organic compounds
6-Amino-9H-purine-1,7-diium bis(4-methylbenzenesulfonate) monohydrate
aCenter of Analysis and Testing, Nanchang Hangkong University, Nanchang 330063, People's Republic of China, and bState Key Laboratory of Food Science and Technology, Nanchang University, Nanchang 330047, People's Republic of China
*Correspondence e-mail: xiongzq@163.com
The 5H7N52+·2C7H7O3S−·H2O, consists of one diprotonated adeninium cation, two p-toluenesulfonic acid anions and one water molecule. In the crystal, the cations and anions are connected through N—H⋯O hydrogen bonds forming R22(8) and R22(9) graph-set motifs. The solvent water molecule links cations and anions through O—H⋯O and N—H⋯O hydrogen bonds, generating a two-dimensional layer parallel to (10).
of the title compound, CRelated literature
For biological activity of purine and its derivatives, see: Barral et al. (2006); Sridhar & Ravikumar (2007); Sridhar et al. (2009); Xing et al. (2008). For hydrogen-bonding motifs, see: Etter (1990); Bernstein et al. (1995).
Experimental
Crystal data
|
Refinement
|
Data collection: APEX2 (Bruker, 2006); cell SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Pearce et al., 2000); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Supporting information
https://doi.org/10.1107/S1600536810000413/dn2513sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810000413/dn2513Isup2.hkl
A mixture of purin-6-amine (10.0 mmol) and toluene sulfonic acid (20.0 mmol) was dissolved in ethanol (40 ml) in batches over a period of 2 h under reflux, heating was continued for 1 h. The mixture was cooled to room temperature and separated, the solvent of the organic phase was removed and the residue recrystallized with ethyl acetate. Yellow crystals of the title compound suitable for X-ray
were obtained after several days. Yield 77.3%.The water H atoms were located in a difference Fourier map but were included in fixed positions in riding-model approximation with the O—H distances in the range 0.8252–0.8381Å and Uiso(H) = 1.5Ueq(O); all other H atoms were placed in geometrically idealized positions with C<–H(methylene) = 0.96 Å, C–H(aromatic) = 0.93 Å, N—H = 0.86 Å, and Uiso(H) = 1.2 Ueq(C,N).
Purin and its derivatives, as one kind of important nucleobase compounds, are essential for understanding many mechanisms of basic importance in the biological process (Xing et al., 2008), and belongs to a group of cytokinin-derived compounds which are indispensable for plant growth. The concept of the acyclic nucleoside phosphonate (ANPs) has been used to design chain terminators for antiviral and therapy proved to be valid (Barral et al., 2006). In C5H6N5+.C8H7O2–.C8H8O2–.H2O and C5H6N5+.C4H3O4–.H2O compounds, the adeninium cations form N-H···O hydrogen bonds with their anion counterparts and adeninium-adeninium self-association base pairs (Sridhar et al., 2007). In C5H7N52+.0.5C2O42–.2Cl– compound, adenine is doubly protonated, while in C5H6N5+.C2HO4–.0.5C2H2O4.H2O compound, adenine is monoprotonated (Sridhar et al., 2009).
In the title compound, C5H7N52+.2C7H7SO3–.H2O, the
contains one diprotonated adeninium cation, two p-toluenesulfonic acid anions and one water molecule. The two anions are connected to the purin molecule through N-H···O hydrogen bonds building R22(8) and R22(9) graph set motifs (Table 1, Fig.1) (Etter, 1990; Bernstein et al., 1995) . In the same the water molecule is connected through O-H···O hydrogen bond to one of the p-toluenesulfonic acid (Table 1, Fig. 1).Futhermore The water links cation and anion through O-H···O and N-H···O hydrogen bonds forming a R66(20) graph set motif and buiding a two dimensional layer parallel to the (1 0 -1) plane (Fig. 2, Table 1).
In the 9H-purin-6-amine molecule, all atoms are coplanar, the dihedral angles between the plane of the 9H-purin-6-amine and the benzene rings of the p-toluenesulfonate anions are 87.78 (5)° and 87.15 (5)°, respectively, indicating that the 9H-purin-6-amine is almost perpendicular to the two benzene rings.
For biological activity of purin and its derivatives, see: Barral et al. (2006); Sridhar & Ravikumar (2007); Sridhar et al. (2009); Xing et al. (2008). For hydrogen-bonding motifs, see: Etter (1990); Bernstein et al. (1995).
Data collection: APEX2 (Bruker, 2006); cell
SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Pearce et al., 2000); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. : A view of the structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines. | |
Fig. 2. : Partial packing view of the title compound, viewed down the b axis. Hydrogen bonds are shown as dashed lines. |
C5H7N52+·2C7H7O3S−·H2O | F(000) = 1040 |
Mr = 497.54 | Dx = 1.482 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 7679 reflections |
a = 16.2462 (11) Å | θ = 2.5–28.1° |
b = 6.0370 (4) Å | µ = 0.29 mm−1 |
c = 22.7390 (15) Å | T = 296 K |
β = 90.625 (1)° | Block, yellow |
V = 2230.1 (3) Å3 | 0.31 × 0.21 × 0.21 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | 4153 independent reflections |
Radiation source: fine-focus sealed tube | 3452 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.100 |
φ and ω scans | θmax = 25.5°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | h = −19→19 |
Tmin = 0.915, Tmax = 0.942 | k = −7→7 |
16652 measured reflections | l = −27→26 |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.059P)2 + 0.6101P] where P = (Fo2 + 2Fc2)/3 |
4153 reflections | (Δ/σ)max < 0.001 |
300 parameters | Δρmax = 0.46 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C5H7N52+·2C7H7O3S−·H2O | V = 2230.1 (3) Å3 |
Mr = 497.54 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 16.2462 (11) Å | µ = 0.29 mm−1 |
b = 6.0370 (4) Å | T = 296 K |
c = 22.7390 (15) Å | 0.31 × 0.21 × 0.21 mm |
β = 90.625 (1)° |
Bruker APEXII CCD diffractometer | 4153 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | 3452 reflections with I > 2σ(I) |
Tmin = 0.915, Tmax = 0.942 | Rint = 0.100 |
16652 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.46 e Å−3 |
4153 reflections | Δρmin = −0.31 e Å−3 |
300 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.58230 (11) | 0.6806 (3) | 0.70038 (8) | 0.0345 (4) | |
C2 | 0.68007 (12) | 0.9106 (3) | 0.75121 (9) | 0.0424 (5) | |
H2 | 0.7096 | 0.9311 | 0.7860 | 0.051* | |
C3 | 0.64254 (11) | 1.0129 (3) | 0.66210 (8) | 0.0342 (4) | |
C4 | 0.58820 (11) | 0.8401 (3) | 0.65534 (8) | 0.0342 (4) | |
C5 | 0.58704 (13) | 1.0362 (3) | 0.57478 (9) | 0.0439 (5) | |
H5 | 0.5744 | 1.0860 | 0.5371 | 0.053* | |
C6 | 0.12147 (18) | 0.2967 (6) | 0.73440 (13) | 0.0827 (9) | |
H6A | 0.1439 | 0.2918 | 0.7736 | 0.124* | |
H6B | 0.0967 | 0.1566 | 0.7250 | 0.124* | |
H6C | 0.0806 | 0.4113 | 0.7319 | 0.124* | |
C7 | 0.18958 (15) | 0.3450 (4) | 0.69138 (11) | 0.0578 (6) | |
C8 | 0.19569 (15) | 0.5466 (4) | 0.66313 (11) | 0.0605 (6) | |
H8 | 0.1573 | 0.6566 | 0.6709 | 0.073* | |
C9 | 0.25782 (14) | 0.5885 (4) | 0.62340 (10) | 0.0523 (5) | |
H9 | 0.2609 | 0.7254 | 0.6048 | 0.063* | |
C10 | 0.31520 (12) | 0.4262 (3) | 0.61154 (9) | 0.0410 (5) | |
C11 | 0.30975 (16) | 0.2236 (4) | 0.63958 (11) | 0.0577 (6) | |
H11 | 0.3479 | 0.1129 | 0.6318 | 0.069* | |
C12 | 0.24765 (16) | 0.1866 (4) | 0.67901 (12) | 0.0653 (7) | |
H12 | 0.2449 | 0.0501 | 0.6979 | 0.078* | |
C13 | 0.30034 (16) | 0.4904 (5) | 1.01182 (12) | 0.0714 (8) | |
H13A | 0.2502 | 0.4442 | 0.9928 | 0.107* | |
H13B | 0.2984 | 0.6471 | 1.0189 | 0.107* | |
H13C | 0.3066 | 0.4135 | 1.0485 | 0.107* | |
C14 | 0.37220 (13) | 0.4378 (4) | 0.97288 (9) | 0.0470 (5) | |
C15 | 0.40420 (16) | 0.5906 (4) | 0.93554 (12) | 0.0622 (7) | |
H15 | 0.3813 | 0.7317 | 0.9344 | 0.075* | |
C16 | 0.46944 (16) | 0.5434 (4) | 0.89932 (11) | 0.0595 (6) | |
H16 | 0.4907 | 0.6524 | 0.8749 | 0.071* | |
C17 | 0.50300 (12) | 0.3336 (3) | 0.89954 (8) | 0.0374 (4) | |
C18 | 0.47223 (15) | 0.1783 (4) | 0.93719 (10) | 0.0558 (6) | |
H18 | 0.4949 | 0.0369 | 0.9382 | 0.067* | |
C19 | 0.40759 (15) | 0.2304 (4) | 0.97374 (11) | 0.0599 (6) | |
H19 | 0.3876 | 0.1236 | 0.9994 | 0.072* | |
N1 | 0.53750 (11) | 0.5001 (3) | 0.69920 (7) | 0.0431 (4) | |
H1A | 0.5384 | 0.4109 | 0.7287 | 0.052* | |
H1B | 0.5072 | 0.4708 | 0.6689 | 0.052* | |
N2 | 0.63051 (10) | 0.7299 (3) | 0.74765 (7) | 0.0397 (4) | |
H2A | 0.6296 | 0.6412 | 0.7772 | 0.048* | |
N3 | 0.68966 (10) | 1.0571 (3) | 0.71004 (7) | 0.0398 (4) | |
N4 | 0.64043 (10) | 1.1311 (3) | 0.61096 (7) | 0.0394 (4) | |
H4 | 0.6690 | 1.2476 | 0.6036 | 0.047* | |
N5 | 0.55420 (10) | 0.8603 (3) | 0.59990 (7) | 0.0416 (4) | |
H5A | 0.5180 | 0.7738 | 0.5844 | 0.050* | |
O1 | 0.40025 (13) | 0.7072 (3) | 0.55042 (8) | 0.0729 (5) | |
O2 | 0.37421 (11) | 0.3460 (3) | 0.50891 (7) | 0.0669 (5) | |
O3 | 0.46938 (10) | 0.3929 (4) | 0.58895 (7) | 0.0720 (5) | |
O4 | 0.53719 (10) | 0.2035 (3) | 0.79461 (6) | 0.0519 (4) | |
O5 | 0.63123 (10) | 0.4573 (3) | 0.84146 (6) | 0.0547 (4) | |
O6 | 0.62452 (10) | 0.0766 (3) | 0.87476 (7) | 0.0567 (4) | |
O7 | 0.28741 (10) | 0.4810 (2) | 0.40726 (7) | 0.0553 (4) | |
H1W | 0.2375 | 0.4616 | 0.3992 | 0.083* | |
H2W | 0.2988 | 0.4323 | 0.4403 | 0.083* | |
S1 | 0.57997 (3) | 0.26166 (8) | 0.84914 (2) | 0.04219 (17) | |
S2 | 0.39453 (3) | 0.47017 (9) | 0.56027 (2) | 0.04297 (17) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0338 (9) | 0.0381 (10) | 0.0317 (9) | 0.0065 (8) | 0.0063 (8) | 0.0004 (7) |
C2 | 0.0416 (11) | 0.0517 (12) | 0.0336 (10) | 0.0055 (9) | −0.0047 (8) | −0.0050 (9) |
C3 | 0.0328 (9) | 0.0382 (9) | 0.0316 (9) | 0.0051 (7) | 0.0052 (7) | −0.0012 (7) |
C4 | 0.0346 (9) | 0.0406 (10) | 0.0275 (9) | 0.0017 (8) | 0.0024 (7) | 0.0000 (7) |
C5 | 0.0521 (12) | 0.0470 (11) | 0.0326 (10) | −0.0033 (9) | −0.0002 (9) | 0.0057 (8) |
C6 | 0.0648 (17) | 0.112 (2) | 0.0718 (19) | −0.0161 (16) | 0.0225 (15) | 0.0054 (17) |
C7 | 0.0492 (13) | 0.0741 (16) | 0.0503 (13) | −0.0088 (12) | 0.0086 (10) | 0.0015 (12) |
C8 | 0.0550 (14) | 0.0653 (15) | 0.0614 (15) | 0.0093 (12) | 0.0104 (12) | −0.0015 (12) |
C9 | 0.0560 (13) | 0.0478 (12) | 0.0531 (13) | 0.0019 (10) | 0.0022 (11) | 0.0063 (10) |
C10 | 0.0415 (11) | 0.0442 (11) | 0.0372 (10) | −0.0045 (9) | −0.0008 (8) | 0.0013 (8) |
C11 | 0.0584 (14) | 0.0510 (13) | 0.0639 (15) | 0.0063 (11) | 0.0151 (12) | 0.0119 (11) |
C12 | 0.0716 (17) | 0.0554 (14) | 0.0692 (16) | −0.0057 (12) | 0.0161 (13) | 0.0190 (12) |
C13 | 0.0567 (15) | 0.096 (2) | 0.0615 (16) | 0.0150 (14) | 0.0110 (13) | −0.0165 (14) |
C14 | 0.0411 (11) | 0.0591 (13) | 0.0408 (11) | 0.0044 (10) | 0.0006 (9) | −0.0061 (10) |
C15 | 0.0678 (16) | 0.0438 (12) | 0.0752 (17) | 0.0182 (11) | 0.0124 (13) | 0.0016 (11) |
C16 | 0.0696 (16) | 0.0404 (11) | 0.0687 (16) | 0.0089 (11) | 0.0183 (13) | 0.0168 (11) |
C17 | 0.0373 (10) | 0.0396 (10) | 0.0354 (10) | 0.0028 (8) | 0.0009 (8) | 0.0067 (8) |
C18 | 0.0631 (14) | 0.0431 (11) | 0.0616 (14) | 0.0145 (11) | 0.0203 (12) | 0.0172 (10) |
C19 | 0.0622 (15) | 0.0613 (15) | 0.0568 (14) | 0.0064 (11) | 0.0233 (12) | 0.0174 (11) |
N1 | 0.0495 (10) | 0.0433 (9) | 0.0364 (9) | −0.0034 (8) | 0.0008 (7) | 0.0074 (7) |
N2 | 0.0455 (9) | 0.0448 (9) | 0.0286 (8) | 0.0059 (7) | 0.0007 (7) | 0.0048 (7) |
N3 | 0.0354 (9) | 0.0472 (9) | 0.0368 (9) | 0.0007 (7) | −0.0010 (7) | −0.0037 (7) |
N4 | 0.0404 (9) | 0.0411 (9) | 0.0367 (9) | −0.0048 (7) | 0.0047 (7) | 0.0043 (7) |
N5 | 0.0485 (10) | 0.0443 (9) | 0.0319 (8) | −0.0097 (8) | −0.0050 (7) | 0.0037 (7) |
O1 | 0.0845 (13) | 0.0551 (10) | 0.0795 (13) | −0.0160 (9) | 0.0234 (10) | 0.0090 (9) |
O2 | 0.0717 (11) | 0.0869 (12) | 0.0421 (9) | −0.0227 (10) | 0.0037 (8) | −0.0136 (8) |
O3 | 0.0437 (9) | 0.1191 (16) | 0.0532 (10) | 0.0023 (10) | −0.0032 (8) | −0.0017 (10) |
O4 | 0.0592 (9) | 0.0593 (9) | 0.0374 (8) | −0.0005 (7) | 0.0032 (7) | 0.0043 (7) |
O5 | 0.0508 (9) | 0.0690 (10) | 0.0443 (9) | −0.0112 (7) | 0.0028 (7) | 0.0169 (7) |
O6 | 0.0532 (9) | 0.0628 (10) | 0.0543 (9) | 0.0222 (8) | 0.0087 (7) | 0.0125 (7) |
O7 | 0.0526 (9) | 0.0561 (9) | 0.0571 (9) | −0.0114 (7) | 0.0004 (8) | 0.0093 (7) |
S1 | 0.0414 (3) | 0.0495 (3) | 0.0358 (3) | 0.0052 (2) | 0.0047 (2) | 0.0099 (2) |
S2 | 0.0426 (3) | 0.0509 (3) | 0.0354 (3) | −0.0092 (2) | 0.0005 (2) | 0.0004 (2) |
C1—N1 | 1.311 (2) | C13—C14 | 1.507 (3) |
C1—N2 | 1.356 (2) | C13—H13A | 0.9600 |
C1—C4 | 1.410 (3) | C13—H13B | 0.9600 |
C2—N3 | 1.299 (3) | C13—H13C | 0.9600 |
C2—N2 | 1.357 (3) | C14—C15 | 1.361 (3) |
C2—H2 | 0.9300 | C14—C19 | 1.377 (3) |
C3—N3 | 1.352 (2) | C15—C16 | 1.379 (3) |
C3—N4 | 1.365 (2) | C15—H15 | 0.9300 |
C3—C4 | 1.374 (3) | C16—C17 | 1.379 (3) |
C4—N5 | 1.376 (2) | C16—H16 | 0.9300 |
C5—N4 | 1.320 (3) | C17—C18 | 1.368 (3) |
C5—N5 | 1.321 (3) | C17—S1 | 1.760 (2) |
C5—H5 | 0.9300 | C18—C19 | 1.382 (3) |
C6—C7 | 1.513 (3) | C18—H18 | 0.9300 |
C6—H6A | 0.9600 | C19—H19 | 0.9300 |
C6—H6B | 0.9600 | N1—H1A | 0.8602 |
C6—H6C | 0.9600 | N1—H1B | 0.8608 |
C7—C12 | 1.374 (4) | N2—H2A | 0.8595 |
C7—C8 | 1.380 (4) | N4—H4 | 0.8601 |
C8—C9 | 1.385 (3) | N5—H5A | 0.8592 |
C8—H8 | 0.9300 | O1—S2 | 1.4513 (18) |
C9—C10 | 1.381 (3) | O2—S2 | 1.4237 (16) |
C9—H9 | 0.9300 | O3—S2 | 1.4506 (17) |
C10—C11 | 1.383 (3) | O4—S1 | 1.4576 (16) |
C10—S2 | 1.767 (2) | O5—S1 | 1.4569 (16) |
C11—C12 | 1.375 (3) | O6—S1 | 1.4498 (15) |
C11—H11 | 0.9300 | O7—H1W | 0.8376 |
C12—H12 | 0.9300 | O7—H2W | 0.8259 |
N1—C1—N2 | 120.98 (17) | C15—C14—C19 | 117.6 (2) |
N1—C1—C4 | 126.53 (17) | C15—C14—C13 | 121.8 (2) |
N2—C1—C4 | 112.49 (17) | C19—C14—C13 | 120.6 (2) |
N3—C2—N2 | 125.47 (18) | C14—C15—C16 | 122.3 (2) |
N3—C2—H2 | 117.3 | C14—C15—H15 | 118.9 |
N2—C2—H2 | 117.3 | C16—C15—H15 | 118.9 |
N3—C3—N4 | 126.33 (17) | C17—C16—C15 | 119.6 (2) |
N3—C3—C4 | 126.72 (17) | C17—C16—H16 | 120.2 |
N4—C3—C4 | 106.96 (16) | C15—C16—H16 | 120.2 |
C3—C4—N5 | 106.63 (16) | C18—C17—C16 | 119.0 (2) |
C3—C4—C1 | 119.08 (17) | C18—C17—S1 | 120.36 (16) |
N5—C4—C1 | 134.12 (18) | C16—C17—S1 | 120.54 (16) |
N4—C5—N5 | 110.20 (17) | C17—C18—C19 | 120.4 (2) |
N4—C5—H5 | 124.9 | C17—C18—H18 | 119.8 |
N5—C5—H5 | 124.9 | C19—C18—H18 | 119.8 |
C7—C6—H6A | 109.5 | C14—C19—C18 | 121.2 (2) |
C7—C6—H6B | 109.5 | C14—C19—H19 | 119.4 |
H6A—C6—H6B | 109.5 | C18—C19—H19 | 119.4 |
C7—C6—H6C | 109.5 | C1—N1—H1A | 120.0 |
H6A—C6—H6C | 109.5 | C1—N1—H1B | 120.0 |
H6B—C6—H6C | 109.5 | H1A—N1—H1B | 120.0 |
C12—C7—C8 | 117.7 (2) | C1—N2—C2 | 124.11 (16) |
C12—C7—C6 | 120.5 (2) | C1—N2—H2A | 117.9 |
C8—C7—C6 | 121.8 (2) | C2—N2—H2A | 118.0 |
C7—C8—C9 | 121.4 (2) | C2—N3—C3 | 112.03 (17) |
C7—C8—H8 | 119.3 | C5—N4—C3 | 108.31 (16) |
C9—C8—H8 | 119.3 | C5—N4—H4 | 125.9 |
C10—C9—C8 | 119.7 (2) | C3—N4—H4 | 125.8 |
C10—C9—H9 | 120.1 | C5—N5—C4 | 107.90 (16) |
C8—C9—H9 | 120.1 | C5—N5—H5A | 126.1 |
C9—C10—C11 | 119.4 (2) | C4—N5—H5A | 126.0 |
C9—C10—S2 | 121.40 (16) | H1W—O7—H2W | 110.9 |
C11—C10—S2 | 119.21 (17) | O6—S1—O5 | 112.91 (10) |
C12—C11—C10 | 119.7 (2) | O6—S1—O4 | 112.80 (10) |
C12—C11—H11 | 120.1 | O5—S1—O4 | 111.18 (9) |
C10—C11—H11 | 120.1 | O6—S1—C17 | 106.48 (9) |
C7—C12—C11 | 122.0 (2) | O5—S1—C17 | 106.79 (10) |
C7—C12—H12 | 119.0 | O4—S1—C17 | 106.13 (9) |
C11—C12—H12 | 119.0 | O2—S2—O3 | 112.64 (12) |
C14—C13—H13A | 109.5 | O2—S2—O1 | 114.04 (12) |
C14—C13—H13B | 109.5 | O3—S2—O1 | 109.38 (13) |
H13A—C13—H13B | 109.5 | O2—S2—C10 | 107.32 (10) |
C14—C13—H13C | 109.5 | O3—S2—C10 | 105.60 (10) |
H13A—C13—H13C | 109.5 | O1—S2—C10 | 107.35 (10) |
H13B—C13—H13C | 109.5 | ||
N3—C3—C4—N5 | −179.98 (17) | C13—C14—C19—C18 | 178.4 (2) |
N4—C3—C4—N5 | −0.4 (2) | C17—C18—C19—C14 | 0.6 (4) |
N3—C3—C4—C1 | −4.1 (3) | N1—C1—N2—C2 | 178.16 (18) |
N4—C3—C4—C1 | 175.47 (16) | C4—C1—N2—C2 | −1.0 (3) |
N1—C1—C4—C3 | −175.61 (18) | N3—C2—N2—C1 | −1.6 (3) |
N2—C1—C4—C3 | 3.5 (2) | N2—C2—N3—C3 | 1.3 (3) |
N1—C1—C4—N5 | −1.2 (3) | N4—C3—N3—C2 | −177.93 (18) |
N2—C1—C4—N5 | 177.89 (19) | C4—C3—N3—C2 | 1.6 (3) |
C12—C7—C8—C9 | 0.3 (4) | N5—C5—N4—C3 | −0.2 (2) |
C6—C7—C8—C9 | −179.4 (2) | N3—C3—N4—C5 | 179.97 (18) |
C7—C8—C9—C10 | 0.0 (4) | C4—C3—N4—C5 | 0.4 (2) |
C8—C9—C10—C11 | 0.0 (3) | N4—C5—N5—C4 | 0.0 (2) |
C8—C9—C10—S2 | 178.90 (18) | C3—C4—N5—C5 | 0.3 (2) |
C9—C10—C11—C12 | −0.3 (4) | C1—C4—N5—C5 | −174.7 (2) |
S2—C10—C11—C12 | −179.2 (2) | C18—C17—S1—O6 | −26.8 (2) |
C8—C7—C12—C11 | −0.6 (4) | C16—C17—S1—O6 | 157.08 (19) |
C6—C7—C12—C11 | 179.1 (3) | C18—C17—S1—O5 | −147.66 (19) |
C10—C11—C12—C7 | 0.6 (4) | C16—C17—S1—O5 | 36.2 (2) |
C19—C14—C15—C16 | 0.2 (4) | C18—C17—S1—O4 | 93.6 (2) |
C13—C14—C15—C16 | −179.4 (2) | C16—C17—S1—O4 | −82.5 (2) |
C14—C15—C16—C17 | 1.4 (4) | C9—C10—S2—O2 | −106.24 (19) |
C15—C16—C17—C18 | −2.0 (4) | C11—C10—S2—O2 | 72.7 (2) |
C15—C16—C17—S1 | 174.2 (2) | C9—C10—S2—O3 | 133.38 (19) |
C16—C17—C18—C19 | 1.0 (4) | C11—C10—S2—O3 | −47.7 (2) |
S1—C17—C18—C19 | −175.2 (2) | C9—C10—S2—O1 | 16.7 (2) |
C15—C14—C19—C18 | −1.2 (4) | C11—C10—S2—O1 | −164.35 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O4 | 0.86 | 1.95 | 2.813 (2) | 178 |
N1—H1B···O3 | 0.86 | 1.97 | 2.805 (2) | 163 |
N2—H2A···O5 | 0.86 | 1.84 | 2.694 (2) | 178 |
N4—H4···O7i | 0.86 | 1.80 | 2.653 (2) | 170 |
N5—H5A···O1 | 0.86 | 2.09 | 2.884 (3) | 152 |
N5—H5A···O3 | 0.86 | 2.43 | 3.149 (3) | 141 |
O7—H1W···O6ii | 0.84 | 1.93 | 2.762 (2) | 176 |
O7—H2W···O2 | 0.83 | 2.04 | 2.815 (2) | 156 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C5H7N52+·2C7H7O3S−·H2O |
Mr | 497.54 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 16.2462 (11), 6.0370 (4), 22.7390 (15) |
β (°) | 90.625 (1) |
V (Å3) | 2230.1 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.29 |
Crystal size (mm) | 0.31 × 0.21 × 0.21 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2006) |
Tmin, Tmax | 0.915, 0.942 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16652, 4153, 3452 |
Rint | 0.100 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.120, 1.05 |
No. of reflections | 4153 |
No. of parameters | 300 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.46, −0.31 |
Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Pearce et al., 2000), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O4 | 0.86 | 1.95 | 2.813 (2) | 178.1 |
N1—H1B···O3 | 0.86 | 1.97 | 2.805 (2) | 163.3 |
N2—H2A···O5 | 0.86 | 1.84 | 2.694 (2) | 177.8 |
N4—H4···O7i | 0.86 | 1.80 | 2.653 (2) | 169.5 |
N5—H5A···O1 | 0.86 | 2.09 | 2.884 (3) | 152.4 |
N5—H5A···O3 | 0.86 | 2.43 | 3.149 (3) | 141.1 |
O7—H1W···O6ii | 0.84 | 1.93 | 2.762 (2) | 175.7 |
O7—H2W···O2 | 0.83 | 2.04 | 2.815 (2) | 156.00 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1/2, −y+1/2, z−1/2. |
Acknowledgements
This work was supported by the National Natural Science Foundation of China (20662007).
References
Barral, K., Priet, S., Sire, J., Neyts, J., Balzarini, J., Canard, B. & Alvarez, K. (2006). J. Med. Chem. 49, 7799-7806. Web of Science CrossRef PubMed CAS Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2006). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Etter, M. C. (1990). Acc. Chem. Res. 23, 120–126. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Pearce, L., Prout, C. K. & Watkin, D. J. (2000). CAMERON. Chemical Crystallography Laboratory, University of Oxford, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sridhar, B. & Ravikumar, K. (2007). Acta Cryst. C63, o415–o418. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sridhar, B., Ravikumar, K. & Varghese, B. (2009). Acta Cryst. C65, o202–o206. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xing, D., Tan, X., Chen, X. & Bu, Y. (2008). J. Phys. Chem. A, 112, 7418-7425. Web of Science CrossRef PubMed CAS Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Purin and its derivatives, as one kind of important nucleobase compounds, are essential for understanding many mechanisms of basic importance in the biological process (Xing et al., 2008), and belongs to a group of cytokinin-derived compounds which are indispensable for plant growth. The concept of the acyclic nucleoside phosphonate (ANPs) has been used to design chain terminators for antiviral and therapy proved to be valid (Barral et al., 2006). In C5H6N5+.C8H7O2–.C8H8O2–.H2O and C5H6N5+.C4H3O4–.H2O compounds, the adeninium cations form N-H···O hydrogen bonds with their anion counterparts and adeninium-adeninium self-association base pairs (Sridhar et al., 2007). In C5H7N52+.0.5C2O42–.2Cl– compound, adenine is doubly protonated, while in C5H6N5+.C2HO4–.0.5C2H2O4.H2O compound, adenine is monoprotonated (Sridhar et al., 2009).
In the title compound, C5H7N52+.2C7H7SO3–.H2O, the asymmetric unit contains one diprotonated adeninium cation, two p-toluenesulfonic acid anions and one water molecule. The two anions are connected to the purin molecule through N-H···O hydrogen bonds building R22(8) and R22(9) graph set motifs (Table 1, Fig.1) (Etter, 1990; Bernstein et al., 1995) . In the same asymmetric unit, the water molecule is connected through O-H···O hydrogen bond to one of the p-toluenesulfonic acid (Table 1, Fig. 1).
Futhermore The water links cation and anion through O-H···O and N-H···O hydrogen bonds forming a R66(20) graph set motif and buiding a two dimensional layer parallel to the (1 0 -1) plane (Fig. 2, Table 1).
In the 9H-purin-6-amine molecule, all atoms are coplanar, the dihedral angles between the plane of the 9H-purin-6-amine and the benzene rings of the p-toluenesulfonate anions are 87.78 (5)° and 87.15 (5)°, respectively, indicating that the 9H-purin-6-amine is almost perpendicular to the two benzene rings.