(1-Bromo­naphthalen-2-yl)acetonitrile

Harris, A.D.; Baucom, A.D.; Brown, J.L.; Jones, D.S.; Ogle, C.A.

doi:10.1107/S1600536808017418

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1284

doi:10.1107/S1600536808017418

Open

access

(1-Bromonaphthalen-2-yl)acetonitrile

Andria D. Harris,^a Amy D. Baucom,^a Jessica L. Brown,^a Daniel S. Jones ^a ^* and Craig A. Ogle ^a ^*

^aDepartment of Chemistry, The University of North Carolina at Charlotte, 9201 University City Blvd, Charlotte, NC 28223, USA
^*Correspondence e-mail: djones@uncc.edu, cogle@uncc.edu

(Received 29 December 2007; accepted 9 June 2008; online 19 June 2008)

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 ); CONQUEST (Bruno et al., 2002 )] yielded one comparable structure, (4-bromonaphthalen-2-yl)acetonitrile (Refcode BAGTEJ; Duthie et al., 2001 ).

Experimental

Crystal data

C₁₂H₈BrN
M_r = 246.1
Monoclinic, P 2₁ /n
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[F² > 2σ(F²)] = 0.025
wR(F²) = 0.063
S = 1.01
1729 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.51 e Å⁻³

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

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

	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.

(1-Bromonaphthalen-2-yl)acetonitrile top

Crystal data top

C₁₂H₈BrN	F(000) = 488
M_r = 246.1	D_x = 1.713 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yn	Cell parameters from 22 reflections
a = 11.3599 (13) Å	θ = 8.6–16.7°
b = 7.2379 (8) Å	µ = 5.47 mm⁻¹
c = 11.8901 (15) Å	T = 295 K
β = 102.538 (10)°	Prism, yellow
V = 954.31 (19) Å³	0.5 × 0.2 × 0.2 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	θ_max = 67.5°, θ_min = 4.9°
Nonprofiled θ/2θ scans	h = −13→13
6502 measured reflections	k = −8→8
1729 independent reflections	l = −14→14
1558 reflections with I > 2σ(I)	3 standard reflections every 75 reflections
R_int = 0.031	intensity decay: 2%

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.025	w = 1/[σ²(F_o²) + (0.0276P)² + 0.7384P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.063	(Δ/σ)_max < 0.001
S = 1.01	Δρ_max = 0.35 e Å⁻³
1729 reflections	Δρ_min = −0.51 e Å⁻³
127 parameters

Crystal data top

C₁₂H₈BrN	V = 954.31 (19) Å³
M_r = 246.1	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 11.3599 (13) Å	µ = 5.47 mm⁻¹
b = 7.2379 (8) Å	T = 295 K
c = 11.8901 (15) Å	0.5 × 0.2 × 0.2 mm
β = 102.538 (10)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.031
6502 measured reflections	3 standard reflections every 75 reflections
1729 independent reflections	intensity decay: 2%
1558 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.063	H-atom parameters constrained
S = 1.01	Δρ_max = 0.35 e Å⁻³
1729 reflections	Δρ_min = −0.51 e Å⁻³
127 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Br	0.22261 (2)	0.12936 (4)	0.490726 (19)	0.04829 (11)
N	−0.2239 (2)	−0.0251 (4)	0.2063 (2)	0.0621 (6)
C2	0.0751 (2)	0.1301 (3)	0.2652 (2)	0.0364 (5)
C9	0.29263 (19)	0.1292 (3)	0.2734 (2)	0.0339 (4)
C1	0.1920 (2)	0.1289 (3)	0.32691 (18)	0.0334 (4)
C10	0.2689 (2)	0.1334 (3)	0.1517 (2)	0.0353 (5)
C4	0.1481 (2)	0.1373 (3)	0.0887 (2)	0.0416 (5)
H4	0.132	0.1414	0.0087	0.05*
C8	0.4149 (2)	0.1250 (3)	0.3346 (2)	0.0421 (5)
H8	0.4327	0.1222	0.4147	0.051*
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	−0.0082	0.0694	0.3968	0.058*
H11B	−0.0498	0.2593	0.3384	0.058*
C3	0.0552 (2)	0.1353 (3)	0.1439 (2)	0.0416 (5)
H3	−0.0235	0.1373	0.1007	0.05*
C5	0.3660 (2)	0.1332 (3)	0.0944 (2)	0.0435 (5)
H5	0.3506	0.1351	0.0143	0.052*
C7	0.5062 (2)	0.1252 (3)	0.2767 (2)	0.0488 (6)
H7	0.5857	0.1219	0.3181	0.059*
C6	0.4826 (2)	0.1302 (3)	0.1566 (2)	0.0484 (6)
H6	0.5462	0.1314	0.1187	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.05003 (18)	0.06614 (18)	0.03112 (16)	−0.00544 (11)	0.01412 (12)	−0.00341 (10)
N	0.0373 (12)	0.0871 (17)	0.0637 (15)	−0.0030 (12)	0.0149 (11)	−0.0019 (13)
C2	0.0366 (11)	0.0376 (10)	0.0387 (12)	−0.0030 (8)	0.0163 (10)	−0.0017 (9)
C9	0.0362 (11)	0.0297 (9)	0.0391 (11)	−0.0019 (8)	0.0152 (10)	−0.0016 (8)
C1	0.0398 (11)	0.0328 (10)	0.0302 (10)	−0.0025 (8)	0.0133 (9)	−0.0015 (8)
C10	0.0393 (11)	0.0323 (10)	0.0383 (12)	−0.0023 (8)	0.0170 (10)	0.0000 (8)
C4	0.0449 (13)	0.0510 (13)	0.0311 (11)	−0.0025 (10)	0.0132 (10)	0.0018 (9)
C8	0.0389 (12)	0.0459 (12)	0.0421 (13)	−0.0006 (9)	0.0099 (10)	0.0001 (10)
C12	0.0353 (12)	0.0531 (13)	0.0465 (13)	0.0060 (11)	0.0195 (11)	0.0062 (11)
C11	0.0406 (13)	0.0632 (15)	0.0476 (14)	−0.0070 (11)	0.0222 (12)	−0.0079 (11)
C3	0.0346 (11)	0.0530 (13)	0.0380 (12)	−0.0023 (10)	0.0092 (10)	0.0011 (10)
C5	0.0496 (14)	0.0430 (12)	0.0451 (13)	−0.0010 (10)	0.0260 (12)	0.0002 (10)
C7	0.0336 (12)	0.0531 (13)	0.0609 (16)	0.0003 (10)	0.0130 (12)	−0.0011 (11)
C6	0.0413 (13)	0.0485 (13)	0.0636 (17)	−0.0002 (10)	0.0292 (13)	0.0008 (11)

Geometric parameters (Å, º) top

Br—C1	1.903 (2)	C8—C7	1.364 (3)
N—C12	1.132 (3)	C8—H8	0.93
C2—C1	1.371 (3)	C12—C11	1.455 (4)
C2—C3	1.410 (3)	C11—H11A	0.97
C2—C11	1.515 (3)	C11—H11B	0.97
C9—C10	1.413 (3)	C3—H3	0.93
C9—C1	1.424 (3)	C5—C6	1.370 (4)
C9—C8	1.422 (3)	C5—H5	0.93
C10—C5	1.417 (3)	C7—C6	1.396 (4)
C10—C4	1.413 (3)	C7—H7	0.93
C4—C3	1.358 (3)	C6—H6	0.93
C4—H4	0.93

C1—C2—C3	117.95 (19)	C12—C11—C2	114.1 (2)
C1—C2—C11	122.1 (2)	C12—C11—H11A	108.7
C3—C2—C11	119.9 (2)	C2—C11—H11A	108.7
C10—C9—C1	117.7 (2)	C12—C11—H11B	108.7
C10—C9—C8	118.25 (19)	C2—C11—H11B	108.7
C1—C9—C8	124.1 (2)	H11A—C11—H11B	107.6
C2—C1—C9	122.6 (2)	C4—C3—C2	121.7 (2)
C2—C1—Br	119.22 (15)	C4—C3—H3	119.1
C9—C1—Br	118.16 (17)	C2—C3—H3	119.1
C5—C10—C9	119.7 (2)	C6—C5—C10	120.2 (2)
C5—C10—C4	120.9 (2)	C6—C5—H5	119.9
C9—C10—C4	119.36 (19)	C10—C5—H5	119.9
C3—C4—C10	120.7 (2)	C8—C7—C6	121.2 (2)
C3—C4—H4	119.6	C8—C7—H7	119.4
C10—C4—H4	119.6	C6—C7—H7	119.4
C7—C8—C9	120.5 (2)	C5—C6—C7	120.1 (2)
C7—C8—H8	119.8	C5—C6—H6	120
C9—C8—H8	119.8	C7—C6—H6	120
N—C12—C11	178.4 (3)

Experimental details

Crystal data
Chemical formula	C₁₂H₈BrN
M_r	246.1
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	11.3599 (13), 7.2379 (8), 11.8901 (15)
β (°)	102.538 (10)
V (Å³)	954.31 (19)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	5.47
Crystal size (mm)	0.5 × 0.2 × 0.2

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6502, 1729, 1558
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.063, 1.01
No. of reflections	1729
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.51

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), DIRDIF (Beurskens et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Acknowledgements

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

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
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. Google Scholar
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. Web of Science CrossRef CAS IUCr Journals Google Scholar
Duthie, A., Scammells, P. J., Katsifis, A. & Tiekink, E. R. T. (2001). Z. Kristallogr. New Cryst. Struct. 216, 531–532. CAS Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar