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Acta Cryst. (2008). E64, o1055    [ doi:10.1107/S1600536808013512 ]

5,7,9,10-Tetrahydro-5[beta],10[beta]-methano-3a[alpha],8a[alpha]-methylpropenocycloocta[1,2-c:5,6-c']dipyrazole-3,8(2H,4H)-dione monohydrate

D. Djaidi, R. Bishop, D. C. Craig and M. L. Scudder

Abstract top

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 R22(8), R42(8) and R44(12).

Comment top

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).

Related literature top

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

Experimental top

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 top

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.

Computing details top

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

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) showing atom numbering scheme and dispacement ellipsoids drawn at the 30% probability level.
[Figure 2] 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.
(I) top
Crystal data top
C15H16N4O2·H2OZ = 2
Mr = 302.3F000 = 320.0
Triclinic, P1Dx = 1.40 Mg m−3
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 mm−1
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 top
Enraf–Nonius CAD-4
diffractometer		h = −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 top
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 Å−3
2357 reflectionsΔρmin = −0.22 e Å−3
200 parametersExtinction correction: none
Crystal data top
C15H16N4O2·H2Oγ = 67.089 (11)º
Mr = 302.3V = 718.6 (2) Å3
Triclinic, P1Z = 2
a = 6.478 (1) ÅCu Kα
b = 8.157 (1) ŵ = 0.82 mm−1
c = 14.812 (2) ÅT = 294 K
α = 85.412 (9)º0.30 × 0.25 × 0.22 mm
β = 88.369 (8)º
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = ?
Absorption correction: none1 standard reflections
2695 measured reflections every 30 min
2695 independent reflections intensity decay: none
2365 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.045200 parameters
wR(F2) = 0.089H-atom parameters not refined
S = 1.64Δρmax = 0.34 e Å−3
2357 reflectionsΔρmin = −0.22 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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) top
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, °) top
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, °) top
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.
Table 1
Hydrogen-bond geometry (Å, °) top
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.
Acknowledgements top

This research was supported by the Australian Research Council.

references
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