N. H. & Tilley, L. M. (1999). PCT Int. Appl. Patent No. WO 99-AU14419990311.")
); Coulson (1930a,b). For some applications of anthraquinones, see: Alagesan & Samuelson (1997); Chang et al. (1996); Cheng et al. (1994); Kuritani et al. (1973); Lin et al. (1995).
![[Scheme 1]](hb5350scheme1.gif)
Experimental
Crystal data
|
Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
contains datablocks global, I. DOI: 10.1107/S1600536810007993/hb5350sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536810007993/hb5350Isup2.hkl
1,5-Dicyanoanthraquinone was prepared by using a reported procedure by reacting 1,5-dichloroanthraquinone with benzyl cyanide in presence of cuprous cyanide (Coulson, 1930a,b; Casey et al., 1999). The compound is sparingly soluble in common solvents; yellow prisms of (I) were obtained by the slow diffusion of methanol into a DMSO solution of the compound; m.p.> 633 K, decompose).
Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 Å) and were included in the in the riding model approximation, with U(H) set to 1.2U(C).
Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).
![[Figure 1]](./hb5350fig1thm.gif) | Fig. 1. The molecular structure of (I): displacement ellipsoids are drawn at the 50% probability level and H atoms are of arbitrary radius. Unlabelled atoms are generated by the symmetry operation (1–x, 1–y, 1–z). |
![[Figure 2]](./hb5350fig2thm.gif) | Fig. 2. Stacking of the molecules in the unit cell of (I). |
| C16H6N2O2 | F(000) = 264 |
| Mr = 258.23 | Dx = 1.503 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 614 reflections |
| a = 3.8256 (10) Å | θ = 3.1–25.4° |
| b = 7.0183 (19) Å | µ = 0.10 mm−1 |
| c = 21.249 (6) Å | T = 293 K |
| β = 91.064 (4)° | Prism, yellow |
| V = 570.4 (3) Å3 | 0.35 × 0.06 × 0.03 mm |
| Z = 2 |
| Bruker SMART APEX diffractometer | 600 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.048 |
| Graphite monochromator | θmax = 25.0°, θmin = 1.9° |
| ω scans | h = −4→4 |
| 4238 measured reflections | k = −8→8 |
| 1013 independent reflections | l = −25→25 |
| 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)] = 0.053 | H-atom parameters constrained |
| wR(F2) = 0.149 | w = 1/[σ2(Fo2) + (0.0649P)2 + 0.1468P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.06 | (Δ/σ)max = 0.001 |
| 1013 reflections | Δρmax = 0.19 e Å−3 |
| 92 parameters | Δρmin = −0.18 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.033 (9) |
| C16H6N2O2 | V = 570.4 (3) Å3 |
| Mr = 258.23 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 3.8256 (10) Å | µ = 0.10 mm−1 |
| b = 7.0183 (19) Å | T = 293 K |
| c = 21.249 (6) Å | 0.35 × 0.06 × 0.03 mm |
| β = 91.064 (4)° |
| Bruker SMART APEX diffractometer | 600 reflections with I > 2σ(I) |
| 4238 measured reflections | Rint = 0.048 |
| 1013 independent reflections |
| R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
| wR(F2) = 0.149 | H-atom parameters constrained |
| S = 1.06 | Δρmax = 0.19 e Å−3 |
| 1013 reflections | Δρmin = −0.18 e Å−3 |
| 92 parameters |
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.8448 (7) | 0.2052 (3) | 0.55023 (10) | 0.0691 (8) | |
| N1 | 0.0797 (10) | 0.7591 (5) | 0.30574 (16) | 0.0837 (11) | |
| C1 | 0.6782 (8) | 0.3375 (4) | 0.52815 (13) | 0.0407 (7) | |
| C2 | 0.5829 (7) | 0.3390 (4) | 0.46013 (12) | 0.0373 (7) | |
| C3 | 0.6669 (8) | 0.1823 (4) | 0.42375 (14) | 0.0473 (8) | |
| H3 | 0.7752 | 0.0773 | 0.4423 | 0.057* | |
| C4 | 0.5910 (9) | 0.1815 (5) | 0.36042 (15) | 0.0583 (10) | |
| H4 | 0.6438 | 0.0750 | 0.3364 | 0.070* | |
| C5 | 0.4369 (9) | 0.3378 (5) | 0.33232 (15) | 0.0566 (9) | |
| H5 | 0.3903 | 0.3369 | 0.2892 | 0.068* | |
| C6 | 0.3504 (7) | 0.4968 (4) | 0.36757 (13) | 0.0430 (8) | |
| C7 | 0.4220 (7) | 0.4985 (4) | 0.43270 (12) | 0.0373 (7) | |
| C8 | 0.1889 (8) | 0.6593 (5) | 0.33253 (14) | 0.0424 (8) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.097 (2) | 0.0525 (15) | 0.0572 (15) | 0.0343 (13) | −0.0103 (13) | 0.0056 (11) |
| N1 | 0.090 (3) | 0.093 (3) | 0.068 (2) | −0.006 (2) | 0.0044 (19) | −0.0029 (19) |
| C1 | 0.0450 (18) | 0.0323 (16) | 0.0450 (17) | 0.0043 (13) | 0.0016 (13) | 0.0035 (13) |
| C2 | 0.0383 (17) | 0.0308 (16) | 0.0427 (16) | 0.0014 (12) | 0.0011 (12) | 0.0016 (12) |
| C3 | 0.053 (2) | 0.0347 (18) | 0.0540 (19) | 0.0052 (13) | 0.0015 (14) | −0.0067 (14) |
| C4 | 0.063 (2) | 0.052 (2) | 0.060 (2) | 0.0047 (16) | 0.0011 (17) | −0.0155 (17) |
| C5 | 0.058 (2) | 0.070 (2) | 0.0414 (17) | −0.0024 (17) | −0.0007 (15) | −0.0078 (16) |
| C6 | 0.0400 (17) | 0.0455 (18) | 0.0437 (17) | −0.0032 (14) | 0.0028 (12) | −0.0009 (14) |
| C7 | 0.0325 (15) | 0.0377 (17) | 0.0416 (16) | −0.0027 (12) | 0.0024 (11) | 0.0024 (12) |
| C8 | 0.0388 (18) | 0.050 (2) | 0.0382 (17) | 0.0024 (14) | −0.0053 (13) | 0.0059 (15) |
| O1—C1 | 1.216 (3) | C4—C5 | 1.376 (4) |
| N1—C8 | 0.991 (4) | C4—H4 | 0.9300 |
| C1—C7i | 1.475 (4) | C5—C6 | 1.387 (4) |
| C1—C2 | 1.484 (4) | C5—H5 | 0.9300 |
| C2—C3 | 1.386 (4) | C6—C7 | 1.406 (3) |
| C2—C7 | 1.399 (4) | C6—C8 | 1.490 (4) |
| C3—C4 | 1.371 (4) | C7—C1i | 1.475 (4) |
| C3—H3 | 0.9300 | ||
| O1—C1—C7i | 121.2 (3) | C5—C4—H4 | 119.9 |
| O1—C1—C2 | 119.9 (3) | C4—C5—C6 | 120.8 (3) |
| C7i—C1—C2 | 118.8 (2) | C4—C5—H5 | 119.6 |
| C3—C2—C7 | 120.5 (3) | C6—C5—H5 | 119.6 |
| C3—C2—C1 | 118.8 (2) | C5—C6—C7 | 119.6 (3) |
| C7—C2—C1 | 120.7 (2) | C5—C6—C8 | 116.5 (3) |
| C4—C3—C2 | 120.2 (3) | C7—C6—C8 | 123.9 (3) |
| C4—C3—H3 | 119.9 | C2—C7—C6 | 118.7 (3) |
| C2—C3—H3 | 119.9 | C2—C7—C1i | 120.4 (2) |
| C3—C4—C5 | 120.2 (3) | C6—C7—C1i | 120.9 (3) |
| C3—C4—H4 | 119.9 | N1—C8—C6 | 174.6 (4) |
| O1—C1—C2—C3 | 4.2 (4) | C4—C5—C6—C8 | 179.3 (3) |
| C7i—C1—C2—C3 | −177.9 (3) | C3—C2—C7—C6 | −0.5 (4) |
| O1—C1—C2—C7 | −173.6 (3) | C1—C2—C7—C6 | 177.2 (2) |
| C7i—C1—C2—C7 | 4.3 (4) | C3—C2—C7—C1i | 177.9 (3) |
| C7—C2—C3—C4 | −0.4 (4) | C1—C2—C7—C1i | −4.4 (4) |
| C1—C2—C3—C4 | −178.2 (3) | C5—C6—C7—C2 | 0.6 (4) |
| C2—C3—C4—C5 | 1.3 (5) | C8—C6—C7—C2 | −178.4 (3) |
| C3—C4—C5—C6 | −1.2 (5) | C5—C6—C7—C1i | −177.8 (3) |
| C4—C5—C6—C7 | 0.2 (4) | C8—C6—C7—C1i | 3.2 (4) |
| Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
| Crystal data | |
| Chemical formula | C16H6N2O2 |
| Mr | 258.23 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 293 |
| a, b, c (Å) | 3.8256 (10), 7.0183 (19), 21.249 (6) |
| β (°) | 91.064 (4) |
| V (Å3) | 570.4 (3) |
| Z | 2 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.10 |
| Crystal size (mm) | 0.35 × 0.06 × 0.03 |
| Data collection | |
| Diffractometer | Bruker SMART APEX diffractometer |
| Absorption correction | – |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 4238, 1013, 600 |
| Rint | 0.048 |
| (sin θ/λ)max (Å−1) | 0.595 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.149, 1.06 |
| No. of reflections | 1013 |
| No. of parameters | 92 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.19, −0.18 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).
Acknowledgements
We thank Shahid Beheshti University and the University of Malaya for supporting this study.
References
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
The title substituted anthraquinone (Scheme I, Fig. 1) was synthesized to study its ability to absorb sulfur from oil when immobilized on silica surface (MCM-41). Anthraquinones are a class of anthracene derivatives having useful industrial applications (Alagesan & Samuelson, 1997; Chang et al., 1996; Cheng et al., 1994; Kuritani et al., 1973; Lin et al., 1995). However, they are usually only sparingly soluble in common oragnic solvents. In the present study, the synthesis involves the exchange of chlorine of 1,5-dichloroanthraquinone with the cyanide of copper cyanide (Coulson, 1930; Casey et al., 1999). The compound is somewhat soluble in DMSO but the recrystallized product is a yellow powder. Crystals were ultimately obtained by diffusing methanol into a DMSO solution of the compound.
The molecule of 1,5-dicyanoanthraquinone, which lies about a center-of-inversion, is planar (max. r.m.s.deviation 0.04 Å). Adjacent molecules are stacked over each other along the a-axis of the monoclinic unit cell; the distance is that of the a-axial length itself (Fig. 2).