Acta Cryst. (2009). E65, m215-m216 [ doi:10.1107/S1600536809002025 ]
![[mu]](/logos/entities/mu_rmgif.gif)
-chlorido-cadmate(II)]The framework of the title compound, {(NH3CH2CH2NH3)[CdCl4]}n, is built upon layers parallel to (100) made up from corner-sharing [CdCl6] octahedra. NH3CH2CH2NH32+ cations are situated between the layers and are linked to the layers via an N-H
Cl hydrogen-bonding network. The Cd atom is located on an inversion centre and the coordination environment is described as highly distorted octahedral.
Crystals of the title compound were obtained by mixing solutions of K4P2O7 (10 ml, 0.1M), CdCl2 (10 ml, 0.1M) and three drops of isopropylamine, (CH3)2(CH)NH3. The pH of the resulting solution was controlled with hydrochloric acid (pH = 2.5), stirred for 30 min, and then left to stand at ambient temperatures. After 5 d, colourless crystals appeared that were filtred off and washed with a solution of ethanol-water (80/20). Under the given reaction conditions isopropylamine will not convert into ethylenediamine (en), as evidenced by the structure analysis. Therefore it is most likely that the two supply bottles with isopropylamine and ethylenediamine were confused for synthesis.
All hydrogen atoms were discernible from difference Fourier maps and could be refined to a reasonable geometry. In the last refinement cycles they were nevertheless kept in ideal positions with N—H and C—H distances restrained to 0.87 Å and 0.96 Å, respectively, and with Uiso(H) = 1.2×Ueq of the respective parent atom.
Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: JANA2006 (Petříček et al., 2007); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: JANA2006 (Petříček et al., 2007).
![[Figure 1]](./wm2213fig1thm.gif)
| Fig. 1. Part of the structure of (NH3CH2CH2NH3)[CdCl4]. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are represented by dashed lines. [Symmetry codes: (i) 1 - x, 1- y, 2 - z; (ii) x, 0.5 - y, 0.5 + z; (iii) 2 - x, -0.5 + y, 1.5 - z; (iv) 2 - x, -y, 2 - z; (v) 2 - x, 0.5 + y, 1.5 - z] |
![[Figure 2]](./wm2213fig2thm.gif)
| Fig. 2. Packing of (NH3CH2CH2NH3)[CdCl4] viewed along a. Color code: Pink balls (Cd), green balls (Cl), grey balls (C), blue balls (N), black balls (H). |
| (C2H10N2)[CdCl4] | F(000) = 304 |
| Mr = 316.3 | Dx = 2.278 (1) Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 5814 reflections |
| a = 8.6205 (5) Å | θ = 2.8–26.5° |
| b = 7.3425 (8) Å | µ = 3.45 mm−1 |
| c = 7.2937 (7) Å | T = 298 K |
| β = 92.791 (6)° | Irregular shape, colourless |
| V = 461.11 (7) Å3 | 0.27 × 0.13 × 0.08 mm |
| Z = 2 |
| Oxford Diffraction Gemini diffractometer with Atlas CCD detector | 960 independent reflections |
| Radiation source: X-ray tube | 899 reflections with I > 3σ(I) |
| graphite | Rint = 0.023 |
| Detector resolution: 20.7491 pixels mm-1 | θmax = 26.5°, θmin = 3.6° |
| Rotation method data acquisition using ω scans | h = −10→10 |
| Absorption correction: analytical [implemented in CrysAlis RED (Oxford Diffraction, 2008), according to Clark & Reid (1995)] | k = −9→9 |
| Tmin = 0.605, Tmax = 0.841 | l = −9→9 |
| 6603 measured reflections |
| Refinement on F2 | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.010 | Weighting scheme based on measured s.u.'s w = 1/[σ2(I) + 0.0004I2] |
| wR(F2) = 0.027 | (Δ/σ)max = 0.014 |
| S = 1.08 | Δρmax = 0.13 e Å−3 |
| 960 reflections | Δρmin = −0.13 e Å−3 |
| 44 parameters | Extinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974) |
| 0 restraints | Extinction coefficient: 1620 (80) |
| 20 constraints |
| (C2H10N2)[CdCl4] | V = 461.11 (7) Å3 |
| Mr = 316.3 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 8.6205 (5) Å | µ = 3.45 mm−1 |
| b = 7.3425 (8) Å | T = 298 K |
| c = 7.2937 (7) Å | 0.27 × 0.13 × 0.08 mm |
| β = 92.791 (6)° |
| Oxford Diffraction Gemini diffractometer with Atlas CCD detector | 960 independent reflections |
| Absorption correction: analytical [implemented in CrysAlis RED (Oxford Diffraction, 2008), according to Clark & Reid (1995)] | 899 reflections with I > 3σ(I) |
| Tmin = 0.605, Tmax = 0.841 | Rint = 0.023 |
| 6603 measured reflections | θmax = 26.5° |
| R[F2 > 2σ(F2)] = 0.010 | H-atom parameters constrained |
| wR(F2) = 0.027 | Δρmax = 0.13 e Å−3 |
| S = 1.08 | Δρmin = −0.13 e Å−3 |
| 960 reflections | Absolute structure: ? |
| 44 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Refinement. The refinement was carried out against all reflections. The conventional R-factor is always based on F. The goodness of fit as well as the weighted R-factor are based on F and F2 for refinement carried out on F and F2, respectively. The threshold expression is used only for calculating R-factors etc. and it is not relevant to the choice of reflections for refinement. The program used for refinement, Jana2006, uses the weighting scheme based on the experimental expectations, see _refine_ls_weighting_details, that does not force S to be one. Therefore the values of S are usually larger than the ones from the SHELX program. |
| x | y | z | Uiso*/Ueq | ||
| Cd1 | 1 | 0 | 1 | 0.01781 (5) | |
| Cl1 | 1.03989 (4) | 0.20870 (4) | 0.71088 (4) | 0.02864 (10) | |
| Cl2 | 0.70621 (4) | 0.05039 (5) | 0.96946 (5) | 0.02895 (10) | |
| N1 | 0.71742 (15) | 0.48402 (15) | 1.0216 (2) | 0.0310 (4) | |
| C1 | 0.56378 (15) | 0.55139 (19) | 0.95400 (19) | 0.0286 (4) | |
| H3 | 0.789703 | 0.53995 | 0.964335 | 0.0372* | |
| H4 | 0.729665 | 0.504914 | 1.138852 | 0.0372* | |
| H5 | 0.723446 | 0.367498 | 1.001561 | 0.0372* | |
| H1 | 0.55253 | 0.534368 | 0.823527 | 0.0344* | |
| H2 | 0.555534 | 0.678959 | 0.980677 | 0.0344* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cd1 | 0.01855 (9) | 0.01728 (9) | 0.01754 (9) | 0.00042 (4) | 0.00020 (5) | 0.00048 (4) |
| Cl1 | 0.03678 (18) | 0.02466 (16) | 0.02474 (16) | 0.00197 (13) | 0.00416 (13) | 0.00987 (12) |
| Cl2 | 0.01873 (15) | 0.03278 (18) | 0.03532 (19) | 0.00157 (13) | 0.00114 (13) | −0.00058 (15) |
| N1 | 0.0225 (7) | 0.0334 (7) | 0.0369 (7) | −0.0008 (4) | −0.0004 (5) | 0.0011 (5) |
| C1 | 0.0237 (7) | 0.0291 (6) | 0.0331 (7) | 0.0005 (6) | 0.0017 (6) | 0.0080 (6) |
| Cd1—Cl1 | 2.6427 (5) | N1—H3 | 0.87 |
| Cd1—Cl1i | 2.6471 (5) | N1—H4 | 0.87 |
| Cd1—Cl1ii | 2.6427 (5) | N1—H5 | 0.87 |
| Cd1—Cl1iii | 2.6471 (5) | C1—C1iv | 1.5169 (19) |
| Cd1—Cl2 | 2.5585 (4) | C1—H1 | 0.96 |
| Cd1—Cl2ii | 2.5585 (4) | C1—H2 | 0.96 |
| N1—C1 | 1.4760 (18) | ||
| Cl1—Cd1—Cl1i | 91.326 (12) | Cl2—Cd1—Cl2ii | 180 |
| Cl1—Cd1—Cl1ii | 180 | Cd1—Cl1—Cd1v | 156.050 (14) |
| Cl1—Cd1—Cl1iii | 88.674 (12) | C1—N1—H3 | 109.471 |
| Cl1—Cd1—Cl2 | 90.766 (12) | C1—N1—H4 | 109.4712 |
| Cl1—Cd1—Cl2ii | 89.234 (12) | C1—N1—H5 | 109.4713 |
| Cl1i—Cd1—Cl1ii | 88.674 (12) | H3—N1—H4 | 109.4717 |
| Cl1i—Cd1—Cl1iii | 180 | H3—N1—H5 | 109.471 |
| Cl1i—Cd1—Cl2 | 88.066 (11) | H4—N1—H5 | 109.4711 |
| Cl1i—Cd1—Cl2ii | 91.934 (11) | N1—C1—C1iv | 110.09 (11) |
| Cl1ii—Cd1—Cl1iii | 91.326 (12) | N1—C1—H1 | 109.4717 |
| Cl1ii—Cd1—Cl2 | 89.234 (12) | N1—C1—H2 | 109.4714 |
| Cl1ii—Cd1—Cl2ii | 90.766 (12) | C1iv—C1—H1 | 109.4709 |
| Cl1iii—Cd1—Cl2 | 91.934 (11) | C1iv—C1—H2 | 109.4709 |
| Cl1iii—Cd1—Cl2ii | 88.066 (11) | H1—C1—H2 | 108.8487 |
| Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) −x+2, −y, −z+2; (iii) x, −y+1/2, z+1/2; (iv) −x+1, −y+1, −z+2; (v) −x+2, y+1/2, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H3···Cl1v | 0.87 | 2.35 | 3.2123 (14) | 173 |
| N1—H4···Cl2iii | 0.87 | 2.46 | 3.2824 (15) | 157 |
| N1—H5···Cl2 | 0.87 | 2.34 | 3.2075 (12) | 172 |
| Symmetry codes: (v) −x+2, y+1/2, −z+3/2; (iii) x, −y+1/2, z+1/2. |
| Cd1—Cl1 | 2.6427 (5) | Cd1—Cl2 | 2.5585 (4) |
| Cd1—Cl1i | 2.6471 (5) |
| Symmetry codes: (i) −x+2, y−1/2, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H3···Cl1ii | 0.87 | 2.35 | 3.2123 (14) | 173 |
| N1—H4···Cl2iii | 0.87 | 2.46 | 3.2824 (15) | 157 |
| N1—H5···Cl2 | 0.87 | 2.34 | 3.2075 (12) | 172 |
| Symmetry codes: (ii) −x+2, y+1/2, −z+3/2; (iii) x, −y+1/2, z+1/2. |
We acknowledge the Grant Agency of the Czech Republic (grant No 202/07/J007). BEB thanks Dr R. Essehli for his kind collaboration.
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Crystals of the new title compound (NH3CH2CH2NH3)[CdCl4] were obtained as a side product during the preparation of a phosphate in solution. We report here on its crystal structure. Compounds including cadmium chloride and an organic moiety are frequently found in the form CdCl2.X, where X is the organic moiety, for example: CdCl2.CH5N2S.H2O (Woode et al., 1987), CdCl2.CO(NH2)2 (Furmanova et al., 1996), CdCl2.NH2NHCONH2 (Wang et al., 1993), or CdCl2.2(C2H5N3O2) (Cavalca et al., 1960). The title compound, however, contains cadmium in the anionic part of the crystal structure and is isotypic with (NH3CH2CH2NH3)[PdCl4] (Berg & Sotofte, 1976), (NH3CH2CH2NH3)[CuCl4] (Birrell & Zaslow, 1972), (NH3CH2CH2NH3)[MnCl4] (Tichý et al., 1978) and (NH3CH2CH2NH3)[NiCl4] (Skaarup & Berg, 1978).
Fig. 1 shows [CdCl6] octahedra and the 1,2-ethanediammonium cation connected via hydrogen bonds N1-H3···Cl1, N1-H4···Cl2 and N1-H5···Cl2. All chloride ligands of the CdCl6 octahedron participate in hydrogen bonding, as well as all hydrogens that are attached to N1.
Packing of (NH3CH2CH2NH3)[CdCl4] viewed along a (Fig. 2) shows a layer of corner sharing [CdCl6] octahedra and the neighbouring layer of 1,2-ethanediammonium cations. The minimal Cd—Cd distance within a layer is 5.1747 (8) Å.
The interlayer space is large enough to allow minimal distorsions of the 1,2-ethanediammonium cation molecule, the angles and distances of which have usual values as reported in known compounds containing this cation.