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Acta Cryst. (2008). E64, m628    [ doi:10.1107/S160053680800874X ]

1,1'-(Butane-1,4-diyl)diimidazole-3,3'-diium tetrachloridozincate(II) dihydrate

Y.-H. Yu, A.-E. Shi, Y. Su, G.-F. Hou and J.-S. Gao

Abstract top

In the title compound, (C10H16N4)[ZnCl4]·2H2O, the cation lies abouton a center of inversion and the anion about a twofold rotation axis. The ZnII atom is four-coordinate in a tetrahedral environment. The cations, anions and water molecules are linked by N-H...O, N-H...Cl and O-H...Cl hydrogen bonds into a two-dimensional network.

Comment top

The 1,1'-(1,4-butanediyl)diimidazole can be used as a flexible ligand to construct coordination polymer materials(Ma et al.., 2003). In our attempt to synthesize the zinc complex with the 1,1'-(1,4-butanediyl)diimidazole, we unexpectedly obtained the title compound (I). Herein, we report its crystal structure.

The ZnII atom lies on an inversion center and is coordinated by four chlorine anions in an tetrahedronal environment(Figure 1). The 1,1'-(1,4-butanediyl)diimidazole molecule also lies on an inversion center and its N atom is protonated.

In the crystal structure, the cations and anions are linked by N—H···Cl hydrogen bonds. In addition, the water molecules are both as acceptor and donor of hydrogen bond link these molecule into a two-dimensional supramolecular network via N—H···O, O—H···Cl hydrogen bonds (Table 1; Figure 2).

Related literature top

For background and the synthesis of 1,1'-(1,4-butanediyl)diimidazole, see: Ma et al. (2003)

Experimental top

1,1'-(1,4-Butanediyl)diimidazole was prepared of imidazole and 1,4-dibromobutane in dimethylsulfoxide solution (Ma et al.., 2003). ZnCl2 (0.272 g, 2 mmol) and 1,1'-(1,4-butanediyl)diimidazole (0.380 g, 2 mmol) were dissolved in hot methanol solution (15 ml) and added two drops hydrochloric acid then a clear solution was obtained. The resulting solution was allowed to stand in a desiccator at room temperature for several days. Colroless crystals of (I) were obtained. Unexpectedly, the salt-type adducts of this ligands was crystallized from solution.

Refinement top

H atoms bound to C atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å (Caromatic) and with Uiso(H) = 1.2Ueq(C). The N-bound H atoms were located in a difference Fourier map and free refined, Water H atoms were initially located in a difference Fourier map but they were treated as riding on their parent atoms with O—H = 0.85 Å, H···H = 1.39 and with Uiso(H) = 1.5Ueq(O).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); 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: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing displacement ellipsoids at the 30% probability level for non-H atoms. Dashed lines indicate the intramolecular hydrogen bonding interactions.
[Figure 2] Fig. 2. A partial packing view, showing the two-dimensional hydrogen-bonding network. Dashed lines indicate the hydrogen-bonding interactions. H atoms not involved in hydrogen bonds have been omitted for clarity.
1,1'-(Butane-1,4-diyl)diimidazole-3,3'-diium tetrachloridozincate(II) dihydrate top
Crystal data top
(C10H16N4)[ZnCl4]·2H2OF000 = 444
Mr = 435.47Dx = 1.624 Mg m−3
Monoclinic, P2/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2yacCell parameters from 6883 reflections
a = 7.4010 (15) Åθ = 3.2–27.5º
b = 10.927 (2) ŵ = 1.99 mm−1
c = 11.058 (2) ÅT = 291 (2) K
β = 95.23 (3)ºBlock, colorless
V = 890.6 (3) Å30.18 × 0.17 × 0.15 mm
Z = 2
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2042 independent reflections
Radiation source: fine-focus sealed tube1760 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.042
T = 291(2) Kθmax = 27.5º
ω scansθmin = 3.2º
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −9→9
Tmin = 0.713, Tmax = 0.751k = −14→14
8575 measured reflectionsl = −14→14
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of
independent and constrained refinement
R[F2 > 2σ(F2)] = 0.032  w = 1/[σ2(Fo2) + (0.0301P)2 + 0.5173P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.081(Δ/σ)max = 0.001
S = 1.07Δρmax = 0.47 e Å−3
2042 reflectionsΔρmin = −0.37 e Å−3
101 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.038 (3)
Secondary atom site location: difference Fourier map
Crystal data top
(C10H16N4)[ZnCl4]·2H2OV = 890.6 (3) Å3
Mr = 435.47Z = 2
Monoclinic, P2/nMo Kα
a = 7.4010 (15) ŵ = 1.99 mm−1
b = 10.927 (2) ÅT = 291 (2) K
c = 11.058 (2) Å0.18 × 0.17 × 0.15 mm
β = 95.23 (3)º
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2042 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		1760 reflections with I > 2σ(I)
Tmin = 0.713, Tmax = 0.751Rint = 0.042
8575 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.032101 parameters
wR(F2) = 0.081H atoms treated by a mixture of
independent and constrained refinement
S = 1.07Δρmax = 0.47 e Å−3
2042 reflectionsΔρmin = −0.37 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
xyzUiso*/Ueq
Zn10.75000.75494 (3)0.25000.03710 (15)
C10.4713 (3)0.1878 (2)0.2017 (2)0.0405 (5)
H10.44990.11040.16840.049*
C20.4320 (4)0.2946 (2)0.1464 (2)0.0469 (6)
H20.37900.30560.06760.056*
C30.5555 (4)0.3335 (2)0.3300 (2)0.0448 (6)
H40.60190.37520.39930.054*
C40.6136 (3)0.1221 (2)0.4085 (2)0.0450 (6)
H50.67710.16410.47700.054*
H60.69950.06800.37420.054*
C50.4626 (3)0.0464 (2)0.4529 (2)0.0376 (5)
H70.39850.00400.38490.045*
H80.37700.09970.48850.045*
Cl20.87983 (10)0.63431 (6)0.11389 (5)0.0543 (2)
Cl30.96871 (9)0.86758 (5)0.35304 (6)0.0529 (2)
H30.475 (4)0.461 (3)0.216 (3)0.066 (9)*
N10.5489 (2)0.21294 (16)0.31649 (16)0.0347 (4)
N20.4846 (3)0.3841 (2)0.2278 (2)0.0499 (5)
O10.3280 (3)0.6019 (2)0.1132 (2)0.0775 (7)
H90.21920.60420.13190.116*
H100.38140.67080.11910.116*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0465 (2)0.0277 (2)0.0365 (2)0.0000.00102 (15)0.000
C10.0413 (12)0.0380 (12)0.0412 (12)0.0001 (10)−0.0009 (10)−0.0065 (10)
C20.0495 (14)0.0545 (14)0.0359 (12)0.0036 (12)0.0001 (10)0.0056 (11)
C30.0631 (16)0.0326 (11)0.0393 (12)−0.0061 (10)0.0085 (11)−0.0020 (10)
C40.0403 (13)0.0434 (13)0.0499 (13)−0.0007 (10)−0.0029 (10)0.0146 (11)
C50.0362 (11)0.0354 (11)0.0408 (12)0.0017 (9)0.0019 (9)0.0055 (10)
Cl20.0739 (5)0.0480 (4)0.0405 (3)0.0215 (3)0.0029 (3)−0.0024 (3)
Cl30.0563 (4)0.0355 (3)0.0639 (4)−0.0094 (3)−0.0101 (3)0.0011 (3)
N10.0374 (10)0.0297 (8)0.0371 (9)−0.0009 (7)0.0030 (8)0.0036 (7)
N20.0659 (15)0.0330 (10)0.0522 (12)0.0040 (10)0.0135 (10)0.0086 (9)
O10.0740 (15)0.0611 (13)0.0940 (17)−0.0160 (11)−0.0113 (12)0.0114 (12)
Geometric parameters (Å, °) top
Zn1—Cl32.2577 (8)C3—H40.9300
Zn1—Cl3i2.2577 (8)C4—N11.470 (3)
Zn1—Cl22.2782 (8)C4—C51.508 (3)
Zn1—Cl2i2.2782 (7)C4—H50.9700
C1—C21.337 (3)C4—H60.9700
C1—N11.372 (3)C5—C5ii1.521 (4)
C1—H10.9300C5—H70.9700
C2—N21.362 (3)C5—H80.9700
C2—H20.9300N2—H30.85 (3)
C3—N21.322 (3)O1—H90.8500
C3—N11.326 (3)O1—H100.8501
Cl3—Zn1—Cl3i113.93 (4)C5—C4—H5109.0
Cl3—Zn1—Cl2108.83 (3)N1—C4—H6109.0
Cl3i—Zn1—Cl2107.95 (3)C5—C4—H6109.0
Cl3—Zn1—Cl2i107.95 (3)H5—C4—H6107.8
Cl3i—Zn1—Cl2i108.83 (3)C4—C5—C5ii110.7 (2)
Cl2—Zn1—Cl2i109.29 (4)C4—C5—H7109.5
C2—C1—N1107.7 (2)C5ii—C5—H7109.5
C2—C1—H1126.2C4—C5—H8109.5
N1—C1—H1126.2C5ii—C5—H8109.5
C1—C2—N2106.7 (2)H7—C5—H8108.1
C1—C2—H2126.7C3—N1—C1108.14 (19)
N2—C2—H2126.7C3—N1—C4125.9 (2)
N2—C3—N1108.1 (2)C1—N1—C4125.95 (19)
N2—C3—H4125.9C3—N2—C2109.4 (2)
N1—C3—H4125.9C3—N2—H3125 (2)
N1—C4—C5113.02 (19)C2—N2—H3126 (2)
N1—C4—H5109.0H9—O1—H10113.5
Symmetry codes: (i) −x+3/2, y, −z+1/2; (ii) −x+1, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H10···Cl3i0.852.433.275 (2)177
O1—H9···Cl2iii0.852.523.337 (3)161
N2—H3···Cl2i0.85 (3)2.82 (3)3.350 (2)122 (3)
N2—H3···O10.85 (3)2.15 (3)2.890 (3)145 (3)
Symmetry codes: (i) −x+3/2, y, −z+1/2; (iii) x−1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H10···Cl3i0.852.433.275 (2)177
O1—H9···Cl2ii0.852.523.337 (3)161
N2—H3···Cl2i0.85 (3)2.82 (3)3.350 (2)122 (3)
N2—H3···O10.85 (3)2.15 (3)2.890 (3)145 (3)
Symmetry codes: (i) −x+3/2, y, −z+1/2; (ii) x−1, y, z.
Acknowledgements top

The authors thank Heilongjiang University for supporting this study.

references
References top

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Ma, J.-F., Yang, J., Zheng, G.-L. & Liu, J.-F. (2003). Inorg. Chem. 42, 7531–7534.

Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.