Guaninium sulfate monohydrate

organic papers

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Structure Reports

Online ISSN 1600-5368

Guaninium sulfate monohydrate

Aouatef Cherouana,

Nourredine Benali-Cherif* and Lamia Bendjeddou

Laboratoire de Chimie MoleÂculaire, du ControÃle de l'Environnement et des Mesures Physico-Chimiques, Faculte des Sciences, DeÂpartement de Chimie, Universite Mentouri de Constantine, 25000 Constantine, Algeria

Correspondence e-mail: [email protected]

Key indicators Single-crystal X-ray study T= 293 K

Mean(C±C) = 0.003 AÊ Rfactor = 0.032 wRfactor = 0.081

Data-to-parameter ratio = 11.3

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2003 International Union of Crystallography Printed in Great Britain ± all rights reserved

In the crystal structure of the title compound, C5H7N5O2+SO42ÿH2O, the guaninium cation, the sulfate

anion and the water molecule form a network of hydrogen bonds. The structure consists of layers of guaninium ions and water molecules parallel to the diagonal of theacplane, linked by strong hydrogen bonds.

Comment

The structure elucidation of nucleic acids and their derivatives is of interest, because of their widespread biological occur-rence (Richardset al., 1972; Perutz & Eyck, 1972). A number of these compounds are effective metabolic inhibitors with useful chemotherapeutic activity (Roy-Burman, 1970; Balis, 1968; Hitchings & Elion, 1963). In several crystal structures of compounds with organic bases and inorganic acids, the structural cohesion is assured by strong hydrogen bonds, as was observed in guaninium dinitrate dihydrate (Bouchouitet al., 2002), adeninium sulfate (Langer & Huml, 1978a), adeninium hemisulfate hydrate (Langer & Huml, 1978b) and adeninium hydrobromide hemihydrate (Langer & Huml, 1978c). Two structures of guanine with inorganic acids have been reported, namely guaninium dinitrate dihydrate and guaninium dichloride (MatkovicÂ-CÏalogovic & SankovicÂ, 1999).

The determination of the crystal and molecular structure of guaninium sulfate hydrate, (I), forms part of a study of the interactions between organic bases and inorganic acids. The dimensions of the sulfate anion (Fig. 1) are comparable with those found in other sulfates (e.g. Cherouana et al., 2002; Srinivasan et al., 2001). The SÐO bond lengths are in the range 1.4653 (16)±1.4874 (13) AÊ, while the OÐSÐO angles range from 108.23 (8) to 110.88 (9)_{. As was observed in}

guaninium dinitrate dihydrate, the imino groups of the py-rimidine and imidazolyl moieties (N3 and N7) in guanine are protonated. There is an intricate hydrogen-bond network (Fig. 2). The diprotonated guanine in (I) is hydrogen bonded

to four sulfate groups [viaN1ÐH1 O2 for the ®rst group, N3ÐH3 O3 and N2ÐH21 O1 for the second group, N9Ð H9 O1 for the third and N2ÐH21 O3 and N2ÐH22 O4 for the last group]. We also observed that the water molecule forms three hydrogen bonds with the guaninium and sulfate ions, in two modes,viz. as donor with the sulfate anion [via

O1WÐH1W O4 and O1WÐH2W O6] and as acceptor with the guaninium ion [viaN7ÐH7 O1W]. This system of hydrogen bonds among the guaninium cations, the sulfate anions and the water molecule generates a succession of layers parallel to the diagonal of the ac plane (Fig. 3). Layers of guaninium cations and water molecules are linked by strong anion±cation and anion±water hydrogen bondsviathe sand-wiched sulfates.

Experimental

Colorless single crystals of guaninium sulfate monohydrate were obtained after two weeks by slow evaporation, at room temperature, of an equimolar aqueous solution of guanine and sulfuric acid.

Crystal data C5H7N5O2+SO42ÿH2O

Mr= 267.24

Monoclinic,P21=c

a= 8.9940 (3) AÊ

b= 10.2020 (2) AÊ

c= 11.0440 (3) AÊ

= 106.04 (2)

V= 973.9 (1) AÊ3

Z= 4

Dx= 1.823 Mg mÿ3

MoKradiation Cell parameters from 6875

re¯ections

= 2.8±26.4

= 0.37 mmÿ1

T= 293 (2) K Plate, colorless 0.400.100.01 mm Data collection

Nonius KappaCCD diffractometer

'scans

Absorption correction: none 6875 measured re¯ections 1821 independent re¯ections 1631 re¯ections withI> 2(I)

Rint= 0.033

max= 26.4

h=ÿ11!11

k=ÿ12!12

l=ÿ12!12

Re®nement Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.032}

wR(F2_{) = 0.081}

S= 1.11 1821 re¯ections 161 parameters

H atoms treated by a mixture of independent and constrained re®nement

w= 1/[2_(F

o2) + (0.0361P)2

+ 0.4753P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.26 e AÊÿ3

min=ÿ0.41 e AÊÿ3

Table 1

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

N3ÐH3 O3i _{0.86 1.75 2.6011 (19) 167}

N9ÐH9 O1ii _{0.86 1.81 2.6526 (19) 167}

N7ÐH7 O1Wiii _{0.86 1.80 2.637 (2) 164}

N1ÐH1 O2iv _{0.86 1.91 2.738 (2) 160}

N2ÐH2A O1i _{0.86 2.09 2.934 (2) 166}

N2ÐH2B O4 0.86 2.07 2.829 (2) 146 O1WÐH1W O4iv _{0.86 (2) 2.00 (2) 2.838 (2) 164 (3)}

O1WÐH2W O6 0.86 (2) 1.93 (2) 2.793 (2) 178 (1) Symmetry codes: (i) ÿx;1

2‡y;32ÿz; (ii) x;1‡y;z; (iii) 1ÿx;12‡y;12ÿz; (iv)

x;1 2ÿy;zÿ12.

Acta Cryst.(2003). E59, o180±o182 Aouatef Cherouanaet al. C₅H₇N₅O2+SO₄2ÿH₂O

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Figure 2

ORTEP-3 (Farrugia, 1997) view, showing the intricate hydrogen-bond

interactions between anions and cations. [Symmetry codes: (i)ÿx, y+1 2,

ÿz+3

2; (ii)x,y+ 1,z; (iii)ÿx+ 1,y+12,ÿz+12; (iv)x,ÿy+12,zÿ12.]

Figure 3

ORTEP-3 (Farrugia, 1997) diagram of the layered packing of the title

compound, viewed down thebaxis.

Figure 1

ORTEP-3 (Farrugia, 1997) view of the title compound, with the atomic

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o182

H atoms attached to C and N atoms were ®xed at localized posi-tions and re®ned using a riding model. H atoms belonging to the water molecule were re®ned with an overall isotropic displacement parameter, using restraints.

Data collection:KappaCCD Reference Manual(Nonius, 1998); cell re®nement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction:DENZOandSCALEPACK; program(s) used to solve structure:SIR92 (Altomareet al., 1993); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication:WinGX(Farrugia, 1999).

This work is supported by Mentouri-Constantine Univer-sity, Algeria. We thank Drs M. Pierrot and M. Giorgi (LBS-UMR 6517, Faculte des Sciences et Techniques de Saint JeÂroÃme, Avenue Escadrille Normandie Niemen, 13397 Marseille Cedex 20, France) for providing diffraction facilities.

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993).J. Appl. Cryst.26, 343±350.

Balis, M. E. (1968). Antagonists and Nucleic Acids. New York: American Elsevier.

Bouchouit, K., Benali-Cherif, N., Benguedouar, L., Bendheif, L. & Merazig, H. (2002).Acta Cryst.E58, o1397±o1399.

Cherouana, A., Benali-Cherif, N., Bendjeddou, L. & Merazig, H. (2002)Acta Cryst.E58, o1351±o1353.

Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Farrugia, L. J. (1999).J. Appl. Cryst.32, 837±838.

Hitchings, G. H. & Elion, G. B. (1963). InMetabolic Inhibitors, Vol. I, edited by J. H. Quastel and R. M. Hochster, pp. 215±237. New York: Academic Press. Langer, V. & Huml, K. (1978a).Acta Cryst.B34, 1157±1163.

Langer, V. & Huml, K. (1978b).Acta Cryst.B34, 2229±2234. Langer, V. & Huml, K. (1978c).Acta Cryst.B34, 1881±1884.

MatkovicÂ-CÏalogovicÂ, D. & SankovicÂ, K. (1999).Acta Cryst.C55, 467±469. Nonius (1998). KappaCCD Reference Manual. Nonius BV, Delft, The

Netherlands.

Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,

Macromolecular Crystallography, Part A, edited by C. W. Carter Jr and R. M. Sweet, pp. 307±326. New York: Academic Press.

Perutz, M. F. & Ten Eyck, L. F. (1972).Cold Spring Harbor Symp. Quant. Biol.

36, 295±310.

Richards, M. F., Wyckoff, H. W., Carlson, W. D., Allewell, N. M., Lee, M. & Mitsui, Y. (1972).Cold Spring Harbor Symp. Quant. Biol.36, 25±43. Roy-Burman, P. (1970).Analogs of Nucleic Acid Components. New York:

Springer-Verlag.

Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Srinivasan, N., Sridhar, B. & Rajaram, R. K. (2001),Acta Cryst.E57, o754±

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Acta Cryst. (2003). E59, o180–o182 [doi:10.1107/S1600536803000953]

Guaninium sulfate monohydrate

Aouatef Cherouana, Nourredine Benali-Cherif and Lamia Bendjeddou

S1. Comment

The structure elucidation of nucleic acids and their derivatives is of interest, because of their widespread biological

occurrence (Richards et al., 1972; Perutz & Eyck, 1972). A number of these compounds are effective metabolic inhibitors

with useful chemotherapeutic activity (Roy-burman, 1970; Balis, 1968; Hitchings & Elion, 1963). In several crystals of

compounds with organic bases and inorganic acids, the structure cohesion is assured by strong hydrogen bonds as was

observed in guaninium dinitrate dihydrate (Bouchouit et al., 2002), adeninium sulfate (Langer & Huml, 1978a),

adeninium hemisulfate hydrate (Langer & Huml, 1978b) and adeninium hydroboromide hemihydrate (Langer & Huml,

1978c). Two structures of guanine with inorganic acids have been reported, namely guaninium dinitrate dihydrate and

guaninium dichloride (Matkovic-Calogovic & Sankovic, 1999).

The determination of the crystal and molecular structure of guaninium sulfate hydrate, (I), forms part of a study on the

interactions between organic bases and inorganic acids. The dimensions of the sulfate anion (Fig. 1) are comparable with

those found in other sulfates (e.g. Cherouana et al., 2002; Srinivasan et al., 2001). The S—O bond lengths are in the

range 1.4653 (16)–1.4874 (13) Å, while the O—S—O angles range from 108.23 (8) to 110.88 (9)°. As was observed in

guanium dinitrate dihydrate, the imino groups of the pyrimidine and imidazolyl moieties (N3 and N7) in guanine are

protonated. There is an intricate hydrogen-bond network (Fig. 2). The diprotonated guanine in (I) is hydrogen bonded to

four sulfate groups [via N1—H1···O2 for the first group, N3—H3···O3 and N2—H21···O1 for the second group, N9—

H9···O1 for the third and N2—H21···O3 and N2—H22···O4 for the last group]. We also observed that the water molecule

forms three hydrogen bonds with the guaninium and sulfate ions, where it has two different behaviors, viz. as donor with

the sulfate anion [via O1w—H1w···O4 and O1w—H2w···O6] and as acceptor with the guaninium ion [via N7—

H7···O1w]. This system of hydrogen bonds among the guaninium cations, the sulfate anions and the water molecule

generates a succession of layers parallel to the diagonal of ac plane (Fig. 3). Layers of guaninium cations and water

molecules are linked by strong anion–cation and anion–water hydrogen bonds via the sandwiched sulfates.

S2. Experimental

Colorless single crystals of guaninium sulfate monohydrate were obtained after two weeks by slow evaporation at room

temperature of an equimolar solution of guanine and sulfuric acid.

S3. Refinement

H atoms attached to C and N atoms were fixed at localized positions and refined using a riding model. H atoms belonging

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Figure 1

ORTEP-3 (Farrugia, 1997) view of the title compound with the atomic labelling scheme. Displacement ellipsoids are

drawn at the 50% probability level.

Figure 2

ORTEP-3 (Farrugia, 1997) view showing the intricated hydrogen-bond interactions between anions and cations.

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Figure 3

ORTEP-3 (Farrugia, 1997) diagram of the layered packing of the title compound, viewed down the b axis.

(I)

Crystal data

C5H7N5O2+_·SO42−_·H2O

Mr = 267.24 Monoclinic, P21/c

Hall symbol: -P 2ybc

a = 8.9940 (3) Å

b = 10.2020 (2) Å

c = 11.0440 (3) Å

β = 106.04 (2)°

V = 973.9 (1) Å3

Z = 4

F(000) = 552

Dx = 1.823 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 6875 reflections

θ = 2.8–26.4°

µ = 0.37 mm−1

T = 293 K Plate, colorless 0.4 × 0.1 × 0.01 mm

Data collection

Nonius KappaCCD diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ scans

6875 measured reflections 1821 independent reflections

1631 reflections with I > 2σ(I)

Rint = 0.033

θmax = 26.4°, θmin = 2.8°

h = −11→11

k = −12→12

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Refinement

Refinement on F2 Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.032}

wR(F2_{) = 0.081}

S = 1.11 1821 reflections 161 parameters 1 restraint

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2_(F

o2) + (0.0361P)2 + 0.4753P] where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001 Δρmax = 0.26 e Å−3 Δρmin = −0.41 e Å−3

Special details

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 F}2_, conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

S1 0.15170 (5) 0.18894 (4) 0.76616 (4) 0.01967 (15)

O1 0.07493 (16) 0.06048 (12) 0.72724 (13) 0.0277 (3)

O4 0.23663 (17) 0.22839 (13) 0.67648 (14) 0.0312 (3)

O3 0.03023 (17) 0.28698 (12) 0.76575 (14) 0.0320 (3)

O2 0.25598 (18) 0.17756 (13) 0.89364 (14) 0.0357 (4)

O6 0.39762 (17) 0.64077 (14) 0.34702 (14) 0.0346 (4)

N3 0.15176 (17) 0.71507 (13) 0.59978 (14) 0.0198 (3)

H3 0.0981 0.7299 0.6518 0.024*

N9 0.18591 (17) 0.94558 (14) 0.55504 (14) 0.0203 (3)

H9 0.1365 0.9819 0.6026 0.024*

N7 0.32181 (17) 0.92071 (14) 0.42100 (14) 0.0221 (3)

H7 0.3735 0.9382 0.3681 0.027*

N1 0.26823 (17) 0.57203 (14) 0.48693 (14) 0.0211 (3)

H1 0.2857 0.4919 0.4708 0.025*

N2 0.13960 (18) 0.49136 (14) 0.62537 (15) 0.0244 (3)

H2A 0.0872 0.5038 0.6787 0.029*

H2B 0.1615 0.4130 0.6073 0.029*

C4 0.2061 (2) 0.81454 (16) 0.54207 (17) 0.0185 (4)

C8 0.2576 (2) 1.00756 (17) 0.47956 (17) 0.0230 (4)

H8 0.2614 1.0980 0.4700 0.028*

C5 0.2918 (2) 0.79703 (16) 0.45925 (17) 0.0197 (4)

C2 0.18605 (19) 0.59172 (16) 0.57161 (16) 0.0189 (4)

C6 0.3272 (2) 0.66855 (17) 0.42342 (17) 0.0218 (4)

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H1W 0.438 (3) 0.367 (2) 0.225 (3) 0.059 (6)*

H2W 0.472 (3) 0.493 (2) 0.271 (3) 0.059 (6)*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

S1 0.0285 (2) 0.0127 (2) 0.0228 (3) 0.00125 (16) 0.01545 (18) 0.00129 (15) O1 0.0373 (7) 0.0177 (6) 0.0332 (8) −0.0060 (5) 0.0185 (6) −0.0062 (5) O4 0.0410 (8) 0.0238 (7) 0.0397 (9) 0.0050 (6) 0.0294 (7) 0.0076 (6) O3 0.0409 (8) 0.0187 (7) 0.0478 (9) 0.0089 (6) 0.0313 (7) 0.0072 (6) O2 0.0531 (9) 0.0231 (7) 0.0276 (9) −0.0035 (6) 0.0054 (7) 0.0021 (5) O6 0.0496 (9) 0.0269 (7) 0.0398 (9) 0.0010 (6) 0.0335 (7) −0.0051 (6) N3 0.0254 (8) 0.0176 (7) 0.0215 (9) −0.0007 (6) 0.0147 (6) −0.0010 (5) N9 0.0255 (7) 0.0156 (7) 0.0225 (8) 0.0017 (6) 0.0111 (6) −0.0023 (6) N7 0.0289 (8) 0.0198 (8) 0.0212 (9) −0.0028 (6) 0.0130 (6) 0.0014 (6) N1 0.0306 (8) 0.0145 (7) 0.0213 (9) 0.0010 (6) 0.0123 (6) −0.0027 (5) N2 0.0317 (8) 0.0184 (8) 0.0266 (9) −0.0011 (6) 0.0140 (7) 0.0024 (6) C4 0.0215 (8) 0.0163 (8) 0.0189 (10) −0.0009 (6) 0.0074 (7) −0.0008 (6) C8 0.0302 (9) 0.0167 (8) 0.0221 (10) −0.0012 (7) 0.0075 (7) 0.0002 (7) C5 0.0253 (9) 0.0176 (8) 0.0196 (10) −0.0016 (7) 0.0117 (7) −0.0004 (6) C2 0.0205 (8) 0.0186 (8) 0.0175 (9) −0.0006 (6) 0.0054 (6) −0.0013 (6) C6 0.0257 (9) 0.0205 (9) 0.0220 (10) −0.0004 (7) 0.0113 (7) −0.0020 (7) O1W 0.0284 (7) 0.0383 (9) 0.0367 (9) −0.0038 (6) 0.0184 (6) −0.0123 (6)

Geometric parameters (Å, º)

S1—O4 1.4643 (13) N9—C4 1.362 (2)

S1—O2 1.4647 (16) N7—C8 1.320 (2)

S1—O3 1.4803 (13) N7—C5 1.381 (2)

S1—O1 1.4883 (13) N1—C2 1.358 (2)

O6—C6 1.220 (2) N1—C6 1.396 (2)

N3—C2 1.352 (2) N2—C2 1.309 (2)

N3—C4 1.359 (2) C4—C5 1.361 (2)

N9—C8 1.345 (2) C5—C6 1.431 (2)

O4—S1—O2 110.90 (9) C5—C4—N9 108.44 (15)

O4—S1—O3 109.55 (8) N7—C8—N9 109.73 (15)

O2—S1—O3 109.42 (9) C4—C5—N7 106.31 (14)

O4—S1—O1 109.50 (8) C4—C5—C6 121.14 (15)

O2—S1—O1 109.31 (8) N7—C5—C6 132.47 (16)

O3—S1—O1 108.12 (8) N2—C2—N3 120.14 (16)

C2—N3—C4 116.90 (15) N2—C2—N1 119.97 (15)

C8—N9—C4 107.20 (14) N3—C2—N1 119.89 (15)

C8—N7—C5 108.32 (15) O6—C6—N1 121.71 (16)

C2—N1—C6 126.63 (14) O6—C6—C5 127.03 (17)

N3—C4—C5 124.13 (15) N1—C6—C5 111.26 (15)

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Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N3—H3···O3i _{0.86 1.75 2.6011 (19) 167}

N9—H9···O1ii _{0.86 1.81 2.6526 (19) 167}

N7—H7···O1Wiii _{0.86 1.80 2.637 (2) 164}

N1—H1···O2iv _{0.86 1.91 2.738 (2) 160}

N2—H2A···O1i _{0.86 2.09 2.934 (2) 166}

N2—H2B···O4 0.86 2.07 2.829 (2) 146

O1W—H1W···O4iv _{0.86 (2) 2.00 (2) 2.838 (2) 164 (3)}

O1W—H2W···O6 0.86 (2) 1.93 (2) 2.793 (2) 178 (1)