1,5-Dicyano­anthraquinone

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.053
• wR factor = 0.149
• Data-to-parameter ratio = 11.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    N1     --  C8      ..      17.58 su

Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C8
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C6     -   C8     ...       1.49 Ang.

Alert level G
PLAT333_ALERT_2_G Check Large Av C6-Ring C-C Dist. C1     -C7_a          1.45 Ang.
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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).

S3. Refinement

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

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

	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).
	Fig. 2. Stacking of the molecules in the unit cell of (I).

1,5-Dicyanoanthraquinone

Crystal data

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) Å^3	0.35 × 0.06 × 0.03 mm
Z = 2

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.053	H-atom parameters constrained
wR(F^2) = 0.149	w = 1/[σ^2(Fo^2) + (0.0649P)^2 + 0.1468P] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.033 (9)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

O1—C1	1.216 (3)	C4—C5	1.376 (4)
N1—C8	0.991 (4)	C4—H4	0.9300
C1—C7^i	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—C1^i	1.475 (4)
C3—H3	0.9300
O1—C1—C7^i	121.2 (3)	C5—C4—H4	119.9
O1—C1—C2	119.9 (3)	C4—C5—C6	120.8 (3)
C7^i—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—C1^i	120.4 (2)
C3—C4—C5	120.2 (3)	C6—C7—C1^i	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)
C7^i—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)
C7^i—C1—C2—C7	4.3 (4)	C3—C2—C7—C1^i	177.9 (3)
C7—C2—C3—C4	−0.4 (4)	C1—C2—C7—C1^i	−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—C1^i	−177.8 (3)
C4—C5—C6—C7	0.2 (4)	C8—C6—C7—C1^i	3.2 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.