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

Experimental

Crystal data

• (C₂H₁₀N₂)[CdCl₄]

• M _r = 316.3

• Monoclinic,

• a = 8.6205 (5) Å

• b = 7.3425 (8) Å

• c = 7.2937 (7) Å

• β = 92.791 (6)°

• V = 461.11 (7) ų

• 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 ▶), according to Clark & Reid (1995 ▶)] 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

• Δρ_max = 0.13 e Å⁻³

• Δρ_min = −0.13 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2005 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; 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.

Supplementary Material

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

Table 1. Selected bond lengths (Å).

Cd1—Cl1	2.6427 (5)
Cd1—Cl1i	2.6471 (5)
Cd1—Cl2	2.5585 (4)

Symmetry code: (i) .

Table 2. Hydrogen-bond geometry (Å, °).

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) ; (iii) .

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 U_iso(H) = 1.2×U_eq 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 - z; (iv) 2 - x, -y, 2 - z; (v) 2 - x, 0.5 + y, 1.5 - z]

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 = 316.3	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

Data collection

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

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

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	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)

Geometric parameters (Å, °)

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.

Hydrogen-bond geometry (Å, °)

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.