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In the title compound, C6H6AsBrO3, the As—O bond lengths are normal. Inter­molecular O—H...O hydrogen bonds with O...O distances of 2.600 (2) and 2.627 (2) Å link the mol­ecules into two-dimensional layers parallel to bc plane.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807043140/cv2298sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807043140/cv2298Isup2.hkl
Contains datablock I

CCDC reference: 663567

Key indicators

  • Single-crystal X-ray study
  • T = 200 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.022
  • wR factor = 0.049
  • Data-to-parameter ratio = 17.7

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ?
Author Response: checked, values determined correctly
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)         30 Ang.
Author Response: checked, values determined correctly

0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

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.

Related literature top

An example containing an electron-withdrawing substituent in the para position to the arsonic acid group is para-nitrophenylarsonic acid (van der Lee et al., 2005). For details of synthesis and hydrogen-bonding motifs, see: Bart (1922) and Jeffrey & Saenger (1991), respectively.

Experimental top

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.

Refinement top

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.

Structure description top

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.

An example containing an electron-withdrawing substituent in the para position to the arsonic acid group is para-nitrophenylarsonic acid (van der Lee et al., 2005). For details of synthesis and hydrogen-bonding motifs, see: Bart (1922) and Jeffrey & Saenger (1991), respectively.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and displacement ellipsoids drawn at the 70% probability level.
[Figure 2] Fig. 2. The separation of hydrophilic (arsonic-acid functions) and hydrophobic (bromophenyl residues) blocks (view along [0 1 0], 50% ellipsoid probability).
[Figure 3] 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.
(4-Bromophenyl)arsonic acid top
Crystal data top
C6H6AsBrO3F(000) = 536
Mr = 280.94Dx = 2.326 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8505 reflections
a = 9.6435 (3) Åθ = 3.1–27.5°
b = 9.1107 (3) ŵ = 9.17 mm1
c = 10.2872 (3) ÅT = 200 K
β = 117.429 (2)°Platelet, colourless
V = 802.22 (4) Å30.10 × 0.09 × 0.03 mm
Z = 4
Data collection top
KappaCCD
diffractometer
1838 independent reflections
Radiation source: rotating anode1603 reflections with I > 2σ(I)
MONTEL, graded multilayered X-ray optics monochromatorRint = 0.028
CCD; rotation images; thick slices scansθmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan
(Otwinowski & Minor, 1997)
h = 1211
Tmin = 0.388, Tmax = 0.759k = 1111
12919 measured reflectionsl = 1313
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)] = 0.022Hydrogen site location: difference Fourier map
wR(F2) = 0.049Only H-atom displacement parameters refined
S = 1.06 w = 1/[σ2(Fo2) + (0.0525P)2]
where P = (Fo2 + 2Fc2)/3
1838 reflections(Δ/σ)max = 0.001
104 parametersΔρmax = 0.47 e Å3
0 restraintsΔρmin = 0.40 e Å3
Crystal data top
C6H6AsBrO3V = 802.22 (4) Å3
Mr = 280.94Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.6435 (3) ŵ = 9.17 mm1
b = 9.1107 (3) ÅT = 200 K
c = 10.2872 (3) Å0.10 × 0.09 × 0.03 mm
β = 117.429 (2)°
Data collection top
KappaCCD
diffractometer
1838 independent reflections
Absorption correction: multi-scan
(Otwinowski & Minor, 1997)
1603 reflections with I > 2σ(I)
Tmin = 0.388, Tmax = 0.759Rint = 0.028
12919 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0220 restraints
wR(F2) = 0.049Only H-atom displacement parameters refined
S = 1.06Δρmax = 0.47 e Å3
1838 reflectionsΔρmin = 0.40 e Å3
104 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
Br0.63333 (3)0.41380 (3)0.87179 (3)0.03591 (10)
As0.04233 (3)0.41520 (2)0.21560 (2)0.01942 (9)
O10.01715 (19)0.58148 (16)0.14968 (16)0.0246 (3)
O20.0899 (2)0.30778 (17)0.10672 (17)0.0297 (4)
H820.06800.35210.02800.037 (3)*
O30.11214 (19)0.33032 (18)0.22333 (18)0.0281 (4)
H830.08410.24740.26240.037 (3)*
C10.2162 (3)0.4138 (2)0.4049 (2)0.0205 (4)
C20.2096 (3)0.5001 (3)0.5130 (2)0.0256 (5)
H20.12070.55950.49140.037 (3)*
C30.3341 (3)0.4986 (3)0.6529 (2)0.0268 (5)
H30.33110.55560.72890.037 (3)*
C40.4626 (3)0.4130 (2)0.6799 (2)0.0242 (5)
C50.4712 (3)0.3275 (3)0.5733 (3)0.0292 (5)
H50.56140.26990.59500.037 (3)*
C60.3459 (3)0.3272 (3)0.4339 (3)0.0274 (5)
H60.34860.26840.35880.037 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br0.02573 (15)0.04840 (18)0.02244 (14)0.00390 (11)0.00156 (11)0.00221 (10)
As0.02334 (14)0.01677 (13)0.01538 (13)0.00266 (9)0.00654 (10)0.00137 (8)
O10.0337 (9)0.0173 (8)0.0195 (7)0.0058 (7)0.0094 (7)0.0027 (6)
O20.0464 (11)0.0216 (8)0.0222 (8)0.0109 (7)0.0166 (8)0.0035 (6)
O30.0256 (8)0.0257 (9)0.0292 (9)0.0009 (7)0.0093 (7)0.0045 (7)
C10.0216 (11)0.0201 (11)0.0168 (10)0.0001 (9)0.0063 (9)0.0025 (8)
C20.0234 (12)0.0277 (13)0.0249 (11)0.0017 (10)0.0104 (10)0.0006 (9)
C30.0278 (12)0.0289 (12)0.0219 (11)0.0037 (10)0.0101 (10)0.0044 (9)
C40.0228 (12)0.0265 (12)0.0184 (10)0.0043 (9)0.0052 (9)0.0040 (9)
C50.0259 (12)0.0317 (13)0.0256 (12)0.0078 (10)0.0082 (10)0.0045 (10)
C60.0302 (12)0.0273 (12)0.0234 (11)0.0062 (10)0.0111 (10)0.0008 (9)
Geometric parameters (Å, º) top
Br—C41.901 (2)C2—C31.386 (3)
As—O11.6509 (14)C2—H20.9500
As—O21.7016 (15)C3—C41.380 (3)
As—O31.7125 (16)C3—H30.9500
As—C11.896 (2)C4—C51.378 (3)
O2—H820.8400C5—C61.386 (3)
O3—H830.8400C5—H50.9500
C1—C21.387 (3)C6—H60.9500
C1—C61.390 (3)
O1—As—O2113.91 (8)C1—C2—H2120.4
O1—As—O3106.76 (8)C4—C3—C2118.8 (2)
O2—As—O3105.95 (8)C4—C3—H3120.6
O1—As—C1113.80 (8)C2—C3—H3120.6
O2—As—C1107.06 (9)C5—C4—C3122.5 (2)
O3—As—C1109.01 (8)C5—C4—Br119.18 (18)
As—O2—H82109.5C3—C4—Br118.33 (17)
As—O3—H83109.5C4—C5—C6118.7 (2)
C2—C1—C6121.3 (2)C4—C5—H5120.6
C2—C1—As118.31 (16)C6—C5—H5120.6
C6—C1—As120.43 (16)C5—C6—C1119.4 (2)
C3—C2—C1119.3 (2)C5—C6—H6120.3
C3—C2—H2120.4C1—C6—H6120.3
O1—As—C1—C250.0 (2)C1—C2—C3—C41.1 (3)
O2—As—C1—C2176.79 (17)C2—C3—C4—C50.7 (4)
O3—As—C1—C269.02 (19)C2—C3—C4—Br179.35 (17)
O1—As—C1—C6130.51 (18)C3—C4—C5—C60.2 (4)
O2—As—C1—C63.7 (2)Br—C4—C5—C6179.75 (18)
O3—As—C1—C6110.45 (19)C4—C5—C6—C10.7 (4)
C6—C1—C2—C30.7 (3)C2—C1—C6—C50.2 (4)
As—C1—C2—C3178.80 (17)As—C1—C6—C5179.69 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H82···O1i0.841.772.600 (2)171
O3—H83···O1ii0.841.802.627 (2)167
Symmetry codes: (i) x, y+1, z; (ii) x, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC6H6AsBrO3
Mr280.94
Crystal system, space groupMonoclinic, P21/c
Temperature (K)200
a, b, c (Å)9.6435 (3), 9.1107 (3), 10.2872 (3)
β (°) 117.429 (2)
V3)802.22 (4)
Z4
Radiation typeMo Kα
µ (mm1)9.17
Crystal size (mm)0.10 × 0.09 × 0.03
Data collection
DiffractometerKappaCCD
Absorption correctionMulti-scan
(Otwinowski & Minor, 1997)
Tmin, Tmax0.388, 0.759
No. of measured, independent and
observed [I > 2σ(I)] reflections
12919, 1838, 1603
Rint0.028
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.022, 0.049, 1.06
No. of reflections1838
No. of parameters104
H-atom treatmentOnly H-atom displacement parameters refined
Δρmax, Δρmin (e Å3)0.47, 0.40

Computer programs: COLLECT (Nonius, 2004), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H82···O1i0.841.772.600 (2)171.2
O3—H83···O1ii0.841.802.627 (2)167.4
Symmetry codes: (i) x, y+1, z; (ii) x, y1/2, z+1/2.
 

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