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Acta Crystallogr Sect E Struct Rep Online. 2010 March 1; 66(Pt 3): o561.
Published online 2010 February 6. doi:  10.1107/S1600536810004071
PMCID: PMC2983686

(S)-Perillaldehyde azine

Abstract

The C=N–N=C linkage [torsion angle −172.5 (2)°] in the title azine, C20H28N2, adopts a trans conformation. The six-membered rings adopt sofa conformations.

Related literature

A previous study reported the oxime derivative of S-perillaldehyde; see Yuan et al. (2009 [triangle]). Only few crystal structures of azines have been reported, see: Berthou et al. (1970 [triangle]); Kim & Lee (2008 [triangle]); Marek et al. (1997 [triangle]); Rizal et al. (2008 [triangle]); Sanz et al. (1999 [triangle]).

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Object name is e-66-0o561-scheme1.jpg

Experimental

Crystal data

  • C20H28N2
  • M r = 296.44
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o561-efi1.jpg
  • a = 8.8200 (5) Å
  • b = 9.7603 (6) Å
  • c = 10.1710 (6) Å
  • β = 94.970 (1)°
  • V = 872.29 (9) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.07 mm−1
  • T = 173 K
  • 0.48 × 0.46 × 0.21 mm

Data collection

  • Bruker SMART APEX diffractometer
  • 7179 measured reflections
  • 2013 independent reflections
  • 1802 reflections with I > 2σ(I)
  • R int = 0.035

Refinement

  • R[F 2 > 2σ(F 2)] = 0.046
  • wR(F 2) = 0.141
  • S = 1.12
  • 2013 reflections
  • 201 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: SMART (Bruker, 2003 [triangle]); cell refinement: SAINT (Bruker, 2003 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810004071/bt5184sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810004071/bt5184Isup2.hkl

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

Acknowledgments

We thank the Key Subject Construction Project of Hunan Province (No. 2006–180), the Key Scientific Research Project of Hunan Provincial Education Department (No. 08 A023, 05 C736), the NSF of Hunan Province (09 J J3028) and the University of Malaya for supporting this study.

supplementary crystallographic information

Experimental

An ethanol solution (10 ml) of hydrazinium hydroxide (0.5 g, 0.01 mol) was added to a 50% ethanol solution (50 ml) of perillaldehyde (3 g, 0.02 mol); acetic acid (2 ml) was then added. The mixture was heated for two hours. The product was recrystallized from ethyl acetate to afford light-yellow crystals (yield 70%).

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95–1.00 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C). In the absence of anomalous scatterers Friedel pairs were merged. The chiral carbon atoms were assumed to have an S-configuration, i.e., the configuration of perillaldehyde itself.

Figures

Fig. 1.
Anisotropic displacement ellipsoid plot (Barbour, 2001) of C20H28N2 at the 70% probability level; hydrogen atoms are shown as spheres of arbitrary radius.

Crystal data

C20H28N2F(000) = 324
Mr = 296.44Dx = 1.129 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 4048 reflections
a = 8.8200 (5) Åθ = 2.3–27.2°
b = 9.7603 (6) ŵ = 0.07 mm1
c = 10.1710 (6) ÅT = 173 K
β = 94.970 (1)°Block, yellow
V = 872.29 (9) Å30.48 × 0.46 × 0.21 mm
Z = 2

Data collection

Bruker SMART APEX diffractometer1802 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.035
graphiteθmax = 27.2°, θmin = 2.0°
ω scansh = −11→11
7179 measured reflectionsk = −12→12
2013 independent reflectionsl = −12→12

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141H-atom parameters constrained
S = 1.12w = 1/[σ2(Fo2) + (0.074P)2 + 0.242P] where P = (Fo2 + 2Fc2)/3
2013 reflections(Δ/σ)max = 0.001
201 parametersΔρmax = 0.22 e Å3
1 restraintΔρmin = −0.23 e Å3

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

xyzUiso*/Ueq
N11.1573 (3)0.4999 (3)0.9681 (2)0.0344 (5)
N21.2864 (3)0.5570 (3)1.0416 (2)0.0340 (5)
C10.3418 (3)0.5570 (4)0.6676 (3)0.0432 (7)
H1A0.25560.53110.60530.065*
H1B0.35810.65610.66310.065*
H1C0.32000.53170.75730.065*
C20.4821 (3)0.4836 (3)0.6326 (3)0.0335 (6)
C30.4827 (4)0.4131 (4)0.5213 (3)0.0451 (8)
H3A0.39330.40850.46230.054*
H3B0.57250.36720.50060.054*
C40.6201 (3)0.4954 (3)0.7323 (3)0.0303 (6)
H40.58810.46060.81820.036*
C50.6657 (4)0.6461 (3)0.7542 (3)0.0403 (7)
H5A0.67170.69070.66740.048*
H5B0.58560.69330.79950.048*
C60.8147 (3)0.6631 (3)0.8341 (3)0.0369 (6)
H60.84070.75180.86730.044*
C70.9134 (3)0.5613 (3)0.8618 (3)0.0302 (6)
C80.8822 (3)0.4179 (3)0.8139 (3)0.0373 (7)
H8A0.85240.36120.88820.045*
H8B0.97670.37850.78370.045*
C90.7568 (3)0.4114 (3)0.7014 (3)0.0356 (6)
H9A0.79620.44650.61960.043*
H9B0.72550.31490.68600.043*
C101.0558 (3)0.5917 (3)0.9402 (3)0.0325 (6)
H101.07390.68240.97160.039*
C111.3954 (3)0.4699 (3)1.0567 (3)0.0321 (6)
H111.38160.38101.01950.038*
C121.5398 (3)0.5041 (3)1.1296 (3)0.0302 (6)
C131.6523 (3)0.4117 (3)1.1373 (3)0.0340 (6)
H131.63350.32591.09480.041*
C141.8062 (3)0.4349 (3)1.2089 (3)0.0349 (6)
H14A1.88140.45001.14360.042*
H14B1.83700.35171.26030.042*
C151.8082 (3)0.5578 (3)1.3023 (3)0.0318 (6)
H151.74720.53191.37690.038*
C161.7255 (3)0.6772 (3)1.2292 (3)0.0370 (7)
H16A1.73320.76001.28550.044*
H16B1.77480.69741.14750.044*
C171.5580 (3)0.6425 (3)1.1939 (3)0.0384 (7)
H17A1.50350.64371.27500.046*
H17B1.51160.71311.13310.046*
C181.9656 (3)0.5985 (3)1.3620 (3)0.0342 (6)
C191.9691 (4)0.7035 (4)1.4708 (3)0.0460 (8)
H19A2.07500.72401.50180.069*
H19B1.91600.66741.54420.069*
H19C1.91860.78751.43730.069*
C202.0927 (3)0.5473 (4)1.3233 (3)0.0407 (7)
H20A2.18810.57661.36410.049*
H20B2.08880.48121.25460.049*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0284 (11)0.0386 (13)0.0355 (12)−0.0022 (11)−0.0012 (9)−0.0030 (11)
N20.0286 (12)0.0386 (13)0.0342 (11)−0.0017 (11)−0.0011 (9)−0.0028 (11)
C10.0339 (15)0.0515 (18)0.0434 (15)0.0057 (15)−0.0007 (12)−0.0029 (15)
C20.0291 (13)0.0356 (15)0.0352 (13)−0.0007 (13)−0.0007 (11)0.0034 (12)
C30.0401 (16)0.052 (2)0.0420 (17)0.0017 (16)−0.0050 (13)−0.0098 (16)
C40.0303 (13)0.0304 (13)0.0297 (12)0.0008 (12)−0.0003 (10)−0.0007 (11)
C50.0366 (16)0.0284 (14)0.0547 (17)0.0077 (13)−0.0036 (13)−0.0055 (14)
C60.0350 (15)0.0281 (14)0.0466 (15)−0.0013 (12)−0.0019 (12)−0.0054 (13)
C70.0287 (13)0.0328 (14)0.0289 (12)−0.0008 (12)0.0010 (10)−0.0031 (11)
C80.0349 (15)0.0314 (15)0.0438 (15)0.0055 (13)−0.0064 (12)−0.0025 (14)
C90.0356 (14)0.0275 (14)0.0426 (15)0.0031 (12)−0.0031 (12)−0.0060 (13)
C100.0316 (14)0.0328 (15)0.0334 (13)−0.0029 (12)0.0038 (11)−0.0045 (11)
C110.0336 (14)0.0330 (16)0.0296 (13)−0.0038 (12)0.0029 (10)0.0011 (11)
C120.0299 (13)0.0320 (14)0.0288 (12)−0.0032 (12)0.0037 (10)0.0027 (11)
C130.0343 (14)0.0320 (14)0.0349 (13)−0.0020 (13)−0.0015 (11)0.0011 (12)
C140.0309 (14)0.0318 (15)0.0411 (15)0.0020 (12)−0.0027 (11)0.0006 (12)
C150.0290 (13)0.0362 (15)0.0302 (12)−0.0040 (12)0.0027 (10)0.0031 (12)
C160.0342 (15)0.0318 (15)0.0434 (15)−0.0035 (12)−0.0054 (12)−0.0012 (12)
C170.0335 (15)0.0349 (16)0.0451 (16)0.0027 (13)−0.0061 (12)−0.0021 (14)
C180.0351 (15)0.0372 (16)0.0296 (13)−0.0048 (12)−0.0011 (11)0.0054 (11)
C190.0404 (17)0.059 (2)0.0382 (16)−0.0084 (16)0.0010 (12)−0.0103 (15)
C200.0319 (15)0.0471 (18)0.0416 (15)−0.0016 (14)−0.0048 (12)0.0004 (15)

Geometric parameters (Å, °)

N1—C101.280 (4)C10—H100.9500
N1—N21.421 (3)C11—C121.456 (4)
N2—C111.282 (4)C11—H110.9500
C1—C21.499 (4)C12—C131.338 (4)
C1—H1A0.9800C12—C171.503 (4)
C1—H1B0.9800C13—C141.501 (4)
C1—H1C0.9800C13—H130.9500
C2—C31.325 (4)C14—C151.529 (4)
C2—C41.519 (4)C14—H14A0.9900
C3—H3A0.9500C14—H14B0.9900
C3—H3B0.9500C15—C181.519 (4)
C4—C91.513 (4)C15—C161.533 (4)
C4—C51.537 (4)C15—H151.0000
C4—H41.0000C16—C171.528 (4)
C5—C61.493 (4)C16—H16A0.9900
C5—H5A0.9900C16—H16B0.9900
C5—H5B0.9900C17—H17A0.9900
C6—C71.335 (4)C17—H17B0.9900
C6—H60.9500C18—C201.318 (4)
C7—C101.459 (4)C18—C191.507 (4)
C7—C81.500 (4)C19—H19A0.9800
C8—C91.523 (4)C19—H19B0.9800
C8—H8A0.9900C19—H19C0.9800
C8—H8B0.9900C20—H20A0.9500
C9—H9A0.9900C20—H20B0.9500
C9—H9B0.9900
C10—N1—N2110.8 (3)C7—C10—H10119.0
C11—N2—N1111.2 (2)N2—C11—C12121.5 (3)
C2—C1—H1A109.5N2—C11—H11119.3
C2—C1—H1B109.5C12—C11—H11119.3
H1A—C1—H1B109.5C13—C12—C11119.1 (3)
C2—C1—H1C109.5C13—C12—C17122.0 (3)
H1A—C1—H1C109.5C11—C12—C17118.9 (3)
H1B—C1—H1C109.5C12—C13—C14124.2 (3)
C3—C2—C1121.0 (3)C12—C13—H13117.9
C3—C2—C4123.2 (3)C14—C13—H13117.9
C1—C2—C4115.8 (3)C13—C14—C15112.4 (2)
C2—C3—H3A120.0C13—C14—H14A109.1
C2—C3—H3B120.0C15—C14—H14A109.1
H3A—C3—H3B120.0C13—C14—H14B109.1
C9—C4—C2115.3 (2)C15—C14—H14B109.1
C9—C4—C5110.2 (2)H14A—C14—H14B107.9
C2—C4—C5110.7 (2)C18—C15—C14114.5 (2)
C9—C4—H4106.7C18—C15—C16112.0 (2)
C2—C4—H4106.7C14—C15—C16108.4 (2)
C5—C4—H4106.7C18—C15—H15107.2
C6—C5—C4113.1 (2)C14—C15—H15107.2
C6—C5—H5A108.9C16—C15—H15107.2
C4—C5—H5A108.9C17—C16—C15110.8 (2)
C6—C5—H5B108.9C17—C16—H16A109.5
C4—C5—H5B108.9C15—C16—H16A109.5
H5A—C5—H5B107.8C17—C16—H16B109.5
C7—C6—C5124.0 (3)C15—C16—H16B109.5
C7—C6—H6118.0H16A—C16—H16B108.1
C5—C6—H6118.0C12—C17—C16111.4 (3)
C6—C7—C10118.6 (3)C12—C17—H17A109.3
C6—C7—C8121.9 (2)C16—C17—H17A109.3
C10—C7—C8119.5 (3)C12—C17—H17B109.3
C7—C8—C9112.5 (2)C16—C17—H17B109.3
C7—C8—H8A109.1H17A—C17—H17B108.0
C9—C8—H8A109.1C20—C18—C19120.9 (3)
C7—C8—H8B109.1C20—C18—C15123.6 (3)
C9—C8—H8B109.1C19—C18—C15115.6 (3)
H8A—C8—H8B107.8C18—C19—H19A109.5
C4—C9—C8111.2 (2)C18—C19—H19B109.5
C4—C9—H9A109.4H19A—C19—H19B109.5
C8—C9—H9A109.4C18—C19—H19C109.5
C4—C9—H9B109.4H19A—C19—H19C109.5
C8—C9—H9B109.4H19B—C19—H19C109.5
H9A—C9—H9B108.0C18—C20—H20A120.0
N1—C10—C7122.1 (3)C18—C20—H20B120.0
N1—C10—H10119.0H20A—C20—H20B120.0
C10—N1—N2—C11−172.5 (2)N1—N2—C11—C12−179.6 (2)
C3—C2—C4—C9−4.6 (4)N2—C11—C12—C13−176.9 (3)
C1—C2—C4—C9175.2 (3)N2—C11—C12—C173.0 (4)
C3—C2—C4—C5121.3 (4)C11—C12—C13—C14179.7 (2)
C1—C2—C4—C5−58.9 (4)C17—C12—C13—C14−0.2 (4)
C9—C4—C5—C6−42.0 (3)C12—C13—C14—C1515.4 (4)
C2—C4—C5—C6−170.7 (2)C13—C14—C15—C18−171.5 (2)
C4—C5—C6—C712.8 (4)C13—C14—C15—C16−45.7 (3)
C5—C6—C7—C10179.6 (3)C18—C15—C16—C17−168.8 (2)
C5—C6—C7—C8−0.1 (5)C14—C15—C16—C1763.9 (3)
C6—C7—C8—C917.4 (4)C13—C12—C17—C1616.9 (4)
C10—C7—C8—C9−162.3 (2)C11—C12—C17—C16−163.0 (2)
C2—C4—C9—C8−173.8 (3)C15—C16—C17—C12−48.7 (3)
C5—C4—C9—C860.0 (3)C14—C15—C18—C209.7 (4)
C7—C8—C9—C4−47.3 (4)C16—C15—C18—C20−114.2 (3)
N2—N1—C10—C7178.1 (2)C14—C15—C18—C19−170.4 (3)
C6—C7—C10—N1−178.4 (3)C16—C15—C18—C1965.7 (3)
C8—C7—C10—N11.2 (4)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT5184).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Berthou, J., Marzin, C., Rérat, B., Rérat, C. & Uesu, Y. (1970). C. R. Acad. Sci. Ser. C, pp. 918–921.
  • Bruker (2003). SAINT and SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Kim, S. H. & Lee, S. W. (2008). Inorg. Chim. Acta, 361, 137–144.
  • Marek, R., St’astná-Sedláčková, I., Toušek, J., Marek, J. & Potacek, M. (1997). Bull. Soc. Chim. Belg.106, 645–649.
  • Rizal, M. R., Ali, H. M. & Ng, S. W. (2008). Acta Cryst. E64, o555. [PMC free article] [PubMed]
  • Sanz, D., Ponce, M. J., Claramunt, R. M., Fernández-Castaño, C., Foces-Foces, C. & Elguero, J. (1999). J. Phys. Org. Chem.12, 455–469.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2010). publCIF In preparation.
  • Yuan, X.-Y., Zhang, M. & Ng, S. W. (2009). Acta Cryst. E65, o2149. [PMC free article] [PubMed]

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