Supra­molecular motifs in 1-(2-cyano­ethyl)thymine and 1-(3-cyano­propyl)­thymine

In both 1-(2-cyano­ethyl)thymine [systematic name: 3-(5-methyl-2,4-dioxo-1,2,3,4-tetra­hydro­pyrimidin-1-yl)propane­nitrile], C₈H₉N₃O₂, (I), and 1-(3-cyano­propyl)thymine [systematic name: 4-(5-methyl-2,4-dioxo-1,2,3,4-tetra­hydro­pyrimidin-1-yl)butane­nitrile], C₉H₁₁N₃O₂, (II), the core of the supra­molecular structure is formed by centrosymmetric dimers generated by N—H...O hydrogen bonds. Further weak hydrogen bonds of C—H...O and C—H...N types generate mol­ecular tapes and sheets that resemble those in uracil and its methyl derivatives. The steric hindrance that arises from the cyano­alkyl substituents perturbs the conformations of the tapes and sheets.

S1. Comment

In the course of our studies of the hierarchy of intermolecular interactions in crystals (Borowiak et al., 2006; Kubicki et al., 2001, 2002; Kubicki, 2004), the supramolecular structures of two thymine derivatives, 1-(2-cyanoethyl)thymine, (I), and 1-(3-cyanopropyl)thymine, (II), have been determined. Both molecules contain a planar thymine ring and, of the several possible tautomeric forms for the ring, the diketo tautomer is observed in the solid state (Figs. 1 and 2). Appreciable differences are observed in the values of the C═O bond lengths [C2═O2 = 1.216 (1) and 1.221 (1) Å for (I) and (II), respectively; C4═O4 = 1.233 (1) and 1.237 (2) Å for (I) and (II), respectively]. The existence of two different C═O groups can be easily rationalized by observing the respective crystal structures.

In (I) and (II), centrosymmetric dimers are formed via N3—H3···O4═ C4 hydrogen bonds. For this reason, C4═O4 is longer than the standard carbonyl double bond (Standard reference?). The second carbonyl group, C2═O2, is involved only in weak C—H···O hydrogen bonds (Table 1 and 2), and this bond is shorter [Than what?]. The geometric perturbation is mainly due to self-association and confirms the fundamental role of conjugative stabilization of the intermolecular hydrogen bonding.

The C═O bond-length pattern in (I) and (II) is in agreement with those in other uracil derivatives. In the structure of (1-thyminyl)acetamide (Borowiak et al., 2006), the centrosymmetric dimers are formed via N3—H3···O2═C2 hydrogen bonds and, in consequence, the C2═O2 bond is longer. Similar appreciable discrepancies in the C═O bond lengths have also been found in the structures of uracil (Portalone et al., 1999), thymine (Portalone et al., 1999) or 1-methyluracil (McMullan & Craven, 1989). The hydrogen bonding in the crystal structures of uracil and 1-methyluracil involves atom O4 as acceptor of a strong hydrogen bond but not atom O2. In the structure of 1,3-dimethyluracil, the equivalence of the carbonyl groups is explained by the fact that no C═O···H—N hydrogen bond is possible (Banerjee et al., 1977).

Although the molecules of (I) and (II) differ only by one CH₂ group in the substituent at N1 and intermolecular interactions are of the same type, the supramolecular motifs in their crystal structures differ due to the steric factor determined by the length of the chain. The centrosymmetric dimers form the cores of the supramolecular structures, which are further based on continuous tapes.

In (I), the planar N3—H3···O4 dimers are connected by C12—H12B···O2 and C11—H11B···O2 hydrogen bonds, thus forming the second kind of dimer, a non-centrosymmetric one (Fig. 3a). These two consecutive dimers extend to form a molecular tape. On the other hand, two centrosymmetric dimers separated by a non-centrosymmetric one in each tape are set almost perpendicular to one another, giving rise to a sinusoidal shape of tapes (the angle between the planes of two flat dimers is about 78° (Fig. 3b).

The tapes are connected in turn by weak C6—H6···N13 hydrogen bonds. Moreover, the thymine moieties of (I) are mutually oriented in a parallel mode along the shortest unit cell axis [b = 4.412 (1) Å] (Fig. 3b). As a consequence of the tape conformation, two different orientations of columns are observed, with the distance between mutually parallel rings being 3.42 (1) Å. The stacking of molecules in (I) occurs with no overlap of pyrimidine rings.

In (II), the core of the supramolecular structure is also defined by centrosymmetric dimers formed via the same type of hydrogen bonds, N3—H3···O4 (Table 2). These dimers are further connected by weak C12—H12B···O2 hydrogen bonds that form another centrosymmetric dimer (Fig. 4a). These consecutive dimers are linked into continuous tapes which are, however, not planar, as small steps are found in their conformation (Fig. 4b).

The tapes are further connected into sheets by the third type of centrosymmetric dimer created via weak C6—H6···N14 hydrogen bonds (Fig. 4a). The same steps occur in the conformation of the sheets. As in (I), the uracil moieties in (II) also form a parallel mode of packing along the shortest unit cell axis [a = 4.859 (1) Å]. Also in (II), no overlap of the pyrimidine rings is observed.

The features of the supramolecular structures of uracil and its methyl derivatives are retained in compounds (I) and (II), although steric hindrance causes disturbances in the conformations of the tapes and sheets. No carbonyl–carbonyl interactions are found, although this kind of interaction is able to compete successfully with hydrogen bonds (Allen et al., 1998).

Related literature

For related literature, see: Allen et al. (1998); Banerjee et al. (1977); Borowiak et al. (2006); Kubicki (2004); Kubicki et al. (2001, 2002); McMullan & Craven (1989); Portalone et al. (1999); Spychała (2000).

S2. Experimental

The synthesis of 1-(3-cyanopropyl)thymine, (II), was described by Spychała (2000). Crystals of (II) suitable for X-ray data collection were grown from a solution in methanol by slow cooling. 1-(2-Cyanoethyl)thymine, (I), was prepared by the same N-alkylation procedure from thymine and 3-bromopropionitrile and recrystallized from methanol (m.p. 472–474 K). Spectroscopic analysis: ¹H NMR (DMSO-d₆, TMS, δ, p.p.m.): 1.75 (s, 3H, CH₃), 2.88 (t, 2H, J = 6.4 Hz, CH₂), 3.89 (t, 2H, J = 6.6 Hz, CH₂), 7.55 (s, 1H, C6H), 11.33 (br s, 1H, N3H); ¹³C NMR (DMSO-d₆, TMS, δ, p.p.m.): 11.9, 16.8, 43.0, 99.8, 108.8, 118.8, 150.7, 164.2; FT–IR (KBr, ν_max, cm^-1): 3032, 2831, 2245, 1720, 1666, 1480, 1459, 1430, 1389; HRMS (EI): M⁺, found 179.0693; C₈H₉N₃O₂ requires 179.0695. The instrumentation and analysis methods have been described by Spychała (2000).

Computing details

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989) and Mercury (Macrae et al., 2006); software used to prepare material for publication: Please provide missing details.

Figures

	Fig. 1. A view of the molecule of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are depicted as spheres of arbitrary radii.
	Fig. 2. A view of the molecule of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are depicted as spheres of arbitrary radii.
	Fig. 3. (a) The molecular tapes in (I) generated by N3–H3···O4^i hydrogen bonds and by weak C11—H11B···O2^ii and C12—H12A···O2^ii hydrogen bonds. C6—H6···N13^iv hydrogen bonds connect the tapes. Hydrogen bonds are indicated by dotted lines. [Symmetry codes: (i) -x + 1, -y + 2, -z, (ii) -x + 1, 1/2 + y, 1/2 - z, (iii) -x + 2, 1/2 + y, 1/2 - z.] (b) The molecular tapes in (I), expanded along the c axis. A sinusoidal conformation of the tapes is shown. Hydrogen bonds are indicated by dotted lines.
	Fig. 4. (a) The molecular tapes in (II) generated by two consecutive centrosymmetric dimers: one of them via N3—H3···O4^i and the other via weak C12—H12B···O2^iv hydrogen bonds. The C6—H6···N14^ii hydrogen bonds connect the tapes into sheets. Hydrogen bonds are indicated by dotted lines. [Symmetry codes: (i) -x, -y + 1, -z + 1, (ii) -x + 2, -y, -z + 2, (iii) -x, -y + 1, -z + 2.] (b) The molecular tape in (II), expanded along the c axis. Small steps in the tape and sheet conformations are shown.

(I) 3-(5-methyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-yl)propanenitrile

Crystal data

C8H9N3O2	F(000) = 376
Mr = 179.18	Dx = 1.374 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.2597 (4) Å	Cell parameters from 3997 reflections
b = 4.4118 (2) Å	θ = 2.3–29.6°
c = 17.6256 (6) Å	µ = 0.10 mm^−1
β = 98.253 (3)°	T = 293 K
V = 866.49 (6) Å^3	Block, colourless
Z = 4	0.45 × 0.2 × 0.2 mm

Data collection

Kuma KM4 CCD area-detector diffractometer	2187 independent reflections
Radiation source: fine-focus sealed tube	1423 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ω scans	θmax = 29.6°, θmin = 2.3°
Absorption correction: multi-scan CrysAlis RED (Oxford Diffraction 2006)	h = −15→15
Tmin = 0.837, Tmax = 0.980	k = −5→5
8802 measured reflections	l = −23→22

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	All H-atom parameters refined
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0659P)^2 + 0.0478P] where P = (Fo^2 + 2Fc^2)/3
2187 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.69015 (9)	0.4338 (2)	0.16614 (5)	0.0330 (3)
C2	0.57613 (10)	0.5355 (3)	0.13772 (7)	0.0328 (3)
O2	0.48757 (8)	0.4579 (2)	0.16478 (5)	0.0470 (3)
N3	0.57166 (9)	0.7327 (3)	0.07725 (6)	0.0355 (3)
H3	0.4986 (15)	0.804 (3)	0.0571 (8)	0.048 (4)*
C4	0.66662 (11)	0.8317 (3)	0.04233 (7)	0.0349 (3)
O4	0.65004 (8)	1.0135 (2)	−0.01110 (5)	0.0503 (3)
C5	0.78282 (10)	0.7107 (3)	0.07342 (7)	0.0345 (3)
C6	0.78883 (11)	0.5213 (3)	0.13305 (7)	0.0341 (3)
C11	0.70402 (13)	0.2323 (3)	0.23290 (7)	0.0375 (3)
H11A	0.7741 (13)	0.116 (3)	0.2274 (8)	0.042 (4)*
H11B	0.6311 (13)	0.113 (4)	0.2313 (8)	0.044 (4)*
C12	0.72076 (13)	0.4038 (4)	0.30899 (8)	0.0416 (3)
H12A	0.7238 (13)	0.257 (3)	0.3547 (8)	0.053 (4)*
H12B	0.6548 (15)	0.530 (4)	0.3159 (9)	0.055 (4)*
C13	0.83109 (14)	0.5819 (4)	0.31961 (8)	0.0483 (4)
N13	0.91629 (13)	0.7239 (4)	0.32592 (8)	0.0734 (5)
C51	0.88965 (13)	0.8001 (5)	0.03697 (9)	0.0513 (4)
H51A	0.8989 (17)	1.027 (5)	0.0298 (12)	0.086 (6)*
H51B	0.8827 (15)	0.719 (4)	−0.0157 (11)	0.071 (5)*
H51C	0.9619 (16)	0.713 (4)	0.0613 (10)	0.070 (5)*
H6	0.8604 (13)	0.430 (3)	0.1547 (8)	0.039 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0316 (5)	0.0355 (6)	0.0317 (5)	0.0039 (4)	0.0033 (4)	0.0017 (4)
C2	0.0300 (6)	0.0359 (7)	0.0325 (6)	0.0004 (5)	0.0046 (5)	−0.0016 (5)
O2	0.0339 (5)	0.0557 (6)	0.0534 (6)	0.0004 (4)	0.0129 (4)	0.0100 (5)
N3	0.0261 (5)	0.0456 (7)	0.0341 (6)	0.0046 (4)	0.0018 (4)	0.0051 (5)
C4	0.0316 (6)	0.0435 (8)	0.0291 (6)	0.0011 (5)	0.0027 (5)	0.0019 (5)
O4	0.0372 (5)	0.0688 (7)	0.0443 (6)	0.0050 (4)	0.0033 (4)	0.0213 (5)
C5	0.0279 (6)	0.0453 (8)	0.0305 (6)	0.0024 (5)	0.0045 (5)	−0.0017 (5)
C6	0.0279 (6)	0.0408 (7)	0.0330 (6)	0.0059 (5)	0.0024 (5)	−0.0020 (5)
C11	0.0412 (7)	0.0340 (7)	0.0367 (7)	0.0031 (6)	0.0041 (6)	0.0051 (5)
C12	0.0444 (8)	0.0461 (8)	0.0342 (7)	0.0010 (6)	0.0052 (6)	0.0030 (6)
C13	0.0531 (9)	0.0515 (9)	0.0362 (7)	−0.0002 (7)	−0.0071 (6)	0.0060 (6)
N13	0.0664 (9)	0.0809 (11)	0.0661 (10)	−0.0210 (8)	−0.0135 (7)	0.0097 (8)
C51	0.0337 (7)	0.0759 (13)	0.0463 (9)	0.0046 (7)	0.0127 (6)	0.0107 (8)

Geometric parameters (Å, º)

N1—C6	1.3820 (16)	C2—N3	1.3709 (16)
N1—C2	1.3841 (15)	N3—C4	1.3791 (16)
N1—C11	1.4652 (15)	N3—H3	0.903 (16)
C11—C12	1.5279 (18)	C4—O4	1.2306 (15)
C11—H11A	0.958 (15)	C4—C5	1.4462 (17)
C11—H11B	0.972 (15)	C5—C6	1.3365 (18)
C12—C13	1.459 (2)	C5—C51	1.4958 (18)
C12—H12A	1.030 (15)	C51—H51A	1.02 (2)
C12—H12B	0.951 (17)	C51—H51B	0.988 (18)
C13—N13	1.1378 (19)	C51—H51C	0.945 (17)
C2—O2	1.2148 (14)	C6—H6	0.933 (14)
C6—N1—C2	121.12 (10)	C2—N3—C4	127.13 (10)
C6—N1—C11	120.60 (10)	C2—N3—H3	117.0 (9)
C2—N1—C11	118.28 (10)	C4—N3—H3	115.8 (9)
N1—C11—C12	112.95 (11)	O4—C4—N3	120.39 (11)
N1—C11—H11A	103.8 (9)	O4—C4—C5	124.07 (11)
C12—C11—H11A	110.8 (8)	N3—C4—C5	115.54 (11)
N1—C11—H11B	108.2 (8)	C6—C5—C4	118.01 (11)
C12—C11—H11B	106.9 (8)	C6—C5—C51	123.33 (12)
H11A—C11—H11B	114.2 (13)	C4—C5—C51	118.65 (12)
C13—C12—C11	112.01 (12)	C5—C51—H51A	114.6 (11)
C13—C12—H12A	107.8 (8)	C5—C51—H51B	110.3 (10)
C11—C12—H12A	111.2 (8)	H51A—C51—H51B	103.6 (16)
C13—C12—H12B	109.5 (10)	C5—C51—H51C	112.9 (10)
C11—C12—H12B	113.8 (9)	H51A—C51—H51C	111.2 (16)
H12A—C12—H12B	102.0 (12)	H51B—C51—H51C	103.1 (14)
N13—C13—C12	178.12 (15)	C5—C6—N1	123.60 (11)
O2—C2—N3	122.92 (11)	C5—C6—H6	122.4 (8)
O2—C2—N1	122.51 (12)	N1—C6—H6	113.9 (8)
N3—C2—N1	114.56 (10)
C6—N1—C11—C12	92.05 (14)	C2—N3—C4—C5	0.37 (19)
C2—N1—C11—C12	−87.42 (14)	O4—C4—C5—C6	178.10 (12)
N1—C11—C12—C13	−63.62 (15)	N3—C4—C5—C6	−1.20 (18)
C6—N1—C2—O2	178.61 (11)	O4—C4—C5—C51	−2.6 (2)
C11—N1—C2—O2	−1.93 (18)	N3—C4—C5—C51	178.13 (13)
C6—N1—C2—N3	−2.00 (17)	C4—C5—C6—N1	0.44 (19)
C11—N1—C2—N3	177.47 (10)	C51—C5—C6—N1	−178.86 (13)
O2—C2—N3—C4	−179.40 (12)	C2—N1—C6—C5	1.27 (19)
N1—C2—N3—C4	1.21 (18)	C11—N1—C6—C5	−178.19 (12)
C2—N3—C4—O4	−178.96 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O4^i	0.903 (16)	1.929 (17)	2.8301 (14)	174.8 (14)
C11—H11B···O2^ii	0.972 (15)	2.513 (14)	3.2386 (17)	131.4 (10)
C12—H12B···O2^iii	0.951 (17)	2.530 (18)	3.4645 (18)	167.6 (13)
C6—H6···N13^iv	0.933 (14)	2.649 (15)	3.5468 (19)	161.7 (11)

Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+2, y−1/2, −z+1/2.

(II) 4-(5-methyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-yl)butanenitrile

Crystal data

C9H11N3O2	Z = 2
Mr = 193.21	F(000) = 204
Triclinic, P1	Dx = 1.345 Mg m^−3
a = 4.8591 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.8205 (12) Å	Cell parameters from 2362 reflections
c = 10.5979 (11) Å	θ = 2.6–29.7°
α = 75.815 (10)°	µ = 0.10 mm^−1
β = 78.364 (12)°	T = 293 K
γ = 80.780 (11)°	Plate, colourless
V = 476.94 (11) Å^3	0.6 × 0.3 × 0.1 mm

Data collection

Kuma KM4 CCD area-detector diffractometer	2368 independent reflections
Radiation source: fine-focus sealed tube	1842 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.011
ω scans	θmax = 29.7°, θmin = 2.6°
Absorption correction: multi-scan CrysAlis RED (Oxford Diffraction 2006)	h = −6→4
Tmin = 0.969, Tmax = 1.000	k = −13→13
4787 measured reflections	l = −14→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	All H-atom parameters refined
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0762P)^2 + 0.0211P] where P = (Fo^2 + 2Fc^2)/3
2368 reflections	(Δ/σ)max < 0.001
171 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.50209 (17)	0.33709 (9)	0.79194 (8)	0.0372 (2)
C2	0.2855 (2)	0.43986 (11)	0.75638 (10)	0.0361 (2)
O2	0.16684 (18)	0.52289 (9)	0.82454 (8)	0.0500 (2)
N3	0.20966 (17)	0.44027 (9)	0.63776 (8)	0.0364 (2)
H3	0.068 (3)	0.5047 (16)	0.6142 (14)	0.051 (3)*
C4	0.3384 (2)	0.35642 (11)	0.55030 (10)	0.0342 (2)
O4	0.25319 (16)	0.37071 (9)	0.44499 (8)	0.0464 (2)
C5	0.5724 (2)	0.25585 (10)	0.59085 (10)	0.0370 (2)
C6	0.6387 (2)	0.25031 (11)	0.70908 (10)	0.0378 (2)
H6	0.786 (3)	0.1834 (15)	0.7423 (15)	0.056 (4)*
C11	0.5778 (2)	0.31798 (13)	0.92343 (11)	0.0413 (3)
H11B	0.754 (3)	0.2562 (15)	0.9210 (14)	0.053 (4)*
H11A	0.620 (3)	0.4062 (16)	0.9349 (14)	0.054 (4)*
C12	0.3514 (2)	0.25179 (14)	1.03188 (11)	0.0458 (3)
H12B	0.174 (3)	0.3214 (17)	1.0369 (16)	0.070 (4)*
H12A	0.311 (3)	0.1647 (15)	1.0101 (14)	0.050 (3)*
C13	0.4400 (3)	0.21409 (16)	1.16776 (12)	0.0543 (3)
H13B	0.274 (4)	0.1850 (18)	1.237 (2)	0.086 (5)*
H13A	0.497 (4)	0.296 (2)	1.1906 (17)	0.080 (5)*
C14	0.6690 (3)	0.09841 (14)	1.17855 (12)	0.0532 (3)
N14	0.8451 (3)	0.00833 (16)	1.18472 (16)	0.0857 (5)
C51	0.7281 (3)	0.16313 (16)	0.50001 (15)	0.0551 (3)
H51C	0.809 (4)	0.225 (2)	0.412 (2)	0.095 (6)*
H51B	0.614 (4)	0.100 (2)	0.485 (2)	0.095 (6)*
H51A	0.876 (4)	0.106 (2)	0.536 (2)	0.099 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0355 (4)	0.0418 (5)	0.0327 (4)	0.0032 (3)	−0.0084 (3)	−0.0077 (3)
C2	0.0341 (5)	0.0386 (5)	0.0334 (5)	0.0011 (4)	−0.0051 (4)	−0.0077 (4)
O2	0.0535 (5)	0.0530 (5)	0.0428 (4)	0.0127 (4)	−0.0094 (4)	−0.0202 (4)
N3	0.0323 (4)	0.0397 (5)	0.0354 (4)	0.0056 (3)	−0.0086 (3)	−0.0091 (4)
C4	0.0316 (5)	0.0366 (5)	0.0339 (5)	−0.0027 (4)	−0.0048 (4)	−0.0084 (4)
O4	0.0434 (4)	0.0575 (5)	0.0407 (4)	0.0060 (3)	−0.0143 (3)	−0.0173 (3)
C5	0.0362 (5)	0.0334 (5)	0.0409 (5)	0.0011 (4)	−0.0059 (4)	−0.0109 (4)
C6	0.0346 (5)	0.0354 (5)	0.0404 (5)	0.0043 (4)	−0.0081 (4)	−0.0068 (4)
C11	0.0396 (5)	0.0491 (6)	0.0366 (5)	0.0002 (5)	−0.0137 (4)	−0.0096 (4)
C12	0.0417 (6)	0.0579 (7)	0.0354 (5)	0.0019 (5)	−0.0102 (4)	−0.0080 (5)
C13	0.0618 (8)	0.0637 (8)	0.0346 (6)	0.0053 (6)	−0.0124 (5)	−0.0104 (5)
C14	0.0564 (7)	0.0564 (7)	0.0427 (6)	−0.0067 (6)	−0.0151 (5)	0.0025 (5)
N14	0.0721 (8)	0.0768 (9)	0.0889 (10)	0.0134 (7)	−0.0226 (7)	0.0109 (8)
C51	0.0574 (7)	0.0521 (7)	0.0595 (8)	0.0139 (6)	−0.0144 (6)	−0.0286 (6)

Geometric parameters (Å, º)

N1—C6	1.3743 (14)	C2—O2	1.2203 (13)
N1—C2	1.3788 (13)	C2—N3	1.3786 (12)
N1—C11	1.4728 (13)	N3—C4	1.3797 (13)
C11—C12	1.5191 (17)	N3—H3	0.888 (15)
C11—H11B	0.966 (15)	C4—O4	1.2362 (12)
C11—H11A	0.962 (16)	C4—C5	1.4427 (13)
C12—C13	1.5277 (15)	C5—C6	1.3420 (14)
C12—H12B	1.010 (16)	C5—C51	1.4977 (16)
C12—H12A	0.996 (14)	C51—H51C	1.02 (2)
C13—C14	1.4578 (19)	C51—H51B	0.96 (2)
C13—H13B	1.00 (2)	C51—H51A	0.92 (2)
C13—H13A	0.988 (18)	C6—H6	0.953 (14)
C14—N14	1.1272 (18)
C6—N1—C2	121.12 (8)	O2—C2—N3	122.29 (9)
C6—N1—C11	120.22 (8)	O2—C2—N1	123.18 (9)
C2—N1—C11	118.61 (9)	N3—C2—N1	114.53 (9)
N1—C11—C12	111.35 (9)	C2—N3—C4	126.95 (8)
N1—C11—H11B	104.9 (8)	C2—N3—H3	115.6 (9)
C12—C11—H11B	110.8 (9)	C4—N3—H3	117.3 (9)
N1—C11—H11A	110.0 (9)	O4—C4—N3	120.22 (9)
C12—C11—H11A	113.2 (9)	O4—C4—C5	124.29 (9)
H11B—C11—H11A	106.1 (11)	N3—C4—C5	115.49 (8)
C11—C12—C13	112.52 (10)	C6—C5—C4	117.84 (9)
C11—C12—H12B	109.2 (9)	C6—C5—C51	123.33 (10)
C13—C12—H12B	107.2 (9)	C4—C5—C51	118.83 (10)
C11—C12—H12A	108.5 (8)	C5—C51—H51C	109.4 (11)
C13—C12—H12A	109.4 (8)	C5—C51—H51B	113.8 (13)
H12B—C12—H12A	110.0 (12)	H51C—C51—H51B	109.3 (17)
C14—C13—C12	112.22 (11)	C5—C51—H51A	110.1 (13)
C14—C13—H13B	108.2 (10)	H51C—C51—H51A	108.7 (17)
C12—C13—H13B	109.6 (10)	H51B—C51—H51A	105.5 (17)
C14—C13—H13A	108.9 (11)	C5—C6—N1	123.91 (9)
C12—C13—H13A	112.3 (10)	C5—C6—H6	121.4 (9)
H13B—C13—H13A	105.3 (15)	N1—C6—H6	114.7 (9)
N14—C14—C13	178.63 (15)
C6—N1—C11—C12	−106.37 (12)	C2—N3—C4—O4	−177.87 (9)
C2—N1—C11—C12	71.29 (13)	C2—N3—C4—C5	1.72 (15)
N1—C11—C12—C13	173.01 (10)	O4—C4—C5—C6	−178.88 (10)
C11—C12—C13—C14	−68.41 (16)	N3—C4—C5—C6	1.55 (14)
C6—N1—C2—O2	−176.83 (10)	O4—C4—C5—C51	0.99 (17)
C11—N1—C2—O2	5.53 (16)	N3—C4—C5—C51	−178.57 (11)
C6—N1—C2—N3	4.14 (15)	C4—C5—C6—N1	−1.78 (17)
C11—N1—C2—N3	−173.50 (9)	C51—C5—C6—N1	178.35 (11)
O2—C2—N3—C4	176.44 (10)	C2—N1—C6—C5	−1.24 (17)
N1—C2—N3—C4	−4.51 (15)	C11—N1—C6—C5	176.36 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O4^i	0.888 (15)	1.932 (16)	2.8165 (12)	173.6 (13)
C6—H6···N14^ii	0.953 (14)	2.472 (15)	3.4211 (16)	173.6 (11)
C13—H13A···O2^iii	0.988 (18)	2.557 (18)	3.4751 (19)	154.5 (14)
C12—H12B···O2^iv	1.010 (16)	2.560 (17)	3.4454 (15)	146.3 (12)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+2, −y, −z+2; (iii) −x+1, −y+1, −z+2; (iv) −x, −y+1, −z+2.