organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

rac-2,3-Di­bromo­propionamide

aBAM Federal Institute for Materials Research and Testing, Department of Analytical Chemistry, Reference Materials, Richard-Willstätter-Strasse 11, D-12489 Berlin-Adlershof, Germany
*Correspondence e-mail: robert.koeppen@bam.de

(Received 26 October 2012; accepted 19 December 2012; online 4 January 2013)

The racemic title compound, C3H5Br2NO, was crystallized from methanol. In the crystal, adjacent mol­ecules are linked through N—H⋯O hydrogen bonds, forming chains along the c-axis direction. These chains are linked through N—H⋯O hydrogen bonds, forming an undulating two-dimensional network lying parallel to the bc plane. There are also short Br⋯Br contacts present [3.514 (3) Å].

Related literature

For the crystal structure of the starting material, see: Zhou et al. (2007[Zhou, Q.-L., Zhang, Z.-H. & Jing, Z.-L. (2007). Acta Cryst. E63, o3039.]). For the development and application of acryl­amide analysis in food, see: Rosén & Hellenäs (2002[Rosén, J. & Hellenäs, K.-E. (2002). Analyst, 127, 880-882.]); Hashimoto (1976[Hashimoto, A. (1976). Analyst, 101, 932-938.]); Nemoto et al. (2002[Nemoto, S., Takatsuki, S., Sasaki, K. & Maitani, T. (2002). J. Food Hyg. Soc. Jpn, 43, 371-376.]); Cheng et al. (2006[Cheng, W. C., Hsiao, S. W., Chou, S. S., Sun-Hwang, L., Lu, T. J. & Yeh, A. I. (2006). J. Food Drug Anal. 14, 207-214.]); Mizukami et al. (2006[Mizukami, Y., Kohata, K., Yamaguchi, Y., Hayashi, N., Sawai, Y., Chuda, Y., Ono, H., Yada, H. & Yoshida, M. (2006). J. Agric. Food Chem. 54, 7370-7377.]), Zhang et al. (2005[Zhang, Y., Zhang, G. Y. & Zhang, Y. (2005). J. Chromatogr. A, 1075, 1-21.], 2006[Zhang, Y., Dong, Y., Ren, Y. P. & Zhang, Y. (2006). J. Chromatogr. A, 1116, 209-216.]). For halogen inter­actions, see: Pedireddim et al. (1994[Pedireddim, J., Reddy, D., Goud, B., Craig, D., Rae, A. & Desiraju, G. (1994). J. Chem. Soc. Perkin Trans. 2, pp. 2353-2360.]).

[Scheme 1]

Experimental

Crystal data
  • C3H5Br2NO

  • Mr = 230.88

  • Monoclinic, P 21 /c

  • a = 11.926 (3) Å

  • b = 6.5911 (14) Å

  • c = 8.991 (2) Å

  • β = 103.574 (14)°

  • V = 687.0 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 11.70 mm−1

  • T = 296 K

  • 0.14 × 0.11 × 0.05 mm

Data collection
  • Bruker APEX CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2001[Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.23, Tmax = 0.56

  • 4500 measured reflections

  • 1556 independent reflections

  • 470 reflections with I > 2σ(I)

  • Rint = 0.181

Refinement
  • R[F2 > 2σ(F2)] = 0.066

  • wR(F2) = 0.184

  • S = 0.77

  • 1556 reflections

  • 64 parameters

  • H-atom parameters constrained

  • Δρmax = 0.86 e Å−3

  • Δρmin = −0.50 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯O1i 0.86 2.55 3.185 (11) 132
N1—H2⋯O1ii 0.86 2.09 2.942 (12) 173
Symmetry codes: (i) [-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) [x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}].

Data collection: SMART (Bruker, 2001[Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and ORTEPIII (Burnett & Johnson, 1996[Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

Since April 2002 researchers from the Swedish National Food Administration and Stockholm University reported the detection of acrylamide (AA) in fried and baked foods (Rosén & Hellenäs, 2002) for the first time, a lot of attention was attracted to studies and investigations of AA in a wide variety of food matrices. As a result, the number of published papers concerning the development and application of AA analysis in food has increased enormously in the past years and led to an extensive bibliography.

The discovery of AA in food was, and still is, a matter of public concern, due to its neurotoxic, clastogenic and probably carcinogenic effects. For the determination of AA various sample handling techniques such as defatting, liquid–liquid extraction, solid-phase extraction using different types of cartridges were applied followed either by high-performance liquid chromatography (HPLC) with mass spectrometric (MS) or diode array detection (DAD) or by gas chromatography (GC) with electron-capture (ECD) or MS detection.

When using GC—MS, AA can be analysed without derivatization but is normally brominated to form a derivative revealing improved GC properties (more volatile and less polar). A conversion of AA to 2,3-dibromopropionamide (2,3-DBPA) is usually performed by addition of anhydrous potassium bromide, hydrobromic acid and a saturated solution of bromine in water (protocol by Hashimoto, 1976) or by using KBr-KBrO3 to avoid elemental bromine (Nemoto et al., 2002). The resulting 2,3-DBPA is extracted from aqueous solutions and can be more easily detected with GC-ECD/MS. However, different studies have shown that under certain conditions, 2,3-DBPA can be decomposed to the more stable derivative 2-bromopropenamide (2-BPA) during GC-analysis. Therefore, triethylamine is meanwhile used to convert 2,3-DBPA to the stable 2-BPA in a second derivatization step prior to GC analysis. The compound crystallizes in the monoclinic space group P21/c. The molecular structure of the compound and the atom-labeling scheme are displayed in Fig 1. Within each molecule an intramolecular N—H···O hydrogen bond between the amide and the carboxyl group is formed. Adjacent molecules are connected via N—H···O hydrogen bonds to form chains along the [0 0 1] direction (see dashed bonds bonds in Fig. 2). Between two of the bromine atoms a type I halogene interactions can be observed (Pedireddim et al., 1994). These halogen···halogen contacts C—X···X—C are defined as type I if the C—X···X angle α1 is equal or nearly equal to the X···X—C angle α2. Type I contacts arise as a result of close packing about an inversion center.

Related literature top

For the crystal structure of the starting material, see: Zhou et al. (2007). For the development and application of acrylamide analysis in food, see: Rosén & Hellenäs (2002); Hashimoto (1976); Nemoto et al. (2002). For halogen interactions, see: Pedireddim et al. (1994). For related literature [on what subject(s)?], see: Cheng et al. (2006); Mizukami et al. (2006), Zhang et al. (2005, 2006).

Experimental top

A 250 mL three-necked round-bottomed flask fitted with a thermometer, a magnetic stirrer, a condenser and a 100 mL dropping funnel, was charged with 60 mL chloroform followed by 5 g (70.33 mmol) of acrylamide. The solution was cooled to 0–5°C in an ice bath, and bromine (11.24 g, 70.33 mmol) dissolved in 20 mL chloroform was added cautiously (dropwise) over a period of about 4 h under vigorous stirring. After the addition, stirring in the cold was continued for 1 h followed by stirring at room temperature for 2 h. Evaporation of the chloroform (rotary evaporator) and subsequent recrystallization (methanol) of the residue affords the product in about 94.3% yield (mp 132.8°C/1.013 bar). Despite repeated recrystallization it was not possible to completely avoid builtups degradation products. Therfore, larger crystals were chosen for X-ray single-crystal structure analysis to reduce the influence of buitups on the crystal surface.

Refinement top

Decomposition of the crystals during the measurments was observed, but repeated measurements using different crystals did not lead to a better dataset. All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.93 Å, Uiso=1.2Ueq (C) for aromatic 0.98 Å, Uiso = 1.2Ueq (C) for CH, 0.97 Å, Uiso = 1.2Ueq (C) for CH2, 0.96 Å, and 0.82 Å, Uiso = 1.5Ueq (N) for the amino group.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. : ORTEP representation of the title compound with atomic labeling shown with 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. : View of the unit cell of the title compound along [010] showing the hydrogen-bonded chains along the [001] direction. Hydrogen bonds are drawn as dashed green lines.
rac-2,3-Dibromopropionamide top
Crystal data top
C3H5Br2NOF(000) = 432
Mr = 230.88Dx = 2.232 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 756 reflections
a = 11.926 (3) Åθ = 2.5–20.6°
b = 6.5911 (14) ŵ = 11.70 mm1
c = 8.991 (2) ÅT = 296 K
β = 103.574 (14)°Block, colourless
V = 687.0 (3) Å30.14 × 0.11 × 0.05 mm
Z = 4
Data collection top
Bruker APEX CCD area-detector
diffractometer
1556 independent reflections
Radiation source: fine-focus sealed tube470 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.181
ω/2θ scansθmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 1515
Tmin = 0.23, Tmax = 0.56k = 88
4500 measured reflectionsl = 1011
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.066Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.184H-atom parameters constrained
S = 0.77 w = 1/[σ2(Fo2) + (0.0796P)2]
where P = (Fo2 + 2Fc2)/3
1556 reflections(Δ/σ)max < 0.001
64 parametersΔρmax = 0.86 e Å3
0 restraintsΔρmin = 0.50 e Å3
Crystal data top
C3H5Br2NOV = 687.0 (3) Å3
Mr = 230.88Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.926 (3) ŵ = 11.70 mm1
b = 6.5911 (14) ÅT = 296 K
c = 8.991 (2) Å0.14 × 0.11 × 0.05 mm
β = 103.574 (14)°
Data collection top
Bruker APEX CCD area-detector
diffractometer
1556 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
470 reflections with I > 2σ(I)
Tmin = 0.23, Tmax = 0.56Rint = 0.181
4500 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0660 restraints
wR(F2) = 0.184H-atom parameters constrained
S = 0.77Δρmax = 0.86 e Å3
1556 reflectionsΔρmin = 0.50 e Å3
64 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.

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) top
xyzUiso*/Ueq
Br10.40891 (12)0.3123 (3)0.39780 (17)0.1139 (8)
Br20.19816 (12)0.1953 (2)0.11104 (17)0.1065 (7)
O10.1347 (5)0.0988 (12)0.3970 (9)0.067 (2)
N10.0718 (7)0.2806 (13)0.1819 (10)0.072 (3)
H10.01100.32150.20880.087*
H20.08440.31840.09570.087*
C10.3463 (10)0.030 (2)0.3142 (14)0.107 (5)
H40.39950.03960.26520.129*
H50.32910.05500.39390.129*
C20.2455 (8)0.0907 (19)0.2077 (12)0.077 (3)
H30.26220.18650.13250.092*
C30.1452 (8)0.1613 (15)0.2720 (13)0.054 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.1008 (11)0.1465 (16)0.1073 (13)0.0630 (10)0.0505 (9)0.0552 (10)
Br20.1118 (12)0.0981 (12)0.1182 (13)0.0294 (8)0.0443 (9)0.0549 (9)
O10.070 (5)0.080 (5)0.059 (5)0.007 (4)0.034 (4)0.011 (4)
N10.067 (6)0.082 (7)0.071 (6)0.025 (5)0.022 (5)0.021 (5)
C10.085 (9)0.163 (15)0.088 (10)0.048 (9)0.048 (8)0.029 (9)
C20.050 (6)0.115 (10)0.069 (8)0.019 (6)0.021 (6)0.023 (7)
C30.063 (7)0.057 (8)0.050 (7)0.001 (5)0.031 (6)0.003 (6)
Geometric parameters (Å, º) top
Br1—C12.077 (15)C1—C21.407 (14)
Br2—C22.097 (12)C1—H40.9700
O1—C31.231 (10)C1—H50.9700
N1—C31.307 (12)C2—C31.518 (13)
N1—H10.8597C2—H30.9800
N1—H20.8604
C3—N1—H1120.1C1—C2—C3116.9 (10)
C3—N1—H2119.9C1—C2—Br297.5 (9)
H1—N1—H2120.0C3—C2—Br2105.9 (7)
C2—C1—Br199.8 (9)C1—C2—H3111.8
C2—C1—H4111.8C3—C2—H3111.8
Br1—C1—H4111.8Br2—C2—H3111.8
C2—C1—H5111.8O1—C3—N1124.8 (9)
Br1—C1—H5111.8O1—C3—C2120.2 (10)
H4—C1—H5109.5N1—C3—C2114.9 (10)
Br1—C1—C2—C374.1 (11)Br2—C2—C3—O180.6 (10)
Br1—C1—C2—Br2173.7 (4)C1—C2—C3—N1156.6 (12)
C1—C2—C3—O126.7 (17)Br2—C2—C3—N196.1 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.553.185 (11)132
N1—H2···O1ii0.862.092.942 (12)173
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC3H5Br2NO
Mr230.88
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)11.926 (3), 6.5911 (14), 8.991 (2)
β (°) 103.574 (14)
V3)687.0 (3)
Z4
Radiation typeMo Kα
µ (mm1)11.70
Crystal size (mm)0.14 × 0.11 × 0.05
Data collection
DiffractometerBruker APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.23, 0.56
No. of measured, independent and
observed [I > 2σ(I)] reflections
4500, 1556, 470
Rint0.181
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.066, 0.184, 0.77
No. of reflections1556
No. of parameters64
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.86, 0.50

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and ORTEPIII (Burnett & Johnson, 1996), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.553.185 (11)132
N1—H2···O1ii0.862.092.942 (12)173
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x, y+1/2, z1/2.
 

References

First citationBruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationBurnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.
First citationCheng, W. C., Hsiao, S. W., Chou, S. S., Sun-Hwang, L., Lu, T. J. & Yeh, A. I. (2006). J. Food Drug Anal. 14, 207–214.  CAS
First citationHashimoto, A. (1976). Analyst, 101, 932–938.  CrossRef PubMed CAS Web of Science
First citationMizukami, Y., Kohata, K., Yamaguchi, Y., Hayashi, N., Sawai, Y., Chuda, Y., Ono, H., Yada, H. & Yoshida, M. (2006). J. Agric. Food Chem. 54, 7370–7377.  Web of Science CrossRef PubMed CAS
First citationNemoto, S., Takatsuki, S., Sasaki, K. & Maitani, T. (2002). J. Food Hyg. Soc. Jpn, 43, 371–376.  CrossRef CAS
First citationPedireddim, J., Reddy, D., Goud, B., Craig, D., Rae, A. & Desiraju, G. (1994). J. Chem. Soc. Perkin Trans. 2, pp. 2353–2360.
First citationRosén, J. & Hellenäs, K.-E. (2002). Analyst, 127, 880–882.  Web of Science PubMed
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationZhang, Y., Dong, Y., Ren, Y. P. & Zhang, Y. (2006). J. Chromatogr. A, 1116, 209–216.  Web of Science CrossRef PubMed CAS
First citationZhang, Y., Zhang, G. Y. & Zhang, Y. (2005). J. Chromatogr. A, 1075, 1–21.  Web of Science CrossRef PubMed CAS
First citationZhou, Q.-L., Zhang, Z.-H. & Jing, Z.-L. (2007). Acta Cryst. E63, o3039.  Web of Science CSD CrossRef IUCr Journals

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COMMUNICATIONS
ISSN: 2056-9890
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