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ISSN: 2056-9890

1,5-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

(Received 2 March 2010; accepted 2 March 2010; online 6 March 2010)

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.]); Coulson (1930a[Coulson, E. A. (1930a). J. Chem. Soc. pp. 1931-1936.],b[Coulson, E. A. (1930b). Chem. Abstr. 24, 49079.]). For some applications of anthraquinones, see: Alagesan & Samuelson (1997[Alagesan, K. & Samuelson, A. G. (1997). Synth. Met. 87, 37-44.]); Chang et al. (1996[Chang, J. S., Liu, L. K. & Wang, C. M. (1996). Jpn J. Appl. Phys. 35, L1042-L1043.]); Cheng et al. (1994[Cheng, H. W., Wang, C. M. & Liu, L. K. (1994). Jpn J. Appl. Phys. 33, L607-L609.]); Kuritani et al. (1973[Kuritani, M., Sakata, Y., Ogura, F. & Nakagawa, M. (1973). Bull. Chem. Soc. Jpn, 46, 605-610.]); Lin et al. (1995[Lin, H. L., Liu, L. K. & Wang, C. M. (1995). J. Phys. Chem. 99, 9136-9142.]).

[Scheme 1]

Experimental

Crystal data
  • C16H6N2O2

  • Mr = 258.23

  • Monoclinic, P 21 /c

  • a = 3.8256 (10) Å

  • b = 7.0183 (19) Å

  • c = 21.249 (6) Å

  • β = 91.064 (4)°

  • V = 570.4 (3) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 293 K

  • 0.35 × 0.06 × 0.03 mm

Data collection
  • Bruker SMART APEX diffractometer

  • 4238 measured reflections

  • 1013 independent reflections

  • 600 reflections with I > 2σ(I)

  • Rint = 0.048

Refinement
  • R[F2 > 2σ(F2)] = 0.053

  • wR(F2) = 0.149

  • S = 1.06

  • 1013 reflections

  • 92 parameters

  • H-atom parameters constrained

  • Δρmax = 0.19 e Å−3

  • Δρmin = −0.18 e Å−3

Data collection: APEX2 (Bruker, 2009[Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). publCIF. In preparation.]).

Supporting information


Comment top

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).

Related literature top

For the synthesis, see: Casey et al. (1999); 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).

Experimental top

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).

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: 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).

Figures top
[Figure 1] 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] Fig. 2. Stacking of the molecules in the unit cell of (I).
1,5-Dicyanoanthraquinone top
Crystal data top
C16H6N2O2F(000) = 264
Mr = 258.23Dx = 1.503 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 614 reflections
a = 3.8256 (10) Åθ = 3.1–25.4°
b = 7.0183 (19) ŵ = 0.10 mm1
c = 21.249 (6) ÅT = 293 K
β = 91.064 (4)°Prism, yellow
V = 570.4 (3) Å30.35 × 0.06 × 0.03 mm
Z = 2
Data collection top
Bruker SMART APEX
diffractometer
600 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.048
Graphite monochromatorθmax = 25.0°, θmin = 1.9°
ω scansh = 44
4238 measured reflectionsk = 88
1013 independent reflectionsl = 2525
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053H-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 reflectionsΔρmax = 0.19 e Å3
92 parametersΔρmin = 0.18 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.033 (9)
Crystal data top
C16H6N2O2V = 570.4 (3) Å3
Mr = 258.23Z = 2
Monoclinic, P21/cMo Kα radiation
a = 3.8256 (10) ŵ = 0.10 mm1
b = 7.0183 (19) ÅT = 293 K
c = 21.249 (6) Å0.35 × 0.06 × 0.03 mm
β = 91.064 (4)°
Data collection top
Bruker SMART APEX
diffractometer
600 reflections with I > 2σ(I)
4238 measured reflectionsRint = 0.048
1013 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.149H-atom parameters constrained
S = 1.06Δρmax = 0.19 e Å3
1013 reflectionsΔρmin = 0.18 e Å3
92 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.8448 (7)0.2052 (3)0.55023 (10)0.0691 (8)
N10.0797 (10)0.7591 (5)0.30574 (16)0.0837 (11)
C10.6782 (8)0.3375 (4)0.52815 (13)0.0407 (7)
C20.5829 (7)0.3390 (4)0.46013 (12)0.0373 (7)
C30.6669 (8)0.1823 (4)0.42375 (14)0.0473 (8)
H30.77520.07730.44230.057*
C40.5910 (9)0.1815 (5)0.36042 (15)0.0583 (10)
H40.64380.07500.33640.070*
C50.4369 (9)0.3378 (5)0.33232 (15)0.0566 (9)
H50.39030.33690.28920.068*
C60.3504 (7)0.4968 (4)0.36757 (13)0.0430 (8)
C70.4220 (7)0.4985 (4)0.43270 (12)0.0373 (7)
C80.1889 (8)0.6593 (5)0.33253 (14)0.0424 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.097 (2)0.0525 (15)0.0572 (15)0.0343 (13)0.0103 (13)0.0056 (11)
N10.090 (3)0.093 (3)0.068 (2)0.006 (2)0.0044 (19)0.0029 (19)
C10.0450 (18)0.0323 (16)0.0450 (17)0.0043 (13)0.0016 (13)0.0035 (13)
C20.0383 (17)0.0308 (16)0.0427 (16)0.0014 (12)0.0011 (12)0.0016 (12)
C30.053 (2)0.0347 (18)0.0540 (19)0.0052 (13)0.0015 (14)0.0067 (14)
C40.063 (2)0.052 (2)0.060 (2)0.0047 (16)0.0011 (17)0.0155 (17)
C50.058 (2)0.070 (2)0.0414 (17)0.0024 (17)0.0007 (15)0.0078 (16)
C60.0400 (17)0.0455 (18)0.0437 (17)0.0032 (14)0.0028 (12)0.0009 (14)
C70.0325 (15)0.0377 (17)0.0416 (16)0.0027 (12)0.0024 (11)0.0024 (12)
C80.0388 (18)0.050 (2)0.0382 (17)0.0024 (14)0.0053 (13)0.0059 (15)
Geometric parameters (Å, º) top
O1—C11.216 (3)C4—C51.376 (4)
N1—C80.991 (4)C4—H40.9300
C1—C7i1.475 (4)C5—C61.387 (4)
C1—C21.484 (4)C5—H50.9300
C2—C31.386 (4)C6—C71.406 (3)
C2—C71.399 (4)C6—C81.490 (4)
C3—C41.371 (4)C7—C1i1.475 (4)
C3—H30.9300
O1—C1—C7i121.2 (3)C5—C4—H4119.9
O1—C1—C2119.9 (3)C4—C5—C6120.8 (3)
C7i—C1—C2118.8 (2)C4—C5—H5119.6
C3—C2—C7120.5 (3)C6—C5—H5119.6
C3—C2—C1118.8 (2)C5—C6—C7119.6 (3)
C7—C2—C1120.7 (2)C5—C6—C8116.5 (3)
C4—C3—C2120.2 (3)C7—C6—C8123.9 (3)
C4—C3—H3119.9C2—C7—C6118.7 (3)
C2—C3—H3119.9C2—C7—C1i120.4 (2)
C3—C4—C5120.2 (3)C6—C7—C1i120.9 (3)
C3—C4—H4119.9N1—C8—C6174.6 (4)
O1—C1—C2—C34.2 (4)C4—C5—C6—C8179.3 (3)
C7i—C1—C2—C3177.9 (3)C3—C2—C7—C60.5 (4)
O1—C1—C2—C7173.6 (3)C1—C2—C7—C6177.2 (2)
C7i—C1—C2—C74.3 (4)C3—C2—C7—C1i177.9 (3)
C7—C2—C3—C40.4 (4)C1—C2—C7—C1i4.4 (4)
C1—C2—C3—C4178.2 (3)C5—C6—C7—C20.6 (4)
C2—C3—C4—C51.3 (5)C8—C6—C7—C2178.4 (3)
C3—C4—C5—C61.2 (5)C5—C6—C7—C1i177.8 (3)
C4—C5—C6—C70.2 (4)C8—C6—C7—C1i3.2 (4)
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC16H6N2O2
Mr258.23
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)3.8256 (10), 7.0183 (19), 21.249 (6)
β (°) 91.064 (4)
V3)570.4 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.35 × 0.06 × 0.03
Data collection
DiffractometerBruker SMART APEX
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4238, 1013, 600
Rint0.048
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.149, 1.06
No. of reflections1013
No. of parameters92
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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

First citationAlagesan, K. & Samuelson, A. G. (1997). Synth. Met. 87, 37–44.  CrossRef CAS Web of Science Google Scholar
First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationBruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCasey, 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.  Google Scholar
First citationChang, J. S., Liu, L. K. & Wang, C. M. (1996). Jpn J. Appl. Phys. 35, L1042–L1043.  CrossRef CAS Google Scholar
First citationCheng, H. W., Wang, C. M. & Liu, L. K. (1994). Jpn J. Appl. Phys. 33, L607–L609.  CrossRef CAS Web of Science Google Scholar
First citationCoulson, E. A. (1930a). J. Chem. Soc. pp. 1931–1936.  CrossRef Google Scholar
First citationCoulson, E. A. (1930b). Chem. Abstr. 24, 49079.  Google Scholar
First citationKuritani, M., Sakata, Y., Ogura, F. & Nakagawa, M. (1973). Bull. Chem. Soc. Jpn, 46, 605–610.  CrossRef CAS Web of Science Google Scholar
First citationLin, H. L., Liu, L. K. & Wang, C. M. (1995). J. Phys. Chem. 99, 9136–9142.  CrossRef CAS Web of Science Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2010). publCIF. In preparation.  Google Scholar

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