Propane-1,3-diaminium hydrogenarsenate monohydrate

Todd, M.J.; Harrison, W.T.A.

doi:10.1107/S1600536805020702

metal-organic compounds

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ISSN: 2056-9890

Volume 61| Part 8| August 2005| Pages m1459-m1461

https://doi.org/10.1107/S1600536805020702

Propane-1,3-diaminium hydrogenarsenate monohydrate

Malcolm J. Todd ^a and William T. A. Harrison ^a ^*

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 6 June 2005; accepted 29 June 2005; online 6 July 2005)

The title compound, (C₃H₁₂N₂)[HAsO₄]·H₂O, contains a network of propane-1,3-diaminium cations, hydrogenarsenate anions [mean As—O = 1.687 (2) Å] and water molecules. The crystal packing involves anion-to-anion and water-to-anion O—H⋯O hydrogen bonds, resulting in infinite chains containing the unusual R₃³(10) graph-set motif. Cation-to-anion and cation-to-water N—H⋯O hydrogen bonds generate a three-dimensional overall structure.

Comment

The title compound, (C₃H₁₂N₂)[HAsO₄]·H₂O, (I) (Fig. 1), was prepared as part of our ongoing structural studies of hydrogen-bonding interactions in protonated-amine (di)hydrogen arsenates (Lee & Harrison, 2003a ; Wilkinson & Harrison, 2004 ; Todd & Harrison, 2005 ). In particular, (I) complements propane-1,3-diaminium bis(dihydrogenarsenate), (C₃H₁₂N₂)[H₂AsO₄]₂ (Wilkinson & Harrison, 2005 ), prepared under different pH conditions.

The [HAsO₄]²⁻ hydrogenarsenate group in (I) has normal tetrahedral geometry [mean As—O = 1.687 (2) Å], with the protonated As1—O4 vertex showing its usual lengthening relative to the unprotonated As—O bonds (Table 1). The propane-1,3-diaminium cation shows no unusual geometrical features.

As well as electrostatic attractions, the component species in (I) interact by means of a network of O—H⋯O and N—H⋯O hydrogen bonds (Table 2). The [HAsO₄]²⁻ units and water molecules are linked into polymeric chains (Fig. 2) propagating along [010] by way of anion-to-anion O4—H1⋯O2ⁱ and water-to-anion O5—H14⋯O1 and O5—H15⋯O2ⁱⁱ bonds (Table 2). This arrangement results in an unusual R₃³(10) graph-set (Bernstein et al., 1995 ) motif. The As1⋯As1ⁱ separation is 4.7991 (3) Å.

The organic species interacts with the hydrogenarsenate/water chains by way of six N—H⋯O hydrogen bonds [mean H⋯O = 1.89 Å, mean N—H⋯O = 171° and mean N⋯O = 2.793 (2) Å]. One of the acceptor O atoms is part of a water molecule, and the other five are parts of hydrogenarsenate groups. This hydrogen-bonding scheme results in a three-dimensional network (Fig. 3).

The hydrogen-bonded hydrogenarsenate/water chains in (I) are different from the motifs seen in related structures. In bis(cycloheptylaminium) hydrogenarsenate monohydrate (Todd & Harrison, 2005) and bis(benzylammonium) hydrogenarsenate monohydrate (Lee & Harrison, 2003c ), hydrogen-bonded dimers of [HAsO₄]²⁻ units occur, with the dimers bridged into double chains by intervening water molecules. In the unhydrated piperidinium dihydrogenarsenate (Lee & Harrison, 2003b ) and t-butylammonium dihydrogenarsenate (Wilkinson & Harrison, 2004), single chains of [H₂AsO₄]⁻ anions occur with each adjacent dihydrogenarsenate pair linked by a pair of hydrogen bonds. In propane-1,3-diaminium bis(dihydrogenarsenate) (Wilkinson & Harrison, 2005), the same organic cation as found in (I) is combined with dihydrogenarsenate [H₂AsO₄]⁻ groups, with the latter forming double chains.

Figure 1
A view of (I)

with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are indicated by dashed lines.

Figure 2
Detail of a hydrogen-bonded (dashed lines) hydrogenarsenate/water chain in (I)

Figure 3
The crystal packing of (I)

. Dashed lines indicate hydrogen bonds.

Experimental

0.5 M aqueous propane-1,3-diamine solution (10 ml) was added to 0.5 M aqueous H₃AsO₄ solution (10 ml) to result in a clear solution. Aqueous ammonia was added to this solution to raise the pH to about 12, which is beyond the second end-point for H₃AsO₄ (i.e. the predominant species is [HAsO₄]²⁻). Platy crystals of (I) grew as the water evaporated over the course of a few days.

Crystal data

(C₃H₁₂N₂)[HAsO₄]·H₂O
M_r = 234.09
Monoclinic, P 2₁ /c
a = 7.1327 (2) Å
b = 16.8046 (6) Å
c = 7.9402 (2) Å
β = 113.253 (2)°
V = 874.42 (5) Å³
Z = 4
D_x = 1.778 Mg m⁻³
Mo Kα radiation
Cell parameters from 2043 reflections
θ = 2.9–27.5°
μ = 3.87 mm⁻¹
T = 120 (2) K
Plate, colourless
0.32 × 0.24 × 0.03 mm

Data collection

Nonius KappaCCD diffractometer
ω and φ scans
Absorption correction: multi-scan(SADABS; Bruker, 1999 )T_min = 0.370, T_max = 0.892
11562 measured reflections
2002 independent reflections
1804 reflections with I > 2σ(I)
R_int = 0.036
θ_max = 27.5°
h = −9 → 8
k = −20 → 21
l = −10 → 10

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.055
S = 1.05
2002 reflections
103 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0218P)² + 0.7899P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.53 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.0032 (6)

Table 1
Selected geometric parameters (Å, °)

As1—O1	1.6612 (14)
As1—O2	1.6746 (13)
As1—O3	1.6814 (14)
As1—O4	1.7302 (13)

N1—C1—C2—C3	175.33 (16)
C1—C2—C3—N2	175.49 (16)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H1⋯O2ⁱ	0.93	1.71	2.6207 (19)	166
O5—H14⋯O1	0.92	1.79	2.709 (2)	177
O5—H15⋯O2ⁱⁱ	0.89	1.98	2.858 (2)	169
N1—H2⋯O1ⁱⁱⁱ	0.91	1.81	2.711 (2)	173
N1—H3⋯O3ⁱ	0.91	1.96	2.855 (2)	166
N1—H4⋯O5^iv	0.91	1.90	2.798 (2)	168
N2—H11⋯O3ⁱⁱ	0.91	1.90	2.802 (2)	170
N2—H12⋯O2^v	0.91	1.95	2.851 (2)	172
N2—H13⋯O3	0.91	1.84	2.743 (2)	175
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x+1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (v) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

The O-bound H atoms were found in difference maps and refined as riding on their carrier O atoms in their as-found relative positions. H atoms bonded to C and N atoms were placed in idealized positions (C—H = 0.99 Å and N—H = 0.91 Å) and refined as riding, allowing for free rotation of the –NH₃ groups. The constraint U_iso(H) = 1.2U_eq(carrier) was applied in all cases.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK, DENZO (Otwinowski & Minor, 1997) and SORTAV (Blessing, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536805020702/hk6019sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805020702/hk6019Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK, DENZO (Otwinowski & Minor, 1997) and SORTAV (Blessing, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Propane-1,3-diaminium hydrogenarsenate monohydrate top

Crystal data top

(C₃H₁₂N₂)[HAsO₄]·H₂O	F(000) = 480
M_r = 234.09	D_x = 1.778 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2043 reflections
a = 7.1327 (2) Å	θ = 2.9–27.5°
b = 16.8046 (6) Å	µ = 3.87 mm⁻¹
c = 7.9402 (2) Å	T = 120 K
β = 113.253 (2)°	Plate, colourless
V = 874.42 (5) Å³	0.32 × 0.24 × 0.03 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	2002 independent reflections
Radiation source: fine-focus sealed tube	1804 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ω and φ scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −9→8
T_min = 0.370, T_max = 0.892	k = −20→21
11562 measured reflections	l = −10→10

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difmap (O-H) and geom (others)
R[F² > 2σ(F²)] = 0.022	H-atom parameters constrained
wR(F²) = 0.055	w = 1/[σ²(F_o²) + (0.0218P)² + 0.7899P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
2002 reflections	Δρ_max = 0.49 e Å⁻³
103 parameters	Δρ_min = −0.53 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0032 (6)

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

	x	y	z	U_iso*/U_eq
As1	0.33625 (3)	0.169777 (11)	0.40666 (2)	0.00857 (9)
O1	0.2831 (2)	0.08464 (8)	0.48468 (19)	0.0146 (3)
O2	0.1852 (2)	0.24466 (8)	0.41487 (19)	0.0128 (3)
O3	0.5862 (2)	0.19099 (9)	0.51186 (19)	0.0128 (3)
O4	0.2905 (2)	0.15016 (8)	0.17988 (18)	0.0147 (3)
O5	0.1693 (2)	0.09842 (9)	0.7709 (2)	0.0209 (3)
N1	0.7723 (3)	0.44871 (10)	0.2130 (2)	0.0125 (3)
N2	0.7725 (3)	0.30904 (10)	0.7604 (2)	0.0108 (3)
C1	0.7251 (3)	0.45673 (12)	0.3780 (3)	0.0128 (4)
C2	0.7718 (3)	0.37949 (12)	0.4861 (3)	0.0140 (4)
C3	0.7418 (3)	0.38739 (12)	0.6644 (3)	0.0136 (4)
H1	0.2575	0.1935	0.1001	0.018*
H2	0.7457	0.4955	0.1504	0.015*
H3	0.6938	0.4095	0.1398	0.015*
H4	0.9065	0.4361	0.2476	0.015*
H5	0.5792	0.4703	0.3407	0.015*
H6	0.8075	0.5004	0.4562	0.015*
H7	0.9146	0.3637	0.5135	0.017*
H8	0.6814	0.3370	0.4107	0.017*
H9	0.8402	0.4266	0.7447	0.016*
H10	0.6023	0.4071	0.6384	0.016*
H11	0.7252	0.3118	0.8512	0.013*
H12	0.9079	0.2969	0.8097	0.013*
H13	0.7033	0.2706	0.6788	0.013*
H14	0.2035	0.0940	0.6706	0.025*
H15	0.1674	0.1492	0.8009	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
As1	0.00955 (13)	0.00763 (13)	0.00873 (12)	−0.00002 (7)	0.00380 (9)	−0.00067 (7)
O1	0.0223 (8)	0.0088 (7)	0.0165 (7)	−0.0030 (6)	0.0117 (6)	−0.0006 (6)
O2	0.0129 (7)	0.0109 (7)	0.0148 (7)	0.0027 (6)	0.0057 (6)	−0.0021 (5)
O3	0.0095 (7)	0.0155 (7)	0.0127 (7)	−0.0013 (6)	0.0039 (6)	−0.0021 (6)
O4	0.0223 (8)	0.0119 (7)	0.0089 (7)	0.0029 (6)	0.0052 (6)	−0.0001 (6)
O5	0.0312 (9)	0.0169 (8)	0.0229 (8)	−0.0060 (7)	0.0195 (7)	−0.0049 (6)
N1	0.0148 (8)	0.0095 (8)	0.0116 (8)	−0.0023 (7)	0.0034 (7)	0.0008 (6)
N2	0.0112 (8)	0.0119 (8)	0.0105 (8)	−0.0013 (7)	0.0055 (7)	0.0005 (7)
C1	0.0143 (10)	0.0107 (10)	0.0139 (10)	0.0005 (8)	0.0061 (8)	0.0001 (8)
C2	0.0170 (10)	0.0114 (10)	0.0157 (10)	0.0038 (8)	0.0086 (9)	0.0018 (8)
C3	0.0172 (10)	0.0095 (10)	0.0160 (10)	−0.0001 (8)	0.0086 (9)	0.0017 (8)

Geometric parameters (Å, º) top

As1—O1	1.6612 (14)	C2—C3	1.518 (3)
As1—O2	1.6746 (13)	C2—H7	0.9900
As1—O3	1.6814 (14)	C2—H8	0.9900
As1—O4	1.7302 (13)	C3—N2	1.493 (2)
O4—H1	0.9323	C3—H9	0.9900
N1—C1	1.482 (2)	C3—H10	0.9900
N1—H2	0.9100	N2—H11	0.9100
N1—H3	0.9100	N2—H12	0.9100
N1—H4	0.9100	N2—H13	0.9100
C1—C2	1.519 (3)	O5—H14	0.9237
C1—H5	0.9900	O5—H15	0.8880
C1—H6	0.9900

O1—As1—O2	112.81 (7)	C1—C2—C3	111.85 (16)
O1—As1—O3	110.52 (7)	C1—C2—H7	109.2
O2—As1—O3	113.18 (7)	C3—C2—H7	109.2
O1—As1—O4	104.30 (7)	C1—C2—H8	109.2
O2—As1—O4	108.90 (7)	C3—C2—H8	109.2
O3—As1—O4	106.54 (7)	H7—C2—H8	107.9
As1—O4—H1	116.9	N2—C3—C2	110.64 (16)
C1—N1—H2	109.5	N2—C3—H9	109.5
C1—N1—H3	109.5	C2—C3—H9	109.5
H2—N1—H3	109.5	N2—C3—H10	109.5
C1—N1—H4	109.5	C2—C3—H10	109.5
H2—N1—H4	109.5	H9—C3—H10	108.1
H3—N1—H4	109.5	C3—N2—H11	109.5
N1—C1—C2	110.27 (16)	C3—N2—H12	109.5
N1—C1—H5	109.6	H11—N2—H12	109.5
C2—C1—H5	109.6	C3—N2—H13	109.5
N1—C1—H6	109.6	H11—N2—H13	109.5
C2—C1—H6	109.6	H12—N2—H13	109.5
H5—C1—H6	108.1	H14—O5—H15	110.2

N1—C1—C2—C3	175.33 (16)	C1—C2—C3—N2	175.49 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1···O2ⁱ	0.93	1.71	2.6207 (19)	166
O5—H14···O1	0.92	1.79	2.709 (2)	177
O5—H15···O2ⁱⁱ	0.89	1.98	2.858 (2)	169
N1—H2···O1ⁱⁱⁱ	0.91	1.81	2.711 (2)	173
N1—H3···O3ⁱ	0.91	1.96	2.855 (2)	166
N1—H4···O5^iv	0.91	1.90	2.798 (2)	168
N2—H11···O3ⁱⁱ	0.91	1.90	2.802 (2)	170
N2—H12···O2^v	0.91	1.95	2.851 (2)	172
N2—H13···O3	0.91	1.84	2.743 (2)	175

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y+1/2, −z+1/2; (iv) x+1, −y+1/2, z−1/2; (v) x+1, −y+1/2, z+1/2.

Acknowledgements

We thank the EPSRC National Crystallography Service (University of Southampton, England) for the data collection.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–37. CrossRef CAS Web of Science IUCr Journals Google Scholar
Bruker (1999). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Lee, C. & Harrison, W. T. A. (2003a). Acta Cryst. E59, m739–m741. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lee, C. & Harrison, W. T. A. (2003b). Acta Cryst. E59, m959–m960. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lee, C. & Harrison, W. T. A. (2003c). Acta Cryst. E59, m1151–m1153. Web of Science CSD CrossRef IUCr Journals Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
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. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Todd, M. J. & Harrison, W. T. A. (2005). Acta Cryst. E61, m1024–m1026. Web of Science CSD CrossRef IUCr Journals Google Scholar
Wilkinson, H. S. & Harrison, W. T. A. (2004). Acta Cryst. E60, m1359–m1361. Web of Science CSD CrossRef IUCr Journals Google Scholar
Wilkinson, H. S. & Harrison, W. T. A. (2005). Acta Cryst. E61, m1289–m1291. Web of Science CrossRef IUCr Journals Google Scholar

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ISSN: 2056-9890

Volume 61| Part 8| August 2005| Pages m1459-m1461

https://doi.org/10.1107/S1600536805020702

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Propane-1,3-diaminium hydrogenarsenate monohydrate

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds