Hexaaqua­copper(II) dichloride bis­(hexa­methyl­enetetra­mine) tetra­hydrate

Zhan Lin Li; Xin Jian Yao; Wen Wu; Ya Wen Xuan

doi:10.1107/S1600536808020916

. 2008 Jul 12;64(Pt 8):m1024. doi: 10.1107/S1600536808020916

Hexaaquacopper(II) dichloride bis(hexamethylenetetramine) tetrahydrate

Zhan Lin Li ^a, Xin Jian Yao ^a, Wen Wu ^a, Ya Wen Xuan ^a,^*

PMCID: PMC2961946 PMID: 21203016

Abstract

The title compound, [Cu(H₂O)₆]Cl₂·2C₆H₁₂N₄·4H₂O, was prepared under mild hydrothermal conditions. The asymmetric unit consists of one half of the [Cu(H₂O)₆]²⁺ cation, a hexamethylenetetramine molecule, two solvent water molecules and a chloride ion. The formula unit is generated by crystallographic inversion symmetry. The Cu atom lies on a crystallographic inversion centre. It is in a slightly distorted octahedral coordination environment. In the crystal structure, intermolecular O—H⋯O, O—H⋯N and O—H⋯Cl hydrogen bonds link the components into a three-dimensional network.

Related literature

For a related structure, see: Kinzhibalo et al. (2002 ▶).

Experimental

Crystal data

[Cu(H₂O)₆]Cl₂·2C₆H₁₂N₄·4H₂O
M _r = 594.99
Triclinic,
a = 9.321 (3) Å
b = 9.3923 (16) Å
c = 9.4261 (16) Å
α = 119.523 (2)°
β = 94.153 (3)°
γ = 101.065 (3)°
V = 691.1 (3) Å³
Z = 1
Mo Kα radiation
μ = 1.04 mm⁻¹
T = 291 (2) K
0.36 × 0.29 × 0.15 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.709, T _max = 0.860
5328 measured reflections
2551 independent reflections
2083 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.108
S = 1.05
2551 reflections
151 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808020916/lh2645sup1.cif

e-64-m1024-sup1.cif^{(18.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808020916/lh2645Isup2.hkl

e-64-m1024-Isup2.hkl^{(125.3KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Cu1—O2	2.017 (2)
Cu1—O1	2.045 (2)
Cu1—O3	2.053 (2)

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O2—Cu1—O2ⁱ	180
O2—Cu1—O1	87.24 (9)
O2—Cu1—O1ⁱ	92.76 (9)
O1—Cu1—O1ⁱ	180
O2—Cu1—O3ⁱ	90.30 (10)
O1—Cu1—O3ⁱ	86.64 (9)
O2—Cu1—O3	89.70 (10)
O1—Cu1—O3	93.36 (9)
O3ⁱ—Cu1—O3	180

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Symmetry code: (i) Inline graphic .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1W⋯N3	0.82	2.04	2.814 (3)	158
O1—H2W⋯O5ⁱⁱ	0.83	1.94	2.734 (3)	162
O2—H3W⋯N2ⁱⁱⁱ	0.83	1.99	2.800 (3)	167
O2—H4W⋯O4ⁱⁱⁱ	0.83	1.89	2.700 (3)	165
O3—H5W⋯Cl1	0.82	2.54	3.190 (2)	137
O3—H6W⋯N1^iv	0.82	2.00	2.805 (3)	165
O4—H7W⋯Cl1	0.83	2.35	3.170 (3)	168
O4—H8W⋯N4^v	0.84	2.00	2.829 (4)	174
O5—H9W⋯Cl1	0.83	2.43	3.245 (3)	169
O5—H10W⋯Cl1^vi	0.83	2.37	3.200 (3)	175

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Symmetry codes: (ii) Inline graphic ; (iii) ; (iv) ; (v) ; (vi) .

Acknowledgments

We thank the Natural Science Foundation of Henan Province and the Key Discipline Foundation of Zhoukou Normal University for financial support of this research.

supplementary crystallographic information

Comment

The asymmetric unit and some symmetry related atoms are shown in Fig.1. The asymmetric unit consists of one half of hexaaqua Cu^II cation, one chloride anion, one uncoordinated neutral hexamethylenetetramine molecule and two molecules of water of crystallization. In the crystal structure, hydrogen bonding between [Cu(H₂O)₆]²⁺ cations and hexamethylenetetramine molecules, and those between [Cu(H₂O)₆]²⁺ cations and chloride ions are shown in Fig. 2 and Fig.3, respectively. A 16-membered ring formed by cations and hexamethylenetetramine moieties via the H-bonding interactions propagates along the c-axis. The chloride ion H-bonded with the uncoordinated water molecules gives rise to a number of anionic ring systems (Fig. 3). One of the hydrogen atoms of the uncoordinated water molecule connects the chloride ion and forms a 16-membered ring. The combonation of these anionic and cationic frameworks results in the formation of a three-dimensional network.

Experimental

All reagents were of AR grade and used without further purification. C₆H₁₂N₄ (1.401 g, 10 mmol) was dissolved in 50 ml EtOH/H₂O (V:V = 1:1) solution, then the resultant solution was added in 10 ml double-distilled water containing CuCl₂.2H₂O (0.171 g, 1 mmol), The resulting solution was heated at 373 K for 96 h. After cooling to room temperature, blue crystals were obtained in a yield up to 48.6%.