Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536812043565/hb6976sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536812043565/hb6976Isup2.hkl |
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (As-O) = 0.002 Å
- R factor = 0.022
- wR factor = 0.055
- Data-to-parameter ratio = 16.6
checkCIF/PLATON results
No syntax errors found Datablock: I
Alert level G PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension . 1 PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF .... ? PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings Differ ? PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature 293 K PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels .......... 8 PLAT960_ALERT_3_G Number of Intensities with I .LT. - 2*sig(I) ... 1
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 0 ALERT level C = Check. Ensure it is not caused by an omission or oversight 7 ALERT level G = General information/check it is not something unexpected 3 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 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
Crystals of the title compound were grown from an aqueous solution containing diluted arsenic acid (20%wt) mixed with a concentrated aqueous solution of ammonia in excess. The solution was kept in a desiccator with CaCl2 as drying agent. The first crystals, mostly with a plate-like form, appeared approximately after one week.
For better comparison, the same unit cell setting as in the previous determination of (NH4)2HAsO4 (Khan et al., 1970) was used. The current setting is not reduced and can be transformed to the reduced setting by application of the matrix (101, 010, 001). For refinement, the atomic coordinates of the As, O and N atoms (Khan et al., 1972) were used as starting parameters. All H atoms were clearly discernible from difference Fourier maps and were refined freely.
Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ATOMS (Dowty, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).
(NH4)2HAsO4 | F(000) = 352 |
Mr = 176.01 | Dx = 2.026 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2800 reflections |
a = 11.3426 (4) Å | θ = 3.6–30.0° |
b = 6.8512 (3) Å | µ = 5.82 mm−1 |
c = 8.1130 (3) Å | T = 293 K |
β = 113.784 (4)° | Plate, colourless |
V = 576.92 (4) Å3 | 0.14 × 0.12 × 0.02 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | 1674 independent reflections |
Radiation source: fine-focus sealed tube | 1413 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ω– and ϕ–scans | θmax = 30.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −15→15 |
Tmin = 0.496, Tmax = 0.873 | k = −6→9 |
6318 measured reflections | l = −11→10 |
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)] = 0.022 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.055 | All H-atom parameters refined |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0304P)2] where P = (Fo2 + 2Fc2)/3 |
1676 reflections | (Δ/σ)max = 0.001 |
101 parameters | Δρmax = 0.59 e Å−3 |
0 restraints | Δρmin = −0.84 e Å−3 |
(NH4)2HAsO4 | V = 576.92 (4) Å3 |
Mr = 176.01 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.3426 (4) Å | µ = 5.82 mm−1 |
b = 6.8512 (3) Å | T = 293 K |
c = 8.1130 (3) Å | 0.14 × 0.12 × 0.02 mm |
β = 113.784 (4)° |
Bruker APEXII CCD diffractometer | 1674 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 1413 reflections with I > 2σ(I) |
Tmin = 0.496, Tmax = 0.873 | Rint = 0.033 |
6318 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.055 | All H-atom parameters refined |
S = 1.04 | Δρmax = 0.59 e Å−3 |
1676 reflections | Δρmin = −0.84 e Å−3 |
101 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. |
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. |
x | y | z | Uiso*/Ueq | ||
As1 | 0.249593 (18) | 0.89261 (3) | 0.42786 (3) | 0.00648 (7) | |
O1 | 0.20879 (15) | 0.9789 (2) | 0.2115 (2) | 0.0126 (3) | |
O2 | 0.25894 (13) | 0.0977 (2) | 0.5442 (2) | 0.0098 (3) | |
O3 | 0.38858 (13) | 0.7692 (2) | 0.4982 (2) | 0.0114 (3) | |
O4 | 0.13017 (13) | 0.7484 (2) | 0.4289 (2) | 0.0098 (3) | |
N1 | 0.44933 (18) | 0.1231 (3) | 0.1532 (3) | 0.0111 (3) | |
N2 | 0.12140 (18) | 0.3798 (3) | 0.2643 (3) | 0.0100 (3) | |
H1N1 | 0.494 (3) | 0.131 (3) | 0.275 (4) | 0.017 (7)* | |
H2N1 | 0.422 (2) | 0.003 (4) | 0.114 (4) | 0.013 (6)* | |
H3N1 | 0.388 (3) | 0.209 (4) | 0.117 (4) | 0.022 (7)* | |
H4N1 | 0.509 (3) | 0.167 (4) | 0.111 (4) | 0.016 (7)* | |
H1N2 | 0.118 (3) | 0.491 (5) | 0.302 (4) | 0.020 (7)* | |
H2N2 | 0.169 (3) | 0.392 (3) | 0.201 (4) | 0.013 (7)* | |
H3N2 | 0.046 (3) | 0.336 (4) | 0.209 (4) | 0.022 (7)* | |
H4N2 | 0.164 (2) | 0.297 (4) | 0.358 (4) | 0.013 (6)* | |
H1O | 0.186 (3) | 0.907 (4) | 0.139 (5) | 0.032 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
As1 | 0.00865 (10) | 0.00455 (11) | 0.00669 (11) | 0.00021 (7) | 0.00355 (7) | −0.00027 (8) |
O1 | 0.0228 (7) | 0.0084 (8) | 0.0071 (7) | −0.0016 (6) | 0.0064 (6) | −0.0004 (6) |
O2 | 0.0134 (7) | 0.0062 (7) | 0.0105 (7) | −0.0002 (5) | 0.0056 (6) | −0.0026 (6) |
O3 | 0.0102 (6) | 0.0113 (7) | 0.0131 (7) | 0.0031 (5) | 0.0051 (6) | 0.0011 (6) |
O4 | 0.0111 (6) | 0.0068 (7) | 0.0119 (7) | −0.0018 (5) | 0.0051 (5) | 0.0003 (6) |
N1 | 0.0117 (8) | 0.0096 (9) | 0.0123 (9) | 0.0008 (7) | 0.0052 (7) | 0.0006 (7) |
N2 | 0.0121 (8) | 0.0071 (9) | 0.0120 (9) | 0.0003 (7) | 0.0059 (7) | −0.0005 (7) |
As1—O2i | 1.6718 (14) | N1—H2N1 | 0.89 (3) |
As1—O3 | 1.6732 (14) | N1—H3N1 | 0.87 (3) |
As1—O4 | 1.6793 (14) | N1—H4N1 | 0.92 (3) |
As1—O1 | 1.7293 (15) | N2—H1N2 | 0.83 (3) |
O1—H1O | 0.73 (3) | N2—H2N2 | 0.89 (3) |
O2—As1ii | 1.6718 (14) | N2—H3N2 | 0.85 (3) |
N1—H1N1 | 0.91 (3) | N2—H4N2 | 0.92 (3) |
O2i—As1—O3 | 113.29 (7) | H1N1—N1—H4N1 | 103 (2) |
O2i—As1—O4 | 111.04 (7) | H2N1—N1—H4N1 | 112 (2) |
O3—As1—O4 | 110.62 (7) | H3N1—N1—H4N1 | 105 (2) |
O2i—As1—O1 | 102.46 (7) | H1N2—N2—H2N2 | 105 (2) |
O3—As1—O1 | 110.40 (7) | H1N2—N2—H3N2 | 110 (3) |
O4—As1—O1 | 108.67 (7) | H2N2—N2—H3N2 | 116 (3) |
As1—O1—H1O | 117 (3) | H1N2—N2—H4N2 | 111 (3) |
H1N1—N1—H2N1 | 114 (2) | H2N2—N2—H4N2 | 107 (2) |
H1N1—N1—H3N1 | 110 (2) | H3N2—N2—H4N2 | 108 (2) |
H2N1—N1—H3N1 | 113 (3) |
Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H3N1···O2iii | 0.87 (3) | 1.88 (3) | 2.750 (2) | 178 (3) |
N1—H1N1···O3iv | 0.91 (3) | 1.91 (3) | 2.780 (3) | 158 (2) |
N1—H2N1···O3iii | 0.89 (3) | 2.06 (3) | 2.930 (3) | 167 (2) |
N1—H4N1···O3v | 0.92 (3) | 1.86 (3) | 2.777 (2) | 173 (3) |
N2—H4N2···O2 | 0.92 (3) | 2.00 (3) | 2.910 (2) | 174 (2) |
N2—H2N2···O2iii | 0.89 (3) | 1.93 (3) | 2.809 (2) | 174 (2) |
N2—H1N2···O4 | 0.83 (3) | 2.02 (3) | 2.840 (2) | 171 (3) |
N2—H3N2···O4vi | 0.85 (3) | 1.95 (3) | 2.793 (2) | 176 (3) |
O1—H1O···O4vii | 0.73 (3) | 1.89 (3) | 2.613 (2) | 171 (4) |
Symmetry codes: (iii) x, −y+1/2, z−1/2; (iv) −x+1, −y+1, −z+1; (v) −x+1, y−1/2, −z+1/2; (vi) −x, y−1/2, −z+1/2; (vii) x, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | (NH4)2HAsO4 |
Mr | 176.01 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.3426 (4), 6.8512 (3), 8.1130 (3) |
β (°) | 113.784 (4) |
V (Å3) | 576.92 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.82 |
Crystal size (mm) | 0.14 × 0.12 × 0.02 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.496, 0.873 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6318, 1674, 1413 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.055, 1.04 |
No. of reflections | 1676 |
No. of parameters | 101 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.59, −0.84 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ATOMS (Dowty, 2006), publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H3N1···O2i | 0.87 (3) | 1.88 (3) | 2.750 (2) | 178 (3) |
N1—H1N1···O3ii | 0.91 (3) | 1.91 (3) | 2.780 (3) | 158 (2) |
N1—H2N1···O3i | 0.89 (3) | 2.06 (3) | 2.930 (3) | 167 (2) |
N1—H4N1···O3iii | 0.92 (3) | 1.86 (3) | 2.777 (2) | 173 (3) |
N2—H4N2···O2 | 0.92 (3) | 2.00 (3) | 2.910 (2) | 174 (2) |
N2—H2N2···O2i | 0.89 (3) | 1.93 (3) | 2.809 (2) | 174 (2) |
N2—H1N2···O4 | 0.83 (3) | 2.02 (3) | 2.840 (2) | 171 (3) |
N2—H3N2···O4iv | 0.85 (3) | 1.95 (3) | 2.793 (2) | 176 (3) |
O1—H1O···O4v | 0.73 (3) | 1.89 (3) | 2.613 (2) | 171 (4) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z+1; (iii) −x+1, y−1/2, −z+1/2; (iv) −x, y−1/2, −z+1/2; (v) x, −y+3/2, z−1/2. |
(NH4)2HAsO4 is a frequently used precursor material for preparation of arsenate(V) compounds, starting either from (aqueous) solutions or via ceramic routes. The crystal structure of (NH4)2HAsO4 has originally been determined by Khan et al. (1970) based on Weissenberg photographs. In the original study all atoms were refined with isotropic displacement parameters. Since H atoms could not be localized, the authors could make only assumptions with respect to the resulting hydrogen bonding pattern, deduced from N···O and O···O distances. These assumptions included three models: i) the NH4 ions exhibit rotatory oscillations; ii) the NH4 ions are in static disorder; iii) each of the two N atoms forms a bifurcated bond in addition to three normal hydrogen bonds (Khan et al., 1970). Somewhat later Khan et al. (1972) showed for the isotypic phosphate analogue (NH4)2HPO4 that dynamic or static disorder can be ruled out for the NH4 groups and that the ammonium tetrahedra form four classical hydrogen bonds to the PO3(OH) groups. The current redetermination of the structure of (NH4)2HAsO4 using modern CCD-based data was intended to shed some light on its hydrogen bonding pattern and to compare the results with the phosphate analogue.
The redetermination confirmed the basic features of the original study, however with the unambiguous localization of all H atoms and, as expected, with higher precision and accuracy. Like in (NH4)2HPO4, the ammonium groups show no static or dynamic disorder and four normal N—H···O hydrogen bonds are formed between the constituents. The largest difference between the two determinations pertains to the O···O distance of the O—H···O (O1···O4) hydrogen bond. In the original study this distance was determined as 2.669 (13) Å, whereas it is 2.613 (2) Å in this study. The latter matches very well with 2.615 (1) Å for the phosphate analogue for which all H atoms could be localized (Khan et al., 1972). In the latter study it was suggested that the difference between these O···O distances of the phosphate (2.615 (1) Å) and the arsenate (2.669 (13) Å) structure is a consequence of the different size of the P5+ and the As5+ ions. However, the current redetermination of (NH4)2HAsO4 shows that the influence of the different sizes for the phosphate (average P—O distance 1.54 Å) and the arsenate (average As—O distance 1.68 Å) tetrahedra can in fact be neglected.
Fig. 1 shows the structural set-up of the two different NH4 and the AsO3(OH) tetrahedra. All tetrahedra show slight angular distortions; the difference in As—O bond lengths for the three As—O bonds (average 1.674 Å) and the longer As—OH bond (1.7291 (15) Å) is normal. The ammonium cations and hydrogenarsenate anions are linked into a three-dimensional network by classical O—H···O and N—H···O hydrogen bonds, the numerical details of which are given in Table 1. The latter are very similar to those of the isotypic phosphate (NH4)2HPO4 (Khan et al., 1972).
For (NH4)2HPO4 another crystalline polymorph has been described, resulting from hydrolysis of the educt, viz. ammonium hexafluoridophosphate (Kunz et al., 2010). It would be interesting to know whether an arsenate polymorph isotypic with the phosphate analogue or another polymorph (NH4)2HAsO4 exist as well.