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

Arranz Mascarós, P.; Gutiérrez Valero, M.D.; Low, J.N.; Glidewell, C.

doi:10.1107/S010827010402222X

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 60| Part 11| November 2004| Pages o795-o797

doi:10.1107/S010827010402222X

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

Paloma Arranz Mascarós,^a M. Dolores Gutiérrez Valero,^a John N. Low ^b and Christopher Glidewell ^c ^*

^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), 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 π–π 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 water.

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 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). 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). 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). The combination of these chains generates a (001) sheet in the form of a (4,4)-net (Batten & Robson, 1998 ) built from centrosymmetric R $[{_4^4}]$ (22) and R $[{_4^4}]$ (30) rings alternating in a chess-board fashion (Fig. 4). 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 π–π 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). 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
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
Part of the crystal structure of (I

), 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
Part of the crystal structure of (I

), 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
A stereoview of part of the crystal structure of (I

), 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
Part of the crystal structure of (I

), showing the π–π 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 ; 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 anylysis.

Crystal data

C₉H₉N₅O₃
M_r = 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
D_x = 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 ) T_min = 0.974, T_max = 0.996
13 945 measured reflections
1899 independent reflections
1347 reflections with I > 2σ(I)
R_int = 0.095
θ_max = 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(F_o²) + (0.0312P)² + 1.3421P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.22 e Å⁻³
Δρ_min = −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	D⋯A	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 U_iso(H) = 1.2U_eq(C,N), 1.5U_eq(C) for methyl H, and 1.5U_eq(O).

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S010827010402222X/sk1769sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S010827010402222X/sk1769Isup2.hkl

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 π–π 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.

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 π–π 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.

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

	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.
	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.
	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.
	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.
	Fig. 5. Part of the crystal structure of (I), showing the π–π 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

C₉H₉N₅O₃	F(000) = 976
M_r = 235.21	D_x = 1.616 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 1899 reflections
a = 9.6497 (7) Å	θ = 3.4–26.0°
b = 12.1378 (5) Å	µ = 0.13 mm⁻¹
c = 16.5063 (11) Å	T = 120 K
V = 1933.3 (2) Å³	Plate, pale brown
Z = 8	0.16 × 0.14 × 0.03 mm

Data collection top

Nonius KappaCCD area-detector diffractometer	1899 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1347 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.095
Detector resolution: 9.091 pixels mm^-1	θ_max = 26.0°, θ_min = 3.4°
ϕ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −14→14
T_min = 0.974, T_max = 0.996	l = −20→17
13945 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.070	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0312P)² + 1.3421P] where P = (F_o² + 2F_c²)/3
1899 reflections	(Δ/σ)_max < 0.001
156 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₉H₉N₅O₃	V = 1933.3 (2) Å³
M_r = 235.21	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 9.6497 (7) Å	µ = 0.13 mm⁻¹
b = 12.1378 (5) Å	T = 120 K
c = 16.5063 (11) Å	0.16 × 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)
T_min = 0.974, T_max = 0.996	R_int = 0.095
13945 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.070	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.08	Δρ_max = 0.22 e Å⁻³
1899 reflections	Δρ_min = −0.22 e Å⁻³
156 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O4	0.24116 (17)	0.56211 (13)	0.25672 (10)	0.0211 (4)
O21	0.19593 (18)	0.11809 (13)	0.47641 (10)	0.0235 (4)
O22	0.09896 (18)	−0.03756 (13)	0.42924 (10)	0.0263 (5)
N1	−0.0209 (2)	0.36572 (15)	0.38752 (12)	0.0183 (5)
N2	0.0983 (2)	0.21795 (15)	0.33592 (12)	0.0198 (5)
N3	0.1676 (2)	0.39162 (15)	0.29511 (11)	0.0163 (5)
N5	0.0439 (2)	0.66045 (15)	0.35630 (11)	0.0198 (5)
N8	−0.1353 (2)	0.51761 (15)	0.43987 (12)	0.0184 (5)
C2	0.0787 (2)	0.32640 (18)	0.34161 (14)	0.0167 (5)
C3	0.2756 (3)	0.34055 (19)	0.24421 (15)	0.0220 (6)
C4	0.1609 (3)	0.50534 (19)	0.29725 (14)	0.0178 (5)
C4a	0.0534 (2)	0.55023 (18)	0.34992 (14)	0.0172 (5)
C6	−0.0541 (3)	0.6977 (2)	0.40535 (14)	0.0214 (6)
C7	−0.1440 (3)	0.62632 (19)	0.44616 (14)	0.0203 (6)
C8a	−0.0328 (2)	0.47735 (18)	0.39167 (14)	0.0173 (5)
C21	0.0164 (3)	0.13720 (19)	0.38056 (15)	0.0220 (6)
C22	0.1077 (3)	0.06184 (19)	0.43079 (14)	0.0198 (6)
H2	0.1641	0.1938	0.3035	0.024*
H21	0.2458	0.0740	0.5027	0.035*
H3A	0.3286	0.3983	0.2166	0.033*
H3B	0.2320	0.2925	0.2039	0.033*
H3C	0.3380	0.2969	0.2784	0.033*
H6	−0.0636	0.7749	0.4130	0.026*
H7	−0.2140	0.6570	0.4797	0.024*
H21A	−0.0382	0.0925	0.3419	0.026*
H21B	−0.0494	0.1761	0.4167	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O4	0.0195 (10)	0.0202 (9)	0.0237 (9)	−0.0051 (8)	0.0010 (8)	0.0013 (7)
O21	0.0224 (10)	0.0201 (9)	0.0278 (10)	0.0004 (8)	−0.0026 (8)	0.0015 (8)
O22	0.0323 (11)	0.0150 (9)	0.0315 (10)	−0.0004 (8)	0.0026 (9)	0.0001 (7)
N1	0.0166 (11)	0.0180 (10)	0.0203 (11)	0.0005 (9)	−0.0011 (10)	0.0002 (9)
N2	0.0195 (11)	0.0165 (11)	0.0235 (11)	0.0021 (9)	0.0033 (9)	−0.0004 (8)
N3	0.0150 (11)	0.0156 (10)	0.0183 (11)	0.0016 (9)	−0.0003 (9)	−0.0004 (8)
N5	0.0219 (12)	0.0181 (10)	0.0193 (11)	0.0004 (9)	−0.0022 (10)	−0.0011 (8)
N8	0.0170 (11)	0.0204 (11)	0.0176 (11)	0.0031 (9)	−0.0026 (9)	−0.0020 (8)
C2	0.0149 (13)	0.0188 (13)	0.0165 (13)	−0.0011 (11)	−0.0059 (10)	0.0005 (10)
C3	0.0194 (14)	0.0224 (12)	0.0242 (14)	0.0040 (11)	0.0043 (11)	0.0014 (11)
C4	0.0176 (13)	0.0184 (12)	0.0175 (13)	−0.0013 (11)	−0.0068 (11)	0.0015 (10)
C4a	0.0178 (13)	0.0172 (12)	0.0166 (12)	0.0004 (10)	−0.0039 (11)	−0.0009 (10)
C6	0.0259 (15)	0.0172 (12)	0.0212 (13)	0.0039 (11)	−0.0049 (12)	−0.0019 (10)
C7	0.0216 (15)	0.0223 (13)	0.0171 (14)	0.0060 (11)	−0.0028 (11)	−0.0021 (10)
C8a	0.0191 (14)	0.0177 (12)	0.0151 (13)	0.0016 (10)	−0.0070 (11)	0.0004 (10)
C21	0.0199 (14)	0.0182 (12)	0.0280 (14)	−0.0036 (11)	−0.0008 (12)	0.0011 (11)
C22	0.0187 (14)	0.0206 (14)	0.0199 (13)	0.0001 (11)	0.0076 (11)	−0.0011 (10)

Geometric parameters (Å, º) top

N1—C2	1.314 (3)	C22—O22	1.210 (3)
C2—N3	1.397 (3)	N2—C21	1.459 (3)
N3—C4	1.382 (3)	N2—H2	0.88
C4—C4a	1.459 (3)	C21—C22	1.517 (3)
C4a—N5	1.345 (3)	C21—H21A	0.99
N5—C6	1.324 (3)	C21—H21B	0.99
C6—C7	1.398 (3)	O21—H21	0.84
C7—N8	1.326 (3)	N3—C3	1.475 (3)
N8—C8a	1.360 (3)	C3—H3A	0.98
C8a—N1	1.362 (3)	C3—H3B	0.98
C4a—C8a	1.396 (3)	C3—H3C	0.98
C2—N2	1.333 (3)	C6—H6	0.95
C4—O4	1.234 (3)	C7—H7	0.95
C22—O21	1.326 (3)

C2—N1—C8a	116.9 (2)	H3A—C3—H3B	109.5
N1—C2—N2	120.2 (2)	N3—C3—H3C	109.5
N1—C2—N3	124.1 (2)	H3A—C3—H3C	109.5
N2—C2—N3	115.7 (2)	H3B—C3—H3C	109.5
C2—N2—C21	123.4 (2)	O4—C4—N3	121.0 (2)
C2—N2—H2	118.3	O4—C4—C4a	124.1 (2)
C21—N2—H2	118.3	N3—C4—C4a	114.9 (2)
N2—C21—C22	111.5 (2)	N5—C4a—C8a	123.4 (2)
N2—C21—H21A	109.3	N5—C4a—C4	117.8 (2)
C22—C21—H21A	109.3	C8a—C4a—C4	118.8 (2)
N2—C21—H21B	109.3	N5—C6—C7	121.7 (2)
C22—C21—H21B	109.3	N5—C6—H6	119.1
H21A—C21—H21B	108.0	C7—C6—H6	119.1
O22—C22—O21	124.8 (2)	N8—C7—C6	122.7 (2)
O22—C22—C21	123.3 (2)	N8—C7—H7	118.7
O21—C22—C21	111.9 (2)	C6—C7—H7	118.7
C22—O21—H21	109.5	C6—N5—C4a	115.8 (2)
C4—N3—C2	121.6 (2)	C7—N8—C8a	116.7 (2)
C4—N3—C3	117.84 (19)	N8—C8a—N1	116.7 (2)
C2—N3—C3	120.56 (19)	N8—C8a—C4a	119.6 (2)
N3—C3—H3A	109.5	N1—C8a—C4a	123.7 (2)
N3—C3—H3B	109.5

C8a—N1—C2—N2	178.7 (2)	N3—C4—C4a—N5	178.3 (2)
C8a—N1—C2—N3	−2.7 (3)	O4—C4—C4a—C8a	178.9 (2)
N1—C2—N2—C21	−1.9 (3)	N3—C4—C4a—C8a	−0.9 (3)
N3—C2—N2—C21	179.4 (2)	N5—C6—C7—N8	1.4 (4)
C2—N2—C21—C22	−124.3 (2)	C7—C6—N5—C4a	−1.5 (3)
N2—C21—C22—O21	51.0 (3)	C8a—C4a—N5—C6	−0.1 (3)
N2—C21—C22—O22	−129.6 (2)	C4—C4a—N5—C6	−179.3 (2)
N1—C2—N3—C4	3.2 (3)	C6—C7—N8—C8a	0.5 (3)
N2—C2—N3—C4	−178.1 (2)	C7—N8—C8a—N1	177.7 (2)
N1—C2—N3—C3	−179.1 (2)	C7—N8—C8a—C4a	−2.1 (3)
N2—C2—N3—C3	−0.5 (3)	C2—N1—C8a—N8	−179.4 (2)
C2—N3—C4—O4	179.0 (2)	C2—N1—C8a—C4a	0.4 (3)
C3—N3—C4—O4	1.3 (3)	N5—C4a—C8a—N8	2.1 (3)
C2—N3—C4—C4a	−1.2 (3)	C4—C4a—C8a—N8	−178.8 (2)
C3—N3—C4—C4a	−178.92 (19)	N5—C4a—C8a—N1	−177.8 (2)
O4—C4—C4a—N5	−1.9 (3)	C4—C4a—C8a—N1	1.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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) x+1/2, −y+1/2, −z+1; (ii) −x+1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₉H₉N₅O₃
M_r	235.21
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	120
a, b, c (Å)	9.6497 (7), 12.1378 (5), 16.5063 (11)
V (Å³)	1933.3 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.16 × 0.14 × 0.03

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.974, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	13945, 1899, 1347
R_int	0.095
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.070, 0.106, 1.08
No. of reflections	1899
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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—C2	1.314 (3)	N8—C8a	1.360 (3)
C2—N3	1.397 (3)	C8a—N1	1.362 (3)
N3—C4	1.382 (3)	C4a—C8a	1.396 (3)
C4—C4a	1.459 (3)	C2—N2	1.333 (3)
C4a—N5	1.345 (3)	C4—O4	1.234 (3)
N5—C6	1.324 (3)	C22—O21	1.326 (3)
C6—C7	1.398 (3)	C22—O22	1.210 (3)
C7—N8	1.326 (3)

N1—C2—N2—C21	−1.9 (3)	N2—C21—C22—O21	51.0 (3)
C2—N2—C21—C22	−124.3 (2)	N2—C21—C22—O22	−129.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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) x+1/2, −y+1/2, −z+1; (ii) −x+1/2, 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.

References

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. CrossRef Web of Science Google Scholar
Batten, S. R. & Robson, R. (1998). Angew. Chem. Int. Ed. 37, 1460–1494. Web of Science CrossRef Google Scholar
Bernstein, 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
Coughlin, R. W. & Ezra, F. S. (1968). Environ. Sci. Technol. 2, 291–297. CrossRef CAS Google Scholar
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. Google Scholar
Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Leon y Leon, C. A., Solar, J. M., Calemma, V. & Radovic, L. R. (1992). Carbon, 30, 797–811. Google Scholar
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. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland. Google Scholar
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. CrossRef CAS Web of Science Google Scholar
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. Google Scholar
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. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 60| Part 11| November 2004| Pages o795-o797

doi:10.1107/S010827010402222X

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Search term		doi		Advanced search
Author		volume	page

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