supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

dn2693 scheme

Acta Cryst. (2011). E67, o1607    [ doi:10.1107/S1600536811021337 ]

2-Ureido-1,3-thiazol-3-ium dihydrogen phosphate

K. Gubina, I. Shatrava, V. Ovchynnikov and V. Amirkhanov

Abstract top

The title compound, C4H6N3OS+·H2PO4-, (I), was obtained as a result of hydrolysis of [(1,3-thiazol-2-ylamino)carbonyl]phosphoramidic acid, (II), in water. X-ray analysis has shown that the N-P bond in (II) breaks, leading to the formation of the substituted carbamide (I). This compound exists as an internal salt. The unit cell consists of a urea cation and an anion of H2PO4-. Protonation of the N atom of the heterocyclic ring was confirmed by the location of the H atom in a difference Fourier map. The molecules of substituted urea are connected by O...O hydrogen bonds into unlimited planes. In turn, those planes are connected to each other via N-H...O hydrogen bonds with molecules of phosphoric acid, forming a three-dimensional polymer.

Comment top

The compound N-1,3-thiazol-2-yl-urea phosphate (I) can be synthesized by hydrolyzation of the [(1,3-thiazol-2-ylamino)carbonyl]phosphoramidic acid (II) in the water solution by heating (Scheme 1). The crystal structure investigation shows that the break up of N—P bond in [(1,3-thiazol-2-ylamino)carbonyl]phosphoramidic leads to the forming of substituted carbamide (Fig.1).

The proton of the phosphoric acid locates at the nitrogen atom of the heterocyclic ring from difference-Fourier map. The molecules of substituted urea connected by hydrogen bonds O(4)H(4)O(3) and O(5)H(5)O(2) into unlimited planes (Table 1). In turn those planes are connected to each other forming three-dimensional polymer via hydrogen bonds with molecules of phosphoric acid: N(3)H(3)O(3), N(2)H(2)O(2) and N(1)H(1 A)O(1), N(1)H(1B)O(5) (Table 1, Fig.2). The interaction of nonbonded S and O atoms can be described as attractive (Angyan, et al., 1987). In the molecule the S O nonbonded distances are significantly shorter (2.653 Å) than the sum of the corresponding van der Waals radii (3.25 Å).

Related literature top

For background to the chemistry of phosphorus–organic compounds, see: Ly & Woollins (1998). For details of the synthesis and properties of the [(1,3-thiazol-2-ylamino)carbonyl]phosphoramidic acid, see: Kirsanov & Levchenko (1957); Smaliy et al.(2003). For structural analogues of phosphorylated carbacylamides and their properties, see: Amirkhanov et al. (1997). For a structural investigation of phosphortriamidic compounds, see: Ovchynnikov et al. (1997). For the synthesis of the aminothiazol-containing phosphortiamides, see: Shatrava et al. (2009). For a description of the attractive interaction in thiazole compounds, see: Burling & Goldstein (1992); Angyan et al. (1987).

Experimental top

The synthesis of [(1,3-thiazol-2-ylamino)carbonyl]phosphoramidic acid (II) was carried out according to the method described by Kirsanov (Kirsanov & Levchenko, 1957). The compound N-1,3-thiazol-2-yl-urea phosphate (I) was obtained due to hydrolyzation of (II) in the water solution (Smaliy et al., 2003). The crystals (I) suitable for X-ray analysis were obtained by heating of [(1,3-thiazol-2-ylamino)carbonyl]phosphoramidic acid in water and evaporating the solvent at room temperature for about 2 days.

Refinement top

H2,H3A and H4A atoms were included in the refinement in the riding motion approximation but with refined isotropic thermal parameter. Other hydrogen atoms were refine isotropically.

Computing details top

Data collection: SMART-NT (Bruker, 1999); cell refinement: SAINT-NT (Bruker, 1999); data reduction: SAINT-NT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP within SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. View of N-1,3-thiazol-2-yl-urea phosphate with the atom labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. three-dimensional-view of the N-1,3-thiazol-2-yl-urea phosphate.
[Figure 3] Fig. 3. The formation of the title compound.
2-ureido-1,3-thiazol-3-ium dihydrogen phosphate top
Crystal data top
C4H6N3OS+·H2PO4−F(000) = 496
Mr = 241.16Dx = 1.691 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2646 reflections
a = 11.9038 (11) Åθ = 1.7–28.0°
b = 9.7936 (10) ŵ = 0.51 mm−1
c = 8.1914 (12) ÅT = 293 K
β = 97.231 (9)°Block, colourless
V = 947.37 (19) Å30.30 × 0.20 × 0.20 mm
Z = 4
Data collection top
Siemens SMART CCD area-detector
diffractometer		2239 independent reflections
Radiation source: fine-focus sealed tube1893 reflections with I > 2σ(I)
graphiteRint = 0.014
ω scansθmax = 28.0°, θmin = 1.7°
Absorption correction: empirical (using intensity measurements)
(SADABS; Bruker, 1999)		h = −14→15
Tmin = 0.861, Tmax = 0.904k = −12→10
2644 measured reflectionsl = −10→10
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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0666P)2 + 0.4134P]
where P = (Fo2 + 2Fc2)/3
2239 reflections(Δ/σ)max = 0.001
150 parametersΔρmax = 0.58 e Å−3
0 restraintsΔρmin = −0.43 e Å−3
Crystal data top
C4H6N3OS+·H2PO4−V = 947.37 (19) Å3
Mr = 241.16Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.9038 (11) ŵ = 0.51 mm−1
b = 9.7936 (10) ÅT = 293 K
c = 8.1914 (12) Å0.30 × 0.20 × 0.20 mm
β = 97.231 (9)°
Data collection top
Siemens SMART CCD area-detector
diffractometer		2239 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Bruker, 1999)		1893 reflections with I > 2σ(I)
Tmin = 0.861, Tmax = 0.904Rint = 0.014
2644 measured reflectionsθmax = 28.0°
Refinement top
R[F2 > 2σ(F2)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.109Δρmax = 0.58 e Å−3
S = 1.05Δρmin = −0.43 e Å−3
2239 reflectionsAbsolute structure: ?
150 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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*/Ueq
S10.76064 (4)0.11536 (5)0.89426 (7)0.03929 (16)
O10.93971 (13)0.18350 (15)0.7497 (2)0.0487 (4)
N11.00646 (16)0.3959 (2)0.7104 (3)0.0450 (4)
C10.93508 (16)0.30721 (18)0.7630 (2)0.0343 (4)
P10.71692 (4)0.70375 (4)0.89068 (5)0.02801 (15)
N20.84692 (14)0.36706 (16)0.8367 (2)0.0341 (3)
H20.84380.45450.84480.061 (8)*
C20.76722 (15)0.29001 (18)0.8948 (2)0.0302 (4)
O20.77229 (12)0.62295 (13)0.76649 (16)0.0368 (3)
N30.68142 (13)0.34568 (18)0.9603 (2)0.0341 (3)
C30.63845 (18)0.1230 (2)0.9884 (3)0.0456 (5)
H3A0.59880.04671.01730.076 (9)*
O30.66290 (12)0.61762 (13)1.01208 (16)0.0357 (3)
C40.60814 (17)0.2511 (2)1.0144 (3)0.0414 (4)
H4A0.54460.27451.06360.062 (8)*
O40.62286 (13)0.79913 (17)0.80225 (19)0.0460 (4)
O50.80967 (14)0.79873 (16)0.98184 (19)0.0457 (4)
H1A1.001 (2)0.483 (3)0.731 (3)0.042 (6)*
H1B1.054 (3)0.359 (3)0.660 (3)0.053 (8)*
H30.676 (2)0.427 (3)0.969 (3)0.041 (6)*
H40.633 (3)0.815 (4)0.710 (5)0.080 (11)*
H50.800 (3)0.806 (4)1.077 (4)0.077 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0400 (3)0.0256 (2)0.0531 (3)0.00031 (17)0.0089 (2)0.00314 (18)
O10.0451 (8)0.0277 (7)0.0769 (11)0.0041 (6)0.0221 (8)−0.0017 (7)
N10.0420 (9)0.0316 (9)0.0659 (12)0.0008 (7)0.0243 (9)−0.0012 (8)
C10.0320 (9)0.0295 (9)0.0424 (10)0.0045 (7)0.0085 (7)0.0015 (7)
P10.0337 (3)0.0256 (3)0.0268 (2)0.00013 (16)0.01202 (17)0.00036 (15)
N20.0372 (8)0.0241 (7)0.0433 (8)0.0027 (6)0.0138 (7)0.0017 (6)
C20.0316 (8)0.0272 (9)0.0320 (8)0.0023 (6)0.0052 (7)0.0016 (6)
O20.0511 (8)0.0299 (7)0.0328 (7)0.0094 (5)0.0179 (6)0.0025 (5)
N30.0340 (8)0.0306 (8)0.0390 (8)0.0012 (6)0.0099 (6)0.0002 (6)
C30.0366 (10)0.0407 (11)0.0605 (13)−0.0074 (8)0.0107 (9)0.0076 (9)
O30.0473 (8)0.0300 (7)0.0328 (6)−0.0065 (5)0.0171 (6)−0.0001 (5)
C40.0321 (9)0.0472 (12)0.0461 (11)−0.0024 (8)0.0102 (8)0.0043 (9)
O40.0461 (8)0.0575 (10)0.0377 (8)0.0196 (7)0.0185 (6)0.0120 (6)
O50.0513 (9)0.0550 (10)0.0337 (7)−0.0228 (7)0.0174 (6)−0.0071 (6)
Geometric parameters (Å, °) top
S1—C21.7122 (18)N2—C21.345 (2)
S1—C31.732 (2)N2—H20.8600
O1—C11.218 (2)C2—N31.329 (2)
N1—C11.324 (3)N3—C41.383 (3)
N1—H1A0.87 (3)N3—H30.80 (3)
N1—H1B0.82 (3)C3—C41.330 (3)
C1—N21.403 (2)C3—H3A0.9300
P1—O21.5048 (12)C4—H4A0.9300
P1—O31.5083 (13)O4—H40.80 (4)
P1—O51.5602 (16)O5—H50.81 (4)
P1—O41.5642 (15)
C2—S1—C389.80 (10)C1—N2—H2119.4
C1—N1—H1A121.0 (16)N3—C2—N2121.65 (17)
C1—N1—H1B113 (2)N3—C2—S1111.93 (14)
H1A—N1—H1B126 (3)N2—C2—S1126.41 (14)
O1—C1—N1125.79 (19)C2—N3—C4113.74 (18)
O1—C1—N2119.90 (17)C2—N3—H3120.7 (19)
N1—C1—N2114.29 (17)C4—N3—H3125.5 (18)
O2—P1—O3114.27 (8)C4—C3—S1111.84 (15)
O2—P1—O5107.05 (9)C4—C3—H3A124.1
O3—P1—O5110.65 (8)S1—C3—H3A124.1
O2—P1—O4110.48 (8)C3—C4—N3112.69 (18)
O3—P1—O4107.43 (8)C3—C4—H4A123.7
O5—P1—O4106.73 (10)N3—C4—H4A123.7
C2—N2—C1121.12 (16)P1—O4—H4112 (3)
C2—N2—H2119.4P1—O5—H5110 (3)
O1—C1—N2—C20.6 (3)N2—C2—N3—C4−179.63 (17)
N1—C1—N2—C2179.39 (19)S1—C2—N3—C40.8 (2)
C1—N2—C2—N3−177.96 (17)C2—S1—C3—C40.44 (19)
C1—N2—C2—S11.6 (3)S1—C3—C4—N3−0.1 (3)
C3—S1—C2—N3−0.69 (15)C2—N3—C4—C3−0.4 (3)
C3—S1—C2—N2179.74 (18)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O20.861.932.697 (2)148.
N3—H3···O30.80 (3)1.91 (3)2.710 (2)174 (3)
N1—H1A···O1i0.87 (3)2.09 (3)2.898 (2)155 (2)
N1—H1B···O5ii0.82 (3)2.20 (3)3.007 (2)170 (3)
O5—H5···O2iii0.81 (4)1.77 (4)2.546 (2)162 (4)
O4—H4···O3iv0.80 (4)1.82 (4)2.613 (2)170 (4)
Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+2, y−1/2, −z+3/2; (iii) x, −y+3/2, z+1/2; (iv) x, −y+3/2, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O20.861.932.697 (2)148.
N3—H3···O30.80 (3)1.91 (3)2.710 (2)174 (3)
N1—H1A···O1i0.87 (3)2.09 (3)2.898 (2)155 (2)
N1—H1B···O5ii0.82 (3)2.20 (3)3.007 (2)170 (3)
O5—H5···O2iii0.81 (4)1.77 (4)2.546 (2)162 (4)
O4—H4···O3iv0.80 (4)1.82 (4)2.613 (2)170 (4)
Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+2, y−1/2, −z+3/2; (iii) x, −y+3/2, z+1/2; (iv) x, −y+3/2, z−1/2.
references
References top

Amirkhanov, V. M., Ovchynnikov, V. A., Glowiak, T. & Kozlowski, H. (1997). Z. Naturforsh. Teil B, 52, 1331–1336.

Angyan, J. G., Poirier, R. A., Kucsman, A. & Csizmadia, I. G. (1987). J. Am. Chem. Soc. 109, 2237–2245.

Bruker (1999). SMART-NT, SAINT-Plus-NT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. SAINTPlusNT or just SAINT-NT as above?

Burling, F. T. & Goldstein, B. M. (1992). J. Am. Chem. Soc. 114, 2313–2320.

Kirsanov, A. & Levchenko, V. (1957). Zh. Obshch. Khim. 27, 2313–2320.

Ly, T. Q. & Woollins, J. D. (1998). Coord. Chem. Rev. 176, 451–481.

Ovchynnikov, V. A., Amirkhanov, V. M., Timoshenko, T. P., Glowiak, T. & Kozlowski, H. (1997). Z. Naturforsh. Teil B, 53, 481–484.

Shatrava, I., Ovchynnikov, O., Sliva, T., Amirkhanov, V. & Skopenko, V. (2009). Zh. Dopov. Nats. Akad. Nauk, 5, 179–185.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Smaliy, R. V., Chaikovskay, A. A., Pinchyk, A. M. & Tolmachev, A. A. (2003). Synthesis, 16, 2525–2529.