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Acta Cryst. (2007). E63, m2603    [ doi:10.1107/S1600536807046545 ]

catena-Poly[[dichloridozinc(II)]-[mu]-1-carboxylatomethyl-3-methylimidazolium-[kappa]2O:O']

X. Shi, J. Zhang, T.-K. Ying and G.-L. Zhao

Abstract top

The crystal structure of the title compound, [ZnCl2(C6H8N2O2)]n, consists of a zigzag chain in which adjacent ZnCl2 groups are bridged by 1-carboxylatomethyl-3-methylimidazolium through its two O atoms. The environment around the Zn atom can be described as a cis-ZnO2Cl2 tetrahedron. The formation of the chain is strengthened by [pi]-[pi] stacking interactions between adjacent imidazole ring planes ([pi]-[pi] distance = 3.618 Å).

Comment top

It is known that the research of coordination polymers receives great interest nowadays, because they may afford new materials with useful properties, such as catalytic activity, microporosity and so on (Shi et al., 2004). Recently, we have synthesized and reported cadmium polymer with 1-methyl-3-carboxymethylimidazole (Shi et al., 2007). As an extension of our work in this field, we synthesized the title compound and solved its crystal structure (I).

The asymmetric unit of (I) contains one Zn atom, one 1-methyl-3-carboxymethylimidazole molecule, and two chlorine atoms (Fig. 1). The structure of (I) is a one-dimensional coordination chain in which the adjacent (ZnCl2) groups are bridged by 1-methyl-3-carboxymethylimidazole through its two O atoms with the distance of 4.8362 (4)Å (a-translation) between two adjacent Zn atoms. There exists π-π interaction between the adjacent imidazole-ring planes (π-π distance = 3.618 Å), which strengthens the formation of the chain.

Related literature top

For related literature, see: Shi et al. (2004, 2007).

For related literature, see: Sheldrick (1997).

Experimental top

A mixture of ZnCl2 (1 mmol), ion liquid 1-methyl-3-carboxymethylimidazole hydroxide (1 mmol) and water (20 ml) was sealed in a 25 ml Teflon-lined stainless steel reactor and heated at 393 K for 48 h. A colourless solution was obtained after cooling the reaction to room temperature, colourless single crystals were obtained after three weeks.

Refinement top

The H atoms bonded to C atoms were positioned geometrically (aromatic C–H = 0.93Å and aliphatic C–H = 0.97 Å, Uiso(H) = 1.2Ueq(C)). In the X-ray diffraction experiment 794 Friedel pairs were measured.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SMART (Bruker, 2004) and SAINT (Bruker, 2004); data reduction: XPREP (Bruker 2002); program(s) used to solve structure: SHELXTL (Bruker 2002); program(s) used to refine structure: SHELXTL (Bruker 2002); molecular graphics: SHELXTL (Bruker 2002); software used to prepare material for publication: SHELXTL (Bruker 2002).

Figures top
[Figure 1] Fig. 1. A view of the molecule of (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability. H atoms are presented as spheres with arbitrary radius. Symmetry code: (i) −1 + x, y, z;
[Figure 2] Fig. 2. The one-dimensional chain in crystal structure of (I).
catena-Poly[[dichloridozinc(II)]-µ-1-carboxylatomethyl-3-methylimidazolium-\ κ2O:O'] top
Crystal data top
[ZnCl2(C6H8N2O2)]F000 = 276
Mr = 276.43Dx = 1.814 Mg m−3
Monoclinic, PcMo Kα radiation
λ = 0.71073 Å
Hall symbol: P -2ycCell parameters from 1309 reflections
a = 4.8362 (4) Åθ = 2.8–27.7º
b = 10.5820 (9) ŵ = 2.92 mm−1
c = 10.1164 (7) ÅT = 296 (2) K
β = 102.183 (5)ºPrism, colourless
V = 506.06 (7) Å30.35 × 0.11 × 0.05 mm
Z = 2
Data collection top
Bruker P4
diffractometer		1994 independent reflections
Radiation source: fine-focus sealed tube1691 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.020
T = 296(2) Kθmax = 27.7º
ω scansθmin = 2.8º
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)		h = −6→6
Tmin = 0.687, Tmax = 0.864k = −13→13
3003 measured reflectionsl = −12→12
Refinement top
Refinement on F2Hydrogen site location: Geom
Least-squares matrix: FullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.033  w = 1/[σ2(Fo2) + (0.025P)2],
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.068(Δ/σ)max < 0.001
S = 1.01Δρmax = 0.45 e Å−3
1994 reflectionsΔρmin = −0.59 e Å−3
118 parametersExtinction correction: none
Primary atom site location: DirectAbsolute structure: Flack (1983)
Secondary atom site location: DifmapFlack parameter: 0.055 (15)
Crystal data top
[ZnCl2(C6H8N2O2)]V = 506.06 (7) Å3
Mr = 276.43Z = 2
Monoclinic, PcMo Kα
a = 4.8362 (4) ŵ = 2.92 mm−1
b = 10.5820 (9) ÅT = 296 (2) K
c = 10.1164 (7) Å0.35 × 0.11 × 0.05 mm
β = 102.183 (5)º
Data collection top
Bruker P4
diffractometer		1994 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)		1691 reflections with I > 2σ(I)
Tmin = 0.687, Tmax = 0.864Rint = 0.020
3003 measured reflectionsStandard reflections: none
Refinement top
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.068Δρmax = 0.45 e Å−3
S = 1.01Δρmin = −0.59 e Å−3
1994 reflectionsAbsolute structure: Flack (1983)
118 parametersFlack parameter: 0.055 (15)
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 > 2σ(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
Zn10.03320 (7)0.76339 (4)−0.06177 (5)0.03457 (14)
Cl10.0646 (3)0.96102 (10)−0.13316 (14)0.0511 (3)
Cl2−0.0059 (2)0.61405 (10)−0.21919 (13)0.0468 (3)
C10.3986 (10)0.8408 (5)0.6340 (4)0.0485 (12)
H1A0.45900.92680.62880.073*
H1B0.49070.80520.71920.073*
H1C0.19740.83860.62630.073*
C20.4180 (10)0.6411 (4)0.5010 (5)0.0415 (11)
H2A0.32300.58930.55100.050*
C30.5240 (9)0.6061 (4)0.3952 (4)0.0395 (11)
H3A0.51460.52600.35660.047*
C40.6128 (8)0.8075 (4)0.4347 (5)0.0339 (10)
H4A0.67560.88990.42890.041*
C50.7844 (8)0.7217 (4)0.2374 (4)0.0352 (9)
H5A0.89720.64650.23350.042*
H5B0.91110.79380.24950.042*
C60.5754 (8)0.7356 (4)0.1059 (4)0.0317 (9)
N10.4738 (8)0.7668 (3)0.5229 (4)0.0355 (9)
N20.6513 (7)0.7124 (4)0.3538 (4)0.0305 (8)
O10.6675 (6)0.7498 (3)0.0018 (3)0.0518 (9)
O20.3161 (5)0.7312 (3)0.1078 (3)0.0481 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.02622 (18)0.0510 (3)0.0276 (2)0.0024 (3)0.00809 (14)0.0035 (3)
Cl10.0555 (6)0.0378 (6)0.0633 (8)0.0024 (5)0.0199 (6)−0.0084 (6)
Cl20.0494 (6)0.0366 (6)0.0562 (7)0.0000 (5)0.0149 (5)−0.0038 (5)
C10.060 (3)0.056 (3)0.032 (3)0.006 (2)0.014 (2)−0.005 (2)
C20.045 (2)0.045 (3)0.038 (3)−0.006 (2)0.014 (2)0.005 (2)
C30.046 (2)0.035 (3)0.039 (3)−0.002 (2)0.012 (2)−0.0028 (19)
C40.031 (2)0.041 (2)0.030 (2)−0.0055 (16)0.007 (2)0.002 (2)
C50.0240 (17)0.051 (3)0.032 (2)0.0018 (18)0.0103 (16)0.003 (2)
C60.0272 (18)0.041 (2)0.029 (2)0.0004 (17)0.0096 (16)0.0044 (18)
N10.035 (2)0.045 (2)0.027 (2)0.0004 (16)0.0067 (17)0.0027 (17)
N20.0275 (17)0.042 (2)0.024 (2)−0.0023 (16)0.0103 (15)0.0028 (17)
O10.0256 (13)0.105 (3)0.0262 (18)0.0044 (15)0.0089 (12)0.0114 (16)
O20.0210 (13)0.091 (3)0.0336 (17)0.0011 (14)0.0078 (12)0.0107 (17)
Geometric parameters (Å, °) top
Zn1—O21.985 (3)C3—H3A0.9300
Zn1—O1i2.011 (3)C4—N11.298 (6)
Zn1—Cl22.2231 (13)C4—N21.335 (6)
Zn1—Cl12.2281 (12)C4—H4A0.9300
C1—N11.477 (6)C5—N21.460 (6)
C1—H1A0.9600C5—C61.499 (6)
C1—H1B0.9600C5—H5A0.9700
C1—H1C0.9600C5—H5B0.9700
C2—C31.334 (6)C6—O11.235 (5)
C2—N11.366 (5)C6—O21.259 (5)
C2—H2A0.9300O1—Zn1ii2.011 (3)
C3—N21.388 (6)
O2—Zn1—O1i101.74 (11)N1—C4—H4A125.3
O2—Zn1—Cl2115.85 (11)N2—C4—H4A125.3
O1i—Zn1—Cl2103.34 (11)N2—C5—C6113.2 (3)
O2—Zn1—Cl1111.06 (11)N2—C5—H5A108.9
O1i—Zn1—Cl1107.20 (11)C6—C5—H5A108.9
Cl2—Zn1—Cl1115.87 (5)N2—C5—H5B108.9
N1—C1—H1A109.5C6—C5—H5B108.9
N1—C1—H1B109.5H5A—C5—H5B107.8
H1A—C1—H1B109.5O1—C6—O2123.9 (4)
N1—C1—H1C109.5O1—C6—C5118.1 (3)
H1A—C1—H1C109.5O2—C6—C5118.0 (3)
H1B—C1—H1C109.5C4—N1—C2108.9 (4)
C3—C2—N1107.7 (4)C4—N1—C1126.4 (4)
C3—C2—H2A126.1C2—N1—C1124.6 (4)
N1—C2—H2A126.1C4—N2—C3107.3 (4)
C2—C3—N2106.7 (4)C4—N2—C5125.9 (4)
C2—C3—H3A126.7C3—N2—C5126.6 (4)
N2—C3—H3A126.7C6—O1—Zn1ii141.3 (3)
N1—C4—N2109.4 (4)C6—O2—Zn1119.1 (3)
N1—C2—C3—N21.1 (5)C2—C3—N2—C5−176.8 (4)
N2—C5—C6—O1176.9 (4)C6—C5—N2—C4−96.5 (5)
N2—C5—C6—O2−3.7 (5)C6—C5—N2—C378.6 (5)
N2—C4—N1—C20.2 (5)O2—C6—O1—Zn1ii−180.0 (4)
N2—C4—N1—C1177.2 (4)C5—C6—O1—Zn1ii−0.6 (7)
C3—C2—N1—C4−0.8 (5)O1—C6—O2—Zn1−5.6 (6)
C3—C2—N1—C1−178.0 (4)C5—C6—O2—Zn1175.0 (3)
N1—C4—N2—C30.5 (5)O1i—Zn1—O2—C6−178.3 (3)
N1—C4—N2—C5176.4 (4)Cl2—Zn1—O2—C670.5 (3)
C2—C3—N2—C4−1.0 (5)Cl1—Zn1—O2—C6−64.5 (3)
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z.
Acknowledgements top

The authors thank the Foundation of the Zhejiang Key Laboratory for Reactive Chemistry on Solid Surface for supporting this work.

references
References top

Bruker (2002). SHELXTL and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2004). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Shi, J.-M., Yin, H.-L. & Wu, C.-J. (2004). Chin. J. Struct. Chem. 23, 1363–1365.

Shi, X., Zhang, J., Ying, T.-K. & Zhao, G.-L. (2007). Acta Cryst. E63, m2157–?.