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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1711.
Published online 2009 June 27. doi:  10.1107/S1600536809023988
PMCID: PMC2969460

2-(1,2,3,4-Tetra­hydro­phenanthren-1-yl­idene)malononitrile

Abstract

In the title complex, C17H12N2, the non-aromatic six-membered ring adopts an envelope conformation. The dihedral angle between the eight-membered plane containing the malononitrile group and the aromatic system is 25.88 (4)°. The distance from the central C atom of the malononitrile group to the centroid of the n-glide-related distal aromatic ring is 3.66 Å, suggesting π–π inter­actions.

Related literature

For a related structure, see: Nesterov et al. (2001 [triangle]). For solvatochromism in 2-(naphthalen-1-ylmethyl­ene)malononitrile and related systems, see: Katritzky et al. (1991 [triangle]). For a description of the Cambridge Structural Database, see: Allen et al. (2002 [triangle]);

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Object name is e-65-o1711-scheme1.jpg

Experimental

Crystal data

  • C17H12N2
  • M r = 244.29
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1711-efi1.jpg
  • a = 7.3990 (9) Å
  • b = 16.190 (3) Å
  • c = 10.4570 (13) Å
  • β = 93.016 (7)°
  • V = 1250.9 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 293 K
  • 0.5 × 0.2 × 0.2 mm

Data collection

  • Bruker P4 diffractometer
  • Absorption correction: none
  • 4319 measured reflections
  • 3151 independent reflections
  • 1297 reflections with I > 2σ(I)
  • R int = 0.044
  • 3 standard reflections every 97 reflections intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.072
  • wR(F 2) = 0.176
  • S = 0.98
  • 3151 reflections
  • 173 parameters
  • H-atom parameters constrained
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: XSCANS (Bruker, 1996 [triangle]); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809023988/pv2168sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809023988/pv2168Isup2.hkl

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

Acknowledgments

The authors thank Dee Ann Casteel for assistance in this project and the National Science Foundation for grant No. ILI8951058.

supplementary crystallographic information

Comment

The title complex was prepared and the structure determined as part of a study on solvatochromism by fluorescence emission. Solvatochromism in 2-(naphthalen-1-ylmethylene)malononitrile and related systems (reported as dicyanovinyl substituted aromatics) was attributed to formation of a "twisted intramolecular charge transfer" (TICT) emitting state, involving rotation about a single covalent bond with charge transfer from the aromatic groups to the electrophilic moeity (Katritzky et al., 1991). The structure of 2-(naphthalen-1-ylmethylene)malononitrile (reported as 1,1-dicyano-2-(1-naphthyl)ethylene) has since been reported (Nesterov et al., 2001). The dihdral angle between the 8-atom plane containing the malononitrile group and the 10-atom aromatic system is 41° [based on coordinates reported in the Cambridge Structural Database (Allen et al., 2002) as refcode XINCUS]. This large twist angle may result from the close H—H distance between the ethylene-hydrogen and the peri-hydrogen of 2.2 Å.

The study currently underway removes the constraint of a peri-hydrogen by looking at 2-(naphthalen-2-ylmethylene)malononitriles. In terms of rotation about the single bond, these compounds are analogous to simple 2-benzylidenemalononitrile derivatives. Forty-nine such compounds are reported in the CSD. In these compounds the dihedral angle between the 8-atom plane containing the malononitrile group and the benzene group ranges from 2° to 27°, with an average of 10 (6) °. The dihedral angle between the 8-atom plane containing the malononitrile group and the 10-atom aromatic system in the title compound is 25.88 (0.04) °.

In the title complex the non-aromatic six-membered ring is constrained by both the fused aromatic ring and the conjugated alkene functional group. The plane C1 C1b C4 C4b makes a dihedral angle of 6.12 (0.07) ° with the aromatic system; the displacements of C2 and C3 from this plane are -0.35 Å and -0.89 Å, respectively, resulting in an envelope conformation.

The packing diagram shown in Fig. 2 shows the overlap of the malononitrile group with the distal aromatic ring of a molecule related by the n-glide (-1/2 + x, 1.5 - y, -1/2 + z). The distance from C11 to the centroid of this ring is 3.66 Å, suggesting π-π interactions.

Experimental

The title compound was synthesized by mixing 0.24 g (1.2 mmol) 3,4-dihydrophenanthren-1(2H)-one with 0.26 g (3.9 mmol) malononitrile and 0.22 g (1.1 mmol) of sodium acetate trihydrate in approximately 20 ml of absolute ethanol. The solution was stirred and refluxed under nitrogen for 13 h. The solution initially is yellow, becoming progressively darker with heating and resulting in a green/yellow precipitate in a brown solution. Solid was then collected by vacuum filtration for a crude yield of 0.15 g. This was then separated by flash chromatography using 20% ethylacetate in hexanes yielding 0.03 g (0.12 mmol, 10% yield). Crystals of the title compound were grown at room temperature by vapor diffusion of ethanol into a dichloromethane solution.

Refinement

Hydrogen positions were calculated and refined using a riding model using the following C—H distances: methylene 0.97 Å and aromatic 0.93 Å. The isotropic U values for the H atoms were set at 20% above that of the bonded carbon.

Figures

Fig. 1.
The molecular structure of the title compound, with atom labels and 50% probability displacement ellipsoids for non-H atoms.
Fig. 2.
The packing of the title compound, looking at the bc-face showing the overlap of the malononitrile group of one molecule with the distal aromatic ring of an n-glide related molecule.

Crystal data

C17H12N2F(000) = 512
Mr = 244.29Dx = 1.297 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 27 reflections
a = 7.3990 (9) Åθ = 20–25°
b = 16.190 (3) ŵ = 0.08 mm1
c = 10.4570 (13) ÅT = 293 K
β = 93.016 (7)°Needle, yellow
V = 1250.9 (3) Å30.5 × 0.2 × 0.2 mm
Z = 4

Data collection

Bruker P4 diffractometerRint = 0.044
Radiation source: fine-focus sealed tubeθmax = 28.5°, θmin = 2.5°
graphiteh = −9→1
2θ/ω scansk = −1→21
4319 measured reflectionsl = −14→14
3151 independent reflections3 standard reflections every 97 reflections
1297 reflections with I > 2σ(I) intensity decay: none

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)] = 0.072Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.176H-atom parameters constrained
S = 0.98w = 1/[σ2(Fo2) + (0.0683P)2] where P = (Fo2 + 2Fc2)/3
3151 reflections(Δ/σ)max = 0.003
173 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = −0.21 e Å3

Special details

Experimental. 1H NMR (400 MHz, CDCl3): δ 2.207 (2H, m), 3.073 (2H, t), 3.348 (2H,t), 7.626 (2H, m), 7.800 (1H, d), 8.873(1H, dd), 8.102 (1H, dd), 8.159 (1H, d).13C NMR (400 MHz, CDCl3): δ 22.444, 25.919, 32.966, 79.691, 113.691,114.153, 123.313, 124.839, 127.220, 127.428, 127.570, 128.842, 123.857,131.357, 135.443, 140.012, 173.573
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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.

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

xyzUiso*/Ueq
N10.2071 (5)0.50142 (17)0.3832 (3)0.0865 (11)
N20.1459 (4)0.60547 (17)0.0118 (3)0.0799 (10)
C10.0989 (4)0.71078 (16)0.2975 (2)0.0385 (7)
C1B0.0931 (4)0.73306 (16)0.4337 (2)0.0397 (7)
C20.0720 (4)0.77843 (16)0.1988 (2)0.0457 (7)
H2A0.18360.78560.15530.055*
H2B−0.02080.76130.13540.055*
C30.0184 (4)0.86019 (17)0.2540 (2)0.0507 (8)
H3A−0.10660.85770.27740.061*
H3B0.02830.90320.19010.061*
C40.1393 (4)0.88100 (16)0.3713 (2)0.0505 (8)
H4A0.26390.88530.34760.061*
H4B0.10380.93380.40590.061*
C4B0.1234 (4)0.81471 (16)0.4709 (2)0.0408 (7)
C50.1765 (4)0.91533 (18)0.6502 (3)0.0533 (8)
H50.20170.95680.59230.064*
C5B0.1328 (4)0.83533 (17)0.6048 (2)0.0416 (7)
C60.1823 (4)0.9326 (2)0.7785 (3)0.0633 (10)
H60.21300.98550.80670.076*
C70.1429 (5)0.8722 (2)0.8671 (3)0.0652 (10)
H70.14420.88530.95370.078*
C80.1028 (4)0.7944 (2)0.8277 (3)0.0583 (9)
H80.07810.75430.88790.070*
C8B0.0979 (4)0.77342 (18)0.6966 (2)0.0445 (7)
C90.0578 (4)0.69297 (17)0.6539 (2)0.0479 (8)
H90.03240.65250.71350.057*
C100.0553 (4)0.67254 (17)0.5278 (2)0.0452 (7)
H100.02860.61860.50260.054*
C110.1345 (4)0.63407 (17)0.2542 (2)0.0457 (7)
C120.1745 (5)0.5615 (2)0.3295 (3)0.0573 (9)
C130.1401 (4)0.61857 (17)0.1187 (3)0.0552 (8)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.129 (3)0.0574 (17)0.076 (2)0.026 (2)0.028 (2)0.0168 (16)
N20.114 (3)0.074 (2)0.0535 (17)0.005 (2)0.0163 (17)−0.0116 (15)
C10.0392 (16)0.0427 (16)0.0338 (14)−0.0053 (14)0.0044 (12)0.0037 (12)
C1B0.0420 (17)0.0416 (16)0.0358 (15)0.0017 (14)0.0051 (12)0.0059 (12)
C20.0520 (19)0.0472 (17)0.0379 (15)−0.0008 (16)0.0028 (13)0.0093 (13)
C30.063 (2)0.0458 (17)0.0430 (15)0.0042 (16)0.0012 (15)0.0085 (14)
C40.067 (2)0.0387 (16)0.0465 (16)−0.0031 (16)0.0056 (15)0.0064 (13)
C4B0.0412 (17)0.0423 (16)0.0391 (14)0.0022 (14)0.0028 (13)0.0051 (13)
C50.061 (2)0.0454 (17)0.0531 (18)0.0064 (16)−0.0051 (15)−0.0029 (15)
C5B0.0403 (17)0.0437 (16)0.0407 (15)0.0057 (14)0.0011 (13)−0.0006 (13)
C60.075 (3)0.057 (2)0.0558 (19)0.0150 (19)−0.0113 (18)−0.0187 (17)
C70.075 (2)0.078 (2)0.0421 (17)0.013 (2)−0.0020 (16)−0.0074 (18)
C80.065 (2)0.072 (2)0.0369 (16)0.0093 (19)−0.0006 (15)−0.0003 (16)
C8B0.0421 (18)0.0534 (18)0.0379 (15)0.0060 (16)0.0019 (13)0.0017 (14)
C90.0543 (19)0.0487 (17)0.0410 (16)−0.0011 (16)0.0063 (14)0.0073 (14)
C100.0542 (19)0.0390 (16)0.0427 (16)−0.0006 (15)0.0053 (14)0.0043 (13)
C110.056 (2)0.0419 (16)0.0396 (15)−0.0025 (15)0.0080 (14)0.0013 (14)
C120.075 (2)0.0450 (17)0.0533 (18)0.0090 (18)0.0137 (16)−0.0025 (16)
C130.067 (2)0.0502 (18)0.0494 (18)0.0001 (17)0.0098 (16)−0.0040 (15)

Geometric parameters (Å, °)

N1—C121.143 (3)C5—C61.368 (4)
N2—C131.140 (3)C5—C5B1.411 (4)
C1—C111.353 (3)C5—H50.9300
C1—C1B1.472 (3)C5B—C8B1.421 (4)
C1—C21.511 (3)C6—C71.388 (4)
C1B—C4B1.393 (3)C6—H60.9300
C1B—C101.427 (3)C7—C81.353 (4)
C2—C31.506 (4)C7—H70.9300
C2—H2A0.9700C8—C8B1.411 (4)
C2—H2B0.9700C8—H80.9300
C3—C41.517 (4)C8B—C91.404 (4)
C3—H3A0.9700C9—C101.359 (3)
C3—H3B0.9700C9—H90.9300
C4—C4B1.504 (3)C10—H100.9300
C4—H4A0.9700C11—C121.436 (4)
C4—H4B0.9700C11—C131.442 (4)
C4B—C5B1.438 (3)
C11—C1—C1B124.4 (2)C6—C5—H5119.6
C11—C1—C2117.2 (2)C5B—C5—H5119.6
C1B—C1—C2118.3 (2)C5—C5B—C8B117.8 (2)
C4B—C1B—C10119.6 (2)C5—C5B—C4B122.6 (2)
C4B—C1B—C1119.4 (2)C8B—C5B—C4B119.5 (3)
C10—C1B—C1121.0 (2)C5—C6—C7120.9 (3)
C3—C2—C1113.7 (2)C5—C6—H6119.6
C3—C2—H2A108.8C7—C6—H6119.6
C1—C2—H2A108.8C8—C7—C6120.2 (3)
C3—C2—H2B108.8C8—C7—H7119.9
C1—C2—H2B108.8C6—C7—H7119.9
H2A—C2—H2B107.7C7—C8—C8B121.0 (3)
C2—C3—C4110.4 (2)C7—C8—H8119.5
C2—C3—H3A109.6C8B—C8—H8119.5
C4—C3—H3A109.6C9—C8B—C8121.8 (3)
C2—C3—H3B109.6C9—C8B—C5B118.8 (2)
C4—C3—H3B109.6C8—C8B—C5B119.3 (3)
H3A—C3—H3B108.1C10—C9—C8B121.8 (3)
C4B—C4—C3109.7 (2)C10—C9—H9119.1
C4B—C4—H4A109.7C8B—C9—H9119.1
C3—C4—H4A109.7C9—C10—C1B120.6 (3)
C4B—C4—H4B109.7C9—C10—H10119.7
C3—C4—H4B109.7C1B—C10—H10119.7
H4A—C4—H4B108.2C1—C11—C12127.2 (2)
C1B—C4B—C5B119.4 (2)C1—C11—C13120.4 (2)
C1B—C4B—C4120.1 (2)C12—C11—C13112.4 (2)
C5B—C4B—C4120.5 (2)N1—C12—C11176.2 (3)
C6—C5—C5B120.8 (3)N2—C13—C11179.1 (4)
C11—C1—C1B—C4B155.9 (3)C4—C4B—C5B—C8B173.2 (3)
C2—C1—C1B—C4B−21.1 (4)C5B—C5—C6—C7−0.9 (5)
C11—C1—C1B—C10−24.7 (4)C5—C6—C7—C81.8 (5)
C2—C1—C1B—C10158.3 (3)C6—C7—C8—C8B−0.8 (5)
C11—C1—C2—C3175.4 (3)C7—C8—C8B—C9179.5 (3)
C1B—C1—C2—C3−7.4 (4)C7—C8—C8B—C5B−1.0 (5)
C1—C2—C3—C447.2 (3)C5—C5B—C8B—C9−178.7 (3)
C2—C3—C4—C4B−59.5 (3)C4B—C5B—C8B—C91.0 (4)
C10—C1B—C4B—C5B5.8 (4)C5—C5B—C8B—C81.9 (4)
C1—C1B—C4B—C5B−174.8 (2)C4B—C5B—C8B—C8−178.4 (3)
C10—C1B—C4B—C4−172.0 (3)C8—C8B—C9—C10−179.2 (3)
C1—C1B—C4B—C47.3 (4)C5B—C8B—C9—C101.4 (4)
C3—C4—C4B—C1B32.9 (4)C8B—C9—C10—C1B−0.2 (4)
C3—C4—C4B—C5B−144.9 (3)C4B—C1B—C10—C9−3.4 (4)
C6—C5—C5B—C8B−1.0 (4)C1—C1B—C10—C9177.2 (3)
C6—C5—C5B—C4B179.4 (3)C1B—C1—C11—C12−0.7 (5)
C1B—C4B—C5B—C5175.1 (3)C2—C1—C11—C12176.3 (3)
C4—C4B—C5B—C5−7.1 (4)C1B—C1—C11—C13−179.0 (3)
C1B—C4B—C5B—C8B−4.6 (4)C2—C1—C11—C13−1.9 (4)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2168).

References

  • Allen, F. H. (2002). Acta Cryst. B58, 380–388. [PubMed]
  • Bruker (1996). XSCANS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Katritzky, A. R., Zhu, D.-W. & Schanze, K. S. (1991). J. Phys. Chem.95, 5737–5742.
  • Nesterov, V. N., Kuleshova, L. N. & Antipin, M. Yu. (2001). Kristallografiya, 46, 1041–1044.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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