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Acta Cryst. (2007). E63, m2157    [ doi:10.1107/S1600536807033508 ]

Poly[1-carboxymethyl-3-methylimidazolium [aquadi-[mu]3-chlorido-di-[mu]2-chlorido-chloridodicadmate(II)]]

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

Abstract top

The title compound, {(C6H9N2O2)[Cd2Cl5(H2O)]}n, consists of 1-methyl-3-carboxymethylimidazole cations and infinite one-dimensional polymeric inorganic chains of {[Cd2Cl5(H2O)]-}n running along the a axis. The imidazole-ring cations form one-dimensional chains adjacent to the inorganic chains via [pi]-[pi] stacking interactions ([pi]-[pi] distance = 3.736 Å).

Comment top

In recent years, there has been an increasing interest in the coordination chemistry of cadmium due to the increased recognition of it's role in biological organisms and molecular-based materials (Jian et al., 2006). Here, we report a novel one-dimensional Cd string complex (I), which contains one [Cd2Cl5(H2O)]- anion and one 1-methyl-3-carboxymethylimidazole cation in the asymmetric unit, (Fig.1).

The inorganic chain is formed by two paralleled chains of corner-sharing [Cd2Cl2] quadrangular, which are displaced by half distance of Cd1—Cd2 and connected by tridentate bridging chlorine atoms. In the crystal structure, two independent cadmium atoms are present, which are connected by a bidentate and a tridentate bridging chlorine atom. The six-coordination is completed on the Cd(1) atom by a tridentate bridging chlorine atom and a coordinated water molecule, while on the Cd(2) atom by a tridentate bridging and a terminal chlorine atom. In each one of paralled chains, the terminal atoms (chlorine atom and water molecule) are in cis-position to each other, but in trans-position to the terminal atoms in the other paralled chain.

Each Cd atom shows a distorted octahedral geometry, gives rise to a polymeric linear chain of edge-sharing octahedra running along the a axis. Cd—C1 distances vary according to the different bonding mode of the C1 atoms; their values normally increasing in the order terminal < dibridged < tribridged, which are in agreement with the compound repoted by Corradi (Corradi et al., 1993).

Imidazole cations form one-dimensional chains next to the inorganic chain via π-π stacking interactions. Furthermore, there are O–H···Cl and O–H···O intermolecule hydrogen bond involving coordinated water O1w atom and terminate Cl atom, as well as carboxyl O1 atom and carboxyl O2 atom (see table), which stabilize the three-dimensional network.

Related literature top

For related literature, see: Corrad et al. (1993); Jian et al. (2006).

Experimental top

A mixture of CdCl2 (1 mmol), 1-methyl-3-carboxymethylimidazole ion liquid (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 two weeks.

Refinement top

The structure was solved by direct methods and successive Fourier difference synthesis. The H atoms bonded to C atoms were positioned geometrically and refined using a riding model [C—H = 0.97 (2) Å and Uiso(H) = 1.2Ueq(C)]. The H atoms bonded to O atoms were located in a difference Fourier maps and refined with O—H distance restraints of 0.85 (2) Å and Uiso(H) = 1.2Ueq(O).

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of the molecule of (I) showing the atom-labelling scheme, with displacement ellipsoids drawn at the 30% probability.
Poly[1-methyl-1-carboxymethyl-3-methylimidazolium [aqua-di-µ3-chlorido-di-µ2-chlorido-chloridodicadmate(II)]] top
Crystal data top
(C6H9N2O2)[Cd2Cl5(H2O)]Z = 2
Mr = 561.24F(000) = 532
Triclinic, P1Dx = 2.411 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.580 (2) ÅCell parameters from 5396 reflections
b = 10.339 (3) Åθ = 2.5–27.8°
c = 10.371 (3) ŵ = 3.61 mm−1
α = 74.593 (15)°T = 296 K
β = 81.568 (17)°Block, colourless
γ = 83.781 (16)°0.56 × 0.20 × 0.10 mm
V = 773.0 (4) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		3446 independent reflections
Radiation source: fine-focus sealed tube3191 reflections with I > 2σ(I)
graphiteRint = 0.022
ω scansθmax = 27.8°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→9
Tmin = 0.424, Tmax = 0.697k = −13→13
9462 measured reflectionsl = −13→13
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.021Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.056H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.033P)2 + 0.3014P]
where P = (Fo2 + 2Fc2)/3
3446 reflections(Δ/σ)max = 0.002
163 parametersΔρmax = 0.52 e Å−3
0 restraintsΔρmin = −0.90 e Å−3
Crystal data top
(C6H9N2O2)[Cd2Cl5(H2O)]γ = 83.781 (16)°
Mr = 561.24V = 773.0 (4) Å3
Triclinic, P1Z = 2
a = 7.580 (2) ÅMo Kα radiation
b = 10.339 (3) ŵ = 3.61 mm−1
c = 10.371 (3) ÅT = 296 K
α = 74.593 (15)°0.56 × 0.20 × 0.10 mm
β = 81.568 (17)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		3446 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3191 reflections with I > 2σ(I)
Tmin = 0.424, Tmax = 0.697Rint = 0.022
9462 measured reflectionsθmax = 27.8°
Refinement top
R[F2 > 2σ(F2)] = 0.021H-atom parameters constrained
wR(F2) = 0.056Δρmax = 0.52 e Å−3
S = 1.01Δρmin = −0.90 e Å−3
3446 reflectionsAbsolute structure: ?
163 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Cd1−0.65421 (2)1.144477 (16)0.049066 (16)0.02828 (6)
Cd2−0.84758 (2)0.825988 (16)−0.030118 (16)0.02783 (6)
C1−0.8088 (3)1.0934 (2)0.5265 (2)0.0318 (5)
C2−0.6479 (3)1.1611 (2)0.5415 (2)0.0322 (5)
H2A−0.60951.11990.62930.039*
H2B−0.55031.14750.47360.039*
C3−0.7179 (4)1.3985 (2)0.4081 (3)0.0441 (6)
H3A−0.71171.38160.32380.053*
C4−0.7576 (4)1.5190 (3)0.4378 (3)0.0440 (6)
H4A−0.78351.60080.37740.053*
C5−0.7114 (3)1.3677 (2)0.6260 (2)0.0331 (5)
H5A−0.70051.32720.71620.040*
C6−0.7922 (5)1.5991 (3)0.6535 (3)0.0551 (8)
H6A−0.77771.55700.74600.083*
H6B−0.91301.63690.64720.083*
H6C−0.71151.66920.61880.083*
N1−0.7525 (3)1.49781 (19)0.5738 (2)0.0362 (5)
N2−0.6886 (3)1.30571 (17)0.52722 (18)0.0308 (4)
O1−0.7649 (2)0.97628 (16)0.50150 (18)0.0440 (5)
H1−0.85200.93800.49350.053*
O1W−0.6345 (3)1.37162 (17)−0.07118 (18)0.0430 (4)
H1WA−0.53081.3949−0.06910.052*
H1WB−0.71301.4161−0.03130.052*
O2−0.9607 (2)1.14584 (16)0.53634 (17)0.0381 (4)
Cl1−0.43258 (8)1.17746 (6)0.20317 (6)0.03400 (13)
Cl2−0.62407 (8)0.87957 (5)0.13734 (5)0.02852 (11)
Cl3−1.13417 (7)0.89355 (5)0.12270 (5)0.02748 (11)
Cl4−1.06544 (8)0.81267 (6)−0.19757 (6)0.03600 (13)
Cl5−0.80425 (10)0.58296 (6)0.09300 (7)0.04500 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.02405 (10)0.03030 (9)0.03304 (10)−0.00022 (6)−0.00257 (7)−0.01366 (7)
Cd20.02290 (10)0.02877 (9)0.03250 (10)0.00080 (6)−0.00173 (7)−0.01092 (7)
C10.0441 (14)0.0252 (10)0.0267 (11)0.0008 (9)−0.0075 (10)−0.0073 (8)
C20.0343 (13)0.0279 (10)0.0343 (12)0.0020 (9)−0.0016 (10)−0.0109 (9)
C30.0650 (18)0.0354 (12)0.0289 (12)−0.0021 (12)−0.0034 (12)−0.0048 (10)
C40.0580 (18)0.0327 (12)0.0378 (13)−0.0015 (11)−0.0099 (12)−0.0013 (10)
C50.0410 (14)0.0289 (10)0.0299 (11)−0.0022 (9)−0.0038 (10)−0.0087 (9)
C60.075 (2)0.0373 (14)0.0616 (18)0.0083 (13)−0.0160 (16)−0.0276 (13)
N10.0445 (13)0.0269 (9)0.0393 (11)0.0003 (8)−0.0078 (9)−0.0118 (8)
N20.0376 (11)0.0258 (9)0.0286 (9)−0.0020 (7)−0.0010 (8)−0.0082 (7)
O10.0427 (11)0.0308 (8)0.0657 (13)0.0035 (7)−0.0139 (10)−0.0231 (8)
O1W0.0531 (12)0.0322 (8)0.0447 (10)0.0042 (8)−0.0075 (9)−0.0140 (7)
O20.0369 (10)0.0319 (8)0.0479 (10)0.0032 (7)−0.0071 (8)−0.0153 (7)
Cl10.0270 (3)0.0497 (3)0.0301 (3)−0.0041 (2)−0.0004 (2)−0.0195 (2)
Cl20.0282 (3)0.0285 (2)0.0297 (3)−0.00082 (19)−0.0014 (2)−0.0105 (2)
Cl30.0262 (3)0.0310 (2)0.0255 (2)−0.00225 (19)−0.0002 (2)−0.00919 (19)
Cl40.0278 (3)0.0518 (3)0.0336 (3)0.0035 (2)−0.0023 (2)−0.0231 (3)
Cl50.0624 (4)0.0270 (3)0.0432 (3)−0.0011 (3)−0.0051 (3)−0.0063 (2)
Geometric parameters (Å, °) top
Cd1—O1W2.3575 (18)C3—N21.379 (3)
Cd1—Cl4i2.5066 (9)C3—H3A0.9300
Cd1—Cl12.5873 (8)C4—N11.374 (4)
Cd1—Cl22.6430 (9)C4—H4A0.9300
Cd1—Cl2ii2.6822 (9)C5—N21.328 (3)
Cd1—Cl3i2.6922 (8)C5—N11.331 (3)
Cd2—Cl52.5082 (9)C5—H5A0.9300
Cd2—Cl1ii2.5753 (9)C6—N11.479 (3)
Cd2—Cl42.6037 (9)C6—H6A0.9600
Cd2—Cl32.6398 (9)C6—H6B0.9600
Cd2—Cl22.7876 (8)C6—H6C0.9600
Cd2—Cl3i2.7968 (10)O1—H10.8303
C1—O21.221 (3)O1W—H1WA0.8511
C1—O11.303 (2)O1W—H1WB0.8405
C1—C21.517 (3)Cl1—Cd2ii2.5753 (9)
C2—N21.465 (3)Cl2—Cd1ii2.6822 (9)
C2—H2A0.9700Cl3—Cd1i2.6922 (8)
C2—H2B0.9700Cl3—Cd2i2.7968 (10)
C3—C41.353 (3)Cl4—Cd1i2.5066 (9)
O1W—Cd1—Cl4i94.81 (5)N2—C2—H2B109.3
O1W—Cd1—Cl189.02 (5)C1—C2—H2B109.3
Cl4i—Cd1—Cl196.61 (3)H2A—C2—H2B107.9
O1W—Cd1—Cl2166.91 (5)C4—C3—N2106.7 (2)
Cl4i—Cd1—Cl297.76 (3)C4—C3—H3A126.7
Cl1—Cd1—Cl293.17 (3)N2—C3—H3A126.7
O1W—Cd1—Cl2ii79.77 (5)C3—C4—N1107.2 (2)
Cl4i—Cd1—Cl2ii172.27 (2)C3—C4—H4A126.4
Cl1—Cd1—Cl2ii88.85 (3)N1—C4—H4A126.4
Cl2—Cd1—Cl2ii87.37 (3)N2—C5—N1108.3 (2)
O1W—Cd1—Cl3i90.75 (5)N2—C5—H5A125.8
Cl4i—Cd1—Cl3i87.22 (3)N1—C5—H5A125.8
Cl1—Cd1—Cl3i176.167 (17)N1—C6—H6A109.5
Cl2—Cd1—Cl3i86.20 (2)N1—C6—H6B109.5
Cl2ii—Cd1—Cl3i87.34 (3)H6A—C6—H6B109.5
Cl5—Cd2—Cl1ii95.21 (3)N1—C6—H6C109.5
Cl5—Cd2—Cl4101.03 (3)H6A—C6—H6C109.5
Cl1ii—Cd2—Cl493.72 (3)H6B—C6—H6C109.5
Cl5—Cd2—Cl398.51 (3)C5—N1—C4108.8 (2)
Cl1ii—Cd2—Cl3166.00 (2)C5—N1—C6124.2 (2)
Cl4—Cd2—Cl386.37 (3)C4—N1—C6127.0 (2)
Cl5—Cd2—Cl286.97 (3)C5—N2—C3109.01 (19)
Cl1ii—Cd2—Cl286.83 (3)C5—N2—C2126.23 (19)
Cl4—Cd2—Cl2171.891 (18)C3—N2—C2124.70 (19)
Cl3—Cd2—Cl291.15 (3)C1—O1—H1113.3
Cl5—Cd2—Cl3i168.10 (2)Cd1—O1W—H1WA108.9
Cl1ii—Cd2—Cl3i87.15 (3)Cd1—O1W—H1WB106.3
Cl4—Cd2—Cl3i90.43 (3)H1WA—O1W—H1WB110.4
Cl3—Cd2—Cl3i78.85 (3)Cd2ii—Cl1—Cd195.48 (3)
Cl2—Cd2—Cl3i81.51 (2)Cd1—Cl2—Cd1ii92.63 (3)
O2—C1—O1125.2 (2)Cd1—Cl2—Cd296.80 (2)
O2—C1—C2122.34 (19)Cd1ii—Cl2—Cd288.60 (3)
O1—C1—C2112.4 (2)Cd2—Cl3—Cd1i90.45 (3)
N2—C2—C1111.75 (18)Cd2—Cl3—Cd2i101.15 (3)
N2—C2—H2A109.3Cd1i—Cl3—Cd2i95.46 (2)
C1—C2—H2A109.3Cd1i—Cl4—Cd295.57 (3)
O2—C1—C2—N2−17.3 (3)Cl2ii—Cd1—Cl2—Cd2−88.90 (3)
O1—C1—C2—N2162.16 (18)Cl3i—Cd1—Cl2—Cd2−1.392 (15)
N2—C3—C4—N1−0.2 (3)Cl5—Cd2—Cl2—Cd1−175.66 (2)
N2—C5—N1—C40.5 (3)Cl1ii—Cd2—Cl2—Cd188.94 (3)
N2—C5—N1—C6178.5 (2)Cl3—Cd2—Cl2—Cd1−77.20 (3)
C3—C4—N1—C5−0.2 (4)Cl3i—Cd2—Cl2—Cd11.352 (14)
C3—C4—N1—C6−178.0 (2)Cl5—Cd2—Cl2—Cd1ii91.85 (3)
N1—C5—N2—C3−0.7 (3)Cl1ii—Cd2—Cl2—Cd1ii−3.542 (16)
N1—C5—N2—C2−177.8 (2)Cl3—Cd2—Cl2—Cd1ii−169.681 (17)
C4—C3—N2—C50.6 (3)Cl3i—Cd2—Cl2—Cd1ii−91.13 (3)
C4—C3—N2—C2177.7 (2)Cl5—Cd2—Cl3—Cd1i−96.13 (3)
C1—C2—N2—C5106.3 (3)Cl1ii—Cd2—Cl3—Cd1i95.29 (7)
C1—C2—N2—C3−70.3 (3)Cl4—Cd2—Cl3—Cd1i4.490 (17)
O1W—Cd1—Cl1—Cd2ii−75.96 (5)Cl2—Cd2—Cl3—Cd1i176.764 (15)
Cl4i—Cd1—Cl1—Cd2ii−170.68 (2)Cl3i—Cd2—Cl3—Cd1i95.65 (3)
Cl2—Cd1—Cl1—Cd2ii91.13 (3)Cl5—Cd2—Cl3—Cd2i168.22 (2)
Cl2ii—Cd1—Cl1—Cd2ii3.828 (18)Cl1ii—Cd2—Cl3—Cd2i−0.36 (8)
O1W—Cd1—Cl2—Cd1ii10.7 (2)Cl4—Cd2—Cl3—Cd2i−91.16 (3)
Cl4i—Cd1—Cl2—Cd1ii174.183 (18)Cl2—Cd2—Cl3—Cd2i81.11 (3)
Cl1—Cd1—Cl2—Cd1ii−88.70 (3)Cl3i—Cd2—Cl3—Cd2i0.0
Cl2ii—Cd1—Cl2—Cd1ii0.0Cl5—Cd2—Cl4—Cd1i93.13 (3)
Cl3i—Cd1—Cl2—Cd1ii87.51 (3)Cl1ii—Cd2—Cl4—Cd1i−170.82 (2)
O1W—Cd1—Cl2—Cd2−78.2 (2)Cl3—Cd2—Cl4—Cd1i−4.846 (18)
Cl4i—Cd1—Cl2—Cd285.28 (3)Cl3i—Cd2—Cl4—Cd1i−83.64 (3)
Cl1—Cd1—Cl2—Cd2−177.604 (17)
Symmetry codes: (i) −x−2, −y+2, −z; (ii) −x−1, −y+2, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2iii0.831.842.673 (3)176
O1W—H1WA···Cl5ii0.852.543.375 (2)165
O1W—H1WB···Cl5iv0.842.403.171 (2)152
Symmetry codes: (iii) −x−2, −y+2, −z+1; (ii) −x−1, −y+2, −z; (iv) x, y+1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.831.842.673 (3)176
O1W—H1WA···Cl5ii0.852.543.375 (2)165
O1W—H1WB···Cl5iii0.842.403.171 (2)152
Symmetry codes: (i) −x−2, −y+2, −z+1; (ii) −x−1, −y+2, −z; (iii) x, y+1, z.
references
References top

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

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

Corrad, A. B., Bruckner, S., Cramarossa, M. R., Manfredini, T., Menabue, L., Saladini, M., Saccani, A., Sandrolini, F. & Giusti, J. (1993). Chem. Mater. 5, 90–97. [Is first author spelled Corradi?]

Fang-Fang, J., Pu-Su, Z., Qing-Xiang, W. & Ying, L. (2006). Inorg. Chim. Acta, 359, 1473–1477. [Please ensure authors are cited by their family names, not their given names]

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

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