Acta Cryst. (2007). E63, m2483 [ doi:10.1107/S1600536807043140 ]
In the title compound, C6H6AsBrO3, the As-O bond lengths are normal. Intermolecular O-H
O hydrogen bonds with OO distances of 2.600 (2) and 2.627 (2) Å link the molecules into two-dimensional layers parallel to bc plane.
The title compound was prepared according to standard procedures upon alkaline coupling of sodium arsenite with para-diazo bromobenzene in alkaline media and subsequent acidic workup (Bart, 1922). Crystals suitable for X-ray analysis were obtained upon recrystallization of the crude reaction product from boiling water.
All H atoms were located in a difference map and refined as riding on their parent atoms, with one common isotropic displacement parameter refined to Uiso(H) = 0.037 (3) Å2.
Data collection: COLLECT (Nonius, 2004); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (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).
![[Figure 1]](./cv2298fig1thm.gif)
| Fig. 1. The molecular structure of (I), with atom labels and displacement ellipsoids drawn at the 70% probability level. |
![[Figure 2]](./cv2298fig2thm.gif)
| Fig. 2. The separation of hydrophilic (arsonic-acid functions) and hydrophobic (bromophenyl residues) blocks (view along [0 1 0], 50% ellipsoid probability). |
![[Figure 3]](./cv2298fig3thm.gif)
| Fig. 3. The molecular packing in a hydrophilic sheet in the (100) plane of (I) (50% ellipsoid probability). Colour codes: pink As, brown Br, red O. The colours attributed to the hydrogen bonds are explained in the text. |
| C6H6AsBrO3 | F000 = 536 |
| Mr = 280.94 | Dx = 2.326 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 8505 reflections |
| a = 9.6435 (3) Å | θ = 3.1–27.5º |
| b = 9.1107 (3) Å | µ = 9.17 mm−1 |
| c = 10.2872 (3) Å | T = 200 (2) K |
| β = 117.429 (2)º | Platelet, colourless |
| V = 802.22 (4) Å3 | 0.10 × 0.09 × 0.03 mm |
| Z = 4 |
| KappaCCD diffractometer | 1838 independent reflections |
| Radiation source: rotating anode | 1603 reflections with I > 2σ(I) |
| Monochromator: MONTEL, graded multilayered X-ray optics | Rint = 0.028 |
| T = 200(2) K | θmax = 27.5º |
| CCD; rotation images; thick slices scans | θmin = 3.2º |
| Absorption correction: multi-scan (Otwinowski & Minor, 1997) | h = −12→11 |
| Tmin = 0.388, Tmax = 0.759 | k = −11→11 |
| 12919 measured reflections | l = −13→13 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.022 | Only H-atom displacement parameters refined |
| wR(F2) = 0.049 | w = 1/[σ2(Fo2) + (0.0525P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.06 | (Δ/σ)max = 0.001 |
| 1838 reflections | Δρmax = 0.47 e Å−3 |
| 104 parameters | Δρmin = −0.40 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C6H6AsBrO3 | V = 802.22 (4) Å3 |
| Mr = 280.94 | Z = 4 |
| Monoclinic, P21/c | Mo Kα |
| a = 9.6435 (3) Å | µ = 9.17 mm−1 |
| b = 9.1107 (3) Å | T = 200 (2) K |
| c = 10.2872 (3) Å | 0.10 × 0.09 × 0.03 mm |
| β = 117.429 (2)º |
| KappaCCD diffractometer | 1838 independent reflections |
| Absorption correction: multi-scan (Otwinowski & Minor, 1997) | 1603 reflections with I > 2σ(I) |
| Tmin = 0.388, Tmax = 0.759 | Rint = 0.028 |
| 12919 measured reflections |
| R[F2 > 2σ(F2)] = 0.022 | 104 parameters |
| wR(F2) = 0.049 | Only H-atom displacement parameters refined |
| S = 1.06 | Δρmax = 0.47 e Å−3 |
| 1838 reflections | Δρmin = −0.40 e Å−3 |
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 > 2sigma(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. |
| x | y | z | Uiso*/Ueq | ||
| Br | 0.63333 (3) | 0.41380 (3) | 0.87179 (3) | 0.03591 (10) | |
| As | 0.04233 (3) | 0.41520 (2) | 0.21560 (2) | 0.01942 (9) | |
| O1 | −0.01715 (19) | 0.58148 (16) | 0.14968 (16) | 0.0246 (3) | |
| O2 | 0.0899 (2) | 0.30778 (17) | 0.10672 (17) | 0.0297 (4) | |
| H82 | 0.0680 | 0.3521 | 0.0280 | 0.037 (3)* | |
| O3 | −0.11214 (19) | 0.33032 (18) | 0.22333 (18) | 0.0281 (4) | |
| H83 | −0.0841 | 0.2474 | 0.2624 | 0.037 (3)* | |
| C1 | 0.2162 (3) | 0.4138 (2) | 0.4049 (2) | 0.0205 (4) | |
| C2 | 0.2096 (3) | 0.5001 (3) | 0.5130 (2) | 0.0256 (5) | |
| H2 | 0.1207 | 0.5595 | 0.4914 | 0.037 (3)* | |
| C3 | 0.3341 (3) | 0.4986 (3) | 0.6529 (2) | 0.0268 (5) | |
| H3 | 0.3311 | 0.5556 | 0.7289 | 0.037 (3)* | |
| C4 | 0.4626 (3) | 0.4130 (2) | 0.6799 (2) | 0.0242 (5) | |
| C5 | 0.4712 (3) | 0.3275 (3) | 0.5733 (3) | 0.0292 (5) | |
| H5 | 0.5614 | 0.2699 | 0.5950 | 0.037 (3)* | |
| C6 | 0.3459 (3) | 0.3272 (3) | 0.4339 (3) | 0.0274 (5) | |
| H6 | 0.3486 | 0.2684 | 0.3588 | 0.037 (3)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br | 0.02573 (15) | 0.04840 (18) | 0.02244 (14) | −0.00390 (11) | 0.00156 (11) | 0.00221 (10) |
| As | 0.02334 (14) | 0.01677 (13) | 0.01538 (13) | 0.00266 (9) | 0.00654 (10) | 0.00137 (8) |
| O1 | 0.0337 (9) | 0.0173 (8) | 0.0195 (7) | 0.0058 (7) | 0.0094 (7) | 0.0027 (6) |
| O2 | 0.0464 (11) | 0.0216 (8) | 0.0222 (8) | 0.0109 (7) | 0.0166 (8) | 0.0035 (6) |
| O3 | 0.0256 (8) | 0.0257 (9) | 0.0292 (9) | 0.0009 (7) | 0.0093 (7) | 0.0045 (7) |
| C1 | 0.0216 (11) | 0.0201 (11) | 0.0168 (10) | −0.0001 (9) | 0.0063 (9) | 0.0025 (8) |
| C2 | 0.0234 (12) | 0.0277 (13) | 0.0249 (11) | 0.0017 (10) | 0.0104 (10) | −0.0006 (9) |
| C3 | 0.0278 (12) | 0.0289 (12) | 0.0219 (11) | −0.0037 (10) | 0.0101 (10) | −0.0044 (9) |
| C4 | 0.0228 (12) | 0.0265 (12) | 0.0184 (10) | −0.0043 (9) | 0.0052 (9) | 0.0040 (9) |
| C5 | 0.0259 (12) | 0.0317 (13) | 0.0256 (12) | 0.0078 (10) | 0.0082 (10) | 0.0045 (10) |
| C6 | 0.0302 (12) | 0.0273 (12) | 0.0234 (11) | 0.0062 (10) | 0.0111 (10) | 0.0008 (9) |
| Br—C4 | 1.901 (2) | C2—C3 | 1.386 (3) |
| As—O1 | 1.6509 (14) | C2—H2 | 0.9500 |
| As—O2 | 1.7016 (15) | C3—C4 | 1.380 (3) |
| As—O3 | 1.7125 (16) | C3—H3 | 0.9500 |
| As—C1 | 1.896 (2) | C4—C5 | 1.378 (3) |
| O2—H82 | 0.8400 | C5—C6 | 1.386 (3) |
| O3—H83 | 0.8400 | C5—H5 | 0.9500 |
| C1—C2 | 1.387 (3) | C6—H6 | 0.9500 |
| C1—C6 | 1.390 (3) | ||
| O1—As—O2 | 113.91 (8) | C1—C2—H2 | 120.4 |
| O1—As—O3 | 106.76 (8) | C4—C3—C2 | 118.8 (2) |
| O2—As—O3 | 105.95 (8) | C4—C3—H3 | 120.6 |
| O1—As—C1 | 113.80 (8) | C2—C3—H3 | 120.6 |
| O2—As—C1 | 107.06 (9) | C5—C4—C3 | 122.5 (2) |
| O3—As—C1 | 109.01 (8) | C5—C4—Br | 119.18 (18) |
| As—O2—H82 | 109.5 | C3—C4—Br | 118.33 (17) |
| As—O3—H83 | 109.5 | C4—C5—C6 | 118.7 (2) |
| C2—C1—C6 | 121.3 (2) | C4—C5—H5 | 120.6 |
| C2—C1—As | 118.31 (16) | C6—C5—H5 | 120.6 |
| C6—C1—As | 120.43 (16) | C5—C6—C1 | 119.4 (2) |
| C3—C2—C1 | 119.3 (2) | C5—C6—H6 | 120.3 |
| C3—C2—H2 | 120.4 | C1—C6—H6 | 120.3 |
| O1—As—C1—C2 | 50.0 (2) | C1—C2—C3—C4 | 1.1 (3) |
| O2—As—C1—C2 | 176.79 (17) | C2—C3—C4—C5 | −0.7 (4) |
| O3—As—C1—C2 | −69.02 (19) | C2—C3—C4—Br | 179.35 (17) |
| O1—As—C1—C6 | −130.51 (18) | C3—C4—C5—C6 | −0.2 (4) |
| O2—As—C1—C6 | −3.7 (2) | Br—C4—C5—C6 | 179.75 (18) |
| O3—As—C1—C6 | 110.45 (19) | C4—C5—C6—C1 | 0.7 (4) |
| C6—C1—C2—C3 | −0.7 (3) | C2—C1—C6—C5 | −0.2 (4) |
| As—C1—C2—C3 | 178.80 (17) | As—C1—C6—C5 | −179.69 (18) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H82···O1i | 0.84 | 1.77 | 2.600 (2) | 171 |
| O3—H83···O1ii | 0.84 | 1.80 | 2.627 (2) | 167 |
| Symmetry codes: (i) −x, −y+1, −z; (ii) −x, y−1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H82···O1i | 0.84 | 1.77 | 2.600 (2) | 171 |
| O3—H83···O1ii | 0.84 | 1.80 | 2.627 (2) | 167 |
| Symmetry codes: (i) −x, −y+1, −z; (ii) −x, y−1/2, −z+1/2. |
Bart, H. (1922). Liebigs Ann. Chem. 429, 55–103.
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.
Jeffrey, G. A. & Saenger, W. (1991). Hydrogen Bonding in Biological Structures, p. 34. Berlin, Heidelberg: Springer-Verlag.
Lee, A. van der, Richez, P. & Tapiero, C. (2005). J. Mol. Struct. 743, 223–228.
Nonius (2004). COLLECT. Nonius BV, Delft, The Netherlands.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
The title compound, C6H6AsBrO3, was prepared as a starting material for attempted condensation reactions with diols.
The intramolecular atomic distances in the title compound, (I) (Fig. 1), are in the expected range (cf. van der Lee et al., 2005, for para-nitrophenylarsonic acid). In particular, the bond length of the arsenic atom to the formally double-bonded oxygen atom is about 0.05 Å shorter than the bond lengths to the hydroxyl-O atoms.
The hydrophobic bromophenyl moieties and the hydrophilic arsonic-acid functions are separated in the crystal structure. Hydrophobic and hydrophilic sheets alternate along [100] (Fig. 2). A characteristic hydrogen-bond system is established in the hydrophilic sheets (Fig. 3). There are two kinds of hydrogen bonds. A pair of bonds of the first kind combine pairs of arsonic-acid molecules to dimers (the yellow bonds in Fig. 3) – a bonding motif well known from carbonic acids (Jeffrey & Saenger, 1991). One hydroxy-donor site and one of two acceptor sites of the terminally bonded oxygen atom are spent for these bonds. A second acceptor site at the same oxygen atom and the second hydroxy function connect the dimers to a two-dimensional network in the (100) plane (the green bonds in Fig. 3). Infinite cooperativity may be attributed to the latter hydrogen bonds since chains of alternating O–H and O–As vectors are running along the [010] direction. Accordingly, the As–OH bonds in the infinite chains are slightly longer than those in the dimers.