Bis(2-phenyl­ethyl­ammonium) tetra­chloridocobaltate(II)

In-Hwan Oh; Dahye Kim; Young-Duk Huh; Younbong Park; J M Sungil Park; Seong-Hun Park

doi:10.1107/S1600536811011603

. 2011 Apr 7;67(Pt 5):m522–m523. doi: 10.1107/S1600536811011603

Bis(2-phenylethylammonium) tetrachloridocobaltate(II)

In-Hwan Oh ^a, Dahye Kim ^b, Young-Duk Huh ^b, Younbong Park ^c, J M Sungil Park ^a, Seong-Hun Park ^d,^*

PMCID: PMC3089155 PMID: 21754265

Abstract

Crystals of the title compound, (C₆H₅CH₂CH₂NH₃)₂[CoCl₄], were grown by the solvent-evaporation method. This inorganic–organic hybrid compound exhibits a layered structure in which isolated CoCl₄ inorganic layers alternate with bilayers of phenylethylammonium cations. Although the inorganic anion is zero-dimensional, the layered structure is stabilized via N—H⋯Cl hydrogen bonds. The CoCl₄ tetrahedra connect to the cations through N—H⋯Cl hydrogen bonds, building a two-dimensional network extending parallel to (010).

Related literature

For inorganic–organic hybrids containing tetrahedral anions, see: Abdi et al. (2005 ▶); Huh et al. (2006 ▶); Zouari & Ben Salah, (2004 ▶). For low-dimensional magnetism in inorganic–organic perovskite systems, see: de Jongh (1986 ▶); Park & Lee (2005 ▶, 2006 ▶); Depmeier (2009 ▶); Mitzi (1999 ▶). For classification of hydrogen bonds depending on bond lengths, see: Steiner (1998 ▶, 2002 ▶).

Experimental

Crystal data

(C₈H₁₂N)₂[CoCl₄]
M _r = 445.10
Monoclinic,
a = 7.4623 (13) Å
b = 24.664 (3) Å
c = 11.1997 (16) Å
β = 91.769 (13)°
V = 2060.3 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.35 mm⁻¹
T = 296 K
0.50 × 0.40 × 0.35 mm

Data collection

Bruker P4 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.237, T _max = 0.265
4692 measured reflections
3595 independent reflections
1566 reflections with I > 2σ(I)
R _int = 0.041
3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.161
S = 1.03
3595 reflections
211 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: XSCANS (Bruker, 1996 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811011603/si2347sup1.cif

e-67-0m522-sup1.cif^{(17.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011603/si2347Isup2.hkl

e-67-0m522-Isup2.hkl^{(172.7KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Co1—Cl4	2.229 (2)
Co1—Cl2	2.251 (2)
Co1—Cl1	2.272 (2)
Co1—Cl3	2.276 (2)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2C⋯Cl1ⁱ	0.89	2.62	3.445 (6)	156
N2—H2A⋯Cl4ⁱⁱ	0.89	2.51	3.321 (6)	152
N1—H1C⋯Cl3ⁱⁱⁱ	0.89	2.42	3.291 (8)	167
N1—H1B⋯Cl1	0.89	2.55	3.382 (7)	156

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

IHO thanks Professor G. Heger for discussion of the results and for suggestions.

supplementary crystallographic information

Comment

The title compound, (C₆H₅CH₂CH₂NH₃)₂CoCl₄, belongs to the layered inorganic-organic hybrid systems of general formula A₂MX₄ (where A = organic cation, M = divalent metal, X = halides). These systems are of special interest because of typical low-dimensional magnetic systems (de Jongh, 1986; Mitzi, 1999). To investigate the role of interlayer spacing on the magnetic properties, a variety of hybrid systems using long-chain alkylamine have been developed. However, their crystallographic studies are limited because their insolubility make it difficult to obtain a good single-crystal. As a part of our research interest in the low-dimensional magnetism (Park & Lee 2005, 2006), we synthesized a series of the layered inorganic-organic perovskite materials using phenethylamine and present the crystal structure of (C₆H₅CH₂CH₂NH₃)₂CoCl₄. Among the phenethylammonium-based compounds, several examples with tetrahedral anions are known to literature, for example, (C₆H₅C₂H₄NH₃)₂ZnBr₄ (Huh et al., 2006), (C₆H₅(CH₂)₂NH₃)₂Cd_0.75Hg_0.25Br₄ (Zouari & Ben Salah, 2004), (C₈H₁₂N)TlBr₄ (Abdi et al., 2005). Except for (C₈H₁₂N)TlBr₄, in which the heavy atom has trivalent, the other bivalent compounds have tetrahedral MBr₄ anions with non-magnetic ions in common. The present paper is the first report of the tetrahedral MCl₄ with magnetic ion using phenethylamine.

Fig. 1 shows the molecular structure of (C₆H₅CH₂CH₂NH₃)₂CoCl₄. The asymmetric unit of the title compound consists of two phenethylammonium cations and one isolated CoCl₄ anion; the latter is arranged as an distorted tetrahedron, whose bond lengths ranging from 2.229 (2) to 2.276 (2) Å (Table 1). Interestingly, the crystal structure exhibits a layered inorganic-organic structure although the dimension of inorganic backbone is 0-dimensional or isolated CoCl₄ tetrahedra, as shown in Fig. 2. The CoCl₄ tetrahedral groups are isolated and are connected to the organic cations by N—H···Cl hydrogen bonds via the NH₃-groups. Tab. 2 and Fig. 2 display also the N—H···Cl hydrogen bonds of (C₆H₅CH₂CH₂NH₃)₂CoCl₄. Between the CoCl₄ layers, —CNH₃⁺ ions are located in the space between CoCl₄ tetrahedra, which is formed by Cl atoms. N—H···Cl hydrogen bonds connect the two groups. The CoCl₄ tetrahedra connect the C₆H₅CH₂CH₂NH₃⁺ ions through hydrogen bonds to build a two-dimensional hydrogen-bonded NH₃—CoCl₄ network. Due to the hydrogen bonds, the Co—Cl bond lengths increase, resulting in slightly deformed CoCl₄ tetrahedra. The obtained bond lengths suggest that the strength of the N—H···Cl hydrogen bonds in the structure can be classified as weak (Steiner, 1998; Steiner, 2002).

Experimental

CoCl₂^.6H₂O (99%, Aldrich), phenethylamine (C₆H₅CH₂CH₂NH₂, 99.5%, Aldrich), HCl (37 wt % in water, Aldrich), and methanol (anhydrous, 99.8%, Aldrich) are used as received. For the preparation of single-crystal (C₆H₅CH₂CH₂NH₃)₂CoCl₄, 10 ml of a 0.25M CoCl₂^.6H₂O methanol solution were mixed with 10 ml of a 0.5M phenethylamine methanol solution. 1 mL of an HCl solution was added to the mixed solution. Blue crystals of (C₆H₅CH₂CH₂NH₃)₂CoCl₄ were obtained after 7 days at room temperature. Elemental analysis of C, H, and N was carried out by CHNS analysis (CE Instrument EA 1112 series). The expected formula of C₁₆H₂₄N₂Cl₄Co was confirmed. The relative weights calculated for C₁₆H₂₄N₂Cl₄Co were: C, 43.17%, H, 5.43%, N, 6.29%; found: C, 43.14%, H, 5.44%, N, 6.23%.