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addenda and errata

Acta Cryst.(2006). E62, e5 doi:10.1107/S1600536806000754 #2006 International Union of Crystallography

e5

Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

(

RS

)-2,3-Dibromosuccinic acid. Erratum

Margareta Eriksson,aAndreas Fischer,a* Johan Lindband A˚ sa Zazzia

aInorganic Chemistry, School of Chemical

Science and Engineering, Royal Institute of Technology, 100 44 Stockholm, Sweden, and bNuclear Chemistry, School of Chemical

Science and Engineering, Royal Institute of Technology, 100 44 Stockholm, Sweden

Correspondence e-mail: andif@inorg.kth.se

#2006 International Union of Crystallography Printed in Great Britain – all rights reserved

In the paper by Eriksson, Fischer, Lind & Zazzi [Acta Cryst. (2006), E62, o200–o201], the correct name of the title compound is ‘(2R,3S)-2,3-Dibromosuccinic acid’.

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organic papers

o200

Erikssonet al. C

4H4Br2O4 doi:10.1107/S1600536805040493 Acta Cryst.(2006). E62, o200–o201

Acta Crystallographica Section E Structure Reports

Online

ISSN 1600-5368

(2

R

,3

S

)-2,3-Dibromosuccinic acid

Margareta Eriksson,aAndreas Fischer,a* Johan Lindband A˚ sa Zazzia

aInorganic Chemistry, School of Chemical

Science and Engineering, Royal Institute of Technology, 100 44 Stockholm, Sweden, and

bNuclear Chemistry, School of Chemical

Science and Engineering, Royal Institute of Technology, 100 44 Stockholm, Sweden

Correspondence e-mail: andif@inorg.kth.se

Key indicators

Single-crystal X-ray study T= 298 K

Mean(C–C) = 0.013 A˚ Rfactor = 0.045 wRfactor = 0.102

Data-to-parameter ratio = 18.1

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2006 International Union of Crystallography Printed in Great Britain – all rights reserved

Crystals of the title compound, C4H4Br2O4, were grown from an aqueous solution. The structure features centrosymmetric molecules, each of which forms hydrogen bonds with two adjacent acid molecules, yielding long chains.

Comment

Some time ago, the structure of racemic 2,3-dibromosuccinic acid, which had been obtained by an electrophilic reaction between maleic acid and bromine, was determined (Bolte & Degen, 2000). The structure features a complex pattern of hydrogen bonds between carboxy groups of adjacent acid molecules. Inspired by the fact that the melting points of the racemic and the meso compounds are extremely different (racemate: 444 K; meso compound: 528 K), we expected very different hydrogen-bonding patterns in the two phases and decided therefore to determine the structure of the meso compound. From a reaction between bromine and fumaric acid, we obtained single crystals of the meso compound, (I), whose structure is described here. The molecule lies about an inversion centre located at the mid-point of the C2—C2ibond [symmetry code: (i)12x,

1

2y, 1z)]. The geometry of the molecule is essentially the same as in the structure of pyri-done–(RS)-2,3-dibromosuccinic acid (1:1) (Aakero¨y et al., 2000). In the crystal structure, the carboxy groups link pairs of molecules, forming an inversion-related closed hydrogen-bonding loop and infinite chains along theaaxis (Fig. 2).

Experimental

An aqueous solution (2.5 ml) containing 0.69 mol l1of fumaric acid, 2.1 mol l1of KBr and 1.9 mol l1of Br

2was placed in a boiling water bath. To avoid precipitation of KBr, the volume of the solution was kept constant by addition of deionized water. After 10 min, crystals of (I) were vacuum-filtered and placed in a heated cabinet at 373 K for 1 h.

Crystal data

C4H4Br2O4

Mr= 275.89

Monoclinic,C2=c a= 14.244 (1) A˚ b= 5.1664 (6) A˚ c= 11.3736 (8) A˚ = 117.684 (9)

V= 741.17 (13) A˚3 Z= 4

Dx= 2.477 Mg m 3

MoKradiation Cell parameters from 37

reflections = 4.3–21.0

= 10.91 mm1 T= 298 K Block, colourless 0.330.300.27 mm

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Data collection

Bruker–Nonius KappaCCD diffractometer

’scans

Absorption correction: numerical HABITUS(Herrendorf & Ba¨rnighausen, 1997) Tmin= 0.091,Tmax= 0.137

5265 measured reflections

849 independent reflections 679 reflections withI> 2(I) Rint= 0.039

max= 27.5

h=15!18 k=6!6 l=14!14

Refinement

Refinement onF2

R[F2> 2(F2)] = 0.045

wR(F2) = 0.102

S= 1.08 849 reflections 47 parameters

H-atom parameters constrained

w= 1/[2(F

o2) + (0.0299P)2

+ 8.0961P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 1.14 e A˚

3

min=0.73 e A˚

3

Table 1

Selected bond lengths (A˚ ).

Br1—C2 1.969 (8)

O1—C1 1.229 (10)

O2—C1 1.244 (9)

C1—C2 1.605 (11)

C2—C2i

1.403 (16)

Symmetry code: (i)xþ1 2;yþ

1 2;zþ1.

Table 2

Hydrogen-bond geometry (A˚ ,).

D—H A D—H H A D A D—H A

O1—H1 O2ii

0.82 1.83 2.650 (7) 175

Symmetry code: (ii)x;y;zþ1.

The H atoms were located in a difference Fourier map and were refined using a riding model, with C—H = 0.96 A˚ and Uiso(H) =

1.2Ueq(C), and with O—H = 0.82 A˚ andUiso(H) = 1.5Ueq(O). The highest peak is located 0.97 A˚ from atom C2.

Data collection: COLLECT (Nonius, 1999); cell refinement:

DIRAX/LSQ(Duisenberget al., 2003); data reduction:EVALCCD

(Duisenberg, 1992); program(s) used to solve structure:SHELXS97

(Sheldrick, 1997); program(s) used to refine structure:SHELXL97

(Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication:MAXUS

(Mackayet al., 1999).

The Swedish Research Council (VR) is acknowledged for providing funding for the single-crystal diffractometer.

References

Aakero¨y, C. B., Beatty, A. M., Nieuwenhuyzen, M. & Zou, M. (2000). Tetrahedron,56, 6693–6699.

Bolte, M. & Degen, A. (2000).Acta Cryst.C56, e410.

Brandenburg, K. (2005).DIAMOND.Release 3.1. Crystal Impact GbR, Bonn, Germany.

Duisenberg, A. J. M. (1992).J. Appl. Cryst.25, 92–96.

Duisenberg, A. J. M., Kroon-Batenburg, L. M. J. & Schreurs, A. M. M. (2003). J. Appl. Cryst.36, 220–229.

Herrendorf, W. & Ba¨rnighausen, H. (1997). HABITUS. Universities of Giessen and Karlsruhe, Germany.

Mackay, S., Gilmore, C. J., Edwards, C., Stewart, N. & Shankland, K. (1999). MAXUS. Bruker–Nonius, The Netherlands, MacScience, Japan, and The University of Glasgow, Scotland.

Nonius (1999).COLLECT. Nonius BV, Delft, The Netherlands.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.

organic papers

Acta Cryst.(2006). E62, o200–o201 Erikssonet al. C

[image:3.610.319.555.69.280.2]

4H4Br2O4

o201

Figure 2

[image:3.610.105.229.75.181.2]

The chains formed by hydrogen bonds in (I). Hydrogen bonds are indicated by dashed lines.

Figure 1

The (R,S)-2,3-dibromosuccinic acid molecule. Displacement ellipsoids are drawn at the 50% probability level [symmetry code: (i)1

2x, 1

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supporting information

sup-1

Acta Cryst. (2006). E62, o200–o201

supporting information

Acta Cryst. (2006). E62, o200–o201 [doi:10.1107/S1600536805040493]

(

RS

)-2,3-Dibromosuccinic acid

Margareta Eriksson, Andreas Fischer, Johan Lind and

Å

sa Zazzi

S1. Comment

Some time ago, the structure of racemic 2,3-dibromosuccinic acid, which had been obtained by an electrophilic reaction

between maleic acid and bromine, was determined (Bolte & Degen, 2000). The structure features a complex pattern of

hydrogen bonds between carboxy groups of adjacent acid molecules. Inspired by the fact that the melting points of the

racemic and the meso compounds are extremely different (racemate: 444 K; meso compound: 528 K), we expected very

different hydrogen-bonding patterns in the two phases and decided therefore to determine the structure of the meso

compound. From a reaction between bromine and fumaric acid, we obtained single crystals of the meso compound, (I),

whose structure is described here. The molecule lies about an inversion centre located at the mid-point of the C2—C2i

bond [symmetry code: (i) 1/2 − x, 1/2 − y, 1 − z). The geometry of the molecule is essentially the same as in the structure

of pyridone.(R,S)-2,3-dibromosuccinic acid (1:1) (Aakeröy et al., 2000). In the crystal structure, the carboxy groups link

pairs of molecules, forming an inversion-related closed hydrogen-bonding loop and infinite chains along the a axis (Fig

2).

S2. Experimental

An aqueous solution (2.5 ml) with the respective concentrations 0.69 mol l−1 of fumaric acid, 2.1 mol l−1 of KBr and 1.9

mol l−1 of Br

2 was placed in a boiling water bath. To avoid precipitation of KBr, the volume of the solution was kept

constant by addition of deionized water. After 10 min, crystals of (I) were vacuum-filtered and placed in a heated cabinet

at 373 K for one hour.

S3. Refinement

The H atoms were located in a difference Fourier map and were refined using a riding model, with C—H = 0.96 Å and

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supporting information

sup-2

[image:5.610.129.483.71.382.2]

Acta Cryst. (2006). E62, o200–o201 Figure 1

The (R,S)-2,3-dibromosuccinic acid molecule. Displacement ellipsoids are drawn at the 50% probability level [symmetry

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supporting information

sup-3

[image:6.610.122.489.73.393.2]

Acta Cryst. (2006). E62, o200–o201 Figure 2

The chains formed by hydrogen bonds in (I). Hydrogen bonds are indicated by dashed lines.

(I)

Crystal data

C4H4Br2O4

Mr = 275.89

Monoclinic, C2/c

Hall symbol: -C 2yc

a = 14.244 (1) Å

b = 5.1664 (6) Å

c = 11.3736 (8) Å

β = 117.684 (9)°

V = 741.17 (13) Å3

Z = 4

Dx = 2.477 Mg m−3

Mo radiation, λ = 0.71073 Å Cell parameters from 37 reflections

θ = 4.3–21.0°

µ = 10.91 mm−1

T = 298 K Cube, colourless 0.33 × 0.30 × 0.27 mm

Data collection

Bruker–Nonius KappaCCD diffractometer

Radiation source: fine-focus sealed tube

φ scans

Absorption correction: numerical

HABITUS (Herrendorf & Bärnighausen, 1997)

Tmin = 0.091, Tmax = 0.137

5265 measured reflections

849 independent reflections 679 reflections with I > 2σ(I)

Rint = 0.039

θmax = 27.5°, θmin = 4.5°

h = −15→18

k = −6→6

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supporting information

sup-4

Acta Cryst. (2006). E62, o200–o201

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 > 2σ(F2)] = 0.045

wR(F2) = 0.102

S = 1.08 849 reflections 47 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2(F

o2) + (0.0299P)2 + 8.0961P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 1.14 e Å−3

Δρmin = −0.73 e Å−3

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.

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)

x y z Uiso*/Ueq

Br1 0.15304 (5) 0.36080 (15) 0.28052 (6) 0.0568 (3) O1 0.0918 (5) −0.1270 (12) 0.4481 (7) 0.0808 (17)

H1 0.0395 −0.1590 0.4580 0.121*

O2 0.0784 (4) 0.2541 (10) 0.5270 (5) 0.0636 (13) C1 0.1201 (5) 0.0978 (18) 0.4820 (8) 0.065 (2) C2 0.2153 (7) 0.1680 (17) 0.4492 (8) 0.080 (2)

H2 0.2491 0.0147 0.4392 0.096*

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

Br1 0.0415 (3) 0.0827 (5) 0.0441 (4) 0.0038 (3) 0.0182 (3) 0.0114 (3) O1 0.077 (4) 0.073 (4) 0.130 (5) 0.002 (3) 0.079 (4) 0.007 (3) O2 0.052 (3) 0.057 (3) 0.074 (3) −0.021 (2) 0.023 (2) −0.004 (3) C1 0.035 (3) 0.083 (6) 0.084 (5) 0.003 (4) 0.033 (3) 0.025 (4) C2 0.089 (6) 0.074 (6) 0.069 (5) 0.016 (4) 0.030 (4) −0.003 (4)

Geometric parameters (Å, º)

Br1—C2 1.969 (8) C1—C2 1.605 (11)

O1—C1 1.229 (10) C2—C2i 1.403 (16)

O1—H1 0.8200 C2—H2 0.9600

O2—C1 1.244 (9)

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supporting information

sup-5

Acta Cryst. (2006). E62, o200–o201

O1—C1—O2 126.1 (6) C1—C2—Br1 107.1 (5)

O1—C1—C2 109.2 (7) C2i—C2—H2 113.1

O2—C1—C2 124.5 (7) C1—C2—H2 111.5

C2i—C2—C1 107.1 (9) Br1—C2—H2 108.9

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

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O1—H1···O2ii 0.82 1.83 2.650 (7) 175

Figure

Figure 2
Figure 1The (R,S)-2,3-dibromosuccinic acid molecule. Displacement ellipsoids are drawn at the 50% probability level [symmetry
Figure 2

References

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