Propane-1,3-diaminium bis­(dihydrogenarsenate)

Wilkinson, H.S.; Harrison, W.T.A.

doi:10.1107/S1600536805017411

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 7| July 2005| Pages m1289-m1291

https://doi.org/10.1107/S1600536805017411

Propane-1,3-diaminium bis(dihydrogenarsenate)

Hazel S. Wilkinson ^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 31 May 2005; accepted 2 June 2005; online 10 June 2005)

The title compound, (C₃H₁₂N₂)[H₂AsO₄]₂, contains a network of propane-1,3-diaminium cations and dihydrogenarsenate anions [mean As—O = 1.682 (2) Å]. The crystal packing involves anion-to-anion O—H⋯O hydrogen bonds, resulting in double chains of dihydrogenarsenate tetrahedra. Cation-to-anion N—H⋯O hydrogen bonds generate a three-dimensional overall structure. One C atom occupies a special position with twofold symmetry.

Comment

The title compound, C₃H₁₂N₂²⁺·2[H₂AsO₄)]⁻, (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 ,b ,c ; Wilkinson & Harrison, 2004 ; Todd & Harrison, 2005a ).

The [H₂AsO₄]⁻ dihydrogenarsenate group in (I) has normal tetrahedral geometry [mean As—O = 1.682 (2) Å], with the protonated As1—O1 and As1—O2 vertices showing their expected lengthening relative to the unprotonated As1—O3 and As1—O4 bonds, which have formal partial double-bond character (Table 1). The propane-1,3-diaminium cation, which is generated by twofold symmetry from the atoms of the asymmetric unit (C2 occupies a special position with site symmetry 2), shows no unusual geometrical features.

As well as electrostatic attractions, the component species in (I) interact by means of a network of cation-to-anion N—H⋯O and anion-to-anion O—H⋯O hydrogen bonds (Table 2). The [H₂AsO₄]⁻ units are linked into polymeric double chains (Fig. 2) propagating along [010] by way of inversion-symmetry-generated pairs of O2—H2⋯O4ⁱⁱⁱ and O1—H1⋯O4ⁱⁱ bonds (see Table 2 for symmetry codes). The first of these bonds results in `dimers' of dihydrogenarsenate tetrahedra, which in turn are linked into double chains by the second hydrogen bond. In graph-set notation (Bernstein et al., 1995 ), these bonding patterns correspond to R₂²(8) and R₄⁴(12) loops, respectively. This scheme results in every [H₂AsO₄]⁻ group in the chain forming two hydrogen bonds to its neighbours and accepting two hydrogen bonds from its neighbours. The As⋯Asⁱⁱⁱ (via O2—H2⋯O4ⁱⁱⁱ) and As⋯Asⁱⁱ (via O1—H1⋯O4ⁱⁱ) separations are 4.5325 (4) and 4.6549 (4) Å, respectively (symmetry codes as in Table 2).

The organic species interacts with the dihydrogenarsenate anions by way of three N—H⋯O hydrogen bonds [mean H⋯O = 2.00 Å, mean N—H⋯O = 158° and mean N⋯O = 2.892 (3) Å], such that the [010] dihydrogenarsenate double chains are crosslinked in the a and c directions to result in a three-dimensional network (Fig. 3). A PLATON (Spek, 2003 ) analysis of (I) indicated the presence of two short C—H⋯O contacts (Table 2) although their structural significance is not clear.

The hydrogen-bonded tetrahedral double chains in (I) are different from the motifs seen in related structures. In bis(cycloheptylaminium) hydrogenarsenate monohydrate (Todd & Harrison, 2005a) 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 piperidinum 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 hydrogenarsenate monohydate (Todd & Harrison, 2005b ), containing the same cation as (I) but prepared at higher pH, yet another hydrogen-bonded chain motif occurs.

Figure 1
View of (I)

, showing 50% probability displacement ellipsoids (H atoms are drawn as spheres of arbitrary radii and the hydrogen bond is indicated by dashed lines). Symmetry code as in Table 1

Figure 2
Detail of a hydrogen-bonded (dashed lines) dihydrogenarsenate double chain in (I)

. Symmetry codes as in Table 2

Figure 3
Projection of the unit cell contents of (I)

on to (010). 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. A mass of plate- and slab-like crystals of (I) grew as the water evaporated over the course of a few days.

Crystal data

(C₃H₁₂N₂)[AsH₂O₄]₂
M_r = 358.02
Monoclinic, I 2/a
a = 15.5563 (8) Å
b = 4.6549 (2) Å
c = 15.0454 (7) Å
β = 103.399 (1)°
V = 1059.83 (9) Å³
Z = 4
D_x = 2.244 Mg m⁻³
Mo Kα radiation
Cell parameters from 3458 reflections
θ = 2.7–32.5°
μ = 6.33 mm⁻¹
T = 293 (2) K
Plate, colourless
0.50 × 0.19 × 0.03 mm

Data collection

Bruker SMART 1000 CCD diffractometer
ω scans
Absorption correction: multi-scan(SADABS; Bruker, 1999 )T_min = 0.144, T_max = 0.833
5128 measured reflections
1899 independent reflections
1667 reflections with I > 2σ(I)
R_int = 0.044
θ_max = 32.5°
h = −23 → 23
k = −7 → 5
l = −22 → 17

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.094
S = 1.02
1899 reflections
71 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0677P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.002
Δρ_max = 1.07 e Å⁻³
Δρ_min = −1.49 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.0037 (6)

Table 1
Selected geometric parameters (Å, °)

As1—O3	1.6375 (17)
As1—O4	1.6669 (16)
As1—O1	1.7071 (17)
As1—O2	1.7180 (18)

N1—C1—C2—C1ⁱ	179.5 (3)
Symmetry code: (i) $[-x+{\script{3\over 2}}, y, -z+1]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O4ⁱⁱ	0.83	1.82	2.608 (3)	159
O2—H2⋯O4ⁱⁱⁱ	0.90	1.74	2.603 (3)	161
N1—H3⋯O3^iv	0.89	1.89	2.740 (3)	160
N1—H4⋯O4	0.89	2.13	2.967 (3)	156
N1—H5⋯O3^v	0.89	1.97	2.818 (3)	158
C1—H7⋯O2^vi	0.97	2.48	3.389 (3)	156
C2—H8⋯O2^v	0.97	2.52	3.482 (3)	174
Symmetry codes: (ii) x, y-1, z; (iii) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vi) $[x, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

The I-centred unit cell was chosen in preference to the C-centred setting (space group C2/c) to avoid a very obtuse β angle of 127° (Mighell, 2003 ). 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 = 0.97 Å and N—H = 0.89 Å) and refined as riding, allowing for free rotation of the –NH₃ group. The constraint U_iso(H) = 1.2U_eq(carrier) was applied in all cases. The highest difference peak is 0.95 Å from O3 and the deepestdifference hole is 1.20 Å from As1.

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 (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/S1600536805017411/lh6441sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805017411/lh6441Isup2.hkl

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 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Propane-1,3-diaminium bis(dihydrogenarsenate) top

Crystal data top

(C₃H₁₂N₂)[AsH₂O₄]₂	F(000) = 712
M_r = 358.02	D_x = 2.244 Mg m⁻³
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2ya	Cell parameters from 3458 reflections
a = 15.5563 (8) Å	θ = 2.7–32.5°
b = 4.6549 (2) Å	µ = 6.33 mm⁻¹
c = 15.0454 (7) Å	T = 293 K
β = 103.399 (1)°	Plate, colourless
V = 1059.83 (9) Å³	0.50 × 0.19 × 0.03 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD diffractometer	1899 independent reflections
Radiation source: fine-focus sealed tube	1667 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ω scans	θ_max = 32.5°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −23→23
T_min = 0.144, T_max = 0.833	k = −7→5
5128 measured reflections	l = −22→17

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)] = 0.037	H-atom parameters constrained
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0677P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.002
1899 reflections	Δρ_max = 1.07 e Å⁻³
71 parameters	Δρ_min = −1.49 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: 0.0037 (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	0.610145 (14)	0.09809 (4)	0.190204 (14)	0.01589 (11)
O1	0.55861 (13)	−0.1697 (4)	0.23548 (14)	0.0284 (4)
H1	0.5753	−0.3385	0.2364	0.034*
O2	0.70063 (13)	−0.0671 (4)	0.16560 (14)	0.0250 (4)
H2	0.7484	0.0281	0.1966	0.030*
O3	0.54520 (12)	0.2119 (5)	0.09502 (11)	0.0304 (4)
O4	0.64362 (12)	0.3454 (3)	0.27093 (12)	0.0212 (3)
N1	0.58882 (16)	0.1073 (4)	0.43221 (15)	0.0242 (4)
H3	0.5430	−0.0066	0.4097	0.029*
H4	0.5975	0.2257	0.3887	0.029*
H5	0.5778	0.2094	0.4783	0.029*
C1	0.66881 (18)	−0.0695 (5)	0.46541 (19)	0.0262 (5)
H6	0.6782	−0.1908	0.4161	0.031*
H7	0.6599	−0.1934	0.5143	0.031*
C2	0.7500	0.1146 (7)	0.5000	0.0252 (7)
H8	0.7405	0.2370	0.5490	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
As1	0.01398 (14)	0.01850 (15)	0.01456 (14)	0.00068 (6)	0.00202 (9)	0.00031 (6)
O1	0.0256 (9)	0.0181 (7)	0.0455 (11)	0.0000 (7)	0.0163 (8)	0.0041 (7)
O2	0.0154 (8)	0.0319 (9)	0.0282 (9)	0.0004 (6)	0.0061 (7)	−0.0091 (6)
O3	0.0263 (9)	0.0458 (10)	0.0166 (7)	0.0110 (8)	−0.0004 (6)	0.0049 (7)
O4	0.0193 (7)	0.0216 (7)	0.0223 (8)	−0.0016 (6)	0.0039 (6)	−0.0038 (6)
N1	0.0206 (10)	0.0326 (11)	0.0184 (9)	−0.0023 (7)	0.0025 (8)	−0.0023 (6)
C1	0.0214 (11)	0.0290 (11)	0.0253 (12)	−0.0015 (9)	−0.0007 (9)	0.0031 (9)
C2	0.0181 (15)	0.0301 (16)	0.0251 (16)	0.000	0.0004 (12)	0.000

Geometric parameters (Å, º) top

As1—O3	1.6375 (17)	N1—H4	0.8900
As1—O4	1.6669 (16)	N1—H5	0.8900
As1—O1	1.7071 (17)	C1—C2	1.515 (3)
As1—O2	1.7180 (18)	C1—H6	0.9700
O1—H1	0.8265	C1—H7	0.9700
O2—H2	0.8979	C2—C1ⁱ	1.515 (3)
N1—C1	1.479 (3)	C2—H8	0.9700
N1—H3	0.8900

O3—As1—O4	116.04 (9)	H3—N1—H5	109.5
O3—As1—O1	109.49 (10)	H4—N1—H5	109.5
O4—As1—O1	108.06 (9)	N1—C1—C2	111.72 (19)
O3—As1—O2	109.06 (9)	N1—C1—H6	109.3
O4—As1—O2	109.45 (9)	C2—C1—H6	109.3
O1—As1—O2	104.07 (8)	N1—C1—H7	109.3
As1—O1—H1	121.7	C2—C1—H7	109.3
As1—O2—H2	106.8	H6—C1—H7	107.9
C1—N1—H3	109.5	C1—C2—C1ⁱ	111.1 (3)
C1—N1—H4	109.5	C1—C2—H8	109.4
H3—N1—H4	109.5	C1ⁱ—C2—H8	109.4
C1—N1—H5	109.5

N1—C1—C2—C1ⁱ	179.5 (3)

Symmetry code: (i) −x+3/2, y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4ⁱⁱ	0.83	1.82	2.608 (3)	159
O2—H2···O4ⁱⁱⁱ	0.90	1.74	2.603 (3)	161
N1—H3···O3^iv	0.89	1.89	2.740 (3)	160
N1—H4···O4	0.89	2.13	2.967 (3)	156
N1—H5···O3^v	0.89	1.97	2.818 (3)	158
C1—H7···O2^vi	0.97	2.48	3.389 (3)	156
C2—H8···O2^v	0.97	2.52	3.482 (3)	174

Symmetry codes: (ii) x, y−1, z; (iii) −x+3/2, −y+1/2, −z+1/2; (iv) −x+1, y−1/2, −z+1/2; (v) x, −y+1/2, z+1/2; (vi) x, −y−1/2, z+1/2.

Acknowledgements

HSW thanks the Carnegie Trust for the Universities of Scotland for an undergraduate vacation studentship.

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