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

Lamhamdi, A.; Mejdoubi, E.; Fejfarová, K.; Dušek, M.; El Bali, B.

doi:10.1107/S1600536809002025

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Pages m215-m216

doi:10.1107/S1600536809002025

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

Abdellatif Lamhamdi,^a Elmiloud Mejdoubi,^a Karla Fejfarová,^b Michal Dušek ^b and Brahim El Bali ^a ^*

^aDepartment of Chemistry, Faculty of Sciences, University Mohammed 1st, Po Box 717, 60000 Oujda, Morocco, and ^bInstitute of Physics, Na Slovance 2, 182 21 Praha 8, Czech Republic
^*Correspondence e-mail: belbali@fso.ump.ma

(Received 17 December 2008; accepted 15 January 2009; online 23 January 2009)

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.

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, P 2₁ /c
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 $[Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ), 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[F² > 2σ(F²)] = 0.010
wR(F²) = 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

Table 1
Selected bond lengths (Å)

Cd1—Cl1	2.6427 (5)
Cd1—Cl1ⁱ	2.6471 (5)
Cd1—Cl2	2.5585 (4)
Symmetry code: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2005 $[Oxford Diffraction (2005). CrysAlis CCD. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); 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.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

Isotypic structures have been reported by Berg & Sotofte (1976), (NH₃CH₂CH₂NH₃)[PdCl₄]; Birrell & Zaslow (1972), (NH₃CH₂CH₂NH₃)[CuCl₄]; Tichý et al. (1978), (NH₃CH₂CH₂NH₃)[MnCl₄]; and 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 top

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.

Computing details top

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).

Figures top

	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).

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

Crystal data top

(C₂H₁₀N₂)[CdCl₄]	F(000) = 304
M_r = 316.3	D_x = 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 top

Oxford Diffraction Gemini diffractometer with Atlas CCD detector	960 independent reflections
Radiation source: X-ray tube	899 reflections with I > 3σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 20.7491 pixels mm^-1	θ_max = 26.5°, θ_min = 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
T_min = 0.605, T_max = 0.841	l = −9→9
6603 measured reflections

Refinement top

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	Δρ_max = 0.13 e Å⁻³
960 reflections	Δρ_min = −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

Crystal data top

(C₂H₁₀N₂)[CdCl₄]	V = 461.11 (7) Å³
M_r = 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)°

Data collection top

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)
T_min = 0.605, T_max = 0.841	R_int = 0.023
6603 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.010	0 restraints
wR(F²) = 0.027	H-atom parameters constrained
S = 1.08	Δρ_max = 0.13 e Å⁻³
960 reflections	Δρ_min = −0.13 e Å⁻³
44 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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—C1^iv	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—Cd1^v	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—C1^iv	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)	C1^iv—C1—H1	109.4709
Cl1ⁱⁱⁱ—Cd1—Cl2	91.934 (11)	C1^iv—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, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H3···Cl1^v	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: (iii) x, −y+1/2, z+1/2; (v) −x+2, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	(C₂H₁₀N₂)[CdCl₄]
M_r	316.3
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	8.6205 (5), 7.3425 (8), 7.2937 (7)
β (°)	92.791 (6)
V (Å³)	461.11 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.45
Crystal size (mm)	0.27 × 0.13 × 0.08

Data collection
Diffractometer	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, T_max	0.605, 0.841
No. of measured, independent and observed [I > 3σ(I)] reflections	6603, 960, 899
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.010, 0.027, 1.08
No. of reflections	960
No. of parameters	44
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.13

Computer programs: CrysAlis CCD (Oxford Diffraction, 2005), CrysAlis RED (Oxford Diffraction, 2008), SIR2002 (Burla et al., 2003), JANA2006 (Petříček et al., 2007), DIAMOND (Brandenburg & Putz, 2005).

Selected bond lengths (Å) top

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

Symmetry code: (i) −x+2, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

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.

Acknowledgements

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

References

Becker, P. J. & Coppens, P. (1974). Acta Cryst. A30, 129–147. CrossRef IUCr Journals Web of Science Google Scholar
Berg, R. W. & Sotofte, I. (1976). Acta Chem. Scand. Ser. A, 30, 843–844. CrossRef Web of Science Google Scholar
Birrell, G. B. & Zaslow, B. (1972). J. Inorg. Nucl. Chem. 34, 1751. CSD CrossRef Web of Science Google Scholar
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Burla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Polidori, G. & Spagna, R. (2003). J. Appl. Cryst. 36, 1103. CrossRef IUCr Journals Google Scholar
Cavalca, L., Nardelli, M. & Fava, G. (1960). Acta Cryst. 13, 594–600. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897. CrossRef CAS Web of Science IUCr Journals Google Scholar
Furmanova, N. G., Sulaimankulova, D. K., Resnyanskii, V. F. & Sulaimankulov, K. S. (1996). Kristallografiya, 41, 669–672. CAS Google Scholar
Oxford Diffraction (2005). CrysAlis CCD. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Petříček, V., Dušek, M. & Palatinus, L. (2007). JANA2006. Institute of Physics, Praha, Czech Republic. Google Scholar
Skaarup, S. & Berg, R. W. (1978). J. Solid State Chem. 26, 59–67. CSD CrossRef CAS Web of Science Google Scholar
Tichý, K., Beneš, J., Hälg, W. & Arend, H. (1978). Acta Cryst. B34, 2970–2981. CSD CrossRef IUCr Journals Web of Science Google Scholar
Wang, B.-G., Cao, Y., Zhang, H.-F. & Ye, C. (1993). Rengong Jingti Xuebao 22, 341–344. CAS Google Scholar
Woode, M. K., Bryan, R. F. & Bekoe, D. A. (1987). Acta Cryst. C43, 2324–2327. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar