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In the crystal structure of the title compound, (NH4)[AsO2(OH)(C6H4NO2)], the 4-nitro­phenyl­arsonate anions and ammonium cations are linked through hydrogen bonds to form infinite chains along the b axis. The hydroxyl O atom of the 4-nitro­phenyl­arsonate anion acts as both an acceptor and a donor of hydrogen bonds. All atoms are located in general positions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102020462/de1196sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102020462/de1196Isup2.hkl
Contains datablock I

CCDC reference: 201267

Comment top

The realm of phosphonate chemistry has developed rapidly and many new compounds have been prepared and characterized, due to interest in their potential applications in the areas of sorption and ion exchange (Wang et al., 1993), sensors (Cao et al., 1992; Alberti & Polombari, 1989), nonlinear optics (Thompson, 1994; Ungashe et al., 1992) and catalysis (Wan et al., 1986). In contrast, arsonate chemistry has received only limited attention. To our knowledge, few studies have been undertaken of the synthesis and characterization of metal arsonates with the goal of preparing functional compounds analogous to the reported metal phosphonates (Huan et al., 1990; Morizzi et al., 2000). In this context, the synthesis and structure of the title compound, (I), are presented here. \sch

The structure of (I) is shown in Fig. 1, and selected bond lengths and angles are given in Table 1. The arsonate anion contains an As atom tetrahedrally connected to one C atom of the benzene ring and three O atoms (Nuttall & Hunter, 1996; Percino et al., 2001). The As—O bond lengths range from 1.655 (3) to 1.732 (2) Å and the O—As—O angles vary from 108.8 (1) to 116.6 (1)°. The As—O5 (hydroxyl) bond is longer than the other two As—O bonds. The As—C distance of 1.93 Å is near to that reported (1.95 Å) in the 4-aminobenzenearsonic acid complex (Shimada, 1961). The phenyl ring and nitro group are not coplanar, with a dihedral angle of 6.4°.

The molecules of (I) are held together by an infinite chain of hydrogen bonds along the b axis (Fig. 2). The hydrogen bonds in this study have been considered with a liberal distance cut-off criterion of 2.5 < D···A < 3.0 Å and an angle cut-off criterion of 120 < D—H···A < 180°. Hydrogen-bond distances and angles are listed in Table 2.

From Fig. 2 it can be seen that there are five H atoms available for hydrogen bonding in the asymmetric unit. One of these comes from the arsonate hydroxyl group and the remaining four come from the ammonium cation. There are three hydrogen bonds between the ammonium cation and O atoms from three different symmetry-related 4-nitrophenylarsonate anions. In dicyclohexylammonium arsonomethylphosphonate, the N atoms of the cation and O atoms of the anion are also involved in hydrogen bonding (Falvello et al., 1977). There is another hydrogen bond between the arsonate hydroxyl group and an arsonate O atom from another arsonate anion.

A comparison of this structure with that of benezenearsonic acid (Shimada, 1959) is interesting. The two structures are closely similar in having endless chains formed by the hydrogen bonds. However, in 4-aminobenzenearsonic acid, there are additional hydrogen bonds to connect these chains to form a beautiful network (Shimada, 1961).

In summary, the 4-nitrophenylarsonate anions and ammonium cations of (I) are linked through hydrogen bonds to form infinite chains along the b axis. The hydroxyl O atom of the 4-nitrophenylarsonate anion acts as both acceptor and donor in the hydrogen bonds, and the N atom of the ammonium cation plays only the role of donor.

Table 2. Short O—H···O and N—H···O contacts (Å, °)

Experimental top

An aqueous solution of ammonia was added to an aqueous solution of 4-nitrophenylarsonic acid until pH 6.5 was reached. Pale-yellow needle crystals of (I) were obtained after evaporating the solution at room temperature for several weeks. Analysis calculated for C6H9AsN2O5: C 27.27, H 3.41%; found: C 27.41, H 3.26%. IR data (KBr, ν, cm-1): 2814 (O—H), 1524 and 1349 (NO2), 1089 (As—C), 1087 (AsO).

Refinement top

All H atoms on C atoms were generated geometrically and refined as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The H atoms of the ammonium cation were located in the difference Fourier map and refined freely. The H atom of the hydroxyl group was generated theoretically and refined as a riding atom, with O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O).

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990).

Figures top
[Figure 1] Fig. 1. A view of the cation and anion of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The infinite chains of (I) linked by hydrogen bonds along the b axis.
Ammonium 4-nitrophenylarsonate top
Crystal data top
(NH4)[AsO2(OH)(C6H4NO2)]F(000) = 528
Mr = 264.07Dx = 1.913 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 24 reflections
a = 11.670 (3) Åθ = 4.7–8.9°
b = 6.5073 (16) ŵ = 3.71 mm1
c = 12.693 (3) ÅT = 293 K
β = 107.975 (18)°Prism, pale yellow
V = 916.9 (4) Å30.52 × 0.36 × 0.23 mm
Z = 4
Data collection top
Siemens P4
diffractometer
1285 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.036
Graphite monochromatorθmax = 25.0°, θmin = 2.1°
ω scansh = 113
Absorption correction: ψ scan
(North et al., 1968)
k = 17
Tmin = 0.223, Tmax = 0.426l = 1514
2283 measured reflections3 standard reflections every 97 reflections
1602 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.077 w = 1/[σ2(Fo2) + (0.0412P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.98(Δ/σ)max < 0.001
1602 reflectionsΔρmax = 0.49 e Å3
144 parametersΔρmin = 0.57 e Å3
2 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0271 (17)
Crystal data top
(NH4)[AsO2(OH)(C6H4NO2)]V = 916.9 (4) Å3
Mr = 264.07Z = 4
Monoclinic, P21/nMo Kα radiation
a = 11.670 (3) ŵ = 3.71 mm1
b = 6.5073 (16) ÅT = 293 K
c = 12.693 (3) Å0.52 × 0.36 × 0.23 mm
β = 107.975 (18)°
Data collection top
Siemens P4
diffractometer
1285 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.036
Tmin = 0.223, Tmax = 0.4263 standard reflections every 97 reflections
2283 measured reflections intensity decay: none
1602 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0302 restraints
wR(F2) = 0.077H atoms treated by a mixture of independent and constrained refinement
S = 0.98Δρmax = 0.49 e Å3
1602 reflectionsΔρmin = 0.57 e Å3
144 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
As0.32227 (3)0.07896 (6)0.49177 (3)0.02143 (18)
O10.0982 (3)0.5224 (5)0.6879 (3)0.0445 (8)
O20.0302 (3)0.7704 (5)0.7164 (2)0.0420 (7)
O30.4218 (2)0.2402 (4)0.4657 (2)0.0323 (6)
O40.2365 (2)0.0536 (4)0.3853 (2)0.0331 (7)
O50.3985 (2)0.0896 (4)0.5953 (2)0.0317 (6)
H50.44090.16590.57180.048*
N10.0025 (3)0.5946 (5)0.6866 (2)0.0298 (7)
N20.3531 (3)0.5938 (6)0.3338 (3)0.0291 (7)
C10.2247 (3)0.2361 (6)0.5608 (3)0.0215 (7)
C20.1221 (3)0.1489 (6)0.5766 (3)0.0285 (9)
H20.10360.01200.55790.034*
C30.0481 (3)0.2631 (6)0.6194 (3)0.0289 (9)
H30.02040.20580.63040.035*
C40.0787 (3)0.4661 (6)0.6457 (3)0.0243 (8)
C50.1815 (3)0.5542 (6)0.6344 (3)0.0268 (8)
H5A0.20100.68960.65590.032*
C60.2549 (3)0.4394 (6)0.5908 (3)0.0251 (8)
H60.32410.49700.58150.030*
H120.316 (4)0.552 (8)0.268 (2)0.073 (19)*
H130.307 (4)0.697 (7)0.354 (3)0.031 (11)*
H110.374 (4)0.480 (7)0.379 (3)0.034 (12)*
H140.425 (2)0.640 (7)0.347 (4)0.058 (16)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
As0.0243 (2)0.0171 (2)0.0265 (2)0.00235 (18)0.01314 (15)0.00002 (18)
O10.0293 (15)0.049 (2)0.063 (2)0.0015 (15)0.0256 (15)0.0152 (16)
O20.0451 (16)0.0299 (17)0.0595 (17)0.0037 (15)0.0284 (15)0.0122 (15)
O30.0312 (14)0.0222 (14)0.0514 (15)0.0048 (13)0.0244 (12)0.0058 (13)
O40.0372 (15)0.0325 (17)0.0294 (13)0.0024 (14)0.0100 (12)0.0087 (12)
O50.0364 (14)0.0306 (15)0.0320 (13)0.0110 (14)0.0160 (12)0.0070 (13)
N10.0286 (17)0.0347 (19)0.0274 (15)0.0070 (17)0.0105 (13)0.0042 (16)
N20.0296 (18)0.0246 (19)0.0354 (19)0.0003 (18)0.0134 (16)0.0023 (18)
C10.0217 (17)0.0209 (19)0.0233 (16)0.0033 (17)0.0090 (14)0.0013 (16)
C20.030 (2)0.0177 (18)0.039 (2)0.0035 (17)0.0130 (17)0.0023 (17)
C30.0280 (19)0.030 (2)0.0328 (18)0.0052 (19)0.0161 (16)0.0019 (19)
C40.0250 (19)0.026 (2)0.0232 (17)0.0055 (17)0.0095 (15)0.0002 (15)
C50.0299 (19)0.019 (2)0.0317 (19)0.0016 (18)0.0102 (16)0.0028 (17)
C60.0231 (18)0.021 (2)0.0330 (19)0.0019 (18)0.0116 (16)0.0033 (17)
Geometric parameters (Å, º) top
As—O41.655 (3)N2—H140.86 (2)
As—O31.673 (3)C1—C61.392 (5)
As—O51.732 (2)C1—C21.395 (5)
As—C11.930 (3)C2—C31.372 (5)
O1—N11.216 (4)C2—H20.9300
O2—N11.229 (4)C3—C41.382 (5)
O5—H50.8200C3—H30.9300
N1—C41.472 (5)C4—C51.377 (5)
N2—H120.86 (2)C5—C61.375 (5)
N2—H130.94 (4)C5—H5A0.9300
N2—H110.92 (4)C6—H60.9300
O4—As—O3116.59 (13)C6—C1—As119.6 (3)
O4—As—O5109.22 (14)C2—C1—As120.2 (3)
O3—As—O5108.79 (13)C3—C2—C1120.7 (4)
O4—As—C1110.75 (14)C3—C2—H2119.6
O3—As—C1107.48 (15)C1—C2—H2119.6
O5—As—C1103.16 (13)C2—C3—C4117.8 (3)
As—O5—H5109.5C2—C3—H3121.1
O1—N1—O2123.6 (3)C4—C3—H3121.1
O1—N1—C4118.6 (3)C5—C4—C3122.8 (3)
O2—N1—C4117.8 (3)C5—C4—N1118.4 (3)
H12—N2—H13110 (4)C3—C4—N1118.8 (3)
H12—N2—H11108 (4)C6—C5—C4119.2 (3)
H13—N2—H11118 (4)C6—C5—H5A120.4
H12—N2—H14118 (5)C4—C5—H5A120.4
H13—N2—H14108 (4)C5—C6—C1119.4 (3)
H11—N2—H1496 (4)C5—C6—H6120.3
C6—C1—C2120.2 (3)C1—C6—H6120.3
O4—As—C1—C6135.8 (3)C2—C3—C4—N1177.0 (3)
O3—As—C1—C67.4 (3)O1—N1—C4—C5173.9 (3)
O5—As—C1—C6107.5 (3)O2—N1—C4—C55.3 (5)
O4—As—C1—C241.8 (3)O1—N1—C4—C35.5 (5)
O3—As—C1—C2170.2 (3)O2—N1—C4—C3175.3 (3)
O5—As—C1—C275.0 (3)C3—C4—C5—C62.8 (6)
C6—C1—C2—C31.5 (5)N1—C4—C5—C6176.6 (3)
As—C1—C2—C3176.0 (3)C4—C5—C6—C11.0 (5)
C1—C2—C3—C40.2 (5)C2—C1—C6—C51.1 (5)
C2—C3—C4—C52.4 (6)As—C1—C6—C5176.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H11···O30.92 (4)1.89 (4)2.813 (4)176 (3)
N2—H12···O4i0.86 (3)1.97 (3)2.819 (3)169 (su)
N2—H13···O4ii0.94 (5)1.92 (5)2.844 (4)168 (su)
O5—H5···O3iii0.821.872.638 (4)156
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x, y+1, z; (iii) x+1, y, z+1.

Experimental details

Crystal data
Chemical formula(NH4)[AsO2(OH)(C6H4NO2)]
Mr264.07
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)11.670 (3), 6.5073 (16), 12.693 (3)
β (°) 107.975 (18)
V3)916.9 (4)
Z4
Radiation typeMo Kα
µ (mm1)3.71
Crystal size (mm)0.52 × 0.36 × 0.23
Data collection
DiffractometerSiemens P4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.223, 0.426
No. of measured, independent and
observed [I > 2σ(I)] reflections
2283, 1602, 1285
Rint0.036
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.077, 0.98
No. of reflections1602
No. of parameters144
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.49, 0.57

Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1990).

Selected geometric parameters (Å, º) top
As—O41.655 (3)N1—C41.472 (5)
As—O31.673 (3)C1—C61.392 (5)
As—O51.732 (2)C1—C21.395 (5)
As—C11.930 (3)C2—C31.372 (5)
O1—N11.216 (4)C3—C41.382 (5)
O2—N11.229 (4)C4—C51.377 (5)
O5—H50.8200C5—C61.375 (5)
O4—As—O3116.59 (13)C6—C1—As119.6 (3)
O4—As—O5109.22 (14)C2—C1—As120.2 (3)
O3—As—O5108.79 (13)C3—C2—C1120.7 (4)
O4—As—C1110.75 (14)C2—C3—C4117.8 (3)
O3—As—C1107.48 (15)C5—C4—C3122.8 (3)
O5—As—C1103.16 (13)C5—C4—N1118.4 (3)
O1—N1—O2123.6 (3)C3—C4—N1118.8 (3)
O1—N1—C4118.6 (3)C6—C5—C4119.2 (3)
O2—N1—C4117.8 (3)C5—C6—C1119.4 (3)
C6—C1—C2120.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H11···O30.92 (4)1.89 (4)2.813 (4)176 (3)
N2—H12···O4i0.86 (3)1.97 (3)2.819 (3)169(su)
N2—H13···O4ii0.94 (5)1.92 (5)2.844 (4)168(su)
O5—H5···O3iii0.821.872.638 (4)156
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x, y+1, z; (iii) x+1, y, z+1.
 

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