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The title compound, [H3NCH2CH(NH3)CH3][HAsO4]·H2O, contains a network of doubly protonated propane-1,2-di­ammonium cations, hydrogenarsenate anions [dav(As—O) = 1.682 (1) Å] and water mol­ecules. Crystal symmetry generates a racemic mixture of the two enantiomers of the organic species. The crystal packing is controlled by N—H...O [dav(H...O) = 1.89 Å, θav(N—H...O) = 167° and dav(N...O) = 2.760 (1) Å] and O—H...O [dav(H...O) = 1.86 Å, θav(O—H...O) = 175° and dav(O...O) = 2.712 (1) Å] hydrogen bonds. It is isostructural with its hydrogenphosphate congener.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803017239/bt6320sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803017239/bt6320Isup2.hkl
Contains datablock I

CCDC reference: 222804

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.023
  • wR factor = 0.051
  • Data-to-parameter ratio = 31.3

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ..... 0.99 PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ..... ? PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.# 3 H2 O
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 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 2 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The title compound, (I) (Fig. 1), complements recently reported (protonated) amine phosphates, such as triethanolammonium dihydrogenphosphate, NH(CH2CH2OH)3·H2PO4 (Demir et al., 2003). It is isostructural with its hydrogenphosphate congener, [H3NCH2CH(NH3)CH3](HPO4)·H2O (Baouab & Jouini, 1998). One interesting use of [H3NCH2CH(NH3)CH3]2+ is as a template in the synthesis of new open-framework materials (Natarajan, 1999).

The structure of (I) contains propane-1,2-diammonium cations, hydrogenarsenate (HAsO4)2− anions and water molecules. Each [H3NCH2CH(NH3)CH3]2+ molecule is chiral (in the asymmetric unit, atom C2 has an R configuration), with crystal symmetry generating a 50:50 mixture of the two enantiomers, which is consistent with the racemic starting material. Its geometrical parameters [dav(C—N) = 1.495 (2) Å and dav(C—C) = 1.516 (2) Å] are similar to those of the same cation in [H3NCH2CH(NH3)CH3](BF4) (Gerrard & Weller, 2002). The (HAsO4)2− hydrogenarsenate group shows its standard tetrahedral geometry [dav(As—O) = 1.682 (1) Å and θav(O—As—O) = 109.4 (1)°], with the protonated As–O4 vertex showing its expected lengthening relative to the other As—O bonds.

As well as electrostatic attractions, the component species in (I) interact by means of a network of N—H···O and O—H···O links (Table 2). The (HAsO4)2− units and the water molecule (atom O5) are linked into a polymeric chain in the [010] direction by hydrogen bonds mediated by the water molecules (Fig. 2); each hydrogenarsenate tetrahedron is associated with three water neighbouring molecules. There are no direct inter-tetrahedral As—OH···O—As bonds, contrary to the commonly seen P—OH···O—P bonds in amine phosphates (Demir et al., 2003).

The organic species crosslink the chains in the [100] and [010] directions by way of N—H···O—As hydrogen bonds (Table 2). All six of the –NH3+ H atoms are involved in these links [dav(H···O) = 1.89 Å, θav(N—H···O) = 166.9° and dav(N···O) = 2.760 (1) Å]. This results in pseudo (001) layers of alternating hydrogenarsenate/water and organic moieties (Fig. 3).

A short C1—H8···O4ii intermolecular contact [d(C—H) = 0.97 Å, d(H···O) = 2.51 Å, θ(C—H···O) = 138.1° and d(C···O) = 3.2929 (19) Å] was identified in a PLATON (Spek, 2003) analysis of the structure. If it not merely a packing artefact, it may provide some additional coherence betweem the (001) pseudo-layers.

Experimental top

Ra cemic propane-1,2-diammonium (1 ml) was added to 8 ml of 0.5 M H3AsO4 giving a clear solution. Chunky faceted crystals of (I) grew as the water evaporated over the course of a few days.

Refinement top

O–H hydrogen atoms were found in difference maps and were refined by riding in their as-found positions. H atoms bonded to carbon and nitrogen were placed in calculated positions [d(C—H) = 0.96–0.98 Å and d(N—H) = 0.89 Å] and refined as riding [free rotation of the rigid R—NH3 and R—CH3 groups about the R—N and R—C bonds, respectively, was allowed by means of SHELXL97 (Sheldrick, 1997) AFIX 137 cards].

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97; molecular graphics: ORTEP-3 (Farrugia, 1997) and ATOMS (Shape Software, 1999); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I) (50% displacement ellipsoids). H atoms are drawn as small spheres of arbitrary radius and hydrogen bonds are indicated by dashed lines.
[Figure 2] Fig. 2. Detail of a hydrogen-bonded dihydrogenarsenate/water chain in (I) Colour key: [HAsO4]2− tetrahedra green, O atoms rose and H atoms grey. The H···O portions of the hydrogen bonds are highlighted in yellow. Symmetry codes as in Table 2; additionally (vi) x, 1 − y, z; (vii) −1/2 − x, y − 1/2, 1/2 − z.
[Figure 3] Fig. 3. [010] projection of (I). Colour key as in Fig. 2; additionally C atoms blue, N atoms green. The H···O portions of the hydrogen bonds are highlighted in yellow.
(I) top
Crystal data top
(C3H12N2)[HAsO4]·H2OF(000) = 480
Mr = 234.09Dx = 1.734 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 10.9115 (5) ÅCell parameters from 3887 reflections
b = 6.1530 (3) Åθ = 2.4–32.2°
c = 13.3653 (6) ŵ = 3.78 mm1
β = 92.315 (1)°T = 293 K
V = 896.59 (7) Å3Chunk, colourless
Z = 40.23 × 0.21 × 0.19 mm
Data collection top
Bruker SMART1000 CCD
diffractometer
3224 independent reflections
Radiation source: fine-focus sealed tube2519 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ω scansθmax = 32.5°, θmin = 2.4°
Absorption correction: multi-scan
(SADBAS; Bruker, 1999)
h = 1615
Tmin = 0.431, Tmax = 0.488k = 95
8758 measured reflectionsl = 1920
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)] = 0.023Hydrogen site location: difmap (O-H) and geom (N-H, C-H)
wR(F2) = 0.051H-atom parameters constrained
S = 0.92 w = 1/[σ2(Fo2) + (0.0251P)2]
where P = (Fo2 + 2Fc2)/3
3224 reflections(Δ/σ)max = 0.001
103 parametersΔρmax = 0.42 e Å3
0 restraintsΔρmin = 0.33 e Å3
Crystal data top
(C3H12N2)[HAsO4]·H2OV = 896.59 (7) Å3
Mr = 234.09Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.9115 (5) ŵ = 3.78 mm1
b = 6.1530 (3) ÅT = 293 K
c = 13.3653 (6) Å0.23 × 0.21 × 0.19 mm
β = 92.315 (1)°
Data collection top
Bruker SMART1000 CCD
diffractometer
3224 independent reflections
Absorption correction: multi-scan
(SADBAS; Bruker, 1999)
2519 reflections with I > 2σ(I)
Tmin = 0.431, Tmax = 0.488Rint = 0.022
8758 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0230 restraints
wR(F2) = 0.051H-atom parameters constrained
S = 0.92Δρmax = 0.42 e Å3
3224 reflectionsΔρmin = 0.33 e Å3
103 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
As10.001478 (13)0.13876 (2)0.203532 (10)0.02109 (5)
O10.12954 (10)0.00642 (19)0.21175 (8)0.0323 (3)
O20.12469 (10)0.01347 (19)0.19198 (9)0.0354 (3)
O30.00525 (10)0.32636 (18)0.11311 (8)0.0319 (2)
O40.00121 (11)0.2754 (2)0.31667 (8)0.0385 (3)
H10.04360.38820.31400.046*
N10.20796 (12)0.6149 (2)0.13668 (10)0.0288 (3)
H20.18130.74330.15730.035*
H30.26500.56490.18020.035*
H40.14560.52170.13230.035*
N20.14992 (12)0.3446 (2)0.05134 (9)0.0288 (3)
H50.10990.44730.08630.035*
H60.10830.31120.00250.035*
H70.15740.22680.08930.035*
C10.26149 (15)0.6395 (3)0.03651 (12)0.0306 (3)
H80.34160.70690.04500.037*
H90.20980.73630.00390.037*
C20.27488 (14)0.4264 (3)0.01915 (11)0.0292 (3)
H100.31920.45720.07990.035*
C30.34566 (16)0.2523 (3)0.03851 (13)0.0385 (4)
H110.35670.12860.00400.046*
H120.30080.20940.09560.046*
H130.42430.30820.06050.046*
O50.14005 (11)0.6264 (2)0.31626 (11)0.0449 (3)
H140.21980.59250.31090.054*
H150.13930.73160.27850.054*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
As10.02180 (7)0.01843 (7)0.02295 (7)0.00023 (6)0.00027 (5)0.00066 (6)
O10.0286 (6)0.0297 (6)0.0381 (6)0.0103 (5)0.0038 (5)0.0061 (5)
O20.0274 (6)0.0282 (6)0.0505 (7)0.0070 (5)0.0020 (5)0.0034 (6)
O30.0341 (6)0.0296 (6)0.0318 (5)0.0010 (5)0.0012 (4)0.0094 (5)
O40.0514 (8)0.0351 (7)0.0284 (6)0.0137 (6)0.0059 (5)0.0092 (5)
N10.0292 (6)0.0239 (7)0.0328 (6)0.0012 (5)0.0043 (5)0.0056 (6)
N20.0350 (7)0.0257 (7)0.0254 (6)0.0007 (6)0.0010 (5)0.0013 (5)
C10.0345 (8)0.0249 (8)0.0318 (8)0.0038 (7)0.0035 (6)0.0018 (7)
C20.0296 (8)0.0299 (8)0.0284 (7)0.0003 (7)0.0034 (6)0.0004 (7)
C30.0370 (9)0.0378 (10)0.0405 (9)0.0113 (8)0.0003 (7)0.0009 (8)
O50.0354 (7)0.0348 (7)0.0651 (8)0.0054 (6)0.0078 (6)0.0111 (6)
Geometric parameters (Å, º) top
As1—O11.6583 (10)N2—H70.8900
As1—O21.6671 (11)C1—C21.517 (2)
As1—O31.6730 (11)C1—H80.9700
As1—O41.7302 (11)C1—H90.9700
O4—H10.8489C2—C31.514 (2)
N1—C11.490 (2)C2—H100.9800
N1—H20.8900C3—H110.9600
N1—H30.8900C3—H120.9600
N1—H40.8900C3—H130.9600
N2—C21.500 (2)O5—H140.8953
N2—H50.8900O5—H150.8211
N2—H60.8900
O1—As1—O2113.20 (6)N1—C1—C2113.69 (13)
O1—As1—O3111.98 (6)N1—C1—H8108.8
O2—As1—O3111.41 (6)C2—C1—H8108.8
O1—As1—O4103.59 (5)N1—C1—H9108.8
O2—As1—O4108.87 (6)C2—C1—H9108.8
O3—As1—O4107.28 (6)H8—C1—H9107.7
As1—O4—H1112.5N2—C2—C3110.33 (14)
C1—N1—H2109.5N2—C2—C1109.04 (13)
C1—N1—H3109.5C3—C2—C1114.80 (13)
H2—N1—H3109.5N2—C2—H10107.5
C1—N1—H4109.5C3—C2—H10107.5
H2—N1—H4109.5C1—C2—H10107.5
H3—N1—H4109.5C2—C3—H11109.5
C2—N2—H5109.5C2—C3—H12109.5
C2—N2—H6109.5H11—C3—H12109.5
H5—N2—H6109.5C2—C3—H13109.5
C2—N2—H7109.5H11—C3—H13109.5
H5—N2—H7109.5H12—C3—H13109.5
H6—N2—H7109.5H14—O5—H1599.7
N1—C1—C2—C354.09 (18)N1—C1—C2—N270.26 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H1···O50.851.812.6534 (17)177
N1—H2···O1i0.891.802.6904 (17)174
N1—H3···O1ii0.891.862.7412 (17)169
N1—H4···O30.891.962.8436 (18)176
N2—H5···O3iii0.891.902.7449 (17)158
N2—H6···O30.891.902.7596 (17)163
N2—H7···O2iv0.891.922.7782 (17)161
O5—H14···O2v0.901.822.7056 (17)172
O5—H15···O2i0.821.962.7782 (17)176
Symmetry codes: (i) x, y+1, z; (ii) x+1/2, y+1/2, z+1/2; (iii) x, y+1, z; (iv) x, y, z; (v) x1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula(C3H12N2)[HAsO4]·H2O
Mr234.09
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)10.9115 (5), 6.1530 (3), 13.3653 (6)
β (°) 92.315 (1)
V3)896.59 (7)
Z4
Radiation typeMo Kα
µ (mm1)3.78
Crystal size (mm)0.23 × 0.21 × 0.19
Data collection
DiffractometerBruker SMART1000 CCD
diffractometer
Absorption correctionMulti-scan
(SADBAS; Bruker, 1999)
Tmin, Tmax0.431, 0.488
No. of measured, independent and
observed [I > 2σ(I)] reflections
8758, 3224, 2519
Rint0.022
(sin θ/λ)max1)0.756
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.051, 0.92
No. of reflections3224
No. of parameters103
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.42, 0.33

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97, ORTEP-3 (Farrugia, 1997) and ATOMS (Shape Software, 1999).

Selected geometric parameters (Å, º) top
As1—O11.6583 (10)N1—C11.490 (2)
As1—O21.6671 (11)N2—C21.500 (2)
As1—O31.6730 (11)C1—C21.517 (2)
As1—O41.7302 (11)C2—C31.514 (2)
N1—C1—C2—C354.09 (18)N1—C1—C2—N270.26 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H1···O50.851.812.6534 (17)177
N1—H2···O1i0.891.802.6904 (17)174
N1—H3···O1ii0.891.862.7412 (17)169
N1—H4···O30.891.962.8436 (18)176
N2—H5···O3iii0.891.902.7449 (17)158
N2—H6···O30.891.902.7596 (17)163
N2—H7···O2iv0.891.922.7782 (17)161
O5—H14···O2v0.901.822.7056 (17)172
O5—H15···O2i0.821.962.7782 (17)176
Symmetry codes: (i) x, y+1, z; (ii) x+1/2, y+1/2, z+1/2; (iii) x, y+1, z; (iv) x, y, z; (v) x1/2, y+1/2, z+1/2.
 

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