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In the title compound, C7H7N2S+·C4H5O5, the ions are con­nected by N—H...O hydrogen bonds. The hydrogen oxydiacetate residues are linked together by O—H...O hydrogen bonds disordered about centres of inversion into hydrogen-bonded ribbon layers cross­linked by weak C—H...O and stacking inter­actions. The cation exists mainly in the 2,3-dihydro-1,3-benzothia­zol-2-iminium form, with a small participation of the 2-amino­benzothia­zolium form, based on the structural data and quantum mechanical calculations. This study provides structural insights relevant to the biochemical activity of benzothia­zole mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108038365/ga3105sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108038365/ga3105Isup2.hkl
Contains datablock I

CCDC reference: 718124

Comment top

Benzothiazole derivatives possess antitumor properties (Jin et al., 2006; Mortimer et al., 2006; Akhtar et al., 2008). The precise mechanism of action for these selectively acting compounds has not yet been identified (O'Brien et al., 2003; Choi et al., 2006). It has been postulated that benzothiazoles are metabolized to as-yet unidentified reactive species, which then form DNA adducts provoking cancer cell death. Knowledge of geometrical parameters, the primary sites available for noncovalent interactions, charge distribution, stereoelectronic properties and conformation flexibility is helpful in determining the mechanism of drug molecular interactions. Since 2-aminobenzothiazole is often used as a model for complex biological active molecules (Padilla-Martinez et al., 2003), the crystal structure of its adduct with oxydiacetic acid, the title compound, (I), as well as the results of quantum-mechanical calculations, are reported herein. This dicarboxylic acid was chosen because it contains different hydrogen bond donor/acceptor groups (two carboxylic groups and one ether oxygen atom), which may serve for the better understanding of macromolecules containing these functional groups.

One of the oxydiacetic acid protons is transferred to the 2-aminobenzothiazole molecule, so that the asymmetric unit of (I) consists of a 2-aminobenzothiazolium ion and an oxydiacetic acid in a monoionized state (Fig. 1). The oxygen bonded hydrogen atoms (H2O and H4O) of the oxydiacetate anion are disordered (by symmetry centres) over two positions. The cation is slightly distorted from planarity, with the largest deviation being for atom N2 at 0.0205 (11) Å from the weighted least-squares plane calculated through all non-hydrogen atoms of cation. Each of the five- and six-membered rings of the cation is planar and they are inclined at 0.92 (8)° to each other. The anion is also close to planarity, but the distortion is larger than in the cation, with a maximum deviation of 0.0742 (12)Å for atom O5. The 2-aminobenzothiazolium and diglycolate ions are almost coplanar, with an interplanar angle of 6.69 (5)°.

The bond distances and angles within the anion show no unusual values (Table 1). The bond lengths and angles of the 2-aminobenzothiazolium moiety are within the ranges reported for its adducts with organic anions (Lynch et al., 1998; Lynch et al., 1999; Smith et al., 1999), and are close to these of pure 2-aminobenzothiazole (ABT) (Goubitz et al., 2001). In comparison with ABT, the C2—N1, S1—C3 and C1—N2 bonds of (I) are shortened insignificantly [by 0.012 (11), 0.017 (9) and 0.035 (12) Å, respectively], while the C1—N1 bond is elongated by 0.049 (8) Å (C1—S1 bond has the same length in both compounds). For similar 2-aminoheterocyclic compounds shortening of the C—NH2 bond has been explained by the attraction of a more electron-accepting heterocyclic ring (Lynch & Jones, 2004). The C1—N2 distance (Table 1) is close to that of exocyclic carbon-nitrogen double bonds found in iminobenzothiazole derivatives (Garcia-Hernandez et al., 2006; Shi et al., 2003; Tellez et al., 2004). These observations point to a significant contribution of the exocyclic iminium resonance form, the 2,3-dihydro-1,3-benzothiazol-2-iminium (Fig. 2b), to the overall molecular electronic structure, with a lesser contribution from the 2-aminobenzothiazolium form (Fig. 2a). Thus, (I) is the first reported example of a compound containing the 2,3-dihydro-1,3-benzothiazol-2-iminium ion. Exocyclic imines or iminium ions in equilibrium with endocyclic ones have previously been found and discussed for other compounds containing the NexocyclicCNendocyclic moiety (Lynch and Jones, 2004; Lynch et al., 2000; Low et al., 2003; Donga et al., 2002).

The 2,3-dihydro-1,3-benzothiazol-2-iminium cations and oxydiacetate anions of (I) are linked by NH···O(carboxylate) hydrogen bonds (Table 2) forming N2R22(10), N2R44(16) and N2R44(24) rings (Bernstein et al., 1995). The small N2—H2NA···O3 and N2—H2NB···O3 angles, the existence of N2—H···O(carboxylate) hydrogen bonds and the weak (in comparison with carboxylate oxygen atoms) electron-donating properties of the ether oxygen atoms indicate that the N2—H···O3 interactions are forced by the relative arrangement of the ions. Additionally, between the oxydiacetate anions there exist O—H···O hydrogen bonds, which generate the (averaged) N1C(8) chain structure (Fig. 3). Oxydiacetate anions linked end-to-end by hydrogen bonds have been observed in two structures to date, namely ammonium hydrogen oxydiacetate (Herbertsson & Hedman, 1982) and pentane-1,5-diammonium bis(oxydiacetate) monohydrate (Urbanczyk-Lipkowska, 2000). The above-mentioned interactions link molecules into hydrogen bonded ribbons parallel to the (12–1) plane and these ribbons extend along the [2–10] axis. An interesting feature of the structure of (I) is the presence of weak π···π stacking interactions (along [010] axis) between the almost parallel [inclined at 0.92 (8)°] five-membered heterocyclic and benzene rings of adjacent 2,3-dihydro-1,3-benzothiazol-2-iminium ions orientated in opposite directions [symmetry codes: -x, -y, -z; -x, -y + 1, -z]. The perpendicular distances between the first ring centroid on the second ring are 3.964 (3) and 3.805 (3) Å and the angles between the vectors linking the ring centroids and the normal to five membered ring plane are 26.7 (2) and 24.5 (2)°, respectively. The molar enthalpy of π-π stacking interaction, as calculated by total self-consistent field energy method (for two interacting cations) is 1.4 kcal mol-1 (1 kcal mol-1 = 4.184 kJ mol-1), including a basis set superposition error calculated by the counterpoize method of Boys & Bernardi (1970). Moreover, there are two short C—H···O contacts in the structure which, according to Desiraju & Steiner (1999), can be classified as weak hydrogen bonds (Table 2). These weak C–H···O hydrogen bonds and π···π stacking interactions thus provide some linkage between the hydrogen-bonded ribbons.

The molecular electronic properties of (I) have been calculated at a single point for both diffraction-derived coordinates and the optimized structure. Sets containing from one to four cation-anion pairs were used for calculations. The cation and anion of each pair were arranged as in the asymmetric unit and then the second and following pairs were added one by one to the first pair along the crystallographic [2–10] axis (i.e. along the chain created by anions linked by O—H···O hydrogen bonds). The B3LYP functional (Becke, 1993; Lee et al., 1988) in the triple zeta 6–31++G(d,p) basis set was used, as implemented in GAUSSIAN03 (Frisch et al., 2004). The differences in electronic properties and energies originating from the different numbers of molecules used in the calculations are given in parentheses (as standard deviations) in Table 2. For example, the N2—H2NB···O1 hydrogen bond energy calculated for one cation-anion pair was slightly different than the two energies calculated for the set containing two pairs (with three energies calculated for the set containing three pairs, and so on). Thus, for all calculations ten values were obtained. The arithmetic mean and standard deviation of this ten-element discrete data set were then calculated. Where no deviation is given, the values were the same within the range of reported precision.

The atomic charges were calculated according to natural population analysis, (NPA) (Foster and Weinhold, 1980; Reed and Weinhold, 1985; Reed et al., 1988), Merz-Kollman-Singh (MKS) (Singh & Kollman, 1984; Besler et al., 1990) and Breneman (Breneman & Wiberg, 1990) schemes. Although the calculation of effective atomic charges plays an important role in the application of quantum mechanical calculations to molecular systems, the unambiguous dividing up of the overall molecular charge density in atomic contributions is still an unresolved problem, and none of known procedures give fully reliable values of atomic charges. Thus, a discussion of atomic charges should cover more than one algorithm used for charge density division (Table 3). Generally, it can be stated that less reliable values are given by the Mulliken population analysis and more reliable results are provided by the Breneman method [for a detailed discussion on the methodology and reliability of the methods used, see Martin & Zipse (2005), and references therein]. The results show that, in general, the atomic charges do not depend on the method used for calculation (Table 3). Both nitrogen atoms are negatively charged, but the NH group of thiazole ring has a negative group charge whereas the NH2 group has a positive group charge. Such distribution of charges can be observed only in 2,3-dihydro-1,3-benzothiazol-2-iminium ion (Fig. 2b), so these calculated values confirm the postulate about the dominance of the exocyclic iminium resonance form.

To determine the multiplicity of C—-N bonds in (I), the bond orders were calculated by means of the bond-valence method (BVM) (Brown, 2002; Mohri, 2000) using the Brown-Altermatt equation (Brown & Altermatt, 1985): νij = exp[(Rij-dij)/0.37]. The bond-valence parameters (Rij) taken as mean single bond lengths were RC—N(exocyclic) = 1.47 Å, RC—N(endocyclic) = 1.35 Å and RC—S(endocyclic) = 1.75 Å. The BVM bond orders are then 1.06, 1.58 and 1.04 v.u. (valence units), respectively, for C1—N1, C1—N2 and C1—S1 bonds, which suggests a considerable degree of double bond character between atoms C1 and N2. The natural localized molecular orbital bond orders (Reed & Schleyer, 1988, 1990) are 0.952 for the C1—N1 bond, 0.968 for S1—C1 and 1.262 for C1—N2. The Wiberg bond indexes (Wiberg, 1968) are higher (1.217, 1.179 and 1.438, respectively) but they exhibit similar dependence. Moreover, Natural Bond Orbital (NBO) analysis shows that there are two C1—N2 bonding orbitals (σ and π) occupied by 1.991 and 1.993 electrons, respectively, and only one C1—N1 bonding orbital occupied by 1.986 electrons. These observations clearly indicate that π-electron density is localized in the exocyclic rather than in heterocyclic C—N bond, and again confirms that the resonance equilibrium is largely shifted towards the exocyclic iminium resonance form. It is worth mentioning that during geometry optimization process, one proton of the imine group migrated to the oxydiacetate anion, forming the adduct of 2-imino-1,3(3H)-benzothiazoline and oxydiacetic acid.

The energies of hydrogen bonds calculated in terms of an NBO energetic analysis (Foster and Weinhold, 1980; Reed and Weinhold, 1985; Reed et al., 1988) are presented in Table 2. In general, the values obtained lie in ranges typical for similar hydrogen bonds (Desiraju & Steiner, 1999). The small energy values of both the N2—H2NA···O3 and N2—H2NB···O3 hydrogen bonds (entries 4 & 5, Table 2) confirm that these are fortuitous interactions forced by the relative arrangement of the ions. It is noteworthy that the energy of the two seemingly similar O—H···O hydrogen bonds differs by about 19 kcal/mol. This originates from the arrangement of the hydrogen atoms towards the anion backbone (cis for H2O, trans for H4O). Thus, in both cases the distance between donor and acceptor is short enough to allow interaction, but the unfavorable arrangement of orbitals (electron lone pairs of the oxygen atom) leads to a decrease in the O4—H4O···O4i bond strength (entry 7, Table 2).

Experimental top

An ethanolic solution [Volume?] of 2-aminobenzothiazole (0.150 g, 1 mmol) was mixed with a hot aqueous solution [Volume?] of oxydiacetic acid (0.270 g, 2 mmol). The resulting solution was allowed to cool to room temperature and, after several days, colourless crystals of (I) suitable for X-ray diffraction were separated (yield 76%).

Refinement top

The carbon-bonded H atoms were placed in calculated positions, while the other H atoms were found from difference Fourier synthesis after eight cycles of anisotropic refinement. The isotropic displacement parameters of these latter H atoms were then refined to check the correctness of their positions. After eight cycles, the refinement reached stable convergence with isotropic displacement parameters of 0.061, 0.053, 0.079, 0.133 and 0.128 Å2, respectively, for H1N, H2NA, H2NB, H2O and H4O. The relatively large values of isotropic displacement parameters of the oxygen-bonded H atoms suggested that these atoms, placed on symmetry centers on the basis of difference Fourier synthesis, might be in wrong positions (the O2—H2O and O4—H4O distances were 1.23 and 1.24Å). Atoms H2O and H4O were therefore manually shifted off the special positions (with sites occupancies set to 0.5). Refinement of this model converged with isotropic displacement parameters adopting more reasonable values (0.057 and 0.058Å2, respectively, for H2O and H4O) and with acceptable though short O—H bonds distances (Table 2). So in the final model, atoms H2O and H4O atoms were set as equally disordered (by symmetry) over two positions. We note that difference Fourier maps show maxima at symmetry centers with slightly elongated shoulders along the O···O lines. Because elongation can be caused by polarization of the electron density by the O atoms, there is a distinct possibility that oxygen-bonded H atoms are ordered and reside at symmetry centers outside the crystalline state. Thus, existence of symmetric hydrogen bonds cannot be categorically excluded without supporting neutron diffraction data. Additionally we note the presence of windows (Albert, 1961) in the IR spectrum of (I) (at 821 and 849 cm-1) which also suggests symmetric O—H···O hydrogen bonds. All H atoms were refined as riding, with Uiso(H) = 1.2Ueq(C,N). The 001 reflection, affected by the beam stop (Fo2 = 0.00, Fc2 = 67.34), was excluded from the refinement.

Computing details top

Data collection: CrysAlis CCD (UNIL IC & Kuma 2000); cell refinement: CrysAlis RED (UNIL IC & Kuma 2000); data reduction: CrysAlis RED (UNIL IC & Kuma 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL/PC (Sheldrick, 2008) and ORTEP-3 (version 1.062; Farrugia 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. A view of the asymmetric unit of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as spheres of arbitrary radii. Atoms H2O and H4O lie on special positions. Hydrogen bonds are indicated by dashed lines.
[Figure 2] Fig. 2. (a) The endocylic and (b) the exocyclic iminium resonance forms of the cation of (I).
[Figure 3] Fig. 3. Part of the packing of molecules in (I). Dashed lines indicate close interactions (see text).
2,3-Dihydro-1,3-benzothiazol-2-iminium hydrogen oxydiacetate top
Crystal data top
C4H5O5+·C7H7N2SZ = 2
Mr = 284.29F(000) = 296
Triclinic, P1Dx = 1.527 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.0414 (3) ÅCell parameters from 2981 reflections
b = 7.6933 (3) Åθ = 2–20°
c = 11.4621 (6) ŵ = 0.28 mm1
α = 87.216 (3)°T = 291 K
β = 89.845 (3)°Needle, colourless
γ = 85.364 (3)°0.38 × 0.08 × 0.08 mm
V = 618.16 (5) Å3
Data collection top
Kuma KM4 CCD
diffractometer
2182 independent reflections
Radiation source: fine-focus sealed tube1662 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
Detector resolution: 1048576 pixels mm-1θmax = 25.1°, θmin = 2.7°
ω scansh = 88
Absorption correction: numerical
(X-RED; Stoe & Cie, 1999)
k = 99
Tmin = 0.967, Tmax = 0.979l = 1313
6112 measured reflections
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)] = 0.033Hydrogen site location: mixed
wR(F2) = 0.091H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0551P)2 + ]
where P = (Fo2 + 2Fc2)/3
2182 reflections(Δ/σ)max < 0.001
172 parametersΔρmax = 0.15 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C4H5O5+·C7H7N2Sγ = 85.364 (3)°
Mr = 284.29V = 618.16 (5) Å3
Triclinic, P1Z = 2
a = 7.0414 (3) ÅMo Kα radiation
b = 7.6933 (3) ŵ = 0.28 mm1
c = 11.4621 (6) ÅT = 291 K
α = 87.216 (3)°0.38 × 0.08 × 0.08 mm
β = 89.845 (3)°
Data collection top
Kuma KM4 CCD
diffractometer
2182 independent reflections
Absorption correction: numerical
(X-RED; Stoe & Cie, 1999)
1662 reflections with I > 2σ(I)
Tmin = 0.967, Tmax = 0.979Rint = 0.031
6112 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.091H-atom parameters constrained
S = 1.02Δρmax = 0.15 e Å3
2182 reflectionsΔρmin = 0.28 e Å3
172 parameters
Special details top

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

treatment of cell esds is used for estimating esds 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)
N10.02638 (18)0.31143 (17)0.16983 (11)0.0361 (3)
H1N0.04530.36550.22130.043*
C10.2067 (2)0.2544 (2)0.19006 (15)0.0374 (4)
S10.31425 (6)0.16495 (6)0.06783 (4)0.04831 (18)
C20.0381 (2)0.2899 (2)0.05704 (14)0.0340 (4)
C30.1018 (2)0.2096 (2)0.01154 (15)0.0391 (4)
C40.0646 (3)0.1755 (2)0.12662 (17)0.0537 (5)
H40.15740.11950.17260.064*
C50.1130 (3)0.2268 (3)0.17064 (17)0.0610 (6)
H50.14010.20700.24800.073*
C60.2530 (3)0.3076 (3)0.10198 (17)0.0568 (6)
H60.37240.34060.13400.068*
C70.2179 (2)0.3400 (2)0.01340 (16)0.0437 (4)
H70.31190.39340.05980.052*
N20.2957 (2)0.2653 (2)0.28827 (14)0.0520 (4)
H2NA0.22720.30160.35400.062*
H2NB0.42160.21760.29880.062*
O10.65382 (17)0.09502 (16)0.31142 (10)0.0493 (3)
C80.7523 (2)0.0840 (2)0.39999 (15)0.0369 (4)
O20.92056 (17)0.00620 (18)0.40394 (11)0.0595 (4)
H2O0.96460.01050.46810.071*0.50
C90.6850 (2)0.1588 (2)0.51319 (14)0.0342 (4)
H9A0.67880.06500.57240.041*
H9B0.77570.23730.53910.041*
O30.50322 (15)0.25077 (14)0.50037 (10)0.0399 (3)
C100.4434 (2)0.3251 (2)0.60564 (15)0.0410 (4)
H10A0.53570.40400.62870.049*
H10B0.43960.23320.66640.049*
O40.15973 (16)0.42035 (16)0.49886 (14)0.0590 (4)
H4O0.05300.47370.51100.071*0.50
C110.2501 (3)0.4238 (2)0.59567 (19)0.0476 (5)
O50.1932 (2)0.5020 (2)0.68088 (14)0.0752 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0323 (7)0.0443 (8)0.0312 (8)0.0057 (6)0.0037 (6)0.0116 (6)
C10.0312 (9)0.0385 (9)0.0416 (10)0.0027 (7)0.0001 (8)0.0033 (7)
S10.0373 (3)0.0513 (3)0.0553 (3)0.0082 (2)0.0120 (2)0.0119 (2)
C20.0373 (9)0.0353 (9)0.0301 (9)0.0049 (7)0.0034 (7)0.0065 (7)
C30.0449 (10)0.0371 (10)0.0360 (10)0.0050 (8)0.0101 (8)0.0069 (8)
C40.0711 (14)0.0546 (12)0.0382 (11)0.0148 (10)0.0209 (10)0.0167 (9)
C50.0812 (16)0.0727 (14)0.0326 (11)0.0244 (13)0.0058 (11)0.0067 (10)
C60.0594 (13)0.0667 (14)0.0455 (12)0.0137 (11)0.0147 (11)0.0001 (10)
C70.0384 (10)0.0509 (11)0.0418 (10)0.0021 (8)0.0019 (8)0.0055 (8)
N20.0395 (9)0.0689 (11)0.0457 (10)0.0102 (7)0.0083 (7)0.0057 (8)
O10.0415 (7)0.0675 (9)0.0369 (7)0.0155 (6)0.0074 (6)0.0158 (6)
C80.0290 (9)0.0425 (10)0.0378 (10)0.0100 (7)0.0007 (8)0.0098 (7)
O20.0388 (7)0.0914 (10)0.0435 (8)0.0342 (7)0.0033 (6)0.0203 (7)
C90.0263 (8)0.0399 (9)0.0348 (10)0.0100 (7)0.0023 (7)0.0069 (7)
O30.0285 (6)0.0533 (7)0.0356 (7)0.0180 (5)0.0003 (5)0.0138 (5)
C100.0406 (10)0.0435 (10)0.0383 (11)0.0062 (8)0.0091 (8)0.0114 (8)
O40.0315 (7)0.0595 (9)0.0832 (11)0.0189 (6)0.0065 (7)0.0122 (7)
C110.0405 (10)0.0375 (10)0.0635 (14)0.0064 (8)0.0221 (10)0.0040 (9)
O50.0751 (10)0.0682 (10)0.0797 (11)0.0195 (8)0.0423 (9)0.0210 (8)
Geometric parameters (Å, º) top
N1—C11.327 (2)N2—H2NA0.94
N1—C21.393 (2)N2—H2NB0.94
N1—H1N0.87O1—C81.2267 (19)
C1—N21.299 (2)C8—O21.283 (2)
C1—S11.7360 (18)C8—C91.505 (2)
S1—C31.7544 (18)O2—H2O0.80
C2—C71.381 (2)C9—O31.4160 (17)
C2—C31.384 (2)C9—H9A0.97
C3—C41.387 (2)C9—H9B0.97
C4—C51.371 (3)O3—C101.409 (2)
C4—H40.93C10—C111.506 (2)
C5—C61.386 (3)C10—H10A0.97
C5—H50.93C10—H10B0.97
C6—C71.384 (3)O4—C111.283 (2)
C6—H60.93O4—H4O0.84
C7—H70.93C11—O51.222 (3)
C1—N1—C2115.08 (15)C1—N2—H2NA119.5
C1—N1—H1N123.0C1—N2—H2NB121.2
C2—N1—H1N121.7H2NA—N2—H2NB118.2
N2—C1—N1124.95 (17)O1—C8—O2122.70 (16)
N2—C1—S1123.14 (14)O1—C8—C9122.78 (14)
N1—C1—S1111.90 (13)O2—C8—C9114.52 (14)
C1—S1—C390.38 (8)C8—O2—H2O114.8
C7—C2—C3121.42 (16)O3—C9—C8111.26 (13)
C7—C2—N1126.53 (16)O3—C9—H9A109.4
C3—C2—N1112.05 (15)C8—C9—H9A109.4
C2—C3—C4120.71 (17)O3—C9—H9B109.4
C2—C3—S1110.59 (13)C8—C9—H9B109.4
C4—C3—S1128.70 (15)H9A—C9—H9B108.0
C5—C4—C3118.04 (19)C10—O3—C9111.06 (12)
C5—C4—H4121.0O3—C10—C11112.68 (15)
C3—C4—H4121.0O3—C10—H10A109.1
C4—C5—C6121.22 (18)C11—C10—H10A109.1
C4—C5—H5119.4O3—C10—H10B109.1
C6—C5—H5119.4C11—C10—H10B109.1
C7—C6—C5121.14 (19)H10A—C10—H10B107.8
C7—C6—H6119.4C11—O4—H4O104.7
C5—C6—H6119.4O5—C11—O4125.47 (18)
C2—C7—C6117.46 (18)O5—C11—C10116.76 (19)
C2—C7—H7121.3O4—C11—C10117.77 (17)
C6—C7—H7121.3
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O5i0.871.822.6915 (19)174
N2—H2NA···O40.941.972.872 (2)161
N2—H2NB···O10.941.822.7535 (19)172
N2—H2NA···O30.942.562.8328 (18)97
N2—H2NB···O30.942.412.8328 (18)107
O2—H2O···O2ii0.801.682.467 (2)168
O4—H4O···O4i0.841.652.474 (2)167
C10—H10B···O1iii0.972.663.446 (2)138
C4—H4···O1iv0.932.633.534 (2)164
Symmetry codes: (i) x, y+1, z+1; (ii) x+2, y, z+1; (iii) x+1, y, z+1; (iv) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC4H5O5+·C7H7N2S
Mr284.29
Crystal system, space groupTriclinic, P1
Temperature (K)291
a, b, c (Å)7.0414 (3), 7.6933 (3), 11.4621 (6)
α, β, γ (°)87.216 (3), 89.845 (3), 85.364 (3)
V3)618.16 (5)
Z2
Radiation typeMo Kα
µ (mm1)0.28
Crystal size (mm)0.38 × 0.08 × 0.08
Data collection
DiffractometerKuma KM4 CCD
diffractometer
Absorption correctionNumerical
(X-RED; Stoe & Cie, 1999)
Tmin, Tmax0.967, 0.979
No. of measured, independent and
observed [I > 2σ(I)] reflections
6112, 2182, 1662
Rint0.031
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.091, 1.02
No. of reflections2182
No. of parameters172
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.15, 0.28

Computer programs: CrysAlis CCD (UNIL IC & Kuma 2000), CrysAlis RED (UNIL IC & Kuma 2000), SHELXS97 (Sheldrick, 2008), XP in SHELXTL/PC (Sheldrick, 2008) and ORTEP-3 (version 1.062; Farrugia 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Selected bond lengths (Å) top
N1—C11.327 (2)O1—C81.2267 (19)
N1—C21.393 (2)C8—O21.283 (2)
C1—N21.299 (2)O4—C111.283 (2)
C1—S11.7360 (18)C11—O51.222 (3)
S1—C31.7544 (18)
Hydrogen-bond geometry (Å, °) and molar enthalpy E (kcal mol-1) calculated on the NBO basis top
D—H···AD—HH···AD···AD—H···AEa
N1—H1N···O5i0.871.822.691 (2)17414.2 (1)
N2—H2NA···O40.941.972.872 (2)1619.4 (3)
N2—H2NB···O10.941.822.753 (2)17121.7 (8)
N2—H2NA···O30.942.562.833 (2)970.2
N2—H2NB···O30.942.412.833 (2)1070.8
O2—H2O···O2ii0.801.682.467 (2)16834.6 (6)
O4—H4O···O4i0.841.652.474 (2)16715.9 (4)
C10—H10B···O1iii0.972.663.446 (2)1380.03
C4—H4···O1iv0.932.633.534 (2)1640.03
(a) For numbers in brackets (and a discussion of the N—H···O3 interactions), see the text. Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x+2, -y, -z+1; (iii) -x+1, -y, -z+1; (iv) -x+1, -y, -z.
Calculated atomic charges for an isolated molecule of (I) (atomic units) top
Atom/groupNPA chargeNPA group chargeBreneman chargeBreneman group chargeMKS chargeMKS group charge
N1/NH-0.526-0.124-0.623-0.158-0.518-0.075
H1N0.4020.4650.443
N2/NH2-0.6950.196-0.6610.044-0.5700.056
H2NA0.4250.3600.335
H2NB0.4660.3450.291
1 atomic unit = 1.60217653 (14) × 10-19 coulombs. See text for a detailed description of the abbreviations and methods used.
 

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