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The crystal structure of a dihydrate of the title compound, 3-[(2-hy­droxy­eth­oxy)methyl]-6-methyl-3H-imidazolo­[1,2-a]-purin-9(5H)-one, C11H13N5O3·2H2O, has been reinvestigated. The asymmetric unit contains two mol­ecules of tricyclic acyclovir and four mol­ecules of water. The structure consists of a three-dimensional network of strong hydrogen bonds that integrates all of the components. While the crystal structure and the formation of an (H2O)8 solvent water mol­ecule cluster through a disordered strong hydrogen bond [O...O = 2.807 (3) Å] between two water mol­ecules across an inversion centre has been described previously [Suwinska, Golankiewicz & Zielenkiewicz (2001). Acta Cryst. C57, 767-769], the disorder was incompletely modelled. In this work, the disorder model is extended and includes disorder of one tricyclic a­cyclo­vir hy­droxy group across another inversion centre [O...O = 2.644 (4) Å]. The resulting infinite O-H...O hydrogen-bonded water-hy­droxy chains, analogous to the `proton wires' found in the membrane protein gramicidin A, are discussed and an unusual disorder model involving infinite concerted chains of O-H...O hydrogen bonds is provided.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113021082/sf3206sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113021082/sf3206Isup2.hkl
Contains datablock I

CCDC reference: 964776

Introduction top

When a­cyclo­vir, denoted ACV, was converted into tricyclic a­cyclo­vir, TACV {3-[(2-hy­droxy­eth­oxy)­methyl]-6-methyl-3H-imidazolo­[1,2-a]purin-9(5H)-one}, it was expected to be inactive since the NH2 group at C2 of ACV was blocked by the closure of the third ring (Boryski et al., 1988). However, TACV exhibits a marked anti­herpetic activity, with potent and selective activity against herpes simplex virus types 1 and 2, varicella-zoster virus and cytomegalovirus, and at the same time lower cytotoxicity (Boryski et al., 1991; Balzarini et al., 2002). The structure of TACV has been reported previously in a study aimed at improved understanding of the nature of the solvation and the relationships between the structure and thermodynamic parameters (Suwińska et al., 2001). Our inter­est was piqued by the observation that the structure contained an infinite zigzag chain of strong O···O contacts with an average O···O distance of 2.72 Å, passing through the (H2O)8 water clusters identified in the previous report. This chain is analogous to the one-dimensional zigzag water chain (average O···O = 2.78 Å) reported and studied (Cheruzel et al., 2003) as a potential model for biologically relevant proton wires. The zigzag structure is the second probable proton-wire structure proposed by Nagle & Morowitz (1978).

Experimental top

Synthesis and crystallization top

The previous structural parameters and structure-factor data for SX1107 were obtained from the IUCr electronic archives (Suwińska et al., 2001). The previously reported synthesis was described by Boryski et al. (1988) and Golankiewicz et al. (1991), with recrystallization from aqueous solution to produce colourless crystals of TACV.2H2O.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. The CIF for the previous refinement contains two complete TACV molecules and four water molecules in the asymmetric unit. Molecule B has atoms O16B and C17B as the major component and atoms O16C and C17C as the minor component of a 75:25 disorder model. The published structure includes the minor component H atoms only on C17B and C17C. Minor-component H atoms on C15B and C18B were not included and the corresponding major-component H atoms were assigned full occupancy factors. Full-matrix least-squares refinement was initiated from the previous model non-H positions.

The disorder model was extended to include alternate positions for C18B/C and all the minor- and major-component disordered H atoms. Atomic displacement parameters were constrained to be equivalent between components B and C using EADP instructions [Please express in non-software specific terms]. Bond distances for the side chains were held similar in all three components using SADI instructions [Please express in non-software specific terms]. The positions of all the H atoms, including the disordered H atoms, were located from electron-density difference Fourier maps. The water atoms H1WB/C on O1W and the disordered hy­droxy atoms H19B/C were modelled as simple statistical disorders. The positions of all the water H atoms were allowed to refine, with bond distances held similar using SADI instructions [Please express in non-software specific terms]. The positions of the hy­droxy H atoms were modelled as a freely rotating group (H19A) or as riding atoms (H19B/C), with constraints of a tetra­hedral bond angle and O—H = 0.82 Å. Methyl and methyl­ene H atoms were refined as riding atoms in idealized tetra­hedral positions, with C—H = 0.96 and 0.97 Å, respectively; methyl groups were allowed to rotate freely. The remaining H atoms were allowed to ride in idealized trigonal geometry, with C—H = 0.93 Å or N—H = 0.86 Å. Non-H atoms were assumed to vibrate anisotropically and H-atom isotropic displacement parameters were constrained to be a multiple of the equivalent displacement parameter of the atom they are bonded to (1.5Ueq for methyl and O-bound H atoms, and 1.2Ueq for other H atoms). The occupancy of the disorder in the side chain of molecule B refined to 0.746 (2):0.262.

Results and discussion top

TACV crystallizes as the water disolvate, (I), with Z' = 2. The independent units of the structure are shown in Fig. 1. The original report of the TACV structure included two disordered regions. Firstly, one H atom of one water molecule in an (H2O)8 cluster, located near an inversion centre, is statistically disordered, and secondly the ether O atom in concert with the adjacent methyl­ene C atom of molecule B occupies two positions in a 0.75:0.25 ratio.

The molecular geometry of TACV, including the conformations of the side chains and the planarity of the delocalized fused-ring system, was discussed and compared with the molecular geometry of ACV; there were no surprising features. Hydrogen bonding, linking eight water molecules into the cluster noted above and linking the TACV molecules into infinite ABAB-type chains via N3A—H3A···N12B [2.803 (2) Å] and N3B—H3B···O11A [2.749 (2) Å] hydrogen bonds with a water-mediated link supporting the BA portions [O2W—H2WA···N12A = 2.793 (3) Å and O2W—H2WB···N7B = 2.983 (2) Å], was also described. Not noted was the near coplanarity of the crystallographically independent A and B ring systems as connected by this R33(11) motif (Etter et al., 1990). The r.m.s. deviations of the fitted atoms for the 12-atom planes are 0.021 and 0.007 Å for ring systems A and B, respectively, and only 0.058 Å for the fit to the combined 24 atoms (positions as in the CIF file). The inter­planar angle between the A and B ring systems is 4.43 (7)°. The chains (pseudo ribbons) form face-to-face stacks in the ab direction (Fig. 2), with contacts ranging from 3.183 (3) Å [to upper limit of?] between inversion-related C9/C10O11/N12 edge contacts for B. Numerous other contacts in the range 3.2–3.4 Å to the tops and bottoms of both rings are in the expected range for aromatic ring contacts, as discussed previously (Haller et al., 1979). The stacked aromatic ribbon layers (the region from about 0.2 to 0.8 along c) alternate with layers containing the TACV side chains and the water molecules (Fig. 2).

When analysing the O···O inter­actions in the previous report we discovered a one-dimensional chain involving alternating water–water and hy­droxy–hy­droxy O atoms. A difficulty was that there were no hy­droxy H atoms connecting atom O19B to the water molecules, and only half an H atom from O1W connecting to the hy­droxy O atom. Furthermore, the distance between inversion-related atoms H19B was 1.55 Å, too short to be real (Steiner, 2002). The solution was simple: a difference Fourier map revealed the alternate H-atom position between atoms O19B and O1W, thus defining a one-dimensional chain propagating parallel to a through y = 1/2, z = 0, displaying an unusual disorder of an elaborate concerted unit containing pair-wise alternating TACV molecules and water molecules across the inversion centres. The concerted placement of H atoms for one of the half-occupied chains is illustrated in Fig. 3(a). The inversion centres between O1W—O1W [symmetry code?] and O19B—O19B [symmetry code?] generate the second half-occupied one-dimensional chain, as illustrated in Fig. 3(b). The two chains have coincident O atoms and differ only in the concerted placement of the H atoms, which are bound to the right of the O atoms in Fig. 3(a) and to the left of the O atoms in Fig. 3(b). Similar disordered one-dimensional water chains stabilized by imidazole channels have been suggested for models of biologically relevant proton wires (Pomès & Roux, 2002; Cheruzel et al., 2003), in which protons may hop along a single-file chain of water molecules in a de Grotthuss relay mechanism (de Grotthuss, 1806; Cukierman, 2006).

The water molecules form an (H2O)8 cluster, located on an inversion centre at (1/2, 1/2, 0), consisting of a six-molecule hydrogen-bonded chain (horizontal in Fig. 4) with two additional water molecules hydrogen-bonded to the second and fifth molecules. The chain orients more or less parallel to c and each end of the chain acts as an acceptor for a hydrogen bond from molecule A [O19A—H19A···O3W = 2.740 (3) Å] and as a donor to molecule B [O3W—H3WB···O11B = 2.824 (3) Å]. Perpendicular to the chain, atom O2W donates to molecules A [O2W—H2WA···N12A = 2.793 (3) Å] and B [O2W—H2WB···N7B = 2.983 (2) Å]. Thus, both crystallographically independent TACV molecules participate via strong O—H···O water–water and water–drug inter­actions, and via O—H···N water–drug inter­actions, in a two-dimensional sheet structure for which the H-atom disorder is irrelevant. The one-dimensional concerted disorder water chain inter­sects the cluster plane at an angle, as illustrated in Fig. 4, creating the extensively hydrogen-bonded three-dimensional supra­molecular network.

Related literature top

For related literature, see: Balzarini et al. (2002); Boryski et al. (1988, 1991); Cheruzel et al. (2003); Cukierman (2006); Etter et al. (1990); Golankiewicz et al. (1991); Haller et al. (1979); Nagle & Morowitz (1978); Pomès & Roux (2002); Steiner (2002); Suwińska et al. (2001); de Grotthuss (1806).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: SDP (Enraf–Nonius, 1985); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top
Fig. 1. The asymmetric unit in the crystal structure of TACV. The disordered H-atom positions on O19B and H1W are shown, but the minor-occupancy atoms O16C, C17C and C18C, and related H-atom positions of the disordered portion of the 2-hydroxy(ethoxy)methyl side chain in molecule B, have been omitted for clarity. Water molecules in the illustration are related to the positions in the CIF by the symmetry operator (-x, -y + 1, -z + 1). Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds. [Added text OK?]

Fig. 2. A packing diagram, viewed down the TACV ABAB one-dimensional chains. The ab direction is approximately vertical. The region between about 0.8 and 1.2 along c contains the TACV side chains and the water molecules. Dashed lines indicate hydrogen bonds. [Added text OK?]

Fig. 3. The positions of the H atoms in the concerted O···O bonded one-dimensional chains (two unit cells of the structure, 50% probability displacement ellipsoids). (a) Hydrogen-bond donors progressing left-to-right in the chain. (b) Alternate inversion-related disorder positions with hydrogen-bond donors progressing right to left in the chain. Dashed lines indicate hydrogen bonds. [Added text OK?] [Symmetry codes: (i) -x + 1, -y + 1, -z; (ii) x, y, z - 1; (iv) x + 1, y, z - 1; (vi) -x + 1, -y + 1, -z + 1; (xii) x - 2, y, z; (xiii) -x + 2, -y + 1, -z; (xiv) -x + 2, -y + 1, -z + 1.]

Fig. 4. The environment about the (H2O)8 water cluster. Wavy lines in three types indicate the three-dimensional hydrogen-bonded chain nodes. The long-dashed line from upper left to lower right (through atoms O19Bii, O1W, O1Wi and O19Bvi ?) indicates the concerted disordered O···O chains of Fig. 2. The solid line in the horizontal direction coincides with the long direction through the water cluster and continues to four different TACV clusters, all through O—H···O hydrogen bonds. The short-dashed line from upper right to lower left (through atoms O2Wi, O1Wi, O1W and O2W ?) completes the network node, connecting to four different TACV molecules through O—H···N hydrogen bonds. Displacement ellipsoids are drawn at the 50% probability level. Other dashed lines indicate hydrogen bonds. [Added text OK?] [Symmetry codes: (i) -x + 1, -y + 1, -z; (ii) x, y, z - 1; (iii) x, y - 1, z; (iv) x + 1, y, z - 1; (v) -1 - x, -y, -z + 1; (vi) -x + 1, -y + 1, -z + 1; (vii) -x, -y + 1, -z + 1; (viii) x + 2, y + 1, z - 1; (ix) -x + 1, -y + 2, -z; (x) x + 2, y, z - 1.]
3-[(2-Hydroxyethoxy)methyl]-6-methyl-6H-imidazol[1,2-a]purin-9(5H)-one top
Crystal data top
C11H13N5O3·2H2OZ = 4
Mr = 299.30F(000) = 632
Triclinic, P1Dx = 1.434 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.450 (1) ÅCell parameters from 25 reflections
b = 11.665 (2) Åθ = 5–12°
c = 14.930 (3) ŵ = 0.12 mm1
α = 75.44 (2)°T = 293 K
β = 76.65 (2)°Equant, colourless
γ = 86.44 (2)°0.32 × 0.28 × 0.22 mm
V = 1385.9 (4) Å3
Data collection top
Enraf–Nonius CAD-4
diffractometer
Rint = 0.0000
Radiation source: fine-focus sealed tubeθmax = 28.3°, θmin = 2.0°
Graphite monochromatorh = 1011
ω/2θ scansk = 1415
6873 measured reflectionsl = 019
6873 independent reflections3 standard reflections every 60 min
3922 reflections with I > 2σ(I) intensity decay: 0.3%
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.055 w = 1/[σ2(Fo2) + (0.0626P)2 + 0.0618P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.137(Δ/σ)max = 0.004
S = 1.03Δρmax = 0.21 e Å3
6873 reflectionsΔρmin = 0.21 e Å3
420 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
64 restraintsExtinction coefficient: 0.0009 (9)
Primary atom site location: difference Fourier map
Crystal data top
C11H13N5O3·2H2Oγ = 86.44 (2)°
Mr = 299.30V = 1385.9 (4) Å3
Triclinic, P1Z = 4
a = 8.450 (1) ÅMo Kα radiation
b = 11.665 (2) ŵ = 0.12 mm1
c = 14.930 (3) ÅT = 293 K
α = 75.44 (2)°0.32 × 0.28 × 0.22 mm
β = 76.65 (2)°
Data collection top
Enraf–Nonius CAD-4
diffractometer
Rint = 0.0000
6873 measured reflections3 standard reflections every 60 min
6873 independent reflections intensity decay: 0.3%
3922 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.05564 restraints
wR(F2) = 0.137H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.21 e Å3
6873 reflectionsΔρmin = 0.21 e Å3
420 parameters
Special details top

Experimental. The data set was obtained from the IUCr electronic archives (Reference: SX1107). The data as obtained contained only independent reflections so no value for Rint is given. The data yield near the limiting 2θ value of 30.0° in the original report was near 10%. Reducing the limiting 2θ value to 28.3° did not significantly change any refined parameter, but did greatly improve the analysis of variance. The data yield near the limit 2θ = 28.3° is 24%. The data/variable ratio is 16.4 and the observed data/variable ratio is 9.4 for 2θmax = 28.3°.

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

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C1A0.5278 (3)0.1795 (2)0.32363 (16)0.0515 (6)
H1A10.48530.24370.27050.077*
H1A20.63870.16540.32410.077*
H1A30.46430.10940.31850.077*
C2A0.5203 (2)0.21076 (18)0.41290 (15)0.0393 (5)
N3A0.5959 (2)0.14096 (15)0.49999 (12)0.0405 (4)
H3A0.65130.07840.50770.049*
C4A0.5711 (2)0.18410 (16)0.57057 (14)0.0345 (4)
N5A0.47562 (19)0.28411 (14)0.52840 (11)0.0350 (4)
C6A0.4467 (2)0.29946 (19)0.42962 (15)0.0405 (5)
H6A0.38710.36030.38390.049*
N7A0.6284 (2)0.14190 (14)0.66214 (12)0.0382 (4)
C8A0.5783 (2)0.20906 (17)0.71063 (14)0.0363 (5)
C9A0.4781 (2)0.30839 (18)0.67730 (15)0.0380 (5)
C10A0.4176 (2)0.35325 (17)0.57892 (15)0.0381 (5)
O11A0.32745 (18)0.43791 (13)0.53514 (11)0.0506 (4)
N12A0.4559 (2)0.34984 (17)0.75287 (13)0.0485 (5)
C13A0.5403 (3)0.2783 (2)0.82742 (17)0.0503 (6)
H13A0.54730.28570.88880.060*
N14A0.6181 (2)0.19097 (16)0.80796 (12)0.0437 (4)
C15A0.7247 (3)0.0978 (2)0.87231 (17)0.0559 (6)
H15A0.69880.02460.85230.067*
H15B0.70560.08540.93570.067*
O16A0.89030 (19)0.12573 (16)0.87480 (11)0.0619 (5)
C17A0.9596 (3)0.1915 (3)0.9419 (2)0.0795 (9)
H17A0.89190.25940.93320.095*
H17B0.96620.14261.00560.095*
C18A1.1260 (3)0.2323 (2)0.9290 (2)0.0772 (9)
H18A1.16590.28790.96780.093*
H18B1.11900.27380.86320.093*
O19A1.2375 (2)0.13963 (18)0.95344 (14)0.0736 (5)
H19A1.23220.11200.90750.110*
C1B0.1151 (3)0.5772 (2)0.32987 (16)0.0464 (5)
H1B10.07510.61210.26350.070*
H1B20.23170.57400.34370.070*
H1B30.07190.49850.34570.070*
C2B0.0637 (2)0.64984 (18)0.38643 (14)0.0373 (5)
N3B0.11869 (19)0.62660 (14)0.48456 (11)0.0362 (4)
H3B0.18480.57080.51820.043*
C4B0.0536 (2)0.70413 (16)0.51928 (14)0.0318 (4)
N5B0.04382 (19)0.77778 (13)0.44161 (11)0.0337 (4)
C6B0.0354 (3)0.74304 (18)0.36021 (15)0.0400 (5)
H6B0.08920.77850.29850.048*
N7B0.07729 (19)0.70948 (14)0.60840 (11)0.0343 (4)
C8B0.0080 (2)0.80017 (16)0.61518 (13)0.0324 (4)
C9B0.1091 (2)0.87950 (16)0.54220 (14)0.0339 (4)
C10B0.1349 (2)0.87283 (17)0.44699 (14)0.0350 (4)
O11B0.21977 (18)0.93474 (13)0.37513 (10)0.0482 (4)
N12B0.1736 (2)0.95951 (14)0.57861 (12)0.0399 (4)
C13B0.1130 (3)0.92958 (18)0.66930 (15)0.0405 (5)
H13B0.13570.96940.71150.049*
N14B0.0115 (2)0.83282 (15)0.69690 (11)0.0374 (4)
C15B0.0673 (3)0.77597 (19)0.79408 (14)0.0434 (5)0.746 (2)
H15C0.12420.83550.82480.052*0.746 (2)
H15D0.14720.72020.79350.052*0.746 (2)
O16B0.0439 (2)0.71594 (17)0.84681 (13)0.0443 (5)0.746 (2)
C17B0.1090 (4)0.6156 (3)0.81347 (19)0.0522 (8)0.746 (2)
H17C0.16130.63950.74660.063*0.746 (2)
H17D0.02280.56040.82120.063*0.746 (2)
C18B0.2307 (4)0.5579 (4)0.8700 (2)0.0620 (10)0.746 (2)
H18C0.30150.50670.83590.074*0.746 (2)
H18D0.29740.61850.87690.074*0.746 (2)
O19B0.1556 (3)0.4912 (2)0.95997 (13)0.0955 (8)0.50
H19B0.05700.50230.96890.143*0.50
C15C0.0673 (3)0.77597 (19)0.79408 (14)0.0434 (5)0.254 (2)
H15E0.05310.82390.83610.052*0.254 (2)
H15F0.18290.76900.79900.052*0.254 (2)
O16C0.0008 (7)0.6622 (3)0.8216 (4)0.0443 (5)0.254 (2)
C17C0.1641 (8)0.6655 (6)0.8296 (5)0.0522 (8)0.254 (2)
H17E0.17140.71230.87370.063*0.254 (2)
H17F0.23210.70200.76820.063*0.254 (2)
C18C0.2214 (12)0.5417 (10)0.8641 (4)0.0620 (10)0.254 (2)
H18E0.19360.49250.82650.074*0.254 (2)
H18F0.33900.54190.85400.074*0.254 (2)
O19C0.1556 (3)0.4912 (2)0.95997 (13)0.0955 (8)0.50
H19C0.22880.47660.98890.143*0.50
O1W0.3885 (2)0.41374 (17)0.05933 (12)0.0578 (4)
H1WA0.358 (3)0.430 (3)0.1120 (13)0.087*
H1WB0.310 (3)0.403 (6)0.037 (3)0.087*0.50
H1WC0.454 (6)0.464 (4)0.021 (3)0.087*0.50
O2W0.2876 (3)0.46018 (19)0.23122 (13)0.0799 (6)
H2WA0.333 (4)0.515 (2)0.243 (2)0.120*
H2WB0.233 (4)0.416 (3)0.2800 (16)0.120*
O3W0.2824 (3)0.0208 (2)0.17533 (14)0.0842 (6)
H3WA0.348 (4)0.035 (3)0.152 (2)0.126*
H3WB0.269 (4)0.041 (3)0.2344 (10)0.126*
O4W0.4741 (3)0.1711 (2)0.07309 (19)0.0982 (8)
H4WA0.454 (5)0.2404 (16)0.078 (3)0.147*
H4WB0.565 (3)0.165 (3)0.038 (3)0.147*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C1A0.0546 (14)0.0526 (14)0.0497 (13)0.0052 (11)0.0103 (11)0.0170 (11)
C2A0.0354 (11)0.0358 (11)0.0449 (12)0.0045 (9)0.0070 (9)0.0071 (9)
N3A0.0405 (10)0.0324 (9)0.0483 (11)0.0117 (8)0.0071 (8)0.0095 (8)
C4A0.0285 (9)0.0283 (10)0.0455 (12)0.0071 (8)0.0055 (9)0.0076 (9)
N5A0.0324 (8)0.0297 (8)0.0404 (9)0.0094 (7)0.0042 (7)0.0053 (7)
C6A0.0375 (11)0.0396 (11)0.0399 (12)0.0092 (9)0.0013 (9)0.0058 (9)
N7A0.0386 (9)0.0312 (9)0.0419 (10)0.0103 (7)0.0040 (8)0.0058 (7)
C8A0.0327 (10)0.0323 (10)0.0404 (11)0.0024 (8)0.0044 (8)0.0054 (9)
C9A0.0348 (10)0.0331 (11)0.0473 (12)0.0058 (9)0.0071 (9)0.0125 (9)
C10A0.0319 (10)0.0323 (10)0.0504 (13)0.0053 (9)0.0070 (9)0.0114 (9)
O11A0.0525 (9)0.0411 (8)0.0549 (10)0.0261 (7)0.0050 (7)0.0058 (7)
N12A0.0496 (11)0.0491 (11)0.0488 (11)0.0128 (9)0.0100 (9)0.0133 (9)
C13A0.0543 (14)0.0536 (14)0.0448 (13)0.0082 (11)0.0099 (11)0.0145 (11)
N14A0.0447 (10)0.0414 (10)0.0419 (10)0.0077 (8)0.0072 (8)0.0051 (8)
C15A0.0607 (16)0.0518 (14)0.0454 (13)0.0144 (12)0.0020 (11)0.0001 (11)
O16A0.0563 (10)0.0780 (12)0.0495 (10)0.0192 (9)0.0031 (8)0.0214 (9)
C17A0.072 (2)0.095 (2)0.076 (2)0.0237 (17)0.0047 (15)0.0423 (18)
C18A0.0720 (19)0.0674 (18)0.081 (2)0.0154 (15)0.0105 (16)0.0204 (16)
O19A0.0646 (11)0.0776 (13)0.0715 (13)0.0184 (10)0.0051 (10)0.0199 (11)
C1B0.0522 (13)0.0442 (13)0.0461 (13)0.0060 (10)0.0116 (10)0.0148 (10)
C2B0.0367 (11)0.0355 (11)0.0388 (11)0.0014 (9)0.0071 (9)0.0081 (9)
N3B0.0370 (9)0.0293 (8)0.0401 (10)0.0118 (7)0.0040 (7)0.0058 (7)
C4B0.0281 (9)0.0247 (9)0.0387 (11)0.0045 (8)0.0040 (8)0.0026 (8)
N5B0.0341 (8)0.0284 (8)0.0349 (9)0.0068 (7)0.0035 (7)0.0034 (7)
C6B0.0426 (11)0.0400 (11)0.0347 (11)0.0074 (10)0.0031 (9)0.0073 (9)
N7B0.0350 (9)0.0310 (8)0.0343 (9)0.0095 (7)0.0047 (7)0.0037 (7)
C8B0.0302 (10)0.0290 (10)0.0372 (11)0.0008 (8)0.0088 (8)0.0056 (8)
C9B0.0305 (10)0.0272 (10)0.0424 (11)0.0061 (8)0.0096 (8)0.0029 (8)
C10B0.0291 (10)0.0286 (10)0.0435 (12)0.0054 (8)0.0054 (9)0.0032 (9)
O11B0.0485 (9)0.0449 (9)0.0426 (9)0.0211 (7)0.0033 (7)0.0023 (7)
N12B0.0408 (9)0.0339 (9)0.0465 (11)0.0097 (8)0.0142 (8)0.0063 (8)
C13B0.0433 (12)0.0354 (11)0.0458 (13)0.0064 (9)0.0158 (10)0.0084 (9)
N14B0.0389 (9)0.0354 (9)0.0373 (9)0.0064 (7)0.0104 (7)0.0047 (7)
C15B0.0426 (12)0.0466 (12)0.0377 (11)0.0001 (10)0.0063 (9)0.0069 (10)
O16B0.0575 (12)0.0451 (12)0.0345 (10)0.0039 (10)0.0149 (9)0.0143 (8)
C17B0.078 (2)0.0471 (19)0.0346 (15)0.0088 (17)0.0155 (15)0.0149 (13)
C18B0.0556 (16)0.069 (2)0.0546 (16)0.0099 (15)0.0123 (13)0.0049 (14)
O19B0.0791 (14)0.1174 (18)0.0651 (13)0.0011 (13)0.0233 (11)0.0294 (12)
C15C0.0426 (12)0.0466 (12)0.0377 (11)0.0001 (10)0.0063 (9)0.0069 (10)
O16C0.0575 (12)0.0451 (12)0.0345 (10)0.0039 (10)0.0149 (9)0.0143 (8)
C17C0.078 (2)0.0471 (19)0.0346 (15)0.0088 (17)0.0155 (15)0.0149 (13)
C18C0.0556 (16)0.069 (2)0.0546 (16)0.0099 (15)0.0123 (13)0.0049 (14)
O19C0.0791 (14)0.1174 (18)0.0651 (13)0.0011 (13)0.0233 (11)0.0294 (12)
O1W0.0573 (11)0.0663 (12)0.0451 (9)0.0124 (9)0.0054 (8)0.0079 (9)
O2W0.1107 (17)0.0789 (14)0.0481 (10)0.0560 (12)0.0060 (10)0.0204 (10)
O3W0.1060 (17)0.0781 (15)0.0609 (12)0.0121 (12)0.0017 (12)0.0159 (11)
O4W0.0967 (17)0.0738 (14)0.1005 (17)0.0038 (13)0.0265 (13)0.0216 (13)
Geometric parameters (Å, º) top
C1A—C2A1.483 (3)C4B—N7B1.316 (2)
C1A—H1A10.9599C4B—N5B1.381 (2)
C1A—H1A20.9599N5B—C6B1.392 (3)
C1A—H1A30.9599N5B—C10B1.417 (2)
C2A—C6A1.342 (3)C6B—H6B0.9300
C2A—N3A1.382 (3)N7B—C8B1.353 (2)
N3A—C4A1.338 (3)C8B—N14B1.373 (3)
N3A—H3A0.8600C8B—C9B1.391 (3)
C4A—N7A1.316 (3)C9B—N12B1.385 (2)
C4A—N5A1.386 (2)C9B—C10B1.409 (3)
N5A—C6A1.405 (3)C10B—O11B1.227 (2)
N5A—C10A1.409 (3)N12B—C13B1.297 (3)
C6A—H6A0.9300C13B—N14B1.379 (3)
N7A—C8A1.336 (3)C13B—H13B0.9300
C8A—N14A1.378 (3)N14B—C15B1.454 (3)
C8A—C9A1.395 (3)C15B—O16B1.406 (2)
C9A—N12A1.388 (3)C15B—H15C0.9700
C9A—C10A1.412 (3)C15B—H15D0.9700
C10A—O11A1.234 (2)O16B—C17B1.417 (3)
N12A—C13A1.298 (3)C17B—C18B1.500 (4)
C13A—N14A1.369 (3)C17B—H17C0.9700
C13A—H13A0.9300C17B—H17D0.9700
N14A—C15A1.453 (3)C18B—O19B1.398 (3)
C15A—O16A1.411 (2)C18B—H18C0.9700
C15A—H15A0.9700C18B—H18D0.9700
C15A—H15B0.9700O19B—H19B0.8200
O16A—C17A1.412 (3)O16C—C17C1.415 (3)
C17A—C18A1.496 (3)C17C—C18C1.497 (4)
C17A—H17A0.9700C17C—H17E0.9700
C17A—H17B0.9700C17C—H17F0.9700
C18A—O19A1.399 (3)C18C—H18E0.9700
C18A—H18A0.9700C18C—H18F0.9700
C18A—H18B0.9700O1W—H1WA0.836 (13)
O19A—H19A0.8200O1W—H1WB0.835 (13)
C1B—C2B1.481 (3)O1W—H1WC0.835 (13)
C1B—H1B10.9599O2W—H2WA0.834 (13)
C1B—H1B20.9599O2W—H2WB0.833 (13)
C1B—H1B30.9599O3W—H3WA0.835 (13)
C2B—C6B1.335 (3)O3W—H3WB0.836 (13)
C2B—N3B1.392 (3)O4W—H4WA0.835 (13)
N3B—C4B1.349 (2)O4W—H4WB0.834 (13)
N3B—H3B0.8600
C2A—C1A—H1A1109.5N3B—C2B—C1B121.73 (18)
C2A—C1A—H1A2109.5C4B—N3B—C2B110.31 (16)
H1A1—C1A—H1A2109.5C4B—N3B—H3B124.8
C2A—C1A—H1A3109.5C2B—N3B—H3B124.8
H1A1—C1A—H1A3109.5N7B—C4B—N3B127.60 (17)
H1A2—C1A—H1A3109.5N7B—C4B—N5B126.71 (17)
C6A—C2A—N3A107.28 (18)N3B—C4B—N5B105.69 (16)
C6A—C2A—C1A132.0 (2)C4B—N5B—C6B108.88 (16)
N3A—C2A—C1A120.72 (18)C4B—N5B—C10B124.00 (17)
C4A—N3A—C2A110.65 (16)C6B—N5B—C10B127.12 (16)
C4A—N3A—H3A124.7C2B—C6B—N5B107.89 (18)
C2A—N3A—H3A124.7C2B—C6B—H6B126.1
N7A—C4A—N3A127.06 (17)N5B—C6B—H6B126.1
N7A—C4A—N5A126.37 (18)C4B—N7B—C8B110.32 (16)
N3A—C4A—N5A106.56 (17)N7B—C8B—N14B126.46 (17)
C4A—N5A—C6A107.65 (16)N7B—C8B—C9B127.83 (18)
C4A—N5A—C10A124.29 (17)N14B—C8B—C9B105.70 (16)
C6A—N5A—C10A128.04 (16)N12B—C9B—C8B110.00 (17)
C2A—C6A—N5A107.85 (18)N12B—C9B—C10B128.42 (17)
C2A—C6A—H6A126.1C8B—C9B—C10B121.58 (18)
N5A—C6A—H6A126.1O11B—C10B—C9B129.70 (19)
C4A—N7A—C8A109.79 (16)O11B—C10B—N5B120.74 (18)
N7A—C8A—N14A125.02 (18)C9B—C10B—N5B109.56 (16)
N7A—C8A—C9A129.43 (19)C13B—N12B—C9B105.02 (17)
N14A—C8A—C9A105.55 (18)N12B—C13B—N14B113.34 (18)
N12A—C9A—C8A110.07 (18)N12B—C13B—H13B123.3
N12A—C9A—C10A129.56 (18)N14B—C13B—H13B123.3
C8A—C9A—C10A120.36 (19)C8B—N14B—C13B105.94 (16)
O11A—C10A—N5A119.61 (19)C8B—N14B—C15B128.36 (17)
O11A—C10A—C9A130.72 (19)C13B—N14B—C15B125.64 (18)
N5A—C10A—C9A109.67 (17)O16B—C15B—N14B112.39 (17)
C13A—N12A—C9A104.41 (18)O16B—C15B—H15C109.1
N12A—C13A—N14A114.2 (2)N14B—C15B—H15C109.1
N12A—C13A—H13A122.9O16B—C15B—H15D109.1
N14A—C13A—H13A122.9N14B—C15B—H15D109.1
C13A—N14A—C8A105.72 (17)H15C—C15B—H15D107.9
C13A—N14A—C15A129.63 (19)C15B—O16B—C17B110.61 (18)
C8A—N14A—C15A124.63 (19)O16B—C17B—C18B108.1 (3)
O16A—C15A—N14A112.02 (19)O16B—C17B—H17C110.1
O16A—C15A—H15A109.2C18B—C17B—H17C110.1
N14A—C15A—H15A109.2O16B—C17B—H17D110.1
O16A—C15A—H15B109.2C18B—C17B—H17D110.1
N14A—C15A—H15B109.2H17C—C17B—H17D108.4
H15A—C15A—H15B107.9O19B—C18B—C17B112.0 (3)
C15A—O16A—C17A113.29 (19)O19B—C18B—H18C109.2
O16A—C17A—C18A109.2 (2)C17B—C18B—H18C109.2
O16A—C17A—H17A109.8O19B—C18B—H18D109.2
C18A—C17A—H17A109.8C17B—C18B—H18D109.2
O16A—C17A—H17B109.8H18C—C18B—H18D107.9
C18A—C17A—H17B109.8C18B—O19B—H19B109.5
H17A—C17A—H17B108.3O16C—C17C—C18C109.0 (5)
O19A—C18A—C17A113.3 (2)O16C—C17C—H17E109.9
O19A—C18A—H18A108.9C18C—C17C—H17E109.9
C17A—C18A—H18A108.9O16C—C17C—H17F109.9
O19A—C18A—H18B108.9C18C—C17C—H17F109.9
C17A—C18A—H18B108.9H17E—C17C—H17F108.3
H18A—C18A—H18B107.7C17C—C18C—H18E108.8
C18A—O19A—H19A109.5C17C—C18C—H18F108.8
C2B—C1B—H1B1109.5H18E—C18C—H18F107.7
C2B—C1B—H1B2109.5H1WA—O1W—H1WB112 (2)
H1B1—C1B—H1B2109.5H1WA—O1W—H1WC112 (2)
C2B—C1B—H1B3109.5H1WB—O1W—H1WC112 (6)
H1B1—C1B—H1B3109.5H2WA—O2W—H2WB113 (2)
H1B2—C1B—H1B3109.5H3WA—O3W—H3WB112 (2)
C6B—C2B—N3B107.23 (18)H4WA—O4W—H4WB112 (2)
C6B—C2B—C1B131.0 (2)
C6A—C2A—N3A—C4A0.0 (2)C6B—C2B—N3B—C4B0.4 (2)
C1A—C2A—N3A—C4A178.84 (19)C1B—C2B—N3B—C4B179.51 (18)
C2A—N3A—C4A—N7A178.20 (19)C2B—N3B—C4B—N7B179.93 (18)
C2A—N3A—C4A—N5A0.5 (2)C2B—N3B—C4B—N5B0.2 (2)
N7A—C4A—N5A—C6A177.91 (19)N7B—C4B—N5B—C6B179.76 (18)
N3A—C4A—N5A—C6A0.8 (2)N3B—C4B—N5B—C6B0.1 (2)
N7A—C4A—N5A—C10A3.6 (3)N7B—C4B—N5B—C10B0.1 (3)
N3A—C4A—N5A—C10A177.71 (17)N3B—C4B—N5B—C10B179.77 (16)
N3A—C2A—C6A—N5A0.5 (2)N3B—C2B—C6B—N5B0.5 (2)
C1A—C2A—C6A—N5A178.2 (2)C1B—C2B—C6B—N5B179.4 (2)
C4A—N5A—C6A—C2A0.8 (2)C4B—N5B—C6B—C2B0.4 (2)
C10A—N5A—C6A—C2A177.62 (18)C10B—N5B—C6B—C2B179.98 (18)
N3A—C4A—N7A—C8A179.63 (19)N3B—C4B—N7B—C8B179.45 (18)
N5A—C4A—N7A—C8A1.2 (3)N5B—C4B—N7B—C8B0.4 (3)
C4A—N7A—C8A—N14A178.97 (19)C4B—N7B—C8B—N14B179.46 (17)
C4A—N7A—C8A—C9A1.4 (3)C4B—N7B—C8B—C9B0.3 (3)
N7A—C8A—C9A—N12A179.21 (19)N7B—C8B—C9B—N12B179.83 (18)
N14A—C8A—C9A—N12A0.5 (2)N14B—C8B—C9B—N12B0.0 (2)
N7A—C8A—C9A—C10A1.8 (3)N7B—C8B—C9B—C10B0.1 (3)
N14A—C8A—C9A—C10A178.57 (18)N14B—C8B—C9B—C10B179.89 (17)
C4A—N5A—C10A—O11A176.88 (18)N12B—C9B—C10B—O11B0.5 (3)
C6A—N5A—C10A—O11A1.3 (3)C8B—C9B—C10B—O11B179.6 (2)
C4A—N5A—C10A—C9A2.9 (3)N12B—C9B—C10B—N5B179.52 (18)
C6A—N5A—C10A—C9A178.94 (18)C8B—C9B—C10B—N5B0.4 (3)
N12A—C9A—C10A—O11A2.0 (4)C4B—N5B—C10B—O11B179.69 (18)
C8A—C9A—C10A—O11A179.2 (2)C6B—N5B—C10B—O11B0.7 (3)
N12A—C9A—C10A—N5A178.31 (19)C4B—N5B—C10B—C9B0.3 (2)
C8A—C9A—C10A—N5A0.5 (3)C6B—N5B—C10B—C9B179.30 (18)
C8A—C9A—N12A—C13A0.4 (2)C8B—C9B—N12B—C13B0.3 (2)
C10A—C9A—N12A—C13A178.5 (2)C10B—C9B—N12B—C13B179.6 (2)
C9A—N12A—C13A—N14A0.1 (3)C9B—N12B—C13B—N14B0.5 (2)
N12A—C13A—N14A—C8A0.1 (3)N7B—C8B—N14B—C13B179.57 (19)
N12A—C13A—N14A—C15A178.6 (2)C9B—C8B—N14B—C13B0.3 (2)
N7A—C8A—N14A—C13A179.33 (19)N7B—C8B—N14B—C15B3.2 (3)
C9A—C8A—N14A—C13A0.4 (2)C9B—C8B—N14B—C15B176.98 (18)
N7A—C8A—N14A—C15A1.9 (3)N12B—C13B—N14B—C8B0.5 (2)
C9A—C8A—N14A—C15A178.45 (19)N12B—C13B—N14B—C15B176.87 (18)
C13A—N14A—C15A—O16A100.3 (3)C8B—N14B—C15B—O16B107.3 (2)
C8A—N14A—C15A—O16A78.2 (3)C13B—N14B—C15B—O16B69.4 (3)
N14A—C15A—O16A—C17A87.4 (3)N14B—C15B—O16B—C17B68.8 (3)
C15A—O16A—C17A—C18A171.5 (2)C15B—O16B—C17B—C18B178.1 (2)
O16A—C17A—C18A—O19A67.9 (3)O16B—C17B—C18B—O19B77.7 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3A—H3A···N12Bi0.862.012.803 (2)154
O19A—H19A···O3Wii0.821.952.740 (3)162
N3B—H3B···O11A0.861.952.749 (2)153
O19B—H19B···O19Biii0.821.872.644 (4)157
O19C—H19C···O1Wiv0.821.902.709 (3)170
O1W—H1WA···O2W0.84 (1)1.86 (1)2.690 (2)177 (3)
O1W—H1WB···O19Bv0.84 (1)2.00 (4)2.709 (3)142 (6)
O1W—H1WC···O1Wvi0.84 (1)1.98 (1)2.807 (3)174 (4)
O2W—H2WA···N12Avii0.83 (1)1.97 (1)2.793 (3)171 (3)
O2W—H2WB···N7Bvii0.83 (1)2.16 (1)2.983 (2)171 (3)
O3W—H3WA···O4W0.84 (1)1.93 (1)2.748 (3)167 (3)
O3W—H3WB···O11Bviii0.84 (1)2.00 (1)2.824 (3)171 (4)
O4W—H4WA···O1W0.84 (1)2.03 (2)2.846 (3)166 (5)
O4W—H4WB···O19Aix0.83 (1)1.90 (1)2.734 (3)174 (4)
Symmetry codes: (i) x1, y1, z; (ii) x1, y, z+1; (iii) x, y+1, z+2; (iv) x, y, z+1; (v) x, y, z1; (vi) x+1, y+1, z; (vii) x, y+1, z+1; (viii) x, y1, z; (ix) x+2, y, z1.

Experimental details

Crystal data
Chemical formulaC11H13N5O3·2H2O
Mr299.30
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)8.450 (1), 11.665 (2), 14.930 (3)
α, β, γ (°)75.44 (2), 76.65 (2), 86.44 (2)
V3)1385.9 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.32 × 0.28 × 0.22
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
6873, 6873, 3922
Rint0.0000
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.137, 1.03
No. of reflections6873
No. of parameters420
No. of restraints64
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.21, 0.21

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), SDP (Enraf–Nonius, 1985), SHELXS97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3A—H3A···N12Bi0.862.012.803 (2)153.6
O19A—H19A···O3Wii0.821.952.740 (3)161.6
N3B—H3B···O11A0.861.952.749 (2)153.4
O19B—H19B···O19Biii0.821.872.644 (4)156.5
O19C—H19C···O1Wiv0.821.902.709 (3)169.6
O1W—H1WA···O2W0.836 (13)1.855 (13)2.690 (2)177 (3)
O1W—H1WB···O19Bv0.835 (13)2.00 (4)2.709 (3)142 (6)
O1W—H1WC···O1Wvi0.835 (13)1.975 (14)2.807 (3)174 (4)
O2W—H2WA···N12Avii0.834 (13)1.967 (14)2.793 (3)171 (3)
O2W—H2WB···N7Bvii0.833 (13)2.157 (13)2.983 (2)171 (3)
O3W—H3WA···O4W0.835 (13)1.928 (14)2.748 (3)167 (3)
O3W—H3WB···O11Bviii0.836 (13)1.995 (14)2.824 (3)171 (4)
O4W—H4WA···O1W0.835 (13)2.030 (17)2.846 (3)166 (5)
O4W—H4WB···O19Aix0.834 (13)1.903 (13)2.734 (3)174 (4)
Symmetry codes: (i) x1, y1, z; (ii) x1, y, z+1; (iii) x, y+1, z+2; (iv) x, y, z+1; (v) x, y, z1; (vi) x+1, y+1, z; (vii) x, y+1, z+1; (viii) x, y1, z; (ix) x+2, y, z1.
 

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