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Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): o1284.
Published online 2008 June 19. doi:  10.1107/S1600536808017418
PMCID: PMC2961673

(1-Bromo­naphthalen-2-yl)acetonitrile

Abstract

The title compound, C12H8BrN, was prepared as a starting material for a Suzuki cross-coupling reaction with a pinacol ester. The torsion angle about the ring–methylene C—C bond is 30.7 (3)°, such that the N atom is displaced by 1.174 (4) Å from the plane of the naphthalene ring system.

Related literature

A search of the Cambridge Structural Database [Version 5.29 (Allen, 2002 [triangle]); CONQUEST (Bruno et al., 2002 [triangle])] yielded one comparable structure, (4-bromo­naphthalen-2-yl)acetonitrile (Refcode BAGTEJ; Duthie et al., 2001 [triangle]).

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Object name is e-64-o1284-scheme1.jpg

Experimental

Crystal data

  • C12H8BrN
  • M r = 246.1
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1284-efi1.jpg
  • a = 11.3599 (13) Å
  • b = 7.2379 (8) Å
  • c = 11.8901 (15) Å
  • β = 102.538 (10)°
  • V = 954.31 (19) Å3
  • Z = 4
  • Cu Kα radiation
  • μ = 5.47 mm−1
  • T = 295 (2) K
  • 0.5 × 0.2 × 0.2 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: none
  • 6502 measured reflections
  • 1729 independent reflections
  • 1558 reflections with I > 2σ(I)
  • R int = 0.031
  • 3 standard reflections every 75 reflections intensity decay: 2%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.025
  • wR(F 2) = 0.063
  • S = 1.01
  • 1729 reflections
  • 127 parameters
  • H-atom parameters constrained
  • Δρmax = 0.35 e Å−3
  • Δρmin = −0.51 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 [triangle]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: DIRDIF (Beurskens et al., 1999 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808017418/fl2183sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808017418/fl2183Isup2.hkl

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

Acknowledgments

This work was supported in part by funds provided by the University of North Carolina at Charlotte.

supplementary crystallographic information

Comment

The title compound (Fig.1) was prepared as a starting material for a Suzuki cross coupling reaction with a pinacol ester. The C11—C12—N angle is 178.4 (3)°, and the plane of that grouping makes an angle of 42.5 (1)° with the plane of the naphthalene ring, while the N atom is displaced 1.174 (4) Å from the plane of the naphthalene ring. As shown in Figs. 2 and 3, the molecules form alternating layers when viewed edge-on and form columns when viewed along the b axis.

A search of the Cambridge Structural Database [Version 5.29; (Allen, 2002); CONQUEST, Version 1.10 (Bruno et al., 2002)] yielded one comparable structure, (4-bromonapthalen-2-yl)acetonitrile (Refcode BAGTEJ; Duthie et al., 2001). In that structure the acetonitrile C—C—N angle was 179.3°, and the plane of that grouping made an angle of 23.1° with the plane of the naphthalene ring. The N atom was displaced 0.287 Å from the plane of the naphthalene ring.

Experimental

Synthesis of 1-bromo-2-methylnaphthalene (II) (Fig. 4). A solution of 2-methylnaphthalene (I) in acetic acid was stirred while an equivalent amount of Br2 in acetic acid was added dropwise at a rate that allowed the bromine color to dissipate between drops. Upon completion of addition the mixture was allowed to stir for 1 h at which time the entire mixture was poured into water. The organic phase was separated and washed repeatedly with water to remove the acetic acid. The product was dried with K2CO3 and used in the next step without further purification.

Synthesis of 1-bromo-2-(bromomethyl)naphthalene (III). N-Bromosuccinimide (1 eq) and benzoylperoxide (0.01 eq) were added to a solution of (II) dissolved in CCl4. The reaction was then heated to reflux and the reaction progress was monitored with GC/MS. The reaction seemed to stall out at 3 h, and an additional portion of benzoylperoxide (0.01 eq) was added and allowed to reflux for an additional 3 h. The succinimide byproduct was removed by filtration from the cooled mixture. The CCl4 was removed and the product (III) was recrystallized from isooctane.

Synthesis of the title compound (IV). KCN (1.1 eq) was dissolved in DMSO with stirring. III (1.0 eq) was added along with additional DMSO to the stirred reaction mixture. A slight exotherm was observed, and the homogeneous mixture was allowed to stir overnight. The reaction was judged to be complete by GC/MS analysis. The reaction mixture was poured into water with stirring. The product precipitated upon addition to water. After filtering, the product was dried on a watch glass, and crystals for the diffraction study were obtained by recrystallization from a 2:1 mixture of 1,2-dimethoxyethane and ethanol.

Refinement

H atoms were constrained using a riding model. The methylene C—H bond lengths were fixed at 0.97 Å, using an idealized tetrahedral geometry, with Uiso(H) = 1.2 Ueq. (C). The aromatic C—H bond lengths were fixed at 0.93 Å, with Uiso(H) = 1.2 Ueq. (C).

Figures

Fig. 1.
View of the title compound (IV) showing 50% probability displacement ellipsoids.
Fig. 2.
Diagram showing how the molecules of (IV) pack in alternating layers when viewed edge-on.
Fig. 3.
Diagram showing how the molecules of (IV) form columns when viewed along the b axis.
Fig. 4.
The formation of the title compound.

Crystal data

C12H8Br1N1F000 = 488
Mr = 246.1Dx = 1.713 Mg m3
Monoclinic, P21/nCu Kα radiation λ = 1.54184 Å
Hall symbol: -P 2ynCell parameters from 22 reflections
a = 11.3599 (13) Åθ = 8.6–16.7º
b = 7.2379 (8) ŵ = 5.47 mm1
c = 11.8901 (15) ÅT = 295 (2) K
β = 102.538 (10)ºPrism, yellow
V = 954.31 (19) Å30.5 × 0.2 × 0.2 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometerθmin = 4.9º
Nonprofiled θ/2θ scansh = −13→13
Absorption correction: nonek = −8→8
6502 measured reflectionsl = −14→14
1729 independent reflections3 standard reflections
1558 reflections with I > 2σ(I) every 75 reflections
Rint = 0.031 intensity decay: 2%
θmax = 67.5º

Refinement

Refinement on F2H-atom parameters constrained
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.0276P)2 + 0.7384P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.025(Δ/σ)max < 0.001
wR(F2) = 0.063Δρmax = 0.35 e Å3
S = 1.01Δρmin = −0.51 e Å3
1729 reflectionsExtinction correction: none
127 parameters

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.

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

xyzUiso*/Ueq
Br0.22261 (2)0.12936 (4)0.490726 (19)0.04829 (11)
N−0.2239 (2)−0.0251 (4)0.2063 (2)0.0621 (6)
C20.0751 (2)0.1301 (3)0.2652 (2)0.0364 (5)
C90.29263 (19)0.1292 (3)0.2734 (2)0.0339 (4)
C10.1920 (2)0.1289 (3)0.32691 (18)0.0334 (4)
C100.2689 (2)0.1334 (3)0.1517 (2)0.0353 (5)
C40.1481 (2)0.1373 (3)0.0887 (2)0.0416 (5)
H40.1320.14140.00870.05*
C80.4149 (2)0.1250 (3)0.3346 (2)0.0421 (5)
H80.43270.12220.41470.051*
C12−0.1394 (2)0.0450 (3)0.2562 (2)0.0434 (5)
C11−0.0312 (2)0.1321 (4)0.3232 (2)0.0485 (6)
H11A−0.00820.06940.39680.058*
H11B−0.04980.25930.33840.058*
C30.0552 (2)0.1353 (3)0.1439 (2)0.0416 (5)
H3−0.02350.13730.10070.05*
C50.3660 (2)0.1332 (3)0.0944 (2)0.0435 (5)
H50.35060.13510.01430.052*
C70.5062 (2)0.1252 (3)0.2767 (2)0.0488 (6)
H70.58570.12190.31810.059*
C60.4826 (2)0.1302 (3)0.1566 (2)0.0484 (6)
H60.54620.13140.11870.058*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br0.05003 (18)0.06614 (18)0.03112 (16)−0.00544 (11)0.01412 (12)−0.00341 (10)
N0.0373 (12)0.0871 (17)0.0637 (15)−0.0030 (12)0.0149 (11)−0.0019 (13)
C20.0366 (11)0.0376 (10)0.0387 (12)−0.0030 (8)0.0163 (10)−0.0017 (9)
C90.0362 (11)0.0297 (9)0.0391 (11)−0.0019 (8)0.0152 (10)−0.0016 (8)
C10.0398 (11)0.0328 (10)0.0302 (10)−0.0025 (8)0.0133 (9)−0.0015 (8)
C100.0393 (11)0.0323 (10)0.0383 (12)−0.0023 (8)0.0170 (10)0.0000 (8)
C40.0449 (13)0.0510 (13)0.0311 (11)−0.0025 (10)0.0132 (10)0.0018 (9)
C80.0389 (12)0.0459 (12)0.0421 (13)−0.0006 (9)0.0099 (10)0.0001 (10)
C120.0353 (12)0.0531 (13)0.0465 (13)0.0060 (11)0.0195 (11)0.0062 (11)
C110.0406 (13)0.0632 (15)0.0476 (14)−0.0070 (11)0.0222 (12)−0.0079 (11)
C30.0346 (11)0.0530 (13)0.0380 (12)−0.0023 (10)0.0092 (10)0.0011 (10)
C50.0496 (14)0.0430 (12)0.0451 (13)−0.0010 (10)0.0260 (12)0.0002 (10)
C70.0336 (12)0.0531 (13)0.0609 (16)0.0003 (10)0.0130 (12)−0.0011 (11)
C60.0413 (13)0.0485 (13)0.0636 (17)−0.0002 (10)0.0292 (13)0.0008 (11)

Geometric parameters (Å, °)

Br—C11.903 (2)C8—C71.364 (3)
N—C121.132 (3)C8—H80.93
C2—C11.371 (3)C12—C111.455 (4)
C2—C31.410 (3)C11—H11A0.97
C2—C111.515 (3)C11—H11B0.97
C9—C101.413 (3)C3—H30.93
C9—C11.424 (3)C5—C61.370 (4)
C9—C81.422 (3)C5—H50.93
C10—C51.417 (3)C7—C61.396 (4)
C10—C41.413 (3)C7—H70.93
C4—C31.358 (3)C6—H60.93
C4—H40.93
C1—C2—C3117.95 (19)C12—C11—C2114.1 (2)
C1—C2—C11122.1 (2)C12—C11—H11A108.7
C3—C2—C11119.9 (2)C2—C11—H11A108.7
C10—C9—C1117.7 (2)C12—C11—H11B108.7
C10—C9—C8118.25 (19)C2—C11—H11B108.7
C1—C9—C8124.1 (2)H11A—C11—H11B107.6
C2—C1—C9122.6 (2)C4—C3—C2121.7 (2)
C2—C1—Br119.22 (15)C4—C3—H3119.1
C9—C1—Br118.16 (17)C2—C3—H3119.1
C5—C10—C9119.7 (2)C6—C5—C10120.2 (2)
C5—C10—C4120.9 (2)C6—C5—H5119.9
C9—C10—C4119.36 (19)C10—C5—H5119.9
C3—C4—C10120.7 (2)C8—C7—C6121.2 (2)
C3—C4—H4119.6C8—C7—H7119.4
C10—C4—H4119.6C6—C7—H7119.4
C7—C8—C9120.5 (2)C5—C6—C7120.1 (2)
C7—C8—H8119.8C5—C6—H6120
C9—C8—H8119.8C7—C6—H6120
N—C12—C11178.4 (3)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FL2183).

References

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  • Beurskens, P. T., Beurskens, G., de Gelder, R., Garciía-Granda, S., Gould, R. O., Israel, R. & Smits, J. M. M. (1999). The DIRDIF99 Program System Technical Report of the Crystallography Laboratory, University of Nijmegen, The Netherlands.
  • Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389-397. [PubMed]
  • Duthie, A., Scammells, P. J., Katsifis, A. & Tiekink, E. R. T. (2001). Z. Kristallogr. New Cryst. Struct.216, 531–532.
  • Enraf–Nonius (1994). CAD-4 EXPRESS Enraf–Nonius, Delft, The Netherlands.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
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