4 (2 Meth­­oxy 4 nitro­phen­yl)morpholine 3,5 dione

organic papers

Acta Cryst.(2007). E63, o1115–o1116 doi:10.1107/S1600536807004692 Bhuiyanet al. _C

11H10N2O6

o1115

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

4-(2-Methoxy-4-nitrophenyl)morpholine-3,5-dione

M. Delower H. Bhuiyan,aPaul Jensen,bPeter Turnerband Andrew C. Trya*

a_{Department of Chemistry and Biomolecular}

Sciences, Building F7B, Macquarie University, NSW 2109, Australia, andb_{Crystal Structure}

Analysis Facility, School of Chemistry, F11, The University of Sydney, NSW 2006, Australia

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 150 K

Mean(C–C) = 0.002 A˚

Rfactor = 0.032

wRfactor = 0.092

Data-to-parameter ratio = 14.1

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

Received 19 December 2006 Accepted 29 January 2007

#2007 International Union of Crystallography All rights reserved

The crystal structure of the title compound, C11H10N2O6, is

stabilized by C—H interactions.

Comment

The reaction between anilines, or substituted anilines, and either succinic or glutaric acid in polyphosphoric acid (PPA) to afford N-phenyl succinimides and glutarimides was recently reported (Mederski et al., 2003). An analogous reaction between 4-nitroaniline and diglycolic acid failed to afford a cyclic diamide but unexpectedly yielded the first synthesis of 2,8-dinitro Tro¨ger’s base. In contrast, the synthesis of (I) was achieved by reacting 2-methoxy-4-nitroaniline with diglycolic acid in PPA,i.e.the anticipated cyclic diamide product.

We were interested in preparing a range of dinitro Tro¨ger’s base compounds and isolated (I) as a by-product in one of these reactions.

A short contact of 2.838 (2) A˚ exists between N1 and O6 of an adjacent molecule, as shown in Fig. 2. There are two C— H interactions which put this close contact in perspective. H9Ais 2.94 A˚ from the centroid of the benzene ring attached to N1; however, H11Awhich is in contact with the opposite side of the benzene ring is able to approach more closely at 2.76 A˚ from the centroid (symmetry codes for O6 and H9A:x, y 1,z; for H11A: 1 x, y, z). Atoms H9Aand H11Aare, respectively, 2.92 and 2.75 A˚ from the plane of the benzene ring and the close proximity of atom O6 also forces N1 to be pushed 0.104 (2) A˚ away from this plane.

Experimental

evaporated to dryness to yield a pale-yellow solid. The crude material was chromatographed (silica gel, dichloromethane) to afford (I) (546 mg, 34%) as a white solid. A second compound (the 4,10-dimethoxy-2,8-dinitro Tro¨ger’s base analogue, 224 mg, 20%) was subsequently eluted from the column.

Crystal data

C11H10N2O6

Mr= 266.21

Triclinic,P1

a= 7.526 (2) A˚

b= 7.554 (2) A˚

c= 10.259 (3) A˚ = 100.460 (4) = 102.539 (4) = 94.732 (4)

V= 555.3 (3) A˚3

Z= 2

Dx= 1.592 Mg m 3

MoKradiation = 0.13 mm 1

T= 150 (2) K Prism, yellow 0.540.320.29 mm

Data collection

Bruker SMART 1000 CCD diffractometer

!scans

Absorption correction: Gaussian [GAUSSIAN(Coppenset al., 1965) andXPREP

(Siemens, 1995)]

Tmin= 0.939,Tmax= 0.972

5320 measured reflections 2433 independent reflections 2109 reflections withI> 2(I)

Rint= 0.030 max= 27.1

Refinement

Refinement onF2

R[F2> 2(F2)] = 0.032

wR(F2_{) = 0.092}

S= 1.09 2433 reflections 173 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.046P)2

+ 0.1137P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.27 e A˚ 3

min= 0.26 e A˚ 3

H atoms were positioned geometrically, with C—H = 0.95, 0.99 and 0.98 A˚ for aromatic, methylene and methyl H atoms, respectively, and constrained to ride on their parent atoms, withUiso(H) =xUeq(C),

wherex= 1.5 for methyl H andx= 1.2 for all other H atoms. The

methyl group was free to rotate about the C—O bond in the refinement.

Data collection: SMART (Siemens, 1995); cell refinement:

SMART; data reduction: SAINT (Siemens, 1995) and XPREP

(Siemens, 1995); program(s) used to solve structure: SHELXS97

(Sheldrick, 1997); program(s) used to refine structure:SHELXL97

(Sheldrick, 1997); molecular graphics: Xtal3.6 (Hall et al., 1999),

ORTEPII(Johnson, 1976), andWinGX (Farrugia, 1999); software used to prepare material for publication:WinGX.

The authors thank the Australian Research Council for a Discovery Project grant to ACT (No. DP0345180), and Macquarie University for the award of a Macquarie University Research Development grant and the award of an iMURS grant to DHB.

References

Coppens, P., Leiserowitz, L. & Rabinovich, D. (1965).Acta Cryst.18, 1035– 1038.

Farrugia, L. J. (1999).J. Appl. Cryst.32, 837–838.

Hall, S. R., du Boulay, D. J. & Olthof-Hazekamp, R. (1999). Editors.Xtal3.6 System. University of Western Australia, Australia.

Johnson, C. K. (1976).ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.

Mederski, W. W. K. R., Baumgarth, M., Germann, M., Kux, D. & Weitzel, T. (2003).Tetrahedron Lett.44, 2133–2136.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.

Siemens (1995).SMART,SAINT and XPREP. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Figure 1

The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2

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Acta Cryst. (2007). E63, o1115–o1116

supporting information

Acta Cryst. (2007). E63, o1115–o1116 [https://doi.org/10.1107/S1600536807004692]

4-(2-Methoxy-4-nitrophenyl)morpholine-3,5-dione

M. Delower H. Bhuiyan, Paul Jensen, Peter Turner and Andrew C. Try

4-(2-methoxy-4-nitrophenyl)morpholine-3,5-dione

Crystal data

C11H10N2O6

Mr = 266.21

Triclinic, P1 Hall symbol: -P 1

a = 7.526 (2) Å

b = 7.554 (2) Å

c = 10.259 (3) Å

α = 100.460 (4)°

β = 102.539 (4)°

γ = 94.732 (4)°

V = 555.3 (3) Å3

Z = 2

F(000) = 276

Dx = 1.592 Mg m−3

Melting point: 486 K

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 863 reflections

θ = 3.1–28.2°

µ = 0.13 mm−1

T = 150 K Prism, yellow

0.54 × 0.32 × 0.29 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

Absorption correction: gaussian

[GAUSSIAN (Coppens et al., 1965) and XPREP (Siemens, 1995)]

Tmin = 0.939, Tmax = 0.972

5320 measured reflections 2433 independent reflections 2109 reflections with I > 2σ(I)

Rint = 0.030

θmax = 27.1°, θmin = 2.1°

h = −9→9

k = −9→9

l = −13→13

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.032}

wR(F2_{) = 0.092}

S = 1.09 2433 reflections 173 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2_(F

o2) + (0.046P)2 + 0.1137P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.27 e Å−3

Special details

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 F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

N1 0.79995 (13) −0.32869 (13) 0.13488 (11) 0.0225 (2)

N2 0.40014 (12) 0.23002 (12) 0.30811 (9) 0.0181 (2)

O1 0.93364 (12) −0.35848 (12) 0.21646 (10) 0.0341 (2)

O2 0.75368 (12) −0.40508 (12) 0.01449 (9) 0.0298 (2)

O3 0.24896 (10) −0.02408 (10) 0.07797 (8) 0.02107 (19)

O4 0.27752 (11) 0.52558 (11) 0.43958 (8) 0.0246 (2)

O5 0.19626 (11) 0.04616 (11) 0.37299 (9) 0.0265 (2)

O6 0.58401 (11) 0.41966 (11) 0.22981 (9) 0.0252 (2)

C1 0.68987 (15) −0.18997 (14) 0.18464 (12) 0.0186 (2)

C2 0.51785 (15) −0.18451 (14) 0.10317 (11) 0.0181 (2)

H2 0.4698 −0.2713 0.0207 0.022*

C3 0.41798 (14) −0.04716 (14) 0.14657 (11) 0.0173 (2)

C4 0.49643 (15) 0.07950 (14) 0.26773 (11) 0.0177 (2)

C5 0.66624 (15) 0.06711 (15) 0.34738 (12) 0.0209 (2)

H5 0.7149 0.1529 0.4303 0.025*

C6 0.76636 (15) −0.07093 (15) 0.30651 (12) 0.0212 (2)

H6 0.8828 −0.0825 0.3606 0.025*

C7 0.24866 (15) 0.19713 (15) 0.36230 (11) 0.0199 (2)

C8 0.15673 (16) 0.36161 (16) 0.40643 (13) 0.0255 (3)

H8A 0.0510 0.3691 0.3319 0.031*

H8B 0.1091 0.3463 0.4869 0.031*

C9 0.35197 (17) 0.55177 (15) 0.32763 (12) 0.0235 (3)

H9A 0.4337 0.6684 0.3533 0.028*

H9B 0.2510 0.5591 0.2496 0.028*

C10 0.45934 (15) 0.39991 (15) 0.28422 (11) 0.0189 (2)

C11 0.15733 (16) −0.16597 (16) −0.03647 (12) 0.0237 (3)

H11A 0.2304 −0.1785 −0.1052 0.036*

H11B 0.0361 −0.1353 −0.0764 0.036*

H11C 0.1431 −0.2807 −0.0057 0.036*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

N1 0.0186 (5) 0.0171 (5) 0.0328 (6) 0.0037 (4) 0.0082 (4) 0.0048 (4)

N2 0.0183 (5) 0.0157 (4) 0.0199 (5) 0.0030 (3) 0.0058 (4) 0.0006 (4)

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Acta Cryst. (2007). E63, o1115–o1116

O2 0.0336 (5) 0.0256 (5) 0.0309 (5) 0.0110 (4) 0.0112 (4) 0.0004 (4)

O3 0.0184 (4) 0.0197 (4) 0.0218 (4) 0.0061 (3) 0.0005 (3) −0.0008 (3)

O4 0.0289 (4) 0.0211 (4) 0.0233 (4) 0.0046 (3) 0.0096 (3) −0.0016 (3)

O5 0.0243 (4) 0.0240 (4) 0.0317 (5) −0.0003 (3) 0.0100 (4) 0.0049 (4)

O6 0.0279 (4) 0.0217 (4) 0.0294 (5) 0.0041 (3) 0.0133 (4) 0.0056 (3)

C1 0.0181 (5) 0.0139 (5) 0.0262 (6) 0.0042 (4) 0.0086 (4) 0.0052 (4)

C2 0.0194 (5) 0.0152 (5) 0.0194 (5) 0.0018 (4) 0.0053 (4) 0.0023 (4)

C3 0.0169 (5) 0.0165 (5) 0.0196 (5) 0.0025 (4) 0.0048 (4) 0.0055 (4)

C4 0.0187 (5) 0.0147 (5) 0.0210 (5) 0.0027 (4) 0.0078 (4) 0.0034 (4)

C5 0.0209 (5) 0.0186 (5) 0.0206 (6) 0.0001 (4) 0.0032 (4) 0.0005 (4)

C6 0.0165 (5) 0.0216 (5) 0.0250 (6) 0.0029 (4) 0.0029 (4) 0.0059 (5)

C7 0.0171 (5) 0.0233 (6) 0.0172 (5) 0.0014 (4) 0.0027 (4) 0.0011 (4)

C8 0.0223 (6) 0.0254 (6) 0.0296 (6) 0.0048 (5) 0.0102 (5) 0.0018 (5)

C9 0.0283 (6) 0.0193 (6) 0.0242 (6) 0.0065 (5) 0.0086 (5) 0.0035 (5)

C10 0.0213 (5) 0.0169 (5) 0.0167 (5) 0.0019 (4) 0.0027 (4) 0.0015 (4)

C11 0.0192 (5) 0.0231 (6) 0.0240 (6) 0.0046 (4) −0.0003 (4) −0.0023 (5)

Geometric parameters (Å, º)

N1—O2 1.2251 (14) C2—H2 0.9500

N1—O1 1.2262 (14) C3—C4 1.4019 (15)

N1—C1 1.4756 (14) C4—C5 1.3798 (16)

N2—C7 1.3961 (14) C5—C6 1.3925 (16)

N2—C10 1.4046 (14) C5—H5 0.9500

N2—C4 1.4440 (13) C6—H6 0.9500

O3—C3 1.3551 (13) C7—C8 1.5169 (16)

O3—C11 1.4396 (14) C8—H8A 0.9900

O4—C8 1.4154 (15) C8—H8B 0.9900

O4—C9 1.4198 (15) C9—C10 1.5136 (15)

O5—C7 1.2075 (14) C9—H9A 0.9900

O6—C10 1.2037 (14) C9—H9B 0.9900

C1—C6 1.3774 (16) C11—H11A 0.9800

C1—C2 1.3885 (16) C11—H11B 0.9800

C2—C3 1.3949 (15) C11—H11C 0.9800

O2—N1—O1 124.11 (10) C5—C6—H6 121.3

O2—N1—C1 118.09 (9) O5—C7—N2 121.20 (10)

O1—N1—C1 117.79 (10) O5—C7—C8 122.90 (10)

C7—N2—C10 123.71 (9) N2—C7—C8 115.90 (10)

C7—N2—C4 118.44 (9) O4—C8—C7 112.59 (9)

C10—N2—C4 117.77 (9) O4—C8—H8A 109.1

C3—O3—C11 116.97 (8) C7—C8—H8A 109.1

C8—O4—C9 111.09 (9) O4—C8—H8B 109.1

C6—C1—C2 124.24 (10) C7—C8—H8B 109.1

C6—C1—N1 118.03 (10) H8A—C8—H8B 107.8

C2—C1—N1 117.69 (10) O4—C9—C10 112.13 (9)

C1—C2—C3 117.69 (10) O4—C9—H9A 109.2

C3—C2—H2 121.2 O4—C9—H9B 109.2

O3—C3—C2 124.48 (10) C10—C9—H9B 109.2

O3—C3—C4 116.60 (9) H9A—C9—H9B 107.9

C2—C3—C4 118.91 (10) O6—C10—N2 121.45 (10)

C5—C4—C3 121.61 (10) O6—C10—C9 123.25 (10)

C5—C4—N2 119.05 (10) N2—C10—C9 115.27 (9)

C3—C4—N2 119.30 (9) O3—C11—H11A 109.5

C4—C5—C6 120.11 (10) O3—C11—H11B 109.5

C4—C5—H5 119.9 H11A—C11—H11B 109.5

C6—C5—H5 119.9 O3—C11—H11C 109.5

C1—C6—C5 117.36 (10) H11A—C11—H11C 109.5

C1—C6—H6 121.3 H11B—C11—H11C 109.5

O2—N1—C1—C6 −162.82 (10) N2—C4—C5—C6 −176.34 (10)

O1—N1—C1—C6 16.23 (15) C2—C1—C6—C5 −2.31 (17)

O2—N1—C1—C2 15.20 (15) N1—C1—C6—C5 175.57 (10)

O1—N1—C1—C2 −165.75 (10) C4—C5—C6—C1 0.79 (17)

C6—C1—C2—C3 1.33 (17) C10—N2—C7—O5 175.29 (10)

N1—C1—C2—C3 −176.56 (9) C4—N2—C7—O5 −1.45 (16)

C11—O3—C3—C2 9.19 (15) C10—N2—C7—C8 −4.92 (15)

C11—O3—C3—C4 −172.13 (10) C4—N2—C7—C8 178.34 (9)

C1—C2—C3—O3 179.80 (10) C9—O4—C8—C7 57.74 (13)

C1—C2—C3—C4 1.15 (15) O5—C7—C8—O4 154.73 (11)

O3—C3—C4—C5 178.63 (10) N2—C7—C8—O4 −25.06 (14)

C2—C3—C4—C5 −2.62 (16) C8—O4—C9—C10 −60.01 (12)

O3—C3—C4—N2 −3.40 (15) C7—N2—C10—O6 −175.51 (10)

C2—C3—C4—N2 175.35 (9) C4—N2—C10—O6 1.26 (16)

C7—N2—C4—C5 −106.57 (12) C7—N2—C10—C9 2.73 (15)

C10—N2—C4—C5 76.49 (14) C4—N2—C10—C9 179.49 (9)

C7—N2—C4—C3 75.41 (13) O4—C9—C10—O6 −152.49 (11)

C10—N2—C4—C3 −101.53 (12) O4—C9—C10—N2 29.32 (13)