Bis[5-oxo-4,5-dihydro-8H-2-azonia-4,8,9-trizabicyclo[4.3.0]nona-2,6,9(1)-triene] sulfate

Ravindra, N.V.; Panpalia, G.M.; Sarma, J.A.R.P.

doi:10.1107/S1600536808038026

organic compounds

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Bis[5-oxo-4,5-dihydro-8H-2-azonia-4,8,9-trizabicyclo[4.3.0]nona-2,6,9(1)-triene] sulfate

Nittala V. Ravindra,^a Gopal M. Panpalia ^a and Jagarlapudi A. R. P. Sarma ^b ^*

^aBirla Institute of Technology, Department of Pharmaceutical Sciences, Mesra, Ranchi 835 215, India, and ^bGVK Biosciences Private Limited, S-1, Phase-1 Technocrats Industrial Estate, Balanagar, Hyderabad 500 037, India
^*Correspondence e-mail: sarma@gvkbio.com

(Received 24 October 2008; accepted 15 November 2008; online 22 November 2008)

In the crystal structure of the title compound, 2C₅H₅N₄O⁺·SO₄²⁻, N—H⋯O hydrogen bonds assemble the molecules into a two-dimensional network structure parallel to the cb plane. The S atom of the sulfate ion lies on a special position on a twofold axis.

Related literature

For general background, see: Elion et al. (1962 ); Rundles et al. (1966 ). For related structures, see: Prusiner & Sundaralingam (1972 ); Gadret et al. (1974 ); Sheldrick & Bell (1987 ); Singh & Pedersen (1993 ).

Experimental

Crystal data

2C₅H₅N₄O⁺·SO₄²⁻
M_r = 370.32
Monoclinic, C 2/c
a = 12.337 (3) Å
b = 10.054 (2) Å
c = 11.064 (2) Å
β = 102.42 (3)°
V = 1340.2 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 298 (2) K
0.20 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
3561 measured reflections
1323 independent reflections
1252 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.096
S = 1.05
1323 reflections
132 parameters
All H-atom parameters refined
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H3⋯O3ⁱ	0.936 (10)	1.698 (14)	2.628 (2)	173 (3)
N3—H5⋯O2	0.819 (10)	1.957 (18)	2.753 (3)	164 (3)
N1—H1⋯O3ⁱⁱ	0.906 (10)	1.838 (13)	2.716 (3)	163 (3)
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) x, y, z+1.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808038026/gw2054sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808038026/gw2054Isup2.hkl

checkCIF report

Comment top

Allopurinol is known to be a potent inhibitor of xanthine oxidase and is used extensively for treatment of gout (Rundles et al., 1966). It is used in conjunction with anticancer drugs which impede RNA biosynthesis and as adjunct therapy in conjunction with 6-mecaptopurine in treatment of leukemia (Elion et al., 1962). As part of our interest in salts and co-crystals of drugs, we have investigated the crystal structure of Allopurinol sulfate, (I) (Fig. 1). The least-squares plane of the six-membered ring makes an angle of 5.79 (11)° with the least-squares planes of the five-membered ring of the purine ring. The N3 nitrogen is protonated similar to the reported structure of chloride salt (Sheldrick & Bell, 1987). The molecules are linked via N—H···O hydrogen bonds,forming two-dimensional infinite chains along the cb plane. These sheets are linked together by the sulfate molecules which act as acceptors of H atoms, assembling the molecules in an infinite two-dimensional network (Fig. 2).

Related literature top

For related literature, see: Elion et al. (1962); Rundles et al. (1966); Prusiner & Sundaralingam (1972); Gadret et al. (1974); Sheldrick & Bell (1987); Singh & Hodgson (1993). Please check _publ_section_exptl_refinement section in CIF; not in agreement with data elsewhere in CIF

Experimental top

Allopurinol (0.1361 g, 1 mmol) and Sulfuric acid (0.27 ml, 5 mmol) were added to Dimethylformamide. The mixture was stirred and heated on a water bath. After solution was complete, it was filtered and allowed to evaporate at room temperature. Colorless plate like crystals, suitable for x-ray analysis grew over a period of two days when the solution was exposed to air.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing of (I), viewed down the b axis, showing the layers of molecules and sulfate molecules connected by N—H···O hydrogen bonds (dashed lines).

bis[5-oxo-4,5-dihydro-8H-2-azonia-4,8,9-trizabicyclo[4.3.0]nona-2,6,9(1)-triene] sulfate top

Crystal data top

2C₅H₅N₄O⁺·SO₄²⁻	F(000) = 760
M_r = 370.32	D_x = 1.835 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1323 reflections
a = 12.337 (3) Å	θ = 2.6–26.1°
b = 10.054 (2) Å	µ = 0.30 mm⁻¹
c = 11.064 (2) Å	T = 298 K
β = 102.42 (3)°	Plate, colourless
V = 1340.2 (5) Å³	0.20 × 0.20 × 0.10 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1252 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.017
Graphite monochromator	θ_max = 26.1°, θ_min = 2.6°
ϕ and ω scans	h = −15→11
3561 measured reflections	k = −10→12
1323 independent reflections	l = −13→13

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	All H-atom parameters refined
wR(F²) = 0.096	w = 1/[σ²(F_o²) + (0.0621P)² + 0.9856P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1323 reflections	Δρ_max = 0.32 e Å⁻³
132 parameters	Δρ_min = −0.38 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0068 (13)

Crystal data top

2C₅H₅N₄O⁺·SO₄²⁻	V = 1340.2 (5) Å³
M_r = 370.32	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 12.337 (3) Å	µ = 0.30 mm⁻¹
b = 10.054 (2) Å	T = 298 K
c = 11.064 (2) Å	0.20 × 0.20 × 0.10 mm
β = 102.42 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1252 reflections with I > 2σ(I)
3561 measured reflections	R_int = 0.017
1323 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.096	All H-atom parameters refined
S = 1.05	Δρ_max = 0.32 e Å⁻³
1323 reflections	Δρ_min = −0.38 e Å⁻³
132 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
S1	0.5000	0.24338 (5)	0.2500	0.0248 (2)
O3	0.41241 (12)	0.33107 (12)	0.17777 (11)	0.0458 (4)
O2	0.45510 (13)	0.16122 (14)	0.33449 (12)	0.0472 (4)
O1	0.32972 (10)	0.07703 (11)	0.91973 (10)	0.0354 (3)
N1	0.35100 (11)	0.30200 (13)	0.92837 (12)	0.0279 (3)
C4	0.35629 (12)	0.19500 (15)	0.73986 (13)	0.0244 (3)
N3	0.38403 (11)	0.18821 (14)	0.55266 (13)	0.0289 (3)
N4	0.38369 (11)	0.32129 (13)	0.57759 (12)	0.0290 (3)
N2	0.36693 (11)	0.43601 (13)	0.76273 (12)	0.0281 (3)
C1	0.34391 (12)	0.17773 (15)	0.86560 (14)	0.0254 (3)
C3	0.36700 (12)	0.32242 (14)	0.69190 (14)	0.0245 (3)
C5	0.36919 (13)	0.11072 (16)	0.64455 (14)	0.0275 (3)
C2	0.36240 (13)	0.41996 (16)	0.87928 (14)	0.0287 (4)
H2	0.3674 (16)	0.4935 (19)	0.9297 (18)	0.033 (5)*
H4	0.3710 (16)	0.018 (2)	0.6442 (18)	0.036 (5)*
H3	0.3781 (18)	0.522 (2)	0.735 (2)	0.049 (6)*
H5	0.3967 (18)	0.168 (2)	0.485 (2)	0.045 (6)*
H1	0.3606 (18)	0.299 (2)	1.012 (2)	0.044 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0361 (3)	0.0221 (3)	0.0175 (3)	0.000	0.0085 (2)	0.000
O3	0.0595 (8)	0.0395 (7)	0.0306 (6)	0.0168 (6)	−0.0078 (6)	−0.0102 (5)
O2	0.0712 (9)	0.0445 (8)	0.0339 (7)	−0.0155 (7)	0.0293 (7)	−0.0026 (6)
O1	0.0502 (7)	0.0289 (6)	0.0290 (6)	−0.0007 (5)	0.0131 (5)	0.0064 (5)
N1	0.0360 (7)	0.0293 (7)	0.0196 (7)	0.0007 (5)	0.0085 (5)	−0.0018 (5)
C4	0.0280 (7)	0.0244 (8)	0.0212 (7)	−0.0003 (5)	0.0063 (6)	−0.0002 (5)
N3	0.0348 (7)	0.0323 (8)	0.0208 (6)	0.0000 (5)	0.0088 (5)	−0.0051 (5)
N4	0.0354 (7)	0.0306 (7)	0.0220 (7)	0.0002 (5)	0.0081 (5)	0.0016 (5)
N2	0.0372 (7)	0.0218 (7)	0.0256 (7)	0.0006 (5)	0.0075 (5)	0.0001 (5)
C1	0.0268 (7)	0.0279 (8)	0.0220 (7)	0.0008 (6)	0.0065 (6)	−0.0001 (5)
C3	0.0267 (7)	0.0259 (8)	0.0209 (7)	0.0008 (5)	0.0051 (6)	−0.0011 (5)
C5	0.0320 (8)	0.0264 (8)	0.0246 (7)	−0.0005 (6)	0.0071 (6)	−0.0044 (6)
C2	0.0333 (8)	0.0273 (8)	0.0251 (7)	0.0017 (6)	0.0056 (6)	−0.0052 (6)

Geometric parameters (Å, º) top

S1—O2ⁱ	1.4442 (12)	C4—C1	1.442 (2)
S1—O2	1.4443 (12)	N3—C5	1.324 (2)
S1—O3	1.4873 (13)	N3—N4	1.366 (2)
S1—O3ⁱ	1.4873 (13)	N3—H5	0.82 (2)
O1—C1	1.2081 (18)	N4—C3	1.324 (2)
N1—C2	1.324 (2)	N2—C2	1.313 (2)
N1—C1	1.423 (2)	N2—C3	1.3851 (19)
N1—H1	0.91 (2)	N2—H3	0.94 (2)
C4—C5	1.388 (2)	C5—H4	0.94 (2)
C4—C3	1.404 (2)	C2—H2	0.92 (2)

O2ⁱ—S1—O2	110.23 (11)	C2—N2—C3	117.38 (13)
O2ⁱ—S1—O3	109.07 (8)	C2—N2—H3	118.7 (13)
O2—S1—O3	110.57 (9)	C3—N2—H3	123.5 (13)
O2ⁱ—S1—O3ⁱ	110.57 (9)	O1—C1—N1	119.61 (14)
O2—S1—O3ⁱ	109.07 (8)	O1—C1—C4	129.47 (14)
O3—S1—O3ⁱ	107.30 (11)	N1—C1—C4	110.91 (13)
C2—N1—C1	125.94 (13)	N4—C3—N2	124.51 (14)
C2—N1—H1	116.4 (14)	N4—C3—C4	113.56 (13)
C1—N1—H1	116.7 (14)	N2—C3—C4	121.80 (13)
C5—C4—C3	103.56 (13)	N3—C5—C4	106.34 (14)
C5—C4—C1	135.43 (14)	N3—C5—H4	125.2 (12)
C3—C4—C1	120.84 (13)	C4—C5—H4	128.4 (12)
C5—N3—N4	114.47 (13)	N2—C2—N1	122.93 (14)
C5—N3—H5	129.3 (15)	N2—C2—H2	119.1 (12)
N4—N3—H5	116.1 (15)	N1—C2—H2	118.0 (12)
C3—N4—N3	102.07 (12)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H3···O3ⁱⁱ	0.936 (10)	1.698 (14)	2.628 (2)	173 (3)
N3—H5···O2	0.819 (10)	1.957 (18)	2.753 (3)	164 (3)
N1—H1···O3ⁱⁱⁱ	0.906 (10)	1.838 (13)	2.716 (3)	163 (3)

Symmetry codes: (ii) x, −y+1, z+1/2; (iii) x, y, z+1.

Experimental details

Crystal data
Chemical formula	2C₅H₅N₄O⁺·SO₄²⁻
M_r	370.32
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	12.337 (3), 10.054 (2), 11.064 (2)
β (°)	102.42 (3)
V (Å³)	1340.2 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.20 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3561, 1323, 1252
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.096, 1.05
No. of reflections	1323
No. of parameters	132
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.38

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H3···O3ⁱ	0.936 (10)	1.698 (14)	2.628 (2)	173 (3)
N3—H5···O2	0.819 (10)	1.957 (18)	2.753 (3)	164 (3)
N1—H1···O3ⁱⁱ	0.906 (10)	1.838 (13)	2.716 (3)	163 (3)

Symmetry codes: (i) x, −y+1, z+1/2; (ii) x, y, z+1.

Acknowledgements

NVR thanks Birla Institute of Technology for financial support. NVR also thanks Prashant M. Bhatt and Professor Gautam R. Desiraju, University of Hyderabad, for help in X-ray diffraction, and Matrix Labs Ltd, Hyderabad, for a gift sample of allopurinol.

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Elion, E. B., Callahan, S. W., Hitchings, G. H., Rundles, R. W. & Laszlo, J. (1962). Cancer Chemother. Rep. 16, 197–202. PubMed CAS Google Scholar
Gadret, M., Goursolle, M. & Leger, J. M. (1974). Acta Cryst. B30, 1598–1602. CSD CrossRef IUCr Journals Web of Science Google Scholar
Prusiner, P. & Sundaralingam, M. (1972). Acta Cryst. B28, 2148–2152. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Rundles, R. W., Metz, E. N. & Silberman, H. R. (1966). Ann. Intern. Med. 64, 229–258. CAS PubMed Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, W. S. & Bell, P. (1987). Inorg. Chim. Acta, 137, 181–188. CSD CrossRef CAS Web of Science Google Scholar
Singh, P. & Pedersen, L. G. (1993). Acta Cryst. C49, 1211–1215. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar

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doi:10.1107/S1600536808038026

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Bis[5-oxo-4,5-di­hydro-8H-2-azonia-4,8,9-trizabi­cyclo[4.3.0]nona-2,6,9(1)-triene] sulfate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Bis[5-oxo-4,5-dihydro-8H-2-azonia-4,8,9-trizabicyclo[4.3.0]nona-2,6,9(1)-triene] sulfate