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Acta Crystallogr Sect E Struct Rep Online. 2009 February 1; 65(Pt 2): m215–m216.
Published online 2009 January 23. doi:  10.1107/S1600536809002025
PMCID: PMC2968258

Poly[ethane-1,2-diammonium tetra-μ-chlorido-cadmate(II)]

Abstract

The framework of the title compound, {(NH3CH2CH2NH3)[CdCl4]}n, is built upon layers parallel to (100) made up from corner-sharing [CdCl6] octa­hedra. NH3CH2CH2NH3 2+ 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.

Related literature

Isotypic structures have been reported by Berg & Sotofte (1976 [triangle]), (NH3CH2CH2NH3)[PdCl4]; Birrell & Zaslow (1972 [triangle]), (NH3CH2CH2NH3)[CuCl4]; Tichý et al. (1978 [triangle]), (NH3CH2CH2NH3)[MnCl4]; Skaarup & Berg (1978 [triangle]), (NH3CH2CH2NH3)[NiCl4]. For the structures of related compounds, see: Woode et al. (1987 [triangle]), CdCl2 .CH5N2S·H2O; Furmanova et al. (1996 [triangle]), CdCl2·CO(NH2)2; Wang et al. (1993 [triangle]), CdCl2·NH2NHCONH2; Cavalca et al. (1960 [triangle]), CdCl2 .2(C2H5N3O2). For crystallographic background, see: Becker & Coppens (1974 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0m215-scheme1.jpg

Experimental

Crystal data

  • (C2H10N2)[CdCl4]
  • M r = 316.3
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m215-efi1.jpg
  • a = 8.6205 (5) Å
  • b = 7.3425 (8) Å
  • c = 7.2937 (7) Å
  • β = 92.791 (6)°
  • V = 461.11 (7) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 3.45 mm−1
  • T = 298 K
  • 0.27 × 0.13 × 0.08 mm

Data collection

  • Oxford Diffraction Gemini diffractometer with Atlas CCD detector
  • Absorption correction: analytical [implemented in CrysAlis RED (Oxford Diffraction, 2008 [triangle]), according to Clark & Reid (1995 [triangle])] T min = 0.605, T max = 0.841
  • 6603 measured reflections
  • 960 independent reflections
  • 899 reflections with I > 3σ(I)
  • R int = 0.023

Refinement

  • R[F 2 > 2σ(F 2)] = 0.010
  • wR(F 2) = 0.027
  • S = 1.08
  • 960 reflections
  • 44 parameters
  • H-atom parameters constrained
  • Δρmax = 0.13 e Å−3
  • Δρmin = −0.13 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2005 [triangle]); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 [triangle]); data reduction: CrysAlis RED; program(s) used to solve structure: SIR2002 (Burla et al., 2003 [triangle]); program(s) used to refine structure: JANA2006 (Petříček et al., 2007 [triangle]); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 [triangle]); software used to prepare material for publication: JANA2006.

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809002025/wm2213sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809002025/wm2213Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We acknowledge the Grant Agency of the Czech Republic (grant No 202/07/J007). BEB thanks Dr R. Essehli for his kind collaboration.

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

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.

Figures

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 ...
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).

Crystal data

(C2H10N2)[CdCl4]F(000) = 304
Mr = 316.3Dx = 2.278 (1) Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5814 reflections
a = 8.6205 (5) Åθ = 2.8–26.5°
b = 7.3425 (8) ŵ = 3.45 mm1
c = 7.2937 (7) ÅT = 298 K
β = 92.791 (6)°Irregular shape, colourless
V = 461.11 (7) Å30.27 × 0.13 × 0.08 mm
Z = 2

Data collection

Oxford Diffraction Gemini diffractometer with Atlas CCD detector960 independent reflections
Radiation source: X-ray tube899 reflections with I > 3σ(I)
graphiteRint = 0.023
Detector resolution: 20.7491 pixels mm-1θmax = 26.5°, θmin = 3.6°
Rotation method data acquisition using ω scansh = −10→10
Absorption correction: analytical [implemented in CrysAlis RED (Oxford Diffraction, 2008), according to Clark & Reid (1995)]k = −9→9
Tmin = 0.605, Tmax = 0.841l = −9→9
6603 measured reflections

Refinement

Refinement on F2H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.010Weighting scheme based on measured s.u.'s w = 1/[σ2(I) + 0.0004I2]
wR(F2) = 0.027(Δ/σ)max = 0.014
S = 1.08Δρmax = 0.13 e Å3
960 reflectionsΔρmin = −0.13 e Å3
44 parametersExtinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
0 restraintsExtinction coefficient: 1620 (80)
20 constraints

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Cd11010.01781 (5)
Cl11.03989 (4)0.20870 (4)0.71088 (4)0.02864 (10)
Cl20.70621 (4)0.05039 (5)0.96946 (5)0.02895 (10)
N10.71742 (15)0.48402 (15)1.0216 (2)0.0310 (4)
C10.56378 (15)0.55139 (19)0.95400 (19)0.0286 (4)
H30.7897030.539950.9643350.0372*
H40.7296650.5049141.1388520.0372*
H50.7234460.3674981.0015610.0372*
H10.552530.5343680.8235270.0344*
H20.5555340.6789590.9806770.0344*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cd10.01855 (9)0.01728 (9)0.01754 (9)0.00042 (4)0.00020 (5)0.00048 (4)
Cl10.03678 (18)0.02466 (16)0.02474 (16)0.00197 (13)0.00416 (13)0.00987 (12)
Cl20.01873 (15)0.03278 (18)0.03532 (19)0.00157 (13)0.00114 (13)−0.00058 (15)
N10.0225 (7)0.0334 (7)0.0369 (7)−0.0008 (4)−0.0004 (5)0.0011 (5)
C10.0237 (7)0.0291 (6)0.0331 (7)0.0005 (6)0.0017 (6)0.0080 (6)

Geometric parameters (Å, °)

Cd1—Cl12.6427 (5)N1—H30.87
Cd1—Cl1i2.6471 (5)N1—H40.87
Cd1—Cl1ii2.6427 (5)N1—H50.87
Cd1—Cl1iii2.6471 (5)C1—C1iv1.5169 (19)
Cd1—Cl22.5585 (4)C1—H10.96
Cd1—Cl2ii2.5585 (4)C1—H20.96
N1—C11.4760 (18)
Cl1—Cd1—Cl1i91.326 (12)Cl2—Cd1—Cl2ii180
Cl1—Cd1—Cl1ii180Cd1—Cl1—Cd1v156.050 (14)
Cl1—Cd1—Cl1iii88.674 (12)C1—N1—H3109.471
Cl1—Cd1—Cl290.766 (12)C1—N1—H4109.4712
Cl1—Cd1—Cl2ii89.234 (12)C1—N1—H5109.4713
Cl1i—Cd1—Cl1ii88.674 (12)H3—N1—H4109.4717
Cl1i—Cd1—Cl1iii180H3—N1—H5109.471
Cl1i—Cd1—Cl288.066 (11)H4—N1—H5109.4711
Cl1i—Cd1—Cl2ii91.934 (11)N1—C1—C1iv110.09 (11)
Cl1ii—Cd1—Cl1iii91.326 (12)N1—C1—H1109.4717
Cl1ii—Cd1—Cl289.234 (12)N1—C1—H2109.4714
Cl1ii—Cd1—Cl2ii90.766 (12)C1iv—C1—H1109.4709
Cl1iii—Cd1—Cl291.934 (11)C1iv—C1—H2109.4709
Cl1iii—Cd1—Cl2ii88.066 (11)H1—C1—H2108.8487

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.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H3···Cl1v0.872.353.2123 (14)173
N1—H4···Cl2iii0.872.463.2824 (15)157
N1—H5···Cl20.872.343.2075 (12)172

Symmetry codes: (v) −x+2, y+1/2, −z+3/2; (iii) x, −y+1/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2213).

References

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  • Birrell, G. B. & Zaslow, B. (1972). J. Inorg. Nucl. Chem.34, 1751.
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