A hydrogen-bonded ribbon in 6-amino-3-methyl-5-nitroso-2-(pyrrol­idin-1-yl)pyrimidin-4(3H)-one monohydrate and hydrogen-bonded sheets in 6-amino-2-dimethyl­amino-3-methyl-5-nitroso­pyrimidin-4(3H)-one monohydrate

In each of 6-amino-3-methyl-5-nitroso-2-(pyrrolidin-1-yl)pyri­m­idin-4(3H)-one monohydrate, C₉H₁₃N₅O₂·H₂O, (I), and 6-amino-2-dimethyl­amino-3-methyl-5-nitroso­pyrimidin-4(3H)-one monohydrate, C₇H₁₁N₅O₂·H₂O, (II), the inter­atomic distances indicate significant polarization of the electronic structures of the pyrimidinone mol­ecules. In each compound, the organic component contains an intra­molecular N-H...O hydrogen bond. The mol­ecular components in (I) are linked by a combination of two-centre O-H...O, O-H...N and N-H...O hydrogen bonds and a three-centre O-H...(NO) hydrogen bond to form a broad ribbon containing five distinct ring motifs. In compound (II), three inter­molecular hydrogen bonds, one each of the O-H...O, O-H...N and N-H...O types, link the mol­ecules into sheets containing equal numbers of centrosymmetric R₄⁴(10) and R₁₀⁸(34) rings.

S1. Comment

We report here the crystal structures of 6-amino-3-methyl-5-nitroso-2-(pyrrolidin-1-yl)pyrimidin-4(3H)-one monohydrate, (I), and 6-amino-2-dimethylamino-3-methyl-5-nitrosopyrimidin-4(3H)-one monohydrate, (II) (Figs. 1 and 2), and compare them with those of 6-amino-3-methyl-2-morpholino-5-nitrosopyrimidin-4(3H)-one, (III) (Orozco et al., 2008), and of the amino acid derivatives, (IV)–(VIII) (Low et al., 1997, 1999, 2000). Our interest in the structures of this class of compounds was aroused by the observation that the structures of the amino acid derivatives (IV)–(VIII) are all characterized by short intermolecular O—H···O hydrogen bonds, with the carboxyl group acting as the donor and the nitrosyl O atom acting as the acceptor, and in which the O···O distances are all ca 2.50 Å. At the same time, the intramolecular bond distances show a number of unusual values, and a combination of database analysis and molecular modelling led to an interpretation of the relationship between the unusual intramolecular bond lengths and the very short intermolecular hydrogen bonds in terms of highly polarized electronic structures (Low et al., 2000).

Although the pyrimidinone ring in (III) is effectively planar (Orozco et al., 2008), the rings in both (I) and (II) show a modest distortion towards a twist-boat conformation. The ring-puckering parameters (Cremer & Pople, 1975) are θ = 99.5 (1)° and ϕ = 273.9 (10)° for (I), and θ = 87.1 (10)° and ϕ = 100.2 (11)° for (II); the ideal values, for rings having all bond distances equal, are θ = 90° and ϕ = (60k + 30)°, where k represents an integer. In both compounds, the ring atoms N2 and C5 are displaced to one side of the mean ring plane, and atoms N3 and C6 are displaced to the opposite side. While the ring-atom displacements are modest, in the range 0.04–0.07 Å, the displacements of the exocyclic substituent atoms are much greater, with the maximum displacement being experienced by atom C31 in each case, 0.453 (2) Å in (I) and 0.619 (2) Å in (II). The twist-boat conformation is not uncommon amongst highly substituted pyrimidines of this general type (Quesada et al., 2002; Melguizo et al., 2003). The the boat conformation has also been observed (Quesada et al., 2004), as well as the expected planar forms.

Despite the non-planarity of the pyrimidinone rings, the bond distances in (I) and (II) (Table 1) provide evidence for polarization of the electronic structure, but in a manner which differs slightly from that in (III). The key indicators for compounds of this type have been identified (Low et al., 2000), as (i) the C—N distances in the sequence N21—C2—N1—C6—N6; (ii) the similarity of the distances C4—C5 and C5—C6; (iii) the distances C5—N5 and N5—O5 and, perhaps most importantly, the difference between these distances. On this basis, the extent of the polarization can be identified as greatest in (II) and least in (III), with the extent of the delocalization greater in (I) and (II) than in (III), all indicating the importance of the polarized forms (Ia) and (IIa) in addition to the localized forms (I) and (II), compared with form (IIIa) (Orozco et al., 2008). Accordingly, in both (I) and (II) hydrogen bonds involving atom N6 as the donor or atom O5 as the acceptor can be regarded as charge-assisted hydrogen bonds (Gilli et al., 1994). In (II), where all of the intermolecular hydrogen bonds are of the two-centre type, those involving atoms N6 or O5 exhibit almost linear D—H···A fragments.

Compounds (I) and (II) both crystallize as monohydrates, while (III) crystallizes in the unsolvated form (Orozco et al., 2008). Of the amino acid derivatives, (IV) crystallizes as a dihydrate (Low et al., 1997) and (VII) as a monohydrate (Low et al., 2000), while (V), (VI) and (VIII) all crystallize in the unsolvated forms (Low et al., 1999, 2000).

In each of (I) and (II), the organic components contain an intramolecular N—H···O hydrogen bond forming an S(6) motif (Bernstein et al., 1995) (Table 2), but the remaining details of the hydrogen bonding are very different in the two compounds. In (I), the water molecule acts as a single acceptor, in an N—H···O hydrogen bond, and as a triple donor, forming a two-centre O—H···N hydrogen bond within the selected asymmetric unit (Fig. 1) and a three-centre O—H···(N,O) hydrogen bond, which serves to link two pyrimidinone molecules related by translation (Fig. 3). The hydrogen bonds involving the water molecules, together with the intramolecular N—H···O hydrogen bond, thus generate a chain of edge-fused S(6), R²₂(6) and R²₂(7) rings running parallel to the [010] direction. Pairs of antiparallel chains, related to one another by inversion, are linked by an intermolecular N—H···O hydrogen bond involving only the organic components, so generating a broad ribbon. The central core of this ribbon consists of R²₂(4) rings centred at (1/2, n, 1), where n represents an integer, alternating with R⁵₆(14) rings centred at (1/2, n + 1/2, 1), where n again represents an integer. This central core is flanked by two outer strips, each containing S(6), R²₂(6) and R²₂(7) rings, so that, overall, the ribbon contains five different ring motifs (Fig. 3).

The hydrogen bonding in (II) is simpler than that in (I) (Table 2). In particular, the water molecule does not act as an acceptor of hydrogen bonds. As a double donor, it forms only two-centre hydrogen bonds, one each of O—H···N and O—H···O types, which link a pair of organic components which are related to one another by inversion, thus forming a centrosymmetric four-molecule aggregate centred at (1/2, 0, 1/2) and containing an R₄⁴(10) motif (Fig. 2). This aggregate can conveniently be regarded as the basic building block for the supramolecular structure. The intermolecular N—H···O hydrogen bond links the four-molecule aggregate centred at (1/2, 0, 1/2) to four similar aggregates centred at (0, 1/2, 0), (0, -1/2, 0), (1, 1/2, 1) and (1, -1/2, 1), so generating a sheet parallel to (101) and containing S(6), R₄⁴(10) and R₁₀⁸(34) rings (Fig. 4). Thus, although there are fewer independent hydrogen bonds in the structure of (II) than in (I), the hydrogen-bonded supramolecular structure of (II) is two-dimensional, as opposed to the one-dimensional hydrogen-bonded structure of (I).

In each of (I) and (II), the water component is firmly embedded in the hydrogen-bonded structure. By contrast, (III) contains no water component and its very simple hydrogen-bonded structure is built from just two intermolecular N—H···O hydrogen bonds, in which the ketonic and morpholine O atoms are the acceptors, giving a sheet containing only S(6) and R₄⁴(26) rings. Had the morpholine O atom not been available to accept a hydrogen bond in the structure of (III), then, without further reorganization, the hydrogen-bonded structure would consist of simple C(6) chains, with one of the amino N—H bonds finding no acceptor site. This suggests that the presence of water in (I) and (II), versus its absence in (III), may be connected with the overall ratio of hydrogen-bond donors and acceptors.

Three-dimensional hydrogen-bonded structures are formed by each of (IV)–(VI) and (VIII), despite the fact that, whereas (IV) crystallizes as a dihydrate (Low et al., 1997), the other three compounds all crystallize in solvent-free form (Low et al., 1999, 2000), while the monohydrate, (VII), forms only a two-dimensional hydrogen-bonded structure (Low et al., 2000). The contrast between the two-dimensional structure of (VII) and the three-dimensional structures of (V) and (VI) is both striking and unexpected in view of the considerably greater number of potential hydrogen-bonding donor and acceptor sites available in the asymmetric unit of (VII) compared with (V) and (VI).

S2. Experimental

To a suspension of 6-amino-2-methylsulfanyl-3-methyl-5-nitrosopyrimidin-4(3H)-one (25 mmol) in methanol (80 ml), the appropriate secondary amine (100 mmol), pyrrolidine for (I) and dimethylamine for (II), was added dropwise with magnetic stirring. The reactions proceeded for 6 h with a change of colour from blue to violet and the liberation of methanethiol. The resulting solid products were collected by filtration and washed with cold ethanol, and then recrystallized from dimethylformamide–water (3:1 v/v) to give red–violet crystals suitable for single-crystal X-ray diffraction. Analysis for (I): 87% yield, m.p. 484 K; MS (70 eV) m/z (%) 223 (M⁺, 100), 209 (4), 150 (20), 123 (17), 97 (24). Analysis for (II): 52% yield, m.p. 504 K; MS (70 eV) m/z (%) 197 (M⁺, 90), 183 (32), 152 (56), 92 (100), 42 (73).

S3. Refinement

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 = 0.88 Å, and with U_iso(H) = kU_eq(C,N), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 otherwise. Water H atoms were permitted to ride at the positions deduced from the difference maps, with O—H = 0.86 Å and with U_iso(H) = 1.5U_eq(O).

Computing details

For both compounds, data collection: COLLECT (Nonius, 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: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular components of compound (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. The hydrogen bond linking the two components within the selected asymmetric unit is indicated by a dashed line.
	Fig. 2. The molecular components of compound (II), 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. The hydrogen bonds linking the components into centrosymmetric four-molecule aggregates are indicated by dashed lines. Atoms labelled with the suffix a or b are at the symmetry position (1 - x, -y, 1 - z).
	Fig. 3. Part of the crystal structure of (I), showing the formation of a hydrogen-bonded ribbon running parallel to the [010] direction and containing five distinct types of ring. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms labelled with an asterisk (*), a hash symbol (#) or a dollar sign ($) are at the symmetry positions (x, 1 + y, z), (1 - x, -y, 2 - z) and (1 - x, 1 - y, 2 - z), respectively.
	Fig. 4. A stereoview of part of the crystal structure of (II), showing the formation of a hydrogen-bonded sheet parallel to (101) and containing three types of ring. For the sake of clarity, H atoms bonded to C atoms have been omitted.

(I) 6-amino-3-methyl-5-nitroso-2-(pyrrolidin-1- yl)pyrimidin-4(3H)-one monohydrate

Crystal data

C9H13N5O2·H2O	Z = 2
Mr = 241.26	F(000) = 256
Triclinic, P1	Dx = 1.531 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9734 (18) Å	Cell parameters from 2051 reflections
b = 8.452 (2) Å	θ = 2.8–26.1°
c = 8.9099 (2) Å	µ = 0.12 mm^−1
α = 75.158 (9)°	T = 120 K
β = 84.727 (7)°	Block, red-violet
γ = 64.436 (16)°	0.41 × 0.18 × 0.15 mm
V = 523.46 (19) Å^3

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	2051 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1629 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
Detector resolution: 9.091 pixels mm^-1	θmax = 26.1°, θmin = 2.8°
ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −10→10
Tmin = 0.953, Tmax = 0.983	l = −11→11
12137 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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.116	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.057P)^2 + 0.2677P] where P = (Fo^2 + 2Fc^2)/3
2051 reflections	(Δ/σ)max = 0.001
155 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

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

	x	y	z	Uiso*/Ueq
N1	0.2670 (2)	0.3989 (2)	0.54705 (17)	0.0150 (4)
C2	0.2106 (2)	0.3906 (2)	0.4150 (2)	0.0137 (4)
N3	0.1887 (2)	0.2428 (2)	0.39906 (17)	0.0150 (4)
C4	0.2614 (3)	0.0779 (2)	0.5103 (2)	0.0152 (4)
C5	0.3364 (3)	0.0822 (2)	0.6502 (2)	0.0157 (4)
C6	0.3239 (3)	0.2514 (2)	0.6648 (2)	0.0153 (4)
C31	0.0700 (3)	0.2525 (3)	0.2780 (2)	0.0199 (4)
H31A	−0.0271	0.3760	0.2462	0.030*
H31B	0.0122	0.1690	0.3186	0.030*
H31C	0.1453	0.2190	0.1884	0.030*
O4	0.2530 (2)	−0.05311 (18)	0.48645 (15)	0.0223 (3)
N5	0.4112 (2)	−0.0779 (2)	0.75216 (18)	0.0187 (4)
O5	0.4785 (2)	−0.08538 (18)	0.87926 (15)	0.0243 (4)
N6	0.3725 (2)	0.2663 (2)	0.79564 (17)	0.0189 (4)
H6B	0.3669	0.3703	0.8031	0.023*
H6A	0.4107	0.1723	0.8758	0.023*
N21	0.1696 (2)	0.5355 (2)	0.29804 (16)	0.0153 (4)
C22	0.1742 (3)	0.5409 (3)	0.1302 (2)	0.0186 (4)
H22A	0.0517	0.5621	0.0919	0.022*
H22B	0.2698	0.4266	0.1091	0.022*
C23	0.2225 (3)	0.6978 (3)	0.0555 (2)	0.0198 (4)
H23A	0.1673	0.7567	−0.0506	0.024*
H23B	0.3588	0.6575	0.0500	0.024*
C24	0.1381 (3)	0.8246 (3)	0.1626 (2)	0.0205 (4)
H24A	0.0021	0.8935	0.1448	0.025*
H24B	0.1956	0.9103	0.1489	0.025*
C25	0.1839 (3)	0.6955 (2)	0.3222 (2)	0.0169 (4)
H25A	0.3109	0.6647	0.3573	0.020*
H25B	0.0937	0.7480	0.3997	0.020*
O41	0.39271 (19)	−0.39899 (18)	0.72240 (15)	0.0216 (3)
H41A	0.3933	−0.3005	0.7318	0.032*
H41B	0.3505	−0.3738	0.6298	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0186 (8)	0.0154 (8)	0.0105 (8)	−0.0071 (7)	−0.0012 (6)	−0.0023 (6)
C2	0.0136 (9)	0.0146 (9)	0.0120 (9)	−0.0051 (7)	−0.0006 (7)	−0.0027 (7)
N3	0.0182 (8)	0.0160 (8)	0.0109 (8)	−0.0075 (7)	−0.0030 (6)	−0.0017 (6)
C4	0.0167 (10)	0.0157 (9)	0.0136 (9)	−0.0076 (8)	0.0009 (7)	−0.0030 (7)
C5	0.0171 (9)	0.0160 (9)	0.0129 (9)	−0.0068 (8)	−0.0002 (7)	−0.0019 (7)
C6	0.0157 (9)	0.0174 (9)	0.0119 (9)	−0.0071 (8)	0.0009 (7)	−0.0024 (7)
C31	0.0238 (11)	0.0217 (10)	0.0160 (10)	−0.0117 (9)	−0.0061 (8)	−0.0018 (8)
O4	0.0337 (8)	0.0173 (7)	0.0179 (7)	−0.0124 (6)	−0.0062 (6)	−0.0025 (6)
N5	0.0223 (9)	0.0192 (8)	0.0141 (8)	−0.0093 (7)	−0.0028 (6)	−0.0011 (6)
O5	0.0378 (9)	0.0239 (8)	0.0124 (7)	−0.0156 (7)	−0.0090 (6)	0.0018 (6)
N6	0.0292 (9)	0.0173 (8)	0.0114 (8)	−0.0115 (7)	−0.0036 (6)	−0.0007 (6)
N21	0.0206 (8)	0.0163 (8)	0.0088 (8)	−0.0082 (7)	−0.0006 (6)	−0.0017 (6)
C22	0.0264 (11)	0.0211 (10)	0.0085 (9)	−0.0106 (8)	−0.0013 (7)	−0.0023 (7)
C23	0.0251 (11)	0.0211 (10)	0.0119 (9)	−0.0103 (8)	−0.0030 (8)	0.0002 (8)
C24	0.0283 (11)	0.0168 (10)	0.0133 (10)	−0.0087 (8)	−0.0016 (8)	0.0005 (7)
C25	0.0221 (10)	0.0146 (9)	0.0131 (9)	−0.0077 (8)	−0.0004 (7)	−0.0019 (7)
O41	0.0304 (8)	0.0174 (7)	0.0172 (7)	−0.0105 (6)	−0.0045 (6)	−0.0021 (5)

Geometric parameters (Å, º)

N1—C2	1.326 (2)	N6—H6A	0.8800
N1—C6	1.338 (2)	N21—C25	1.475 (2)
C2—N21	1.325 (2)	N21—C22	1.482 (2)
C2—N3	1.376 (2)	C22—C23	1.514 (3)
N3—C4	1.401 (2)	C22—H22A	0.9900
N3—C31	1.463 (2)	C22—H22B	0.9900
C4—O4	1.209 (2)	C23—C24	1.516 (3)
C4—C5	1.446 (3)	C23—H23A	0.9900
C5—N5	1.336 (2)	C23—H23B	0.9900
C5—C6	1.429 (3)	C24—C25	1.518 (3)
C6—N6	1.313 (2)	C24—H24A	0.9900
C31—H31A	0.9800	C24—H24B	0.9900
C31—H31B	0.9800	C25—H25A	0.9900
C31—H31C	0.9800	C25—H25B	0.9900
N5—O5	1.273 (2)	O41—H41A	0.8600
N6—H6B	0.8800	O41—H41B	0.8600
C2—N1—C6	118.95 (16)	C2—N21—C22	126.77 (15)
N21—C2—N1	116.65 (16)	C25—N21—C22	110.46 (14)
N21—C2—N3	120.68 (16)	N21—C22—C23	103.59 (15)
N1—C2—N3	122.64 (16)	N21—C22—H22A	111.0
C2—N3—C4	121.34 (15)	C23—C22—H22A	111.0
C2—N3—C31	122.82 (15)	N21—C22—H22B	111.0
C4—N3—C31	115.39 (15)	C23—C22—H22B	111.0
O4—C4—N3	119.54 (16)	H22A—C22—H22B	109.0
O4—C4—C5	125.16 (17)	C22—C23—C24	103.53 (15)
N3—C4—C5	115.27 (16)	C22—C23—H23A	111.1
N5—C5—C6	127.53 (17)	C24—C23—H23A	111.1
N5—C5—C4	114.27 (16)	C22—C23—H23B	111.1
C6—C5—C4	118.20 (16)	C24—C23—H23B	111.1
N6—C6—N1	117.27 (17)	H23A—C23—H23B	109.0
N6—C6—C5	120.51 (17)	C23—C24—C25	102.45 (15)
N1—C6—C5	122.20 (16)	C23—C24—H24A	111.3
N3—C31—H31A	109.5	C25—C24—H24A	111.3
N3—C31—H31B	109.5	C23—C24—H24B	111.3
H31A—C31—H31B	109.5	C25—C24—H24B	111.3
N3—C31—H31C	109.5	H24A—C24—H24B	109.2
H31A—C31—H31C	109.5	N21—C25—C24	103.29 (15)
H31B—C31—H31C	109.5	N21—C25—H25A	111.1
O5—N5—C5	118.24 (16)	C24—C25—H25A	111.1
C6—N6—H6B	120.0	N21—C25—H25B	111.1
C6—N6—H6A	120.0	C24—C25—H25B	111.1
H6B—N6—H6A	120.0	H25A—C25—H25B	109.1
C2—N21—C25	119.18 (15)	H41A—O41—H41B	104.8
C6—N1—C2—N21	−174.82 (16)	C4—C5—C6—N6	173.03 (17)
C6—N1—C2—N3	7.2 (3)	N5—C5—C6—N1	171.40 (18)
N21—C2—N3—C4	168.53 (16)	C4—C5—C6—N1	−8.4 (3)
N1—C2—N3—C4	−13.6 (3)	C6—C5—N5—O5	0.9 (3)
N21—C2—N3—C31	−19.5 (3)	C4—C5—N5—O5	−179.22 (16)
N1—C2—N3—C31	158.34 (17)	N1—C2—N21—C25	−1.7 (2)
C2—N3—C4—O4	−173.95 (17)	N3—C2—N21—C25	176.31 (16)
C31—N3—C4—O4	13.5 (2)	N1—C2—N21—C22	154.83 (17)
C2—N3—C4—C5	8.1 (2)	N3—C2—N21—C22	−27.2 (3)
C31—N3—C4—C5	−164.41 (16)	C2—N21—C22—C23	−149.59 (18)
O4—C4—C5—N5	4.6 (3)	C25—N21—C22—C23	8.6 (2)
N3—C4—C5—N5	−177.62 (16)	N21—C22—C23—C24	−30.59 (19)
O4—C4—C5—C6	−175.57 (18)	C22—C23—C24—C25	41.04 (19)
N3—C4—C5—C6	2.3 (2)	C2—N21—C25—C24	176.79 (16)
C2—N1—C6—N6	−177.61 (17)	C22—N21—C25—C24	16.7 (2)
C2—N1—C6—C5	3.8 (3)	C23—C24—C25—N21	−35.16 (19)
N5—C5—C6—N6	−7.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6A···O5	0.88	2.00	2.630 (2)	128
N6—H6A···O5^i	0.88	2.25	2.989 (2)	142
N6—H6B···O41^ii	0.88	1.99	2.808 (2)	154
O41—H41A···N5	0.86	2.00	2.860 (2)	177
O41—H41B···O4	0.86	2.48	2.946 (2)	114
O41—H41B···N1^iii	0.86	2.57	3.082 (2)	119

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

(II) 6-amino-2-dimethylamino-3-methyl-5-nitrosopyrimidin-4(3H)-one monohydrate

Crystal data

C7H11N5O2·H2O	F(000) = 456
Mr = 215.22	Dx = 1.503 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1873 reflections
a = 11.8125 (6) Å	θ = 2.9–26.1°
b = 7.1372 (7) Å	µ = 0.12 mm^−1
c = 11.8588 (19) Å	T = 120 K
β = 107.910 (4)°	Block, red-violet
V = 951.34 (19) Å^3	0.16 × 0.16 × 0.12 mm
Z = 4

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	1873 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1304 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
Detector resolution: 9.091 pixels mm^-1	θmax = 26.1°, θmin = 2.9°
ϕ and ω scans	h = −13→14
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −8→8
Tmin = 0.971, Tmax = 0.986	l = −14→14
9096 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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.109	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0454P)^2 + 0.4921P] where P = (Fo^2 + 2Fc^2)/3
1873 reflections	(Δ/σ)max = 0.001
139 parameters	Δρmax = 0.22 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
N1	0.57117 (14)	0.2239 (2)	0.01496 (15)	0.0162 (4)
C2	0.68354 (18)	0.1716 (3)	0.04242 (18)	0.0158 (5)
N3	0.75402 (14)	0.1340 (2)	0.15621 (15)	0.0166 (4)
C4	0.70340 (19)	0.1162 (3)	0.24691 (18)	0.0181 (5)
C5	0.57916 (18)	0.1618 (3)	0.21776 (18)	0.0166 (5)
C6	0.51939 (18)	0.2291 (3)	0.10021 (19)	0.0170 (5)
C31	0.88350 (18)	0.1612 (3)	0.1939 (2)	0.0218 (5)
H31A	0.9230	0.0397	0.1967	0.033*
H31B	0.9092	0.2187	0.2727	0.033*
H31C	0.9048	0.2433	0.1373	0.033*
O4	0.76681 (13)	0.0702 (2)	0.34577 (13)	0.0236 (4)
N5	0.53510 (15)	0.1451 (3)	0.30806 (15)	0.0213 (4)
O5	0.42701 (13)	0.1931 (2)	0.29178 (13)	0.0252 (4)
N6	0.40982 (15)	0.2914 (2)	0.07244 (16)	0.0208 (4)
H6A	0.3751	0.2896	0.1283	0.025*
H6B	0.3752	0.3325	0.0000	0.025*
N21	0.73167 (14)	0.1569 (2)	−0.04472 (15)	0.0181 (4)
C23	0.66686 (19)	0.2309 (3)	−0.16106 (18)	0.0231 (5)
H23A	0.6042	0.1426	−0.2021	0.035*
H23B	0.7218	0.2486	−0.2075	0.035*
H23C	0.6309	0.3515	−0.1519	0.035*
C22	0.82560 (19)	0.0232 (3)	−0.0445 (2)	0.0256 (5)
H22A	0.8997	0.0910	−0.0371	0.038*
H22B	0.8023	−0.0480	−0.1188	0.038*
H22C	0.8378	−0.0631	0.0224	0.038*
O41	0.64952 (15)	0.0890 (2)	0.56867 (14)	0.0393 (5)
H41A	0.6228	0.0906	0.4925	0.059*
H41B	0.6212	−0.0029	0.5985	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0154 (10)	0.0193 (9)	0.0143 (9)	−0.0004 (7)	0.0053 (7)	−0.0001 (7)
C2	0.0172 (11)	0.0123 (10)	0.0182 (11)	−0.0030 (8)	0.0057 (9)	0.0001 (8)
N3	0.0142 (9)	0.0171 (9)	0.0177 (9)	−0.0001 (7)	0.0036 (7)	0.0019 (8)
C4	0.0229 (12)	0.0127 (11)	0.0173 (12)	−0.0024 (9)	0.0044 (9)	−0.0015 (9)
C5	0.0205 (12)	0.0139 (11)	0.0154 (11)	−0.0002 (9)	0.0054 (9)	0.0006 (9)
C6	0.0188 (12)	0.0140 (11)	0.0177 (11)	−0.0011 (9)	0.0050 (9)	−0.0022 (9)
C31	0.0155 (11)	0.0233 (12)	0.0249 (12)	−0.0013 (9)	0.0034 (9)	0.0009 (10)
O4	0.0247 (9)	0.0266 (9)	0.0167 (8)	0.0001 (7)	0.0022 (7)	0.0033 (7)
N5	0.0235 (11)	0.0217 (10)	0.0193 (10)	0.0005 (8)	0.0073 (8)	−0.0002 (8)
O5	0.0251 (9)	0.0297 (9)	0.0242 (9)	0.0047 (7)	0.0125 (7)	0.0030 (7)
N6	0.0189 (10)	0.0284 (10)	0.0168 (10)	0.0051 (8)	0.0078 (8)	0.0046 (8)
N21	0.0170 (9)	0.0208 (10)	0.0178 (9)	0.0009 (7)	0.0071 (8)	0.0012 (8)
C23	0.0204 (12)	0.0335 (13)	0.0160 (12)	0.0021 (10)	0.0064 (9)	0.0015 (10)
C22	0.0243 (12)	0.0278 (13)	0.0280 (13)	0.0055 (10)	0.0131 (10)	−0.0003 (10)
O41	0.0597 (12)	0.0352 (10)	0.0220 (9)	−0.0144 (9)	0.0110 (8)	0.0019 (8)

Geometric parameters (Å, º)

N1—C2	1.320 (3)	N5—O5	1.278 (2)
N1—C6	1.333 (3)	N6—H6A	0.8800
C2—N21	1.328 (3)	N6—H6B	0.8800
C2—N3	1.377 (3)	N21—C23	1.456 (3)
N3—C4	1.388 (3)	N21—C22	1.463 (3)
N3—C31	1.468 (3)	C23—H23A	0.9800
C4—O4	1.226 (2)	C23—H23B	0.9800
C4—C5	1.438 (3)	C23—H23C	0.9800
C5—N5	1.332 (3)	C22—H22A	0.9800
C5—C6	1.438 (3)	C22—H22B	0.9800
C6—N6	1.311 (3)	C22—H22C	0.9800
C31—H31A	0.9800	O41—H41A	0.8600
C31—H31B	0.9800	O41—H41B	0.8600
C31—H31C	0.9800
C2—N1—C6	118.81 (18)	H31B—C31—H31C	109.5
N1—C2—N21	117.99 (18)	O5—N5—C5	118.27 (17)
N1—C2—N3	123.80 (18)	C6—N6—H6A	117.3
N21—C2—N3	118.21 (18)	C6—N6—H6B	119.0
C2—N3—C4	120.18 (17)	H6A—N6—H6B	123.7
C2—N3—C31	122.12 (17)	C2—N21—C23	118.85 (17)
C4—N3—C31	115.66 (17)	C2—N21—C22	123.81 (17)
O4—C4—N3	118.91 (19)	C23—N21—C22	114.57 (17)
O4—C4—C5	124.7 (2)	N21—C23—H23A	109.5
N3—C4—C5	116.37 (18)	N21—C23—H23B	109.5
N5—C5—C4	114.12 (18)	H23A—C23—H23B	109.5
N5—C5—C6	127.78 (19)	N21—C23—H23C	109.5
C4—C5—C6	117.99 (18)	H23A—C23—H23C	109.5
N6—C6—N1	117.81 (19)	H23B—C23—H23C	109.5
N6—C6—C5	120.62 (19)	N21—C22—H22A	109.5
N1—C6—C5	121.52 (18)	N21—C22—H22B	109.5
N3—C31—H31A	109.5	H22A—C22—H22B	109.5
N3—C31—H31B	109.5	N21—C22—H22C	109.5
H31A—C31—H31B	109.5	H22A—C22—H22C	109.5
N3—C31—H31C	109.5	H22B—C22—H22C	109.5
H31A—C31—H31C	109.5	H41A—O41—H41B	112.2
C6—N1—C2—N21	176.20 (18)	N3—C4—C5—C6	−2.7 (3)
C6—N1—C2—N3	−4.7 (3)	C2—N1—C6—N6	176.25 (18)
N1—C2—N3—C4	11.9 (3)	C2—N1—C6—C5	−6.2 (3)
N21—C2—N3—C4	−169.02 (18)	N5—C5—C6—N6	3.1 (3)
N1—C2—N3—C31	−151.1 (2)	C4—C5—C6—N6	−172.75 (19)
N21—C2—N3—C31	28.0 (3)	N5—C5—C6—N1	−174.3 (2)
C2—N3—C4—O4	175.14 (19)	C4—C5—C6—N1	9.8 (3)
C31—N3—C4—O4	−20.8 (3)	C4—C5—N5—O5	176.07 (17)
C2—N3—C4—C5	−7.4 (3)	C6—C5—N5—O5	0.0 (3)
C31—N3—C4—C5	156.66 (18)	N1—C2—N21—C23	11.2 (3)
O4—C4—C5—N5	−1.8 (3)	N3—C2—N21—C23	−168.00 (18)
N3—C4—C5—N5	−179.11 (18)	N1—C2—N21—C22	−148.94 (19)
O4—C4—C5—C6	174.61 (19)	N3—C2—N21—C22	31.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6A···O5	0.88	1.97	2.641 (2)	132
N6—H6B···O4^i	0.88	2.01	2.874 (2)	168
O41—H41A···N5	0.86	2.15	2.995 (2)	168
O41—H41B···O5^ii	0.86	2.08	2.921 (2)	166

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