Piperazine-1,4-diium bis­[tetra­chlorido­aurate(III)] dihydrate

Polishchuk, A.V.; Karaseva, E.T.; Pushilin, M.A.

doi:10.1107/S1600536809041063

metal-organic compounds

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Volume 65| Part 11| November 2009| Page m1377

https://doi.org/10.1107/S1600536809041063

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Piperazine-1,4-diium bis[tetrachloridoaurate(III)] dihydrate

Anna V. Polishchuk,^a Emilia T. Karaseva ^a and Mikhail A. Pushilin ^a ^*

^aInstitute of Chemistry FEB RAS, 159 Prospekt Stoletiya, Vladivostok 690022, Russian Federation
^*Correspondence e-mail: pumalych@ich.dvo.ru

(Received 30 September 2009; accepted 8 October 2009; online 17 October 2009)

In the title compound, (C₄H₁₂N₂)[AuCl₄]₂·2H₂O, the Au^III atom has a square-planar geometry. The piperazinium dication lies on an inversion centre and adopts a typical chair conformation. In the crystal, a combination of N—H⋯O, N—H⋯Cl and O—H⋯Cl hydrogen bonds results in the formation of a three-dimensional network.

Related literature

For bond distances, see: Allen et al. (1987 ). For similar compounds, see: Kefi & Nasr (2005 ); Sharutin et al. (2008 ); Sutherland & Harrison (2009 ); Zhang et al. (2006 ).

Experimental

Crystal data

(C₄H₁₂N₂)[AuCl₄]₂·2H₂O
M_r = 801.72
Monoclinic, P 2₁ /c
a = 7.7327 (11) Å
b = 10.1114 (15) Å
c = 11.9024 (18) Å
β = 105.565 (3)°
V = 896.5 (2) Å³
Z = 2
Mo Kα radiation
μ = 17.53 mm⁻¹
T = 296 K
0.33 × 0.23 × 0.08 mm

Data collection

Bruker SMART CCD 1000 diffractometer
Absorption correction: gaussian (XPREP and SADABS; Bruker, 2003 ) T_min = 0.043, T_max = 0.251
6689 measured reflections
2630 independent reflections
2446 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.018
wR(F²) = 0.044
S = 1.09
2630 reflections
89 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.36 e Å⁻³
Δρ_min = −0.75 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O1ⁱ	0.90	1.97	2.815 (3)	155
N1—H1B⋯O1ⁱⁱ	0.90	2.39	2.960 (3)	121
O1—H2⋯Cl1ⁱⁱⁱ	0.839 (13)	2.57 (2)	3.3035 (19)	147 (3)
O1—H2⋯Cl4ⁱⁱⁱ	0.839 (13)	2.83 (3)	3.445 (2)	131 (3)
O1—H1⋯Cl4	0.822 (14)	2.71 (3)	3.382 (2)	140 (3)
O1—H1⋯Cl3	0.822 (14)	2.67 (3)	3.268 (2)	131 (3)
N1—H1A⋯Cl1	0.90	2.60	3.373 (2)	144
N1—H1A⋯Cl2	0.90	2.81	3.575 (2)	143
Symmetry codes: (i) x, y-1, z; (ii) -x+1, -y+1, -z; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809041063/su2149sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809041063/su2149Isup2.hkl

checkCIF report

Comment top

The asymmetric unit of the title compound consists of a discrete [AuCl₄]^- complex anion, one water molecule and one-half of a diprotonated piperazinium dication (Fig. 1). The Au atom in the tetrachloridoaurate anion exhibits a square-planar coordination. A similar geometry has been observed, for exemple, in tetraphenylantimony(V) tetrachloroaurate (Sharutin et al., 2008) and bipyridinium tetrachloroaurate (Zhang et al., 2006). The Au—Cl bond lengths are in the range of 2.2802 (6) - 2.2842 (7) Å. In the crystal structure, the anions are stacked into columns along the a axis, parallel to each other. The distances between anion planes are ca. 3.734 and 3.999 Å. The organic piperazinium dication lies at an inversion centre and adopts a typical chair geometry with normal valence bond lengths (Allen et al., 1987) and angles, as observed in the structures of piperazinediium tetrachloridozincate (Sutherland & Harrison, 2009) and piperazinediium tetrachloridozincate monohydrate (Kefi & Nasr, 2005).

The piperazinium dications and water molecules are linked by intermolecular bifurcated N—H···O hydrogen bonds to form chains proagagting along the [100] direction (Fig. 2). The water-piperaziniun chains and the anion stacks form a three-dimensional framework (Fig. 3) via bifurcated N—H···Cl and O—H···Cl hydrogen bonds (Table 1).

Related literature top

For bond distances, see: Allen et al. (1987). For similar compounds, see: Kefi & Nasr (2005); Sharutin et al. (2008); Sutherland & Harrison (2009); Zhang et al. (2006).

Experimental top

The chemicals used were of reagent grade. Ciprofloxacin hydrochloride (37 mg, 0.1 mmol) and gold(III) chloride (AuCl₃ 30 mg, 0.1 mmol) were dissolved in 10 ml of 32% of HCl. Yellow crystals of the title compound, suitable for X-ray analysis, were obtained by slow evaporation in air at rt, after a few days.

Structure description top

For bond distances, see: Allen et al. (1987). For similar compounds, see: Kefi & Nasr (2005); Sharutin et al. (2008); Sutherland & Harrison (2009); Zhang et al. (2006).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

	Fig. 1. The asymmetric unit of the title compound, showing 50% displacement ellipsoids (arbitrary spheres for the H atoms).
	Fig. 2. Fragment of the water-piperazinium hydrogen bonded chain, with the hydrogen bonds indicated by dotted lines. Symmetry codes are the same as in Table 1.
	Fig. 3. A view along the a axis of the crystal packing of the title compound, with the hydrogen bonds shown as dotted lines. All the C-bound H atoms have been omitted for clarity. Symmetry codes are the same as in Table 1.

Piperazine-1,4-diium bis[tetrachloridoaurate(III)] dihydrate top

Crystal data top

(C₄H₁₂N₂)[AuCl₄]₂·2H₂O	F(000) = 728
M_r = 801.72	D_x = 2.970 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1008 reflections
a = 7.7327 (11) Å	θ = 3.4–30.6°
b = 10.1114 (15) Å	µ = 17.53 mm⁻¹
c = 11.9024 (18) Å	T = 296 K
β = 105.565 (3)°	Prism, yellow
V = 896.5 (2) Å³	0.33 × 0.23 × 0.08 mm
Z = 2

Data collection top

Bruker SMART CCD 1000 diffractometer	2630 independent reflections
Radiation source: fine-focus sealed tube	2446 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
Detector resolution: 8.33 pixels mm^-1	θ_max = 31.5°, θ_min = 2.7°
ω scans	h = −10→9
Absorption correction: gaussian (XPREP and SADABS; Bruker, 2003)	k = −13→12
T_min = 0.043, T_max = 0.251	l = −14→17
6689 measured reflections

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)] = 0.018	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.044	w = 1/[σ²(F_o²) + (0.0203P)² + 0.7643P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.002
2630 reflections	Δρ_max = 1.36 e Å⁻³
89 parameters	Δρ_min = −0.75 e Å⁻³
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.01512 (17)

Crystal data top

(C₄H₁₂N₂)[AuCl₄]₂·2H₂O	V = 896.5 (2) Å³
M_r = 801.72	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.7327 (11) Å	µ = 17.53 mm⁻¹
b = 10.1114 (15) Å	T = 296 K
c = 11.9024 (18) Å	0.33 × 0.23 × 0.08 mm
β = 105.565 (3)°

Data collection top

Bruker SMART CCD 1000 diffractometer	2630 independent reflections
Absorption correction: gaussian (XPREP and SADABS; Bruker, 2003)	2446 reflections with I > 2σ(I)
T_min = 0.043, T_max = 0.251	R_int = 0.018
6689 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.018	2 restraints
wR(F²) = 0.044	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 1.36 e Å⁻³
2630 reflections	Δρ_min = −0.75 e Å⁻³
89 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

	x	y	z	U_iso*/U_eq
Au1	0.258077 (10)	0.481141 (8)	0.040268 (7)	0.03248 (2)
Cl1	0.22668 (9)	0.31457 (6)	0.16243 (5)	0.04886 (14)
Cl2	0.12348 (9)	0.34990 (6)	−0.11438 (5)	0.04885 (15)
Cl3	0.29217 (10)	0.64504 (6)	−0.08394 (6)	0.05264 (16)
Cl4	0.39054 (10)	0.60981 (7)	0.19756 (6)	0.05297 (16)
O1	0.5108 (2)	0.88550 (19)	0.07637 (17)	0.0495 (4)
H1	0.499 (5)	0.8047 (14)	0.075 (3)	0.074*
H2	0.546 (5)	0.890 (4)	0.1494 (12)	0.074*
N1	0.1859 (2)	0.02747 (18)	0.01336 (18)	0.0360 (4)
H1A	0.1882	0.1163	0.0188	0.043*
H1B	0.2985	−0.0004	0.0190	0.043*
C2	0.1246 (3)	−0.0285 (2)	0.1115 (2)	0.0390 (5)
H2A	0.2018	0.0029	0.1849	0.047*
H2B	0.1330	−0.1242	0.1106	0.047*
C3	−0.0679 (3)	0.0117 (2)	0.1018 (2)	0.0384 (5)
H3A	−0.1087	−0.0305	0.1632	0.046*
H3B	−0.0741	0.1067	0.1113	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.03239 (3)	0.02880 (4)	0.03751 (4)	0.00020 (3)	0.01157 (3)	−0.00039 (3)
Cl1	0.0685 (3)	0.0368 (3)	0.0414 (3)	−0.0146 (2)	0.0150 (2)	0.0013 (2)
Cl2	0.0623 (3)	0.0419 (3)	0.0398 (3)	−0.0061 (3)	0.0092 (2)	−0.0053 (2)
Cl3	0.0701 (4)	0.0397 (3)	0.0488 (3)	−0.0048 (3)	0.0172 (3)	0.0087 (2)
Cl4	0.0677 (3)	0.0412 (3)	0.0463 (3)	−0.0155 (3)	0.0088 (3)	−0.0056 (2)
O1	0.0402 (7)	0.0474 (9)	0.0594 (10)	0.0011 (7)	0.0107 (7)	0.0196 (8)
N1	0.0297 (7)	0.0361 (9)	0.0450 (9)	−0.0024 (6)	0.0151 (7)	−0.0022 (7)
C2	0.0357 (9)	0.0425 (12)	0.0386 (11)	0.0013 (8)	0.0096 (8)	0.0047 (8)
C3	0.0371 (9)	0.0442 (11)	0.0382 (10)	−0.0045 (8)	0.0176 (8)	−0.0048 (8)

Geometric parameters (Å, º) top

Au1—Cl1	2.2802 (6)	N1—H1A	0.9000
Au1—Cl2	2.2813 (6)	N1—H1B	0.9000
Au1—Cl3	2.2827 (7)	C2—C3	1.517 (3)
Au1—Cl4	2.2842 (7)	C2—H2A	0.9700
O1—H1	0.822 (14)	C2—H2B	0.9700
O1—H2	0.839 (13)	C3—H3A	0.9700
N1—C3ⁱ	1.482 (3)	C3—H3B	0.9700
N1—C2	1.486 (3)

Cl1—Au1—Cl2	88.92 (3)	N1—C2—C3	110.55 (18)
Cl1—Au1—Cl3	178.87 (3)	N1—C2—H2A	109.5
Cl2—Au1—Cl3	90.39 (3)	C3—C2—H2A	109.5
Cl1—Au1—Cl4	89.95 (3)	N1—C2—H2B	109.5
Cl2—Au1—Cl4	178.82 (2)	C3—C2—H2B	109.5
Cl3—Au1—Cl4	90.74 (3)	H2A—C2—H2B	108.1
H1—O1—H2	94 (3)	N1ⁱ—C3—C2	110.31 (19)
C3ⁱ—N1—C2	112.20 (17)	N1ⁱ—C3—H3A	109.6
C3ⁱ—N1—H1A	109.2	C2—C3—H3A	109.6
C2—N1—H1A	109.2	N1ⁱ—C3—H3B	109.6
C3ⁱ—N1—H1B	109.2	C2—C3—H3B	109.6
C2—N1—H1B	109.2	H3A—C3—H3B	108.1
H1A—N1—H1B	107.9

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1ⁱⁱ	0.90	1.97	2.815 (3)	155
N1—H1B···O1ⁱⁱⁱ	0.90	2.39	2.960 (3)	121
O1—H2···Cl1^iv	0.84 (1)	2.57 (2)	3.3035 (19)	147 (3)
O1—H2···Cl4^iv	0.84 (1)	2.83 (3)	3.445 (2)	131 (3)
O1—H1···Cl4	0.82 (1)	2.71 (3)	3.382 (2)	140 (3)
O1—H1···Cl3	0.82 (1)	2.67 (3)	3.268 (2)	131 (3)
N1—H1A···Cl1	0.90	2.60	3.373 (2)	144
N1—H1A···Cl2	0.90	2.81	3.575 (2)	143

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

Experimental details

Crystal data
Chemical formula	(C₄H₁₂N₂)[AuCl₄]₂·2H₂O
M_r	801.72
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	7.7327 (11), 10.1114 (15), 11.9024 (18)
β (°)	105.565 (3)
V (Å³)	896.5 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	17.53
Crystal size (mm)	0.33 × 0.23 × 0.08

Data collection
Diffractometer	Bruker SMART CCD 1000
Absorption correction	Gaussian (XPREP and SADABS; Bruker, 2003)
T_min, T_max	0.043, 0.251
No. of measured, independent and observed [I > 2σ(I)] reflections	6689, 2630, 2446
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.735

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.044, 1.09
No. of reflections	2630
No. of parameters	89
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.36, −0.75

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1ⁱ	0.90	1.97	2.815 (3)	155
N1—H1B···O1ⁱⁱ	0.90	2.39	2.960 (3)	121
O1—H2···Cl1ⁱⁱⁱ	0.839 (13)	2.57 (2)	3.3035 (19)	147 (3)
O1—H2···Cl4ⁱⁱⁱ	0.839 (13)	2.83 (3)	3.445 (2)	131 (3)
O1—H1···Cl4	0.822 (14)	2.71 (3)	3.382 (2)	140 (3)
O1—H1···Cl3	0.822 (14)	2.67 (3)	3.268 (2)	131 (3)
N1—H1A···Cl1	0.90	2.60	3.373 (2)	144
N1—H1A···Cl2	0.90	2.81	3.575 (2)	143

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

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Bruker (2003). XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Kefi, R. & Nasr, C. B. (2005). Z. Kristallogr. New Cryst. Struct. 220, 241–242. CAS Google Scholar
Sharutin, V. V., Senchurin, V. S., Fastovets, O. A., Pakusina, A. P. & Sharutina, O. K. (2008). Russ. J. Coord. Chem. 34, 367–373. Web of Science CrossRef CAS Google Scholar
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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page m1377

https://doi.org/10.1107/S1600536809041063

Open

access