Hydrogen-bonded sheet structures in neutral, anionic and hydrated 6-amino-2-(morpholin-4-yl)-5-nitro­so­pyrimidines

In each of 6-amino-3-methyl-2-(morpholin-4-yl)-5-nitro­so­py­rimi­din-4(3H)-one, C₉H₁₃N₅O₃, (I), morpholin-4-ium 4-am­ino-2-(morpholin-4-yl)-5-nitroso-6-oxo-1,6-dihydro­pyrimidin-1-ide, C₄H₁₀NO⁺·C₈H₁₀N₅O₃⁻, (II), and 6-amino-2-(mor­pho­l­in-4-yl)-5-nitro­sopyrimidin-4(3H)-one hemihydrate, C₈H₁₁N₅O₃·0.5H₂O, (III), the bond distances within the pyrimidine components are consistent with significant electronic polarization, which is most marked in (II) and least marked in (I). Despite the high level of substitution, the pyrimidine rings are all effectively planar, and in each of the pyrimidine components, there are intra­molecular N—H...O hydrogen bonds. In each compound, the organic components are linked by multiple N—H...O hydrogen bonds to form sheets of widely differing construction, and in compound (III) adjacent sheets are linked by the water mol­ecules, so forming a three-dimensional hydrogen-bonded framework. This study also contains the first direct geometric comparison between the electronic polarization in a neutral amino­nitro­sopyrimidine and that in its ring-deprotonated conjugate anion in a metal-free environment.

S1. Comment

Substituted 6-amino-5-nitrosopyrimidines often form intramolecular N—H···O hydrogen bonds and hence they are isoelectronic and approximately isosteric with the correspondingly substituted purines. The presence of the 5-nitroso substituent strongly activates nucleophilic displacement of 2-methoxy or 2-methylsulfanyl substituents and this has proven to provide an effective and versatile synthetic route to a wide range of 2-substituted derivatives (Melguizo et al., 2002). The use of 2-methylsulfanyl derivatives as substrates is particular attractive as the low boiling temperature of the methanethiol by-product (ca 279 K at normal pressure) means that this component is readily removed as the reaction proceeds, so driving the substitution to completion.

Thus, reaction of 6-amino-3-methyl-2-methylsulfanyl-5-nitrosopyrimidin-4(3H)-one with morpholine gave 6-amino-3-methyl-2-(morpholin-4-yl)-5-nitrosopyrimidin-4(3H)-one, (I) (see reaction scheme below), while a similar reaction using 6-amino-2-methylsulfanyl-5-nitrosopyrimidin-4(3H)-one provided 6-amino-2-(morpholin-4-yl)-5-nitrosopyrimidin-4(3H)-one, (IV); recrystallization of (IV) from water gave the hemihydrate (III), while crystallization in the presence of morpholine gave the salt morpholin-4-ium 4-amino-2-(morpholin-4-yl)-5-nitroso-6-oxo-1,6-dihydropyrimidin-1-ide, (II). Accordingly, we have been able to compare the intramolecular metrics of both the neutral pyrimidinone (IV), as it occurs in the hemihydrate (III), and the corresponding conjugate anion, as it occurs in the salt (II).

While the morpholine rings in compounds (I)–(III) (Figs. 1–3) all adopt chair conformations, the pyrimidine rings are, in every case, effectively planar; the maximum deviation from the mean ring planes are 0.033 (2) Å for atom N3 in (I), 0.033 (2) Å for C4 and C5 in (II), and 0.028 (3) Å for N3 in (III). This may be contrasted with the boat conformation found for the pyrimidine ring in the related compound 2-amino-4,6-bis(morpholin-4-yl)-5-nitrosopyrimidine, (V) (Quesada et al., 2004), and the boat (Trilleras et al., 2008) and twist-boat (Quesada et al., 2002, 2003; Melguizo et al., 2003) conformations found in a number of other heavily substituted pyrimidines. In compounds (I)–(III), the three adjacent substituents at positions 4, 5 and 6 are of low steric bulk, and the planarity of the pyrimidine rings in these examples is consistent with our earlier suggestion that the ring puckering in substituted pyrmidines is a direct consequence of steric clashes between bulky substituents in these adjacent positions (Melguizo et al., 2003). The orientation of the nitrosyl substituents, which are all effectively coplanar with the adjacent pyrimidine rings, allowing the formation of intramolecular N—H···O hydrogen bonds (Table 1–3) are almost certainly controlled by the electronic structures discussed below.

The pyrimidine components of compounds (I)–(III) show a number of values (Table 4) which are atypical of their general types (Allen et al., 1987), but which are typical of those commonly observed in related aminonitrosopyrimidines (Low et al., 2000, 2001; Melguizo et al., 2003; Quesada et al., 2002, 2004). The discussion of these distances and their significance is based, to a large extent, on our earlier analysis (Low et al., 2000) of the molecular structures of some nitrosopyrimidinyl derivatives of amino acids, where the analysis of the experimental structures was supported by database and molecular-modelling studies. This analysis showed that the difference between the bond distances C—N and N—O, conveniently denoted as Δ, provides a powerful diagnostic tool for the identification of polarized molecular–electronic structures in such compounds. In simple C-nitroso compounds where there is no possibility of significant electronic delocalization, the difference between the C—N and N—O bond distances usually exceeds 0.20 Å (Talberg, 1977; Schlemper et al., 1986), while the N—O distances rarely exceed 1.25 Å (Davis et al., 1965; Bauer & Andreassen, 1972; Talberg, 1977; Schlemper et al., 1986). However, in each of compounds (I)–(III), the value of Δ is significantly less than 0.10 Å, while the N—O distances always exceed 1.27 Å (Table 4), and the observed values here can be taken as diagnostic of significant electronic delocalization (Low et al., 2000).

In the neutral compound (I), where the polarization is least marked, as judged by the magnitude of Δ, the C6—N6 bond is short for its type (Allen et al., 1987), while the C2—N21 bond distance is fairly typical of its type; in addition, the C4—C5 and C5—C6 distances have very similar lengths, although in the classical representation of (I), these are formally single and double bonds, respectively; on the other hand the N1—C2 bond, which is formally a double bond, is significantly shorter than any other C—N bond within the ring. These observations taken together point to the polarized form (Ia) (see second scheme) as an important contributor to the overall molecular–electronic structure, in addition to the classical unpolarized form (I).

The anionic component of the salt (II) shows the most marked polarization, as indicated by the very small value of Δ. In addition, the C6—N1 and C6—N6 bonds have effectively identical lengths, and the C—O bond is long for its type, while the N3—C4 bond is much shorter in (II) than in (I). The combination of these observations points to the importance of the polarized form (IIa) (see second scheme) as a contributor to the overall molecular–electronic structure. The additional observation that the C2—N1, C2—N3 and C2—N21 bonds have lengths which are identical within experimental uncertainty suggests that form (IIb), where the positive charge is delocalized over four N centres (N1, N3, N6 and N21) in an aminomethyleneguanidinium fragment, may also be significant.

In compound (III), the dimensions of the two independent pyrimidine components are very similar. The values of Δ are intermediate between those in compounds (I) and (II), but the general pattern in the intermolecular distances resembles that in (I). Thus, the Cx4—Cx5 and Cx5—Cx6 distances (x = nil or 1) are identical; the Cx6—Nx6 distances do not differ from the corresponding distance in (I); and the C—O distances are normal, although the Nx3—Cx4 distances are somewhat shorter than the N3—C4 distance in (I), whereas a modest lengthening might have been expected. A polarized structure of the same type as (Ia) is indicated, but with the degree of polarization somewhat enhanced over that in compound (I).

For each of compounds (I)–(III), the supramolecular aggregation is dominated by the formation of hydrogen-bonded sheets. In (I), the sheet is built from just three hydrogen bonds, all of N—H···O type (Table 1). Amino atom N6 in the molecule at (x, y, z) acts as hydrogen-bond donor, via H6A and H6B, respectively, to morpholine atom O24 in the molecule at (1.5 - x, 1/2 + y, 1/2 - z), and ketonic atom O4 in the molecule at (1.5 - x, 1/2 + y, 1.5 - z); the latter of these is, in fact, the longer component of a planar three-centre N—H···(O)₂ system (Table 1). These intermolecular interactions, acting independently, generate C(9) and C(6) chains, respectively, both running parallel to the [010] direction, and in combination they generate a sheet lying parallel to (100) containing equal numbers of S(6) and R₄⁴(26) (Bernstein et al., 1995) rings (Fig. 4). Two sheets of this type, occupying the domains 0 < x < 1/2, and 0.5 < x < 1.0, respectively, and related to one another by inversion, pass through each unit cell, but there are no direction-specific interactions between adjacent sheets.

The formation of the sheet structure of compound (II) is somewhat more complex than that in compound (I); not only are there two independent molecular species present, but the number of hydrogen bonds (Table 2) is also greater. However, the sheet formation is quite easily analysed in terms of a centrosymmetric aggregate containing two ions of each type (Fig. 5). Within the asymmetric unit, ammonium atom N31 acts as hydrogen-bond donor, via H31B, to atom O4 in the anion. The same atom N31 at the cation at (x, y, z) also acts as hydrogen-bond donor, via H31A, to atoms O4 and N5 in the anion at (1.5 - x, 1.5 - y, 1/2 - z), in an effectively planar three-centre N—H···(N,O) system. The resulting centrosymmetric aggregate (Fig. 5), which is centred at (3/4, 3/4, 1/4), contains a central R₄²(8) ring along with two symmetry-related R₁²(5) rings and two S(6) rings. In the final hydrogen bond, atom N6 in the anion at (x, y, z) acts as donor to atom O4 in the anion at (-1/2 + x, 1 - y, z), and by this means the aggregate centred at (3/4, 3/4, 1/4) is directly linked to those at (1/4, 1/4, 1/4), (1/4, 1.25, 1/4), (1.25, 1/4, 1/4) and (1.25, 1.25, 1/4), so forming a sheet parallel to (001). This sheet thus contains four types of ring, S(6), R₁²(5), R₄²(8) and R₈⁸(30), the last two of which are both centrosymmetric (Fig. 6). Two sheets of this type, occupying the domains 0 < z < 1/2, and 0.5 < z < 1.0, respectively, and related to one another by inversion, pass through each unit cell, but there are no direction-specific interactions between adjacent sheets.

There are three independent molecular components, all neutral, in compound (III), and they are linked by a large number of hydrogen bonds, encompassing O—H···O, O—H···N and N—H···O types (Table 3), into a three-dimensional framework. The two organic components are linked into sheets built from six independent intermolecular N—H···O hydrogen bonds, and these sheets are linked by the water molecules to form the three-dimensional structure.

Within the asymmetric unit, atoms N6 and N13 act as hydrogen-bond donors to O14 and O5, respectively (Fig. 3). Similarly, atoms N16 and N3 act as donors, respectively, to O4 at (-1/2 + x, 1/2 - y, 1/2 + z) and O155 at (1/2 + x, 1/2 - y, -1/2 + z). This combination of four hydrogen bonds thus generates a chain of rings running parallel to the [101] direction and built from molecules related by the n-glide plane at y = 0.25 (Fig. 7). In addition, atom N6 at (x, y, z) acts as donor to morpholine atom O124 at (1/2 + x, 1/2 - y, 1/2 + z), so generating a second chain of rings, this time running parallel to the [101] direction, but again built from molecules related by the n-glide plane at y = 1/4, while atom N16 at (x, y, z) acts as donor to morpholine atom O24 at (-1 + x, y, z), so generating by translation a third chain of rings, this time running parallel to the [100] direction. The combination of the chains along [100], [101] and [101] then generates a sheet parallel to (010) and containing five independent types of ring, two each of S(6) and R₂²(6) types, together with one type of R₄⁴(24) ring (Fig. 7).

Two such sheets, occupying the domains 0 < y < 1/2, and 0.5 < y < 1.0, respectively, and related to one another by inversion, pass through each unit cell, and adjacent sheets are linked by the water molecules. A combination of O—H···O and O—H···N hydrogen bonds forms a C₂²(7) chain running parallel to the [010] direction (Fig. 8), which links the sheets into a continuous three-dimensional structure.

In summary, compounds (I)–(III) all show polarized molecular–electronic structures, albeit in differing degrees, and the organic fragments in each compound are linked by hydrogen bonds into sheets of markedly different types, despite the rather small differences in molecular constitution between the pyrimidine fragments involved.

Related literature

For related literature, see: Allen et al. (1987); Bauer & Andreassen (1972); Davis et al. (1965); Low et al. (2000, 2001); Melguizo et al. (2002, 2003); Quesada et al. (2002, 2004); Schlemper et al. (1986); Talberg (1977); Trilleras et al. (2008).

S2. Experimental

For the synthesis of compound (I), morpholine (100 mmol) was added dropwise and with magnetic stirring to a suspension of 6-amino-3-methyl-2-methylsulfanyl-5-nitrosopyrimidin-4(3H)-one (26.8 mmol) in dry ethanol (80 ml). Stirring was continued for 18 h, when the colour changed from blue to violet as methanethiol was liberated. The resulting solid was collected by filtration and washed with cold ethanol. Crystals of (I) suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in dimethylformamide–ethanol (10:1 v/v). Yield 57%; m.p. 508–509 K; MS (30 eV) m/z (%): 239 (M⁺, 89), 209 (2), 181 (6), 153 (4), 139 (10), 125 (20), 113 (13), 109 (13), 86 (29), 69 (92), 57 (76), 42 (100). A similar reaction, but using 6-amino-2-methylsulfanyl-5-nitrosopyrimidin-4(3H)-one in place of the 3-methyl analogue gave 6-amino-2-(morpholin-4-yl)-5-nitrosopyrimidin-4(3H)-one, (IV). Yield 99%, m.p. 507–508 K; MS (30 eV) m/z (%): 225 (M⁺, 72), 208 (94), 195 (2), 139 (2), 113 (49), 113 (49), 95 (24), 86 (21), 69 (100). Recrystallization of this material from a dimethylformamide–ethanol (10:1 v/v) mixture containing a little morpholine gave crystals of compound (II) suitable for single-crystal X-ray diffraction, whereas crystallization from water yielded hemihydrate (III).

S3. Refinement

For each of (I) and (III), the space group P2₁/n was uniquely assigned from the systematic absence. For compound (II), the systematic absences permitted Cc and C2/c as possible space groups; C2/c was selected and confirmed by the structure solution, but the setting was then transformed to the alternative I2/a. All H atoms were located in difference maps and then treated as riding atoms. H atoms bonded to C or N atoms were allowed to ride in geometrically idealized positions, with C—H = 0.98 (CH₃) or 0.99 Å (CH₂) and N—H = 0.92 Å for the cation in (II) and 0.88 Å otherwise, and with U_iso(H) = kU_eq(C,N) where k = 1.5 for the methyl groups and 1.2 otherwise. H atoms bonded to O atoms were permitted to ride at the locations deduced from the difference maps, with U_iso(H) = 1.5U_eq(O), giving O—H distances of 0.89 and 1.19 Å in compound (III).

Computing details

For all 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, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The molecule of compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and, for the sake of clarity, the intramolecular N—H···O hydrogen bond has been omitted.
	Fig. 2. The independent ionic components of compound (II), showing the atom-labelling scheme and the N—H···O hydrogen bond linking the ions. Displacement ellipsoids are drawn at the 30% probability level and, for the sake of clarity, the intramolecular N—H···O hydrogen bond in the anion has been omitted.
	Fig. 3. The independent molecular components of compound (III), showing the atom-labelling scheme and the hydrogen bonds linking the components. Displacement ellipsoids are drawn at the 30% probability level and, for the sake of clarity, the intramolecular N—H···O hydrogen bonds have been omitted.
	Fig. 4. A stereoview of part of the crystal structure of compound (I), showing the formation of a hydrogen-bonded sheet of S(6) and R4^4(26) rings parallel to (100). For the sake of clarity, H atoms bonded to C atoms have been omitted.
	Fig. 5. Part of the crystal structure of compound (II), showing the formation of a centrosymmetric aggregate of two cations and two anions. Atoms marked with an asterisk (*) are at the symmetry position (1.5 - x, 1.5 - y, 1/2 - z). For the sake of clarity, H atoms bonded to C atoms and the unit-cell outline have been omitted.
	Fig. 6. A stereoview of part of the crystal structure of compound (II), showing the formation of a hydrogen-bonded sheet parallel to (001) and containing four independent types of ring. For the sake of clarity, H atoms bonded to C atoms have been omitted.
	Fig. 7. A stereoview of part of the crystal structure of compound (III), showing the formation of a hydrogen-bonded sheet parallel to (010) and containing five independent types of ring. For the sake of clarity, H atoms bonded to C atoms have been omitted.
	Fig. 8. A stereoview of part of the crystal structure of compound (III), showing the formation of a hydrogen-bonded C2^2(7) chain along [010] linking the sheets parallel to (010). For the sake of clarity, H atoms bonded to C atoms have been omitted.

(I) 6-amino-3-methyl-2-(morpholin-4-yl)-5-nitrosopyrimidin-4(3H)-one

Crystal data

C9H13N5O3	F(000) = 504
Mr = 239.24	Dx = 1.494 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2445 reflections
a = 8.9122 (6) Å	θ = 3.2–27.5°
b = 11.9051 (7) Å	µ = 0.12 mm^−1
c = 10.4111 (4) Å	T = 120 K
β = 105.649 (3)°	Block, violet
V = 1063.68 (10) Å^3	0.41 × 0.28 × 0.25 mm
Z = 4

Data collection

Bruker–Nonius KappaCCD diffractometer	2445 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1516 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.068
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
ϕ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −15→15
Tmin = 0.959, Tmax = 0.972	l = −13→13
25676 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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.159	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0708P)^2 + 0.8671P] where P = (Fo^2 + 2Fc^2)/3
2445 reflections	(Δ/σ)max < 0.001
155 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

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

	x	y	z	Uiso*/Ueq
O4	0.5236 (2)	0.28531 (14)	0.73638 (16)	0.0274 (4)
O5	0.7727 (2)	0.56211 (15)	0.86723 (17)	0.0316 (5)
O24	0.6049 (2)	0.21552 (14)	0.07493 (16)	0.0278 (4)
N1	0.7099 (2)	0.45427 (16)	0.47610 (18)	0.0220 (5)
N3	0.5643 (2)	0.30250 (16)	0.53066 (19)	0.0213 (5)
N5	0.6951 (2)	0.47256 (18)	0.82890 (19)	0.0267 (5)
N6	0.8104 (2)	0.59112 (16)	0.6285 (2)	0.0255 (5)
N21	0.6243 (2)	0.31120 (16)	0.32630 (18)	0.0233 (5)
C2	0.6354 (3)	0.3583 (2)	0.4473 (2)	0.0213 (5)
C3	0.4453 (3)	0.2144 (2)	0.4835 (2)	0.0259 (6)
C4	0.5835 (3)	0.3391 (2)	0.6634 (2)	0.0222 (5)
C5	0.6740 (3)	0.4408 (2)	0.7000 (2)	0.0210 (5)
C6	0.7298 (3)	0.49742 (19)	0.6002 (2)	0.0217 (5)
C22	0.6690 (3)	0.1928 (2)	0.3140 (2)	0.0250 (6)
C23	0.5760 (3)	0.1495 (2)	0.1796 (2)	0.0284 (6)
C25	0.5671 (3)	0.3316 (2)	0.0870 (2)	0.0264 (6)
C26	0.6585 (3)	0.3795 (2)	0.2200 (2)	0.0254 (6)
H3A	0.4048	0.2192	0.3864	0.039*
H3B	0.3599	0.2253	0.5250	0.039*
H3C	0.4924	0.1404	0.5080	0.039*
H6A	0.8488	0.6231	0.5680	0.031*
H6B	0.8260	0.6218	0.7079	0.031*
H22A	0.6466	0.1472	0.3862	0.030*
H22B	0.7819	0.1877	0.3215	0.030*
H23A	0.6049	0.0704	0.1689	0.034*
H23B	0.4635	0.1518	0.1745	0.034*
H25A	0.4541	0.3388	0.0784	0.032*
H25B	0.5909	0.3751	0.0138	0.032*
H26A	0.7714	0.3775	0.2270	0.030*
H26B	0.6278	0.4586	0.2281	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O4	0.0303 (10)	0.0281 (9)	0.0263 (9)	−0.0014 (8)	0.0120 (8)	0.0044 (7)
O5	0.0342 (10)	0.0344 (11)	0.0258 (10)	−0.0024 (8)	0.0076 (8)	−0.0067 (8)
O24	0.0336 (10)	0.0282 (9)	0.0228 (9)	0.0014 (8)	0.0098 (7)	−0.0017 (7)
N1	0.0250 (11)	0.0231 (11)	0.0179 (10)	0.0002 (9)	0.0060 (8)	0.0004 (8)
N3	0.0201 (10)	0.0237 (11)	0.0212 (10)	−0.0010 (8)	0.0075 (8)	0.0005 (8)
N5	0.0277 (11)	0.0284 (12)	0.0241 (11)	0.0024 (9)	0.0071 (9)	−0.0021 (9)
N6	0.0351 (12)	0.0228 (11)	0.0196 (10)	−0.0038 (9)	0.0089 (9)	−0.0009 (8)
N21	0.0305 (11)	0.0223 (11)	0.0185 (10)	−0.0013 (9)	0.0091 (8)	−0.0006 (8)
C2	0.0198 (12)	0.0237 (13)	0.0199 (12)	0.0014 (10)	0.0049 (9)	0.0023 (10)
C3	0.0248 (13)	0.0267 (13)	0.0262 (13)	−0.0030 (11)	0.0070 (10)	−0.0006 (10)
C4	0.0222 (12)	0.0246 (13)	0.0198 (12)	0.0045 (10)	0.0060 (10)	0.0027 (10)
C5	0.0207 (12)	0.0257 (13)	0.0173 (12)	0.0030 (10)	0.0062 (9)	0.0006 (9)
C6	0.0223 (12)	0.0218 (12)	0.0211 (12)	0.0046 (10)	0.0059 (10)	0.0025 (10)
C22	0.0256 (13)	0.0248 (13)	0.0252 (13)	0.0014 (10)	0.0080 (10)	0.0006 (10)
C23	0.0346 (14)	0.0244 (13)	0.0277 (13)	−0.0036 (11)	0.0108 (11)	−0.0046 (10)
C25	0.0319 (14)	0.0269 (13)	0.0211 (13)	0.0044 (11)	0.0083 (10)	0.0009 (10)
C26	0.0327 (14)	0.0240 (13)	0.0208 (12)	−0.0017 (11)	0.0095 (10)	0.0005 (10)

Geometric parameters (Å, º)

O24—C23	1.422 (3)	C3—H3A	0.98
O24—C25	1.436 (3)	C3—H3B	0.98
O4—C4	1.221 (3)	C3—H3C	0.98
O5—N5	1.275 (3)	C4—C5	1.447 (3)
N1—C2	1.315 (3)	C5—C6	1.435 (3)
N1—C6	1.357 (3)	C22—C23	1.512 (3)
N3—C2	1.376 (3)	C22—H22A	0.99
N3—C4	1.415 (3)	C22—H22B	0.99
N3—C3	1.478 (3)	C23—H23A	0.99
N5—C5	1.358 (3)	C23—H23B	0.99
N6—C6	1.316 (3)	C25—C26	1.516 (3)
N6—H6A	0.88	C25—H25A	0.99
N6—H6B	0.88	C25—H25B	0.99
N21—C2	1.358 (3)	C26—H26A	0.99
N21—C26	1.470 (3)	C26—H26B	0.99
N21—C22	1.480 (3)
C23—O24—C25	111.72 (18)	N6—C6—N1	117.2 (2)
C2—N1—C6	118.31 (19)	N6—C6—C5	120.7 (2)
C2—N3—C4	120.8 (2)	N1—C6—C5	122.0 (2)
C2—N3—C3	123.00 (19)	N21—C22—C23	108.2 (2)
C4—N3—C3	115.47 (18)	N21—C22—H22A	110.1
O5—N5—C5	117.5 (2)	C23—C22—H22A	110.1
C6—N6—H6A	120.0	N21—C22—H22B	110.1
C6—N6—H6B	120.0	C23—C22—H22B	110.1
H6A—N6—H6B	120.0	H22A—C22—H22B	108.4
C2—N21—C26	119.48 (19)	O24—C23—C22	110.7 (2)
C2—N21—C22	121.29 (19)	O24—C23—H23A	109.5
C26—N21—C22	110.30 (18)	C22—C23—H23A	109.5
N1—C2—N21	118.4 (2)	O24—C23—H23B	109.5
N1—C2—N3	124.5 (2)	C22—C23—H23B	109.5
N21—C2—N3	117.1 (2)	H23A—C23—H23B	108.1
N3—C3—H3A	109.5	O24—C25—C26	111.2 (2)
N3—C3—H3B	109.5	O24—C25—H25A	109.4
H3A—C3—H3B	109.5	C26—C25—H25A	109.4
N3—C3—H3C	109.5	O24—C25—H25B	109.4
H3A—C3—H3C	109.5	C26—C25—H25B	109.4
H3B—C3—H3C	109.5	H25A—C25—H25B	108.0
O4—C4—N3	119.2 (2)	N21—C26—C25	108.1 (2)
O4—C4—C5	125.5 (2)	N21—C26—H26A	110.1
N3—C4—C5	115.26 (19)	C25—C26—H26A	110.1
N5—C5—C6	127.0 (2)	N21—C26—H26B	110.1
N5—C5—C4	114.3 (2)	C25—C26—H26B	110.1
C6—C5—C4	118.7 (2)	H26A—C26—H26B	108.4
C6—N1—C2—N21	−175.7 (2)	N3—C4—C5—N5	−178.07 (19)
C6—N1—C2—N3	5.7 (3)	O4—C4—C5—C6	−176.8 (2)
C26—N21—C2—N1	−15.5 (3)	N3—C4—C5—C6	2.5 (3)
C22—N21—C2—N1	128.6 (2)	C2—N1—C6—N6	177.2 (2)
C26—N21—C2—N3	163.2 (2)	C2—N1—C6—C5	0.8 (3)
C22—N21—C2—N3	−52.7 (3)	N5—C5—C6—N6	−0.4 (4)
C4—N3—C2—N1	−8.0 (3)	C4—C5—C6—N6	178.9 (2)
C3—N3—C2—N1	161.9 (2)	N5—C5—C6—N1	175.9 (2)
C4—N3—C2—N21	173.4 (2)	C4—C5—C6—N1	−4.8 (3)
C3—N3—C2—N21	−16.8 (3)	C2—N21—C22—C23	152.8 (2)
C2—N3—C4—O4	−177.3 (2)	C26—N21—C22—C23	−60.2 (2)
C3—N3—C4—O4	12.1 (3)	C25—O24—C23—C22	−58.3 (3)
C2—N3—C4—C5	3.4 (3)	N21—C22—C23—O24	58.7 (3)
C3—N3—C4—C5	−167.2 (2)	C23—O24—C25—C26	57.8 (3)
O5—N5—C5—C6	0.0 (3)	C2—N21—C26—C25	−152.9 (2)
O5—N5—C5—C4	−179.4 (2)	C22—N21—C26—C25	59.4 (3)
O4—C4—C5—N5	2.7 (3)	O24—C25—C26—N21	−57.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6A···O24^i	0.88	1.98	2.848 (3)	168
N6—H6B···O5	0.88	1.98	2.619 (3)	129
N6—H6B···O4^ii	0.88	2.35	2.896 (3)	121

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

(II) morpholin-4-ium 4-amino-2-(morpholin-4-yl)-5-nitroso-6-oxo-1,6-dihydropyrimidin-1-ide

Crystal data

C4H10NO^+·C8H10N5O3^−	F(000) = 1328
Mr = 312.34	Dx = 1.430 Mg m^−3
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2ya	Cell parameters from 3354 reflections
a = 9.4410 (11) Å	θ = 3.3–27.5°
b = 16.347 (4) Å	µ = 0.11 mm^−1
c = 18.799 (5) Å	T = 120 K
β = 90.045 (15)°	Lath, violet
V = 2901.3 (11) Å^3	0.26 × 0.10 × 0.10 mm
Z = 8

Data collection

Bruker–Nonius KappaCCD diffractometer	3354 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	2361 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.3°
ϕ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −21→21
Tmin = 0.977, Tmax = 0.989	l = −24→24
33473 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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.109	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0306P)^2 + 5.055P] where P = (Fo^2 + 2Fc^2)/3
3354 reflections	(Δ/σ)max < 0.001
199 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

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

	x	y	z	Uiso*/Ueq
O4	0.58426 (14)	0.70724 (9)	0.26537 (7)	0.0239 (3)
O5	0.57948 (14)	0.57129 (9)	0.44197 (7)	0.0227 (3)
O24	−0.02092 (15)	0.55270 (9)	0.09133 (7)	0.0290 (3)
N1	0.22162 (16)	0.58424 (10)	0.31405 (8)	0.0188 (3)
N3	0.36442 (16)	0.66628 (10)	0.23262 (8)	0.0189 (3)
N5	0.58145 (16)	0.61396 (10)	0.38319 (8)	0.0207 (3)
N6	0.31265 (16)	0.53870 (10)	0.41996 (8)	0.0206 (3)
N21	0.14231 (16)	0.61936 (10)	0.20370 (8)	0.0209 (4)
C2	0.24766 (19)	0.62398 (11)	0.25230 (10)	0.0173 (4)
C4	0.47342 (19)	0.66716 (11)	0.27884 (9)	0.0176 (4)
C5	0.46347 (18)	0.61945 (11)	0.34506 (9)	0.0165 (4)
C6	0.32895 (19)	0.58026 (11)	0.35985 (9)	0.0168 (4)
C22	0.1527 (2)	0.65210 (12)	0.13147 (10)	0.0236 (4)
C23	0.1166 (2)	0.58570 (13)	0.07847 (10)	0.0254 (4)
C25	−0.0256 (2)	0.51830 (14)	0.16095 (11)	0.0298 (5)
C26	0.00630 (19)	0.58025 (13)	0.21814 (10)	0.0222 (4)
O34	0.51265 (14)	0.72728 (9)	0.02394 (7)	0.0247 (3)
N31	0.67247 (16)	0.78042 (10)	0.14380 (8)	0.0219 (4)
C32	0.7156 (2)	0.70778 (13)	0.10134 (11)	0.0244 (4)
C33	0.5859 (2)	0.66997 (12)	0.06768 (11)	0.0246 (4)
C35	0.4659 (2)	0.79510 (12)	0.06570 (11)	0.0233 (4)
C36	0.5901 (2)	0.83871 (12)	0.09899 (10)	0.0224 (4)
H6A	0.2317	0.5142	0.4291	0.025*
H6B	0.3828	0.5356	0.4507	0.025*
H22A	0.2500	0.6722	0.1227	0.028*
H22B	0.0865	0.6986	0.1258	0.028*
H23A	0.1201	0.6085	0.0297	0.031*
H23B	0.1878	0.5414	0.0817	0.031*
H25A	0.0440	0.4731	0.1640	0.036*
H25B	−0.1209	0.4950	0.1693	0.036*
H26A	−0.0695	0.6221	0.2194	0.027*
H26B	0.0095	0.5528	0.2651	0.027*
H31A	0.7518	0.8062	0.1614	0.026*
H31B	0.6181	0.7639	0.1817	0.026*
H32A	0.7629	0.6673	0.1325	0.029*
H32B	0.7834	0.7244	0.0639	0.029*
H33A	0.6146	0.6223	0.0386	0.029*
H33B	0.5215	0.6502	0.1055	0.029*
H35A	0.4014	0.7755	0.1035	0.028*
H35B	0.4126	0.8337	0.0352	0.028*
H36A	0.6518	0.8614	0.0613	0.027*
H36B	0.5558	0.8846	0.1287	0.027*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O4	0.0203 (7)	0.0311 (8)	0.0203 (7)	−0.0089 (6)	−0.0016 (5)	0.0041 (6)
O5	0.0209 (7)	0.0293 (8)	0.0180 (7)	0.0027 (6)	−0.0023 (5)	0.0029 (6)
O24	0.0320 (8)	0.0330 (8)	0.0220 (7)	−0.0090 (6)	−0.0062 (6)	−0.0010 (6)
N1	0.0183 (8)	0.0211 (8)	0.0170 (8)	−0.0015 (6)	−0.0007 (6)	0.0007 (6)
N3	0.0181 (8)	0.0204 (8)	0.0181 (8)	−0.0018 (6)	−0.0019 (6)	0.0007 (7)
N5	0.0195 (8)	0.0259 (9)	0.0166 (8)	−0.0001 (7)	−0.0020 (6)	0.0008 (7)
N6	0.0181 (8)	0.0267 (9)	0.0170 (8)	−0.0044 (7)	−0.0011 (6)	0.0024 (7)
N21	0.0194 (8)	0.0239 (9)	0.0195 (8)	−0.0063 (7)	−0.0040 (6)	0.0038 (7)
C2	0.0180 (9)	0.0164 (9)	0.0176 (9)	0.0006 (7)	−0.0017 (7)	−0.0005 (7)
C4	0.0165 (9)	0.0189 (9)	0.0174 (9)	−0.0006 (7)	0.0005 (7)	−0.0028 (7)
C5	0.0165 (9)	0.0173 (9)	0.0157 (9)	0.0007 (7)	0.0006 (7)	−0.0031 (7)
C6	0.0178 (9)	0.0168 (9)	0.0159 (9)	0.0011 (7)	0.0012 (7)	−0.0030 (7)
C22	0.0217 (10)	0.0269 (11)	0.0222 (10)	−0.0063 (8)	−0.0067 (8)	0.0102 (8)
C23	0.0250 (10)	0.0318 (11)	0.0196 (10)	0.0030 (9)	−0.0025 (8)	0.0048 (9)
C25	0.0328 (12)	0.0299 (11)	0.0267 (11)	−0.0107 (9)	−0.0034 (9)	0.0016 (9)
C26	0.0170 (9)	0.0285 (11)	0.0211 (9)	−0.0036 (8)	−0.0019 (7)	0.0007 (8)
O34	0.0279 (7)	0.0241 (7)	0.0221 (7)	0.0003 (6)	−0.0091 (6)	−0.0021 (6)
N31	0.0174 (8)	0.0318 (9)	0.0164 (8)	−0.0064 (7)	−0.0007 (6)	−0.0008 (7)
C32	0.0223 (10)	0.0305 (11)	0.0206 (10)	0.0047 (8)	−0.0026 (8)	0.0002 (8)
C33	0.0270 (10)	0.0194 (10)	0.0272 (11)	0.0004 (8)	−0.0048 (8)	0.0011 (8)
C35	0.0225 (9)	0.0212 (10)	0.0262 (10)	0.0015 (8)	−0.0022 (8)	0.0046 (8)
C36	0.0258 (10)	0.0201 (10)	0.0212 (9)	−0.0032 (8)	0.0019 (8)	0.0011 (8)

Geometric parameters (Å, º)

O4—C4	1.260 (2)	C25—C26	1.507 (3)
O5—N5	1.307 (2)	C25—H25A	0.99
O24—C25	1.425 (2)	C25—H25B	0.99
O24—C23	1.426 (2)	C26—H26A	0.99
N1—C6	1.331 (2)	C26—H26B	0.99
N1—C2	1.353 (2)	O34—C33	1.425 (2)
N3—C4	1.346 (2)	O34—C35	1.429 (2)
N3—C2	1.353 (2)	N31—C32	1.488 (3)
N5—C5	1.327 (2)	N31—C36	1.490 (2)
N6—C6	1.328 (2)	N31—H31A	0.92
N6—H6A	0.88	N31—H31B	0.92
N6—H6B	0.88	C32—C33	1.511 (3)
N21—C2	1.352 (2)	C32—H32A	0.99
N21—C26	1.460 (2)	C32—H32B	0.99
N21—C22	1.463 (2)	C33—H33A	0.99
C4—C5	1.472 (3)	C33—H33B	0.99
C5—C6	1.450 (2)	C35—C36	1.508 (3)
C22—C23	1.512 (3)	C35—H35A	0.99
C22—H22A	0.99	C35—H35B	0.99
C22—H22B	0.99	C36—H36A	0.99
C23—H23A	0.99	C36—H36B	0.99
C23—H23B	0.99
C25—O24—C23	109.51 (15)	H25A—C25—H25B	107.8
C6—N1—C2	116.09 (16)	N21—C26—C25	109.69 (16)
C4—N3—C2	116.84 (16)	N21—C26—H26A	109.7
O5—N5—C5	118.70 (15)	C25—C26—H26A	109.7
C6—N6—H6A	120.0	N21—C26—H26B	109.7
C6—N6—H6B	120.0	C25—C26—H26B	109.7
H6A—N6—H6B	120.0	H26A—C26—H26B	108.2
C2—N21—C26	123.06 (16)	C33—O34—C35	110.06 (14)
C2—N21—C22	123.84 (16)	C32—N31—C36	110.48 (15)
C26—N21—C22	113.10 (15)	C32—N31—H31A	109.6
N21—C2—N1	114.76 (16)	C36—N31—H31A	109.6
N21—C2—N3	116.29 (16)	C32—N31—H31B	109.6
N1—C2—N3	128.94 (16)	C36—N31—H31B	109.6
O4—C4—N3	120.68 (17)	H31A—N31—H31B	108.1
O4—C4—C5	119.92 (16)	N31—C32—C33	109.21 (16)
N3—C4—C5	119.39 (16)	N31—C32—H32A	109.8
N5—C5—C6	126.99 (17)	C33—C32—H32A	109.8
N5—C5—C4	116.01 (16)	N31—C32—H32B	109.8
C6—C5—C4	116.92 (15)	C33—C32—H32B	109.8
N6—C6—N1	119.14 (16)	H32A—C32—H32B	108.3
N6—C6—C5	119.44 (16)	O34—C33—C32	111.43 (16)
N1—C6—C5	121.41 (16)	O34—C33—H33A	109.3
N21—C22—C23	109.49 (16)	C32—C33—H33A	109.3
N21—C22—H22A	109.8	O34—C33—H33B	109.3
C23—C22—H22A	109.8	C32—C33—H33B	109.3
N21—C22—H22B	109.8	H33A—C33—H33B	108.0
C23—C22—H22B	109.8	O34—C35—C36	110.76 (16)
H22A—C22—H22B	108.2	O34—C35—H35A	109.5
O24—C23—C22	111.38 (16)	C36—C35—H35A	109.5
O24—C23—H23A	109.4	O34—C35—H35B	109.5
C22—C23—H23A	109.4	C36—C35—H35B	109.5
O24—C23—H23B	109.4	H35A—C35—H35B	108.1
C22—C23—H23B	109.4	N31—C36—C35	109.73 (16)
H23A—C23—H23B	108.0	N31—C36—H36A	109.7
O24—C25—C26	112.56 (17)	C35—C36—H36A	109.7
O24—C25—H25A	109.1	N31—C36—H36B	109.7
C26—C25—H25A	109.1	C35—C36—H36B	109.7
O24—C25—H25B	109.1	H36A—C36—H36B	108.2
C26—C25—H25B	109.1
C26—N21—C2—N1	4.6 (3)	N5—C5—C6—N6	5.6 (3)
C22—N21—C2—N1	−174.86 (17)	C4—C5—C6—N6	−177.80 (16)
C26—N21—C2—N3	−176.23 (17)	N5—C5—C6—N1	−173.64 (18)
C22—N21—C2—N3	4.3 (3)	C4—C5—C6—N1	3.0 (3)
C6—N1—C2—N21	173.07 (17)	C2—N21—C22—C23	126.43 (19)
C6—N1—C2—N3	−6.0 (3)	C26—N21—C22—C23	−53.1 (2)
C4—N3—C2—N21	−176.11 (17)	C25—O24—C23—C22	−60.2 (2)
C4—N3—C2—N1	2.9 (3)	N21—C22—C23—O24	56.9 (2)
C2—N3—C4—O4	−177.84 (17)	C23—O24—C25—C26	59.4 (2)
C2—N3—C4—C5	3.3 (2)	C2—N21—C26—C25	−127.7 (2)
O5—N5—C5—C6	−2.3 (3)	C22—N21—C26—C25	51.8 (2)
O5—N5—C5—C4	−178.96 (15)	O24—C25—C26—N21	−54.8 (2)
O4—C4—C5—N5	−7.9 (3)	C36—N31—C32—C33	−54.6 (2)
N3—C4—C5—N5	170.98 (17)	C35—O34—C33—C32	−61.1 (2)
O4—C4—C5—C6	175.16 (17)	N31—C32—C33—O34	57.8 (2)
N3—C4—C5—C6	−6.0 (2)	C33—O34—C35—C36	60.9 (2)
C2—N1—C6—N6	−176.74 (17)	C32—N31—C36—C35	55.1 (2)
C2—N1—C6—C5	2.5 (3)	O34—C35—C36—N31	−58.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6A···O5^i	0.88	2.02	2.872 (2)	163
N6—H6B···O5	0.88	1.95	2.608 (2)	130
N31—H31A···O4^ii	0.92	2.08	2.868 (2)	143
N31—H31A···N5^ii	0.92	2.21	2.939 (2)	136
N31—H31B···O4	0.92	1.85	2.711 (2)	154

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

(III) 6-amino-2-(morpholin-4-yl)-5-nitrosopyrimidin-4(3H)-one hemihydrate

Crystal data

C8H11N5O3·0.5H2O	F(000) = 984
Mr = 234.23	Dx = 1.546 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4646 reflections
a = 16.421 (2) Å	θ = 3.0–27.5°
b = 7.3671 (12) Å	µ = 0.12 mm^−1
c = 17.205 (4) Å	T = 120 K
β = 104.794 (12)°	Block, purple
V = 2012.4 (6) Å^3	0.44 × 0.34 × 0.21 mm
Z = 8

Data collection

Bruker–Nonius KappaCCD diffractometer	4646 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	2535 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.098
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ϕ and ω scans	h = −21→21
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −9→9
Tmin = 0.953, Tmax = 0.975	l = −22→22
47024 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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.162	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0672P)^2 + 1.619P] where P = (Fo^2 + 2Fc^2)/3
4646 reflections	(Δ/σ)max < 0.001
298 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.41 e Å^−3

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

	x	y	z	Uiso*/Ueq
O4	0.43256 (12)	0.1500 (3)	0.26365 (11)	0.0230 (5)
O5	0.29659 (11)	0.0472 (3)	0.42316 (12)	0.0242 (5)
O24	0.82727 (11)	0.4401 (3)	0.51666 (12)	0.0239 (5)
N1	0.53493 (14)	0.2730 (3)	0.49908 (14)	0.0189 (5)
N3	0.54131 (14)	0.2458 (3)	0.36435 (13)	0.0197 (5)
N5	0.33894 (14)	0.0758 (3)	0.37107 (14)	0.0204 (5)
N6	0.42037 (14)	0.1755 (3)	0.53801 (14)	0.0201 (5)
N21	0.65296 (14)	0.3651 (3)	0.46270 (14)	0.0222 (6)
C2	0.57578 (16)	0.2949 (4)	0.44264 (16)	0.0181 (6)
C4	0.46065 (17)	0.1777 (4)	0.33577 (17)	0.0183 (6)
C5	0.41619 (16)	0.1458 (4)	0.39736 (16)	0.0168 (6)
C6	0.45776 (16)	0.1982 (4)	0.47945 (16)	0.0174 (6)
C22	0.70206 (17)	0.4150 (4)	0.40547 (17)	0.0235 (7)
C23	0.79284 (17)	0.3612 (4)	0.43935 (18)	0.0245 (7)
C25	0.78156 (17)	0.3764 (4)	0.57213 (18)	0.0253 (7)
C26	0.68964 (17)	0.4318 (4)	0.54463 (17)	0.0231 (7)
O14	0.26393 (12)	0.1139 (3)	0.58789 (11)	0.0239 (5)
O15	0.11595 (12)	0.2754 (3)	0.73012 (12)	0.0275 (5)
O124	−0.01980 (12)	0.1750 (3)	0.19404 (12)	0.0271 (5)
N11	0.01877 (14)	0.2418 (3)	0.48437 (14)	0.0208 (6)
N13	0.15311 (14)	0.1339 (3)	0.47926 (13)	0.0195 (5)
N15	0.16550 (15)	0.2226 (3)	0.68759 (14)	0.0232 (6)
N16	−0.00794 (14)	0.3182 (3)	0.60244 (14)	0.0231 (6)
N121	0.04458 (14)	0.1733 (3)	0.36273 (13)	0.0216 (6)
C12	0.07195 (16)	0.1834 (4)	0.44332 (16)	0.0179 (6)
C14	0.18951 (17)	0.1515 (4)	0.56167 (16)	0.0186 (6)
C15	0.13228 (16)	0.2137 (4)	0.60790 (16)	0.0173 (6)
C16	0.04671 (17)	0.2577 (4)	0.56427 (17)	0.0178 (6)
C122	0.09100 (17)	0.0866 (4)	0.31082 (17)	0.0229 (7)
C123	0.06930 (18)	0.1744 (4)	0.22942 (17)	0.0266 (7)
C125	−0.06061 (18)	0.2797 (4)	0.24350 (17)	0.0232 (7)
C126	−0.04640 (17)	0.1950 (5)	0.32512 (17)	0.0268 (7)
O1	0.26335 (14)	0.4099 (3)	0.27529 (13)	0.0413 (6)
H3	0.5725	0.2584	0.3300	0.024*
H6A	0.4460	0.2089	0.5873	0.024*
H6B	0.3698	0.1270	0.5278	0.024*
H22A	0.6982	0.5476	0.3957	0.028*
H22B	0.6790	0.3525	0.3536	0.028*
H23A	0.7967	0.2273	0.4439	0.029*
H23B	0.8264	0.4007	0.4020	0.029*
H25A	0.8068	0.4276	0.6261	0.030*
H25B	0.7857	0.2425	0.5761	0.030*
H26A	0.6583	0.3808	0.5816	0.028*
H26B	0.6850	0.5657	0.5457	0.028*
H13	0.1840	0.0887	0.4489	0.023*
H16A	−0.0596	0.3455	0.5754	0.028*
H16B	0.0072	0.3312	0.6550	0.028*
H22C	0.0767	−0.0441	0.3053	0.028*
H22D	0.1523	0.0976	0.3354	0.028*
H23C	0.0903	0.3009	0.2344	0.032*
H23D	0.0978	0.1083	0.1937	0.032*
H25C	−0.1218	0.2861	0.2178	0.028*
H25D	−0.0380	0.4049	0.2489	0.028*
H26C	−0.0718	0.2724	0.3597	0.032*
H26D	−0.0742	0.0748	0.3202	0.032*
H1A	0.2263	0.4282	0.2284	0.062*
H1B	0.2993	0.2813	0.2580	0.062*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O4	0.0213 (11)	0.0324 (12)	0.0143 (11)	−0.0041 (9)	0.0029 (8)	−0.0021 (9)
O5	0.0160 (10)	0.0365 (12)	0.0224 (11)	−0.0029 (9)	0.0092 (9)	−0.0029 (9)
O24	0.0161 (10)	0.0312 (12)	0.0250 (12)	−0.0005 (9)	0.0062 (9)	0.0003 (9)
N1	0.0155 (12)	0.0231 (13)	0.0186 (13)	−0.0010 (10)	0.0054 (10)	−0.0012 (10)
N3	0.0157 (12)	0.0284 (14)	0.0160 (13)	−0.0037 (10)	0.0060 (10)	−0.0013 (10)
N5	0.0159 (12)	0.0255 (14)	0.0214 (13)	0.0004 (10)	0.0075 (10)	−0.0023 (11)
N6	0.0150 (12)	0.0301 (14)	0.0152 (12)	−0.0023 (10)	0.0038 (10)	−0.0017 (11)
N21	0.0162 (12)	0.0337 (15)	0.0164 (13)	−0.0048 (10)	0.0038 (10)	−0.0034 (11)
C2	0.0143 (14)	0.0221 (15)	0.0173 (15)	0.0016 (11)	0.0028 (11)	0.0016 (12)
C4	0.0161 (14)	0.0191 (15)	0.0194 (16)	0.0021 (11)	0.0039 (12)	0.0007 (12)
C5	0.0141 (13)	0.0195 (15)	0.0164 (14)	0.0020 (11)	0.0032 (11)	−0.0007 (12)
C6	0.0138 (14)	0.0207 (15)	0.0184 (15)	0.0023 (11)	0.0052 (11)	−0.0007 (12)
C22	0.0211 (15)	0.0280 (17)	0.0225 (16)	−0.0084 (13)	0.0075 (12)	−0.0011 (13)
C23	0.0221 (16)	0.0288 (17)	0.0251 (17)	−0.0014 (13)	0.0103 (13)	−0.0024 (13)
C25	0.0195 (15)	0.0293 (17)	0.0254 (17)	−0.0016 (13)	0.0028 (13)	0.0008 (13)
C26	0.0189 (15)	0.0348 (18)	0.0153 (15)	−0.0034 (13)	0.0038 (12)	−0.0053 (13)
O14	0.0156 (10)	0.0359 (13)	0.0198 (11)	0.0027 (9)	0.0036 (8)	0.0009 (9)
O15	0.0266 (11)	0.0404 (13)	0.0174 (11)	0.0049 (10)	0.0092 (9)	−0.0011 (9)
O124	0.0218 (11)	0.0422 (13)	0.0172 (11)	0.0068 (9)	0.0049 (9)	−0.0006 (9)
N11	0.0169 (12)	0.0299 (14)	0.0162 (13)	0.0029 (10)	0.0051 (10)	0.0004 (10)
N13	0.0186 (12)	0.0250 (13)	0.0154 (12)	0.0029 (10)	0.0050 (10)	−0.0023 (10)
N15	0.0216 (13)	0.0309 (15)	0.0175 (13)	0.0009 (11)	0.0057 (10)	−0.0024 (11)
N16	0.0186 (12)	0.0354 (15)	0.0157 (13)	0.0044 (11)	0.0050 (10)	−0.0003 (11)
N121	0.0161 (12)	0.0342 (15)	0.0147 (13)	0.0018 (10)	0.0043 (10)	−0.0018 (11)
C12	0.0132 (13)	0.0237 (15)	0.0167 (15)	0.0007 (11)	0.0035 (11)	0.0027 (12)
C14	0.0183 (15)	0.0210 (15)	0.0165 (15)	−0.0029 (12)	0.0047 (12)	0.0017 (12)
C15	0.0150 (14)	0.0221 (15)	0.0156 (14)	−0.0003 (11)	0.0057 (11)	0.0011 (12)
C16	0.0184 (14)	0.0191 (15)	0.0172 (15)	−0.0013 (11)	0.0069 (12)	0.0028 (11)
C122	0.0210 (15)	0.0319 (17)	0.0174 (15)	0.0034 (13)	0.0076 (12)	−0.0033 (13)
C123	0.0215 (15)	0.0391 (19)	0.0207 (16)	0.0049 (14)	0.0083 (13)	0.0014 (14)
C125	0.0183 (14)	0.0326 (18)	0.0185 (16)	0.0029 (13)	0.0047 (12)	−0.0018 (13)
C126	0.0137 (14)	0.045 (2)	0.0208 (16)	0.0006 (13)	0.0023 (12)	0.0022 (14)
O1	0.0385 (14)	0.0480 (16)	0.0317 (14)	0.0030 (11)	−0.0015 (11)	0.0038 (11)

Geometric parameters (Å, º)

O4—C4	1.225 (3)	O15—N15	1.286 (3)
O5—N5	1.284 (3)	O124—C123	1.434 (3)
O24—C23	1.429 (3)	O124—C125	1.435 (3)
O24—C25	1.435 (3)	N11—C12	1.327 (3)
N1—C2	1.323 (3)	N11—C16	1.339 (3)
N1—C6	1.344 (3)	N13—C12	1.368 (3)
N3—C2	1.370 (3)	N13—C14	1.397 (3)
N3—C4	1.384 (3)	N13—H13	0.88
N3—H3	0.88	N15—C15	1.341 (3)
N5—C5	1.337 (3)	N16—C16	1.318 (3)
N6—C6	1.317 (3)	N16—H16A	0.88
N6—H6A	0.88	N16—H16B	0.88
N6—H6B	0.88	N121—C12	1.346 (3)
N21—C2	1.330 (3)	N121—C122	1.461 (3)
N21—C26	1.469 (3)	N121—C126	1.477 (3)
N21—C22	1.470 (3)	C14—C15	1.452 (4)
C4—C5	1.451 (4)	C15—C16	1.451 (4)
C5—C6	1.455 (4)	C122—C123	1.501 (4)
C22—C23	1.508 (4)	C122—H22C	0.99
C22—H22A	0.99	C122—H22D	0.99
C22—H22B	0.99	C123—H23C	0.99
C23—H23A	0.99	C123—H23D	0.99
C23—H23B	0.99	C125—C126	1.499 (4)
C25—C26	1.518 (4)	C125—H25C	0.99
C25—H25A	0.99	C125—H25D	0.99
C25—H25B	0.99	C126—H26C	0.99
C26—H26A	0.99	C126—H26D	0.99
C26—H26B	0.99	O1—H1A	0.89
O14—C14	1.222 (3)	O1—H1B	1.19
C23—O24—C25	109.6 (2)	C12—N11—C16	118.4 (2)
C2—N1—C6	119.2 (2)	C12—N13—C14	123.3 (2)
C2—N3—C4	124.2 (2)	C12—N13—H13	118.3
C2—N3—H3	117.9	C14—N13—H13	118.3
C4—N3—H3	117.9	O15—N15—C15	116.4 (2)
O5—N5—C5	117.6 (2)	C16—N16—H16A	120.0
C6—N6—H6A	120.0	C16—N16—H16B	120.0
C6—N6—H6B	120.0	H16A—N16—H16B	120.0
H6A—N6—H6B	120.0	C12—N121—C122	124.4 (2)
C2—N21—C26	120.6 (2)	C12—N121—C126	118.7 (2)
C2—N21—C22	124.9 (2)	C122—N121—C126	114.0 (2)
C26—N21—C22	113.5 (2)	N11—C12—N121	118.3 (2)
N1—C2—N21	119.0 (3)	N11—C12—N13	122.9 (2)
N1—C2—N3	122.0 (2)	N121—C12—N13	118.8 (2)
N21—C2—N3	119.0 (2)	O14—C14—N13	118.8 (2)
O4—C4—N3	119.9 (2)	O14—C14—C15	126.6 (3)
O4—C4—C5	125.7 (2)	N13—C14—C15	114.6 (2)
N3—C4—C5	114.4 (2)	N15—C15—C16	127.3 (2)
N5—C5—C4	115.2 (2)	N15—C15—C14	115.1 (2)
N5—C5—C6	126.9 (2)	C16—C15—C14	117.6 (2)
C4—C5—C6	117.8 (2)	N16—C16—N11	116.3 (2)
N6—C6—N1	117.0 (2)	N16—C16—C15	120.7 (2)
N6—C6—C5	120.9 (2)	N11—C16—C15	123.0 (2)
N1—C6—C5	122.1 (2)	N121—C122—C123	110.2 (2)
N21—C22—C23	109.4 (2)	N121—C122—H22C	109.6
N21—C22—H22A	109.8	C123—C122—H22C	109.6
C23—C22—H22A	109.8	N121—C122—H22D	109.6
N21—C22—H22B	109.8	C123—C122—H22D	109.6
C23—C22—H22B	109.8	H22C—C122—H22D	108.1
H22A—C22—H22B	108.2	O124—C123—C122	111.8 (2)
O24—C23—C22	111.7 (2)	O124—C123—H23C	109.3
O24—C23—H23A	109.3	C122—C123—H23C	109.3
C22—C23—H23A	109.3	O124—C123—H23D	109.3
O24—C23—H23B	109.3	C122—C123—H23D	109.3
C22—C23—H23B	109.3	H23C—C123—H23D	107.9
H23A—C23—H23B	107.9	O124—C125—C126	110.3 (2)
O24—C25—C26	110.6 (2)	O124—C125—H25C	109.6
O24—C25—H25A	109.5	C126—C125—H25C	109.6
C26—C25—H25A	109.5	O124—C125—H25D	109.6
O24—C25—H25B	109.5	C126—C125—H25D	109.6
C26—C25—H25B	109.5	H25C—C125—H25D	108.1
H25A—C25—H25B	108.1	N121—C126—C125	110.7 (2)
N21—C26—C25	109.9 (2)	N121—C126—H26C	109.5
N21—C26—H26A	109.7	C125—C126—H26C	109.5
C25—C26—H26A	109.7	N121—C126—H26D	109.5
N21—C26—H26B	109.7	C125—C126—H26D	109.5
C25—C26—H26B	109.7	H26C—C126—H26D	108.1
H26A—C26—H26B	108.2	H1A—O1—H1B	99.4
C123—O124—C125	109.3 (2)
C6—N1—C2—N21	−178.5 (3)	C16—N11—C12—N121	−177.8 (3)
C6—N1—C2—N3	0.9 (4)	C16—N11—C12—N13	2.0 (4)
C26—N21—C2—N1	−5.2 (4)	C122—N121—C12—N11	−170.3 (3)
C22—N21—C2—N1	−173.2 (3)	C126—N121—C12—N11	−10.9 (4)
C26—N21—C2—N3	175.4 (2)	C122—N121—C12—N13	9.9 (4)
C22—N21—C2—N3	7.5 (4)	C126—N121—C12—N13	169.3 (3)
C4—N3—C2—N1	3.1 (4)	C14—N13—C12—N11	−4.5 (4)
C4—N3—C2—N21	−177.6 (3)	C14—N13—C12—N121	175.3 (2)
C2—N3—C4—O4	174.6 (3)	C12—N13—C14—O14	−175.7 (3)
C2—N3—C4—C5	−5.3 (4)	C12—N13—C14—C15	4.6 (4)
O5—N5—C5—C4	−179.1 (2)	O15—N15—C15—C16	0.2 (4)
O5—N5—C5—C6	−1.6 (4)	O15—N15—C15—C14	−179.3 (2)
O4—C4—C5—N5	1.8 (4)	O14—C14—C15—N15	−2.8 (4)
N3—C4—C5—N5	−178.4 (2)	N13—C14—C15—N15	176.9 (2)
O4—C4—C5—C6	−176.0 (3)	O14—C14—C15—C16	177.7 (3)
N3—C4—C5—C6	3.8 (4)	N13—C14—C15—C16	−2.7 (4)
C2—N1—C6—N6	178.6 (2)	C12—N11—C16—N16	179.2 (3)
C2—N1—C6—C5	−2.1 (4)	C12—N11—C16—C15	−0.2 (4)
N5—C5—C6—N6	1.4 (4)	N15—C15—C16—N16	1.8 (4)
C4—C5—C6—N6	179.0 (2)	C14—C15—C16—N16	−178.7 (3)
N5—C5—C6—N1	−177.9 (3)	N15—C15—C16—N11	−178.9 (3)
C4—C5—C6—N1	−0.3 (4)	C14—C15—C16—N11	0.6 (4)
C2—N21—C22—C23	−139.7 (3)	C12—N121—C122—C123	−151.3 (3)
C26—N21—C22—C23	51.6 (3)	C126—N121—C122—C123	48.5 (3)
C25—O24—C23—C22	61.8 (3)	C125—O124—C123—C122	62.2 (3)
N21—C22—C23—O24	−56.0 (3)	N121—C122—C123—O124	−54.6 (3)
C23—O24—C25—C26	−61.2 (3)	C123—O124—C125—C126	−62.3 (3)
C2—N21—C26—C25	138.8 (3)	C12—N121—C126—C125	149.0 (3)
C22—N21—C26—C25	−52.0 (3)	C122—N121—C126—C125	−49.6 (3)
O24—C25—C26—N21	56.0 (3)	O124—C125—C126—N121	55.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N5^i	0.89	2.08	2.916 (3)	157
O1—H1B···O4	1.19	2.37	3.423 (3)	146
N3—H3···O15^ii	0.88	2.04	2.882 (3)	161
N6—H6A···O124^iii	0.88	1.97	2.835 (3)	166
N6—H6B···O5	0.88	1.98	2.623 (3)	129
N6—H6B···O14	0.88	2.24	2.943 (3)	137
N13—H13···O5	0.88	2.03	2.838 (3)	152
N16—H16A···O24^iv	0.88	2.00	2.875 (3)	173
N16—H16B···O15	0.88	1.96	2.605 (3)	129
N16—H16B···O4^v	0.88	2.49	3.176 (3)	136
C22—H22B···O15^ii	0.99	2.31	3.300 (4)	175
C122—H22D···O5	0.99	2.49	3.447 (3)	162

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