Piperazinium hydrogenarsenate monohydrate

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

doi:10.1107/S1600536807007763

metal-organic compounds

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ISSN: 2056-9890

Volume 63| Part 3| March 2007| Pages m905-m907

https://doi.org/10.1107/S1600536807007763

Piperazinium hydrogenarsenate monohydrate

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 14 February 2007; accepted 15 February 2007; online 28 February 2007)

In the title compound, C₄H₁₂N₂²⁺·HAsO₄²⁻·H₂O, the component species interact by way of N—H⋯O and O—H⋯O hydrogen bonds, the latter leading to infinite sheets of HAsO₄²⁻ anions and water molecules containing R₆⁶(18) loops. The asymmetric unit contains one anion, one water molecule and half each of two centrosymmetric cations.

Comment

The As^V-containing title compound, (I), (Fig. 1), arose unexpectedly as a result of atmospheric oxidation from a solution-mediated reaction containing As^III (Lee & Harrison, 2004 ). It complements C₄H₁₂N₂·2H₂AsO₄, (II) (Wilkinson & Harrison, 2007 ), which contains the same organic cation accompanied by monovalent dihydrogenarsenate anions. Compound (I) is isostructural with its hydrogenphosphate analogue (Riou et al., 1993 ).

The tetrahedral HAsO₄²⁻ anion in (I) shows three short As—O links with formal partial double-bond character, and one longer As—OH bond (Table 1). The mean As—O bond lengths in (I) [1.683 (2) Å] and (II) [1.684 (2) Å] are indistinguishable.

The asymmetric unit contains one anion, one water molecule and half each of two centrosymmetric cations. Each cation adopts a typical chair conformation.

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 HAsO₄²⁻ dianions and water molecules are linked into infinite sheets (Fig. 2) propagating in (010) by way of the O—H⋯O bonds. The water molecule accepts one hydrogen bond and makes two hydrogen bonds. Unlike the case in many related molecular salts (Lee & Harrison, 2003 ), there are no direct hydrogen-bond links between hydrogenarsenate groups. A supramolecular R₆⁶(18) loop (Bernstein et al., 1995 ) arises from this hydrogen-bond topology.

The hydrogenarsenate–water sheets are bridged by the piperazinium cations, which participate in two strong N—H⋯O interactions from each of their NH₂ groups to O atoms of nearby hydrogenarsenate tetrahedra. Thus, there are no hydrogen-bond links between organic cations and water molecules in (I). Overall, a layered architecture (Fig. 3) results, in which layers of organic and inorganic species alternate along [010]. Compound (II) also possesses alternating inorganic and organic layers; in this compound, supramolecular R₆⁶(24) loops arise for each circuit of six H₂AsO₄⁻ tetrahedra within a sheet.

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 showwn as spheres of arbitrary radius. Hydrogen bonds are indicated by double-dashed lines. [Symmetry codes: (i) −x, 1 − y, 1 − z; (ii) −x, 2 − y, 1 − z.]

Figure 2
Detail of a part of an (010) hydrogen-bonded sheet of HAsO₄²⁻ groups and water molecules in (I)

, with H bonds indicated by double-dashed lines. (Symmetry codes as in Table 1

Figure 3
A view down [100] of the unit-cell packing in (I)

, showing the (010) hydrogenarsenate–water layers mediated by the organic cations. Hydrogen bonds are indicated by double-dashed lines and C-bound H atoms have been omitted for clarity.

Experimental

In an attempt to synthesize an analogue of (H₃NCH₂CH₂NH₃)[AsO₂]₂ (Lee & Harrison, 2004), aqueous solutions of piperazine (0.1 M) and As^III₂O₃ (0.1 M) were mixed, resulting in a colourless mixture. Translucent faceted truncated cubes of As₂O₃ recrystallized after one day. After several months, colourless slabs of (I) were dredged from the viscous liquor.

Crystal data

C₄H₁₂N₂²⁺·HAsO₄²⁻·H₂O
M_r = 246.10
Monoclinic, P 2₁ /n
a = 6.5093 (2) Å
b = 12.5329 (3) Å
c = 11.2873 (3) Å
β = 97.0816 (16)°
V = 913.80 (4) Å³
Z = 4
Mo Kα radiation
μ = 3.71 mm⁻¹
T = 120 (2) K
0.40 × 0.28 × 0.14 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.318, T_max = 0.625
15415 measured reflections
2094 independent reflections
1898 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.019
wR(F²) = 0.049
S = 1.09
2094 reflections
119 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Selected bond lengths (Å)

As1—O1	1.6627 (12)
As1—O2	1.6680 (12)
As1—O3	1.6760 (11)
As1—O4	1.7264 (12)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H1⋯O5ⁱ	0.842 (10)	1.812 (10)	2.6492 (19)	173 (2)
N1—H1C⋯O2	0.92	1.73	2.6482 (18)	171
N1—H1D⋯O3ⁱⁱ	0.92	1.76	2.6722 (18)	173
N2—H2C⋯O1ⁱⁱⁱ	0.92	1.77	2.6788 (18)	169
N2—H2D⋯O3	0.92	1.74	2.6548 (18)	172
O5—H2⋯O2	0.842 (10)	1.863 (10)	2.6998 (18)	173 (2)
O5—H3⋯O1^iv	0.836 (10)	1.892 (12)	2.7065 (18)	164 (2)
Symmetry codes: (i) x-1, y, z; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

O-bound H atoms were found in difference maps and their positions were refined with the restraint O—H = 0.85 (1) Å. C- and N-bonded H atoms were positioned geometrically, with C—H = 0.99 Å and N—H = 0.92 Å, and refined as riding atoms. U_iso(H) = 1.2U_eq(carrier) for all H atoms.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK and 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/S1600536807007763/ng2219sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807007763/ng2219Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and 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.

Piperazinium hydrogenarsenate monohydrate top

Crystal data top

C₄H₁₂N₂²⁺·HAsO₄²⁻·H₂O	F(000) = 504
M_r = 246.10	D_x = 1.789 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2149 reflections
a = 6.5093 (2) Å	θ = 2.9–27.5°
b = 12.5329 (3) Å	µ = 3.71 mm⁻¹
c = 11.2873 (3) Å	T = 120 K
β = 97.0816 (16)°	Slab, colourless
V = 913.80 (4) Å³	0.40 × 0.28 × 0.14 mm
Z = 4

Data collection top

Nonius KappaCCD area-detector diffractometer	2094 independent reflections
Radiation source: fine-focus sealed tube	1898 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω and φ scans	θ_max = 27.5°, θ_min = 3.6°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −8→8
T_min = 0.318, T_max = 0.625	k = −16→16
15415 measured reflections	l = −14→14

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.019	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.049	w = 1/[σ²(F_o²) + (0.0187P)² + 0.7794P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
2094 reflections	Δρ_max = 0.46 e Å⁻³
119 parameters	Δρ_min = −0.47 e Å⁻³
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0104 (7)

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	0.14908 (2)	0.754902 (12)	0.858124 (14)	0.00805 (8)
O1	0.2714 (2)	0.73938 (9)	0.99528 (11)	0.0136 (3)
O2	0.26775 (19)	0.69220 (10)	0.75530 (11)	0.0159 (3)
O3	0.10970 (18)	0.88403 (9)	0.82395 (10)	0.0124 (2)
O4	−0.09090 (19)	0.69654 (10)	0.85928 (12)	0.0179 (3)
H1	−0.175 (3)	0.7282 (16)	0.8085 (17)	0.021*
C1	−0.0938 (3)	0.51032 (14)	0.60902 (14)	0.0139 (4)
H1A	−0.1834	0.5738	0.5930	0.017*
H1B	−0.1097	0.4841	0.6901	0.017*
C2	0.1611 (3)	0.57581 (13)	0.48176 (15)	0.0141 (3)
H2A	0.3098	0.5916	0.4806	0.017*
H2B	0.0818	0.6419	0.4607	0.017*
N1	0.1258 (2)	0.54061 (11)	0.60339 (13)	0.0133 (3)
H1C	0.1617	0.5949	0.6568	0.016*
H1D	0.2096	0.4831	0.6255	0.016*
N2	0.0015 (2)	0.92247 (11)	0.59340 (12)	0.0105 (3)
H2C	−0.0643	0.8658	0.5532	0.013*
H2D	0.0352	0.9027	0.6719	0.013*
C3	0.1939 (3)	0.94754 (13)	0.54065 (15)	0.0124 (3)
H3A	0.2824	0.8832	0.5426	0.015*
H3B	0.2720	1.0040	0.5883	0.015*
C4	−0.1414 (3)	1.01496 (13)	0.58730 (15)	0.0119 (3)
H4A	−0.0759	1.0740	0.6366	0.014*
H4B	−0.2701	0.9944	0.6200	0.014*
O5	0.6199 (2)	0.78709 (11)	0.70613 (12)	0.0190 (3)
H2	0.509 (2)	0.7551 (15)	0.715 (2)	0.023*
H3	0.645 (4)	0.7727 (17)	0.6371 (11)	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
As1	0.00945 (11)	0.00745 (10)	0.00729 (12)	−0.00101 (6)	0.00113 (7)	0.00033 (5)
O1	0.0173 (6)	0.0141 (6)	0.0086 (6)	0.0030 (5)	−0.0012 (5)	0.0016 (4)
O2	0.0163 (6)	0.0169 (6)	0.0152 (6)	−0.0024 (5)	0.0046 (5)	−0.0073 (5)
O3	0.0169 (6)	0.0074 (5)	0.0120 (6)	−0.0004 (4)	−0.0019 (5)	0.0021 (4)
O4	0.0135 (6)	0.0175 (6)	0.0225 (7)	−0.0050 (5)	0.0016 (5)	0.0069 (5)
C1	0.0163 (9)	0.0145 (8)	0.0118 (9)	0.0017 (6)	0.0057 (7)	−0.0008 (6)
C2	0.0147 (8)	0.0116 (8)	0.0161 (9)	−0.0020 (6)	0.0025 (7)	0.0008 (6)
N1	0.0163 (7)	0.0109 (7)	0.0118 (7)	0.0020 (6)	−0.0023 (6)	−0.0022 (5)
N2	0.0132 (7)	0.0087 (6)	0.0089 (7)	−0.0002 (5)	−0.0008 (5)	0.0004 (5)
C3	0.0114 (8)	0.0133 (8)	0.0127 (8)	0.0019 (6)	0.0016 (6)	0.0009 (6)
C4	0.0132 (8)	0.0118 (8)	0.0112 (8)	0.0021 (6)	0.0037 (6)	−0.0004 (6)
O5	0.0142 (6)	0.0283 (7)	0.0149 (7)	−0.0046 (6)	0.0038 (5)	−0.0034 (6)

Geometric parameters (Å, º) top

As1—O1	1.6627 (12)	N1—H1D	0.9200
As1—O2	1.6680 (12)	N2—C4	1.482 (2)
As1—O3	1.6760 (11)	N2—C3	1.485 (2)
As1—O4	1.7264 (12)	N2—H2C	0.9200
O4—H1	0.842 (10)	N2—H2D	0.9200
C1—N1	1.488 (2)	C3—C4ⁱⁱ	1.517 (2)
C1—C2ⁱ	1.515 (2)	C3—H3A	0.9900
C1—H1A	0.9900	C3—H3B	0.9900
C1—H1B	0.9900	C4—C3ⁱⁱ	1.517 (2)
C2—N1	1.487 (2)	C4—H4A	0.9900
C2—C1ⁱ	1.515 (2)	C4—H4B	0.9900
C2—H2A	0.9900	O5—H2	0.842 (10)
C2—H2B	0.9900	O5—H3	0.836 (10)
N1—H1C	0.9200

O1—As1—O2	112.53 (6)	C2—N1—H1D	109.2
O1—As1—O3	111.68 (6)	C1—N1—H1D	109.2
O2—As1—O3	111.44 (6)	H1C—N1—H1D	107.9
O1—As1—O4	105.86 (6)	C4—N2—C3	111.79 (12)
O2—As1—O4	107.62 (6)	C4—N2—H2C	109.3
O3—As1—O4	107.33 (6)	C3—N2—H2C	109.3
As1—O4—H1	108.0 (16)	C4—N2—H2D	109.3
N1—C1—C2ⁱ	110.60 (13)	C3—N2—H2D	109.3
N1—C1—H1A	109.5	H2C—N2—H2D	107.9
C2ⁱ—C1—H1A	109.5	N2—C3—C4ⁱⁱ	110.19 (13)
N1—C1—H1B	109.5	N2—C3—H3A	109.6
C2ⁱ—C1—H1B	109.5	C4ⁱⁱ—C3—H3A	109.6
H1A—C1—H1B	108.1	N2—C3—H3B	109.6
N1—C2—C1ⁱ	110.39 (13)	C4ⁱⁱ—C3—H3B	109.6
N1—C2—H2A	109.6	H3A—C3—H3B	108.1
C1ⁱ—C2—H2A	109.6	N2—C4—C3ⁱⁱ	110.66 (13)
N1—C2—H2B	109.6	N2—C4—H4A	109.5
C1ⁱ—C2—H2B	109.6	C3ⁱⁱ—C4—H4A	109.5
H2A—C2—H2B	108.1	N2—C4—H4B	109.5
C2—N1—C1	111.96 (13)	C3ⁱⁱ—C4—H4B	109.5
C2—N1—H1C	109.2	H4A—C4—H4B	108.1
C1—N1—H1C	109.2	H2—O5—H3	107 (2)

C1ⁱ—C2—N1—C1	−56.31 (19)	C4—N2—C3—C4ⁱⁱ	−56.50 (19)
C2ⁱ—C1—N1—C2	56.43 (19)	C3—N2—C4—C3ⁱⁱ	56.77 (19)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1···O5ⁱⁱⁱ	0.84 (1)	1.81 (1)	2.6492 (19)	173 (2)
N1—H1C···O2	0.92	1.73	2.6482 (18)	171
N1—H1D···O3^iv	0.92	1.76	2.6722 (18)	173
N2—H2C···O1^v	0.92	1.77	2.6788 (18)	169
N2—H2D···O3	0.92	1.74	2.6548 (18)	172
O5—H2···O2	0.84 (1)	1.86 (1)	2.6998 (18)	173 (2)
O5—H3···O1^vi	0.84 (1)	1.89 (1)	2.7065 (18)	164 (2)

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

Acknowledgements

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

References

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COMMUNICATIONS

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Volume 63| Part 3| March 2007| Pages m905-m907

https://doi.org/10.1107/S1600536807007763

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

Piperazinium hydrogenarsenate monohydrate

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds