supplementary materials

rz5073 scheme

Acta Cryst. (2013). E69, o1152-o1153    [ doi:10.1107/S1600536813016991 ]

N,N'-Dihydroxybenzene-1,2:4,5-tetracarboximide dihydrate

R. Centore and A. Carella

Abstract top

In the title compound, C10H4N2O6·2H2O, the organic molecule has crystallographically imposed inversion symmetry. The atoms of the three fused rings of the molecule are coplanar within 0.0246 (8) Å, while the two hydroxy O atoms are displaced from the mean plane of the molecule by 0.127 (1) Å. In the crystal, infinite near-planar layers of close-packed molecules are formed by hydrogen bonding between water O-H donor groups and carbonyl O-atom acceptors, and by weak interactions between C-H donor groups and water O-atom acceptors. The layers are parallel to the {102} family of planes. The stacked planes are held together by hydrogen bonding between N-OH donor groups and water O-atom acceptors.

Comment top

The crystal engineering of structures containing stacked infinite planar layers of H bonded aromatic molecules is a hot research topic because of the potential interest of such structures as advanced materials in organic electronics, optoelectronics and photonics (Centore, Causà et al. 2013). Conjugated heterocyclic aromatic compounds are often used as building blocks for assembling active molecules for those advanced applications (Carella et al., 2004; Centore, Concilio et al., 2012). Aromatic diimides, in particular, are well known for their outstanding properties as n-type organic semiconductors (Centore, Ricciotti et al., 2012). Following these issues and our basic interest for crystal structures of conjugated heteroaromatic compounds conditioned by the formation of strong and weak H bonds (Centore et al., 2013a; 2013b) we report the structural investigation of the title compound, which is the dihydrate form of the N,N'-dihydroxy derivative of the simplest aromatic bis(imide).

The molecular structure is shown in Fig. 1. The organic molecule lies in special position on inversion centres and has point symmetry Ci. The atoms of the three fused rings of the molecule are coplanar within 0.0246 (8) Å, while the two hydroxy oxygen atoms are out of the average plane of the molecule by ±0.127 (1) Å. This is related with the torsion angle C2–C5–N1–O3 which is 171.9 (1)°, and would suggest a slight degree of pyramidalization at N1 (the sum of the valence angles around N1 is 359.1 (2)°). The two hydroxy H atoms are off the molecular plane because of the torsion angle C5–N1–O3–H3 = 80 (1)°.

Each organic molecule is in-plane surrounded by six water molecules. With four of them there are H bonds between O–H donors of the water molecules and carbonyl O acceptors of the diimide molecule. With the remaining two water molecules, there are weak interactions involving C–H donor and water O acceptor. Infinite planar layers of close-packed H bonded molecules are formed in this way, Fig. 2(a), in which ring patterns R44(14) and R44(15) are easily spotted. The layers are parallel to the family of planes with Miller indices (1 0 2), Fig. 2(b), and, in fact, the reflection (1 0 2) is the most intense of the whole diffraction pattern because, with the exception for the N–OH hydrogen atoms, all the atoms of the two molecules lie onto those planes. The stacked layers are held together by H bonds involving N–OH donors of a layer and water O acceptors of adjacent layers and this may account for the short interplanar spacing, d102 = 2.99 Å. As it is clear from Fig. 2(b), adjacent stacked layers are related by a 21 screw operation, which is a very efficient way to fulfill the Kitaigorodskii's "bumps in hollows" golden rule of the close packing of layers (Kitaigorodskii, 1961).

Related literature top

For semiconductor, optoelectronic and piezoelectric materials containing heterocycles, see: Centore, Ricciotti et al. (2012); Centore, Concilio et al. (2012). For the structural analysis of conjugation in organic molecules containing heterocycles, see: Carella et al. (2004). For the crystal packing of heterocycles containing nitrogen, see: Centore et al. (2013a,b). For the crystal engineering of structures containing stacked infinite planar layers, see: Centore, Causà et al. (2013). For the principle of close packing in organic crystallography, see: Kitaigorodskii (1961).

Experimental top

Hydroxylamine hydrochloride (3.18 g, 45.8 mmol) was added to pyridine (25 ml) and stirred at room temperature for 10 min until a clear solution was obtained. Pyromellitic anhydride (5.00 g, 22.9 mmol) was added and the solution was refluxed overnight. The solution was cooled to room temperature and the solid precipitate was filtered and washed with methanol and dried in oven at 120 °C for three days. Then it was poured in 100 ml of a solution methanol/conc. HCl (9:1 v/v). The suspension was left on stirring at gentle boiling for 1 h and then cooled to room temperature. The solid precipitate was filtered. The yield was 1.70 g (30%). 1H-NMR (DMSO-d6, 200 MHz): 8.11 (2H, s, C–H); 11.14 (2H, s, N–OH).

Single crystals for X-ray analysis were obtained by slow evaporation of an ethanol/water (1:1 v/v) solution.

Refinement top

The H atoms bonded to O atoms were located in a difference Fourier map and their coordinates were refined. The H atom on benzene ring was generated stereochemically and was refined by the riding model. For all H atoms Uiso(H) = 1.2Ueq(C, O) was assumed.

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top
[Figure 1] Fig. 1. ORTEP view of the molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. Symmetry code: (i) = -x, -y, -z.
[Figure 2] Fig. 2. Partial crystal packing of the title compound, showing some H bonding patterns. H bonds are represented by dashed lines; (a) front view of a layer of H bonded molecules; (b) edge view, along b, of two adjacent layers.
2,6-Dihydroxy-1H,2H,3H,5H,6H,7H-pyrrolo[3,4-f]isoindole-1,3,5,7-tetrone dihydrate top
Crystal data top
C10H4N2O6·2H2OF(000) = 292
Mr = 284.18Dx = 1.736 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 150 reflections
a = 6.874 (3) Åθ = 4.9–23.6°
b = 10.189 (5) ŵ = 0.15 mm1
c = 8.099 (4) ÅT = 293 K
β = 106.58 (2)°Prism, yellow
V = 543.7 (4) Å30.40 × 0.40 × 0.30 mm
Z = 2
Data collection top
Bruker–Nonius KappaCCD
1231 independent reflections
Radiation source: normal-focus sealed tube1100 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
Detector resolution: 9 pixels mm-1θmax = 27.5°, θmin = 3.1°
CCD rotation images, thick slices scansh = 88
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
k = 1113
Tmin = 0.941, Tmax = 0.955l = 109
4484 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.0519P)2 + 0.137P]
where P = (Fo2 + 2Fc2)/3
1231 reflections(Δ/σ)max < 0.001
100 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C10H4N2O6·2H2OV = 543.7 (4) Å3
Mr = 284.18Z = 2
Monoclinic, P21/cMo Kα radiation
a = 6.874 (3) ŵ = 0.15 mm1
b = 10.189 (5) ÅT = 293 K
c = 8.099 (4) Å0.40 × 0.40 × 0.30 mm
β = 106.58 (2)°
Data collection top
Bruker–Nonius KappaCCD
1231 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
1100 reflections with I > 2σ(I)
Tmin = 0.941, Tmax = 0.955Rint = 0.035
4484 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.036H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.100Δρmax = 0.22 e Å3
S = 1.09Δρmin = 0.25 e Å3
1231 reflectionsAbsolute structure: ?
100 parametersAbsolute structure parameter: ?
0 restraintsRogers parameter: ?
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
C10.10245 (17)0.10697 (12)0.05619 (15)0.0244 (3)
C20.05331 (17)0.12613 (11)0.01756 (15)0.0230 (3)
C30.15149 (15)0.02254 (11)0.07171 (14)0.0230 (3)
C40.31036 (17)0.07755 (12)0.14333 (15)0.0254 (3)
C50.14618 (17)0.25083 (12)0.05285 (15)0.0258 (3)
N10.29927 (15)0.21147 (11)0.12231 (14)0.0287 (3)
O10.42607 (13)0.02174 (10)0.20623 (12)0.0346 (3)
O20.10464 (15)0.36247 (8)0.02877 (13)0.0360 (3)
O30.40708 (15)0.29756 (10)0.19205 (13)0.0367 (3)
H30.499 (3)0.3314 (17)0.103 (2)0.044*
O40.32117 (15)0.38853 (10)0.08642 (14)0.0367 (3)
H4A0.249 (2)0.4570 (19)0.067 (2)0.044*
H4B0.387 (3)0.4151 (18)0.163 (2)0.044*
Atomic displacement parameters (Å2) top
C10.0234 (5)0.0230 (6)0.0280 (6)0.0016 (4)0.0092 (4)0.0017 (5)
C20.0226 (5)0.0207 (5)0.0255 (5)0.0009 (4)0.0063 (4)0.0001 (4)
C30.0198 (5)0.0255 (6)0.0246 (5)0.0000 (4)0.0077 (4)0.0006 (4)
C40.0231 (5)0.0285 (6)0.0248 (5)0.0012 (4)0.0074 (4)0.0019 (4)
C50.0268 (6)0.0245 (6)0.0258 (5)0.0030 (4)0.0072 (4)0.0003 (5)
N10.0303 (5)0.0264 (6)0.0335 (5)0.0068 (4)0.0156 (4)0.0007 (4)
O10.0314 (5)0.0382 (6)0.0405 (5)0.0032 (4)0.0202 (4)0.0014 (4)
O20.0436 (6)0.0221 (5)0.0451 (6)0.0019 (4)0.0170 (5)0.0012 (4)
O30.0383 (5)0.0379 (6)0.0369 (5)0.0155 (4)0.0157 (4)0.0047 (4)
O40.0379 (5)0.0324 (5)0.0436 (6)0.0011 (4)0.0178 (4)0.0028 (4)
Geometric parameters (Å, º) top
C1—C3i1.3766 (17)C4—N11.3799 (18)
C1—C21.3806 (17)C5—O21.2022 (16)
C1—H10.9300C5—N11.3866 (16)
C2—C31.3895 (16)N1—O31.3699 (13)
C2—C51.4858 (16)O3—H30.886 (19)
C3—C1i1.3766 (17)O4—H4A0.896 (19)
C3—C41.4848 (16)O4—H4B0.909 (19)
C4—O11.2028 (15)
C3i—C1—C2114.54 (11)O1—C4—C3129.49 (12)
C3i—C1—H1122.7N1—C4—C3104.62 (10)
C2—C1—H1122.7O2—C5—N1125.62 (11)
C1—C2—C3122.39 (11)O2—C5—C2130.01 (11)
C1—C2—C5129.26 (11)N1—C5—C2104.37 (10)
C3—C2—C5108.35 (11)O3—N1—C4121.80 (10)
C1i—C3—C2123.07 (11)O3—N1—C5123.00 (11)
C1i—C3—C4128.62 (11)C4—N1—C5114.27 (10)
C2—C3—C4108.31 (11)N1—O3—H3105.0 (11)
O1—C4—N1125.88 (11)H4A—O4—H4B107.4 (16)
C3i—C1—C2—C30.13 (18)C3—C2—C5—O2178.61 (12)
C3i—C1—C2—C5179.51 (11)C1—C2—C5—N1178.07 (11)
C1—C2—C3—C1i0.1 (2)C3—C2—C5—N11.61 (13)
C5—C2—C3—C1i179.57 (10)O1—C4—N1—O38.09 (19)
C1—C2—C3—C4179.69 (10)C3—C4—N1—O3172.06 (10)
C5—C2—C3—C40.02 (12)O1—C4—N1—C5177.34 (11)
C1i—C3—C4—O11.9 (2)C3—C4—N1—C52.80 (13)
C2—C3—C4—O1178.56 (12)O2—C5—N1—O38.29 (19)
C1i—C3—C4—N1177.92 (11)C2—C5—N1—O3171.92 (10)
C2—C3—C4—N11.59 (12)O2—C5—N1—C4177.40 (12)
C1—C2—C5—O21.7 (2)C2—C5—N1—C42.81 (13)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
O3—H3···O4ii0.886 (19)1.768 (19)2.6516 (18)175.2 (17)
O4—H4A···O2iii0.896 (19)2.15 (2)3.0441 (17)172.4 (16)
O4—H4B···O1iv0.909 (19)1.990 (19)2.8879 (16)169.3 (15)
C1—H1···O40.932.403.280 (2)158
Symmetry codes: (ii) x1, y, z; (iii) x, y+1, z; (iv) x+1, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC10H4N2O6·2H2O
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)6.874 (3), 10.189 (5), 8.099 (4)
β (°) 106.58 (2)
V3)543.7 (4)
Radiation typeMo Kα
µ (mm1)0.15
Crystal size (mm)0.40 × 0.40 × 0.30
Data collection
DiffractometerBruker–Nonius KappaCCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.941, 0.955
No. of measured, independent and
observed [I > 2σ(I)] reflections
4484, 1231, 1100
(sin θ/λ)max1)0.649
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.100, 1.09
No. of reflections1231
No. of parameters100
No. of restraints0
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.22, 0.25

Computer programs: COLLECT (Nonius, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top
O3—H3···O4i0.886 (19)1.768 (19)2.6516 (18)175.2 (17)
O4—H4A···O2ii0.896 (19)2.15 (2)3.0441 (17)172.4 (16)
O4—H4B···O1iii0.909 (19)1.990 (19)2.8879 (16)169.3 (15)
C1—H1···O40.932.403.280 (2)157.8
Symmetry codes: (i) x1, y, z; (ii) x, y+1, z; (iii) x+1, y+1/2, z1/2.
Acknowledgements top

The authors thank the Centro Interdipartimentale di Metodologie Chimico-Fisiche, Università degli Studi di Napoli `Federico II'.

References top

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