Piperazinediium tetra­chloridozincate(II)

Sutherland, P.A.; Harrison, W.T.A.

doi:10.1107/S1600536809013981

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page m565

doi:10.1107/S1600536809013981

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Piperazinediium tetrachloridozincate(II)

Pamela A. Sutherland ^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 April 2009; accepted 14 April 2009; online 25 April 2009)

In the title compound, (C₄H₁₂N₂)[ZnCl₄], the Zn atom adopts a slightly distorted tetrahedral geometry. In the crystal, the dication and dianion interact by way of N—H⋯Cl and N—H⋯(Cl,Cl) hydrogen bonds to result in a layered network propagating in (010). The hydrogen-bonding network is unbalanced, with three Cl atoms accepting two hydrogen bonds each and one Cl atom not accepting any hydrogen bonds: the latter shows the shortest Zn—Cl bond length. The crystal studied was found to be an inversion twin.

Related literature

For related structures, see: Bremner & Harrison (2003 ); Kefi & Nasr (2005 ); Wilkinson & Harrison (2007 ). For reference structural data, see: Allen et al. (1995 ). For details of graph-set theory, see: Bernstein et al. (1995 ).

Experimental

Crystal data

(C₄H₁₂N₂)[ZnCl₄]
M_r = 295.33
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.2309 (3) Å
b = 11.0845 (3) Å
c = 11.8443 (4) Å
V = 1080.62 (6) Å³
Z = 4
Mo Kα radiation
μ = 3.21 mm⁻¹
T = 120 K
0.13 × 0.09 × 0.04 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.681, T_max = 0.882
8838 measured reflections
2388 independent reflections
2194 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.094
S = 1.08
2388 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.92 e Å⁻³
Δρ_min = −0.77 e Å⁻³
Absolute structure: Flack (1983 ), 946 Friedel pairs
Flack parameter: 0.44 (2)

Table 1
Selected bond lengths (Å)

Zn1—Cl1	2.2768 (12)
Zn1—Cl2	2.3119 (12)
Zn1—Cl3	2.2532 (12)
Zn1—Cl4	2.2634 (12)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl2	0.92	2.33	3.239 (5)	171
N1—H2⋯Cl4	0.92	2.77	3.168 (4)	107
N1—H2⋯Cl1ⁱ	0.92	2.49	3.206 (4)	135
N2—H3⋯Cl2ⁱⁱ	0.92	2.28	3.174 (4)	164
N2—H4⋯Cl4ⁱⁱⁱ	0.92	2.50	3.194 (5)	133
N2—H4⋯Cl1ⁱⁱⁱ	0.92	2.70	3.346 (4)	128
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (iii) x+1, y, z.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK, and SORTAV (Blessing, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809013981/bg2253sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809013981/bg2253Isup2.hkl

checkCIF report

Comment top

As part of our ongoing investigations of hydrogen bonding networks in molecular salts containing metal-chlorido complexes, (Bremner & Harrison, 2003), we now report the structure of the title compound, (I). The structure of a monohydrate containing the same cation and anion was reported previously (Kefi & Nasr, 2005).

The Zn atom in (I) adopts a slightly distorted tetrahedral coordination arising from four chloride ions (Table 1, Fig. 1) and the organic dication adopts a typical chair geometry with normal bond lengths and angles (Allen et al., 1995), the two nitrogen atoms being displaced from the mean plane of the four carbon atoms by -0.654 (7)Å and 0.685 (6)Å for N1 and N2, respectively.

In the crystal of (I), the components interact by way of simple N—H···Cl and bifurcated N—H···(Cl,Cl) hydrogen bonds (Table 2), such that each NH₂ group forms one simple and one bifurcated bond. Some of the bifurcated H···Cl contacts are relatively long, but still significantly shorter than the H···Cl van der Waals' contact distance of 2.95 Å.

This hydrogen-bond connectivity results in a layered network propagating in (010) (Fig. 2). It is notable that this H bonding arrangement is unbalanced (Wilkinson & Harrison, 2007), with Cl1, Cl2 and Cl4 accepting two hydrogen bonds each, whereas Cl3 does not accept any H bonds. This may correlate with the fact that the Zn1—Cl3 bond length in (I) is the shortest of the four zinc–chloride links. Within the layers, various graph-set motifs (Bernstein et al., 1995) are apparent, including R²₂(6) and R⁴₄(14) loops.

In (C₄H₁₂N₂).[ZnCl₄].H₂O (Kefi & Nasr, 2005), a combination of N—H···Cl, N—H···O and O—H···Cl hydrogen bonds results in a three-dimensional network.

Related literature top

For related structures, see: Bremner & Harrison (2003); Kefi & Nasr (2005); Wilkinson & Harrison (2007). For reference structural data, see: Allen et al. (1995). For details of graph-set theory, see: Bernstein et al. (1995).

Experimental top

In an attempt to prepare a zinc–arsenite open-framework compound, ZnO, As₂O₃ and piperazine hexahydate were dissolved in a 1:1:1 molar ratio in dilute HCl solution. Colourless slabs of (I) grew as the water slowly evaporated, accompanied by octahedra of As₂O₃.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997), and SORTAV (Blessing, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. View of the molecular structure of (I) showing 50% displacement ellipsoids (arbitrary spheres for the H atoms) with the hydrogen bonds indicated by double dashed lines.
	Fig. 2. Part of an (010) hydrogen bonded sheet in the structure of (I) with the hydrogen bonds shown as double dashed lines. All the carbon-bound H atoms are omitted for clarity. Symmetry codes as in Table 2.

Piperazinediium tetrachloridozincate(II) top

Crystal data top

(C₄H₁₂N₂)[ZnCl₄]	F(000) = 592
M_r = 295.33	D_x = 1.815 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 8676 reflections
a = 8.2309 (3) Å	θ = 2.9–27.5°
b = 11.0845 (3) Å	µ = 3.21 mm⁻¹
c = 11.8443 (4) Å	T = 120 K
V = 1080.62 (6) Å³	Slab, colourless
Z = 4	0.13 × 0.09 × 0.04 mm

Data collection top

Nonius KappaCCD diffractometer	2388 independent reflections
Radiation source: fine-focus sealed tube	2194 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
ω and ϕ scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −9→10
T_min = 0.681, T_max = 0.882	k = −12→14
8838 measured reflections	l = −15→15

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)] = 0.042	H-atom parameters constrained
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0219P)² + 3.2663P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
2388 reflections	Δρ_max = 0.92 e Å⁻³
101 parameters	Δρ_min = −0.77 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 946 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.44 (2)

Crystal data top

(C₄H₁₂N₂)[ZnCl₄]	V = 1080.62 (6) Å³
M_r = 295.33	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.2309 (3) Å	µ = 3.21 mm⁻¹
b = 11.0845 (3) Å	T = 120 K
c = 11.8443 (4) Å	0.13 × 0.09 × 0.04 mm

Data collection top

Nonius KappaCCD diffractometer	2388 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	2194 reflections with I > 2σ(I)
T_min = 0.681, T_max = 0.882	R_int = 0.058
8838 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.094	Δρ_max = 0.92 e Å⁻³
S = 1.08	Δρ_min = −0.77 e Å⁻³
2388 reflections	Absolute structure: Flack (1983), 946 Friedel pairs
101 parameters	Absolute structure parameter: 0.44 (2)
0 restraints

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
Zn1	0.27149 (6)	0.46334 (5)	0.09228 (5)	0.01746 (15)
Cl1	0.06341 (13)	0.59864 (10)	0.09534 (11)	0.0192 (2)
Cl2	0.51483 (13)	0.56726 (10)	0.09893 (11)	0.0193 (2)
Cl3	0.24980 (15)	0.34993 (10)	−0.06487 (9)	0.0212 (3)
Cl4	0.26367 (15)	0.35675 (9)	0.25519 (9)	0.0182 (3)
C1	0.6765 (6)	0.3608 (4)	0.3437 (5)	0.0211 (11)
H1A	0.6095	0.2999	0.3040	0.025*
H1B	0.7022	0.3292	0.4198	0.025*
C2	0.8319 (6)	0.3817 (4)	0.2790 (4)	0.0189 (10)
H2A	0.8947	0.3057	0.2747	0.023*
H2B	0.8062	0.4078	0.2010	0.023*
C3	0.8383 (6)	0.5925 (5)	0.3449 (4)	0.0196 (10)
H3A	0.8136	0.6227	0.2681	0.024*
H3B	0.9052	0.6539	0.3839	0.024*
C4	0.6815 (6)	0.5734 (4)	0.4092 (5)	0.0189 (9)
H4A	0.7063	0.5505	0.4881	0.023*
H4B	0.6185	0.6495	0.4106	0.023*
N1	0.5828 (5)	0.4761 (4)	0.3544 (4)	0.0180 (9)
H1	0.5509	0.5014	0.2839	0.022*
H2	0.4907	0.4625	0.3966	0.022*
N2	0.9310 (5)	0.4768 (4)	0.3369 (4)	0.0189 (9)
H3	0.9583	0.4509	0.4082	0.023*
H4	1.0256	0.4894	0.2972	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0130 (3)	0.0212 (3)	0.0182 (3)	−0.0007 (2)	−0.0003 (3)	−0.0015 (2)
Cl1	0.0164 (5)	0.0221 (5)	0.0191 (5)	0.0024 (4)	−0.0007 (5)	−0.0019 (5)
Cl2	0.0142 (5)	0.0253 (5)	0.0183 (5)	−0.0030 (4)	0.0008 (5)	0.0002 (5)
Cl3	0.0181 (6)	0.0240 (6)	0.0214 (6)	−0.0006 (5)	−0.0002 (5)	−0.0045 (4)
Cl4	0.0151 (6)	0.0188 (5)	0.0205 (5)	−0.0014 (5)	−0.0001 (5)	−0.0003 (4)
C1	0.016 (3)	0.017 (2)	0.030 (3)	−0.001 (2)	0.002 (2)	0.000 (2)
C2	0.019 (2)	0.019 (2)	0.019 (2)	0.0003 (19)	−0.001 (2)	−0.002 (2)
C3	0.013 (2)	0.021 (2)	0.024 (3)	0.001 (2)	0.000 (2)	0.001 (2)
C4	0.013 (2)	0.023 (2)	0.021 (2)	−0.0004 (17)	0.002 (2)	−0.002 (2)
N1	0.0091 (19)	0.025 (2)	0.020 (2)	−0.0019 (18)	0.0000 (16)	0.0001 (18)
N2	0.013 (2)	0.024 (2)	0.020 (2)	0.0030 (19)	0.0031 (17)	−0.0008 (18)

Geometric parameters (Å, º) top

Zn1—Cl1	2.2768 (12)	C3—N2	1.496 (6)
Zn1—Cl2	2.3119 (12)	C3—C4	1.513 (7)
Zn1—Cl3	2.2532 (12)	C3—H3A	0.9900
Zn1—Cl4	2.2634 (12)	C3—H3B	0.9900
C1—N1	1.499 (7)	C4—N1	1.498 (6)
C1—C2	1.510 (7)	C4—H4A	0.9900
C1—H1A	0.9900	C4—H4B	0.9900
C1—H1B	0.9900	N1—H1	0.9200
C2—N2	1.498 (6)	N1—H2	0.9200
C2—H2A	0.9900	N2—H3	0.9200
C2—H2B	0.9900	N2—H4	0.9200

Cl3—Zn1—Cl4	114.25 (4)	N2—C3—H3B	109.6
Cl3—Zn1—Cl1	108.73 (5)	C4—C3—H3B	109.6
Cl4—Zn1—Cl1	107.99 (5)	H3A—C3—H3B	108.1
Cl3—Zn1—Cl2	112.01 (5)	N1—C4—C3	110.2 (4)
Cl4—Zn1—Cl2	104.82 (5)	N1—C4—H4A	109.6
Cl1—Zn1—Cl2	108.84 (5)	C3—C4—H4A	109.6
N1—C1—C2	110.4 (4)	N1—C4—H4B	109.6
N1—C1—H1A	109.6	C3—C4—H4B	109.6
C2—C1—H1A	109.6	H4A—C4—H4B	108.1
N1—C1—H1B	109.6	C4—N1—C1	111.8 (4)
C2—C1—H1B	109.6	C4—N1—H1	109.2
H1A—C1—H1B	108.1	C1—N1—H1	109.2
N2—C2—C1	109.7 (4)	C4—N1—H2	109.2
N2—C2—H2A	109.7	C1—N1—H2	109.2
C1—C2—H2A	109.7	H1—N1—H2	107.9
N2—C2—H2B	109.7	C3—N2—C2	110.8 (4)
C1—C2—H2B	109.7	C3—N2—H3	109.5
H2A—C2—H2B	108.2	C2—N2—H3	109.5
N2—C3—C4	110.3 (4)	C3—N2—H4	109.5
N2—C3—H3A	109.6	C2—N2—H4	109.5
C4—C3—H3A	109.6	H3—N2—H4	108.1

N1—C1—C2—N2	57.4 (5)	C2—C1—N1—C4	−56.6 (5)
N2—C3—C4—N1	−56.4 (5)	C4—C3—N2—C2	58.8 (5)
C3—C4—N1—C1	55.8 (5)	C1—C2—N2—C3	−59.1 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2	0.92	2.33	3.239 (5)	171
N1—H2···Cl4	0.92	2.77	3.168 (4)	107
N1—H2···Cl1ⁱ	0.92	2.49	3.206 (4)	135
N2—H3···Cl2ⁱⁱ	0.92	2.28	3.174 (4)	164
N2—H4···Cl4ⁱⁱⁱ	0.92	2.50	3.194 (5)	133
N2—H4···Cl1ⁱⁱⁱ	0.92	2.70	3.346 (4)	128

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

Experimental details

Crystal data
Chemical formula	(C₄H₁₂N₂)[ZnCl₄]
M_r	295.33
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	120
a, b, c (Å)	8.2309 (3), 11.0845 (3), 11.8443 (4)
V (Å³)	1080.62 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.21
Crystal size (mm)	0.13 × 0.09 × 0.04

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.681, 0.882
No. of measured, independent and observed [I > 2σ(I)] reflections	8838, 2388, 2194
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.094, 1.08
No. of reflections	2388
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.92, −0.77
Absolute structure	Flack (1983), 946 Friedel pairs
Absolute structure parameter	0.44 (2)

Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), and SORTAV (Blessing, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Selected bond lengths (Å) top

Zn1—Cl1	2.2768 (12)	Zn1—Cl3	2.2532 (12)
Zn1—Cl2	2.3119 (12)	Zn1—Cl4	2.2634 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2	0.92	2.33	3.239 (5)	171
N1—H2···Cl4	0.92	2.77	3.168 (4)	107
N1—H2···Cl1ⁱ	0.92	2.49	3.206 (4)	135
N2—H3···Cl2ⁱⁱ	0.92	2.28	3.174 (4)	164
N2—H4···Cl4ⁱⁱⁱ	0.92	2.50	3.194 (5)	133
N2—H4···Cl1ⁱⁱⁱ	0.92	2.70	3.346 (4)	128

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

Acknowledgements

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

References

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