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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o347.
Published online 2007 December 21. doi:  10.1107/S1600536807067025
PMCID: PMC2915388

7-(1,3-Dioxolan-2-ylmeth­yl)-1,3-di­methyl­purine-2,6(1H,3H)-dione trichloro­acetic acid solvate

Abstract

In the title compound, C11H14N4O4·C2HCl3O2, the dioxolane ring adopts an envelope conformation. Doxophylline [7-(1,3-dioxolan-2-yl-meth­yl)-1,3-dimethyl-3,7-dihydro-1H-purine-2,6-dione] and trichloro­acetic acid mol­ecules are linked by O—H(...)N and C—H(...)O hydrogen bonds.

Related literature

For related literature, see: Chen et al. (2006 [triangle], 2007 [triangle]); Feng et al. (2007 [triangle]); Franzone et al. (1981 [triangle]); Li et al. (1995 [triangle]); Villani et al. (1997 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o347-scheme1.jpg

Experimental

Crystal data

  • C11H14N4O4·C2HCl3O2
  • M r = 429.64
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o347-efi1.jpg
  • a = 5.656 (3) Å
  • b = 10.825 (5) Å
  • c = 14.962 (7) Å
  • α = 93.217 (9)°
  • β = 91.090 (8)°
  • γ = 101.725 (9)°
  • V = 895.1 (8) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.55 mm−1
  • T = 293 (2) K
  • 0.38 × 0.28 × 0.17 mm

Data collection

  • Bruker APEX area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.818, T max = 0.912
  • 4717 measured reflections
  • 3124 independent reflections
  • 2915 reflections with I > 2σ(I)
  • R int = 0.015

Refinement

  • R[F 2 > 2σ(F 2)] = 0.073
  • wR(F 2) = 0.167
  • S = 1.15
  • 3124 reflections
  • 238 parameters
  • H-atom parameters constrained
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.41 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL (Bruker, 2000 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807067025/cs2059sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807067025/cs2059Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

Doxophylline, 2-(7'-theophyllinemethyl)1,3-dioxolane, is a theophylline derivative which shows interesting bronchodilating activity (Franzone et al., 1981; Villani et al., 1997). Previously, we have reported some compounds containing doxophylline (Chen et al., 2006; Chen et al., 2007; Feng et al., 2007).

Association of one doxophylline and one trichloroacetic acid molecule leads to the title compound (Fig. 1). The geometric features of the purine ring system are similar to those in doxophylline (Chen et al., 2006;Chen et al., 2007; Feng et al., 2007).

As shown in Fig. 2, the O6—H6···N4 hydrogen bond between trichloroacetic acid and doxophylline molecule is one of the essential forces in crystal formation. In addtion the weak hydrogen bonds of C7—H7···O1i, C10—H10B···O2ii and C5—H5···O5 help to increase the stability of the crystal (Table 2 & Fig. 2).

Experimental

Doxophylline was synthesized according with a published procedure (Li et al., 1995), from theophylline by subsitution, oxidation and condensation. Trichloroacetic acid (10 mmol) was added to a solution of doxophylline (10 mm l) in ethanol (20 ml). The mixture was heated to boiling and a clear solution was obtained. Crystals of the title compound were formed by gradual evaporation of ethanol over a period of one week at 293 K.

Refinement

All of the H atoms were placed in calculated positions and allowed to ride on their parent atoms at distances of 0.82 (hydroxy), 0.93 (C5—H5), 0.96 (methyl), 0.97 (methylene) and 0.98Å (methine), with Uiso(H) = 1.2–1.5 Ueq(C) and Uiso(H) = 1.5 Ueq(O).

Figures

Fig. 1.
A view of the asymmetric unit with atomic labelling, showing 30% probability displacement ellipsoids. Hydrogen bonds are illustrated in broken lines.
Fig. 2.
A view of a portion of the crystal packing. Hydrogen bonds are illustrated in broken lines.

Crystal data

C11H14N4O4·C2HCl3O2Z = 2
Mr = 429.64F000 = 440
Triclinic, P1Dx = 1.594 Mg m3
a = 5.656 (3) ÅMo Kα radiation λ = 0.71073 Å
b = 10.825 (5) ÅCell parameters from 1931 reflections
c = 14.962 (7) Åθ = 2.4–24.7º
α = 93.217 (9)ºµ = 0.55 mm1
β = 91.090 (8)ºT = 293 (2) K
γ = 101.725 (9)ºBlock, colorless
V = 895.1 (8) Å30.38 × 0.28 × 0.17 mm

Data collection

Bruker APEX area-detector diffractometer3124 independent reflections
Radiation source: fine-focus sealed tube2915 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.015
T = 273(2) Kθmax = 25.0º
[var phi] and ω scansθmin = 1.9º
Absorption correction: multi-scan(SADABS; Bruker, 2000)h = −6→6
Tmin = 0.818, Tmax = 0.912k = −12→10
4717 measured reflectionsl = −16→17

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.073H-atom parameters constrained
wR(F2) = 0.167  w = 1/[σ2(Fo2) + (0.0594P)2 + 1.1669P] where P = (Fo2 + 2Fc2)/3
S = 1.15(Δ/σ)max < 0.001
3124 reflectionsΔρmax = 0.32 e Å3
238 parametersΔρmin = −0.41 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Cl11.5096 (2)0.72892 (10)0.71995 (10)0.0764 (4)
Cl21.8985 (2)0.61490 (16)0.77278 (12)0.1021 (6)
Cl31.7335 (3)0.59298 (13)0.58909 (10)0.0997 (6)
O10.3256 (5)−0.0373 (3)0.80906 (17)0.0546 (7)
O20.3073 (6)0.0976 (3)0.5250 (2)0.0733 (9)
O30.4973 (4)0.1851 (3)0.96858 (18)0.0602 (8)
O40.8810 (5)0.2918 (3)0.99418 (19)0.0623 (8)
O51.4500 (7)0.4439 (4)0.7965 (2)0.1070 (15)
O61.3136 (5)0.4325 (3)0.65695 (18)0.0636 (8)
H61.20450.37770.67410.095*
N10.3188 (5)0.0331 (3)0.66788 (19)0.0419 (7)
N20.6381 (6)0.1835 (3)0.61213 (18)0.0449 (7)
N30.8290 (5)0.1395 (3)0.83050 (18)0.0405 (7)
N40.9777 (5)0.2545 (3)0.71822 (18)0.0430 (7)
C10.4252 (6)0.0310 (3)0.7528 (2)0.0393 (8)
C20.4147 (7)0.1040 (4)0.5965 (2)0.0478 (9)
C30.7539 (6)0.1868 (3)0.6938 (2)0.0366 (7)
C40.6551 (6)0.1155 (3)0.7615 (2)0.0359 (7)
C51.0141 (6)0.2218 (3)0.8011 (2)0.0453 (9)
C60.8182 (7)0.0864 (4)0.9184 (2)0.0503 (9)
C70.7322 (7)0.1697 (4)0.9889 (2)0.0556 (10)
C80.4837 (8)0.3052 (6)1.0101 (4)0.0819 (16)
C90.7308 (9)0.3811 (5)1.0075 (4)0.0873 (16)
C100.0798 (7)−0.0510 (4)0.6519 (3)0.0571 (10)
C110.7596 (9)0.2537 (4)0.5391 (3)0.0668 (12)
C121.4565 (7)0.4789 (4)0.7231 (3)0.0495 (9)
C131.6453 (7)0.5977 (4)0.7006 (3)0.0510 (9)
H51.15510.25350.83500.054*
H6A0.97760.07440.93600.060*
H6B0.71000.00420.91440.060*
H70.73540.13251.04700.067*
H8A0.43260.29691.07140.098*
H8B0.37080.34380.97740.098*
H9A0.74450.43730.95880.105*
H9B0.77470.43121.06340.105*
H10A0.0989−0.13710.64470.086*
H10B0.0050−0.02890.59860.086*
H10C−0.0200−0.04180.70200.086*
H11A0.80420.34180.55770.100*
H11B0.65210.24280.48750.100*
H11C0.90190.22230.52420.100*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0576 (7)0.0484 (6)0.1235 (11)0.0101 (5)0.0154 (6)0.0069 (6)
Cl20.0387 (6)0.1176 (12)0.1433 (14)−0.0071 (7)−0.0153 (7)0.0424 (10)
Cl30.1202 (12)0.0764 (9)0.0881 (9)−0.0186 (8)0.0608 (9)0.0041 (7)
O10.0479 (15)0.0548 (16)0.0536 (16)−0.0104 (12)0.0042 (12)0.0136 (13)
O20.072 (2)0.090 (2)0.0536 (17)0.0053 (17)−0.0215 (15)0.0125 (16)
O30.0333 (14)0.082 (2)0.0569 (16)−0.0045 (13)0.0028 (12)−0.0057 (15)
O40.0353 (14)0.079 (2)0.0644 (18)−0.0036 (14)−0.0027 (12)−0.0114 (15)
O50.104 (3)0.112 (3)0.075 (2)−0.056 (2)−0.026 (2)0.045 (2)
O60.0586 (18)0.069 (2)0.0498 (16)−0.0202 (14)0.0089 (13)0.0087 (14)
N10.0351 (15)0.0415 (16)0.0468 (17)0.0035 (12)−0.0024 (12)0.0012 (13)
N20.0542 (18)0.0444 (17)0.0354 (15)0.0063 (14)0.0030 (13)0.0088 (13)
N30.0389 (16)0.0432 (16)0.0365 (15)0.0000 (13)0.0013 (12)0.0077 (12)
N40.0443 (17)0.0416 (16)0.0383 (16)−0.0031 (13)0.0063 (12)0.0038 (12)
C10.0368 (18)0.0346 (17)0.0459 (19)0.0054 (14)0.0054 (15)0.0030 (15)
C20.047 (2)0.050 (2)0.045 (2)0.0095 (17)−0.0058 (16)0.0038 (16)
C30.0375 (18)0.0328 (17)0.0380 (17)0.0035 (14)0.0047 (14)0.0021 (13)
C40.0342 (17)0.0352 (17)0.0378 (17)0.0054 (13)0.0032 (13)0.0033 (14)
C50.0369 (19)0.050 (2)0.044 (2)−0.0031 (16)0.0009 (15)0.0002 (16)
C60.047 (2)0.056 (2)0.047 (2)0.0045 (17)−0.0028 (16)0.0192 (17)
C70.045 (2)0.081 (3)0.038 (2)0.000 (2)−0.0019 (16)0.0173 (19)
C80.048 (3)0.111 (4)0.079 (3)0.006 (3)−0.002 (2)−0.024 (3)
C90.056 (3)0.091 (4)0.107 (4)0.005 (3)−0.005 (3)−0.022 (3)
C100.042 (2)0.056 (2)0.068 (3)0.0014 (18)−0.0051 (18)−0.005 (2)
C110.082 (3)0.073 (3)0.041 (2)0.002 (2)0.007 (2)0.019 (2)
C120.043 (2)0.048 (2)0.054 (2)−0.0007 (17)0.0092 (17)0.0112 (18)
C130.038 (2)0.050 (2)0.063 (2)0.0029 (17)0.0123 (17)0.0080 (18)

Geometric parameters (Å, °)

Cl1—C131.760 (4)N4—C51.331 (5)
Cl2—C131.750 (4)N4—C31.359 (4)
Cl3—C131.752 (4)C1—C41.429 (5)
O1—C11.222 (4)C4—C31.366 (5)
O2—C21.212 (4)C5—H50.9300
O3—C71.402 (5)C6—C71.501 (6)
O3—C81.426 (6)C6—H6A0.9700
O4—C71.413 (5)C6—H6B0.9700
O4—C91.419 (6)C7—H70.9800
O5—C121.181 (5)C8—C91.472 (7)
O6—C121.278 (5)C8—H8A0.9700
O6—H60.8200C8—H8B0.9700
N1—C11.398 (4)C9—H9A0.9700
N1—C21.403 (5)C9—H9B0.9700
N1—C101.475 (5)C10—H10A0.9600
N2—C31.371 (4)C10—H10B0.9600
N2—C21.384 (5)C10—H10C0.9600
N2—C111.468 (5)C11—H11A0.9600
N3—C51.330 (4)C11—H11B0.9600
N3—C41.388 (4)C11—H11C0.9600
N3—C61.462 (4)C12—C131.553 (5)
C1—N1—C2127.5 (3)O3—C8—H8A110.8
C1—N1—C10115.6 (3)O3—C8—H8B110.8
C2—N1—C10116.9 (3)O4—C7—C6110.6 (3)
C2—N2—C11120.1 (3)O4—C7—H7109.5
C3—N2—C2119.3 (3)O4—C9—C8105.2 (4)
C3—N2—C11120.4 (3)O4—C9—H9A110.7
C3—C4—N3105.3 (3)O4—C9—H9B110.7
C3—C4—C1123.0 (3)O5—C12—O6126.9 (4)
C4—N3—C6128.3 (3)O5—C12—C13119.8 (4)
C4—C3—N2122.3 (3)O6—C12—C13113.1 (3)
C5—N3—C4106.2 (3)N1—C1—C4111.3 (3)
C5—N3—C6125.5 (3)N1—C10—H10A109.5
C5—N4—C3104.1 (3)N1—C10—H10B109.5
C6—C7—H7109.5N1—C10—H10C109.5
C7—O3—C8104.9 (3)N2—C2—N1116.6 (3)
C7—O4—C9108.0 (3)N2—C11—H11A109.5
C7—C6—H6A109.1N2—C11—H11B109.5
C7—C6—H6B109.1N2—C11—H11C109.5
C8—C9—H9A110.7N3—C4—C1131.6 (3)
C8—C9—H9B110.7N3—C5—N4113.3 (3)
C9—C8—H8A110.8N3—C5—H5123.3
C9—C8—H8B110.8N3—C6—C7112.3 (3)
C12—O6—H6109.5N3—C6—H6A109.1
C12—C13—Cl2109.4 (3)N3—C6—H6B109.1
C12—C13—Cl3113.0 (3)N4—C3—C4111.1 (3)
Cl2—C13—Cl3109.9 (2)N4—C3—N2126.6 (3)
C12—C13—Cl1107.0 (3)N4—C5—H5123.3
Cl2—C13—Cl1108.7 (2)H6A—C6—H6B107.9
Cl3—C13—Cl1108.6 (2)H8A—C8—H8B108.9
O1—C1—N1121.5 (3)H9A—C9—H9B108.8
O1—C1—C4127.2 (3)H10A—C10—H10B109.5
O2—C2—N2121.3 (4)H10A—C10—H10C109.5
O2—C2—N1122.1 (4)H10B—C10—H10C109.5
O3—C7—O4106.5 (3)H11A—C11—H11B109.5
O3—C7—C6111.3 (3)H11A—C11—H11C109.5
O3—C7—H7109.5H11B—C11—H11C109.5
O3—C8—C9104.8 (4)
C1—C4—C3—N4−177.2 (3)C9—O4—C7—O319.5 (4)
C1—C4—C3—N20.6 (5)C9—O4—C7—C6140.7 (4)
C1—N1—C2—O2179.3 (4)C10—N1—C1—O10.6 (5)
C1—N1—C2—N2−1.6 (5)C10—N1—C1—C4−179.9 (3)
C2—N1—C1—O1−178.2 (3)C10—N1—C2—O20.4 (6)
C2—N1—C1—C41.2 (5)C10—N1—C2—N2179.5 (3)
C2—N2—C3—N4176.5 (3)C11—N2—C3—N42.5 (5)
C2—N2—C3—C4−1.0 (5)C11—N2—C3—C4−175.0 (4)
C3—N2—C2—O2−179.5 (4)C11—N2—C2—O2−5.5 (6)
C3—N2—C2—N11.4 (5)C11—N2—C2—N1175.4 (3)
C3—N4—C5—N3−0.4 (4)N1—C1—C4—C3−0.7 (5)
C4—N3—C5—N4−0.1 (4)N1—C1—C4—N3−176.0 (3)
C4—N3—C6—C7−94.6 (4)N3—C4—C3—N4−0.9 (4)
C5—N3—C6—C785.8 (4)N3—C4—C3—N2177.0 (3)
C5—N3—C4—C30.6 (4)N3—C6—C7—O361.6 (4)
C5—N3—C4—C1176.4 (4)N3—C6—C7—O4−56.6 (4)
C5—N4—C3—C40.8 (4)O1—C1—C4—C3178.8 (3)
C5—N4—C3—N2−176.9 (3)O1—C1—C4—N33.5 (6)
C6—N3—C5—N4179.6 (3)O3—C8—C9—O4−19.2 (6)
C6—N3—C4—C3−179.2 (3)O5—C12—C13—Cl227.5 (5)
C6—N3—C4—C1−3.3 (6)O5—C12—C13—Cl3150.4 (4)
C7—O3—C8—C931.3 (5)O5—C12—C13—Cl1−90.1 (5)
C7—O4—C9—C80.1 (5)O6—C12—C13—Cl2−155.6 (3)
C8—O3—C7—O4−31.7 (4)O6—C12—C13—Cl3−32.7 (4)
C8—O3—C7—C6−152.3 (4)O6—C12—C13—Cl186.8 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O6—H6···N40.821.822.635 (4)176
C5—H5···O50.932.483.079 (5)123
C7—H7···O1i0.982.443.410 (5)171
C10—H10B···O2ii0.962.513.351 (3)147

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CS2059).

References

  • Bruker (2000). SMART (Version 5.618), SADABS (Version 2.05), SAINT (Version 6.02a) and SHELXTL (Version 6.10). Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chen, Z.-H., Tu, B. & Jin, Z.-M. (2007). Acta Cryst. E63, o2676–o2677.
  • Chen, H. X., Tu, B., Shu, Z., Ma, X. J. & Jin, Z. M. (2007). Acta Cryst. E63, o726–o727.
  • Feng, W.-J., Ma, X.-J., Shu, Z. & Jin, Z.-M. (2007). Acta Cryst. E63, o3609.
  • Franzone, J. S., Reboani, C. & Fonzo, D. (1981). Farmacol. Sci.36, 201–219. [PubMed]
  • Li, C. H., Luo, Z. & Li, Z. H. (1995). Chin. J. Pharm.26, 385–386.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.
  • Villani, F., De Maria, P., Ronchi, E. & Galimberti, M. (1997). Int. J. Clin. Pharmacol. Ther.35, 107–111. [PubMed]

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