metal-organic compounds
1,1′-(Butane-1,4-diyl)diimidazole-3,3′-diium tetrachloridozincate(II) dihydrate
aCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China
*Correspondence e-mail: hgf1000@163.com
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.
Related literature
For background and the synthesis of 1,1′-(1,4-butanediyl)diimidazole, see: Ma et al. (2003)
Experimental
Crystal data
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Refinement
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Data collection: RAPID-AUTO (Rigaku, 1998); cell RAPID-AUTO; 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.
Supporting information
10.1107/S160053680800874X/ng2438sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053680800874X/ng2438Isup2.hkl
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.
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).
Data collection: RAPID-AUTO (Rigaku, 1998); cell
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).(C10H16N4)[ZnCl4]·2H2O | F(000) = 444 |
Mr = 435.47 | Dx = 1.624 Mg m−3 |
Monoclinic, P2/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yac | Cell parameters from 6883 reflections |
a = 7.4010 (15) Å | θ = 3.2–27.5° |
b = 10.927 (2) Å | µ = 1.99 mm−1 |
c = 11.058 (2) Å | T = 291 K |
β = 95.23 (3)° | Block, colorless |
V = 890.6 (3) Å3 | 0.18 × 0.17 × 0.15 mm |
Z = 2 |
Rigaku R-AXIS RAPID diffractometer | 2042 independent reflections |
Radiation source: fine-focus sealed tube | 1760 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
ω scans | θmax = 27.5°, θmin = 3.2° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −9→9 |
Tmin = 0.713, Tmax = 0.751 | k = −14→14 |
8575 measured reflections | l = −14→14 |
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)] = 0.032 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.081 | w = 1/[σ2(Fo2) + (0.0301P)2 + 0.5173P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
2042 reflections | Δρmax = 0.47 e Å−3 |
101 parameters | Δρmin = −0.37 e Å−3 |
0 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: 0.038 (3) |
(C10H16N4)[ZnCl4]·2H2O | V = 890.6 (3) Å3 |
Mr = 435.47 | Z = 2 |
Monoclinic, P2/n | Mo Kα radiation |
a = 7.4010 (15) Å | µ = 1.99 mm−1 |
b = 10.927 (2) Å | T = 291 K |
c = 11.058 (2) Å | 0.18 × 0.17 × 0.15 mm |
β = 95.23 (3)° |
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 = 0.751 | Rint = 0.042 |
8575 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.47 e Å−3 |
2042 reflections | Δρmin = −0.37 e Å−3 |
101 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.7500 | 0.75494 (3) | 0.2500 | 0.03710 (15) | |
C1 | 0.4713 (3) | 0.1878 (2) | 0.2017 (2) | 0.0405 (5) | |
H1 | 0.4499 | 0.1104 | 0.1684 | 0.049* | |
C2 | 0.4320 (4) | 0.2946 (2) | 0.1464 (2) | 0.0469 (6) | |
H2 | 0.3790 | 0.3056 | 0.0676 | 0.056* | |
C3 | 0.5555 (4) | 0.3335 (2) | 0.3300 (2) | 0.0448 (6) | |
H4 | 0.6019 | 0.3752 | 0.3993 | 0.054* | |
C4 | 0.6136 (3) | 0.1221 (2) | 0.4085 (2) | 0.0450 (6) | |
H5 | 0.6771 | 0.1641 | 0.4770 | 0.054* | |
H6 | 0.6995 | 0.0680 | 0.3742 | 0.054* | |
C5 | 0.4626 (3) | 0.0464 (2) | 0.4529 (2) | 0.0376 (5) | |
H7 | 0.3985 | 0.0040 | 0.3849 | 0.045* | |
H8 | 0.3770 | 0.0997 | 0.4885 | 0.045* | |
Cl2 | 0.87983 (10) | 0.63431 (6) | 0.11389 (5) | 0.0543 (2) | |
Cl3 | 0.96871 (9) | 0.86758 (5) | 0.35304 (6) | 0.0529 (2) | |
H3 | 0.475 (4) | 0.461 (3) | 0.216 (3) | 0.066 (9)* | |
N1 | 0.5489 (2) | 0.21294 (16) | 0.31649 (16) | 0.0347 (4) | |
N2 | 0.4846 (3) | 0.3841 (2) | 0.2278 (2) | 0.0499 (5) | |
O1 | 0.3280 (3) | 0.6019 (2) | 0.1132 (2) | 0.0775 (7) | |
H9 | 0.2192 | 0.6042 | 0.1319 | 0.116* | |
H10 | 0.3814 | 0.6708 | 0.1191 | 0.116* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0465 (2) | 0.0277 (2) | 0.0365 (2) | 0.000 | 0.00102 (15) | 0.000 |
C1 | 0.0413 (12) | 0.0380 (12) | 0.0412 (12) | 0.0001 (10) | −0.0009 (10) | −0.0065 (10) |
C2 | 0.0495 (14) | 0.0545 (14) | 0.0359 (12) | 0.0036 (12) | 0.0001 (10) | 0.0056 (11) |
C3 | 0.0631 (16) | 0.0326 (11) | 0.0393 (12) | −0.0061 (10) | 0.0085 (11) | −0.0020 (10) |
C4 | 0.0403 (13) | 0.0434 (13) | 0.0499 (13) | −0.0007 (10) | −0.0029 (10) | 0.0146 (11) |
C5 | 0.0362 (11) | 0.0354 (11) | 0.0408 (12) | 0.0017 (9) | 0.0019 (9) | 0.0055 (10) |
Cl2 | 0.0739 (5) | 0.0480 (4) | 0.0405 (3) | 0.0215 (3) | 0.0029 (3) | −0.0024 (3) |
Cl3 | 0.0563 (4) | 0.0355 (3) | 0.0639 (4) | −0.0094 (3) | −0.0101 (3) | 0.0011 (3) |
N1 | 0.0374 (10) | 0.0297 (8) | 0.0371 (9) | −0.0009 (7) | 0.0030 (8) | 0.0036 (7) |
N2 | 0.0659 (15) | 0.0330 (10) | 0.0522 (12) | 0.0040 (10) | 0.0135 (10) | 0.0086 (9) |
O1 | 0.0740 (15) | 0.0611 (13) | 0.0940 (17) | −0.0160 (11) | −0.0113 (12) | 0.0114 (12) |
Zn1—Cl3 | 2.2577 (8) | C3—H4 | 0.9300 |
Zn1—Cl3i | 2.2577 (8) | C4—N1 | 1.470 (3) |
Zn1—Cl2 | 2.2782 (8) | C4—C5 | 1.508 (3) |
Zn1—Cl2i | 2.2782 (7) | C4—H5 | 0.9700 |
C1—C2 | 1.337 (3) | C4—H6 | 0.9700 |
C1—N1 | 1.372 (3) | C5—C5ii | 1.521 (4) |
C1—H1 | 0.9300 | C5—H7 | 0.9700 |
C2—N2 | 1.362 (3) | C5—H8 | 0.9700 |
C2—H2 | 0.9300 | N2—H3 | 0.85 (3) |
C3—N2 | 1.322 (3) | O1—H9 | 0.8500 |
C3—N1 | 1.326 (3) | O1—H10 | 0.8501 |
Cl3—Zn1—Cl3i | 113.93 (4) | C5—C4—H5 | 109.0 |
Cl3—Zn1—Cl2 | 108.83 (3) | N1—C4—H6 | 109.0 |
Cl3i—Zn1—Cl2 | 107.95 (3) | C5—C4—H6 | 109.0 |
Cl3—Zn1—Cl2i | 107.95 (3) | H5—C4—H6 | 107.8 |
Cl3i—Zn1—Cl2i | 108.83 (3) | C4—C5—C5ii | 110.7 (2) |
Cl2—Zn1—Cl2i | 109.29 (4) | C4—C5—H7 | 109.5 |
C2—C1—N1 | 107.7 (2) | C5ii—C5—H7 | 109.5 |
C2—C1—H1 | 126.2 | C4—C5—H8 | 109.5 |
N1—C1—H1 | 126.2 | C5ii—C5—H8 | 109.5 |
C1—C2—N2 | 106.7 (2) | H7—C5—H8 | 108.1 |
C1—C2—H2 | 126.7 | C3—N1—C1 | 108.14 (19) |
N2—C2—H2 | 126.7 | C3—N1—C4 | 125.9 (2) |
N2—C3—N1 | 108.1 (2) | C1—N1—C4 | 125.95 (19) |
N2—C3—H4 | 125.9 | C3—N2—C2 | 109.4 (2) |
N1—C3—H4 | 125.9 | C3—N2—H3 | 125 (2) |
N1—C4—C5 | 113.02 (19) | C2—N2—H3 | 126 (2) |
N1—C4—H5 | 109.0 | H9—O1—H10 | 113.5 |
Symmetry codes: (i) −x+3/2, y, −z+1/2; (ii) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H10···Cl3i | 0.85 | 2.43 | 3.275 (2) | 177 |
O1—H9···Cl2iii | 0.85 | 2.52 | 3.337 (3) | 161 |
N2—H3···Cl2i | 0.85 (3) | 2.82 (3) | 3.350 (2) | 122 (3) |
N2—H3···O1 | 0.85 (3) | 2.15 (3) | 2.890 (3) | 145 (3) |
Symmetry codes: (i) −x+3/2, y, −z+1/2; (iii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | (C10H16N4)[ZnCl4]·2H2O |
Mr | 435.47 |
Crystal system, space group | Monoclinic, P2/n |
Temperature (K) | 291 |
a, b, c (Å) | 7.4010 (15), 10.927 (2), 11.058 (2) |
β (°) | 95.23 (3) |
V (Å3) | 890.6 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.99 |
Crystal size (mm) | 0.18 × 0.17 × 0.15 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.713, 0.751 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8575, 2042, 1760 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.081, 1.07 |
No. of reflections | 2042 |
No. of parameters | 101 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.47, −0.37 |
Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H10···Cl3i | 0.85 | 2.43 | 3.275 (2) | 177.1 |
O1—H9···Cl2ii | 0.85 | 2.52 | 3.337 (3) | 160.6 |
N2—H3···Cl2i | 0.85 (3) | 2.82 (3) | 3.350 (2) | 122 (3) |
N2—H3···O1 | 0.85 (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
The authors thank Heilongjiang University for supporting this study.
References
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Ma, J.-F., Yang, J., Zheng, G.-L. & Liu, J.-F. (2003). Inorg. Chem. 42, 7531–7534. Web of Science CSD CrossRef PubMed CAS Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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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).