research communications
Crystal and molecular structure of meso-2,6-dibromoheptanedioic acid (meso-2,6-dibromopimelic acid)
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
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.
Keywords: crystal structure; hydrogen bonding; halogen bonding.
CCDC reference: 1450356
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; 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 determination.
2. Structural commentary
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.
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) 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 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): (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) − x, y − , z; (iv) − x, y − , 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.
4. Synthesis and crystallization
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 (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. details
Crystal data, data collection and structure . 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.
details are summarized in Table 2Residual 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 (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.
Supporting information
CCDC reference: 1450356
10.1107/S2056989016001754/pk2573sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016001754/pk2573Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989016001754/pk2573Isup3.cml
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
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···O═C 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 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): (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 & 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 (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.
Crystal data, data collection and structure
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 (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.
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
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···O═C 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 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): (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).
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 (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.
detailsCrystal data, data collection and structure
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 (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.
Data collection: APEX2 (Bruker, 2010); cell
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).Fig. 1. The molecular structure of the title compound, with non-H atoms labeled. Displacement ellipsoids are shown at the 60% probability level. | |
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 (C═O···Br, green). |
C7H10Br2O4 | Dx = 2.023 Mg m−3 |
Mr = 317.97 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 9811 reflections |
a = 10.4277 (7) Å | θ = 2.2–34.7° |
b = 10.7014 (7) Å | µ = 7.74 mm−1 |
c = 18.7154 (13) Å | T = 150 K |
V = 2088.5 (2) Å3 | Plate, colourless |
Z = 8 | 0.35 × 0.27 × 0.09 mm |
F(000) = 1232 |
Bruker SMART APEXII CCD diffractometer | 4598 independent reflections |
Radiation source: sealed tube | 3488 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
Detector resolution: 8.333 pixels mm-1 | θmax = 35.0°, θmin = 2.2° |
φ and ω scans | h = −16→16 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008) | k = −17→17 |
Tmin = 0.231, Tmax = 0.498 | l = −30→30 |
35789 measured reflections |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.084 | Only 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 parameters | Δρmax = 2.07 e Å−3 |
0 restraints | Δρmin = −1.14 e Å−3 |
C7H10Br2O4 | V = 2088.5 (2) Å3 |
Mr = 317.97 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 10.4277 (7) Å | µ = 7.74 mm−1 |
b = 10.7014 (7) Å | T = 150 K |
c = 18.7154 (13) Å | 0.35 × 0.27 × 0.09 mm |
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 = 0.498 | Rint = 0.037 |
35789 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.084 | Only H-atom displacement parameters refined |
S = 1.08 | Δρmax = 2.07 e Å−3 |
4598 reflections | Δρmin = −1.14 e Å−3 |
130 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.4428 (2) | 0.35337 (18) | 0.81180 (10) | 0.0271 (4) | |
O2 | 0.5097 (2) | 0.53602 (18) | 0.85748 (10) | 0.0289 (4) | |
H2 | 0.5328 | 0.4903 | 0.8916 | 0.044 (11)* | |
C1 | 0.4560 (2) | 0.4669 (2) | 0.80775 (12) | 0.0200 (4) | |
C2 | 0.4148 (2) | 0.5420 (2) | 0.74305 (12) | 0.0190 (4) | |
H2A | 0.4858 | 0.6007 | 0.7303 | 0.024 (8)* | |
Br2 | 0.26550 (3) | 0.64147 (3) | 0.77267 (2) | 0.02812 (7) | |
C3 | 0.3835 (2) | 0.4638 (2) | 0.67757 (12) | 0.0221 (4) | |
H3A | 0.3411 | 0.5169 | 0.6413 | 0.022 (8)* | |
H3B | 0.3233 | 0.3963 | 0.6910 | 0.013 (7)* | |
C4 | 0.5050 (3) | 0.4068 (3) | 0.64587 (13) | 0.0241 (5) | |
H4A | 0.5692 | 0.4736 | 0.6380 | 0.030 (9)* | |
H4B | 0.5417 | 0.3462 | 0.6802 | 0.033 (9)* | |
C5 | 0.4780 (2) | 0.3408 (2) | 0.57527 (13) | 0.0212 (4) | |
H5A | 0.4112 | 0.2765 | 0.5831 | 0.034 (9)* | |
H5B | 0.4435 | 0.4024 | 0.5408 | 0.037 (10)* | |
C6 | 0.5957 (2) | 0.2790 (2) | 0.54304 (13) | 0.0204 (4) | |
H6A | 0.6299 | 0.2163 | 0.5778 | 0.029 (9)* | |
Br6 | 0.73130 (2) | 0.40137 (2) | 0.52174 (2) | 0.02402 (6) | |
C7 | 0.5646 (2) | 0.2132 (2) | 0.47354 (12) | 0.0204 (4) | |
O3 | 0.5852 (2) | 0.10197 (18) | 0.46621 (11) | 0.0296 (4) | |
O4 | 0.5102 (2) | 0.28358 (18) | 0.42491 (10) | 0.0300 (4) | |
H4 | 0.4863 | 0.2389 | 0.3905 | 0.053 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0382 (10) | 0.0244 (9) | 0.0188 (8) | −0.0048 (8) | −0.0049 (7) | 0.0012 (7) |
O2 | 0.0425 (11) | 0.0238 (9) | 0.0205 (8) | −0.0040 (8) | −0.0098 (8) | 0.0008 (7) |
C1 | 0.0205 (10) | 0.0243 (11) | 0.0152 (9) | 0.0001 (8) | 0.0009 (7) | 0.0002 (8) |
C2 | 0.0185 (9) | 0.0204 (10) | 0.0181 (10) | 0.0006 (8) | 0.0003 (7) | 0.0012 (8) |
Br2 | 0.02097 (11) | 0.03372 (14) | 0.02965 (13) | 0.00479 (10) | 0.00001 (10) | −0.00452 (10) |
C3 | 0.0233 (11) | 0.0270 (11) | 0.0159 (9) | −0.0003 (9) | −0.0012 (8) | 0.0008 (8) |
C4 | 0.0264 (11) | 0.0294 (12) | 0.0166 (9) | 0.0032 (9) | −0.0013 (8) | −0.0036 (9) |
C5 | 0.0226 (11) | 0.0239 (11) | 0.0171 (9) | 0.0003 (8) | −0.0008 (8) | −0.0005 (8) |
C6 | 0.0255 (11) | 0.0190 (10) | 0.0169 (9) | 0.0006 (8) | −0.0024 (8) | 0.0009 (8) |
Br6 | 0.02087 (10) | 0.02733 (12) | 0.02386 (11) | −0.00204 (9) | −0.00007 (9) | −0.00097 (9) |
C7 | 0.0218 (10) | 0.0228 (10) | 0.0165 (9) | −0.0007 (8) | −0.0008 (8) | 0.0014 (8) |
O3 | 0.0387 (11) | 0.0247 (9) | 0.0253 (9) | 0.0061 (8) | −0.0103 (8) | −0.0034 (7) |
O4 | 0.0493 (12) | 0.0215 (8) | 0.0193 (8) | 0.0027 (8) | −0.0100 (8) | −0.0001 (7) |
O1—C1 | 1.225 (3) | C4—H4A | 0.9900 |
O2—C1 | 1.314 (3) | C4—H4B | 0.9900 |
O2—H2 | 0.8400 | C5—C6 | 1.520 (3) |
C1—C2 | 1.516 (3) | C5—H5A | 0.9900 |
C2—C3 | 1.519 (3) | C5—H5B | 0.9900 |
C2—Br2 | 1.966 (2) | C6—C7 | 1.515 (3) |
C2—H2A | 1.0000 | C6—Br6 | 1.968 (2) |
C3—C4 | 1.526 (4) | C6—H6A | 1.0000 |
C3—H3A | 0.9900 | C7—O3 | 1.217 (3) |
C3—H3B | 0.9900 | C7—O4 | 1.310 (3) |
C4—C5 | 1.524 (3) | O4—H4 | 0.8400 |
C1—O2—H2 | 109.5 | C5—C4—H4B | 109.3 |
O1—C1—O2 | 124.2 (2) | C3—C4—H4B | 109.3 |
O1—C1—C2 | 122.9 (2) | H4A—C4—H4B | 108.0 |
O2—C1—C2 | 112.8 (2) | C6—C5—C4 | 113.3 (2) |
C1—C2—C3 | 114.4 (2) | C6—C5—H5A | 108.9 |
C1—C2—Br2 | 106.66 (16) | C4—C5—H5A | 108.9 |
C3—C2—Br2 | 110.85 (16) | C6—C5—H5B | 108.9 |
C1—C2—H2A | 108.2 | C4—C5—H5B | 108.9 |
C3—C2—H2A | 108.2 | H5A—C5—H5B | 107.7 |
Br2—C2—H2A | 108.2 | C7—C6—C5 | 111.7 (2) |
C2—C3—C4 | 110.8 (2) | C7—C6—Br6 | 106.84 (16) |
C2—C3—H3A | 109.5 | C5—C6—Br6 | 111.78 (16) |
C4—C3—H3A | 109.5 | C7—C6—H6A | 108.8 |
C2—C3—H3B | 109.5 | C5—C6—H6A | 108.8 |
C4—C3—H3B | 109.5 | Br6—C6—H6A | 108.8 |
H3A—C3—H3B | 108.1 | O3—C7—O4 | 124.1 (2) |
C5—C4—C3 | 111.6 (2) | O3—C7—C6 | 120.9 (2) |
C5—C4—H4A | 109.3 | O4—C7—C6 | 114.9 (2) |
C3—C4—H4A | 109.3 | C7—O4—H4 | 109.5 |
O1—C1—C2—C3 | −13.0 (3) | C3—C4—C5—C6 | −178.1 (2) |
O2—C1—C2—C3 | 165.5 (2) | C4—C5—C6—C7 | 179.3 (2) |
O1—C1—C2—Br2 | 109.9 (2) | C4—C5—C6—Br6 | −61.1 (2) |
O2—C1—C2—Br2 | −71.6 (2) | C5—C6—C7—O3 | −122.1 (3) |
C1—C2—C3—C4 | −70.5 (3) | Br6—C6—C7—O3 | 115.4 (2) |
Br2—C2—C3—C4 | 168.86 (17) | C5—C6—C7—O4 | 55.2 (3) |
C2—C3—C4—C5 | −173.3 (2) | Br6—C6—C7—O4 | −67.3 (2) |
D—H···A | D—H | H···A | D···A | 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+1/2, z+1/2; (ii) x, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | 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+1/2, z+1/2; (ii) x, −y+1/2, z−1/2. |
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) |
V (Å3) | 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) |
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 (Å−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, −1.14 |
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
Alvarez, S. (2013). Dalton Trans. 42, 8617–8636. Web of Science CrossRef CAS PubMed Google Scholar
Bruker (2010). APEX2, SAINT and XSHELL. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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. Web of Science CrossRef Google Scholar
Fehnel, E. A. & Oppenlander, G. C. (1953). J. Am. Chem. Soc. 75, 4660–4663. CrossRef CAS Web of Science Google Scholar
Hamon, C., Schwarz, J., Becker, W., Kienle, S., Kuhn, K. & Schäfer, J. (2007). Int. Patent Appl. WO2007012849. Google Scholar
Kiessling, A. & Zeller, M. (2011). Acta Cryst. E67, o733–o734. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lingens, F. (1960). Z. Naturforsch. Teil B, 15, 811–811. Google Scholar
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. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Mantina, M., Chamberlin, A. C., Valero, R., Cramer, C. J. & Truhlar, D. G. (2009). J. Phys. Chem. A, 113, 5806–5812. Web of Science CrossRef PubMed CAS Google Scholar
Mitchell, C. A., Yu, L. & Ward, M. D. (2001). J. Am. Chem. Soc. 123, 10830–10839. Web of Science CSD CrossRef PubMed CAS Google Scholar
Miyake, Y., Takada, H., Ohe, K. & Uemura, S. (2000). J. Chem. Soc. Perkin Trans. 1, pp. 1595–1599. Web of Science CrossRef Google Scholar
Peppel, T., Sonneck, M., Spannenberg, A. & Wohlrab, S. (2015a). Acta Cryst. E71, o316. CSD CrossRef IUCr Journals Google Scholar
Peppel, T., Sonneck, M., Spannenberg, A. & Wohlrab, S. (2015b). Acta Cryst. E71, o323. CSD CrossRef IUCr Journals Google Scholar
Peters, D., Timmermann, D. B., Olsen, G. M., Nielsen, E. O. & Jørgensen, T. D. (2006). Int. Patent Appl. WO2006087306. Google Scholar
Schotte, L. (1956a). Ark. Kemi, 9, 407–412. CAS Google Scholar
Schotte, L. (1956b). Ark. Kemi, 9, 413–421. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sonneck, M., Peppel, T., Spannenberg, A. & Wohlrab, S. (2015a). Acta Cryst. E71, o426–o427. CSD CrossRef IUCr Journals Google Scholar
Sonneck, M., Peppel, T., Spannenberg, A. & Wohlrab, S. (2015b). Acta Cryst. E71, o528–o529. CSD CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Thalladi, V. R., Nüsse, M. & Boese, R. (2000). J. Am. Chem. Soc. 122, 9227–9236. Web of Science CSD CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yuan, B. & Lu, S. (2009). Chin. Patent Appl. CN101497626. Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.