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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1658.
Published online 2009 June 20. doi:  10.1107/S1600536809023344
PMCID: PMC2969357

2,2′-Dimethyl-2,2′-(m-phenyl­ene­dimethyl­ene)propane­dinitrile

Abstract

The title compound, C16H14N4, features an aromatic ring with two 2,2′-dicyano­propyl residues in positions 1 and 3, which are located above and below the ring plane. The two residues differ in their conformation with respect to the aromatic ring: whereas one of the Cmeth­yl—C—Cmethyl­ene—Caromatic torsion angles is gauche [68.93 (12)°], the other one is fully staggered [177.63 (9)°]. The crystal structure is stabilized by C—H(...)N hydrogen-bonding inter­actions.

Related literature

Calix[4]arenes, fixed in their cone conformation, offer a platform to attach various ligating functions via amide bonds to their wide or narrow rim, see: Arnaud-Neu et al. (1996 [triangle]); Barboso et al. (1999 [triangle]); Casnati et al. (2005 [triangle]); Danila et al. (2005a [triangle],b [triangle]). Tetranitriles are suitable precursors for the attachment to the narrow rim. The title compound was envisaged as another potential tetranitrile. It is readily available by alkylation of methylmalonodinitrile with 1,3-bis-chloromethylbenzene.

An external file that holds a picture, illustration, etc.
Object name is e-65-o1658-scheme1.jpg

Experimental

Crystal data

  • C16H14N4
  • M r = 262.31
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1658-efi1.jpg
  • a = 11.6475 (10) Å
  • b = 13.3751 (13) Å
  • c = 9.4691 (9) Å
  • β = 99.020 (7)°
  • V = 1456.9 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.07 mm−1
  • T = 173 K
  • 0.47 × 0.24 × 0.22 mm

Data collection

  • Stoe IPDS-II two-circle diffractometer
  • Absorption correction: none
  • 8679 measured reflections
  • 2725 independent reflections
  • 2410 reflections with I > 2σ(I)
  • R int = 0.038

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.101
  • S = 1.04
  • 2725 reflections
  • 182 parameters
  • H-atom parameters constrained
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.16 e Å−3

Data collection: X-AREA (Stoe & Cie, 2001 [triangle]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809023344/at2821sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809023344/at2821Isup2.hkl

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

supplementary crystallographic information

Comment

Calix[4]arenes, fixed in their cone conformation, offer a platform to attach various ligating functions via amide bonds to their wide or narrow rim [e.g. CMPO-groups (Arnaud-Neu et al., 1996; Barboso et al., 1999), picolinamides (Casnati et al., 2005)]. Suitable precursors for the attachment to the narrow rim are tetranitriles obtained by O-alkylation with ω-bromoalkyl nitriles, which can be easily reduced to the respective tetraamines (Danila et al., 2005a,b). The title compound, 1,3-bis-(2,2'-dicyano)propyl benzene, (Fig. 1), was envisaged as another potential tetranitrile. It is readily available by alkylation of methylmalonodinitrile with 1,3-bis-chloromethylbenzene.

The title compound features an aromatic ring with two 2,2'-dicyano-propyl residues in positions 1 and 3, which are located above and below the ring plane. The two residues differ in their conformation with respect to the aromatic ring: whereas one of the Cmethyl-C-Cmethylene-Caromatic torsion angles is gauche [68.93 (12)\%], the other one is fully staggered [177.63 (9)\%]. The crystal structure is stabilized by C—H···N hydrogen-bonding interactions (Table 1).

Experimental

A solution of methylmalonodinitrile (1.59 g, 13.9 mmol) in dry acetone (10 ml) was added to a suspension of K2CO3 (3.95 g, 28.6 mmol) in 20 ml acetone. The mixture was stirred for 30 min. Then 1,3-bischloromethylbenzene (500 mg, 2.86 mmol) and KI (80.5 g) were added and the mixture was stirred 10 h under reflux. The solvent was evaporated to dryness and the residue taken up with CHCl3 (50 ml), washed with 1 M HCl, (2 x 30 ml), water and brine and dried over MgSO4. Evaporation of the solvent and purification by column chromatography (hexane/ethylacetate 5:1) gave 530 mg (71%) of 1,3-bis-(2,2'-dicyano)propyl benzene, m.p. 130–131°C; 1H NMR (400 MHz, CDCl3): δ / p.p.m.: 1.82 (s, 6H), 3.23 (s, 4H), 7.34 (d, 1H), 7.4–7.5 (m, 3H); MS(FD): m/z 262.3 (100%, M+).

Single crystals were obtained by slow evaporation of a solution in hexane/chloroform.

Refinement

All H atoms could be located by difference Fourier synthesis. They were refined with fixed individual displacement parameters [Uiso(H) = 1.2 Ueq(C) or Uiso(H) = 1.5 Ueq(Cmethyl)] using a riding model with Caromatic—H = 0.95 Å, Cmethyl—H = 0.98Å and Cmethylene—H = 0.99 Å.

Figures

Fig. 1.
Perspective view of the title compound with the atom numbering; displacement ellipsoids are at the 50% probability level.

Crystal data

C16H14N4F(000) = 552
Mr = 262.31Dx = 1.196 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8902 reflections
a = 11.6475 (10) Åθ = 3.5–25.7°
b = 13.3751 (13) ŵ = 0.07 mm1
c = 9.4691 (9) ÅT = 173 K
β = 99.020 (7)°Block, colourless
V = 1456.9 (2) Å30.47 × 0.24 × 0.22 mm
Z = 4

Data collection

Stoe IPDS-II two-circle diffractometer2410 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.038
graphiteθmax = 25.6°, θmin = 3.5°
ω scansh = −14→14
8679 measured reflectionsk = −16→16
2725 independent reflectionsl = −11→8

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.101w = 1/[σ2(Fo2) + (0.0522P)2 + 0.3439P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
2725 reflectionsΔρmax = 0.22 e Å3
182 parametersΔρmin = −0.16 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.035 (4)

Special details

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
C10.24600 (9)0.73229 (9)0.32550 (12)0.0222 (3)
C20.32892 (9)0.68926 (8)0.43145 (12)0.0225 (3)
H20.33440.61850.43820.027*
C30.40374 (9)0.74802 (8)0.52747 (12)0.0217 (3)
C40.39613 (10)0.85248 (9)0.51626 (12)0.0256 (3)
H40.44610.89350.58090.031*
C50.31502 (10)0.89599 (9)0.41008 (13)0.0285 (3)
H50.31070.96670.40190.034*
C60.24024 (10)0.83659 (9)0.31583 (12)0.0262 (3)
H60.18490.86720.24450.031*
C110.16383 (10)0.66726 (9)0.22412 (12)0.0242 (3)
H11A0.20930.61290.18830.029*
H11B0.13000.70830.14090.029*
C120.06227 (10)0.61940 (9)0.29147 (12)0.0240 (3)
C13−0.00481 (10)0.69976 (10)0.35020 (14)0.0313 (3)
N13−0.05588 (11)0.76326 (11)0.39209 (16)0.0516 (4)
C140.10897 (10)0.55154 (10)0.41158 (13)0.0280 (3)
N140.14425 (10)0.49664 (10)0.50128 (13)0.0423 (3)
C15−0.01964 (11)0.55815 (10)0.17831 (13)0.0328 (3)
H15A0.02490.50530.13990.049*
H15B−0.05390.60240.10050.049*
H15C−0.08170.52800.22310.049*
C210.48821 (9)0.69770 (9)0.64449 (12)0.0233 (3)
H21A0.45190.63570.67400.028*
H21B0.50170.74260.72850.028*
C220.60898 (9)0.67039 (9)0.59992 (12)0.0227 (3)
C230.59040 (10)0.60957 (9)0.46639 (12)0.0262 (3)
N230.57367 (10)0.56598 (9)0.36058 (12)0.0371 (3)
C240.67231 (10)0.60763 (9)0.71679 (12)0.0256 (3)
N240.71923 (10)0.56270 (8)0.81204 (12)0.0376 (3)
C250.68272 (11)0.76360 (10)0.57854 (14)0.0325 (3)
H25A0.69470.80330.66660.049*
H25B0.64200.80420.50010.049*
H25C0.75820.74250.55540.049*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0200 (5)0.0253 (6)0.0232 (5)0.0021 (4)0.0095 (4)0.0013 (4)
C20.0205 (5)0.0209 (5)0.0280 (6)0.0022 (4)0.0095 (4)0.0023 (4)
C30.0190 (5)0.0245 (6)0.0236 (6)0.0023 (4)0.0100 (4)0.0006 (4)
C40.0249 (6)0.0243 (6)0.0293 (6)0.0005 (5)0.0090 (5)−0.0036 (5)
C50.0318 (6)0.0207 (6)0.0350 (6)0.0053 (5)0.0112 (5)0.0014 (5)
C60.0257 (6)0.0261 (6)0.0280 (6)0.0075 (5)0.0083 (5)0.0049 (5)
C110.0245 (5)0.0275 (6)0.0214 (5)0.0026 (5)0.0064 (4)0.0009 (4)
C120.0224 (5)0.0279 (6)0.0218 (6)0.0015 (5)0.0042 (4)−0.0024 (4)
C130.0207 (5)0.0397 (7)0.0335 (6)−0.0011 (5)0.0047 (5)−0.0086 (5)
N130.0343 (6)0.0557 (8)0.0666 (9)0.0067 (6)0.0131 (6)−0.0225 (7)
C140.0217 (5)0.0377 (7)0.0258 (6)−0.0038 (5)0.0071 (5)0.0008 (5)
N140.0298 (6)0.0580 (8)0.0390 (6)−0.0046 (5)0.0051 (5)0.0170 (6)
C150.0347 (6)0.0351 (7)0.0268 (6)−0.0059 (5)−0.0005 (5)−0.0038 (5)
C210.0225 (5)0.0265 (6)0.0224 (5)0.0015 (4)0.0077 (4)0.0004 (4)
C220.0216 (5)0.0239 (6)0.0233 (5)0.0021 (4)0.0056 (4)0.0013 (4)
C230.0249 (6)0.0286 (6)0.0259 (6)0.0067 (5)0.0064 (5)0.0034 (5)
N230.0407 (6)0.0402 (6)0.0303 (6)0.0102 (5)0.0054 (5)−0.0049 (5)
C240.0257 (6)0.0251 (6)0.0265 (6)0.0031 (5)0.0056 (5)−0.0025 (5)
N240.0444 (7)0.0345 (6)0.0323 (6)0.0110 (5)0.0011 (5)0.0017 (5)
C250.0271 (6)0.0327 (7)0.0391 (7)−0.0043 (5)0.0096 (5)0.0042 (5)

Geometric parameters (Å, °)

C1—C61.3989 (16)C12—C151.5521 (16)
C1—C21.4024 (16)C13—N131.1431 (18)
C1—C111.5185 (16)C14—N141.1489 (17)
C2—C31.3983 (16)C15—H15A0.9800
C2—H20.9500C15—H15B0.9800
C3—C41.4029 (16)C15—H15C0.9800
C3—C211.5189 (15)C21—C221.5737 (15)
C4—C51.3944 (17)C21—H21A0.9900
C4—H40.9500C21—H21B0.9900
C5—C61.3938 (17)C22—C241.4891 (16)
C5—H50.9500C22—C231.4905 (16)
C6—H60.9500C22—C251.5452 (16)
C11—C121.5661 (16)C23—N231.1491 (16)
C11—H11A0.9900C24—N241.1483 (16)
C11—H11B0.9900C25—H25A0.9800
C12—C131.4870 (17)C25—H25B0.9800
C12—C141.4898 (16)C25—H25C0.9800
C6—C1—C2118.46 (11)C15—C12—C11110.88 (9)
C6—C1—C11120.72 (10)N13—C13—C12178.01 (15)
C2—C1—C11120.82 (10)N14—C14—C12177.80 (14)
C3—C2—C1121.57 (10)C12—C15—H15A109.5
C3—C2—H2119.2C12—C15—H15B109.5
C1—C2—H2119.2H15A—C15—H15B109.5
C2—C3—C4119.01 (10)C12—C15—H15C109.5
C2—C3—C21119.45 (10)H15A—C15—H15C109.5
C4—C3—C21121.50 (10)H15B—C15—H15C109.5
C5—C4—C3119.86 (11)C3—C21—C22114.28 (9)
C5—C4—H4120.1C3—C21—H21A108.7
C3—C4—H4120.1C22—C21—H21A108.7
C6—C5—C4120.56 (11)C3—C21—H21B108.7
C6—C5—H5119.7C22—C21—H21B108.7
C4—C5—H5119.7H21A—C21—H21B107.6
C5—C6—C1120.52 (11)C24—C22—C23108.18 (9)
C5—C6—H6119.7C24—C22—C25109.35 (9)
C1—C6—H6119.7C23—C22—C25109.81 (10)
C1—C11—C12114.71 (9)C24—C22—C21106.92 (9)
C1—C11—H11A108.6C23—C22—C21109.70 (9)
C12—C11—H11A108.6C25—C22—C21112.74 (9)
C1—C11—H11B108.6N23—C23—C22177.17 (12)
C12—C11—H11B108.6N24—C24—C22176.36 (12)
H11A—C11—H11B107.6C22—C25—H25A109.5
C13—C12—C14107.77 (10)C22—C25—H25B109.5
C13—C12—C15109.73 (10)H25A—C25—H25B109.5
C14—C12—C15108.47 (10)C22—C25—H25C109.5
C13—C12—C11109.36 (10)H25A—C25—H25C109.5
C14—C12—C11110.56 (9)H25B—C25—H25C109.5
C6—C1—C2—C30.90 (16)C6—C1—C11—C12−104.02 (12)
C11—C1—C2—C3−178.74 (10)C2—C1—C11—C1275.62 (13)
C1—C2—C3—C4−0.63 (16)C1—C11—C12—C1356.49 (13)
C1—C2—C3—C21177.21 (10)C1—C11—C12—C14−62.02 (13)
C2—C3—C4—C5−0.23 (16)C1—C11—C12—C15177.63 (9)
C21—C3—C4—C5−178.02 (10)C2—C3—C21—C2288.93 (12)
C3—C4—C5—C60.80 (17)C4—C3—C21—C22−93.29 (12)
C4—C5—C6—C1−0.52 (17)C3—C21—C22—C24−170.87 (9)
C2—C1—C6—C5−0.32 (17)C3—C21—C22—C23−53.79 (13)
C11—C1—C6—C5179.32 (10)C3—C21—C22—C2568.93 (12)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C11—H11A···N24i0.992.493.4028 (17)153

Symmetry codes: (i) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2821).

References

  • Arnaud-Neu, F., Böhmer, V., Dozol, J.-F., Grüttner, C., Jakobi, R. A., Kraft, D., Mauprivez, O., Rouquette, H., Schwing-Weill, M.-J., Simon, N. & Vogt, W. (1996). J. Chem. Soc. Perkin Trans. 2, pp. 1175–1182.
  • Barboso, S., Garcia Carrera, A., Matthews, S. E., Arnaud-Neu, F., Böhmer, V., Dozol, J.-F., Rouquette, H. & Schwing-Weill, M.-J. (1999). J. Chem. Soc. Perkin Trans. 2, pp. 719–723.
  • Casnati, A., Della Ca’, N., Fontanella, M., Sansone, F., Ugozzoli, F., Ungaro, R., Liger, K. & Dozol, J.-F. (2005). Eur. J. Org. Chem. pp. 2338–2348.
  • Danila, C., Böhmer, V. & Bolte, M. (2005a). Org. Biomol. Chem.3, 172–184. [PubMed]
  • Danila, C., Böhmer, V. & Bolte, M. (2005b). Org. Biomol. Chem.3, 3508–3513. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Stoe & Cie (2001). X-AREA Stoe & Cie, Darmstadt, Germany.

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