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

Abstract

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.

Related literature

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 phosphor­triamides, see: Shatrava et al. (2009 ▶). For a description of the attractive inter­action in thia­zole compounds, see: Burling & Goldstein (1992 ▶); Angyan et al. (1987 ▶).

Experimental

Crystal data

• C₄H₆N₃OS⁺·H₂PO₄ ⁻

• M _r = 241.16

• Monoclinic,

• a = 11.9038 (11) Å

• b = 9.7936 (10) Å

• c = 8.1914 (12) Å

• β = 97.231 (9)°

• V = 947.37 (19) ų

• Z = 4

• Mo Kα radiation

• μ = 0.51 mm⁻¹

• T = 293 K

• 0.30 × 0.20 × 0.20 mm

Data collection

• Siemens SMART CCD area-detector diffractometer

• Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 1999 ▶) T _min = 0.861, T _max = 0.904

• 2644 measured reflections

• 2239 independent reflections

• 1893 reflections with I > 2σ(I)

• R _int = 0.014

Refinement

• R[F ² > 2σ(F ²)] = 0.038

• wR(F ²) = 0.109

• S = 1.05

• 2239 reflections

• 150 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.58 e Å⁻³

• Δρ_min = −0.43 e Å⁻³

Data collection: SMART-NT (Bruker, 1999 ▶); cell refinement: SAINT-NT (Bruker, 1999 ▶); data reduction: SAINT-NT; 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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811021337/dn2693Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2	0.86	1.93	2.697 (2)	148
N3—H3⋯O3	0.80 (3)	1.91 (3)	2.710 (2)	174 (3)
N1—H1A⋯O1i	0.87 (3)	2.09 (3)	2.898 (2)	155 (2)
N1—H1B⋯O5ii	0.82 (3)	2.20 (3)	3.007 (2)	170 (3)
O5—H5⋯O2iii	0.81 (4)	1.77 (4)	2.546 (2)	162 (4)
O4—H4⋯O3iv	0.80 (4)	1.82 (4)	2.613 (2)	170 (4)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

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).

Experimental

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

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.

Figures

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.

Fig. 2.

three-dimensional-view of the N-1,3-thiazol-2-yl-urea phosphate.

Fig. 3.

The formation of the title compound.

Crystal data

C4H6N3OS+·H2PO4−	F(000) = 496
Mr = 241.16	Dx = 1.691 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2646 reflections
a = 11.9038 (11) Å	θ = 1.7–28.0°
b = 9.7936 (10) Å	µ = 0.51 mm−1
c = 8.1914 (12) Å	T = 293 K
β = 97.231 (9)°	Block, colourless
V = 947.37 (19) Å3	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection

Siemens SMART CCD area-detector diffractometer	2239 independent reflections
Radiation source: fine-focus sealed tube	1893 reflections with I > 2σ(I)
graphite	Rint = 0.014
ω scans	θmax = 28.0°, θmin = 1.7°
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 1999)	h = −14→15
Tmin = 0.861, Tmax = 0.904	k = −12→10
2644 measured reflections	l = −10→10

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109	H 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 parameters	Δρmax = 0.58 e Å−3
0 restraints	Δρmin = −0.43 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.76064 (4)	0.11536 (5)	0.89426 (7)	0.03929 (16)
O1	0.93971 (13)	0.18350 (15)	0.7497 (2)	0.0487 (4)
N1	1.00646 (16)	0.3959 (2)	0.7104 (3)	0.0450 (4)
C1	0.93508 (16)	0.30721 (18)	0.7630 (2)	0.0343 (4)
P1	0.71692 (4)	0.70375 (4)	0.89068 (5)	0.02801 (15)
N2	0.84692 (14)	0.36706 (16)	0.8367 (2)	0.0341 (3)
H2	0.8438	0.4545	0.8448	0.061 (8)*
C2	0.76722 (15)	0.29001 (18)	0.8948 (2)	0.0302 (4)
O2	0.77229 (12)	0.62295 (13)	0.76649 (16)	0.0368 (3)
N3	0.68142 (13)	0.34568 (18)	0.9603 (2)	0.0341 (3)
C3	0.63845 (18)	0.1230 (2)	0.9884 (3)	0.0456 (5)
H3A	0.5988	0.0467	1.0173	0.076 (9)*
O3	0.66290 (12)	0.61762 (13)	1.01208 (16)	0.0357 (3)
C4	0.60814 (17)	0.2511 (2)	1.0144 (3)	0.0414 (4)
H4A	0.5446	0.2745	1.0636	0.062 (8)*
O4	0.62286 (13)	0.79913 (17)	0.80225 (19)	0.0460 (4)
O5	0.80967 (14)	0.79873 (16)	0.98184 (19)	0.0457 (4)
H1A	1.001 (2)	0.483 (3)	0.731 (3)	0.042 (6)*
H1B	1.054 (3)	0.359 (3)	0.660 (3)	0.053 (8)*
H3	0.676 (2)	0.427 (3)	0.969 (3)	0.041 (6)*
H4	0.633 (3)	0.815 (4)	0.710 (5)	0.080 (11)*
H5	0.800 (3)	0.806 (4)	1.077 (4)	0.077 (11)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0400 (3)	0.0256 (2)	0.0531 (3)	0.00031 (17)	0.0089 (2)	0.00314 (18)
O1	0.0451 (8)	0.0277 (7)	0.0769 (11)	0.0041 (6)	0.0221 (8)	−0.0017 (7)
N1	0.0420 (9)	0.0316 (9)	0.0659 (12)	0.0008 (7)	0.0243 (9)	−0.0012 (8)
C1	0.0320 (9)	0.0295 (9)	0.0424 (10)	0.0045 (7)	0.0085 (7)	0.0015 (7)
P1	0.0337 (3)	0.0256 (3)	0.0268 (2)	0.00013 (16)	0.01202 (17)	0.00036 (15)
N2	0.0372 (8)	0.0241 (7)	0.0433 (8)	0.0027 (6)	0.0138 (7)	0.0017 (6)
C2	0.0316 (8)	0.0272 (9)	0.0320 (8)	0.0023 (6)	0.0052 (7)	0.0016 (6)
O2	0.0511 (8)	0.0299 (7)	0.0328 (7)	0.0094 (5)	0.0179 (6)	0.0025 (5)
N3	0.0340 (8)	0.0306 (8)	0.0390 (8)	0.0012 (6)	0.0099 (6)	0.0002 (6)
C3	0.0366 (10)	0.0407 (11)	0.0605 (13)	−0.0074 (8)	0.0107 (9)	0.0076 (9)
O3	0.0473 (8)	0.0300 (7)	0.0328 (6)	−0.0065 (5)	0.0171 (6)	−0.0001 (5)
C4	0.0321 (9)	0.0472 (12)	0.0461 (11)	−0.0024 (8)	0.0102 (8)	0.0043 (9)
O4	0.0461 (8)	0.0575 (10)	0.0377 (8)	0.0196 (7)	0.0185 (6)	0.0120 (6)
O5	0.0513 (9)	0.0550 (10)	0.0337 (7)	−0.0228 (7)	0.0174 (6)	−0.0071 (6)

Geometric parameters (Å, °)

S1—C2	1.7122 (18)	N2—C2	1.345 (2)
S1—C3	1.732 (2)	N2—H2	0.8600
O1—C1	1.218 (2)	C2—N3	1.329 (2)
N1—C1	1.324 (3)	N3—C4	1.383 (3)
N1—H1A	0.87 (3)	N3—H3	0.80 (3)
N1—H1B	0.82 (3)	C3—C4	1.330 (3)
C1—N2	1.403 (2)	C3—H3A	0.9300
P1—O2	1.5048 (12)	C4—H4A	0.9300
P1—O3	1.5083 (13)	O4—H4	0.80 (4)
P1—O5	1.5602 (16)	O5—H5	0.81 (4)
P1—O4	1.5642 (15)
C2—S1—C3	89.80 (10)	C1—N2—H2	119.4
C1—N1—H1A	121.0 (16)	N3—C2—N2	121.65 (17)
C1—N1—H1B	113 (2)	N3—C2—S1	111.93 (14)
H1A—N1—H1B	126 (3)	N2—C2—S1	126.41 (14)
O1—C1—N1	125.79 (19)	C2—N3—C4	113.74 (18)
O1—C1—N2	119.90 (17)	C2—N3—H3	120.7 (19)
N1—C1—N2	114.29 (17)	C4—N3—H3	125.5 (18)
O2—P1—O3	114.27 (8)	C4—C3—S1	111.84 (15)
O2—P1—O5	107.05 (9)	C4—C3—H3A	124.1
O3—P1—O5	110.65 (8)	S1—C3—H3A	124.1
O2—P1—O4	110.48 (8)	C3—C4—N3	112.69 (18)
O3—P1—O4	107.43 (8)	C3—C4—H4A	123.7
O5—P1—O4	106.73 (10)	N3—C4—H4A	123.7
C2—N2—C1	121.12 (16)	P1—O4—H4	112 (3)
C2—N2—H2	119.4	P1—O5—H5	110 (3)
O1—C1—N2—C2	0.6 (3)	N2—C2—N3—C4	−179.63 (17)
N1—C1—N2—C2	179.39 (19)	S1—C2—N3—C4	0.8 (2)
C1—N2—C2—N3	−177.96 (17)	C2—S1—C3—C4	0.44 (19)
C1—N2—C2—S1	1.6 (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—N2	179.74 (18)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.86	1.93	2.697 (2)	148.
N3—H3···O3	0.80 (3)	1.91 (3)	2.710 (2)	174 (3)
N1—H1A···O1i	0.87 (3)	2.09 (3)	2.898 (2)	155 (2)
N1—H1B···O5ii	0.82 (3)	2.20 (3)	3.007 (2)	170 (3)
O5—H5···O2iii	0.81 (4)	1.77 (4)	2.546 (2)	162 (4)
O4—H4···O3iv	0.80 (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.