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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

Glyoxal 4-nitro­phenyl­hydrazone: triple helices linked into a three-dimensional channel structure

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 28 June 2005; accepted 30 June 2005; online 23 July 2005)

The mol­ecules of the title compound, C8H7N3O3, which are nearly planar, are linked by an N—H⋯O hydrogen bond into helical chains, three of which are required to define the structure completely. These triply inter­twined helices are linked by a C—H⋯O hydrogen bond into a three-dimensional framework enclosing two distinct types of channel, with average cross-sectional areas of 15.0 and 8.2 Å2.

Comment

The title compound, (I)[link], was prepared as part of our continuing study of the supramolecular arrangements of N-(nitro­phenyl)imide and -hydrazone derivatives.

[Scheme 1]

The mol­ecules of compound (I)[link] (Fig. 1[link]) are almost planar, as shown by the leading torsion angles (Table 1[link]). The side chain between atoms N1 and O1 adopts a planar all-trans conformation, and the nitro group is nearly coplanar with the aryl ring. The bond distances in the 4-nitro­phenyl­hydrazone fragment provide no evidence for the occurrence of the type of quinonoid bond fixation found in 4-nitro­aniline (Tonogaki et al., 1993[Tonogaki, M., Kawata, T., Ohba, S., Iwata, Y. & Shibuya, I. (1993). Acta Cryst. B49, 1031-1039.]), which is also typical of simple substituted 4-nitro­anilines (Cannon et al., 2001[Cannon, D., Glidewell, C., Low, J. N., Quesada, A. & Wardell, J. L. (2001). Acta Cryst. C57, 216-221.]; Ferguson et al., 2001[Ferguson, G., Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2001). Acta Cryst. C57, 315-316.]; Glidewell et al., 2001[Glidewell, C., Cannon, D., Quesada, A., Low, J. N., McWilliam, S. A., Skakle, J. M. S. & Wardell, J. L. (2001). Acta Cryst. C57, 455-458.], 2002[Glidewell, C., Low, J. N., McWilliam, S. A., Skakle, J. M. S. & Wardell, J. L. (2002). Acta Cryst. C58, o100-o102.], 2004[Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2004). Acta Cryst. C60, o35-o37.]). There is strong bond fixation in the side chain, with very short N2—C11 and C12—O1 bonds, with no evidence for bond polarization in this fragment.

The supramolecular structure of (I)[link] is three-dimensional and of considerable complexity, but it is constructed using only two hydrogen bonds, one each of the N—H⋯O and C—H⋯O types (Table 2[link]). The hydrazine atom N1 in the mol­ecule at (x, y, z) acts as hydrogen-bond donor to aldehyde atom O1 in the mol­ecule at ([{3\over 4}] − y, [{1\over 4}] + x, z − [{3\over 4}]), while atom N1 at ([{3\over 4}] − y, [{1\over 4}] + x, z − [{3\over 4}]) in turn acts as donor to atom O1 at ([{1\over 2}] − x, 1 − y, z − [{3\over 2}]), and thence via the mol­ecule at (y − [{1\over 4}], [{3\over 4}] − x, z − [{9\over 4}]) to that at (x, y, z − 3). In this way, a C(6) helical chain is formed running parallel to the [001] direction and generated by the 41 screw axis along ([{1\over 4}], [{1\over 2}], z). One complete turn of this helix spans three unit cells along [001], linking the mol­ecule at (x, y, z) with those at (x, y, n + z) (n = positive or negative integer). Hence, completion of the structure requires three such helical chains, offset by unit translations along [001]. Thus, the effect of the N—H⋯O hydrogen bond is the generation of triply inter­twined helices (Fig. 2[link]). There are no direction-specific inter­actions between the independent helices in each set of three helices.

The effect of the C—H⋯O hydrogen bond is to link the helices into a three-dimensional framework. Aldehyde atom C12 in the mol­ecule at (x, y, z) acts as hydrogen-bond donor to nitro atom O41 in the mol­ecule at (1 − x, 1 − y, 2 − z), so generating a centrosymmetric R22(22) motif centred at ([{1\over 2}], [{1\over 2}], 1) (Fig. 3[link]). The two mol­ecules in this motif form parts of helices along ([{1\over 4}], [{1\over 2}], z) and ([{3\over 4}], [{1\over 2}], −z), generated by 41 and 43 axes, respectively, and propagation of this dimer motif thus links the reference helix along ([{1\over 4}], [{1\over 2}], z) to the four adjacent helices along ([{3\over 4}], [{1\over 2}], −z), ([{1\over 4}], 0, −z), (−[{1\over 4}], [{1\over 2}], −z) and ([{1\over 4}], 1, −z), all of which are of opposite hand to the reference helix. In this way, the helices are linked into a three-dimensional framework (Fig. 4[link]), more strictly described as three inter­woven frameworks.

Within the framework there are channels running parallel to the [001] direction and accounting in total for 340.1 Å3 per unit cell, i.e. some 9.4% of the total volume. This volume is, in fact, partitioned between two types of channel, with four of each type per cell. The larger channels lie along the [\overline{4}] axes, with an average cross-sectional area of ca 15.0 Å2 and an average diameter of ca 4.4 Å, while the smaller channels lie along the 41 and 43 axes and have an average cross-sectional area of ca 8.2 Å2 and an average diameter of ca 3.2 Å. There is evidence for a very low population of water mol­ecules, possibly disordered and/or mobile, within the larger channels, but no tractable refinement of these guest mol­ecules proved possible. It is not clear whether this residual water is a by-product of the preparation or whether it had been absorbed from the atmosphere after crystallization.

The larger channels in (I)[link] are thus of very similar diameter to those found in piperazine–4,4′-sulfonyl­diphenol (1/2) (Coupar et al., 1996[Coupar, P. I., Ferguson, G. & Glidewell, C. (1996). Acta Cryst. C52, 3052-3055.]), where the channels of diameter 4.3 Å are entirely unoccupied. In the channel structures formed by N,N′-dithio­bisphthalimide (Skakle et al., 2001[Skakle, J. M. S., Wardell, J. L., Low, J. N. & Glidewell, C. (2001). Acta Cryst. C57, 742-746.]; Farrell et al., 2002[Farrell, D. M. M., Glidewell, C., Low, J. N., Skakle, J. M. S. & Zakaria, C. M. (2002). Acta Cryst. B58, 289-299.]; Bowes, Ferguson, Glidewell, Lough et al., 2002[Bowes, K. F., Ferguson, G., Glidewell, C., Lough, A. J., Low, J. N. & Zakaria, C. M. (2002). Acta Cryst. C58, o347-o350.]; Bowes, Ferguson, Glidewell, Low & Quesada, 2002[Bowes, K. F., Ferguson, G., Glidewell, C., Low, J. N. & Quesada, A. (2002). Acta Cryst. C58, o551-o554.]), the channels are a little larger, with average cross-sectional areas of ca 20.4 Å2 and average diameters of ca 5.1 Å. The channels in N,N′-dithio­bisphthalimide are always occupied by guest mol­ecules, but the behaviour of the guest can vary from full ordering, as for p-xylene, to intractable disorder of probably mobile mol­ecules for guests such as dichloro­methane or tetra­hydro­furan.

[Figure 1]
Figure 1
The mol­ecule of (I)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2]
Figure 2
A stereoview of part of the crystal structure of (I)[link], showing the formation of triply inter­twined C(6) helices along ([{1\over 4}], [{1\over 2}], z). For the sake of clarity, H atoms bonded to C atoms have been omitted.
[Figure 3]
Figure 3
Part of the crystal structure of (I)[link], showing the formation of a centrosymmetric R22(22) ring. For the sake of clarity, H atoms not involved in the motif shown have been omitted, as has the unit-cell outline. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 2 − z).
[Figure 4]
Figure 4
A space-filling projection, down [001], of part of the crystal structure of (I)[link], showing the formation of the three-dimensional framework enclosing two types of channel along [001].

Experimental

Compound (I)[link] was prepared by heating under reflux for 1 h a solution of glyoxal (1 mmol as a 40% aqueous solution) and 4-nitro­phenyl­hydrazine (1 mmol) in methanol (40 ml). The mixture was cooled to ambient temperature and the solvent removed under reduced pressure. The residue was crystallized from ethanol to yield crystals of (I)[link] suitable for single-crystal X-ray diffraction. IR (KBr disk, ν, cm−1): 3263–2850, 1698 (sh), 1686, 1677 (sh), 1538, 1504, 1331, 1272, 1131, 894, 839, 748, 690, 609, 489, 447.

Crystal data
  • C8H7N3O3

  • Mr = 193.17

  • Tetragonal, I 41 /a

  • a = 31.4722 (12) Å

  • c = 3.65600 (10) Å

  • V = 3621.3 (2) Å3

  • Z = 16

  • Dx = 1.417 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 2066 reflections

  • θ = 4.1–27.5°

  • μ = 0.11 mm−1

  • T = 120 (2) K

  • Rod, red

  • 0.32 × 0.08 × 0.06 mm

Data collection
  • Bruker–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 = 0.974, Tmax = 0.993

  • 2068 measured reflections

  • 2066 independent reflections

  • 1712 reflections with I > 2σ(I)

  • Rint = 0.039

  • θmax = 27.5°

  • h = −27 → 28

  • k = 0 → 40

  • l = 0 → 4

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.037

  • wR(F2) = 0.098

  • S = 1.06

  • 2066 reflections

  • 127 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0445P)2 + 2.7428P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 0.21 e Å−3

  • Δρmin = −0.21 e Å−3

Table 1
Selected geometric parameters (Å, °)[link]

C1—N1 1.3889 (16)
N1—N2 1.3319 (14)
N2—C11 1.2995 (16)
C11—C12 1.4451 (18)
C12—O1 1.2214 (15)
C2—C1—N1—N2 0.20 (18)
C1—N1—N2—C11 −176.38 (11)
N1—N2—C11—C12 −179.62 (11)
N2—C11—C12—O1 −179.34 (13)
C3—C4—N4—O41 −3.42 (18)
C3—C4—N4—O42 174.96 (12)
C5—C4—N4—O41 178.35 (12)
C5—C4—N4—O42 −3.27 (18)

Table 2
Hydrogen-bond geometry (Å, °)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯O1i 0.88 2.03 2.8574 (14) 155
C12—H12⋯O41ii 0.95 2.46 3.2851 (17) 145
Symmetry codes: (i) [{3\over 4}-y, x+{1\over 4}, z-{3\over 4}]; (ii) 1-x, 1-y, 2-z.

Crystals of compound (I)[link] are tetra­gonal. The unit cell has a markedly tabular shape, with an axial c/a ratio of only 0.116. The space group I41/a was uniquely assigned from the systematic absences, and the origin was set to lie at an inversion centre. All H atoms were located from difference maps and then treated as riding atoms, with C—H distances of 0.95 Å and N—H distances of 0.88 Å, and with Uiso(H) = 1.2Ueq(C,N). Examination of the refined structure using PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]) revealed the presence of void spaces having a total volume of 340.1 Å3 per unit cell, arranged into a series of channels running parallel to the [001] direction. There was a low residual electron density of 0.9 e Å−3 located on a [\overline{4}] axis within the larger of the channels, which is most plausibly ascribed to a partial water mol­ecule. When this density was assigned to an O atom and its site occupancy refined, with Uiso(O) fixed at 0.03 Å2, the occupancy refined to 0.0288 (15), corresponding in total to 0.115 of an O atom. In view of this, the SQUEEZE option in PLATON was applied, and the final refinement utilized data so treated. The final Fo/Fc CIF was produced with the CALC FCF option in PLATON, reporting both the original observed structure factors and calculated structure factors including the disordered solvent contri­bution.

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, 7-13.]); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information


Comment top

The title compound, (I), was prepared as part of our continuing study of the supramolecular arrangements of N-(nitrophenyl)imide and -hydrazone derivatives.

The molecules of compound (I) (Fig. 1) are almost planar, as shown by the leading torsion angles (Table 1). The side chain between atoms N1 and O1 adopts a planar all-trans conformation, and the nitro group is nearly coplanar with the aryl ring. The bond distances in the 4-nitrophenylhydrazone fragment provide no evidence for the occurrence of the type of quinonoid bond fixation found in 4-nitroaniline (Tonogaki et al., 1993), which is also typical of simple substituted 4-nitroanilines (Cannon et al., 2001; Ferguson et al., 2001; Glidewell et al., 2001, 2002, 2004). There is strong bond-fixation in the side chain, with very short N2—C11 and C12—O1 bonds, with no evidence for bond polarization in this fragment.

The supramolecular structure of (I) is three-dimensional and of considerable complexity, but it is constructed using only two hydrogen bonds, one each of N—H···O and C—H···O types (Table 2). The hydrazino atom N1 in the molecule at (x, y, z) acts as hydrogen-bond donor to aldehyde atom O1 in the molecule at (3/4 − y, 1/4 + x, z − 3/4), while atom N1 at (3/4 − y, 1/4 + x, z − 3/4) in turn acts as donor to atom O1 at (1/2 − x, 1 − y, z − 3/2), and thence via the molecule at (y − 1/4, 3/4 − x, z − 9/4) to that at (x, y, z − 3). In this way, a C(6) helical chain is formed running parallel to the [001] direction and generated by the 41 screw axis along (1/4, 1/2, z). One complete turn of this helix spans three unit cells along [001], linking the molecule at (x, y, z) with those at (x, y, n + z) (n = positive or negative integer). Hence, completion of the structure requires three such helical chains, offset by unit translations along [001]. Thus, the effect of the N—H···O hydrogen bond is the generation of triply intertwined helices (Fig. 2). There are no direction-specific interactions between the independent helices in each set of three helices.

The effect of the C—H···O hydrogen bond is to link the helices into a three-dimensional framework. The aldehyde atom C12 in the molecule at (x, y, z) acts as hydrogen-bond donor to nitro atom O41 in the molecule at (1 − x, 1 − y, 2 − z), so generating a centrosymmetric R22(22) motif centred at (1/2, 1/2, 1) (Fig. 3). The two molecules in this motif form parts of helices along (1/4, 1/2, z) and (3/4, 1/2, −z), generated by 41 and 43 axes, respectively, and propagation of this dimer motif thus links the reference helix along (1/4, 1/2, z) to the four adjacent helices along (3/4, 1/2, −z), (1/4, 0, −z), (−1/4, 1/2, −z) and (1/4, 1, −z), all of which are of opposite hand to the reference helix. In this way, the helices are linked into a three-dimensional framework (Fig. 4), more strictly described as three interwoven frameworks.

Within the framework there are channels running parallel to the [001] direction and accounting in total for 340.1 Å3 per unit cell, i.e. some 9.4% of the total volume. This volume is, in fact, partitioned between two types of channel, with four of each type per cell. The larger channels lie along the 4 axes, with an average cross-sectional area of ca 15.0 Å2 and average diameter of ca 4.4 Å, while the smaller channels lie along the 41 and 43 axes and have an average cross-sectional area of ca 8.2 Å2 and an average diameter of ca 3.2 Å. There is evidence for a very low population of water molecules, possibly disordered and/or mobile, within the larger channels, but no tractable refinement of these guest molecules proved possible. It is not clear whether this residual water is a by-product of the preparation, or whether it had been absorbed from the atmosphere after crystallization.

The larger channels in (I) are thus of very similar diameter to those found in piperazine–4,4'-sulfonyldiphenol (1/2) (Coupar et al., 1996), where the channels of diameter 4.3 Å are entirely unoccupied. In the channel structures formed by N,N'-dithiobisphthalimide (Skakle et al., 2001; Farrell et al., 2002; Bowes, Ferguson, Glidewell, Lough et al., 2002; Bowes, Ferguson, Glidewell, Low & Quesada, 2002), the channels are a little larger, with average cross-sectional areas of ca 20.4 Å2 and average diameters of ca 5.1 Å. The channels in N,N'-dithiobisphthalimide are always occupied by guest molecules, but the behaviour of the guest can vary from full ordering, as for p-xylene, to intractable disorder of probably mobile molecules, for guests such as dichloromethane or tetrahydrofuran.

Experimental top

Compound (I) was prepared by heating under reflux for 1 h a solution of glyoxal (1 mmol as a 40% aqueous solution) and 4-nitrophenylhydrazine (1 mmol) in methanol (40 ml). The mixture was cooled to ambient temperature and the solvent removed under reduced pressure. The residue was crystallized from ethanol to yield crystals of (I) suitable for single-crystal X-ray diffraction. IR (KBr disk, ν, cm−1): 3263–2850, 1698 (sh), 1686, 1677 (sh), 1538, 1504, 1331, 1272, 1131, 894, 839, 748, 690, 609, 489, 447.

Refinement top

Crystals of compound (I) are tetragonal. The unit cell has a markedly tabular shape, with an axial ratio c/a of only 0.116. The space group I41/a was uniquely assigned from the systematic absences, and the origin was set to lie at an inversion centre. All H atoms were located from difference maps and then treated as riding atoms, with C—H distances of 0.95 Å and N—H distances of 0.88 Å, and with Uiso(H) = 1.2Ueq(C,N). Examination of the refined structure using PLATON (Spek, 2003) revealed the presence of void spaces having a total volume of 340.1 Å3 per unit cell, arranged into a series of channels running parallel to the [001] direction. There was a low residual electron density of 0.9 e Å−3 located on a 4 axis within the larger of the channels, and most plausibly ascribed to a partial water molecule. When this density was assigned to an O atom and its site occupancy refined, with Uiso(O) fixed at 0.03, the occupancy refined to 0.0288 (15), corresponding in total to 0.115 of an O atom. In view of this, the SQUEEZE option in PLATON was applied, and the final refinement utilized data so treated. The final Fo/Fc CIF was produced with the CALC FCF option in PLATON, reporting both the original observed structure factors and calculated structure factors including the disordered solvent contribution.

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.
[Figure 2] Fig. 2. A stereoview of part of the crystal structure of (I), showing the formation of triply intertwined C(6) helices along (1/4, 1/2, z). For the sake of clarity, H atoms bonded to C atoms have been omitted.
[Figure 3] Fig. 3. Part of the crystal structure of (I), showing the formation of a centrosymmetric R22(22) ring. For the sake of clarity, H atoms not involved in the motif shown have been omitted, as has the unit-cell outline. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 2 − z).
[Figure 4] Fig. 4. A space-filling projection, down [001], of part of the crystal structure of (I), showing the formation of the three-dimensional framework enclosing two types of channel along [001].
Glyoxal 4-nitrophenylhydrazone top
Crystal data top
C8H7N3O3Dx = 1.417 Mg m3
Mr = 193.17Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/aCell parameters from 2066 reflections
Hall symbol: -I 4adθ = 4.1–27.5°
a = 31.4722 (12) ŵ = 0.11 mm1
c = 3.6560 (1) ÅT = 120 K
V = 3621.3 (2) Å3Rod, red
Z = 160.32 × 0.08 × 0.06 mm
F(000) = 1600
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2066 independent reflections
Radiation source: Bruker Nonius FR91 rotating anode1712 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.039
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 4.1°
ϕ and ω scansh = 2728
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 040
Tmin = 0.974, Tmax = 0.993l = 04
2068 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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0445P)2 + 2.7428P]
where P = (Fo2 + 2Fc2)/3
2066 reflections(Δ/σ)max = 0.001
127 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = 0.21 e Å3
Crystal data top
C8H7N3O3Z = 16
Mr = 193.17Mo Kα radiation
Tetragonal, I41/aµ = 0.11 mm1
a = 31.4722 (12) ÅT = 120 K
c = 3.6560 (1) Å0.32 × 0.08 × 0.06 mm
V = 3621.3 (2) Å3
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2066 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1712 reflections with I > 2σ(I)
Tmin = 0.974, Tmax = 0.993Rint = 0.039
2068 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.098H-atom parameters constrained
S = 1.06Δρmax = 0.21 e Å3
2066 reflectionsΔρmin = 0.21 e Å3
127 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.32156 (3)0.43155 (3)1.0674 (3)0.0292 (3)
O410.58550 (3)0.60724 (3)0.4461 (3)0.0293 (3)
O420.55171 (3)0.65953 (3)0.1969 (3)0.0356 (3)
N10.39639 (3)0.54756 (3)0.6609 (3)0.0184 (2)
N20.39389 (3)0.50918 (3)0.8129 (3)0.0186 (2)
N40.55227 (3)0.62552 (3)0.3606 (3)0.0219 (3)
C10.43568 (4)0.56610 (4)0.5942 (3)0.0165 (3)
C20.47373 (4)0.54547 (4)0.6818 (3)0.0175 (3)
C30.51203 (4)0.56520 (4)0.6087 (3)0.0183 (3)
C40.51188 (4)0.60533 (4)0.4491 (3)0.0178 (3)
C50.47447 (4)0.62627 (4)0.3621 (3)0.0186 (3)
C60.43627 (4)0.60645 (4)0.4337 (3)0.0179 (3)
C110.35626 (4)0.49273 (4)0.8496 (4)0.0200 (3)
C120.35452 (4)0.45120 (4)1.0175 (4)0.0216 (3)
H10.37300.56130.60220.022*
H20.47320.51810.79090.021*
H30.53810.55150.66650.022*
H50.47510.65380.25510.022*
H60.41030.62020.37390.022*
H110.33140.50710.77070.024*
H120.38040.43851.09330.026*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0262 (5)0.0234 (5)0.0378 (6)0.0071 (4)0.0028 (4)0.0058 (4)
O410.0168 (5)0.0312 (5)0.0399 (6)0.0000 (4)0.0006 (4)0.0023 (5)
O420.0287 (6)0.0286 (5)0.0494 (7)0.0059 (4)0.0046 (5)0.0163 (5)
N10.0149 (5)0.0159 (5)0.0243 (6)0.0005 (4)0.0013 (4)0.0045 (4)
N20.0204 (5)0.0165 (5)0.0188 (5)0.0011 (4)0.0005 (4)0.0013 (4)
N40.0206 (6)0.0220 (6)0.0230 (6)0.0027 (4)0.0021 (4)0.0004 (5)
C10.0173 (6)0.0169 (6)0.0153 (6)0.0012 (5)0.0003 (5)0.0013 (5)
C20.0204 (6)0.0150 (6)0.0172 (6)0.0003 (5)0.0012 (5)0.0014 (5)
C30.0175 (6)0.0191 (6)0.0184 (6)0.0019 (5)0.0020 (5)0.0010 (5)
C40.0164 (6)0.0199 (6)0.0170 (6)0.0033 (5)0.0021 (5)0.0012 (5)
C50.0227 (6)0.0153 (6)0.0178 (6)0.0003 (5)0.0009 (5)0.0021 (5)
C60.0180 (6)0.0175 (6)0.0184 (6)0.0031 (5)0.0010 (5)0.0008 (5)
C110.0179 (6)0.0196 (6)0.0226 (7)0.0005 (5)0.0003 (5)0.0012 (5)
C120.0222 (6)0.0201 (6)0.0224 (6)0.0011 (5)0.0010 (5)0.0010 (5)
Geometric parameters (Å, º) top
C1—N11.3889 (16)C2—H20.95
C1—C61.3991 (17)C3—C41.3913 (17)
C1—C21.3993 (17)C3—H30.95
N1—N21.3319 (14)C4—C51.3861 (17)
N1—H10.88C4—N41.4575 (16)
N2—C111.2995 (16)N4—O421.2264 (14)
C11—C121.4451 (18)N4—O411.2338 (14)
C11—H110.95C5—C61.3795 (17)
C12—O11.2214 (15)C5—H50.95
C12—H120.95C6—H60.95
C2—C31.3821 (17)
N1—C1—C6117.83 (11)C2—C3—C4119.08 (11)
N1—C1—C2121.80 (11)C2—C3—H3120.5
C6—C1—C2120.37 (11)C4—C3—H3120.5
N2—N1—C1120.45 (10)C5—C4—C3122.05 (11)
N2—N1—H1119.8C5—C4—N4118.86 (11)
C1—N1—H1119.8C3—C4—N4119.07 (11)
C11—N2—N1117.27 (10)O42—N4—O41122.87 (11)
N2—C11—C12116.02 (11)O42—N4—C4118.44 (11)
N2—C11—H11122.0O41—N4—C4118.66 (11)
C12—C11—H11122.0C6—C5—C4118.79 (11)
O1—C12—C11123.61 (12)C6—C5—H5120.6
O1—C12—H12118.2C4—C5—H5120.6
C11—C12—H12118.2C5—C6—C1120.12 (11)
C3—C2—C1119.58 (11)C5—C6—H6119.9
C3—C2—H2120.2C1—C6—H6119.9
C1—C2—H2120.2
C6—C1—N1—N2179.96 (11)C3—C4—N4—O413.42 (18)
C2—C1—N1—N20.20 (18)C3—C4—N4—O42174.96 (12)
C1—N1—N2—C11176.38 (11)C5—C4—N4—O41178.35 (12)
N1—N2—C11—C12179.62 (11)C5—C4—N4—O423.27 (18)
N2—C11—C12—O1179.34 (13)C3—C4—C5—C60.53 (19)
N1—C1—C2—C3179.73 (11)N4—C4—C5—C6177.64 (11)
C6—C1—C2—C30.02 (19)C4—C5—C6—C10.55 (19)
C1—C2—C3—C40.05 (19)N1—C1—C6—C5179.95 (11)
C2—C3—C4—C50.23 (19)C2—C1—C6—C50.29 (19)
C2—C3—C4—N4177.94 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.882.032.8574 (14)155
C12—H12···O41ii0.952.463.2851 (17)145
Symmetry codes: (i) y+3/4, x+1/4, z3/4; (ii) x+1, y+1, z+2.

Experimental details

Crystal data
Chemical formulaC8H7N3O3
Mr193.17
Crystal system, space groupTetragonal, I41/a
Temperature (K)120
a, c (Å)31.4722 (12), 3.6560 (1)
V3)3621.3 (2)
Z16
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.32 × 0.08 × 0.06
Data collection
DiffractometerBruker Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.974, 0.993
No. of measured, independent and
observed [I > 2σ(I)] reflections
2068, 2066, 1712
Rint0.039
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.098, 1.06
No. of reflections2066
No. of parameters127
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.21, 0.21

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).

Selected geometric parameters (Å, º) top
C1—N11.3889 (16)C11—C121.4451 (18)
N1—N21.3319 (14)C12—O11.2214 (15)
N2—C111.2995 (16)
C2—C1—N1—N20.20 (18)C3—C4—N4—O413.42 (18)
C1—N1—N2—C11176.38 (11)C3—C4—N4—O42174.96 (12)
N1—N2—C11—C12179.62 (11)C5—C4—N4—O41178.35 (12)
N2—C11—C12—O1179.34 (13)C5—C4—N4—O423.27 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.882.032.8574 (14)155
C12—H12···O41ii0.952.463.2851 (17)145
Symmetry codes: (i) y+3/4, x+1/4, z3/4; (ii) x+1, y+1, z+2.
 

Acknowledgements

The X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton; the authors thank the staff for all their help and advice. JLW thanks CNPq and FAPERJ for financial support.

References

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