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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 60| Part 7| July 2004| Pages o511-o513
doi:10.1107/S0108270104013575

N-(4-Fluoro­phenyl)-4-nitro­phthal­imide: tripartite hydrogen-bonded sheets

CROSSMARK_Color_square_no_text.svg
Christopher Glidewell,a* John N. Low,b Janet M. S. Skakleb and James L. Wardellc

aSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland, bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and cInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, 21945-970 Rio de Janeiro, RJ, Brazil
*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 1 June 2004; accepted 4 June 2004; online 22 June 2004)

Molecules of the title compound, C14H7FN2O4, are linked by two C—H⋯O hydrogen bonds [H⋯O = 2.42 and 2.44 Å, C⋯O = 3.173 (9) and 3.313 (10) Å, and C—H⋯O = 134 and 157°] into deep tripartite sheets, where the central layer is built from hydrogen-bonded R[{_6^6}](24) rings and where the F atoms all lie on the exterior surfaces of the sheets.

Comment

The title compound, (I[link]), was synthesized as part of a study of supramolecular interactions in substituted phthal­imides and related compounds. We present here its molecular and crystal structure.

[Scheme 1]

Within the mol­ecule of (I[link]) (Fig. 1[link]), the dihedral angle between the planes of the heterocyclic rings and the fluorinated aryl ring is 50.5 (4)°, while the dihedral angle between the C—NO2 plane and the adjacent carbocyclic ring is 10.3 (4)°. Consequently, the mol­ecules of (I[link]) have no internal symmetry in the solid state, and hence they are chiral in the solid state, although the bulk material in solution is racemic. Compound (I[link]) crystallizes in the noncentrosymmetric space group P21. If the crystals form inversion twins, which is common in crystals having non-centrosymmetric space groups (Flack & Bernardinelli, 1999[Flack, H. D. & Bernardinelli, G. (1999). Acta Cryst. A55, 908-915.]), then both enantiomers will be present in each such twinned crystal, although in the absence of such twinning, each crystal will contain only a single enantiomer, so that (I[link]) would, in these circumstances, represent an example of conglomerate crystallization associated with spontaneous resolution. The indeterminate nature of the Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]) parameter in (I[link]) prevents any decision between these possibilities. The bond lengths and angles in (I[link]) present no unusual features.

The mol­ecules of (I[link]) are linked into thick sheets by means of two C—H⋯O hydrogen bonds (Table 1[link]). Atom C6 in the mol­ecule at (x, y, z) acts as hydrogen-bond donor to nitro atom O51 in the mol­ecule at (1 − x, [{1 \over 2}] + y, 1 − z), so producing a zigzag C(5) chain (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) running parallel to the [010] direction and generated by the 21 screw axis along ([{1 \over 2}], y, [{1 \over 2}]) (Fig. 2[link]). At the same time, adjacent atom C7 in the mol­ecule at (x, y, z) acts as hydrogen-bond donor to the other nitro O atom, O52, in the mol­ecule at (x − 1, 1 + y, z), so generating by translation a C(6) chain running parallel to the [[\overline 1]10] direction (Fig. 3[link]). The combination of these [010] and [[\overline 1]10] chains generates a tripartite sheet occupying the entire domain of z, in which a central hydrogen-bonded layer built from a single type of R[{_6^6}](24) ring lies between two outer layers of aryl rings, with the F substituents on the outside surfaces of the layer (Fig. 4[link]).

There are neither C—H⋯π(arene) hydrogen bonds nor aromatic π–π stacking interactions in the structure of (I[link]). The only possible direction-specific interaction between the sheets, involving a C—H bond in one layer and an F substituent in the adjacent sheet, in fact, has an H⋯F distance (Table 1[link]) far in excess of those associated with non-trivial interaction energies in C—H⋯F hydrogen bonds (Howard et al., 1996[Howard, J. A. K., Hoy, V. J., O'Hagan, D. & Smith, G. T. (1996). Tetrahedron, 52, 12613-12622.]). Accordingly, any possible structural significance of this H⋯F contact can be discounted, so that the hydrogen-bonded supramolecular structure of (I[link]) is strictly two-dimensional.

The form of the supramolecular structure, as deep sheets partially coated with F, is reflected in the macroscopic behaviour of the crystals, which form very thin flakes which are highly hydro­phobic and which when rubbed between the fingers leave a distinctly greasy coating.

[Figure 1]
Figure 1
The mol­ecule of (I[link]), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2]
Figure 2
Part of the crystal structure of (I[link]), showing the formation of a C(5) chain along [010]. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1 − x, y − [{1 \over 2}], 1 − z) and (x, 1 + y, z), respectively.
[Figure 3]
Figure 3
Part of the crystal structure of (I[link]), showing the formation of a C(6) chain along [[\overline 1]10]. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x − 1, 1 + y, z) and (1 + x, y − 1, z), respectively.
[Figure 4]
Figure 4
A stereoview of part of the crystal structure of (I[link]), showing the formation of an (001) sheet built from R[{_6^6}](24) rings. For the sake of clarity, the H atoms not involved in the motifs shown have been omitted.

Experimental

An equimolar mixture of very finely divided 4-fluoro­aniline and 4-nitro­phthal­imide was heated on an electric hotplate, in the absence of solvent, until the evolution of water had ceased. The reaction product was cooled and dissolved in 1,2-di­chloro­ethane. Activated charcoal was added, and the mixture was then filtered. Evaporation of the solvent gave compound (I[link]). After repeated attempts to obtain crystals suitable for single-crystal X-ray diffraction, some very thin flakes of rather indifferent quality and markedly waxy consistency were finally obtained from ethanol. A number of these crystals were investigated before any satisfactory diffraction data were obtained.

Crystal data

  • C14H7FN2O4

  • Mr = 286.22

  • Monoclinic, P21

  • a = 3.7492 (13) Å

  • b = 6.9376 (14) Å

  • c = 23.099 (8) Å

  • β = 90.118 (11)°

  • V = 600.8 (3) Å3

  • Z = 2

  • Dx = 1.582 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 1099 reflections

  • θ = 3.5–25.0°

  • μ = 0.13 mm−1

  • T = 120 (2) K

  • Plate, yellow

  • 0.15 × 0.08 × 0.02 mm
Data collection

  • Nonius KappaCCD area-detector diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.]) Tmin = 0.976, Tmax = 0.997

  • 4455 measured reflections

  • 1099 independent reflections

  • 757 reflections with I > 2σ(I)

  • Rint = 0.114

  • θmax = 25.0°

  • h = −4 → 4

  • k = −7 → 7

  • l = −27 → 27
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.070

  • wR(F2) = 0.154

  • S = 1.06

  • 1099 reflections

  • 190 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0761P)2] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.26 e Å−3

  • Δρmin = −0.24 e Å−3

Table 1
Geometry of hydrogen bonds and short intermolecular contacts (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C6—H6⋯O51i 0.95 2.44 3.173 (9) 134
C7—H7⋯O52ii 0.95 2.42 3.313 (10) 157
C13—H13⋯F14iii 0.95 2.54 3.438 (9) 157
Symmetry codes: (i) [1-x,{\script{1\over 2}}+y,1-z]; (ii) x-1,1+y,z; (iii) [1-x,y-{\script{1\over 2}},-z].

The systematic absences permitted P21 and P21/m as possible space groups; space group P21 was selected and confirmed by the subsequent structure analysis. All H atoms were located from difference maps and then treated as riding atoms, with C—H distances of 0.95 Å and Uiso(H) = 1.2Ueq(C). In the absence of significant anomalous scattering, the Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]) parameter was indeterminate (Flack & Bernardinelli, 2000[Flack, H. D. & Bernardinelli, G. (2000). J. Appl. Cryst. 33, 1143-1148.]). Accordingly, the Friedel-equivalent reflections were merged prior to the final refinement.

Data collection: COLLECT (Hooft, 1999[Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003[McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.]) and SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 3-17.]); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S0108270104013575/sk1736sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104013575/sk1736Isup2.hkl


Comment top

The title compound, (I), was synthesized as part of a study of supramolecular interactions in substituted phthalimides and related compounds. We present here its molecular and crystal structure. \sch

Within the molecule of (I) (Fig. 1), the dihedral angle between the planes of the heterocyclic rings and the fluorinated aryl ring is 50.5 (4)°, while the dihedral angle between the C—NO2 plane and the adjacent carbocyclic ring is 10.3 (4)°. Consequently, the molecules of (I) have no internal symmetry in the solid state, and hence they are chiral in the solid state, although the bulk material in solution is racemic. Compound (I) crystallizes in the noncentrosymmetric space group P21. If the crystals form inversion twins, which is common in crystals having non-centrosymmetric space groups (Flack & Bernardinelli, 1999), then both enantiomers will be present in each such twinned crystal, although in the absence of such twinning, each crystal will contain only a single enantiomer, so that (I) would, in these circumstances, represent an example of conglomerate crystallization associated with spontaneous resolution. The indeterminate nature of the Flack parameter (Flack, 1983) in (I) prevents any decision between these possibilities. The bond lengths and angles in (I) present no unusual features.

The molecules of (I) are linked into thick sheets by means of two C—H···O hydrogen bonds (Table 1). Atom C6 in the molecule at (x, y, z) acts as hydrogen-bond donor to nitro atom O51 in the molecule at (1 − x, 1/2 + y, 1 − z), so producing a zigzag C(5) chain (Bernstein et al., 1995) running parallel to the [010] direction and generated by the 21 screw axis along (1/2, y, 1/2) (Fig. 2). At the same time, the adjacent atom C7 in the molecule at (x, y, z) acts as hydrogen-bond donor to the other nitro O atom, O52, in the molecule at (x − 1, 1 + y, z), so generating by translation a C(6) chain running parallel to the [110] direction (Fig. 3). The combination of these [010] and [110] chains generates a tripartite sheet occupying the entire domain of z, in which a central hydrogen-bonded layer built from a single type of R66(24) ring lies between two outer layers of aryl rings, with the F substituents on the outside surfaces of the layer (Fig. 4).

There are neither C—H···π(arene) hydrogen bonds nor aromatic π–π stacking interactions in the structure of (I). The only possible direction-specific interaction between the sheets, involving a C—H bond in one layer and an F substituent in the adjacent sheet, in fact has an H···F distance (Table 1) far in excess of those associated with non-trivial interaction energies in C—H···F hydrogen bonds (Howard et al., 1996). Accordingly, any possible structural significance of this H···F contact can be discounted, so that the hydrogen-bonded supramolecular structure of (I) is strictly two-dimensional.

The form of the supramolecular structure, as deep sheets partially coated with F, is reflected in the macroscopic behaviour of the crystals, which form very thin flakes which are highly hydrophobic and which when rubbed between the fingers leave a distinctly greasy coating.

Table 1. Parameters (Å, °) for hydrogen bonds and short intermolecular contacts in compound (I)

Experimental top

An equimolar mixture of very finely divided 4-fluoroaniline and 4-nitrophthalimide was heated on an electric hotplate, in the absence of solvent, until the evolution of water had ceased. The reaction product was cooled and dissolved in 1,2-dichloroethane. Activated charcoal was added, and the mixture was then filtered. Evaporation of the solvent then gave compound (I). After repeated attempts to obtain crystals suitable for single-crystal X-ray diffraction, some very thin flakes of rather indifferent quality and a markedly waxy consistency were finally obtained from ethanol. A number of these crystals were investigated before any satisfactory diffraction data were obtained.

Refinement top

The systematic absences permitted P21 and P21/m as possible space groups. Space group P21 was selected and confirmed by the subsequent structure analysis. All H atoms were located from difference maps and then treated as riding atoms, with C—H distances of 0.95 Å and Uiso(H) = 1.2Ueq(C). In the absence of significant anomalous scattering, the Flack parameter (Flack, 1983) was indeterminate (Flack & Bernardinelli, 2000). Accordingly, the Friedel-equivalent reflections were merged prior to the final refinement.

Computing details top

Data collection: COLLECT (Hooft, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. The molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. Part of the crystal structure of (I), showing formation of a C(5) chain along [010]. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1 − x, y − 1/2, 1 − z) and (x, 1 + y, z), respectively.
[Figure 3] Fig. 3. Part of the crystal structure of (I), showing formation of a C(6) chain along [110]. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x − 1, 1 + y, z) and (1 + x, y − 1, z), respectively.
[Figure 4] Fig. 4. A stereoview of part of the crystal structure of (I), showing formation of an (001) sheet built from R66(24) rings. For the sake of clarity, the H atoms not involved in the motifs shown have been omitted.
N-(4-Fluorophenyl)-4-nitrophthalimide top
Crystal data top
C14H7FN2O4F(000) = 292
Mr = 286.22Dx = 1.582 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 1099 reflections
a = 3.7492 (13) Åθ = 3.5–25.0°
b = 6.9376 (14) ŵ = 0.13 mm−1
c = 23.099 (8) ÅT = 120 K
β = 90.118 (11)°Plate, yellow
V = 600.8 (3) Å30.15 × 0.08 × 0.02 mm
Z = 2
Data collection top
Bruker-Nonius 95mm CCD camera on κ-goniostat
diffractometer		1099 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode757 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.114
Detector resolution: 9.091 pixels mm-1θmax = 25.0°, θmin = 3.5°
ϕ and ω scansh = −4→4
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		k = −7→7
Tmin = 0.976, Tmax = 0.997l = −27→27
4455 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)] = 0.070Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.154H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0761P)2]
where P = (Fo2 + 2Fc2)/3
1099 reflections(Δ/σ)max < 0.001
190 parametersΔρmax = 0.26 e Å−3
1 restraintΔρmin = −0.24 e Å−3
Crystal data top
C14H7FN2O4V = 600.8 (3) Å3
Mr = 286.22Z = 2
Monoclinic, P21Mo Kα radiation
a = 3.7492 (13) ŵ = 0.13 mm−1
b = 6.9376 (14) ÅT = 120 K
c = 23.099 (8) Å0.15 × 0.08 × 0.02 mm
β = 90.118 (11)°
Data collection top
Bruker-Nonius 95mm CCD camera on κ-goniostat
diffractometer		1099 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		757 reflections with I > 2σ(I)
Tmin = 0.976, Tmax = 0.997Rint = 0.114
4455 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0701 restraint
wR(F2) = 0.154H-atom parameters constrained
S = 1.06Δρmax = 0.26 e Å−3
1099 reflectionsΔρmin = −0.24 e Å−3
190 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.8373 (15)0.5621 (8)0.2351 (2)0.0324 (14)
C10.693 (2)0.6393 (11)0.2848 (3)0.0344 (17)
O10.5499 (14)0.7969 (7)0.2890 (2)0.0426 (13)
C20.9774 (19)0.3779 (12)0.2444 (3)0.0366 (19)
O21.1382 (14)0.2786 (7)0.2098 (2)0.0411 (13)
C30.901 (2)0.3314 (10)0.3067 (3)0.0381 (19)
C40.974 (2)0.1666 (11)0.3377 (3)0.0356 (18)
C50.862 (2)0.1736 (11)0.3950 (3)0.0354 (18)
N50.9341 (16)0.0010 (9)0.4310 (3)0.0413 (16)
O510.7959 (16)−0.0063 (9)0.4793 (2)0.0536 (15)
O521.1204 (16)−0.1251 (7)0.4115 (2)0.0524 (15)
C60.703 (2)0.3298 (11)0.4214 (3)0.040 (2)
C70.633 (2)0.4936 (12)0.3887 (3)0.0397 (18)
C80.733 (2)0.4914 (11)0.3306 (3)0.0400 (19)
C110.836 (2)0.6548 (11)0.1781 (3)0.0364 (18)
C120.712 (2)0.5539 (11)0.1311 (3)0.0379 (18)
C130.708 (2)0.6435 (12)0.0778 (3)0.044 (2)
C140.833 (2)0.8282 (12)0.0739 (3)0.043 (2)
F140.8358 (13)0.9151 (6)0.02062 (18)0.0593 (14)
C150.958 (2)0.9307 (11)0.1198 (3)0.046 (2)
C160.965 (2)0.8390 (10)0.1744 (3)0.042 (2)
H11.03881.05970.11530.055*
H41.09120.05790.32140.043*
H60.64150.32540.46120.049*
H70.52170.60340.40530.048*
H120.63030.42490.13510.046*
H130.62120.57830.04450.053*
H161.05570.90330.20760.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.025 (3)0.039 (4)0.033 (3)−0.002 (3)0.001 (3)0.005 (3)
C10.034 (4)0.029 (4)0.041 (4)−0.004 (3)−0.001 (3)−0.007 (3)
O10.050 (4)0.036 (3)0.042 (3)0.002 (3)0.000 (2)−0.004 (2)
C20.025 (4)0.045 (5)0.040 (4)−0.007 (4)0.001 (3)0.000 (4)
O20.047 (3)0.035 (3)0.042 (3)−0.003 (3)0.007 (3)−0.004 (2)
C30.048 (5)0.028 (5)0.038 (4)−0.003 (3)0.006 (4)−0.002 (3)
C40.030 (5)0.036 (4)0.041 (5)−0.004 (3)0.003 (3)−0.003 (4)
C50.025 (4)0.038 (4)0.044 (5)−0.003 (3)0.003 (3)0.001 (4)
N50.039 (4)0.040 (4)0.045 (4)−0.007 (3)0.000 (3)0.002 (3)
O510.063 (4)0.057 (4)0.042 (3)0.007 (3)0.014 (3)0.012 (3)
O520.061 (4)0.040 (3)0.056 (4)0.013 (3)0.010 (3)0.002 (3)
C60.045 (5)0.047 (5)0.029 (4)0.007 (4)0.000 (3)−0.004 (3)
C70.037 (5)0.048 (5)0.035 (4)0.007 (4)0.004 (3)−0.007 (4)
C80.042 (5)0.039 (4)0.039 (4)−0.004 (4)−0.008 (4)0.003 (4)
C110.034 (5)0.042 (5)0.033 (4)−0.001 (4)0.003 (3)0.004 (3)
C120.041 (5)0.034 (4)0.039 (4)0.001 (3)0.000 (3)−0.003 (3)
C130.044 (5)0.044 (5)0.045 (5)0.001 (4)0.004 (4)−0.003 (4)
C140.048 (5)0.050 (6)0.030 (4)0.009 (4)−0.003 (4)0.003 (4)
F140.073 (4)0.066 (3)0.039 (3)−0.002 (3)0.003 (2)0.011 (2)
C150.057 (6)0.035 (5)0.046 (5)0.001 (4)−0.001 (4)0.011 (3)
C160.049 (6)0.034 (5)0.042 (4)0.004 (3)−0.004 (4)0.003 (3)
Geometric parameters (Å, º) top
N1—C11.378 (9)C6—C71.389 (11)
N1—C21.398 (10)C6—H60.95
N1—C111.465 (9)C7—C81.392 (10)
C1—O11.221 (9)C7—H70.95
C1—C81.482 (10)C11—C161.369 (11)
C2—O21.216 (9)C11—C121.373 (10)
C2—C31.502 (10)C12—C131.379 (10)
C3—C41.377 (10)C12—H120.95
C3—C81.392 (10)C13—C141.366 (12)
C4—C51.391 (9)C13—H130.95
C4—H40.95C14—C151.360 (10)
C5—C61.379 (10)C14—F141.372 (8)
C5—N51.483 (10)C15—C161.412 (10)
N5—O521.208 (8)C15—H10.95
N5—O511.233 (7)C16—H160.95
C1—N1—C2112.1 (6)C6—C7—C8117.6 (7)
C1—N1—C11125.2 (6)C6—C7—H7121.2
C2—N1—C11122.7 (6)C8—C7—H7121.2
O1—C1—N1125.9 (7)C7—C8—C3121.0 (7)
O1—C1—C8127.4 (7)C7—C8—C1130.8 (7)
N1—C1—C8106.6 (6)C3—C8—C1108.2 (6)
O2—C2—N1127.1 (7)C16—C11—C12123.0 (7)
O2—C2—C3127.1 (7)C16—C11—N1117.7 (7)
N1—C2—C3105.7 (6)C12—C11—N1119.2 (7)
C4—C3—C8123.0 (7)C11—C12—C13118.6 (7)
C4—C3—C2129.7 (7)C11—C12—H12120.7
C8—C3—C2107.3 (6)C13—C12—H12120.7
C3—C4—C5113.9 (7)C14—C13—C12118.6 (7)
C3—C4—H4123.0C14—C13—H13120.7
C5—C4—H4123.0C12—C13—H13120.7
C6—C5—C4125.5 (7)C15—C14—C13123.9 (7)
C6—C5—N5117.7 (6)C15—C14—F14117.8 (7)
C4—C5—N5116.7 (7)C13—C14—F14118.3 (7)
O52—N5—O51123.6 (6)C14—C15—C16117.7 (7)
O52—N5—C5118.8 (6)C14—C15—H1121.1
O51—N5—C5117.7 (6)C16—C15—H1121.1
C5—C6—C7118.9 (7)C11—C16—C15118.1 (7)
C5—C6—H6120.6C11—C16—H16120.9
C7—C6—H6120.6C15—C16—H16120.9
C2—N1—C1—O1−179.3 (7)C6—C7—C8—C1179.2 (7)
C11—N1—C1—O1−1.6 (11)C4—C3—C8—C71.0 (11)
C2—N1—C1—C8−1.5 (7)C2—C3—C8—C7−178.9 (7)
C11—N1—C1—C8176.2 (6)C4—C3—C8—C1−179.1 (7)
C1—N1—C2—O2−175.7 (7)C2—C3—C8—C11.0 (8)
C11—N1—C2—O26.6 (11)O1—C1—C8—C7−2.2 (13)
C1—N1—C2—C32.1 (7)N1—C1—C8—C7−179.9 (7)
C11—N1—C2—C3−175.6 (6)O1—C1—C8—C3177.9 (7)
O2—C2—C3—C4−3.9 (13)N1—C1—C8—C30.2 (8)
N1—C2—C3—C4178.3 (7)C1—N1—C11—C1652.6 (10)
O2—C2—C3—C8175.9 (7)C2—N1—C11—C16−130.0 (7)
N1—C2—C3—C8−1.9 (7)C1—N1—C11—C12−128.4 (8)
C8—C3—C4—C50.7 (10)C2—N1—C11—C1249.0 (10)
C2—C3—C4—C5−179.5 (7)C16—C11—C12—C13−1.7 (12)
C3—C4—C5—C6−2.5 (10)N1—C11—C12—C13179.3 (7)
C3—C4—C5—N5−179.6 (7)C11—C12—C13—C140.9 (11)
C6—C5—N5—O52−168.8 (7)C12—C13—C14—C15−0.6 (13)
C4—C5—N5—O528.6 (9)C12—C13—C14—F14178.6 (7)
C6—C5—N5—O5112.0 (10)C13—C14—C15—C161.0 (13)
C4—C5—N5—O51−170.6 (6)F14—C14—C15—C16−178.2 (7)
C4—C5—C6—C72.6 (11)C12—C11—C16—C152.1 (12)
N5—C5—C6—C7179.7 (7)N1—C11—C16—C15−178.9 (7)
C5—C6—C7—C8−0.7 (11)C14—C15—C16—C11−1.7 (12)
C6—C7—C8—C3−1.0 (10)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O51i0.952.443.173 (9)134
C7—H7···O52ii0.952.423.313 (10)157
C13—H13···F14iii0.952.543.438 (9)157
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) x−1, y+1, z; (iii) −x+1, y−1/2, −z.

Experimental details

Crystal data
Chemical formulaC14H7FN2O4
Mr286.22
Crystal system, space groupMonoclinic, P21
Temperature (K)120
a, b, c (Å)3.7492 (13), 6.9376 (14), 23.099 (8)
β (°) 90.118 (11)
V (Å3)600.8 (3)
Z2
Radiation typeMo Kα
µ (mm−1)0.13
Crystal size (mm)0.15 × 0.08 × 0.02
Data collection
DiffractometerBruker-Nonius 95mm CCD camera on κ-goniostat
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.976, 0.997
No. of measured, independent and
observed [I > 2σ(I)] reflections		4455, 1099, 757
Rint0.114
(sin θ/λ)max (Å−1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.070, 0.154, 1.06
No. of reflections1099
No. of parameters190
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.26, −0.24

Computer programs: COLLECT (Hooft, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O51i0.952.443.173 (9)134
C7—H7···O52ii0.952.423.313 (10)157
C13—H13···F14iii0.952.543.438 (9)157
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) x−1, y+1, z; (iii) −x+1, y−1/2, −z.
 

Acknowledgements

The X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff for all their help and advice. JNL thanks NCR Self-Service, Dundee, for grants which have provided computing facilities for this work. JLW thanks CNPq and FAPERJ for financial support.

References

First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
 First citationFerguson, G. (1999). PRPKAPPA. University of Guelph, Canada.  Google Scholar
 First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals Google Scholar
 First citationFlack, H. D. & Bernardinelli, G. (1999). Acta Cryst. A55, 908–915.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationFlack, H. D. & Bernardinelli, G. (2000). J. Appl. Cryst. 33, 1143–1148.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationHooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands.  Google Scholar
 First citationHoward, J. A. K., Hoy, V. J., O'Hagan, D. & Smith, G. T. (1996). Tetrahedron, 52, 12613–12622.  CrossRef CAS Web of Science Google Scholar
 First citationMcArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.  Google Scholar
 First citationOtwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.  Google Scholar
 First citationSheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.  Google Scholar
 First citationSheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.  Google Scholar
 First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 3–17.  Web of Science CrossRef IUCr Journals Google Scholar

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Journal logoSTRUCTURAL
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ISSN: 2053-2296
Volume 60| Part 7| July 2004| Pages o511-o513
doi:10.1107/S0108270104013575
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