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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

N-(3-Methyl-4-oxo-3,4-di­hydro­pteridin-2-yl)­glycine: hydrogen-bonded sheets of R44(22) and R44(30) rings

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aDepartamento de Química Inorgánica y Orgánica, Universidad de Jaén, 23071 Jaén, Spain, bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and cSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 6 September 2004; accepted 8 September 2004; online 9 October 2004)

Molecules of the title compound, C9H9N5O3, are linked into sheets by a combination of one O—H⋯N hydrogen bond and one N—H⋯O hydrogen bond.

Comment

The title compound, (I[link]), is of potential biological interest, since it is an N-pteridinyl derivative of the amino acid glycine. Compounds of this general type can be adsorbed on activated carbon, implying ππ interactions between the hetero­aromatic moiety and the carbon surface (Coughlin & Ezra, 1968[Coughlin, R. W. & Ezra, F. S. (1968). Environ. Sci. Technol. 2, 291-297.]; Mattson et al., 1969[Mattson, J. S., Mark, H. B. Jr, Malbin, M. D., Weber, W. J. Jr & Critenden, J. C. (1969). J. Colloid Interface Sci. 31, 116-130.]; Leon y Leon et al., 1992[Leon y Leon, C. A., Solar, J. M., Calemma, V. & Radovic, L. R. (1992). Carbon, 30, 797-811.]; Radovic et al., 1997[Radovic, L. R., Silva, I. F., Ume, J. I., Menéndez, J. A., Leon y Leon, C. A. & Scaroni, A. W. (1997). Carbon, 35, 1339-1348.]), while the carboxyl function remains available in the solvent phase to act as a coordinating site for metal ions in solution, thus providing the basis of a possible method for the removal of toxic metal ions from waste water.

The bond distances within the mol­ecule of (I[link]) present some unexpected values (Table 1[link]), which are not readily reconciled with the classically localized bond-valence form. In particular, the C6—C7 and C4a—C8a bonds, which are formally single and double bonds, respectively, have effectively identical lengths. In addition, the C2—N2 bond, which is formally a single bond, is barely longer than the N5—C6 and C7—N8 bonds, which are formally double bonds. On the other hand, these latter two are significantly shorter than any of C4a—N5, N8—C8a and C8a—N1. These observations render somewhat problematical the graphical representation of the molecular-electronic structure. The polarized form (Ia[link]) can be ruled out on the grounds that the N8—C8a and C8a—N1 bonds have effectively identical lengths, and because C4—C4a is by far the longest C—C bond in the ring system. The bond distances in the N3—C4—O4 amidic fragment are normal for their types (Allen et al., 1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]). Within the carboxyl group, the C—O distances are fully consistent with the localization of the H atom as deduced from a difference map.

While the bicyclic portion of the mol­ecule is effectively planar, with a maximum deviation from the best least-squares plane of 0.052 (2) Å for atom N8, the conformation of the glycinyl side chain (Fig. 1[link] and Table 1[link]) may well be influenced by the short intramolecular contact involving atoms H21B and N1 (Table 2[link]), which generates a nearly planar S(5) ring (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]).

[Scheme 1]

The mol­ecules of (I[link]) are linked via a combination of O—H⋯N and N—H⋯O hydrogen bonds (Table 2[link]) into sheets, within which each of the two hydrogen bonds alone produces a one-dimensional substructure. It is striking that neither of the motifs characteristic of simple carboxylic acids, viz. the C(4) chain and the cyclic R22(8) dimer, is present in the structure of (I[link]). In the first substructure, carboxyl atom O21 in the mol­ecule at (x, y, z) acts as hydrogen-bond donor to atom N8 in the mol­ecule at ([{1 \over 2}] + x, [{1 \over 2}] − y, 1 − z), so forming a C(9) chain running parallel to the [100] direction and generated by the 21 screw axis along (x, [{1 \over 4}], [{1 \over 2}]) (Fig. 2[link]). In the second substructure, amino atom N2 in the mol­ecule at (x, y, z) acts as hydrogen-bond donor to carbonyl atom O4 in the mol­ecule at ([{1 \over 2}] − x, y − [{1 \over 2}], z), so forming a C(6) chain running parallel to the [010] direction and generated by the b-glide plane at x = [{1 \over 4}] (Fig. 3[link]). The combination of these chains generates a (001) sheet in the form of a (4,4)-net (Batten & Robson, 1998[Batten, S. R. & Robson, R. (1998). Angew. Chem. Int. Ed. 37, 1460-1494.]) built from centrosymmetric R[{_4^4}](22) and R[{_4^4}](30) rings alternating in a chess-board fashion (Fig. 4[link]). Around the periphery of the R[{_4^4}](30) rings, each mol­ecule acts as a single donor and single acceptor of hydrogen bonds, while around the periphery of the R[{_4^4}](22) rings, one pair of centrosymmetrically related mol­ecules act as double donors and the other such pair as double acceptors of hydrogen bonds.

Two of these sheets, related to one another by the 21 screw axes parallel to [001], pass through each unit cell, in the domains 0.24 < z < 0.76 and 0.74 < z < 1.26, respectively, and the sole direction-specific interaction between adjacent sheets is a ππ stacking interaction between the pyrimidine ring portions of the mol­ecules at (x, y, z) and (−x, y, [{1 \over 2}] − z). The planes of these two rings make an angle of only 1.9 (2)°; the interplanar spacing is 3.218 (2) Å and the centroid–centroid separation is 3.363 (2) Å, corresponding to a centroid offset of 0.977 (2) Å (Fig. 5[link]). This interaction thus links each (001) sheet to the two neighbouring sheets, so linking all of the sheets into a single three-dimensional aggregate.

[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(9) chain along [100]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions ([{1 \over 2}] + x, [{1 \over 2}] − y, 1 − z) and (x − [{1 \over 2}], [{1 \over 2}] − y, 1 − z), respectively.
[Figure 3]
Figure 3
Part of the crystal structure of (I[link]), showing the formation of a C(6) chain along [010]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions ([{1 \over 2}] − x, y − [{1 \over 2}], z) and ([{1 \over 2}] − x, [{1 \over 2}] + y, z), respectively.
[Figure 4]
Figure 4
A stereoview of part of the crystal structure of (I[link]), showing the formation of an (001) sheet of alternating R[{_4^4}](22) and R[{_4^4}](30) rings. For the sake of clarity, H atoms bonded to C atoms have been omitted.
[Figure 5]
Figure 5
Part of the crystal structure of (I[link]), showing the ππ stacking interaction which links adjacent (001) sheets. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (−x, y, [{1 \over 2}] − z).

Experimental

The title compound was prepared by adding sodium di­thionite (Na2S2O4; 10 g, 60 mmol) to an aqueous solution of potassium N-(6-amino-3,4-di­hydro-3-methyl-5-nitroso-4-oxopyrimidin-2-yl)­glycinate (Low et al., 2001[Low, J. N., Moreno Sánchez, J. M., Arranz Mascarós, P., Godino Salido, M. L., López Garzon, R., Cobo Domingo, J. & Glidewell, C. (2001). Acta Cryst. B57, 317-328.]; 10 g, 37.7 mmol) at ca 340 K. The resulting solution was cooled in an ice bath, and the precipitated solids were filtered off and washed with water and then ethanol. An aqueous solution of the resulting 5,6-di­amine (2.0 g, 9.3 mmol) was then heated with glyoxal (2.01 ml of a 40% aqueous solution) under reflux for 1 h. The mixture was adjusted to pH 2–3 using hydro­chloric acid and then cooled to give a solid, crystallization of which from 50% (v/v) aqueous methanol gave pale-brown crystals of (I[link]) suitable for single-crystal X-ray diffraction anylysis.

Crystal data
  • C9H9N5O3

  • Mr = 235.21

  • Orthorhombic, Pbcn

  • a = 9.6497 (7) Å

  • b = 12.1378 (5) Å

  • c = 16.5063 (11) Å

  • V = 1933.3 (2) Å3

  • Z = 8

  • Dx = 1.616 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 1899 reflections

  • θ = 3.4–26.0°

  • μ = 0.13 mm−1

  • T = 120 (2) K

  • Plate, pale brown

  • 0.16 × 0.14 × 0.03 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 = 0.974, Tmax = 0.996

  • 13 945 measured reflections

  • 1899 independent reflections

  • 1347 reflections with I > 2σ(I)

  • Rint = 0.095

  • θmax = 26.0°

  • h = −11 → 11

  • k = −14 → 14

  • l = −20 → 17

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.070

  • wR(F2) = 0.106

  • S = 1.08

  • 1899 reflections

  • 156 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0312P)2 + 1.3421P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.22 e Å−3

  • Δρmin = −0.22 e Å−3

Table 1
Selected geometric parameters (Å, °)

N1—C2 1.314 (3)
C2—N3 1.397 (3)
N3—C4 1.382 (3)
C4—C4a 1.459 (3)
C4a—N5 1.345 (3)
N5—C6 1.324 (3)
C6—C7 1.398 (3)
C7—N8 1.326 (3)
N8—C8a 1.360 (3)
C8a—N1 1.362 (3)
C4a—C8a 1.396 (3)
C2—N2 1.333 (3)
C4—O4 1.234 (3)
C22—O21 1.326 (3)
C22—O22 1.210 (3)
N1—C2—N2—C21 −1.9 (3)
C2—N2—C21—C22 −124.3 (2)
N2—C21—C22—O21 51.0 (3)
N2—C21—C22—O22 −129.6 (2)

Table 2
Geometry of hydrogen bonds and short intramolecular contacts (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O21—H21⋯N8i 0.84 1.86 2.697 (3) 177
N2—H2⋯O4ii 0.88 2.00 2.773 (3) 146
C21—H21B⋯N1 0.99 2.37 2.799 (3) 105
Symmetry codes: (i) [{\script{1\over 2}}+x,{\script{1\over 2}}-y,1-z]; (ii) [{\script{1\over 2}}-x,y-{\script{1\over 2}},z].

Space group Pbcn was uniquely assigned from the systematic absences. All H atoms were located from difference maps and subsequently treated as riding atoms, with C—H = 0.95 (aromatic), 0.98 (CH3) or 0.99 Å (CH2), N—H = 0.88 Å and O—H = 0.84 Å, and with Uiso(H) = 1.2Ueq(C,N), 1.5Ueq(C) for methyl H, and 1.5Ueq(O).

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), is of potential biological interest, since it is an N-pteridinyl derivative of the amino acid glycine. Compounds of this general type can be adsorbed on activated carbon, implying ππ interactions between the heteroaromatic moiety and the carbon surface (Coughlin & Ezra, 1968; Mattson et al., 1969; Leon y Leon et al., 1992; Radovic et al., 1997), while the carboxyl function remains available in the solvent phase to act as a coordinating site for metal ions in solution, thus providing the basis of a possible method for the removal of toxic metal ions from waste waters. \sch

The bond distances within the molecule of (I) present some unexpected values (Table 1), which are not readily reconciled with the classically localized bond-valence form. In particular, the C6—C7 and C4a—C8a bonds, which are formally single and double bonds, respectively, have effectively identical lengths. In addition, the C2—N2 bond, which is formally a single bond, is barely longer than the N5—C6 and C7—N8 bonds, which are formally double bonds. On the other hand, these latter two are significantly shorter than any of C4a—N5, N8—C8a and C8a—N1. These observations render somewhat problematical the graphical representation of the molecular-electronic structure. The polarized form (Ia) can be ruled out, on the grounds that the N8—C8a and C8a—N1 bonds have effectively identical lengths, and because C4—C4a is by far the longest C—C bond in the ring system. The bond distances in the N3—C4—O4 amidic fragment are normal for their types (Allen et al., 1987). Within the carboxyl group, the C—O distances are fully consistent with the localization of the H atom, as deduced from a difference map.

While the bicyclic portion of the molecule is effectively planar, with a maximum deviation from the best least-squares plane of 0.052 (2) Å for atom N8, the conformation of the glycinyl side chain (Fig. 1 and Table 1) may well be influenced by the short intramolecular contact involving atoms H21B and N1 (Table 2), which generates a nearly planar S(5) ring (Bernstein et al., 1995).

The molecules of (I) are linked via a combination of O—H···N and N—H···O hydrogen bonds (Table 2) into sheets, within which each of the two hydrogen bonds alone produces a one-dimensional sub-structure. It is striking that neither of the motifs characteristic of simple carboxylic acids, the C(4) chain and the cyclic R22(8) dimer, is present in the structure of (I). In the first sub-structure, carboxyl atom O21 in the molecule at (x, y, z) acts as hydrogen-bond donor to atom N8 in the molecule at (1/2 + x, 1/2 − y, 1 − z), so forming a C(9) chain running parallel to the [100] direction and generated by the 21 screw axis along (x, 1/4, 1/2) (Fig. 2). In the second sub-structure, amino atom N2 in the molecule at (x, y, z) acts as hydrogen-bond donor to carbonyl atom O4 in the molecule at (1/2 − x, y − 1/2, z), so forming a C(6) chain running parallel to the [010] direction and generated by the b-glide plane at x = 1/4 (Fig. 3). The combination of these chains generates an (001) sheet in the form of a (4,4) net (Batten & Robson, 1998) built from centrosymmetric R44(22) and R44(30) rings alternating in chess-board fashion (Fig. 4). Around the periphery of the R44(30) rings, each molecule acts as a single donor and single acceptor of hydrogen bonds, while around the periphery of the R44(22) rings, one pair of centrosymmetrically related molecules act as double donors and the other such pair as double acceptors of hydrogen bonds.

Two of these sheets, related to one another by the 21 screw axes parallel to [001], pass through each unit cell, in the domains 0.24 < z < 0.76 and 0.74 < z < 1.26, respectively, and the sole direction-specific interaction between adjacent sheets is a ππ stacking interaction between the pyrimidine ring portions of the molecules at (x, y, z) and (-x, y, 1/2 − z). The planes of these two rings make an angle of only 1.9 (2)°; the interplanar spacing is 3.218 (2) Å and the centroid separation is 3.363 (2) Å, corresponding to a centroid offset of 0.977 (2) Å (Fig. 5). This interaction thus links each (001) sheet to the two neighbouring sheets, so linking all of the sheets into a single three-dimensional aggregate.

Table 2. Parameters (Å, °) for hydrogen bonds and short intramolecular contacts for (I)

Experimental top

The title compound was prepared by adding sodium dithionite (Na2S2O4; 10 g, 60 mmol) to an aqueous solution of potassium N-(6-amino-3,4-dihydro-3-methyl-5-nitroso-4-oxopyrimidin-2-yl)glycinate (Low et al., 2001; 10 g, 37.7 mmol) at ca 340 K. The resulting solution was cooled in an ice bath, and the precipitated solids were filtered off and washed with water and then ethanol. An aqueous solution of the resulting 5,6-diamine (2.0 g, 9.3 mmol) was then heated with glyoxal (2.01 ml of a 40% aqueous solution) under reflux for 1 h. The mixture was adjusted to pH 2–3 using hydrochloric acid and then cooled to give a solid, crystallization of which from 50% (v/v) aqueous methanol gave pale-brown crystals of (I) suitable for single-crystal X-ray diffraction.

Refinement top

Space group Pbcn was uniquely assigned from the systematic absences. All H atoms were located from difference maps and subsequently treated as riding atoms, with C—H = 0.95 (aromatic), 0.98 (CH3) or 0.99 Å (CH2), N—H 0.88 Å and O—H 0.84 Å, and with Uiso(H) = 1.2Ueq(C,N), 1.5Ueq(C) for methyl H, and 1.5Ueq(O).

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(9) chain along [100]. For the sake of clarity, H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1/2 + x, 1/2 − y, 1 − z) and (x − 1/2, 1/2 − y, 1 − z), respectively.
[Figure 3] Fig. 3. Part of the crystal structure of (I), showing formation of a C(6) chain along [010]. For the sake of clarity, H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1/2 − x, y − 1/2, z) and (1/2 − x, 1/2 + y, z), respectively.
[Figure 4] Fig. 4. A stereoview of part of the crystal structure of (I), showing formation of an (001) sheet of alternating R44(22) and R44(30) rings. For the sake of clarity, H atoms bonded to C atoms have been omitted.
[Figure 5] Fig. 5. Part of the crystal structure of (I), showing the ππ stacking interaction which links adjacent (001) sheets. For the sake of clarity, H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*) are at the symmetry position (-x, y, 1/2 − z).
N-(3-Methylpteridin-4-one-2-yl)glycine top
Crystal data top
C9H9N5O3F(000) = 976
Mr = 235.21Dx = 1.616 Mg m3
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 1899 reflections
a = 9.6497 (7) Åθ = 3.4–26.0°
b = 12.1378 (5) ŵ = 0.13 mm1
c = 16.5063 (11) ÅT = 120 K
V = 1933.3 (2) Å3Plate, pale brown
Z = 80.16 × 0.14 × 0.03 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
1899 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode1347 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.095
Detector resolution: 9.091 pixels mm-1θmax = 26.0°, θmin = 3.4°
ϕ and ω scansh = 1111
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1414
Tmin = 0.974, Tmax = 0.996l = 2017
13945 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) = 0.106H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0312P)2 + 1.3421P]
where P = (Fo2 + 2Fc2)/3
1899 reflections(Δ/σ)max < 0.001
156 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = 0.22 e Å3
Crystal data top
C9H9N5O3V = 1933.3 (2) Å3
Mr = 235.21Z = 8
Orthorhombic, PbcnMo Kα radiation
a = 9.6497 (7) ŵ = 0.13 mm1
b = 12.1378 (5) ÅT = 120 K
c = 16.5063 (11) Å0.16 × 0.14 × 0.03 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
1899 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1347 reflections with I > 2σ(I)
Tmin = 0.974, Tmax = 0.996Rint = 0.095
13945 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0700 restraints
wR(F2) = 0.106H-atom parameters constrained
S = 1.08Δρmax = 0.22 e Å3
1899 reflectionsΔρmin = 0.22 e Å3
156 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O40.24116 (17)0.56211 (13)0.25672 (10)0.0211 (4)
O210.19593 (18)0.11809 (13)0.47641 (10)0.0235 (4)
O220.09896 (18)0.03756 (13)0.42924 (10)0.0263 (5)
N10.0209 (2)0.36572 (15)0.38752 (12)0.0183 (5)
N20.0983 (2)0.21795 (15)0.33592 (12)0.0198 (5)
N30.1676 (2)0.39162 (15)0.29511 (11)0.0163 (5)
N50.0439 (2)0.66045 (15)0.35630 (11)0.0198 (5)
N80.1353 (2)0.51761 (15)0.43987 (12)0.0184 (5)
C20.0787 (2)0.32640 (18)0.34161 (14)0.0167 (5)
C30.2756 (3)0.34055 (19)0.24421 (15)0.0220 (6)
C40.1609 (3)0.50534 (19)0.29725 (14)0.0178 (5)
C4a0.0534 (2)0.55023 (18)0.34992 (14)0.0172 (5)
C60.0541 (3)0.6977 (2)0.40535 (14)0.0214 (6)
C70.1440 (3)0.62632 (19)0.44616 (14)0.0203 (6)
C8a0.0328 (2)0.47735 (18)0.39167 (14)0.0173 (5)
C210.0164 (3)0.13720 (19)0.38056 (15)0.0220 (6)
C220.1077 (3)0.06184 (19)0.43079 (14)0.0198 (6)
H20.16410.19380.30350.024*
H210.24580.07400.50270.035*
H3A0.32860.39830.21660.033*
H3B0.23200.29250.20390.033*
H3C0.33800.29690.27840.033*
H60.06360.77490.41300.026*
H70.21400.65700.47970.024*
H21A0.03820.09250.34190.026*
H21B0.04940.17610.41670.026*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O40.0195 (10)0.0202 (9)0.0237 (9)0.0051 (8)0.0010 (8)0.0013 (7)
O210.0224 (10)0.0201 (9)0.0278 (10)0.0004 (8)0.0026 (8)0.0015 (8)
O220.0323 (11)0.0150 (9)0.0315 (10)0.0004 (8)0.0026 (9)0.0001 (7)
N10.0166 (11)0.0180 (10)0.0203 (11)0.0005 (9)0.0011 (10)0.0002 (9)
N20.0195 (11)0.0165 (11)0.0235 (11)0.0021 (9)0.0033 (9)0.0004 (8)
N30.0150 (11)0.0156 (10)0.0183 (11)0.0016 (9)0.0003 (9)0.0004 (8)
N50.0219 (12)0.0181 (10)0.0193 (11)0.0004 (9)0.0022 (10)0.0011 (8)
N80.0170 (11)0.0204 (11)0.0176 (11)0.0031 (9)0.0026 (9)0.0020 (8)
C20.0149 (13)0.0188 (13)0.0165 (13)0.0011 (11)0.0059 (10)0.0005 (10)
C30.0194 (14)0.0224 (12)0.0242 (14)0.0040 (11)0.0043 (11)0.0014 (11)
C40.0176 (13)0.0184 (12)0.0175 (13)0.0013 (11)0.0068 (11)0.0015 (10)
C4a0.0178 (13)0.0172 (12)0.0166 (12)0.0004 (10)0.0039 (11)0.0009 (10)
C60.0259 (15)0.0172 (12)0.0212 (13)0.0039 (11)0.0049 (12)0.0019 (10)
C70.0216 (15)0.0223 (13)0.0171 (14)0.0060 (11)0.0028 (11)0.0021 (10)
C8a0.0191 (14)0.0177 (12)0.0151 (13)0.0016 (10)0.0070 (11)0.0004 (10)
C210.0199 (14)0.0182 (12)0.0280 (14)0.0036 (11)0.0008 (12)0.0011 (11)
C220.0187 (14)0.0206 (14)0.0199 (13)0.0001 (11)0.0076 (11)0.0011 (10)
Geometric parameters (Å, º) top
N1—C21.314 (3)C22—O221.210 (3)
C2—N31.397 (3)N2—C211.459 (3)
N3—C41.382 (3)N2—H20.88
C4—C4a1.459 (3)C21—C221.517 (3)
C4a—N51.345 (3)C21—H21A0.99
N5—C61.324 (3)C21—H21B0.99
C6—C71.398 (3)O21—H210.84
C7—N81.326 (3)N3—C31.475 (3)
N8—C8a1.360 (3)C3—H3A0.98
C8a—N11.362 (3)C3—H3B0.98
C4a—C8a1.396 (3)C3—H3C0.98
C2—N21.333 (3)C6—H60.95
C4—O41.234 (3)C7—H70.95
C22—O211.326 (3)
C2—N1—C8a116.9 (2)H3A—C3—H3B109.5
N1—C2—N2120.2 (2)N3—C3—H3C109.5
N1—C2—N3124.1 (2)H3A—C3—H3C109.5
N2—C2—N3115.7 (2)H3B—C3—H3C109.5
C2—N2—C21123.4 (2)O4—C4—N3121.0 (2)
C2—N2—H2118.3O4—C4—C4a124.1 (2)
C21—N2—H2118.3N3—C4—C4a114.9 (2)
N2—C21—C22111.5 (2)N5—C4a—C8a123.4 (2)
N2—C21—H21A109.3N5—C4a—C4117.8 (2)
C22—C21—H21A109.3C8a—C4a—C4118.8 (2)
N2—C21—H21B109.3N5—C6—C7121.7 (2)
C22—C21—H21B109.3N5—C6—H6119.1
H21A—C21—H21B108.0C7—C6—H6119.1
O22—C22—O21124.8 (2)N8—C7—C6122.7 (2)
O22—C22—C21123.3 (2)N8—C7—H7118.7
O21—C22—C21111.9 (2)C6—C7—H7118.7
C22—O21—H21109.5C6—N5—C4a115.8 (2)
C4—N3—C2121.6 (2)C7—N8—C8a116.7 (2)
C4—N3—C3117.84 (19)N8—C8a—N1116.7 (2)
C2—N3—C3120.56 (19)N8—C8a—C4a119.6 (2)
N3—C3—H3A109.5N1—C8a—C4a123.7 (2)
N3—C3—H3B109.5
C8a—N1—C2—N2178.7 (2)N3—C4—C4a—N5178.3 (2)
C8a—N1—C2—N32.7 (3)O4—C4—C4a—C8a178.9 (2)
N1—C2—N2—C211.9 (3)N3—C4—C4a—C8a0.9 (3)
N3—C2—N2—C21179.4 (2)N5—C6—C7—N81.4 (4)
C2—N2—C21—C22124.3 (2)C7—C6—N5—C4a1.5 (3)
N2—C21—C22—O2151.0 (3)C8a—C4a—N5—C60.1 (3)
N2—C21—C22—O22129.6 (2)C4—C4a—N5—C6179.3 (2)
N1—C2—N3—C43.2 (3)C6—C7—N8—C8a0.5 (3)
N2—C2—N3—C4178.1 (2)C7—N8—C8a—N1177.7 (2)
N1—C2—N3—C3179.1 (2)C7—N8—C8a—C4a2.1 (3)
N2—C2—N3—C30.5 (3)C2—N1—C8a—N8179.4 (2)
C2—N3—C4—O4179.0 (2)C2—N1—C8a—C4a0.4 (3)
C3—N3—C4—O41.3 (3)N5—C4a—C8a—N82.1 (3)
C2—N3—C4—C4a1.2 (3)C4—C4a—C8a—N8178.8 (2)
C3—N3—C4—C4a178.92 (19)N5—C4a—C8a—N1177.8 (2)
O4—C4—C4a—N51.9 (3)C4—C4a—C8a—N11.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O21—H21···N8i0.841.862.697 (3)177
N2—H2···O4ii0.882.002.773 (3)146
C21—H21B···N10.992.372.799 (3)105
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x+1/2, y1/2, z.

Experimental details

Crystal data
Chemical formulaC9H9N5O3
Mr235.21
Crystal system, space groupOrthorhombic, Pbcn
Temperature (K)120
a, b, c (Å)9.6497 (7), 12.1378 (5), 16.5063 (11)
V3)1933.3 (2)
Z8
Radiation typeMo Kα
µ (mm1)0.13
Crystal size (mm)0.16 × 0.14 × 0.03
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.974, 0.996
No. of measured, independent and
observed [I > 2σ(I)] reflections
13945, 1899, 1347
Rint0.095
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.070, 0.106, 1.08
No. of reflections1899
No. of parameters156
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.22, 0.22

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
N1—C21.314 (3)N8—C8a1.360 (3)
C2—N31.397 (3)C8a—N11.362 (3)
N3—C41.382 (3)C4a—C8a1.396 (3)
C4—C4a1.459 (3)C2—N21.333 (3)
C4a—N51.345 (3)C4—O41.234 (3)
N5—C61.324 (3)C22—O211.326 (3)
C6—C71.398 (3)C22—O221.210 (3)
C7—N81.326 (3)
N1—C2—N2—C211.9 (3)N2—C21—C22—O2151.0 (3)
C2—N2—C21—C22124.3 (2)N2—C21—C22—O22129.6 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O21—H21···N8i0.841.862.697 (3)177
N2—H2···O4ii0.882.002.773 (3)146
C21—H21B···N10.992.372.799 (3)105
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x+1/2, y1/2, 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.

References

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