Hexane-1,6-diammonium bis­(dihydrogenarsenate): infinite anionic layers containing R66(24) loops

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

doi:10.1107/S1600536807007672

metal-organic compounds

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ISSN: 2056-9890

Volume 63| Part 3| March 2007| Pages m902-m904

https://doi.org/10.1107/S1600536807007672

Hexane-1,6-diammonium bis(dihydrogenarsenate): infinite anionic layers containing R₆⁶(24) loops

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 13 February 2007; accepted 14 February 2007; online 28 February 2007)

The title compound, C₆H₁₈N₂²⁺·2H₂AsO₄⁻, contains a network of doubly protonated centrosymmetric hexane-1,6-diammonium cations and dihydrogenarsenate anions. These species interact by way of cation-to-anion N—H⋯O and anion-to-anion O—H⋯O hydrogen bonds, the latter leading to infinite sheets of the H₂AsO₄⁻ anions.

Comment

The title compound, (I) (Fig. 1), was prepared as part of our ongoing studies of hydrogen-bonding interactions in the molecular salts of oxo-anions (Wilkinson & Harrison, 2005 ).

The tetrahedral H₂AsO₄⁻ anion in (I) [mean As—O = 1.683 (2) Å] shows the usual distinction (Table 1) between the protonated and unprotonated As—O bond lengths. The complete hexane-1,6-diammonium dication has a centre of symmetry at the mid-point of the C3—C3ⁱ bond [symmetry code: (i) −x, −y, −z]. The N1—C1—C2—C3 torsion angle of −72.87 (18)° indicates a gauche conformation for these four atoms within the dication, whereas C1—C2—C3—C3ⁱ are anti [torsion angle = 179.17 (19)°]

As well as Coulombic forces, the component species in (I) interact by way of a network of O—H⋯O and N—H⋯O hydrogen bonds (Table 2). The H₂AsO₄⁻ units are linked into infinite sheets (Fig. 2) by way of the O—H⋯O bonds. The O3—H1⋯O2ⁱⁱ bond (see Table 2 for symmetry code) results in inversion-generated dimeric pairs of H₂AsO₄⁻ tetrahedra linked by a double (i.e. O—H⋯O + O⋯H—O) hydrogen bond. The O4—H2⋯O1ⁱⁱⁱ bond links the dimers into an infinte sheet (Fig. 3) propagating in (100). The As⋯Asⁱⁱ and As⋯Asⁱⁱⁱ separations are 4.3922 (3) and 4.8900 (3) Å, respectively. A supramolecular R₆⁶(24) loop (Bernstein et al., 1995 ) arises for each circuit of six tetrahedra within the sheet.

The anionic sheets are bridged by the organic cations, each of which participates in three nearly linear N—H⋯O interactions from its –NH₃⁺ group (Table 2), resulting in a layered crystal structure (Fig. 3).

Guanidinium dihydrogenarsenate, CH₆N₃·H₂AsO₄ (Wilkinson & Harrison, 2005), contains a hydrogen-bonded tetrahedral sheet topology similar to that in the title compound, despite the different cation–anion ratio in CH₆N₃·H₂AsO₄.

Figure 1
The molecular structure of (I)

, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as spheres of arbitrary radius. The hydrogen bond is indicated by a double-dashed line. [Symmetry code: (i) −x, −y, −z.]

Figure 2
Detail of a part of a (100) hydrogen-bonded sheet of H₂AsO₄⁻ groups in (I)

, with hydrogen bonds indicated by double-dashed lines. Symmetry codes as in Table 2

Figure 3
The packing in (I)

, viewed down [010], showing the (100) dihydrogenarsenate layers mediated by the organic cations. H atoms have been omitted for clarity.

Experimental

An aqueous 1,6-diaminohexane solution (0.5 M, 10 ml) was added to an aqueous H₃AsO₄ solution (0.5 M, 10 ml), resulting in a clear solution. A mass of chunks and blocks of (I) grew as the water evaporated over the course of a few days.

Crystal data

C₆H₁₈N₂²⁺·2AsH₂O₄⁻
M_r = 400.10
Monoclinic, P 2₁ /c
a = 9.5237 (5) Å
b = 10.1029 (5) Å
c = 8.0747 (4) Å
β = 108.385 (1)°
V = 737.27 (6) Å³
Z = 2
Mo Kα radiation
μ = 4.56 mm⁻¹
T = 293 (2) K
0.33 × 0.31 × 0.13 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.314, T_max = 0.589 (expected range = 0.295–0.553)
7129 measured reflections
2649 independent reflections
2187 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.057
S = 0.99
2649 reflections
83 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Table 1
Selected bond lengths (Å)

As1—O1	1.6501 (11)
As1—O2	1.6656 (11)
As1—O4	1.6998 (13)
As1—O3	1.7169 (11)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H1⋯O2ⁱⁱ	0.92	1.70	2.6103 (15)	169
O4—H2⋯O1ⁱⁱⁱ	0.86	1.71	2.5613 (16)	170
N1—H3⋯O2	0.89	2.01	2.8938 (17)	172
N1—H4⋯O2ⁱⁱⁱ	0.89	2.12	2.9681 (19)	159
N1—H5⋯O1^iv	0.89	1.89	2.7714 (16)	169
Symmetry codes: (ii) -x+1, -y+1, -z+1; (iii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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. The other H atoms were positioned geometrically, with C—H = 0.97 Å and N—H = 0.89 Å, and refined as riding atoms. U_iso(H) = 1.2U_eq(carrier) for all H atoms.

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/S1600536807007672/sj2226sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807007672/sj2226Isup2.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.

Hexane-1,6-diammonium bis(dihydrogenarsenate) top

Crystal data top

C₆H₁₈N₂²⁺·2AsH₂O₄⁻	F(000) = 404
M_r = 400.10	D_x = 1.802 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4034 reflections
a = 9.5237 (5) Å	θ = 2.3–32.5°
b = 10.1029 (5) Å	µ = 4.56 mm⁻¹
c = 8.0747 (4) Å	T = 293 K
β = 108.385 (1)°	Block, colourless
V = 737.27 (6) Å³	0.33 × 0.31 × 0.13 mm
Z = 2

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	2649 independent reflections
Radiation source: fine-focus sealed tube	2187 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ω scans	θ_max = 32.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −14→11
T_min = 0.314, T_max = 0.589	k = −15→10
7129 measured reflections	l = −12→12

Refinement top

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: difmap and geom
wR(F²) = 0.057	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0336P)²] where P = (F_o² + 2F_c²)/3
2649 reflections	(Δ/σ)_max = 0.001
83 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.53 e Å⁻³

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	0.606026 (16)	0.386539 (14)	0.738786 (17)	0.02384 (5)
O1	0.62562 (15)	0.38557 (10)	0.94925 (14)	0.0325 (2)
O2	0.43378 (12)	0.35753 (10)	0.61094 (14)	0.0277 (2)
O3	0.66259 (15)	0.54220 (12)	0.70262 (14)	0.0411 (3)
H1	0.6218	0.5675	0.5883	0.049*
O4	0.72953 (15)	0.28059 (16)	0.69736 (19)	0.0584 (4)
H2	0.6928	0.2329	0.6059	0.070*
N1	0.30110 (15)	0.13220 (12)	0.39759 (17)	0.0276 (3)
H3	0.3475	0.1963	0.4699	0.033*
H4	0.3171	0.1418	0.2954	0.033*
H5	0.3354	0.0539	0.4432	0.033*
C1	0.13969 (19)	0.13983 (17)	0.3713 (2)	0.0341 (3)
H1A	0.1030	0.2257	0.3230	0.041*
H1B	0.1230	0.1316	0.4833	0.041*
C2	0.05421 (18)	0.03200 (17)	0.2497 (2)	0.0330 (3)
H2A	0.1027	−0.0523	0.2869	0.040*
H2B	−0.0445	0.0266	0.2596	0.040*
C3	0.04181 (19)	0.05463 (17)	0.0598 (2)	0.0349 (3)
H3A	−0.0081	0.1382	0.0217	0.042*
H3B	0.1404	0.0612	0.0498	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
As1	0.02682 (8)	0.02320 (8)	0.01871 (7)	−0.00187 (5)	0.00318 (5)	−0.00245 (5)
O1	0.0462 (7)	0.0285 (5)	0.0195 (5)	−0.0035 (5)	0.0055 (5)	0.0019 (4)
O2	0.0270 (5)	0.0288 (5)	0.0230 (5)	−0.0047 (4)	0.0019 (4)	0.0001 (4)
O3	0.0503 (8)	0.0394 (7)	0.0247 (5)	−0.0200 (6)	−0.0007 (5)	0.0064 (5)
O4	0.0353 (7)	0.0683 (10)	0.0603 (9)	0.0106 (6)	−0.0012 (6)	−0.0400 (8)
N1	0.0296 (6)	0.0261 (6)	0.0238 (6)	−0.0021 (5)	0.0035 (5)	−0.0016 (4)
C1	0.0320 (8)	0.0372 (9)	0.0314 (8)	0.0057 (6)	0.0077 (6)	−0.0043 (6)
C2	0.0256 (7)	0.0395 (9)	0.0310 (8)	−0.0040 (6)	0.0049 (6)	0.0003 (6)
C3	0.0334 (8)	0.0365 (9)	0.0303 (8)	−0.0104 (7)	0.0037 (6)	−0.0006 (6)

Geometric parameters (Å, º) top

As1—O1	1.6501 (11)	C1—C2	1.520 (2)
As1—O2	1.6656 (11)	C1—H1A	0.9700
As1—O4	1.6998 (13)	C1—H1B	0.9700
As1—O3	1.7169 (11)	C2—C3	1.518 (2)
O3—H1	0.9179	C2—H2A	0.9700
O4—H2	0.8586	C2—H2B	0.9700
N1—C1	1.486 (2)	C3—C3ⁱ	1.516 (3)
N1—H3	0.8900	C3—H3A	0.9700
N1—H4	0.8900	C3—H3B	0.9700
N1—H5	0.8900

O1—As1—O2	113.99 (6)	C2—C1—H1A	109.2
O1—As1—O4	109.78 (7)	N1—C1—H1B	109.2
O2—As1—O4	112.00 (6)	C2—C1—H1B	109.2
O1—As1—O3	103.94 (5)	H1A—C1—H1B	107.9
O2—As1—O3	110.87 (5)	C3—C2—C1	113.58 (14)
O4—As1—O3	105.64 (8)	C3—C2—H2A	108.8
As1—O3—H1	111.7	C1—C2—H2A	108.8
As1—O4—H2	113.8	C3—C2—H2B	108.8
C1—N1—H3	109.5	C1—C2—H2B	108.8
C1—N1—H4	109.5	H2A—C2—H2B	107.7
H3—N1—H4	109.5	C3ⁱ—C3—C2	113.04 (17)
C1—N1—H5	109.5	C3ⁱ—C3—H3A	109.0
H3—N1—H5	109.5	C2—C3—H3A	109.0
H4—N1—H5	109.5	C3ⁱ—C3—H3B	109.0
N1—C1—C2	111.98 (13)	C2—C3—H3B	109.0
N1—C1—H1A	109.2	H3A—C3—H3B	107.8

N1—C1—C2—C3	−72.87 (18)	C1—C2—C3—C3ⁱ	179.17 (19)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1···O2ⁱⁱ	0.92	1.70	2.6103 (15)	169
O4—H2···O1ⁱⁱⁱ	0.86	1.71	2.5613 (16)	170
N1—H3···O2	0.89	2.01	2.8938 (17)	172
N1—H4···O2ⁱⁱⁱ	0.89	2.12	2.9681 (19)	159
N1—H5···O1^iv	0.89	1.89	2.7714 (16)	169

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

Acknowledgements

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

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
Bruker (1999). SMART (Version 5.624), SAINT (Version 6.02a) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Wilkinson, H. S. & Harrison, W. T. A. (2005). Acta Cryst. E61, m2023–m2025. Web of Science CSD CrossRef IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 63| Part 3| March 2007| Pages m902-m904

https://doi.org/10.1107/S1600536807007672

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