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

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

doi:10.1107/S1600536811021337

organic compounds

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Volume 67| Part 7| July 2011| Page o1607

doi:10.1107/S1600536811021337

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

Kateryna Gubina,^a ^* Iuliia Shatrava,^a Vladimir Ovchynnikov ^a and Vladimir Amirkhanov ^a

^aNational Taras Shevchenko University, Department of Chemistry, Volodymyrska Street 64, 01033 Kyiv, Ukraine
^*Correspondence e-mail: katlig@univ.kiev.ua

(Received 24 May 2011; accepted 2 June 2011; online 11 June 2011)

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, P 2₁ /c
a = 11.9038 (11) Å
b = 9.7936 (10) Å
c = 8.1914 (12) Å
β = 97.231 (9)°
V = 947.37 (19) Å³
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[F² > 2σ(F²)] = 0.038
wR(F²) = 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

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⋯O3^iv	0.80 (4)	1.82 (4)	2.613 (2)	170 (4)
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811021337/dn2693sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811021337/dn2693Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811021337/dn2693Isup3.cml

checkCIF report

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.

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

	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.

2-ureido-1,3-thiazol-3-ium dihydrogen phosphate top

Crystal data top

C₄H₆N₃OS⁺·H₂PO₄⁻	F(000) = 496
M_r = 241.16	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0666P)² + 0.4134P] where P = (F_o² + 2F_c²)/3
2239 reflections	(Δ/σ)_max = 0.001
150 parameters	Δρ_max = 0.58 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

C₄H₆N₃OS⁺·H₂PO₄⁻	V = 947.37 (19) Å³
M_r = 241.16	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.9038 (11) Å	µ = 0.51 mm⁻¹
b = 9.7936 (10) Å	T = 293 K
c = 8.1914 (12) Å	0.30 × 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)
T_min = 0.861, T_max = 0.904	R_int = 0.014
2644 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.58 e Å⁻³
2239 reflections	Δρ_min = −0.43 e Å⁻³
150 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

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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···O3^iv	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.

Experimental details

Crystal data
Chemical formula	C₄H₆N₃OS⁺·H₂PO₄⁻
M_r	241.16
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.9038 (11), 9.7936 (10), 8.1914 (12)
β (°)	97.231 (9)
V (Å³)	947.37 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.51
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Empirical (using intensity measurements) (SADABS; Bruker, 1999)
T_min, T_max	0.861, 0.904
No. of measured, independent and observed [I > 2σ(I)] reflections	2644, 2239, 1893
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.109, 1.05
No. of reflections	2239
No. of parameters	150
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.43

Computer programs: SMART-NT (Bruker, 1999), SAINT-NT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP within SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.86	1.93	2.697 (2)	147.9
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···O3^iv	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.

References

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