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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): o1055.
Published online 2008 May 10. doi:  10.1107/S1600536808013512
PMCID: PMC2961591

5,7,9,10-Tetra­hydro-5β,10β-methano-3aα,8aα-methyl­propenocyclo­octa­[1,2-c:5,6-c′]dipyrazole-3,8(2H,4H)-dione monohydrate

Abstract

The racemic title compound, C15H16N4O2·H2O, crystallizes as a hydrogen-bonded layer structure incorporating the solvent water mol­ecules. Within the layers, there are three distinct hydrogen-bonding motifs which can be classified as R 2 2(8), R 4 2(8) and R 4 4(12).

Related literature

For related literature, see: Chan et al. (2008 [triangle]); Yue et al. (1997 [triangle], 2000 [triangle], 2007 [triangle]). For hydrogen-bonding analysis, see: Etter (1990 [triangle]).

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Object name is e-64-o1055-scheme1.jpg

Experimental

Crystal data

  • C15H16N4O2·H2O
  • M r = 302.3
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1055-efi1.jpg
  • a = 6.478 (1) Å
  • b = 8.157 (1) Å
  • c = 14.812 (2) Å
  • α = 85.412 (9)°
  • β = 88.369 (8)°
  • γ = 67.089 (11)°
  • V = 718.6 (2) Å3
  • Z = 2
  • Cu Kα radiation
  • μ = 0.82 mm−1
  • T = 294 K
  • 0.30 × 0.25 × 0.22 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: none
  • 2695 measured reflections
  • 2695 independent reflections
  • 2365 reflections with I > 2σ(I)
  • 1 standard reflections frequency: 30 min intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.089
  • S = 1.64
  • 2357 reflections
  • 200 parameters
  • H-atom parameters not refined
  • Δρmax = 0.34 e Å−3
  • Δρmin = −0.22 e Å−3

Data collection: CAD-4 (Schagen et al., 1989 [triangle]); cell refinement: CAD-4; data reduction: local program; program(s) used to solve structure: SIR92 (Altomare et al., 1994 [triangle]); program(s) used to refine structure: RAELS (Rae, 2000 [triangle]); molecular graphics: ORTEPII (Johnson, 1976 [triangle]) and CrystalMaker (CrystalMaker Software, 2005 [triangle]); software used to prepare material for publication: local programs.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I. DOI: 10.1107/S1600536808013512/tk2269sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808013512/tk2269Isup2.hkl

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

Acknowledgments

This research was supported by the Australian Research Council.

supplementary crystallographic information

Comment

The structural core of the title compound (I) is the rare tricyclo[5.3.1.13,9]dodecane ring system, the chemistry of which has been described by us earlier (Yue et al. 1997, 2000, 2007; Chan et al. 2008). Compound (I), Fig. 1, forms hydrogen bonded layers that lie in the (1 - 2 1) plane, Fig. 2 & Table 1. There are three motifs, all of which are centrosymmetric, which repeat within the layer. The first of these incorporates pairs of N—H···O=C hydrogen bonds. The second and third alternate along a, one comprising cycles of O—H···O=C hydrogen bonds and involving the lattice water molecules, and the other including N—H···O (water) interactions as well. In Etter's notation, the three cycles can be described as R22(8), R42(8) and R44(12), respectively (Etter, 1990).

Experimental

Racemic 3,7-bis(methoxycarbonyl)-5-methylidenetricyclo[5.3.1.13,9]dodecane-2,8-dione (Yue et al., 1997) (1.00 g, 3.24 mmol) was ground into a fine powder and then a small volume of hydrazine hydrate added. After stirring the mixture for 30 min, the resulting solid was filtered, washed with a small amount of diethyl ether and dried. The creamy material was recrystallized from methanol to give shiny crystals of the dipyrazole product (0.60 g, 68%), m.p. 335–343°C (decomp.). Found: C 61.90, H 6.24, N 20.97; C15H16N4O2.H2O requires C 61.75, H 5.93, N 20.58%. X-ray quality crystals were obtained from a methanol solution of (I).

Refinement

Hydrogen atoms attached to C and N were included at calculated positions (C—H, N—H = 1.0 Å). The water hydrogen atoms were located on a difference map, and then positioned with O—H = 1.0 Å. All hydrogen atoms were refined with isotropic thermal parameters equivalent to those of the atom to which they were bonded. A small number of reflections were omitted from the refinement due to rounding differences between the data processing and refinement programs.

Figures

Fig. 1.
Molecular structure of (I) showing atom numbering scheme and dispacement ellipsoids drawn at the 30% probability level.
Fig. 2.
Part of one hydrogen bonded layer in the crystal structure of (I) showing the three hydrogen bonded packing motifs. Enantiomers are distinguished by C shading and hydrogen bonds are shown as dashed bonds.

Crystal data

C15H16N4O2·H2OZ = 2
Mr = 302.3F000 = 320.0
Triclinic, P1Dx = 1.40 Mg m3
Hall symbol: -P 1Cu Kα radiation λ = 1.54184 Å
a = 6.478 (1) ÅCell parameters from 10 reflections
b = 8.157 (1) Åθ = 20–25º
c = 14.812 (2) ŵ = 0.82 mm1
α = 85.412 (9)ºT = 294 K
β = 88.369 (8)ºIrregular, colourless
γ = 67.089 (11)º0.30 × 0.25 × 0.22 mm
V = 718.6 (2) Å3

Data collection

Enraf–Nonius CAD-4 diffractometerh = −7→7
ω–2θ scansk = −9→9
Absorption correction: nonel = 0→18
2695 measured reflections1 standard reflections
2695 independent reflections every 30 min
2365 reflections with I > 2σ(I) intensity decay: none
θmax = 70º

Refinement

Refinement on FH-atom parameters not refined
R[F2 > 2σ(F2)] = 0.045  w = 1/[σ2(F) + 0.0004F2]
wR(F2) = 0.089(Δ/σ)max = 0.003
S = 1.64Δρmax = 0.34 e Å3
2357 reflectionsΔρmin = −0.22 e Å3
200 parametersExtinction correction: none

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

xyzUiso*/Ueq
O10.2515 (2)0.7918 (2)0.4385 (1)0.0547 (4)
O20.5206 (3)0.2155 (2)−0.00820 (9)0.0554 (5)
N10.7574 (3)0.6073 (2)0.3265 (1)0.0467 (4)
N20.6047 (3)0.7257 (2)0.3836 (1)0.0444 (4)
N30.3972 (3)0.0850 (2)0.2088 (1)0.0454 (4)
N40.4023 (3)0.0817 (2)0.1133 (1)0.0450 (4)
C10.7515 (3)0.2116 (3)0.3103 (1)0.0473 (5)
C20.7756 (3)0.3578 (3)0.2444 (1)0.0423 (5)
C30.6519 (3)0.5264 (2)0.2887 (1)0.0357 (4)
C40.4109 (3)0.5822 (2)0.3178 (1)0.0327 (4)
C50.3650 (3)0.4204 (2)0.3612 (1)0.0389 (4)
C60.5016 (3)0.2421 (2)0.3198 (1)0.0398 (4)
C70.4370 (3)0.2210 (2)0.2270 (1)0.0355 (4)
C80.4732 (3)0.3268 (2)0.1447 (1)0.0344 (4)
C90.6971 (3)0.3513 (3)0.1481 (1)0.0420 (5)
C100.2364 (3)0.7009 (2)0.2481 (1)0.0407 (5)
C110.1748 (3)0.6505 (2)0.1653 (1)0.0399 (4)
C120.2665 (3)0.4969 (2)0.1200 (1)0.0414 (5)
C13−0.0245 (4)0.7972 (3)0.1192 (2)0.0680 (7)
C140.4063 (3)0.7116 (2)0.3883 (1)0.0379 (4)
C150.4741 (3)0.2025 (2)0.0724 (1)0.0386 (4)
OW0.1914 (3)1.1247 (2)0.5054 (1)0.0586 (5)
HN20.64100.81230.41750.044
HN40.3574−0.00130.08010.045
H1C10.81300.21580.37090.047
H2C10.83640.09230.28670.047
HC20.93770.33890.24150.042
H1C50.20210.44620.35350.039
H2C50.40190.40630.42720.039
HC60.49030.14310.36140.040
H1C90.67920.46570.11260.042
H2C90.81500.24930.11940.042
H1C100.28610.80010.22890.041
H2C100.09350.74910.28300.041
HC120.18720.49650.06310.041
H1C13−0.06020.75540.06220.068
H2C13−0.15670.82850.16060.068
H3C130.01150.90480.10420.068
H1OW0.23111.00640.47990.059
H2OW0.03351.16800.52790.059

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0468 (8)0.0597 (9)0.0644 (9)−0.0226 (7)0.0129 (7)−0.0380 (7)
O20.086 (1)0.0521 (8)0.0354 (7)−0.0325 (8)0.0048 (7)−0.0159 (6)
N10.0379 (8)0.057 (1)0.052 (1)−0.0223 (7)0.0050 (7)−0.0231 (8)
N20.0428 (9)0.0485 (9)0.0496 (9)−0.0229 (7)0.0022 (7)−0.0214 (7)
N30.058 (1)0.0384 (8)0.0434 (9)−0.0206 (7)0.0035 (7)−0.0110 (6)
N40.059 (1)0.0396 (8)0.0417 (9)−0.0229 (7)0.0003 (7)−0.0146 (6)
C10.043 (1)0.038 (1)0.047 (1)0.0006 (8)−0.0128 (8)−0.0096 (8)
C20.0272 (8)0.049 (1)0.048 (1)−0.0082 (7)0.0010 (7)−0.0206 (8)
C30.0312 (8)0.0399 (9)0.0380 (9)−0.0143 (7)0.0002 (7)−0.0114 (7)
C40.0288 (8)0.0329 (8)0.0362 (9)−0.0098 (6)0.0000 (6)−0.0135 (7)
C50.046 (1)0.0374 (9)0.0350 (9)−0.0174 (8)0.0046 (7)−0.0101 (7)
C60.052 (1)0.0319 (9)0.0327 (9)−0.0129 (8)−0.0029 (7)−0.0040 (6)
C70.0396 (9)0.0294 (8)0.0360 (9)−0.0108 (7)0.0010 (7)−0.0073 (6)
C80.0405 (9)0.0307 (8)0.0312 (8)−0.0116 (7)−0.0004 (6)−0.0090 (6)
C90.041 (1)0.046 (1)0.041 (1)−0.0179 (8)0.0087 (7)−0.0176 (7)
C100.0388 (9)0.0309 (9)0.049 (1)−0.0086 (7)−0.0059 (8)−0.0092 (7)
C110.0380 (9)0.0348 (9)0.0404 (9)−0.0071 (7)−0.0043 (7)−0.0018 (7)
C120.047 (1)0.0337 (9)0.0417 (9)−0.0115 (8)−0.0104 (8)−0.0063 (7)
C130.063 (1)0.051 (1)0.065 (2)0.007 (1)−0.023 (1)−0.012 (1)
C140.0400 (9)0.0360 (9)0.0396 (9)−0.0146 (7)−0.0001 (7)−0.0148 (7)
C150.046 (1)0.0344 (9)0.0350 (9)−0.0133 (7)−0.0017 (7)−0.0107 (7)
OW0.0515 (8)0.062 (1)0.074 (1)−0.0306 (7)0.0046 (7)−0.0305 (8)

Geometric parameters (Å, °)

O1—C141.229 (2)C5—H1C51.000
O2—C151.229 (2)C5—H2C51.000
N1—N21.402 (2)C6—C71.491 (2)
N1—C31.284 (2)C6—HC61.000
N2—C141.333 (2)C7—C81.503 (2)
N2—HN21.000C8—C91.542 (2)
N3—N41.415 (2)C8—C121.534 (2)
N3—C71.283 (2)C8—C151.531 (2)
N4—C151.342 (3)C9—H1C91.000
N4—HN41.000C9—H2C91.000
C1—C21.533 (3)C10—C111.438 (3)
C1—C61.543 (3)C10—H1C101.000
C1—H1C11.000C10—H2C101.000
C1—H2C11.000C11—C121.380 (3)
C2—C31.490 (2)C11—C131.510 (3)
C2—C91.540 (3)C12—HC121.000
C2—HC21.000C13—H1C131.000
C3—C41.507 (2)C13—H2C131.000
C4—C51.550 (2)C13—H3C131.000
C4—C101.528 (2)OW—H1OW1.000
C4—C141.535 (2)OW—H2OW1.000
C5—C61.543 (2)
N2—N1—C3107.0 (1)N3—C7—C6121.8 (2)
N1—N2—C14113.5 (1)N3—C7—C8113.9 (2)
N1—N2—HN2123.2C6—C7—C8122.4 (2)
C14—N2—HN2123.2C7—C8—C9112.6 (1)
N4—N3—C7106.9 (2)C7—C8—C12112.7 (2)
N3—N4—C15112.4 (1)C7—C8—C1599.0 (1)
N3—N4—HN4123.8C9—C8—C12115.6 (2)
C15—N4—HN4123.8C9—C8—C15112.0 (1)
C2—C1—C6109.5 (1)C12—C8—C15103.3 (1)
C2—C1—H1C1109.5C2—C9—C8114.2 (2)
C2—C1—H2C1109.5C2—C9—H1C9108.3
C6—C1—H1C1109.5C2—C9—H2C9108.3
C6—C1—H2C1109.5C8—C9—H1C9108.3
H1C1—C1—H2C1109.5C8—C9—H2C9108.3
C1—C2—C3104.3 (2)H1C9—C9—H2C9109.5
C1—C2—C9112.1 (2)C4—C10—C11127.5 (2)
C1—C2—HC2108.2C4—C10—H1C10104.8
C3—C2—C9115.7 (2)C4—C10—H2C10104.8
C3—C2—HC2108.2C11—C10—H1C10104.8
C9—C2—HC2108.2C11—C10—H2C10104.8
N1—C3—C2120.9 (2)H1C10—C10—H2C10109.5
N1—C3—C4113.8 (2)C10—C11—C12132.2 (2)
C2—C3—C4122.7 (1)C10—C11—C13112.7 (2)
C3—C4—C5111.0 (1)C12—C11—C13115.1 (2)
C3—C4—C10115.8 (2)C8—C12—C11129.0 (2)
C3—C4—C1498.9 (1)C8—C12—HC12115.5
C5—C4—C10114.7 (1)C11—C12—HC12115.5
C5—C4—C14111.9 (1)C11—C13—H1C13109.5
C10—C4—C14103.2 (1)C11—C13—H2C13109.5
C4—C5—C6114.4 (1)C11—C13—H3C13109.5
C4—C5—H1C5108.2H1C13—C13—H2C13109.5
C4—C5—H2C5108.2H1C13—C13—H3C13109.5
C6—C5—H1C5108.2H2C13—C13—H3C13109.5
C6—C5—H2C5108.2O1—C14—N2125.5 (2)
H1C5—C5—H2C5109.5O1—C14—C4128.1 (2)
C1—C6—C5111.6 (2)N2—C14—C4106.4 (1)
C1—C6—C7103.6 (2)O2—C15—N4126.6 (2)
C1—C6—HC6108.1O2—C15—C8127.0 (2)
C5—C6—C7116.9 (1)N4—C15—C8106.3 (2)
C5—C6—HC6108.1H1OW—OW—H2OW109.5
C7—C6—HC6108.1
C3—N1—N2—C145.0 (2)C5—C4—C10—H2C1062.5
C3—N1—N2—HN2−175.0C14—C4—C10—C11178.2 (2)
N2—N1—C3—C2−162.8 (2)C14—C4—C10—H1C1055.8
N2—N1—C3—C4−0.5 (2)C14—C4—C10—H2C10−59.5
N1—N2—C14—O1174.6 (2)C3—C4—C14—O1−175.7 (2)
N1—N2—C14—C4−7.0 (2)C3—C4—C14—N25.9 (2)
HN2—N2—C14—O1−5.4C5—C4—C14—O1−58.8 (3)
HN2—N2—C14—C4173.0C5—C4—C14—N2122.8 (2)
C7—N3—N4—C158.1 (2)C10—C4—C14—O165.0 (2)
C7—N3—N4—HN4−171.9C10—C4—C14—N2−113.4 (2)
N4—N3—C7—C6−164.3 (2)C4—C5—C6—C147.2 (2)
N4—N3—C7—C80.2 (2)C4—C5—C6—C7−71.8 (2)
N3—N4—C15—O2170.8 (2)C4—C5—C6—HC6166.0
N3—N4—C15—C8−12.5 (2)H1C5—C5—C6—C1167.9
HN4—N4—C15—O2−9.2H1C5—C5—C6—C749.0
HN4—N4—C15—C8167.5H1C5—C5—C6—HC6−73.3
C6—C1—C2—C362.4 (2)H2C5—C5—C6—C1−73.5
C6—C1—C2—C9−63.5 (2)H2C5—C5—C6—C7167.5
C6—C1—C2—HC2177.4H2C5—C5—C6—HC645.3
H1C1—C1—C2—C3−57.6C1—C6—C7—N3108.8 (2)
H1C1—C1—C2—C9176.5C1—C6—C7—C8−54.4 (2)
H1C1—C1—C2—HC257.4C5—C6—C7—N3−128.1 (2)
H2C1—C1—C2—C3−177.6C5—C6—C7—C868.8 (2)
H2C1—C1—C2—C956.5HC6—C6—C7—N3−5.9
H2C1—C1—C2—HC2−62.6HC6—C6—C7—C8−169.0
C2—C1—C6—C5−63.1 (2)N3—C7—C8—C9−125.5 (2)
C2—C1—C6—C763.5 (2)N3—C7—C8—C12101.6 (2)
C2—C1—C6—HC6178.1N3—C7—C8—C15−7.0 (2)
H1C1—C1—C6—C556.9C6—C7—C8—C938.9 (2)
H1C1—C1—C6—C7−176.5C6—C7—C8—C12−94.0 (2)
H1C1—C1—C6—HC6−61.9C6—C7—C8—C15157.4 (2)
H2C1—C1—C6—C5176.9C7—C8—C9—C2−30.6 (2)
H2C1—C1—C6—C7−56.5C7—C8—C9—H1C9−151.3
H2C1—C1—C6—HC658.1C7—C8—C9—H2C990.1
C1—C2—C3—N1105.6 (2)C12—C8—C9—C2100.9 (2)
C1—C2—C3—C4−55.1 (2)C12—C8—C9—H1C9−19.8
C9—C2—C3—N1−130.8 (2)C12—C8—C9—H2C9−138.4
C9—C2—C3—C468.4 (2)C15—C8—C9—C2−141.2 (2)
HC2—C2—C3—N1−9.4C15—C8—C9—H1C998.2
HC2—C2—C3—C4−170.1C15—C8—C9—H2C9−20.5
C1—C2—C9—C845.0 (2)C7—C8—C12—C1169.6 (3)
C1—C2—C9—H1C9165.7C7—C8—C12—HC12−110.4
C1—C2—C9—H2C9−75.7C9—C8—C12—C11−61.8 (3)
C3—C2—C9—C8−74.4 (2)C9—C8—C12—HC12118.2
C3—C2—C9—H1C946.3C15—C8—C12—C11175.5 (2)
C3—C2—C9—H2C9164.9C15—C8—C12—HC12−4.5
HC2—C2—C9—C8164.1C7—C8—C15—O2−172.1 (2)
HC2—C2—C9—H1C9−75.2C7—C8—C15—N411.2 (2)
HC2—C2—C9—H2C943.4C9—C8—C15—O2−53.2 (3)
N1—C3—C4—C5−120.9 (2)C9—C8—C15—N4130.1 (2)
N1—C3—C4—C10106.1 (2)C12—C8—C15—O271.9 (2)
N1—C3—C4—C14−3.3 (2)C12—C8—C15—N4−104.9 (2)
C2—C3—C4—C541.1 (2)C4—C10—C11—C12−9.2 (3)
C2—C3—C4—C10−91.9 (2)C4—C10—C11—C13172.8 (2)
C2—C3—C4—C14158.7 (2)H1C10—C10—C11—C12113.2
C3—C4—C5—C6−33.8 (2)H1C10—C10—C11—C13−64.9
C3—C4—C5—H1C5−154.5H2C10—C10—C11—C12−131.6
C3—C4—C5—H2C587.0H2C10—C10—C11—C1350.4
C10—C4—C5—C699.7 (2)C10—C11—C12—C8−0.9 (4)
C10—C4—C5—H1C5−21.0C10—C11—C12—HC12179.1
C10—C4—C5—H2C5−139.5C13—C11—C12—C8177.1 (2)
C14—C4—C5—C6−143.1 (1)C13—C11—C12—HC12−2.9
C14—C4—C5—H1C596.1C10—C11—C13—H1C13−180.0
C14—C4—C5—H2C5−22.4C10—C11—C13—H2C13−60.0
C3—C4—C10—C1171.3 (2)C10—C11—C13—H3C1360.0
C3—C4—C10—H1C10−51.0C12—C11—C13—H1C131.6
C3—C4—C10—H2C10−166.3C12—C11—C13—H2C13121.6
C5—C4—C10—C11−59.9 (2)C12—C11—C13—H3C13−118.4
C5—C4—C10—H1C10177.7

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—HN2···OWi1.001.832.763 (3)154
N4—HN4···O2ii1.002.002.858 (2)143
OW—H1OW···O11.001.852.844 (2)169
OW—H2OW···O1iii1.001.812.796 (2)169

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2269).

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