A three-dimensional hydrogen-bonded framework in 2-amino-6-(N-methyl­anilino)pyrimidin-4(3H)-one and a ribbon of fused hydrogen-bonded rings in 2-amino-6-(N-methyl­anilino)-5-nitro­pyrimidin-4(3H)-one

The mol­ecular dimensions of both 2-amino-6-(N-methyl­anilino)pyrimidin-4(3H)-one, C₁₁H₁₂N₄O, (I), and 2-amino-6-(N-methyl­anilino)-5-nitro­pyrimidin-4(3H)-one, C₁₁H₁₁N₅O₃, (II), are consistent with considerable polarization of the mol­ecular-electronic structures. The mol­ecules of (I) are linked into a three-dimensional framework by a combination of one N-H...N hydrogen bond, two independent N-H...O hydrogen bonds and one C-H...[pi](arene) hydrogen bond. The mol­ecules of (II) are linked into ribbons containing three types of edge-fused ring by the combination of two independent three-centre N-H...(O)₂ hydrogen bonds.

S1. Comment

As part of a wide-ranging investigation of biologically active heterocyclic compounds, we have initiated a study of pyrimido[4,5-b][1,4]benzodiazepine derivatives that are analogous to the well known benzodiazepine derivatives and which show related pharmacological properties, such as anti-anxiety or antidepressive activity (Dlugosz & Machon, 1990), as well as being candidates as effective anti-HIV-1 inhibitors (Di Braccio et al., 2001). We report here the molecular and supramolecular structures of two compounds, 2-amino-6-(N-methylanilino)pyrimidin-4(3H)-one, (I), and 2-amino-6-(N-methylanilino)-5-nitropyrimidin-4(3H)-one, (II), which were prepared, from the commercially available pyrimidines, (III) and (IV), respectively, for use as intermediates for the syntheses of pyrimido[4,5-b][1,4]benzodiazepines, (V).

In compounds (I) and (II) (Figs. 1 and 2), the coordination at N6 is planar and the methyl atom C67 and the ipso atom of the phenyl ring, atom C61, are very close to the plane of the pyrimidine ring, as indicated by the relevant torsion angles (Table 3). On the other hand, the planes of the phenyl group in each compound are well removed from the pyrimidine planes with dihedral angles between these two planes of 70.1 (2)° in (I) and 58.9 (2)° in (II). In (II), the dihedral angle between the CNO₂ unit and the pyrimidine ring is 47.4 (2)°.

The molecules in each compound exhibit some unusual bond distances, which are indicative of polarized molecular–electronic structures. In compound (I), the C4—C5 and C5—C6 distances are identical within experimental uncertainty, although in the conventional representation these bonds are, respectively, single and double bonds. In addition, the C—O bond is long for its type (Allen et al., 1987), while the C6—N6 bond is short. These data together indicate that the polarized form (Ia) (Scheme 2) may be a significant contributor to the overall molecular–electronic structure of this compound, in addition to the unpolarized form (I).

Despite the large dihedral angle between the pyrimidine and nitro-group planes in (II), the C5—N5 bond is rather short for its type (mean value 1.486 Å; Allen et al., 1987); the C4—O4 bond is significantly shorter in (II) than in (I); and the N1—C2 and C2—N2 distances are effectively identical in (II). These observations indicate that the polarized forms (IIa) and (IIb) (Scheme 2) both contribute to the overall molecular–electronic structure of this compound, in addition to the unpolarized form (II).

The molecules of compound (I) are linked into sheets by three hydrogen bonds, one of N—H···N type and two of N—H···O type (Table 1). It is convenient to consider a centrosymmetric dimer unit, formed by paired N—H···O hydrogen bonds, as the basic building block forming the sheet. The ring atom N3 in the molecule at (x, y, z) acts as a donor, in an almost linear hydrogen bond, to atom O4 in the molecule at (1 - x, -y, 1 - z), so generating by inversion an R²₂(8) motif (Bernstein et al., 1995), centred at (1/2, 0, 1/2). This dimer is linked directly, by the other two hydrogen bonds, to the four dimers centred at (1/2, 1/2, 0), (1/2, -1/2, 0), (1/2, 1/2, 1) and (1/2, -1/2, 1), and propagation by the space group of these hydrogen bonds then generates a rather complex sheet parallel to (100) (Fig. 3). Each such sheet is weakly linked to the two adjacent sheets by a single C—H···π(arene) hydrogen bond (Table 2), so forming a continuous hydrogen-bonded framework structure in three dimensions.

The supramolecular aggregation of (II) is only one-dimensional; despite the presence of the two nitro-group O atoms as additional sites that are potential hydrogen-bond acceptors, one of the N—H bonds of the exocyclic amino group in (II) plays no part in the hydrogen bonding, and the supramolecular aggregation depends entirely on two independent three-centre N—H···(O)₂ hydrogen-bond systems, both them effectively planar (Table 2).

Amino atom N2 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via H2B, to atoms O4 and O51 in the molecules at (-1/2 + x, 3/2 - y, 1 - z) and (-1 + x, y, z), respectively. In the second three-centre system, the ring atom N3 acts as a hydrogen-bond donor to atoms O4 and O51, both in the molecule at (-1/2 + x, 3/2 - y, 1 - z). Hence two of the N—H bonds act as double donors of hydrogen bonds, while the third N—H bond does not participate in the hydrogen bonding; and two of the O atoms act as double acceptors of hydrogen bonds, while the third O atom does not participate in the hydrogen bonding. The combination of all these hydrogen bonds produces a ribbon of edge-fused rings running parallel to the [100] direction and generated by the 2₁ screw axis along (x, 3/4, 1/2) (Fig. 4). The ribbon contains an R¹₂(6) ring where the sole acceptor is an O4 atom; an R²₁(6) ring where both hydrogen bonds involve an H3 atom; and an R²₂(6) ring containing both O4 and O51 atoms as the acceptors. A second ribbon, running antiparallel to the reference ribbon, is generated by the 2₁ screw axis along (x, 1/4, 1/2), but there are no direction-specific interactions between adjacent chains.

Related literature

For related literature, see: Allen et al. (1987); Bernstein et al. (1995); Di Braccio, Grossi, Roma, Vargiu, Mura & Marongiu (2001); Dlugosz & Machon (1990).

S2. Experimental

For the synthesis of (I), a mixture of 2-amino-4-chloro-6-methoxypyrimidine (1.82 mmol) and N-methylaniline (2.80 mmol) was heated to fusion between 563–573 K for 4 min. The reaction mixture was cooled to ambient temperature and the resulting solid mass was broken up; it was washed thrice with ether, and then successively with a saturated aqueous solution of potassium carbonate, with water and finally again with ether. the mixture was then dried in an oven giving (I) as a pale-beige solid (yield 97%, m.p. 552–554 K). For the synthesis of (II), a mixture of 2-amino-6-chloro-5-nitro-4(3H)pyrimidinone (2.78 mmol), N-methylaniline (3.13 mmol) and triethylamine (1 ml) in methanol (20 ml) was stirred magnetically at ambient temperature for 2 h. The resulting yellow solid was collected by filtration, washed with methanol and then dried in an oven to yield (II) (yield 83%, m.p. 585–588 K). Yellow crystals of (I) and (II) suitable for single-crystal X-ray diffraction were obtained from solutions in dimethylsulfoxide.

S3. Refinement

The space groups P2₁/c, for (I), and P2₁2₁2₁, for (II), were both uniquely assigned from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms, with C—H distances of 0.95 Å (aromatic or heteroaromatic) or 0.98 Å (methyl), and N—H of 0.88 Å, and with U_iso(H) = kU_eq(carrier), where k = 1.5 for the methyl groups and k = 1.2 for all other H atoms.

Computing details

For both compounds, data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: Sir2004 (Burla et al., 2005); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The molecular structure of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded sheet parallel to (100). For clarity, H atoms bonded to C atoms have been omitted.
	Fig. 4. Part of the crystal structure of (II), showing the formation of a hydrogen-bonded ribbon of edge-fused rings parallel to [100]. For clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*), a hash (#), a dollar sign ($) or an ampersand (&) are at the symmetry positions (-1/2 + x, 3/2 - y, 1 - z), (1/2 + x, 3/2 - y, 1 - z), (1 + x, y, z) and (-1 + x, y, z), respectively.

(I) 2-amino-6-(methylanilino)pyrimidin-4(3H)-one

Crystal data

C11H12N4O	F(000) = 456
Mr = 216.25	Dx = 1.378 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2396 reflections
a = 10.6860 (12) Å	θ = 4.1–27.5°
b = 7.1647 (14) Å	µ = 0.09 mm^−1
c = 14.4911 (12) Å	T = 120 K
β = 110.024 (9)°	Block, yellow
V = 1042.4 (3) Å^3	0.52 × 0.25 × 0.16 mm
Z = 4

Data collection

Bruker–Nonius KappaCCD diffractometer	2396 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1568 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 4.1°
ϕ & ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −9→9
Tmin = 0.962, Tmax = 0.985	l = −18→18
23278 measured reflections

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.137	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0557P)^2 + 0.7582P] where P = (Fo^2 + 2Fc^2)/3
2396 reflections	(Δ/σ)max < 0.001
146 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

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

	x	y	z	Uiso*/Ueq
N1	0.66081 (15)	0.3959 (2)	0.36165 (12)	0.0190 (4)
C2	0.59095 (19)	0.2415 (3)	0.35541 (14)	0.0194 (4)
N2	0.54735 (16)	0.1509 (2)	0.26918 (12)	0.0234 (4)
N3	0.56134 (15)	0.1688 (2)	0.43183 (11)	0.0192 (4)
C4	0.60352 (19)	0.2548 (3)	0.52379 (14)	0.0190 (4)
O4	0.56750 (13)	0.1799 (2)	0.58994 (10)	0.0226 (3)
C5	0.68257 (18)	0.4133 (3)	0.53313 (14)	0.0196 (4)
C6	0.70970 (18)	0.4795 (3)	0.45137 (14)	0.0193 (4)
N6	0.78848 (16)	0.6308 (2)	0.45421 (12)	0.0219 (4)
C67	0.8052 (2)	0.7070 (3)	0.36560 (16)	0.0322 (5)
C61	0.8560 (2)	0.7336 (3)	0.54195 (15)	0.0212 (4)
C62	0.7878 (2)	0.8511 (3)	0.58287 (16)	0.0255 (5)
C63	0.8565 (2)	0.9632 (3)	0.66180 (16)	0.0284 (5)
C64	0.9941 (2)	0.9555 (3)	0.70086 (15)	0.0263 (5)
C65	1.0629 (2)	0.8378 (3)	0.65976 (16)	0.0270 (5)
C66	0.9943 (2)	0.7277 (3)	0.57988 (16)	0.0256 (5)
H2A	0.5655	0.1946	0.2184	0.028*
H2B	0.5006	0.0477	0.2634	0.028*
H3	0.5145	0.0651	0.4233	0.023*
H5	0.7176	0.4755	0.5945	0.024*
H67A	0.7709	0.6177	0.3116	0.048*
H67B	0.8999	0.7300	0.3778	0.048*
H67C	0.7558	0.8246	0.3480	0.048*
H62	0.6933	0.8553	0.5570	0.031*
H63	0.8091	1.0457	0.6892	0.034*
H64	1.0410	1.0309	0.7557	0.032*
H65	1.1573	0.8323	0.6863	0.032*
H66	1.0418	0.6481	0.5510	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0202 (8)	0.0185 (8)	0.0187 (9)	−0.0018 (7)	0.0070 (7)	0.0004 (7)
C2	0.0201 (10)	0.0193 (10)	0.0188 (10)	0.0031 (8)	0.0068 (8)	0.0026 (8)
N2	0.0315 (9)	0.0217 (9)	0.0178 (9)	−0.0085 (8)	0.0093 (7)	−0.0021 (7)
N3	0.0211 (8)	0.0186 (8)	0.0181 (8)	−0.0057 (7)	0.0071 (7)	−0.0010 (7)
C4	0.0203 (10)	0.0185 (10)	0.0181 (10)	0.0020 (8)	0.0063 (8)	0.0016 (8)
O4	0.0278 (8)	0.0226 (8)	0.0201 (7)	−0.0043 (6)	0.0117 (6)	0.0011 (6)
C5	0.0201 (10)	0.0206 (10)	0.0167 (10)	−0.0020 (8)	0.0044 (8)	−0.0009 (8)
C6	0.0167 (9)	0.0176 (10)	0.0224 (10)	0.0015 (8)	0.0052 (8)	0.0011 (8)
N6	0.0248 (9)	0.0204 (9)	0.0213 (9)	−0.0054 (7)	0.0090 (7)	−0.0012 (7)
C67	0.0394 (13)	0.0318 (13)	0.0259 (12)	−0.0131 (11)	0.0116 (10)	0.0022 (10)
C61	0.0244 (10)	0.0166 (10)	0.0227 (10)	−0.0033 (8)	0.0082 (8)	0.0009 (8)
C62	0.0209 (10)	0.0263 (11)	0.0283 (11)	0.0001 (9)	0.0072 (9)	0.0000 (9)
C63	0.0310 (12)	0.0247 (11)	0.0314 (12)	0.0012 (9)	0.0130 (10)	−0.0027 (10)
C64	0.0285 (11)	0.0235 (11)	0.0251 (11)	−0.0035 (9)	0.0069 (9)	−0.0031 (9)
C65	0.0219 (10)	0.0259 (11)	0.0313 (12)	−0.0031 (9)	0.0067 (9)	−0.0003 (10)
C66	0.0248 (11)	0.0221 (11)	0.0314 (12)	0.0000 (9)	0.0115 (9)	−0.0028 (9)

Geometric parameters (Å, º)

N1—C2	1.321 (3)	C67—H67A	0.98
N1—C6	1.363 (2)	C67—H67B	0.98
C2—N2	1.342 (3)	C67—H67C	0.98
C2—N3	1.355 (2)	C61—C62	1.374 (3)
N2—H2A	0.88	C61—C66	1.390 (3)
N2—H2B	0.88	C62—C63	1.385 (3)
N3—C4	1.396 (2)	C62—H62	0.95
N3—H3	0.88	C63—C64	1.384 (3)
C4—O4	1.268 (2)	C63—H63	0.95
C4—C5	1.394 (3)	C64—C65	1.381 (3)
C5—C6	1.396 (3)	C64—H64	0.95
C5—H5	0.95	C65—C66	1.385 (3)
C6—N6	1.365 (2)	C65—H65	0.95
N6—C61	1.432 (3)	C66—H66	0.95
N6—C67	1.461 (3)
C2—N1—C6	117.17 (17)	N6—C67—H67B	109.5
N1—C2—N2	118.48 (17)	H67A—C67—H67B	109.5
N1—C2—N3	123.41 (18)	N6—C67—H67C	109.5
N2—C2—N3	118.11 (18)	H67A—C67—H67C	109.5
C2—N2—H2A	120.0	H67B—C67—H67C	109.5
C2—N2—H2B	120.0	C62—C61—C66	119.84 (19)
H2A—N2—H2B	120.0	C62—C61—N6	121.15 (18)
C2—N3—C4	121.40 (17)	C66—C61—N6	118.69 (18)
C2—N3—H3	119.3	C61—C62—C63	120.14 (19)
C4—N3—H3	119.3	C61—C62—H62	119.9
O4—C4—C5	127.03 (18)	C63—C62—H62	119.9
O4—C4—N3	116.90 (17)	C64—C63—C62	120.2 (2)
C5—C4—N3	116.06 (17)	C64—C63—H63	119.9
C4—C5—C6	119.32 (18)	C62—C63—H63	119.9
C4—C5—H5	120.3	C65—C64—C63	119.7 (2)
C6—C5—H5	120.3	C65—C64—H64	120.1
N1—C6—N6	114.14 (17)	C63—C64—H64	120.1
N1—C6—C5	122.50 (18)	C64—C65—C66	120.08 (19)
N6—C6—C5	123.35 (18)	C64—C65—H65	120.0
C6—N6—C61	123.60 (17)	C66—C65—H65	120.0
C6—N6—C67	122.00 (17)	C65—C66—C61	119.98 (19)
C61—N6—C67	114.33 (16)	C65—C66—H66	120.0
N6—C67—H67A	109.5	C61—C66—H66	120.0
C6—N1—C2—N2	−176.63 (17)	N1—C6—N6—C67	6.6 (3)
C6—N1—C2—N3	3.1 (3)	C5—C6—N6—C67	−174.3 (2)
N1—C2—N3—C4	0.2 (3)	C6—N6—C61—C62	−73.7 (3)
N2—C2—N3—C4	179.84 (17)	C67—N6—C61—C62	103.3 (2)
C2—N3—C4—O4	177.83 (17)	C6—N6—C61—C66	112.8 (2)
C2—N3—C4—C5	−3.0 (3)	C67—N6—C61—C66	−70.1 (2)
O4—C4—C5—C6	−178.35 (19)	C66—C61—C62—C63	−0.1 (3)
N3—C4—C5—C6	2.6 (3)	N6—C61—C62—C63	−173.43 (19)
C2—N1—C6—N6	175.70 (17)	C61—C62—C63—C64	−1.0 (3)
C2—N1—C6—C5	−3.4 (3)	C62—C63—C64—C65	1.1 (3)
C4—C5—C6—N1	0.6 (3)	C63—C64—C65—C66	−0.1 (3)
C4—C5—C6—N6	−178.46 (18)	C64—C65—C66—C61	−1.0 (3)
N1—C6—N6—C61	−176.53 (17)	C62—C61—C66—C65	1.1 (3)
C5—C6—N6—C61	2.6 (3)	N6—C61—C66—C65	174.58 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O4^i	0.88	2.07	2.940 (2)	168
N2—H2B···N1^ii	0.88	2.30	2.998 (2)	136
N3—H3···O4^iii	0.88	1.94	2.818 (2)	173
C64—H64···Cg^iv	0.95	2.82	3.695 (2)	154

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, −y, −z+1; (iv) −x+2, y+1/2, −z+3/2.

(II) 2-amino-6-(methylanilino)-5-nitropyrimidin-4(3H)-one

Crystal data

C11H11N5O3	F(000) = 544
Mr = 261.25	Dx = 1.493 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1447 reflections
a = 8.955 (3) Å	θ = 4.0–27.6°
b = 11.2165 (15) Å	µ = 0.11 mm^−1
c = 11.5670 (15) Å	T = 120 K
V = 1161.8 (4) Å^3	Plate, yellow
Z = 4	0.32 × 0.26 × 0.09 mm

Data collection

Bruker–Nonius KappaCCD diffractometer	1447 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	879 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.102
Detector resolution: 9.091 pixels mm^-1	θmax = 27.6°, θmin = 4.0°
ϕ & ω scans	h = −11→10
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −14→13
Tmin = 0.923, Tmax = 0.991	l = −13→14
15997 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.054	H-atom parameters constrained
wR(F^2) = 0.138	w = 1/[σ^2(Fo^2) + (0.079P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
1447 reflections	Δρmax = 0.28 e Å^−3
173 parameters	Δρmin = −0.32 e Å^−3
0 restraints	Absolute structure: Friedel pairs merged
Primary atom site location: structure-invariant direct methods

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

	x	y	z	Uiso*/Ueq
N1	0.3771 (4)	0.6396 (3)	0.8030 (3)	0.0256 (8)
C2	0.3091 (4)	0.6763 (3)	0.7084 (3)	0.0225 (10)
N2	0.1616 (4)	0.6755 (3)	0.7050 (3)	0.0311 (9)
N3	0.3820 (4)	0.7154 (3)	0.6128 (3)	0.0248 (8)
C4	0.5375 (4)	0.7283 (4)	0.6109 (3)	0.0227 (9)
O4	0.5987 (3)	0.7719 (2)	0.5250 (2)	0.0299 (7)
C5	0.6088 (4)	0.6946 (3)	0.7157 (3)	0.0221 (9)
N5	0.7627 (4)	0.7276 (3)	0.7223 (3)	0.0269 (8)
O51	0.8462 (3)	0.7031 (3)	0.6411 (2)	0.0348 (8)
O52	0.8067 (3)	0.7805 (3)	0.8104 (3)	0.0358 (8)
C6	0.5281 (4)	0.6463 (3)	0.8086 (3)	0.0219 (9)
N6	0.5892 (4)	0.6038 (3)	0.9073 (3)	0.0252 (8)
C67	0.4899 (4)	0.5663 (4)	1.0026 (4)	0.0339 (11)
C61	0.7436 (4)	0.5716 (3)	0.9177 (3)	0.0248 (9)
C62	0.8086 (5)	0.4956 (4)	0.8391 (3)	0.0280 (11)
C63	0.9581 (5)	0.4656 (4)	0.8498 (4)	0.0335 (11)
C64	1.0402 (5)	0.5102 (4)	0.9414 (4)	0.0353 (11)
C65	0.9747 (4)	0.5831 (4)	1.0209 (4)	0.0341 (11)
C66	0.8255 (4)	0.6142 (4)	1.0112 (4)	0.0289 (10)
H2A	0.1103	0.6507	0.7652	0.037*
H2B	0.1146	0.6997	0.6424	0.037*
H3	0.3303	0.7332	0.5505	0.030*
H67A	0.4460	0.4886	0.9843	0.051*
H67B	0.4102	0.6253	1.0125	0.051*
H67C	0.5478	0.5603	1.0743	0.051*
H62	0.7511	0.4638	0.7774	0.034*
H63	1.0039	0.4146	0.7946	0.040*
H64	1.1428	0.4899	0.9490	0.042*
H65	1.0320	0.6129	1.0836	0.041*
H66	0.7799	0.6639	1.0675	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.023 (2)	0.0324 (19)	0.0218 (19)	0.0003 (15)	0.0027 (15)	0.0009 (17)
C2	0.019 (2)	0.027 (2)	0.021 (2)	0.0012 (17)	0.0026 (18)	0.003 (2)
N2	0.024 (2)	0.046 (2)	0.0233 (19)	−0.0042 (16)	0.0017 (17)	0.0079 (19)
N3	0.0269 (19)	0.0302 (19)	0.0174 (18)	0.0008 (16)	−0.0030 (15)	0.0002 (15)
C4	0.025 (2)	0.022 (2)	0.021 (2)	−0.0012 (19)	−0.001 (2)	−0.0020 (18)
O4	0.0261 (16)	0.0398 (17)	0.0239 (15)	−0.0022 (13)	0.0026 (13)	0.0056 (14)
C5	0.017 (2)	0.026 (2)	0.023 (2)	−0.0013 (17)	0.0000 (17)	−0.0023 (19)
N5	0.028 (2)	0.0332 (19)	0.0197 (18)	−0.0021 (17)	−0.0003 (18)	0.0089 (17)
O51	0.0226 (16)	0.055 (2)	0.0273 (16)	0.0002 (14)	0.0056 (15)	0.0058 (15)
O52	0.0423 (19)	0.0390 (18)	0.0261 (16)	−0.0127 (14)	−0.0073 (14)	−0.0001 (15)
C6	0.025 (2)	0.022 (2)	0.018 (2)	0.0005 (18)	0.0012 (19)	−0.0032 (19)
N6	0.025 (2)	0.0307 (19)	0.0195 (18)	0.0002 (15)	0.0017 (16)	0.0029 (16)
C67	0.035 (3)	0.041 (3)	0.026 (2)	0.001 (2)	0.006 (2)	0.007 (2)
C61	0.021 (2)	0.030 (2)	0.024 (2)	0.0023 (19)	−0.002 (2)	0.001 (2)
C62	0.032 (3)	0.027 (2)	0.024 (2)	−0.005 (2)	−0.002 (2)	0.001 (2)
C63	0.036 (3)	0.030 (2)	0.034 (3)	0.005 (2)	0.009 (2)	0.008 (2)
C64	0.027 (2)	0.038 (3)	0.041 (3)	0.002 (2)	−0.007 (2)	0.012 (2)
C65	0.026 (3)	0.043 (3)	0.033 (2)	−0.005 (2)	−0.009 (2)	0.009 (2)
C66	0.032 (2)	0.032 (2)	0.024 (2)	−0.0023 (18)	0.003 (2)	0.001 (2)

Geometric parameters (Å, º)

N1—C2	1.318 (5)	N6—C67	1.478 (5)
N1—C6	1.356 (5)	C67—H67A	0.98
C2—N2	1.322 (5)	C67—H67B	0.98
C2—N3	1.357 (5)	C67—H67C	0.98
N2—H2A	0.88	C61—C62	1.376 (5)
N2—H2B	0.88	C61—C66	1.392 (5)
N3—C4	1.400 (5)	C62—C63	1.386 (5)
N3—H3	0.88	C62—H62	0.95
C4—O4	1.235 (5)	C63—C64	1.384 (6)
C4—C5	1.421 (5)	C63—H63	0.95
C5—C6	1.403 (5)	C64—C65	1.363 (6)
C5—N5	1.430 (5)	C64—H64	0.95
N5—O51	1.231 (4)	C65—C66	1.385 (6)
N5—O52	1.243 (4)	C65—H65	0.95
C6—N6	1.352 (5)	C66—H66	0.95
N6—C61	1.434 (5)
C2—N1—C6	118.9 (3)	N6—C67—H67A	109.5
N1—C2—N2	119.0 (4)	N6—C67—H67B	109.5
N1—C2—N3	123.7 (3)	H67A—C67—H67B	109.5
N2—C2—N3	117.3 (4)	N6—C67—H67C	109.5
C2—N2—H2A	120.0	H67A—C67—H67C	109.5
C2—N2—H2B	120.0	H67B—C67—H67C	109.5
H2A—N2—H2B	120.0	C62—C61—C66	120.2 (4)
C2—N3—C4	121.7 (3)	C62—C61—N6	120.6 (4)
C2—N3—H3	119.2	C66—C61—N6	119.1 (4)
C4—N3—H3	119.2	C61—C62—C63	120.0 (4)
O4—C4—N3	119.6 (3)	C61—C62—H62	120.0
O4—C4—C5	126.3 (3)	C63—C62—H62	120.0
N3—C4—C5	113.9 (3)	C64—C63—C62	119.6 (4)
C6—C5—C4	121.7 (3)	C64—C63—H63	120.2
C6—C5—N5	123.7 (3)	C62—C63—H63	120.2
C4—C5—N5	114.2 (3)	C65—C64—C63	120.3 (4)
O51—N5—O52	122.6 (3)	C65—C64—H64	119.9
O51—N5—C5	119.1 (3)	C63—C64—H64	119.9
O52—N5—C5	118.3 (3)	C64—C65—C66	120.8 (4)
N6—C6—N1	115.1 (3)	C64—C65—H65	119.6
N6—C6—C5	125.0 (3)	C66—C65—H65	119.6
N1—C6—C5	119.9 (4)	C65—C66—C61	119.0 (4)
C6—N6—C61	123.4 (3)	C65—C66—H66	120.5
C6—N6—C67	119.1 (3)	C61—C66—H66	120.5
C61—N6—C67	116.4 (3)
C6—N1—C2—N2	−176.6 (4)	C4—C5—C6—N1	−5.2 (6)
C6—N1—C2—N3	3.4 (6)	N5—C5—C6—N1	166.8 (4)
N1—C2—N3—C4	−5.0 (6)	N1—C6—N6—C61	161.7 (4)
N2—C2—N3—C4	175.1 (4)	C5—C6—N6—C61	−18.1 (6)
C2—N3—C4—O4	−175.0 (4)	N1—C6—N6—C67	−6.1 (5)
C2—N3—C4—C5	1.2 (5)	C5—C6—N6—C67	174.1 (4)
O4—C4—C5—C6	179.6 (4)	C6—N6—C61—C62	−51.5 (5)
N3—C4—C5—C6	3.6 (6)	C67—N6—C61—C62	116.6 (4)
O4—C4—C5—N5	6.9 (6)	C6—N6—C61—C66	131.1 (4)
N3—C4—C5—N5	−169.1 (3)	C67—N6—C61—C66	−60.7 (5)
C6—C5—N5—O51	138.0 (4)	C66—C61—C62—C63	−2.9 (6)
C4—C5—N5—O51	−49.4 (5)	N6—C61—C62—C63	179.7 (4)
C6—C5—N5—O52	−42.2 (5)	C61—C62—C63—C64	1.5 (6)
C4—C5—N5—O52	130.4 (4)	C62—C63—C64—C65	0.2 (6)
C2—N1—C6—N6	−178.3 (3)	C63—C64—C65—C66	−0.3 (6)
C2—N1—C6—C5	1.6 (6)	C64—C65—C66—C61	−1.1 (6)
C4—C5—C6—N6	174.6 (3)	C62—C61—C66—C65	2.7 (6)
N5—C5—C6—N6	−13.3 (6)	N6—C61—C66—C65	−179.9 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O4^i	0.88	1.97	2.783 (4)	153
N2—H2B···O51^ii	0.88	2.40	2.936 (5)	119
N3—H3···O4^i	0.88	2.25	3.000 (5)	143
N3—H3···O51^i	0.88	2.33	3.093 (4)	145

Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) x−1, y, z.