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In the title compound, 2C10H15N5O4·0.5H2O, there are two independent mol­ecules of the pyrimidinyl­isoleucine in general positions and a water mol­ecule lying on a twofold rotation axis. The bond lengths within the organic moieties demonstrate significant polarization of the electronic structure. Each of the organic mol­ecules participates in 12 intermolecular hydrogen bonds, of O—H...O and N—H...O types, while the water mol­ecule acts as a double donor and as a double acceptor of O—H...O hydrogen bonds. The organic components are linked by the hydrogen bonds into a single three-dimensional framework, reinforced by the water mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101002475/gg1043sup1.cif
Contains datablocks global, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101002475/gg1043IIsup2.hkl
Contains datablock II

CCDC reference: 164664

Comment top

The molecular and supramolecular structures of the nitrosopyrimidine derivatives of amino acids, (I), are characterized by several unexpected features (Low et al., 2000). The bond lengths are consistent with a marked polarization of the electronic charge, and there are very short intermolecular O—H···O hydrogen bonds involving the carboxyl group as donor and the nitrosyl O as acceptor, with O···O distances around 2.50 Å; where the amidic O acts as a hydrogen-bond acceptor, it does so only weakly. We have now investigated an analogous hydrated derivative, (II), formed by L-isoleucine [(2S,3S)-2-amino-3-methylpentanoic acid] in which the amino acid side chain is ortho to the C-nitroso group, rather than para to it as in (I): the molecular and supramolecular structures of (II) exhibit some significant differences compared with those of (I). \sch

Compound (II) crystallizes in space group C2 with two molecules in the asymmetric unit: in addition, there is a water molecule lying on a twofold rotation axis, so that the overall composition is (C10H15N5O4)4·H2O. The conformation of the acidic side chains (Table 1 and Fig. 1) and the hydrogen-bonding characteristics (Table 2) of the two independent organic molecules rule out the possibility of any additional symmetry: in particular, only molecule 1 (Fig. 1) forms hydrogen bonds with the water molecule.

The intramolecular distances for the two molecules are extremely similar, apart from Cn4—Cn5 and Cn5—Cn6 (n = 1, 2) which are both significantly longer in molecule 1: however, in each of the two individual molecules, these two distances are virtually identical. There are a number of metrical features which indicate the inadequacy of representation (2) for the electronic structure. Firstly, in the sequence of C—N bonds Nn2—Cn2—Nn3—Cn4—Nn4 (n = 1,2) it is not possible from the observed distances to assign Cn2—Nn3 as a double bond and the remainder as single bonds; indeed, in these sequences the shortest bonds are the exocyclic bonds Nn2—Cn2. Secondly, the bonds Cn4—Cn5 and Cn5—Cn6 cannot plausibly be assigned as double and single bonds, respectively: the Cn4—Cn5 distances are, in fact, similar to those for single bonds between two three-connected C atoms (Allen et al., 1987). Finally, the differences between the C—N and N—O distances in the C-nitroso fragment are small; in simple neutral compounds where there is no possibility of significant electronic delocalization these distances normally differ by at least 0.20 Å (Talberg, 1977; Schlemper et al., 1986) and the NO distance rarely exceeds 1.25 Å (Davis et al., 1965; Bauer & Andreassen, 1972; Talberg, 1977; Schlemper et al., 1986). These observations point to the importance of the contributions (IIa) and (IIb) to the electronic structure. By contrast, in compounds of type (I), (Low et al., 2000), forms analogous to (IIa) are important contributors to the electronic structures, whereas forms analogous to (IIb) are not. The importance of (IIb) in the title compound is demonstrated by the hydrogen-bonding behaviour, where the amidic O atoms O16 and O26 (Fig. 1) both act as triple acceptors (Table 2).

In each of the two independent molecules of (II) there is an intramolecular N—H···O hydrogen bond: in addition, each molecule acts as a sixfold donor of intermolecular hydrogen bonds and as a sixfold acceptor: finally the water molecule acts as a two fold donor and as a twofold acceptor. The resulting hydrogen-bonded supramolecular structure, a three-dimensional framework, is thus of considerable complexity: however, adoption of the sub-structure approach (Gregson et al., 2000) leads to a rather straightforward description in terms of a single chain motif and the connections between such chains.

Within the asymmetric unit atom N21 acts as hydrogen-bond donor to both N15 and O15 in a nearly planar three-centre hydrogen bond: likewise, N22 acts as donor, via H22B, to both N15 and O16 in a similar, but strictly planar system. In an entirely similar way, N11 at (x, y, z) acts as donor to N25 and O25 at (0.5 + x, 0.5 + y, 1 + z) and N12 at (x, y, z) acts as donor, via H12B, to N25 and O26, also at (0.5 + x, 0.5 + y, 1 + z). Hence these four distinct three-centre hydrogen bonds generate, by translation, a complex chain of rings running parallel to the [112] direction (Fig. 2). There are four chains of this type running through each unit cell: two, related to one another by the action of the C-centring operation are parallel to [112], and a second pair, related to the first pair by the action of the twofold rotation axis, run parallel to [112].

Each two-molecule aggregate within the chain, forms six further hydrogen bonds exterior to its own chain, and these serve to link all of the chains into a single framework, although the behaviour of the two independent organic molecules is quite different. Carboxylic O22 at (x, y, z) acts as hydrogen-bond donor to amidic O26 at (1/2 - x, 1/2 + y, -z), while O22 at (1/2 - x, 1/2 + y, -z), in turn acts as donor to O26 at (x, 1 + y, z), so producing a spiral C(9) chain parallel to the [010] direction, built entirely from type 2 molecules and generated by the 21 screw axis along (1/4, y, 0) (Fig. 3). A second spiral motif parallel to [010] involves molecules of types 1 and 2 and is generated by the 21 screw axis along (1/4, y, 1/2). Amino N12 acts as donor, via H12A, to O26 at (1/2 - x, 1/2 + y, 1 - z) and N12 at (1/2 - x, 1/2 + y, 1 - z) acts in turn as donor to O26 at (x, 1 + y, z), generating a C22(11) motif (Fig. 4). These two [010] motifs serve not only to link parallel [112] chains into sheets, and likewise the [112] chains, but are sufficient to link the [112] and [112] chains into a continuous framework, which can thus be generated without the intervention of the water molecules.

In the event, all four chains are linked by the water molecules: water O1 at (x, y, z) acts as donor to amidic O16 atoms in the molecules at (x, y, z) and (1 - x, y, 1 - z), and as acceptor from carboxylic O12 atoms at (1/2 + x, 1/2 + y, z) and (1/2 - x, 1/2 + y, 1 - z) (Fig. 5). Each of these type 1 molecules lies in a different chain;each water molecule acts as donor to type 1 molecules in one [112] and in one [112] chain, and each water similarly acts as acceptor from type 1 molecules in one [112] and one [112] chain.

Of the three O—H···O hydrogen bonds present (Table 2), the two involving the water molecule have much shorter O···O distances than the one not involving water. Four of the intermolecular N—H···O hydrogen bonds form part of three-centre systems; although the ranges of the N···O distances for the two types of N—H···O hydrogen bonds (two-centre and three-centre) overlap, the average value in the three-centre bonds, 3.088 (3) Å is somewhat larger than that in the two-centre bonds, 2.908 (3) Å. The only N—H···N hydrogen bonds present are all part of three-centre systems: the average value of the N···N distance in these systems, 3.081 (4) Å, is very similar to the corresponding N···O average. In the intermolecular, two-centre hydrogen bonds the D—H···A angles range from 152° to 175°, with mean value 166° (Table 2). While none of the D···A distances is particularly short, the cooperative effect of the multiplicity of hydrogen bonds, particularly within the [112] and [112] chains produces a coherent and stable supramolecular arrangement. However, none of the hydrogen bonds in (II) approaches the very short O—H···O hydrogen bonds in the series (I). All potential hydrogen-bond donors participate in the supramolecular structure, with the exception of N14—H14 and N24—H24, which both form intramolecular hydrogen bonds. It is notable that none of the O atoms in the carboxylic acid groups acts as a hydrogen-bond acceptor. It may be presumed that atoms N13 and N23 do not acts a hydrogen-bond acceptors for steric reasons.

Related literature top

For related literature, see: Allen et al. (1987); Bauer & Andreassen (1972); Davis et al. (1965); Flack (1983); Flack & Bernardinelli (2000); Gregson et al. (2000); Low et al. (2000); Schlemper et al. (1986); Spek (2000); Talberg (1977).

Experimental top

To a suspension of 2-amino-4,6-dimethoxy-5-nitrosopyrimidine (92 mg, 0.5 mmol) in CH3CN (5 cm3) was added a solution of L-isoleucine (79 mg, 0.6 mmol) in aqueous Na2CO3 solution (1 mol dm-3, 0.6 cm3). Water (4.4 cm3) was added and the final mixture was stirred for 8 h at room temperature. The mixture was evaporated to dryness and the residue was suspended in 5 cm3 of water and acidified with concentrated HCl to pH 2–3. Slow evaporation at 277 K gave single crystals of (II) suitable for X-ray diffraction (97 mg, 72%; m.p. 463 K). IR (KBr) ν (cm-1): 3369–3181 (NH/OH), 2971 (C—H), 1736(CO), 1757, 1708 (CO), 1656 (d NH2), 1577, 1539 (CN, CC, NO), 1309 (C—N), 1202 (C—O). 1H-NMR (DMSO-d6) δ (p.p.m.,TMS) 12.87 (d, 8.44 Hz, NH), 10.94 (br, s, NH), 8.29 (br,s, 1H, NH2), 7.01 (br, s, 1H, NH2), 4.70 (dd, 8.46 Hz, 4.51 Hz, CH), 1.98–1.85 (m, CH), 1.51–1.37 (m, 1H, CH2), 1.27–1.13 (m, CH2), 0.91 (d, 7.31 Hz, CH3CH), 0.85 (q, 7.31 Hz, CH3CH2); 13C-NMR (DMSO-d6) δ (p.p.m.,TMS): 171.5, 161.1, 156.3, 151.9, 140.5, 56.6, 36.7, 24.7, 15.5, 11.4. Analysis: found: C 43.9, H 5.8, N 25.4%; C10H15N5O4·0.25H2O: requires C 43.9, H 5.7, N 25.6%.

Refinement top

Compound (II) crystallized in the monoclinic system. The systematic absences permitted C2, Cm and C2/m as possible space groups: of these, Cm and C2/m were ruled out by the chiral nature of the organic moieties, and C2 was subsequently confirmed by the successful structure solution and refinement. All H atoms were located in difference maps and were treated as riding with C—H 0.98 Å (CH3), 0.99 Å (CH2) or 1.00 Å (CH), N—H 0.88 Å, and O—H 0.84 Å or 0.95 Å. In the absence of significant anomalous scattering the refined Flack parameter of -0.5 (8) (Flack, 1983) was inconclusive (Flack & Bernardinelli, 2000): hence the Friedel equivalents were merged and the absolute configuration was set by reference to the known configuration (2S,3S) of L-isoleucine. Examination of the structure with PLATON (Spek, 2000) showed that there were no solvent-accessible voids in the crystal lattice.

Computing details top

Data collection: Kappa-CCD server software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2000); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. The two independent pyrimidine molecules in (II) showing the atom-labelling scheme: (a) molecule 1; (b) molecule 2. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. Part of the crystal structure of (II) showing formation of one of the [112] chains. Atoms marked with a star (*) or hash (#) are at the symmetry positions (1/2 + x, 1/2 + y, 1 + z) and (-1/2 + x, -1/2 + y, -1 + z), respectively: H atoms bonded to C and some leucyl alkyl C atoms are omitted for the sake of clarity.
[Figure 3] Fig. 3. Part of the crystal structure of (2) showing formation of the C(9) spiral motif linking the [112] and [112] chains. Atoms marked with a star (*) or hash (#) are at the symmetry position (1/2 - x, 1/2 + y, -z) and (x, 1 + y, z), respectively: H atoms bonded to C are omitted for the sake of clarity.
[Figure 4] Fig. 4. Part of the crystal structure of (2) showing formation of the C22(11) spiral motif linking the [112] and [1–12] chains. Atoms marked with a hash (#) or dollar sign ($) are at the symmetry positions (x, 1 + y, z) and (1/2 - x, 1/2 + y, 1 - z) respectively: H atoms bonded to C and some leucyl alkyl C atoms are omitted for the sake of clarity.
[Figure 5] Fig. 5. Part of the crystal structure of (2) showing the hydrogen bonds formed by the water molecule. Atoms marked with a star (*), hash (#) or dollar sign ($) are at the symmetry positions (1 - x, y, 1 - z), (1/2 + x, 1/2 + y, z) and (1/2 - x, 1/2 + y, 1 - z), respectively: H atoms bonded to C and some leucyl alkyl atoms are omitted for the sake of clarity.
N-(2-amino-1,6-dihydro-5-nitroso-6-oxopyrimidin-4-yl)-L– isoleucine–water (4/1) top
Crystal data top
2C10H15N5O4·0.5H2OF(000) = 1156
Mr = 547.55Dx = 1.400 Mg m3
Monoclinic, C2Mo Kα radiation, λ = 0.71073 Å
a = 21.4179 (6) ÅCell parameters from 3819 reflections
b = 11.1466 (2) Åθ = 3.5–30.5°
c = 14.9649 (3) ŵ = 0.11 mm1
β = 133.4280 (6)°T = 150 K
V = 2594.61 (10) Å3Plate, red
Z = 40.36 × 0.30 × 0.05 mm
Data collection top
Kappa-CCD
diffractometer
3819 independent reflections
Radiation source: fine-focus sealed X-ray tube3119 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.061
ϕ scans and ω scans with κ offsetsθmax = 29.9°, θmin = 3.5°
Absorption correction: multi-scan
DENZO-SMN (Otwinowski & Minor, 1997)
h = 3028
Tmin = 0.961, Tmax = 0.995k = 1515
21713 measured reflectionsl = 2020
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0624P)2]
where P = (Fo2 + 2Fc2)/3
3819 reflections(Δ/σ)max = 0.001
354 parametersΔρmax = 0.24 e Å3
1 restraintΔρmin = 0.34 e Å3
Crystal data top
2C10H15N5O4·0.5H2OV = 2594.61 (10) Å3
Mr = 547.55Z = 4
Monoclinic, C2Mo Kα radiation
a = 21.4179 (6) ŵ = 0.11 mm1
b = 11.1466 (2) ÅT = 150 K
c = 14.9649 (3) Å0.36 × 0.30 × 0.05 mm
β = 133.4280 (6)°
Data collection top
Kappa-CCD
diffractometer
3819 independent reflections
Absorption correction: multi-scan
DENZO-SMN (Otwinowski & Minor, 1997)
3119 reflections with I > 2σ(I)
Tmin = 0.961, Tmax = 0.995Rint = 0.061
21713 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0421 restraint
wR(F2) = 0.098H-atom parameters constrained
S = 1.04Δρmax = 0.24 e Å3
3819 reflectionsΔρmin = 0.34 e Å3
354 parameters
Special details top

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

Geometry. Mean-plane data from the final SHELXL97 refinement run:-

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.50000.61851 (18)0.50000.0268 (5)
H10.48710.56140.53220.032*
N110.44480 (10)0.52852 (15)0.69535 (15)0.0195 (3)
H110.50020.54420.74940.023*
C120.39650 (12)0.56701 (17)0.71881 (18)0.0181 (4)
N120.43369 (10)0.64238 (16)0.81067 (16)0.0223 (4)
H12A0.40580.66840.83050.027*
H12B0.48650.66690.85240.027*
N130.31660 (10)0.53036 (15)0.65620 (15)0.0192 (3)
C140.27856 (12)0.46259 (17)0.55656 (17)0.0172 (4)
N140.20016 (10)0.42073 (16)0.49368 (15)0.0203 (4)
H140.17330.38600.42250.024*
C150.32039 (11)0.43449 (17)0.51331 (18)0.0169 (4)
N150.28701 (10)0.38180 (15)0.40865 (16)0.0208 (4)
O150.20862 (9)0.34663 (14)0.33245 (14)0.0262 (3)
C160.41009 (12)0.46673 (16)0.59129 (18)0.0184 (4)
O160.45465 (9)0.44099 (12)0.56969 (14)0.0219 (3)
C170.15551 (12)0.42859 (19)0.53504 (19)0.0201 (4)
H170.19560.46270.62010.024*
C180.13032 (12)0.30311 (18)0.53834 (18)0.0201 (4)
O110.12976 (11)0.21762 (13)0.48880 (16)0.0284 (3)
O120.10585 (10)0.30118 (14)0.59959 (14)0.0267 (3)
H120.07630.23940.58010.040*
C190.07362 (14)0.5069 (2)0.4507 (2)0.0278 (5)
H190.04520.50070.48250.033*
C1100.00947 (14)0.4618 (2)0.3187 (2)0.0394 (6)
H11A0.03140.48080.27970.047*
H11B0.00500.37350.31920.047*
C1110.07952 (17)0.5160 (4)0.2417 (3)0.0641 (11)
H11C0.07640.60300.23590.096*
H11D0.10120.49910.28050.096*
H11E0.11840.48090.15900.096*
C1120.0981 (2)0.6379 (2)0.4616 (3)0.0458 (7)
H11F0.04600.68720.40940.069*
H11G0.12880.64690.43500.069*
H11H0.13530.66380.54740.069*
O260.10551 (8)0.19504 (13)0.04600 (13)0.0231 (3)
N210.23517 (11)0.28431 (16)0.17345 (16)0.0216 (4)
H210.23030.29770.22630.026*
N220.36878 (11)0.37132 (19)0.31015 (17)0.0290 (4)
H22A0.41700.39460.33220.035*
H22B0.36110.38210.36020.035*
N230.32167 (11)0.30536 (16)0.12846 (16)0.0220 (4)
N240.27562 (11)0.22919 (17)0.05009 (16)0.0237 (4)
H240.23730.18960.11950.028*
C220.30843 (13)0.32067 (19)0.20265 (19)0.0211 (4)
C240.26018 (13)0.25010 (18)0.02096 (18)0.0197 (4)
C250.18060 (12)0.21137 (18)0.01826 (18)0.0201 (4)
O250.11886 (10)0.13683 (16)0.20393 (14)0.0340 (4)
N250.11403 (11)0.15777 (17)0.12476 (16)0.0260 (4)
C270.35392 (12)0.2700 (2)0.01590 (18)0.0220 (4)
H270.40170.26300.07550.026*
C260.16953 (12)0.22804 (18)0.06538 (18)0.0195 (4)
C280.34503 (13)0.4022 (2)0.0496 (2)0.0246 (4)
C290.37784 (14)0.1929 (2)0.07409 (19)0.0245 (4)
H290.43320.22530.04360.029*
O210.27940 (10)0.45754 (15)0.11418 (17)0.0372 (4)
O220.42100 (9)0.44731 (15)0.00193 (17)0.0331 (4)
H220.41660.52180.00930.050*
C2100.31149 (14)0.2024 (2)0.21465 (19)0.0301 (5)
H21A0.26100.15240.24880.036*
H21B0.29180.28660.23850.036*
C2110.34572 (17)0.1629 (3)0.2712 (2)0.0400 (6)
H21C0.36360.07870.25040.060*
H21D0.39510.21280.23900.060*
H21E0.30050.17170.36090.060*
C2120.39455 (18)0.0632 (2)0.0300 (3)0.0409 (6)
H21F0.34260.02970.05390.061*
H21G0.44180.06080.05970.061*
H21H0.41000.01590.06770.061*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0364 (11)0.0182 (9)0.0467 (13)0.0000.0366 (11)0.000
N110.0137 (7)0.0236 (8)0.0224 (8)0.0010 (6)0.0129 (7)0.0020 (7)
C120.0182 (9)0.0182 (9)0.0199 (9)0.0007 (7)0.0138 (8)0.0014 (7)
N120.0162 (8)0.0280 (9)0.0223 (8)0.0029 (7)0.0131 (7)0.0061 (7)
N130.0170 (8)0.0233 (8)0.0208 (8)0.0017 (7)0.0143 (7)0.0026 (7)
C140.0183 (9)0.0177 (9)0.0201 (9)0.0006 (7)0.0149 (8)0.0004 (7)
N140.0190 (8)0.0267 (9)0.0227 (8)0.0044 (7)0.0171 (7)0.0065 (7)
C150.0173 (9)0.0179 (9)0.0219 (9)0.0001 (7)0.0159 (8)0.0003 (7)
N150.0205 (8)0.0222 (8)0.0229 (8)0.0020 (7)0.0161 (7)0.0024 (7)
O150.0211 (7)0.0337 (8)0.0253 (8)0.0071 (6)0.0165 (7)0.0092 (6)
C160.0192 (9)0.0159 (9)0.0236 (10)0.0001 (7)0.0161 (8)0.0009 (7)
O160.0229 (7)0.0219 (7)0.0316 (8)0.0003 (6)0.0228 (6)0.0016 (6)
C170.0202 (9)0.0241 (10)0.0257 (10)0.0047 (8)0.0195 (9)0.0050 (8)
C180.0168 (9)0.0242 (10)0.0217 (10)0.0014 (8)0.0142 (8)0.0004 (8)
O110.0352 (8)0.0225 (7)0.0380 (9)0.0032 (6)0.0292 (8)0.0040 (7)
O120.0303 (8)0.0303 (8)0.0328 (8)0.0060 (6)0.0269 (7)0.0027 (7)
C190.0291 (11)0.0243 (10)0.0448 (13)0.0035 (9)0.0310 (11)0.0045 (9)
C1100.0273 (11)0.0427 (14)0.0387 (13)0.0055 (11)0.0191 (11)0.0115 (11)
C1110.0321 (14)0.101 (3)0.0569 (18)0.0214 (16)0.0298 (14)0.044 (2)
C1120.0635 (17)0.0248 (12)0.083 (2)0.0041 (12)0.0632 (18)0.0034 (13)
O260.0170 (7)0.0299 (8)0.0267 (8)0.0048 (6)0.0166 (6)0.0023 (6)
N210.0202 (8)0.0277 (9)0.0223 (8)0.0045 (7)0.0167 (7)0.0037 (7)
N220.0236 (9)0.0467 (11)0.0242 (9)0.0144 (8)0.0193 (8)0.0139 (8)
N230.0211 (8)0.0290 (9)0.0215 (8)0.0054 (7)0.0168 (7)0.0047 (7)
N240.0227 (8)0.0316 (9)0.0214 (9)0.0066 (7)0.0169 (8)0.0065 (7)
C220.0201 (9)0.0239 (10)0.0237 (10)0.0018 (8)0.0167 (9)0.0025 (8)
C240.0194 (9)0.0224 (10)0.0188 (10)0.0011 (8)0.0137 (8)0.0008 (7)
C250.0184 (9)0.0224 (9)0.0198 (9)0.0035 (8)0.0132 (8)0.0012 (8)
O250.0331 (8)0.0456 (10)0.0239 (8)0.0117 (8)0.0199 (7)0.0107 (7)
N250.0239 (8)0.0312 (10)0.0203 (8)0.0054 (8)0.0142 (8)0.0028 (7)
C270.0180 (9)0.0300 (11)0.0207 (10)0.0031 (8)0.0143 (9)0.0031 (8)
C260.0172 (9)0.0205 (9)0.0209 (10)0.0018 (7)0.0132 (9)0.0010 (8)
C280.0231 (10)0.0302 (11)0.0246 (10)0.0034 (9)0.0180 (9)0.0058 (9)
C290.0215 (10)0.0314 (11)0.0228 (10)0.0032 (9)0.0160 (9)0.0000 (9)
O210.0248 (8)0.0337 (9)0.0467 (10)0.0003 (7)0.0221 (8)0.0020 (8)
O220.0256 (8)0.0306 (8)0.0456 (10)0.0015 (7)0.0254 (8)0.0003 (7)
C2100.0271 (11)0.0405 (13)0.0217 (10)0.0043 (10)0.0165 (9)0.0032 (9)
C2110.0394 (13)0.0578 (16)0.0326 (13)0.0036 (12)0.0286 (12)0.0053 (12)
C2120.0487 (15)0.0352 (13)0.0421 (14)0.0114 (12)0.0325 (13)0.0055 (11)
Geometric parameters (Å, º) top
O1—H10.95N21—C221.369 (3)
N11—C121.370 (2)C22—N231.332 (3)
C12—N131.330 (2)N23—C241.337 (3)
N13—C141.337 (3)C24—C251.435 (3)
C14—C151.455 (3)C25—C261.437 (3)
C15—C161.449 (3)C26—N211.364 (3)
C16—N111.364 (3)C22—N221.311 (3)
C12—N121.313 (3)C24—N241.333 (3)
C14—N141.323 (2)C25—N251.344 (3)
C15—N151.330 (3)N25—O251.279 (2)
N15—O151.281 (2)C26—O261.246 (2)
C16—O161.234 (2)N21—H210.8800
N11—H110.8800N22—H22A0.8800
N12—H12A0.8800N22—H22B0.8800
N12—H12B0.8800N24—C271.449 (3)
N14—C171.456 (2)N24—H240.8800
N14—H140.8800C27—C281.527 (3)
C17—C181.512 (3)C27—C291.540 (3)
C17—C191.545 (3)C27—H271.0000
C17—H171.0000C28—O211.193 (3)
C18—O111.202 (3)C28—O221.330 (3)
C18—O121.333 (2)C29—C2121.526 (4)
O12—H120.8400C29—C2101.531 (3)
C19—C1101.520 (4)C29—H291.0000
C19—C1121.522 (3)O22—H220.8400
C19—H191.0000C210—C2111.517 (3)
C110—C1111.518 (3)C210—H21A0.9900
C110—H11A0.9900C210—H21B0.9900
C110—H11B0.9900C211—H21C0.9800
C111—H11C0.9800C211—H21D0.9800
C111—H11D0.9800C211—H21E0.9800
C111—H11E0.9800C212—H21F0.9800
C112—H11F0.9800C212—H21G0.9800
C112—H11G0.9800C212—H21H0.9800
C112—H11H0.9800
C16—N11—C12122.39 (16)C26—N21—C22122.38 (17)
C16—N11—H11118.8C26—N21—H21118.8
C12—N11—H11118.8C22—N21—H21118.8
N12—C12—N13119.65 (18)C22—N22—H22A120.0
N12—C12—N11116.56 (17)C22—N22—H22B120.0
N13—C12—N11123.77 (17)H22A—N22—H22B120.0
C12—N12—H12A120.0C22—N23—C24117.62 (17)
C12—N12—H12B120.0C24—N24—C27121.64 (17)
H12A—N12—H12B120.0C24—N24—H24119.2
C12—N13—C14117.50 (16)C27—N24—H24119.2
N14—C14—N13119.67 (17)N22—C22—N23118.86 (18)
N14—C14—C15118.44 (17)N22—C22—N21117.77 (18)
N13—C14—C15121.89 (16)N23—C22—N21123.36 (18)
C14—N14—C17124.04 (17)N24—C24—N23117.43 (18)
C14—N14—H14118.0N24—C24—C25119.81 (18)
C17—N14—H14118.0N23—C24—C25122.75 (18)
N15—C15—C16113.56 (16)N25—C25—C24127.75 (19)
N15—C15—C14128.46 (16)N25—C25—C26114.50 (17)
C16—C15—C14117.99 (17)C24—C25—C26117.73 (18)
O15—N15—C15119.86 (16)O25—N25—C25118.96 (17)
O16—C16—N11120.26 (17)N24—C27—C28109.58 (17)
O16—C16—C15124.58 (18)N24—C27—C29112.29 (17)
N11—C16—C15115.16 (16)C28—C27—C29111.45 (17)
N14—C17—C18108.16 (16)N24—C27—H27107.8
N14—C17—C19113.29 (18)C28—C27—H27107.8
C18—C17—C19108.59 (15)C29—C27—H27107.8
N14—C17—H17108.9O26—C26—N21118.95 (18)
C18—C17—H17108.9O26—C26—C25124.96 (18)
C19—C17—H17108.9N21—C26—C25116.08 (17)
O11—C18—O12124.71 (18)O21—C28—O22124.4 (2)
O11—C18—C17124.44 (18)O21—C28—C27125.2 (2)
O12—C18—C17110.81 (16)O22—C28—C27110.39 (18)
C18—O12—H12109.5C212—C29—C210112.3 (2)
C110—C19—C112113.1 (2)C212—C29—C27110.76 (19)
C110—C19—C17112.29 (19)C210—C29—C27112.51 (17)
C112—C19—C17109.9 (2)C212—C29—H29107.0
C110—C19—H19107.1C210—C29—H29107.0
C112—C19—H19107.1C27—C29—H29107.0
C17—C19—H19107.1C28—O22—H22109.5
C111—C110—C19113.4 (3)C211—C210—C29113.48 (18)
C111—C110—H11A108.9C211—C210—H21A108.9
C19—C110—H11A108.9C29—C210—H21A108.9
C111—C110—H11B108.9C211—C210—H21B108.9
C19—C110—H11B108.9C29—C210—H21B108.9
H11A—C110—H11B107.7H21A—C210—H21B107.7
C110—C111—H11C109.5C210—C211—H21C109.5
C110—C111—H11D109.5C210—C211—H21D109.5
H11C—C111—H11D109.5H21C—C211—H21D109.5
C110—C111—H11E109.5C210—C211—H21E109.5
H11C—C111—H11E109.5H21C—C211—H21E109.5
H11D—C111—H11E109.5H21D—C211—H21E109.5
C19—C112—H11F109.5C29—C212—H21F109.5
C19—C112—H11G109.5C29—C212—H21G109.5
H11F—C112—H11G109.5H21F—C212—H21G109.5
C19—C112—H11H109.5C29—C212—H21H109.5
H11F—C112—H11H109.5H21F—C212—H21H109.5
H11G—C112—H11H109.5H21G—C212—H21H109.5
C16—N11—C12—N12168.83 (18)C24—N23—C22—N22178.0 (2)
C16—N11—C12—N1312.7 (3)C24—N23—C22—N210.9 (3)
N12—C12—N13—C14173.94 (19)C26—N21—C22—N22178.3 (2)
N11—C12—N13—C147.6 (3)C26—N21—C22—N230.6 (3)
C12—N13—C14—N14177.78 (18)C27—N24—C24—N233.2 (3)
C12—N13—C14—C153.2 (3)C27—N24—C24—C25178.05 (19)
N13—C14—N14—C179.3 (3)C22—N23—C24—N24176.48 (19)
C15—C14—N14—C17171.65 (18)C22—N23—C24—C252.3 (3)
N14—C14—C15—N158.3 (3)N24—C24—C25—N252.9 (3)
N13—C14—C15—N15170.75 (19)N23—C24—C25—N25178.4 (2)
N14—C14—C15—C16171.86 (17)N24—C24—C25—C26175.52 (18)
N13—C14—C15—C169.1 (3)N23—C24—C25—C263.2 (3)
C16—C15—N15—O15178.63 (17)C24—C25—N25—O250.1 (3)
C14—C15—N15—O151.5 (3)C26—C25—N25—O25178.52 (18)
C12—N11—C16—O16174.96 (18)C24—N24—C27—C2881.1 (2)
C12—N11—C16—C155.8 (3)C24—N24—C27—C29154.46 (19)
N15—C15—C16—O165.2 (3)C22—N21—C26—O26178.44 (18)
C14—C15—C16—O16174.90 (18)C22—N21—C26—C251.5 (3)
N15—C15—C16—N11175.58 (17)N25—C25—C26—O261.3 (3)
C14—C15—C16—N114.3 (3)C24—C25—C26—O26177.3 (2)
C14—N14—C17—C18123.6 (2)N25—C25—C26—N21178.76 (19)
C14—N14—C17—C19116.0 (2)C24—C25—C26—N212.6 (3)
N14—C17—C18—O1115.5 (3)N24—C27—C28—O2112.9 (3)
C19—C17—C18—O11107.8 (2)C29—C27—C28—O21112.0 (2)
N14—C17—C18—O12166.79 (15)N24—C27—C28—O22167.91 (17)
C19—C17—C18—O1269.9 (2)C29—C27—C28—O2267.2 (2)
N14—C17—C19—C11057.9 (2)N24—C27—C29—C21261.8 (2)
C18—C17—C19—C11062.3 (2)C28—C27—C29—C212174.78 (19)
N14—C17—C19—C11269.0 (2)N24—C27—C29—C21064.8 (2)
C18—C17—C19—C112170.9 (2)C28—C27—C29—C21058.6 (2)
C112—C19—C110—C11169.5 (3)C212—C29—C210—C21173.3 (3)
C17—C19—C110—C111165.4 (2)C27—C29—C210—C211161.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O160.951.772.709 (2)170
N11—H11···O25i0.882.363.147 (3)149
N11—H11···N25i0.882.193.007 (3)155
O12—H12···O1ii0.841.802.619 (2)166
N12—H12A···O26iii0.882.042.851 (3)152
N12—H12B···O26i0.882.202.911 (3)138
N12—H12B···N25i0.882.513.279 (4)146
N14—H14···O150.882.002.672 (3)133
N21—H21···O150.882.012.886 (3)172
N21—H21···N150.882.293.071 (2)148
O22—H22···O26iv0.841.972.811 (2)175
N22—H22A···O16v0.882.102.965 (3)165
N22—H22B···O160.882.373.041 (3)133
N22—H22B···N150.882.152.967 (4)154
N24—H24···O250.881.992.647 (3)130
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x1/2, y1/2, z; (iii) x+1/2, y+1/2, z+1; (iv) x+1/2, y+1/2, z; (v) x+1, y, z+1.

Experimental details

Crystal data
Chemical formula2C10H15N5O4·0.5H2O
Mr547.55
Crystal system, space groupMonoclinic, C2
Temperature (K)150
a, b, c (Å)21.4179 (6), 11.1466 (2), 14.9649 (3)
β (°) 133.4280 (6)
V3)2594.61 (10)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.36 × 0.30 × 0.05
Data collection
DiffractometerKappa-CCD
diffractometer
Absorption correctionMulti-scan
DENZO-SMN (Otwinowski & Minor, 1997)
Tmin, Tmax0.961, 0.995
No. of measured, independent and
observed [I > 2σ(I)] reflections
21713, 3819, 3119
Rint0.061
(sin θ/λ)max1)0.701
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.098, 1.04
No. of reflections3819
No. of parameters354
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.24, 0.34

Computer programs: Kappa-CCD server software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2000), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected geometric parameters (Å, º) top
N11—C121.370 (2)N21—C221.369 (3)
C12—N131.330 (2)C22—N231.332 (3)
N13—C141.337 (3)N23—C241.337 (3)
C14—C151.455 (3)C24—C251.435 (3)
C15—C161.449 (3)C25—C261.437 (3)
C16—N111.364 (3)C26—N211.364 (3)
C12—N121.313 (3)C22—N221.311 (3)
C14—N141.323 (2)C24—N241.333 (3)
C15—N151.330 (3)C25—N251.344 (3)
N15—O151.281 (2)N25—O251.279 (2)
C16—O161.234 (2)C26—O261.246 (2)
C14—N14—C17—C18123.6 (2)C24—N24—C27—C2881.1 (2)
C14—N14—C17—C19116.0 (2)C24—N24—C27—C29154.46 (19)
N14—C17—C18—O12166.79 (15)N24—C27—C28—O22167.91 (17)
N14—C17—C19—C11057.9 (2)N24—C27—C29—C21064.8 (2)
C17—C19—C110—C111165.4 (2)C27—C29—C210—C211161.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O160.951.772.709 (2)170
N11—H11···O25i0.882.363.147 (3)149
N11—H11···N25i0.882.193.007 (3)155
O12—H12···O1ii0.841.802.619 (2)166
N12—H12A···O26iii0.882.042.851 (3)152
N12—H12B···O26i0.882.202.911 (3)138
N12—H12B···N25i0.882.513.279 (4)146
N14—H14···O150.882.002.672 (3)133
N21—H21···O150.882.012.886 (3)172
N21—H21···N150.882.293.071 (2)148
O22—H22···O26iv0.841.972.811 (2)175
N22—H22A···O16v0.882.102.965 (3)165
N22—H22B···O160.882.373.041 (3)133
N22—H22B···N150.882.152.967 (4)154
N24—H24···O250.881.992.647 (3)130
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x1/2, y1/2, z; (iii) x+1/2, y+1/2, z+1; (iv) x+1/2, y+1/2, z; (v) x+1, y, z+1.
 

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