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

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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

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[Elion, E. B., Callahan, S. W., Hitchings, G. H., Rundles, R. W. & Laszlo, J. (1962). Cancer Chemother. Rep. 16, 197-202.]); Rundles et al. (1966[Rundles, R. W., Metz, E. N. & Silberman, H. R. (1966). Ann. Intern. Med. 64, 229-258.]). For related structures, see: Prusiner & Sundaralingam (1972[Prusiner, P. & Sundaralingam, M. (1972). Acta Cryst. B28, 2148-2152.]); Gadret et al. (1974[Gadret, M., Goursolle, M. & Leger, J. M. (1974). Acta Cryst. B30, 1598-1602.]); Sheldrick & Bell (1987[Sheldrick, W. S. & Bell, P. (1987). Inorg. Chim. Acta, 137, 181-188.]); Singh & Pedersen (1993[Singh, P. & Pedersen, L. G. (1993). Acta Cryst. C49, 1211-1215.]).

[Scheme 1]

Experimental

Crystal data
  • 2C5H5N4O+·SO42−

  • Mr = 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)

  • Rint = 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

  • Δρmax = 0.32 e Å−3

  • Δρmin = −0.38 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1997[Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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.

Refinement top

Atoms H1, H3 and H5 on N1, N2 and N3 respectively were located in difference Fourier maps and refined isotropically. All other H atoms were found in difference map but then placed in calculated positions with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for all aromatic H atoms.

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
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
[Figure 2] 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+·SO42F(000) = 760
Mr = 370.32Dx = 1.835 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1323 reflections
a = 12.337 (3) Åθ = 2.6–26.1°
b = 10.054 (2) ŵ = 0.30 mm1
c = 11.064 (2) ÅT = 298 K
β = 102.42 (3)°Plate, colourless
V = 1340.2 (5) Å30.20 × 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 tubeRint = 0.017
Graphite monochromatorθmax = 26.1°, θmin = 2.6°
ϕ and ω scansh = 1511
3561 measured reflectionsk = 1012
1323 independent reflectionsl = 1313
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035All H-atom parameters refined
wR(F2) = 0.096 w = 1/[σ2(Fo2) + (0.0621P)2 + 0.9856P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
1323 reflectionsΔρmax = 0.32 e Å3
132 parametersΔρmin = 0.38 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0068 (13)
Crystal data top
2C5H5N4O+·SO42V = 1340.2 (5) Å3
Mr = 370.32Z = 4
Monoclinic, C2/cMo Kα radiation
a = 12.337 (3) ŵ = 0.30 mm1
b = 10.054 (2) ÅT = 298 K
c = 11.064 (2) Å0.20 × 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 reflectionsRint = 0.017
1323 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.096All H-atom parameters refined
S = 1.05Δρmax = 0.32 e Å3
1323 reflectionsΔρmin = 0.38 e Å3
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
xyzUiso*/Ueq
S10.50000.24338 (5)0.25000.0248 (2)
O30.41241 (12)0.33107 (12)0.17777 (11)0.0458 (4)
O20.45510 (13)0.16122 (14)0.33449 (12)0.0472 (4)
O10.32972 (10)0.07703 (11)0.91973 (10)0.0354 (3)
N10.35100 (11)0.30200 (13)0.92837 (12)0.0279 (3)
C40.35629 (12)0.19500 (15)0.73986 (13)0.0244 (3)
N30.38403 (11)0.18821 (14)0.55266 (13)0.0289 (3)
N40.38369 (11)0.32129 (13)0.57759 (12)0.0290 (3)
N20.36693 (11)0.43601 (13)0.76273 (12)0.0281 (3)
C10.34391 (12)0.17773 (15)0.86560 (14)0.0254 (3)
C30.36700 (12)0.32242 (14)0.69190 (14)0.0245 (3)
C50.36919 (13)0.11072 (16)0.64455 (14)0.0275 (3)
C20.36240 (13)0.41996 (16)0.87928 (14)0.0287 (4)
H20.3674 (16)0.4935 (19)0.9297 (18)0.033 (5)*
H40.3710 (16)0.018 (2)0.6442 (18)0.036 (5)*
H30.3781 (18)0.522 (2)0.735 (2)0.049 (6)*
H50.3967 (18)0.168 (2)0.485 (2)0.045 (6)*
H10.3606 (18)0.299 (2)1.012 (2)0.044 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0361 (3)0.0221 (3)0.0175 (3)0.0000.0085 (2)0.000
O30.0595 (8)0.0395 (7)0.0306 (6)0.0168 (6)0.0078 (6)0.0102 (5)
O20.0712 (9)0.0445 (8)0.0339 (7)0.0155 (7)0.0293 (7)0.0026 (6)
O10.0502 (7)0.0289 (6)0.0290 (6)0.0007 (5)0.0131 (5)0.0064 (5)
N10.0360 (7)0.0293 (7)0.0196 (7)0.0007 (5)0.0085 (5)0.0018 (5)
C40.0280 (7)0.0244 (8)0.0212 (7)0.0003 (5)0.0063 (6)0.0002 (5)
N30.0348 (7)0.0323 (8)0.0208 (6)0.0000 (5)0.0088 (5)0.0051 (5)
N40.0354 (7)0.0306 (7)0.0220 (7)0.0002 (5)0.0081 (5)0.0016 (5)
N20.0372 (7)0.0218 (7)0.0256 (7)0.0006 (5)0.0075 (5)0.0001 (5)
C10.0268 (7)0.0279 (8)0.0220 (7)0.0008 (6)0.0065 (6)0.0001 (5)
C30.0267 (7)0.0259 (8)0.0209 (7)0.0008 (5)0.0051 (6)0.0011 (5)
C50.0320 (8)0.0264 (8)0.0246 (7)0.0005 (6)0.0071 (6)0.0044 (6)
C20.0333 (8)0.0273 (8)0.0251 (7)0.0017 (6)0.0056 (6)0.0052 (6)
Geometric parameters (Å, º) top
S1—O2i1.4442 (12)C4—C11.442 (2)
S1—O21.4443 (12)N3—C51.324 (2)
S1—O31.4873 (13)N3—N41.366 (2)
S1—O3i1.4873 (13)N3—H50.82 (2)
O1—C11.2081 (18)N4—C31.324 (2)
N1—C21.324 (2)N2—C21.313 (2)
N1—C11.423 (2)N2—C31.3851 (19)
N1—H10.91 (2)N2—H30.94 (2)
C4—C51.388 (2)C5—H40.94 (2)
C4—C31.404 (2)C2—H20.92 (2)
O2i—S1—O2110.23 (11)C2—N2—C3117.38 (13)
O2i—S1—O3109.07 (8)C2—N2—H3118.7 (13)
O2—S1—O3110.57 (9)C3—N2—H3123.5 (13)
O2i—S1—O3i110.57 (9)O1—C1—N1119.61 (14)
O2—S1—O3i109.07 (8)O1—C1—C4129.47 (14)
O3—S1—O3i107.30 (11)N1—C1—C4110.91 (13)
C2—N1—C1125.94 (13)N4—C3—N2124.51 (14)
C2—N1—H1116.4 (14)N4—C3—C4113.56 (13)
C1—N1—H1116.7 (14)N2—C3—C4121.80 (13)
C5—C4—C3103.56 (13)N3—C5—C4106.34 (14)
C5—C4—C1135.43 (14)N3—C5—H4125.2 (12)
C3—C4—C1120.84 (13)C4—C5—H4128.4 (12)
C5—N3—N4114.47 (13)N2—C2—N1122.93 (14)
C5—N3—H5129.3 (15)N2—C2—H2119.1 (12)
N4—N3—H5116.1 (15)N1—C2—H2118.0 (12)
C3—N4—N3102.07 (12)
Symmetry code: (i) x+1, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H3···O3ii0.936 (10)1.698 (14)2.628 (2)173 (3)
N3—H5···O20.819 (10)1.957 (18)2.753 (3)164 (3)
N1—H1···O3iii0.906 (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 formula2C5H5N4O+·SO42
Mr370.32
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)12.337 (3), 10.054 (2), 11.064 (2)
β (°) 102.42 (3)
V3)1340.2 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.30
Crystal size (mm)0.20 × 0.20 × 0.10
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3561, 1323, 1252
Rint0.017
(sin θ/λ)max1)0.618
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.096, 1.05
No. of reflections1323
No. of parameters132
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N2—H3···O3i0.936 (10)1.698 (14)2.628 (2)173 (3)
N3—H5···O20.819 (10)1.957 (18)2.753 (3)164 (3)
N1—H1···O3ii0.906 (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

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

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ISSN: 2056-9890
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