1,4-Dihydro-benzo[g]quinoxaline-2,3-dione.

The title compound, C12H8N2O2, was prepared by the reaction of the diethyl ester of naphthalene-bis-(oxamate) with tert-BuNH2. The mol-ecule is nearly planar, with an r.m.s. deviation of 0.017 Å from the plane through all 16 non-H atoms. In the crystal, a three-dimensional network is formed, composed of layers of mol-ecules along the b- and c-axis directions, due to the formation of inter-molecular N-H⋯O hydrogen bonds, as well as of chains along the a-axis direction due to parallel displaced sandwich-type π-π inter-actions with average distances between the inter-acting mol-ecules in the range 3.35-3.40 Å.

Related literature

For the synthesis and structure of 1,4-dihydro­benzo[g]quin­oxaline-2,3-dione·3H2O, see: Oxtoby et al. (2005 ▶). For the use of bis­(oxamates) and bis­(oxamidates) for complex formation, see: Pardo et al. (2008 ▶) and Abdulmalic et al. (2012 ▶); Rüffer et al. (2012 ▶), respectively. For the general synthesis of bis­(oxamidates), see: Ruiz et al. (1997 ▶) and for the synthesis of diethyl N,N’-naphtalene-bis­(oxamate), see: Rüffer et al. (2007 ▶). For thin film formation by bis­(oxamato) complexes, see: Eya’ane Meva (2009 ▶); Bräuer et al. (2006 ▶). For self-organization in supra­molecular chemistry due to inter­molecular π inter­actions and/or hydrogen bonds, see: Burrow et al. (1996 ▶); Chowdhry et al. (1996 ▶); Dai et al. (1997 ▶); Munoz et al. (1998 ▶). For dione tautomerism in the solid state, see: Svenson (1976 ▶).

Experimental

Crystal data

C12H8N2O2

M = 212.20

Monoclinic,

a = 7.1334 (15) Å

b = 8.4229 (18) Å

c = 15.292 (2) Å

β = 99.792 (14)°

V = 905.4 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 293 K

0.3 × 0.2 × 0.1 mm

Data collection

Oxford Gemini S diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 ▶) T min = 0.649, T max = 1.000

5294 measured reflections

1773 independent reflections

875 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.094

wR(F 2) = 0.271

S = 0.92

1773 reflections

153 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.77 e Å−3

Δρmin = −0.57 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2006 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812047526/sj5284sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812047526/sj5284Isup3.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812047526/sj5284Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H8N2O2	F(000) = 440
Mr = 212.20	Dx = 1.557 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5135 reflections
a = 7.1334 (15) Å	θ = 2.9–25.9°
b = 8.4229 (18) Å	µ = 0.11 mm−1
c = 15.292 (2) Å	T = 293 K
β = 99.792 (14)°	Block, yellow
V = 905.4 (3) Å3	0.3 × 0.2 × 0.1 mm
Z = 4

Oxford Gemini S diffractometer	875 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
Graphite monochromator	θmax = 26.0°, θmin = 3.0°
ω scans	h = −8→7
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	k = −10→8
Tmin = 0.649, Tmax = 1.000	l = −18→18
5294 measured reflections	2 standard reflections every 50 reflections
1773 independent reflections	intensity decay: none

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)] = 0.094	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.271	H atoms treated by a mixture of independent and constrained refinement
S = 0.92	w = 1/[σ2(Fo2) + (0.2P)2] where P = (Fo2 + 2Fc2)/3
1773 reflections	(Δ/σ)max = 0.001
153 parameters	Δρmax = 0.77 e Å−3
0 restraints	Δρmin = −0.57 e Å−3

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
C1	0.2609 (4)	−0.2869 (4)	1.1809 (2)	0.0276 (8)
C2	0.1631 (4)	−0.3842 (4)	1.1026 (2)	0.0276 (8)
C3	0.2764 (4)	−0.0662 (4)	1.07897 (19)	0.0257 (8)
C4	0.1859 (4)	−0.1580 (3)	1.0060 (2)	0.0247 (8)
C5	0.3312 (4)	0.0874 (4)	1.06546 (19)	0.0246 (8)
H5	0.3908	0.1472	1.1134	0.030*
C6	0.1489 (4)	−0.0948 (4)	0.92275 (19)	0.0245 (8)
H6	0.0876	−0.1557	0.8757	0.029*
C7	0.2984 (4)	0.1545 (4)	0.9806 (2)	0.0253 (8)
C8	0.2032 (4)	0.0626 (4)	0.9075 (2)	0.0262 (8)
C9	0.3508 (4)	0.3129 (4)	0.9647 (2)	0.0272 (8)
H9	0.4124	0.3738	1.0116	0.033*
C10	0.1628 (4)	0.1342 (4)	0.8220 (2)	0.0284 (8)
H10	0.0984	0.0763	0.7743	0.034*
C11	0.3125 (5)	0.3775 (4)	0.8816 (2)	0.0327 (8)
H11	0.3488	0.4815	0.8726	0.039*
C12	0.2174 (5)	0.2868 (4)	0.8089 (2)	0.0327 (9)
H12	0.1924	0.3313	0.7525	0.039*
N1	0.3053 (4)	−0.1348 (3)	1.16349 (17)	0.0273 (7)
N2	0.1300 (4)	−0.3136 (3)	1.02231 (17)	0.0260 (7)
O1	0.2918 (3)	−0.3464 (3)	1.25533 (14)	0.0361 (7)
O2	0.1113 (3)	−0.5216 (3)	1.11523 (14)	0.0344 (7)
H1N	0.354 (5)	−0.073 (5)	1.211 (2)	0.043 (10)*
H2N	0.053 (6)	−0.366 (5)	0.975 (3)	0.059 (12)*

	U11	U22	U33	U12	U13	U23
C1	0.0346 (19)	0.0156 (17)	0.0319 (17)	0.0018 (13)	0.0036 (13)	−0.0041 (13)
C2	0.0318 (18)	0.0181 (17)	0.0319 (16)	0.0028 (13)	0.0028 (13)	0.0005 (13)
C3	0.0279 (18)	0.0199 (18)	0.0290 (16)	0.0010 (12)	0.0041 (12)	−0.0026 (13)
C4	0.0258 (18)	0.0128 (16)	0.0358 (17)	0.0013 (12)	0.0055 (13)	−0.0030 (12)
C5	0.0273 (17)	0.0139 (16)	0.0316 (16)	0.0028 (12)	0.0023 (12)	−0.0012 (12)
C6	0.0265 (17)	0.0172 (17)	0.0289 (15)	0.0001 (12)	0.0019 (12)	−0.0036 (12)
C7	0.0279 (18)	0.0137 (17)	0.0345 (16)	0.0027 (12)	0.0056 (13)	−0.0020 (13)
C8	0.0307 (18)	0.0146 (17)	0.0347 (17)	0.0018 (12)	0.0099 (13)	0.0023 (13)
C9	0.0272 (18)	0.0195 (18)	0.0347 (17)	−0.0006 (13)	0.0044 (13)	−0.0005 (13)
C10	0.0333 (19)	0.0197 (18)	0.0322 (16)	−0.0007 (13)	0.0052 (13)	−0.0029 (13)
C11	0.042 (2)	0.0199 (18)	0.0370 (18)	−0.0007 (14)	0.0081 (14)	0.0021 (13)
C12	0.044 (2)	0.0243 (19)	0.0300 (16)	0.0043 (14)	0.0064 (14)	0.0065 (13)
N1	0.0394 (17)	0.0154 (15)	0.0257 (14)	−0.0026 (11)	0.0013 (11)	−0.0027 (10)
N2	0.0342 (16)	0.0130 (14)	0.0297 (14)	−0.0001 (10)	0.0021 (11)	−0.0018 (10)
O1	0.0532 (16)	0.0191 (14)	0.0330 (13)	−0.0021 (10)	−0.0007 (10)	0.0033 (9)
O2	0.0459 (15)	0.0148 (13)	0.0400 (14)	−0.0017 (9)	0.0005 (10)	0.0008 (9)

C1—O1	1.230 (4)	C6—H6	0.9300
C1—N1	1.356 (4)	C7—C9	1.417 (4)
C1—C2	1.518 (4)	C7—C8	1.432 (4)
C2—O2	1.240 (4)	C8—C10	1.425 (4)
C2—N2	1.349 (4)	C9—C11	1.366 (4)
C3—C5	1.378 (4)	C9—H9	0.9300
C3—N1	1.399 (4)	C10—C12	1.367 (4)
C3—C4	1.420 (4)	C10—H10	0.9300
C4—C6	1.364 (4)	C11—C12	1.423 (5)
C4—N2	1.404 (4)	C11—H11	0.9300
C5—C7	1.398 (4)	C12—H12	0.9300
C5—H5	0.9300	N1—H1N	0.91 (4)
C6—C8	1.412 (4)	N2—H2N	0.94 (4)
O1—C1—N1	123.8 (3)	C6—C8—C10	122.0 (3)
O1—C1—C2	119.7 (3)	C6—C8—C7	119.1 (3)
N1—C1—C2	116.5 (3)	C10—C8—C7	118.9 (3)
O2—C2—N2	122.8 (3)	C11—C9—C7	121.2 (3)
O2—C2—C1	119.4 (3)	C11—C9—H9	119.4
N2—C2—C1	117.7 (3)	C7—C9—H9	119.4
C5—C3—N1	121.7 (3)	C12—C10—C8	120.9 (3)
C5—C3—C4	119.8 (3)	C12—C10—H10	119.6
N1—C3—C4	118.5 (3)	C8—C10—H10	119.6
C6—C4—N2	121.0 (3)	C9—C11—C12	120.4 (3)
C6—C4—C3	120.7 (3)	C9—C11—H11	119.8
N2—C4—C3	118.3 (3)	C12—C11—H11	119.8
C3—C5—C7	120.8 (3)	C10—C12—C11	120.1 (3)
C3—C5—H5	119.6	C10—C12—H12	120.0
C7—C5—H5	119.6	C11—C12—H12	120.0
C4—C6—C8	120.4 (3)	C1—N1—C3	124.6 (3)
C4—C6—H6	119.8	C1—N1—H1N	117 (2)
C8—C6—H6	119.8	C3—N1—H1N	118 (2)
C5—C7—C9	122.2 (3)	C2—N2—C4	124.2 (3)
C5—C7—C8	119.2 (3)	C2—N2—H2N	119 (3)
C9—C7—C8	118.6 (3)	C4—N2—H2N	117 (3)
O1—C1—C2—O2	1.7 (5)	C5—C7—C8—C10	177.3 (3)
N1—C1—C2—O2	−176.8 (3)	C9—C7—C8—C10	−0.8 (4)
O1—C1—C2—N2	179.3 (3)	C5—C7—C9—C11	−178.1 (3)
N1—C1—C2—N2	0.8 (4)	C8—C7—C9—C11	−0.1 (5)
C5—C3—C4—C6	−1.3 (5)	C6—C8—C10—C12	−179.8 (3)
N1—C3—C4—C6	177.9 (3)	C7—C8—C10—C12	1.5 (5)
C5—C3—C4—N2	−179.3 (3)	C7—C9—C11—C12	0.4 (5)
N1—C3—C4—N2	−0.1 (4)	C8—C10—C12—C11	−1.3 (5)
N1—C3—C5—C7	−179.0 (3)	C9—C11—C12—C10	0.4 (5)
C4—C3—C5—C7	0.2 (5)	O1—C1—N1—C3	178.1 (3)
N2—C4—C6—C8	179.0 (2)	C2—C1—N1—C3	−3.5 (4)
C3—C4—C6—C8	1.1 (5)	C5—C3—N1—C1	−177.6 (3)
C3—C5—C7—C9	179.2 (3)	C4—C3—N1—C1	3.2 (5)
C3—C5—C7—C8	1.2 (5)	O2—C2—N2—C4	179.7 (3)
C4—C6—C8—C10	−178.4 (3)	C1—C2—N2—C4	2.2 (4)
C4—C6—C8—C7	0.3 (5)	C6—C4—N2—C2	179.5 (3)
C5—C7—C8—C6	−1.4 (4)	C3—C4—N2—C2	−2.6 (5)
C9—C7—C8—C6	−179.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1i	0.91 (4)	2.27 (4)	2.866 (3)	122 (3)
N2—H2N···O2ii	0.94 (4)	1.90 (4)	2.843 (4)	176 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1i	0.91 (4)	2.27 (4)	2.866 (3)	122 (3)
N2—H2N⋯O2ii	0.94 (4)	1.90 (4)	2.843 (4)	176 (4)

Symmetry codes: (i) ; (ii) .