1,4-Diazo­niabicyclo­[2.2.2]octane tetra­chloridozincate monohydrate

Wang, F.

doi:10.1107/S1600536809014822

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page m575

doi:10.1107/S1600536809014822

Open

access

1,4-Diazoniabicyclo[2.2.2]octane tetrachloridozincate monohydrate

Fangming Wang ^a ^*

^aSchool of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, People's Republic of China
^*Correspondence e-mail: wangfmzj@yahoo.com.cn

(Received 8 April 2009; accepted 21 April 2009; online 25 April 2009)

In the title compound, (C₆H₁₄N₂)[ZnCl₄]·H₂O, the crystal packing is governed by an extensive three-dimensional network of N—H⋯Cl, N—H⋯O and O—H⋯Cl hydrogen bonds. The zinc(II) metal centre has a slightly distorted tetrahedral coordination geometry.

Related literature

For the applications of ferroelectric materials, see: Fu et al. (2007 ); Dawber et al. (2005 ); Haertling (1999 ); Scott (2007 ). For the properties and structure of a related diazabicyclo[2.2.2]octane (dabco) salt, see: Szafrański et al. (2002 ).

Experimental

Crystal data

(C₆H₁₄N₂)[ZnCl₄]·H₂O
M_r = 339.40
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.4483 (17) Å
b = 11.705 (2) Å
c = 12.976 (3) Å
V = 1283.2 (5) Å³
Z = 4
Mo Kα radiation
μ = 2.72 mm⁻¹
T = 291 K
0.30 × 0.28 × 0.26 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.462, T_max = 0.495
11890 measured reflections
2510 independent reflections
2166 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.121
S = 1.03
2510 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.89 e Å⁻³
Δρ_min = −0.48 e Å⁻³
Absolute structure: Flack (1983 ), 1050 Friedel pairs
Flack parameter: 0.07 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2C⋯O1	0.91	1.96	2.809 (8)	154
N1—H1C⋯Cl1ⁱ	0.91	2.64	3.338 (5)	134
N1—H1C⋯Cl3ⁱ	0.91	2.80	3.383 (5)	123
O1—H1D⋯Cl3ⁱⁱ	0.85	2.82	3.410 (7)	129
O1—H1E⋯Cl1ⁱⁱⁱ	0.85	2.75	3.454 (7)	141
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809014822/rz2310sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809014822/rz2310Isup2.hkl

checkCIF report

Comment top

Ferroelectric materials continue to attract much attention due to their potential applications in memory devices (Fu et al., 2007; Dawber et al., 2005; Haertling, 1999; Scott, 2007). Among these materials, diazabicyclo[2.2.2]octane (dabco) salts with inorganic tetrahedral anions having potassium dihydrophosphate-type (KDP-type) structure have been found to exhibit exceptional dielectric properties (Szafrański et al., 2002). As a contribution to this field, the crystal structure of the title compound is reported here.

The asymmetric unit of the title compound (Fig. 1), contains a doubly protonated C₆H₁₄N₂²⁺ dication, a ZnCl₄^2- dianion and a water molecule. The zinc(II) metal displays a slightly distorted tetrahedral coordination geometry. In the cation, the protonated N1 atom interacts via a bifurcated hydrogen bond with two Cl atoms of a neighbouring anion, while the N2 atom is hydrogen-bonded to a water molecule (Table 1). The water molecule acts as double hydrogen-bond donor to Cl atoms, resulting in an extensive three-dimensional H-bonding network (Fig. 2).

Related literature top

For the applications of ferroelectric materials, see: Fu et al. (2007); Dawber et al. (2005); Haertling (1999); Scott (2007). For the properties and structure of a related diazabicyclo[2.2.2]octane (dabco) salt, see: Szafrański et al. (2002).

Experimental top

Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation at room temperature of a HCl solution (0.5 M) containing diazabicyclo[2.2.2]octane (112 mg) and ZnCl₂.2H₂O (172 mg) in an approximate 1:1 molar ratio.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme with 30% probability displacement ellipsoids.
	Fig. 2. Packing digram of the title compound viewed along the b axis. H-bonding interactions are shown as dashed lines.

1,4-Diazoniabicyclo[2.2.2]octane tetrachloridozincate monohydrate top

Crystal data top

(C₆H₁₄N₂)[ZnCl₄]·H₂O	F(000) = 688
M_r = 339.40	D_x = 1.757 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 11517 reflections
a = 8.4483 (17) Å	θ = 3.1–27.5°
b = 11.705 (2) Å	µ = 2.72 mm⁻¹
c = 12.976 (3) Å	T = 291 K
V = 1283.2 (5) Å³	Block, colourless
Z = 4	0.30 × 0.28 × 0.26 mm

Data collection top

Rigaku Mercury2 diffractometer	2510 independent reflections
Radiation source: fine-focus sealed tube	2166 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
Detector resolution: 13.6612 pixels mm^-1	θ_max = 26.0°, θ_min = 3.1°
ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −14→14
T_min = 0.462, T_max = 0.495	l = −16→16
11890 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)] = 0.046	H-atom parameters constrained
wR(F²) = 0.121	w = 1/[σ²(F_o²) + (0.0665P)² + 1.4482P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
2510 reflections	Δρ_max = 0.89 e Å⁻³
127 parameters	Δρ_min = −0.48 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1050 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.07 (3)

Crystal data top

(C₆H₁₄N₂)[ZnCl₄]·H₂O	V = 1283.2 (5) Å³
M_r = 339.40	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.4483 (17) Å	µ = 2.72 mm⁻¹
b = 11.705 (2) Å	T = 291 K
c = 12.976 (3) Å	0.30 × 0.28 × 0.26 mm

Data collection top

Rigaku Mercury2 diffractometer	2510 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2166 reflections with I > 2σ(I)
T_min = 0.462, T_max = 0.495	R_int = 0.053
11890 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.121	Δρ_max = 0.89 e Å⁻³
S = 1.03	Δρ_min = −0.48 e Å⁻³
2510 reflections	Absolute structure: Flack (1983), 1050 Friedel pairs
127 parameters	Absolute structure parameter: 0.07 (3)
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
C1	0.2122 (7)	0.3775 (6)	0.3733 (5)	0.0434 (17)
H1A	0.1610	0.3189	0.4143	0.052*
H1B	0.2347	0.4422	0.4177	0.052*
C2	0.3645 (8)	0.3316 (7)	0.3286 (5)	0.0489 (18)
H2A	0.3676	0.2490	0.3347	0.059*
H2B	0.4547	0.3632	0.3650	0.059*
C3	0.1700 (9)	0.5158 (6)	0.2364 (5)	0.0415 (16)
H3A	0.1655	0.5809	0.2826	0.050*
H3B	0.1064	0.5330	0.1761	0.050*
C4	0.3402 (8)	0.4934 (6)	0.2046 (6)	0.0474 (18)
H4A	0.3568	0.5167	0.1336	0.057*
H4B	0.4123	0.5361	0.2482	0.057*
C5	0.0884 (7)	0.3177 (5)	0.2132 (5)	0.0371 (15)
H5A	0.0055	0.3356	0.1641	0.045*
H5B	0.0602	0.2477	0.2487	0.045*
C6	0.2468 (8)	0.3030 (5)	0.1574 (4)	0.0405 (14)
H6A	0.2745	0.2227	0.1536	0.049*
H6B	0.2394	0.3328	0.0878	0.049*
Cl1	0.20057 (18)	−0.18534 (13)	1.07634 (13)	0.0420 (4)
Cl2	0.2573 (2)	−0.03346 (13)	0.81713 (10)	0.0444 (4)
Cl3	0.03672 (18)	0.09791 (13)	1.03379 (13)	0.0371 (4)
Cl4	0.47943 (19)	0.06684 (14)	1.03500 (14)	0.0414 (4)
N1	0.1070 (6)	0.4132 (4)	0.2888 (4)	0.0308 (11)
H1C	0.0103	0.4303	0.3156	0.037*
N2	0.3689 (6)	0.3664 (5)	0.2161 (5)	0.0444 (15)
H2C	0.4659	0.3493	0.1899	0.053*
O1	0.6587 (8)	0.2561 (5)	0.1794 (5)	0.086 (2)
H1D	0.6849	0.2659	0.1167	0.128*
H1E	0.7293	0.2845	0.2184	0.128*
Zn1	0.24738 (9)	−0.01799 (5)	0.99321 (4)	0.0333 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.043 (4)	0.054 (4)	0.033 (3)	0.007 (3)	−0.009 (3)	−0.004 (3)
C2	0.042 (4)	0.052 (4)	0.052 (4)	0.006 (3)	−0.020 (3)	−0.008 (4)
C3	0.044 (4)	0.031 (3)	0.050 (4)	0.005 (3)	0.005 (3)	0.003 (3)
C4	0.036 (4)	0.054 (4)	0.053 (4)	−0.011 (3)	0.012 (3)	−0.010 (4)
C5	0.038 (3)	0.037 (4)	0.037 (3)	−0.003 (3)	−0.004 (3)	0.003 (3)
C6	0.034 (3)	0.043 (3)	0.045 (3)	−0.007 (3)	−0.007 (3)	−0.018 (3)
Cl1	0.0443 (9)	0.0383 (8)	0.0435 (8)	0.0001 (7)	0.0069 (6)	0.0048 (7)
Cl2	0.0477 (9)	0.0536 (9)	0.0318 (7)	−0.0048 (9)	0.0041 (8)	−0.0058 (6)
Cl3	0.0322 (8)	0.0407 (8)	0.0384 (9)	0.0023 (6)	0.0004 (7)	−0.0041 (7)
Cl4	0.0368 (8)	0.0459 (8)	0.0414 (9)	−0.0079 (7)	−0.0055 (7)	0.0029 (8)
N1	0.022 (2)	0.042 (3)	0.029 (3)	0.004 (2)	0.0009 (19)	−0.002 (2)
N2	0.022 (3)	0.051 (3)	0.061 (4)	0.003 (2)	0.004 (2)	−0.018 (3)
O1	0.067 (4)	0.083 (5)	0.106 (5)	0.004 (4)	−0.014 (4)	−0.001 (4)
Zn1	0.0317 (3)	0.0375 (3)	0.0307 (3)	−0.0011 (3)	0.0009 (3)	0.0002 (3)

Geometric parameters (Å, º) top

C1—N1	1.472 (7)	C5—C6	1.531 (9)
C1—C2	1.510 (9)	C5—H5A	0.9700
C1—H1A	0.9700	C5—H5B	0.9700
C1—H1B	0.9700	C6—N2	1.482 (8)
C2—N2	1.515 (9)	C6—H6A	0.9700
C2—H2A	0.9700	C6—H6B	0.9700
C2—H2B	0.9700	Cl1—Zn1	2.2710 (17)
C3—N1	1.479 (8)	Cl2—Zn1	2.2936 (15)
C3—C4	1.519 (9)	Cl3—Zn1	2.2989 (17)
C3—H3A	0.9700	Cl4—Zn1	2.2635 (17)
C3—H3B	0.9700	N1—H1C	0.9100
C4—N2	1.514 (9)	N2—H2C	0.9100
C4—H4A	0.9700	O1—H1D	0.8499
C4—H4B	0.9700	O1—H1E	0.8500
C5—N1	1.496 (8)

N1—C1—C2	109.2 (5)	C6—C5—H5B	110.2
N1—C1—H1A	109.8	H5A—C5—H5B	108.5
C2—C1—H1A	109.8	N2—C6—C5	108.0 (5)
N1—C1—H1B	109.8	N2—C6—H6A	110.1
C2—C1—H1B	109.8	C5—C6—H6A	110.1
H1A—C1—H1B	108.3	N2—C6—H6B	110.1
C1—C2—N2	107.2 (5)	C5—C6—H6B	110.1
C1—C2—H2A	110.3	H6A—C6—H6B	108.4
N2—C2—H2A	110.3	C1—N1—C3	110.8 (5)
C1—C2—H2B	110.3	C1—N1—C5	109.9 (5)
N2—C2—H2B	110.3	C3—N1—C5	110.1 (5)
H2A—C2—H2B	108.5	C1—N1—H1C	108.7
N1—C3—C4	109.0 (5)	C3—N1—H1C	108.7
N1—C3—H3A	109.9	C5—N1—H1C	108.7
C4—C3—H3A	109.9	C6—N2—C4	109.2 (5)
N1—C3—H3B	109.9	C6—N2—C2	110.1 (5)
C4—C3—H3B	109.9	C4—N2—C2	110.8 (5)
H3A—C3—H3B	108.3	C6—N2—H2C	108.9
N2—C4—C3	107.1 (5)	C4—N2—H2C	108.9
N2—C4—H4A	110.3	C2—N2—H2C	108.9
C3—C4—H4A	110.3	H1D—O1—H1E	109.5
N2—C4—H4B	110.3	Cl4—Zn1—Cl1	114.55 (7)
C3—C4—H4B	110.3	Cl4—Zn1—Cl2	103.99 (7)
H4A—C4—H4B	108.5	Cl1—Zn1—Cl2	114.29 (6)
N1—C5—C6	107.6 (5)	Cl4—Zn1—Cl3	110.90 (6)
N1—C5—H5A	110.2	Cl1—Zn1—Cl3	105.40 (6)
C6—C5—H5A	110.2	Cl2—Zn1—Cl3	107.63 (7)
N1—C5—H5B	110.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···O1	0.91	1.96	2.809 (8)	154
N1—H1C···Cl1ⁱ	0.91	2.64	3.338 (5)	134
N1—H1C···Cl3ⁱ	0.91	2.80	3.383 (5)	123
O1—H1D···Cl3ⁱⁱ	0.85	2.82	3.410 (7)	129
O1—H1E···Cl1ⁱⁱⁱ	0.85	2.75	3.454 (7)	141

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

Experimental details

Crystal data
Chemical formula	(C₆H₁₄N₂)[ZnCl₄]·H₂O
M_r	339.40
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	291
a, b, c (Å)	8.4483 (17), 11.705 (2), 12.976 (3)
V (Å³)	1283.2 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.72
Crystal size (mm)	0.30 × 0.28 × 0.26

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.462, 0.495
No. of measured, independent and observed [I > 2σ(I)] reflections	11890, 2510, 2166
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.121, 1.03
No. of reflections	2510
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.89, −0.48
Absolute structure	Flack (1983), 1050 Friedel pairs
Absolute structure parameter	0.07 (3)

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···O1	0.91	1.96	2.809 (8)	153.5
N1—H1C···Cl1ⁱ	0.91	2.64	3.338 (5)	134.1
N1—H1C···Cl3ⁱ	0.91	2.80	3.383 (5)	123.2
O1—H1D···Cl3ⁱⁱ	0.85	2.82	3.410 (7)	128.6
O1—H1E···Cl1ⁱⁱⁱ	0.85	2.75	3.454 (7)	141.0

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

References

Dawber, M., Rabe, K. M. & Scott, J. F. (2005). Rev. Mod. Phys. 77, 1083–1130. Web of Science CrossRef CAS Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Fu, D.-W., Song, Y.-M., Wang, G.-X., Ye, Q., Xiong, R.-G., Akutagawa, T., Nakamura, T., Chan, P. W. H. & Huang, S. D. (2007). J. Am. Chem. Soc. 129, 5346–5347. Web of Science CSD CrossRef PubMed CAS Google Scholar
Haertling, G. H. (1999). J. Am. Ceram. Soc. 82, 797–818. CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Scott, J. F. (2007). Science, 315, 954–959. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Szafrański, M., Katrusiak, A. & McIntyre, G. J. (2002). Phys. Rev. Lett. 89, 215507-1–215507-4. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page m575

doi:10.1107/S1600536809014822

Open

access