2-Bromo­benzaldehyde cyano­hydrin

Abstract

The title compound [alternatively called (2-bromo­phen­yl)­(hydr­oxy)acetonitrile], C₈H₆BrNO, is the reaction product of 2-bromo­benzaldehyde and hydrogen cyanide. Bond lengths and angles are normal. In the crystal structure, an intermolecular hydrogen bond between the hydr­oxy group and the nitrile N atom is established. In agreement with bonding considerations, a linear C—N⋯H acceptor geometry is observed. Each mol­ecule is a single donor and a single acceptor; extended hydrogen-bonded chains are formed along [100].

Related literature

For the synthesis of the title compound, see: Becker et al. (2001 ▶). For the crystal structure of a related compound, see: Flores-Morales et al. (2003 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

• C₈H₆BrNO

• M _r = 212.05

• Orthorhombic,

• a = 8.0538 (3) Å

• b = 13.9970 (5) Å

• c = 14.2969 (5) Å

• V = 1611.68 (10) ų

• Z = 8

• Mo Kα radiation

• μ = 5.04 mm⁻¹

• T = 200 (2) K

• 0.14 × 0.09 × 0.03 mm

Data collection

• Nonius KappaCCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T _min = 0.624, T _max = 0.86

• 19593 measured reflections

• 1844 independent reflections

• 1351 reflections with I > 2σ(I)

• R _int = 0.040

Refinement

• R[F ² > 2σ(F ²)] = 0.032

• wR(F ²) = 0.083

• S = 1.02

• 1844 reflections

• 102 parameters

• Only H-atom displacement parameters refined

• Δρ_max = 0.29 e Å⁻³

• Δρ_min = −0.59 e Å⁻³

Data collection: COLLECT (Nonius, 2004 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O—H82⋯Ni	0.84	2.01	2.844 (3)	170

Symmetry code: (i) .

supplementary crystallographic information

Comment

The title compound was prepared as in intermediate in the synthesis of 2-bromomandelic acid.

In the title compound a phenyl moiety, a hydroxy group and a cyano group are bonded to one C atom. The aromatic moiety bears a Br atom in 2- position to this C atom (Fig. 1). Bond lengths and angles show no significant deviations from values apparent in the literature for similar bonds (Allen et al., 1987).

In the crystal structure, hydrogen bonds between the hydroxy groups and the N atom result in the formation of infinite chains along [100]. The aromatic moieties are arranged parallel to each other (Fig. 2).

Experimental

The title compound was obtained as an intermediate in the synthesis of 2-bromomandelic acid according to a published procedure (Becker et al., 2001) upon addition of 2-bromobenzaldehyde to an acidified aqueous solution of potassium cyanide. After workup, crystals suitable for X-ray analysis were obtained upon free evaporation of a solution of the compound in diethylether.

Refinement

All H atoms were located in a difference map and refined as riding on their parent atoms. One common isotropic displacement parameter for all H atoms was refined.

Figures

Fig. 1.

The molecular structure with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level) for non-H atoms.

Fig. 2.

The packing of viewed along [-1 0 0]. Hydrogen bonds are drawn as yellow bars.

Crystal data

C8H6BrNO	F000 = 832
Mr = 212.05	Dx = 1.748 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 10818 reflections
a = 8.0538 (3) Å	θ = 3.1–27.5º
b = 13.9970 (5) Å	µ = 5.04 mm−1
c = 14.2969 (5) Å	T = 200 (2) K
V = 1611.68 (10) Å3	Platelet, colourless
Z = 8	0.14 × 0.09 × 0.03 mm

Data collection

Nonius KappaCCD diffractometer	1844 independent reflections
Radiation source: rotating anode	1351 reflections with I > 2σ(I)
Monochromator: MONTEL, graded multilayered X-ray optics	Rint = 0.040
T = 200(2) K	θmax = 27.5º
CCD; rotation images; thick slices scans	θmin = 3.3º
Absorption correction: multi-scan(SADABS; Sheldrick, 2001)	h = −10→10
Tmin = 0.624, Tmax = 0.86	k = −18→15
19593 measured reflections	l = −18→17

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032	Only H-atom displacement parameters refined
wR(F2) = 0.083	w = 1/[σ2(Fo2) + (0.038P)2 + 1.1081P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
1844 reflections	Δρmax = 0.29 e Å−3
102 parameters	Δρmin = −0.59 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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

	x	y	z	Uiso*/Ueq
Br	0.25307 (3)	0.16689 (2)	0.310767 (19)	0.04887 (13)
O	0.1470 (3)	0.09045 (13)	0.01121 (14)	0.0533 (5)
H82	0.0823	0.1302	−0.0135	0.055 (3)*
N	0.4211 (3)	0.26649 (17)	0.05011 (16)	0.0501 (6)
C1	0.3312 (3)	0.20716 (18)	0.07017 (16)	0.0367 (5)
C2	0.2128 (3)	0.12902 (19)	0.09341 (17)	0.0364 (5)
H2	0.1206	0.1552	0.1327	0.055 (3)*
C3	0.3037 (3)	0.05167 (17)	0.14759 (16)	0.0309 (5)
C4	0.3299 (3)	0.05819 (17)	0.24325 (16)	0.0330 (5)
C5	0.4107 (3)	−0.01275 (19)	0.29246 (18)	0.0410 (6)
H5	0.4253	−0.0075	0.3582	0.055 (3)*
C6	0.4697 (4)	−0.09138 (18)	0.2449 (2)	0.0469 (7)
H6	0.5261	−0.1405	0.2779	0.055 (3)*
C7	0.4473 (3)	−0.09931 (18)	0.1491 (2)	0.0443 (6)
H7	0.4899	−0.1531	0.1164	0.055 (3)*
C8	0.3623 (3)	−0.02833 (17)	0.10115 (18)	0.0392 (6)
H8	0.3442	−0.0347	0.0358	0.055 (3)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br	0.0455 (2)	0.0566 (2)	0.04446 (19)	0.00087 (13)	−0.00098 (12)	−0.01748 (11)
O	0.0627 (14)	0.0467 (11)	0.0505 (12)	0.0086 (9)	−0.0308 (10)	−0.0072 (9)
N	0.0567 (15)	0.0477 (14)	0.0458 (13)	−0.0024 (12)	0.0043 (11)	0.0100 (11)
C1	0.0415 (14)	0.0352 (13)	0.0334 (12)	0.0049 (12)	0.0002 (11)	0.0049 (10)
C2	0.0362 (13)	0.0366 (13)	0.0363 (12)	0.0030 (11)	−0.0045 (10)	−0.0020 (11)
C3	0.0259 (10)	0.0319 (11)	0.0350 (12)	−0.0025 (9)	−0.0007 (10)	0.0051 (10)
C4	0.0272 (12)	0.0357 (12)	0.0361 (12)	−0.0071 (10)	0.0011 (10)	−0.0009 (10)
C5	0.0396 (14)	0.0482 (15)	0.0352 (12)	−0.0121 (12)	−0.0060 (11)	0.0110 (11)
C6	0.0435 (16)	0.0375 (14)	0.0596 (18)	−0.0003 (12)	−0.0086 (14)	0.0154 (13)
C7	0.0455 (16)	0.0302 (13)	0.0573 (17)	0.0032 (11)	−0.0012 (13)	−0.0015 (12)
C8	0.0427 (14)	0.0371 (14)	0.0378 (12)	−0.0015 (11)	0.0004 (11)	0.0001 (10)

Geometric parameters (Å, °)

Br—C4	1.905 (2)	C4—C5	1.380 (3)
O—C2	1.398 (3)	C5—C6	1.379 (4)
O—H82	0.8400	C5—H5	0.9500
N—C1	1.138 (3)	C6—C7	1.386 (4)
C1—C2	1.489 (4)	C6—H6	0.9500
C2—C3	1.519 (3)	C7—C8	1.387 (4)
C2—H2	1.0000	C7—H7	0.9500
C3—C8	1.385 (3)	C8—H8	0.9500
C3—C4	1.387 (3)
C2—O—H82	109.5	C3—C4—Br	120.18 (17)
N—C1—C2	178.3 (3)	C6—C5—C4	119.0 (2)
O—C2—C1	109.8 (2)	C6—C5—H5	120.5
O—C2—C3	109.6 (2)	C4—C5—H5	120.5
C1—C2—C3	109.2 (2)	C5—C6—C7	120.5 (2)
O—C2—H2	109.4	C5—C6—H6	119.8
C1—C2—H2	109.4	C7—C6—H6	119.8
C3—C2—H2	109.4	C6—C7—C8	119.7 (2)
C8—C3—C4	118.3 (2)	C6—C7—H7	120.2
C8—C3—C2	119.7 (2)	C8—C7—H7	120.2
C4—C3—C2	122.0 (2)	C3—C8—C7	120.7 (2)
C5—C4—C3	121.8 (2)	C3—C8—H8	119.6
C5—C4—Br	118.01 (19)	C7—C8—H8	119.6
O—C2—C3—C8	22.9 (3)	C3—C4—C5—C6	1.3 (4)
C1—C2—C3—C8	−97.4 (3)	Br—C4—C5—C6	−178.99 (19)
O—C2—C3—C4	−156.8 (2)	C4—C5—C6—C7	−0.4 (4)
C1—C2—C3—C4	82.9 (3)	C5—C6—C7—C8	−1.1 (4)
C8—C3—C4—C5	−0.6 (3)	C4—C3—C8—C7	−1.0 (4)
C2—C3—C4—C5	179.1 (2)	C2—C3—C8—C7	179.3 (2)
C8—C3—C4—Br	179.68 (18)	C6—C7—C8—C3	1.8 (4)
C2—C3—C4—Br	−0.6 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O—H82···Ni	0.84	2.01	2.844 (3)	170

Symmetry codes: (i) x−1/2, −y+1/2, −z.