2-Bromo­benzaldehyde cyano­hydrin

Betz, R.; Betzler, F.; Klüfers, P.

doi:10.1107/S1600536807049604

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o55

https://doi.org/10.1107/S1600536807049604

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2-Bromobenzaldehyde cyanohydrin

Richard Betz,^a Franziska Betzler ^a and Peter Klüfers ^a ^*

^aLudwig-Maximilians-Universität, Department Chemie und Biochemie, Butenandtstrasse 5–13, 81377 München, Germany
^*Correspondence e-mail: kluef@cup.uni-muenchen.de

(Received 3 October 2007; accepted 9 October 2007; online 6 December 2007)

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, P b c a
a = 8.0538 (3) Å
b = 13.9970 (5) Å
c = 14.2969 (5) Å
V = 1611.68 (10) Å³
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[F² > 2σ(F²)] = 0.032
wR(F²) = 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

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) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807049604/lh2526sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807049604/lh2526Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Structure description top

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

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).

Computing details top

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 (Sheldrick, 1997).

Figures top

	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.

(2-bromophenyl)(hydroxy)acetonitrile top

Crystal data top

C₈H₆BrNO	F(000) = 832
M_r = 212.05	D_x = 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 = 3.1–27.5°
b = 13.9970 (5) Å	µ = 5.04 mm⁻¹
c = 14.2969 (5) Å	T = 200 K
V = 1611.68 (10) Å³	Platelet, colourless
Z = 8	0.14 × 0.09 × 0.03 mm

Data collection top

Nonius KappaCCD diffractometer	1844 independent reflections
Radiation source: rotating anode	1351 reflections with I > 2σ(I)
MONTEL, graded multilayered X-ray optics monochromator	R_int = 0.040
CCD; rotation images; thick slices scans	θ_max = 27.5°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −10→10
T_min = 0.624, T_max = 0.86	k = −18→15
19593 measured reflections	l = −18→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: difference Fourier map
wR(F²) = 0.083	Only H-atom displacement parameters refined
S = 1.02	w = 1/[σ²(F_o²) + (0.038P)² + 1.1081P] where P = (F_o² + 2F_c²)/3
1844 reflections	(Δ/σ)_max < 0.001
102 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

C₈H₆BrNO	V = 1611.68 (10) Å³
M_r = 212.05	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 8.0538 (3) Å	µ = 5.04 mm⁻¹
b = 13.9970 (5) Å	T = 200 K
c = 14.2969 (5) Å	0.14 × 0.09 × 0.03 mm

Data collection top

Nonius KappaCCD diffractometer	1844 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	1351 reflections with I > 2σ(I)
T_min = 0.624, T_max = 0.86	R_int = 0.040
19593 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.083	Only H-atom displacement parameters refined
S = 1.02	Δρ_max = 0.29 e Å⁻³
1844 reflections	Δρ_min = −0.59 e Å⁻³
102 parameters

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

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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) x−1/2, −y+1/2, −z.

Experimental details

Crystal data
Chemical formula	C₈H₆BrNO
M_r	212.05
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	200
a, b, c (Å)	8.0538 (3), 13.9970 (5), 14.2969 (5)
V (Å³)	1611.68 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	5.04
Crystal size (mm)	0.14 × 0.09 × 0.03

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.624, 0.86
No. of measured, independent and observed [I > 2σ(I)] reflections	19593, 1844, 1351
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.083, 1.02
No. of reflections	1844
No. of parameters	102
H-atom treatment	Only H-atom displacement parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.59

Computer programs: COLLECT (Nonius, 2004), SCALEPACK (Otwinowski & Minor, 1997), SCALEPACK and DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O—H82···Nⁱ	0.84	2.01	2.844 (3)	170.1

Symmetry code: (i) x−1/2, −y+1/2, −z.

Acknowledgements

The authors thank Dr Peter Mayer and Sandra Albrecht for professional support.

References

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