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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 72| Part 3| March 2016| Pages 322-324

Crystal and mol­ecular structure of meso-2,6-di­bromo­hepta­nedioic acid (meso-2,6-di­bromo­pimelic acid)

CROSSMARK_Color_square_no_text.svg

aCenter for Biomedical Engineering and Technology, University of Maryland School of Medicine, Baltimore, MD 21201, USA, bDepartment of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742, USA, and cDepartment of Physiology, University of Maryland School of Medicine, Baltimore, MD 21201, USA
*Correspondence e-mail: jkao@umaryland.edu

Edited by S. Parkin, University of Kentucky, USA (Received 23 January 2016; accepted 27 January 2016; online 10 February 2016)

The mol­ecular structure of the title compound, C7H10Br2O4, confirms the meso (2R,6S) configuration. In the crystal, mol­ecules are linked by pairs of O—H⋯O=C hydrogen bonds between their terminal carboxyl groups in an R22(8) motif, forming extended chains that propagate parallel to the c axis. Adjacent chains are linked by C=O⋯Br halogen bonds.

1. Chemical context

meso-2,6-Di­bromo­pimelic acid is a convenient starting point for preparing derivatives 2,6-disubstituted with non-halogen functional groups (for examples: Schotte, 1956b[Schotte, L. (1956b). Ark. Kemi, 9, 413-421.]; Lingens, 1960[Lingens, F. (1960). Z. Naturforsch. Teil B, 15, 811-811.]; Yuan & Lu, 2009[Yuan, B. & Lu, S. (2009). Chin. Patent Appl. CN101497626.]). It also has utility in the synthesis of heterocycles (Schotte, 1956b[Schotte, L. (1956b). Ark. Kemi, 9, 413-421.]; Miyake et al., 2000[Miyake, Y., Takada, H., Ohe, K. & Uemura, S. (2000). J. Chem. Soc. Perkin Trans. 1, pp. 1595-1599.]; Peters et al., 2006[Peters, D., Timmermann, D. B., Olsen, G. M., Nielsen, E. O. & Jørgensen, T. D. (2006). Int. Patent Appl. WO2006087306.]; Hamon et al., 2007[Hamon, C., Schwarz, J., Becker, W., Kienle, S., Kuhn, K. & Schäfer, J. (2007). Int. Patent Appl. WO2007012849.]). In an ongoing study of di­sulfides, the title compound was required as precursor to meso-3,7-dicarb­oxy-1,2-dithiepane. Surprisingly, other than the melting point reported by Schotte (1956a[Schotte, L. (1956a). Ark. Kemi, 9, 407-412.]), no further analytical data have been published on the di­bromo acid. Original stereochemical assignment was based on the lack of optical activity of the acid isolated through crystallization of the acid brucine salt (Schotte, 1956a[Schotte, L. (1956a). Ark. Kemi, 9, 407-412.]). The need to confirm the meso configuration motivated the crystal structure determination.

[Scheme 1]

2. Structural commentary

The mol­ecular structure of the title compound is shown in Fig. 1[link]; the (2R,6S) configuration is apparent, confirming the meso form of the compound. All bond lengths and angles are within normal ranges.

[Figure 1]
Figure 1
The mol­ecular structure of the title compound, with non-H atoms labeled. Displacement ellipsoids are shown at the 60% probability level.

3. Supra­molecular features

In the crystal, the mol­ecules are linked in head-to-tail fashion by pairs of O—H⋯O=C hydrogen bonds (Table 1[link]) between their terminal carboxyl groups in an R22(8) motif, forming extended chains that propagate parallel to the c axis (Fig. 2[link]a). Adjacent chains are cross-linked by inter­actions between a carboxyl C=O group in one chain with a Br atom in an adjacent chain. These linkages meet the criteria for halogen bonds (Desiraju et al., 2013[Desiraju, G. R., Ho, P. S., Kloo, L., Legon, A. C., Marquardt, R., Metrangolo, P., Politzer, P., Resnati, G. & Rissanen, K. (2013). Pure Appl. Chem. 85, 171-1713.]): (i) the =O⋯Br—C bonds are nearly linear [the =O1⋯Br2—C2 and =O3⋯Br6—C6 angles being 168.06 (8) and 170.26 (8)°, respectively], and (ii) the O⋯Br distances [3.224 (2) and 3.058 (2) Å for O1⋯Br2iii and O3⋯Br6iv, respectively [symmetry codes: (iii) [{1\over 2}] − x, y − [{1\over 2}], z; (iv) [{3\over 2}] − x, y − [{1\over 2}], z] are less than the sum of the van der Waals radii of 3.35 Å (Mantina et al., 2009[Mantina, M., Chamberlin, A. C., Valero, R., Cramer, C. J. & Truhlar, D. G. (2009). J. Phys. Chem. A, 113, 5806-5812.]; Alvarez, 2013[Alvarez, S. (2013). Dalton Trans. 42, 8617-8636.]). H and Br bonding are shown in Fig. 2[link].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O2—H2⋯O3i 0.84 1.80 2.635 (3) 177
O4—H4⋯O1ii 0.84 1.83 2.669 (3) 176
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}}].
[Figure 2]
Figure 2
The mol­ecular packing, viewed along the b and a axes [panels (a) and (b)]. Inter­molecular hydrogen bonding (cyan) between terminal carboxyl groups results in head-to-tail linkage of the mol­ecules into chains extending along [001]. Adjacent chains are linked by halogen bonding (C=O⋯Br, green).

4. Synthesis and crystallization

The title compound was first prepared in pure form and its stereochemistry deduced by Fehnel & Oppenlander (1953[Fehnel, E. A. & Oppenlander, G. C. (1953). J. Am. Chem. Soc. 75, 4660-4663.]). The synthesis for the present work followed the method of Schotte (1956a[Schotte, L. (1956a). Ark. Kemi, 9, 407-412.]). Pimelic (hepta­nedioic) acid was converted into the diacid chloride by heating with thionyl chloride. Removal of excess SOCl2 under reduced pressure left the liquid diacid chloride. Over 1 h, bromine (2.3 equivalents) was added dropwise to the stirred diacid chloride maintained at 363 K. Thereafter, stirring and heating continued for an additional hour. The dibrominated acid chloride was hydrolyzed by gradual addition to vigorously stirred formic acid maintained at 353–363 K. When gas evolution ceased, the reaction mixture was refluxed for 15 min, and then allowed to cool to room temperature. Upon cooling in the refrigerator, over two days, the reaction mixture yielded two crops of solids, which were combined and extracted by shaking with ice-cold CHCl3. The remaining solids were recrystallized three times from formic acid to give meso-2,6-dibrohepta­nedioic acid (26% yield).

The 1H NMR spectrum, acquired in Me2SO-d6, is consistent with the mol­ecular structure, with the following resonances (δ referenced to Me4Si): 13.22, singlet, 2H; 4.43, triplet, 2H, J = 7 Hz; 2.01, multiplet, 2H; 1.88, multiplet, 2H; 1.54, multiplet, 1H; 1.39, multiplet, 1H. The high-resolution mass spectrum (electrospray) showed the expected manifold arising from the two stable isotopes of bromine, with the base peak at m/z = 316.884; species containing halogens other than bromine were not observed. To produce crystals suitable for diffraction, 10 mg of the title compound was dissolved in a capped glass vial in minimal formic acid with warming. Once a few seeds became visible, slow evaporation of the solvent over 14 days yielded crystals of good quality.

5. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. H-atom Uiso parameters were refined to confirm proper positioning of the H atoms; this was particularly important for the carboxyl H atoms. Uniquely for H3, its Uiso [0.013 (7)] is smaller than the Ueq of C3 [0.022 (4)], to which it is attached, but by less than two s.u.'s. All other H-atom Uiso values are consistent with expectation: 0.02–0.3 for CH and CH2, and 0.05 for CO2H. These values are in line with H-atom Uiso values in C2–C12 aliphatic acids without heavy-atom substitution, whose structures had been determined at the same temperature (150 K) or lower (Thalladi et al., 2000[Thalladi, V. R., Nüsse, M. & Boese, R. (2000). J. Am. Chem. Soc. 122, 9227-9236.]; Mitchell et al.,2001[Mitchell, C. A., Yu, L. & Ward, M. D. (2001). J. Am. Chem. Soc. 123, 10830-10839.]; Peppel et al., 2015a[Peppel, T., Sonneck, M., Spannenberg, A. & Wohlrab, S. (2015a). Acta Cryst. E71, o316.],b[Peppel, T., Sonneck, M., Spannenberg, A. & Wohlrab, S. (2015b). Acta Cryst. E71, o323.]; Sonneck et al., 2015a[Sonneck, M., Peppel, T., Spannenberg, A. & Wohlrab, S. (2015a). Acta Cryst. E71, o426-o427.],b[Sonneck, M., Peppel, T., Spannenberg, A. & Wohlrab, S. (2015b). Acta Cryst. E71, o528-o529.]). In these structures, Uiso values average 0.033±0.006 for CH and CH2, and 0.068±0.033 for reciprocally hydrogen-bonded CO2H.

Table 2
Experimental details

Crystal data
Chemical formula C7H10Br2O4
Mr 317.97
Crystal system, space group Orthorhombic, Pbca
Temperature (K) 150
a, b, c (Å) 10.4277 (7), 10.7014 (7), 18.7154 (13)
V3) 2088.5 (2)
Z 8
Radiation type Mo Kα
μ (mm−1) 7.74
Crystal size (mm) 0.35 × 0.27 × 0.09
 
Data collection
Diffractometer Bruker SMART APEXII CCD
Absorption correction Multi-scan (SADABS; Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.])
Tmin, Tmax 0.231, 0.498
No. of measured, independent and observed [I > 2σ(I)] reflections 35789, 4598, 3488
Rint 0.037
(sin θ/λ)max−1) 0.807
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.084, 1.08
No. of reflections 4598
No. of parameters 130
H-atom treatment Only H-atom displacement parameters refined
Δρmax, Δρmin (e Å−3) 2.07, −1.15
Computer programs: APEX2, SAINT and XSHELL (Bruker, 2010[Bruker (2010). APEX2, SAINT and XSHELL. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]), PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Residual electron density is somewhat high (Δρmax and Δρmin being 2.07 and −1.14 e Å3, respectively) and localizes near the heavier Br atoms, which suggests Fourier truncation as a possible cause. Other reasons could be translational pseudosymmetry (for example, see Kiessling & Zeller, 2011[Kiessling, A. & Zeller, M. (2011). Acta Cryst. E67, o733-o734.]), or the high geometric anisotropy of the crystal (ratio of largest-to-smallest dimensions being 4), which can yield less accurate absorption correction performed through SADABS software. The irregular shape of the crystal precluded more accurate absorption correction through face indexing.

Supporting information


Chemical context top

meso-2,6-Di­bromo­pimelic acid is a convenient starting point for preparing derivatives 2,6-disubstituted with non-halogen functional groups (for examples: Schotte, 1956b; Lingens, 1960; Yuan & Lu, 2009). It also has utility in the synthesis of heterocycles (Schotte, 1956b; Miyake et al., 2000; Peters et al., 2006; Hamon et al., 2007). In an ongoing study of di­sulfides, the title compound was required as precursor to meso-3,7-di­carb­oxy-1,2-dithiepane. Surprisingly, other than the melting point reported by Schotte (1956a), no further analytical data have been published on the di­bromo acid. Original stereochemical assignment was based on the lack of optical activity of the acid isolated through crystallization of the acid brucine salt (Schotte, 1956a). The need to confirm the meso configuration motivated the crystal structure determination.

Structural commentary top

The molecular structure of the title compound is shown in Fig. 1; the (2R,6S) configuration is apparent, confirming the meso form of the compound. All bond lengths and angles are within normal ranges.

Supra­molecular features top

In the crystal, the molecules are linked in head-to-tail fashion by pairs of O—H···OC hydrogen bonds (Table 1) between their terminal carboxyl groups in an R22(8) motif, forming extended chains that propagate parallel to the c axis (Fig. 2a). Adjacent chains are cross-linked by inter­actions between a carboxyl CO group in one chain with a Br atom in an adjacent chain. These linkages meet the criteria for halogen bonds (Desiraju et al., 2013): (i) the O···Br—C bonds are nearly linear [the O1···Br2—C2 and O3···Br6—C6 angles being 168.06 (8) and 170.26 (8)°, respectively], and (ii) the O···Br distances [3.224 (2) and 3.058 (2) Å for O1···Br2iii and O3···Br6iv, respectively [symmetry codes: (iii) 1/2 − x, y − 1/2, z; (iv) 3/2 − x, y − 1/2, z] are less than the sum of the van der Waals radii of 3.35 Å (Mantina et al., 2009; Alvarez, 2013). H and Br bonding are shown in Fig. 2.

Synthesis and crystallization top

The title compound was first prepared in pure form and its stereochemistry deduced by Fehnel & Oppenlander (1953). The synthesis for the present work followed the method of Schotte (1956a). Pimelic (heptanedioic) acid was converted into the diacid chloride by heating with thio­nyl chloride. Removal of excess SOCl2 under reduced pressure left the liquid diacid chloride. Over 1 h, bromine (2.3 equivalents) was added dropwise to the stirred diacid chloride maintained at ~363 K. Thereafter, stirring and heating continued for an additional hour. The dibrominated acid chloride was hydrolyzed by gradual addition to vigorously stirred formic acid maintained at 353–363 K. When gas evolution ceased, the reaction mixture was refluxed for 15 min, and then allowed to cool to room temperature. Upon cooling in the refrigerator, over two days, the reaction mixture yielded two crops of solids, which were combined and extracted by shaking with ice-cold CHCl3. The remaining solids were recrystallized three times from formic acid to give meso-2,6-dibroheptanedioic acid (26% yield).

The 1H NMR spectrum, acquired in Me2SO-d6, is consistent with the molecular structure, with the following resonances (δ referenced to Me4Si): 13.22, singlet, 2H; 4.43, triplet, 2H, J = 7 Hz; 2.01, multiplet, 2H; 1.88, multiplet, 2H; 1.54, multiplet, 1H; 1.39, multiplet, 1H. The high-resolution mass spectrum (electrospray) showed the expected manifold arising from the two stable isotopes of bromine, with the base peak at m/z = 316.884; species containing halogens other than bromine were not observed. To produce crystals suitable for diffraction, ~10 mg of the title compound was dissolved in a capped glass vial in minimal formic acid with warming. Once a few seeds became visible, slow evaporation of the solvent over 14 days yielded crystals of good quality.

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 2. H-atom Uiso parameters were refined to confirm proper positioning of the H atoms; this was particularly important for the carboxyl H atoms. Uniquely for H3, its Uiso [0.013 (7)] is smaller than the Ueq of C3 [0.022 (4)], to which it is attached, but by less than two s.u.'s. All other H-atom Uiso values are consistent with expe­cta­tion: ~0.02–0.3 for CH and CH2, and ~0.05 for CO2H. These values are in line with H-atom Uiso values in C2–C12 aliphatic acids without heavy-atom substitution, whose structures had been determined at the same temperature (150 K) or lower (Thalladi et al., 2000; Mitchell et al.,2001; Peppel et al., 2015a,b; Sonneck et al., 2015a,b). In these structures, Uiso values average 0.033±0.006 for CH and CH2, and 0.068±0.033 for reciprocally hydrogen-bonded CO2H.

Residual electron density is somewhat high (Δρmax and Δρmin being 2.07 and −1.14 e Å3, respectively) and localizes near the heavier Br atoms, which suggests Fourier truncation as a possible cause. Other reasons could be translational pseudosymmetry (for example, see Kiessling & Zeller, 2011), or the high geometric anisotropy of the crystal (ratio of largest-to-smallest dimensions being ~4), which can yield less accurate absorption correction performed through SADABS software. The irregular shape of the crystal precluded more accurate absorption correction through face indexing.

Related literature top

The title compound was first prepared in pure form and its stereochemistry deduced by Fehnel and Oppenlander (1953). The meso and racemic forms of 2,6-dibromoheptanedioic acid (2,6-dibromopimelic acid) were prepared by Schotte (1956a), who also resolved the enantiomorphs by crystallization of the acid brucine and chiconidine salts. Conversion of the title compound into derivatives 2,6-disubstituted with non-halogen functional groups is exemplified in Schotte (1956b), Lingens (1960), and Yuan & Lu (2009). Use of the title compound in heterocycle synthesis has been reported (Schotte, 1956b; Miyake et al., 2000; Peters et al., 2006; Hamon et al., 2007).

Structure description top

meso-2,6-Di­bromo­pimelic acid is a convenient starting point for preparing derivatives 2,6-disubstituted with non-halogen functional groups (for examples: Schotte, 1956b; Lingens, 1960; Yuan & Lu, 2009). It also has utility in the synthesis of heterocycles (Schotte, 1956b; Miyake et al., 2000; Peters et al., 2006; Hamon et al., 2007). In an ongoing study of di­sulfides, the title compound was required as precursor to meso-3,7-di­carb­oxy-1,2-dithiepane. Surprisingly, other than the melting point reported by Schotte (1956a), no further analytical data have been published on the di­bromo acid. Original stereochemical assignment was based on the lack of optical activity of the acid isolated through crystallization of the acid brucine salt (Schotte, 1956a). The need to confirm the meso configuration motivated the crystal structure determination.

The molecular structure of the title compound is shown in Fig. 1; the (2R,6S) configuration is apparent, confirming the meso form of the compound. All bond lengths and angles are within normal ranges.

In the crystal, the molecules are linked in head-to-tail fashion by pairs of O—H···OC hydrogen bonds (Table 1) between their terminal carboxyl groups in an R22(8) motif, forming extended chains that propagate parallel to the c axis (Fig. 2a). Adjacent chains are cross-linked by inter­actions between a carboxyl CO group in one chain with a Br atom in an adjacent chain. These linkages meet the criteria for halogen bonds (Desiraju et al., 2013): (i) the O···Br—C bonds are nearly linear [the O1···Br2—C2 and O3···Br6—C6 angles being 168.06 (8) and 170.26 (8)°, respectively], and (ii) the O···Br distances [3.224 (2) and 3.058 (2) Å for O1···Br2iii and O3···Br6iv, respectively [symmetry codes: (iii) 1/2 − x, y − 1/2, z; (iv) 3/2 − x, y − 1/2, z] are less than the sum of the van der Waals radii of 3.35 Å (Mantina et al., 2009; Alvarez, 2013). H and Br bonding are shown in Fig. 2.

The title compound was first prepared in pure form and its stereochemistry deduced by Fehnel and Oppenlander (1953). The meso and racemic forms of 2,6-dibromoheptanedioic acid (2,6-dibromopimelic acid) were prepared by Schotte (1956a), who also resolved the enantiomorphs by crystallization of the acid brucine and chiconidine salts. Conversion of the title compound into derivatives 2,6-disubstituted with non-halogen functional groups is exemplified in Schotte (1956b), Lingens (1960), and Yuan & Lu (2009). Use of the title compound in heterocycle synthesis has been reported (Schotte, 1956b; Miyake et al., 2000; Peters et al., 2006; Hamon et al., 2007).

Synthesis and crystallization top

The title compound was first prepared in pure form and its stereochemistry deduced by Fehnel & Oppenlander (1953). The synthesis for the present work followed the method of Schotte (1956a). Pimelic (heptanedioic) acid was converted into the diacid chloride by heating with thio­nyl chloride. Removal of excess SOCl2 under reduced pressure left the liquid diacid chloride. Over 1 h, bromine (2.3 equivalents) was added dropwise to the stirred diacid chloride maintained at ~363 K. Thereafter, stirring and heating continued for an additional hour. The dibrominated acid chloride was hydrolyzed by gradual addition to vigorously stirred formic acid maintained at 353–363 K. When gas evolution ceased, the reaction mixture was refluxed for 15 min, and then allowed to cool to room temperature. Upon cooling in the refrigerator, over two days, the reaction mixture yielded two crops of solids, which were combined and extracted by shaking with ice-cold CHCl3. The remaining solids were recrystallized three times from formic acid to give meso-2,6-dibroheptanedioic acid (26% yield).

The 1H NMR spectrum, acquired in Me2SO-d6, is consistent with the molecular structure, with the following resonances (δ referenced to Me4Si): 13.22, singlet, 2H; 4.43, triplet, 2H, J = 7 Hz; 2.01, multiplet, 2H; 1.88, multiplet, 2H; 1.54, multiplet, 1H; 1.39, multiplet, 1H. The high-resolution mass spectrum (electrospray) showed the expected manifold arising from the two stable isotopes of bromine, with the base peak at m/z = 316.884; species containing halogens other than bromine were not observed. To produce crystals suitable for diffraction, ~10 mg of the title compound was dissolved in a capped glass vial in minimal formic acid with warming. Once a few seeds became visible, slow evaporation of the solvent over 14 days yielded crystals of good quality.

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 2. H-atom Uiso parameters were refined to confirm proper positioning of the H atoms; this was particularly important for the carboxyl H atoms. Uniquely for H3, its Uiso [0.013 (7)] is smaller than the Ueq of C3 [0.022 (4)], to which it is attached, but by less than two s.u.'s. All other H-atom Uiso values are consistent with expe­cta­tion: ~0.02–0.3 for CH and CH2, and ~0.05 for CO2H. These values are in line with H-atom Uiso values in C2–C12 aliphatic acids without heavy-atom substitution, whose structures had been determined at the same temperature (150 K) or lower (Thalladi et al., 2000; Mitchell et al.,2001; Peppel et al., 2015a,b; Sonneck et al., 2015a,b). In these structures, Uiso values average 0.033±0.006 for CH and CH2, and 0.068±0.033 for reciprocally hydrogen-bonded CO2H.

Residual electron density is somewhat high (Δρmax and Δρmin being 2.07 and −1.14 e Å3, respectively) and localizes near the heavier Br atoms, which suggests Fourier truncation as a possible cause. Other reasons could be translational pseudosymmetry (for example, see Kiessling & Zeller, 2011), or the high geometric anisotropy of the crystal (ratio of largest-to-smallest dimensions being ~4), which can yield less accurate absorption correction performed through SADABS software. The irregular shape of the crystal precluded more accurate absorption correction through face indexing.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: APEX2 (Bruker, 2010); data reduction: APEX2 and SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: XSHELL (Bruker, 2010) and Mercury (Macrae et al., 2008); software used to prepare material for publication: APEX2 (Bruker, 2010), SHELXL2014 (Sheldrick, 2015), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with non-H atoms labeled. Displacement ellipsoids are shown at the 60% probability level.
[Figure 2] Fig. 2. The molecular packing, viewed along the b and a axes [panels (a) and (b)]. Intermolecular hydrogen bonding (cyan) between terminal carboxyl groups results in head-to-tail linkage of the molecules into chains extending along [001]. Adjacent chains are linked by halogen bonding (CO···Br, green).
meso-2,6-Dibromoheptanedioic acid top
Crystal data top
C7H10Br2O4Dx = 2.023 Mg m3
Mr = 317.97Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 9811 reflections
a = 10.4277 (7) Åθ = 2.2–34.7°
b = 10.7014 (7) ŵ = 7.74 mm1
c = 18.7154 (13) ÅT = 150 K
V = 2088.5 (2) Å3Plate, colourless
Z = 80.35 × 0.27 × 0.09 mm
F(000) = 1232
Data collection top
Bruker SMART APEXII CCD
diffractometer
4598 independent reflections
Radiation source: sealed tube3488 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
Detector resolution: 8.333 pixels mm-1θmax = 35.0°, θmin = 2.2°
φ and ω scansh = 1616
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)
k = 1717
Tmin = 0.231, Tmax = 0.498l = 3030
35789 measured reflections
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)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084Only H-atom displacement parameters refined
S = 1.08 w = 1/[σ2(Fo2) + (0.020P)2 + 6.P]
where P = (Fo2 + 2Fc2)/3
4598 reflections(Δ/σ)max = 0.001
130 parametersΔρmax = 2.07 e Å3
0 restraintsΔρmin = 1.14 e Å3
Crystal data top
C7H10Br2O4V = 2088.5 (2) Å3
Mr = 317.97Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 10.4277 (7) ŵ = 7.74 mm1
b = 10.7014 (7) ÅT = 150 K
c = 18.7154 (13) Å0.35 × 0.27 × 0.09 mm
Data collection top
Bruker SMART APEXII CCD
diffractometer
4598 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)
3488 reflections with I > 2σ(I)
Tmin = 0.231, Tmax = 0.498Rint = 0.037
35789 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.084Only H-atom displacement parameters refined
S = 1.08Δρmax = 2.07 e Å3
4598 reflectionsΔρmin = 1.14 e Å3
130 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
xyzUiso*/Ueq
O10.4428 (2)0.35337 (18)0.81180 (10)0.0271 (4)
O20.5097 (2)0.53602 (18)0.85748 (10)0.0289 (4)
H20.53280.49030.89160.044 (11)*
C10.4560 (2)0.4669 (2)0.80775 (12)0.0200 (4)
C20.4148 (2)0.5420 (2)0.74305 (12)0.0190 (4)
H2A0.48580.60070.73030.024 (8)*
Br20.26550 (3)0.64147 (3)0.77267 (2)0.02812 (7)
C30.3835 (2)0.4638 (2)0.67757 (12)0.0221 (4)
H3A0.34110.51690.64130.022 (8)*
H3B0.32330.39630.69100.013 (7)*
C40.5050 (3)0.4068 (3)0.64587 (13)0.0241 (5)
H4A0.56920.47360.63800.030 (9)*
H4B0.54170.34620.68020.033 (9)*
C50.4780 (2)0.3408 (2)0.57527 (13)0.0212 (4)
H5A0.41120.27650.58310.034 (9)*
H5B0.44350.40240.54080.037 (10)*
C60.5957 (2)0.2790 (2)0.54304 (13)0.0204 (4)
H6A0.62990.21630.57780.029 (9)*
Br60.73130 (2)0.40137 (2)0.52174 (2)0.02402 (6)
C70.5646 (2)0.2132 (2)0.47354 (12)0.0204 (4)
O30.5852 (2)0.10197 (18)0.46621 (11)0.0296 (4)
O40.5102 (2)0.28358 (18)0.42491 (10)0.0300 (4)
H40.48630.23890.39050.053 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0382 (10)0.0244 (9)0.0188 (8)0.0048 (8)0.0049 (7)0.0012 (7)
O20.0425 (11)0.0238 (9)0.0205 (8)0.0040 (8)0.0098 (8)0.0008 (7)
C10.0205 (10)0.0243 (11)0.0152 (9)0.0001 (8)0.0009 (7)0.0002 (8)
C20.0185 (9)0.0204 (10)0.0181 (10)0.0006 (8)0.0003 (7)0.0012 (8)
Br20.02097 (11)0.03372 (14)0.02965 (13)0.00479 (10)0.00001 (10)0.00452 (10)
C30.0233 (11)0.0270 (11)0.0159 (9)0.0003 (9)0.0012 (8)0.0008 (8)
C40.0264 (11)0.0294 (12)0.0166 (9)0.0032 (9)0.0013 (8)0.0036 (9)
C50.0226 (11)0.0239 (11)0.0171 (9)0.0003 (8)0.0008 (8)0.0005 (8)
C60.0255 (11)0.0190 (10)0.0169 (9)0.0006 (8)0.0024 (8)0.0009 (8)
Br60.02087 (10)0.02733 (12)0.02386 (11)0.00204 (9)0.00007 (9)0.00097 (9)
C70.0218 (10)0.0228 (10)0.0165 (9)0.0007 (8)0.0008 (8)0.0014 (8)
O30.0387 (11)0.0247 (9)0.0253 (9)0.0061 (8)0.0103 (8)0.0034 (7)
O40.0493 (12)0.0215 (8)0.0193 (8)0.0027 (8)0.0100 (8)0.0001 (7)
Geometric parameters (Å, º) top
O1—C11.225 (3)C4—H4A0.9900
O2—C11.314 (3)C4—H4B0.9900
O2—H20.8400C5—C61.520 (3)
C1—C21.516 (3)C5—H5A0.9900
C2—C31.519 (3)C5—H5B0.9900
C2—Br21.966 (2)C6—C71.515 (3)
C2—H2A1.0000C6—Br61.968 (2)
C3—C41.526 (4)C6—H6A1.0000
C3—H3A0.9900C7—O31.217 (3)
C3—H3B0.9900C7—O41.310 (3)
C4—C51.524 (3)O4—H40.8400
C1—O2—H2109.5C5—C4—H4B109.3
O1—C1—O2124.2 (2)C3—C4—H4B109.3
O1—C1—C2122.9 (2)H4A—C4—H4B108.0
O2—C1—C2112.8 (2)C6—C5—C4113.3 (2)
C1—C2—C3114.4 (2)C6—C5—H5A108.9
C1—C2—Br2106.66 (16)C4—C5—H5A108.9
C3—C2—Br2110.85 (16)C6—C5—H5B108.9
C1—C2—H2A108.2C4—C5—H5B108.9
C3—C2—H2A108.2H5A—C5—H5B107.7
Br2—C2—H2A108.2C7—C6—C5111.7 (2)
C2—C3—C4110.8 (2)C7—C6—Br6106.84 (16)
C2—C3—H3A109.5C5—C6—Br6111.78 (16)
C4—C3—H3A109.5C7—C6—H6A108.8
C2—C3—H3B109.5C5—C6—H6A108.8
C4—C3—H3B109.5Br6—C6—H6A108.8
H3A—C3—H3B108.1O3—C7—O4124.1 (2)
C5—C4—C3111.6 (2)O3—C7—C6120.9 (2)
C5—C4—H4A109.3O4—C7—C6114.9 (2)
C3—C4—H4A109.3C7—O4—H4109.5
O1—C1—C2—C313.0 (3)C3—C4—C5—C6178.1 (2)
O2—C1—C2—C3165.5 (2)C4—C5—C6—C7179.3 (2)
O1—C1—C2—Br2109.9 (2)C4—C5—C6—Br661.1 (2)
O2—C1—C2—Br271.6 (2)C5—C6—C7—O3122.1 (3)
C1—C2—C3—C470.5 (3)Br6—C6—C7—O3115.4 (2)
Br2—C2—C3—C4168.86 (17)C5—C6—C7—O455.2 (3)
C2—C3—C4—C5173.3 (2)Br6—C6—C7—O467.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O3i0.841.802.635 (3)177
O4—H4···O1ii0.841.832.669 (3)176
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x, y+1/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O3i0.841.802.635 (3)177
O4—H4···O1ii0.841.832.669 (3)176
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC7H10Br2O4
Mr317.97
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)150
a, b, c (Å)10.4277 (7), 10.7014 (7), 18.7154 (13)
V3)2088.5 (2)
Z8
Radiation typeMo Kα
µ (mm1)7.74
Crystal size (mm)0.35 × 0.27 × 0.09
Data collection
DiffractometerBruker SMART APEXII CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2008)
Tmin, Tmax0.231, 0.498
No. of measured, independent and
observed [I > 2σ(I)] reflections
35789, 4598, 3488
Rint0.037
(sin θ/λ)max1)0.807
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.084, 1.08
No. of reflections4598
No. of parameters130
H-atom treatmentOnly H-atom displacement parameters refined
Δρmax, Δρmin (e Å3)2.07, 1.14

Computer programs: APEX2 and SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), XSHELL (Bruker, 2010) and Mercury (Macrae et al., 2008), APEX2 (Bruker, 2010), SHELXL2014 (Sheldrick, 2015), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

 

Acknowledgements

This work was supported in part by the Nanobiology Fund of the University of Maryl­and Baltimore Foundation.

References

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Volume 72| Part 3| March 2016| Pages 322-324
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