Aqua­(1,10-phenanthroline-κ2 N,N′)(dl-threoninato-κ2 N,O 1)copper(II) chloride dihydrate

Yi-Han Tan; Siang-Guan Teoh; Kei-Lin Sek; Wan-Sin Loh; Hoong-Kun Fun

doi:10.1107/S1600536810015278

. 2010 Apr 30;66(Pt 5):m595–m596. doi: 10.1107/S1600536810015278

Aqua(1,10-phenanthroline-κ² N,N′)(dl-threoninato-κ² N,O ¹)copper(II) chloride dihydrate

Yi-Han Tan ^a, Siang-Guan Teoh ^a, Kei-Lin Sek ^a, Wan-Sin Loh ^b,^‡, Hoong-Kun Fun ^b,^*,^§

PMCID: PMC2979221 PMID: 21579068

Abstract

The asymmetric unit of the title compound, [Cu(C₄H₈NO₃)(C₁₂H₈N₂)(H₂O)]Cl·2H₂O, contains a complex cation, a chloride anion and two water molecules. The Cu^II ion has a distorted square-pyramidal coordination geometry formed by one bidentate phenanthroline ligand, one O,N-bidentate dl-threoninate ligand and one apical water molecule. In the crystal structure, intermolecular O—H⋯O, N—H⋯O, N—H⋯Cl and O—H⋯Cl hydrogen bonds link the components into layers. A single weak intermolecular C—H⋯O interaction connects these layers into a three-dimensional network.

Related literature

For background to the interactions of transition-metal complexes with DNA, see: Vaidyanathan & Nair (2003 ▶); Rao et al. (2007 ▶, 2008 ▶); Kumar & Arunachalam (2007 ▶); Patel et al. (2006 ▶); Wang et al. (2007 ▶); Zhang et al. (2004 ▶). For a related structure, see: Lu et al. (2004 ▶). For standard bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[Cu(C₄H₈NO₃)(C₁₂H₈N₂)(H₂O)]Cl·2H₂O
M _r = 451.36
Triclinic,
a = 7.1972 (1) Å
b = 11.9785 (2) Å
c = 12.2915 (2) Å
α = 65.664 (1)°
β = 78.079 (1)°
γ = 81.345 (1)°
V = 942.15 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.34 mm⁻¹
T = 296 K
0.34 × 0.20 × 0.07 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.656, T _max = 0.911
29845 measured reflections
8056 independent reflections
5995 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.092
S = 1.04
8056 reflections
245 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810015278/lh5025sup1.cif

e-66-0m595-sup1.cif^{(23KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810015278/lh5025Isup2.hkl

e-66-0m595-Isup2.hkl^{(394.1KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯Cl1	0.80	2.36	3.1411 (13)	166
O1W—H2W1⋯O2ⁱ	0.82	1.90	2.7114 (18)	167
O3—H1O3⋯O1ⁱⁱ	0.90	2.03	2.9089 (18)	164
N3—H1N3⋯Cl1ⁱⁱⁱ	0.86	2.62	3.3992 (13)	151
N3—H2N3⋯O2Wⁱ	0.94	2.07	3.0085 (19)	175
O2W—H1W2⋯Cl1ⁱ	0.87	2.35	3.2104 (16)	175
O2W—H2W2⋯Cl1^iv	0.84	2.33	3.1463 (14)	162
O3W—H1W3⋯O2W	1.01	1.95	2.954 (2)	170
O3W—H2W3⋯O3ⁱⁱ	0.91	2.03	2.901 (2)	159
C7—H7A⋯O2^v	0.93	2.41	3.292 (2)	157

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

Acknowledgments

The authors thank Universiti Sains Malaysia (USM) for the RU research grant (PKIMIA/815002). HKF and WSL also thank USM for the Research University Golden Goose Grant (1001/PFIZIK/811012). YHT and WSL are grateful for the award of USM fellowships for financial assistance.

supplementary crystallographic information

Comment

The interaction of transition metal complexes with DNA is a vibrant area of research and has long been investigated in relation to the development of new reagents for molecular biology, biotechnology and medicine (Vaidyanathan et al., 2003; Rao et al., 2008; Kumar et al., 2007). Among all the transition metals, copper is the most widely used metals in these studies as it is a bioessential element with +1 and +2 oxidation states (Patel et al., 2006; Wang et al., 2007; Vaidyanathan et al., 2003). Copper(II) complexes have been found to be useful in the treatment of many diseases as well as cancer. Copper(II) complexes of 1,10-phenanthroline and its derivatives exhibit various biological activities such as antimicrobial, antimycobaterial, anticandida and antitumor activities. Copper complexes of amino acids have been reported to exhibit effective antitumor and artificial nuclease activity. Several reports have also shown that these complexes show efficient DNA cleavage activity by either oxidative or hydrolytic pathways (Kumar et al., 2007; Zhang et al., 2004; Rao et al., 2007). In the title compound, aqua(DL-threoninato-κ²N,O)(1,10-phenanthroline)copper(II) chloride dihydrate, DL-threonine has been selected as the ligand for the complex.

The asymmetric unit of the title compound (Fig. 1) consists of one Cu^II complex cation, one chlorine anion and two water molecules. The Cu^II ion is coordinated by N1 and N2 atoms from the phenanthroline ligand and N3 and O1 atoms from the threoninato ligand in the basal plane and the O1W water molecule is coordinated in the apical site to form a distorted square-pyramidal geometry. The bond lengths are within normal values (Allen et al., 1987) and are comparable to those observed for a closely related structure (Lu et al., 2004).

In the crystal structure (Fig. 2), intermolecular C7—H7A···O2 hydrogen bonds (Table 1) link the Cu^II complex cations into chains along the c axis. Intermolecular O1W—H2W1···O2, O3—H1O3···O1, N3—H2N3···O2W, O3W—H2W3···O3, O3W—H1W3···O2W, N3—H1N3···Cl1, O2W—H1W2···Cl1, O2W—H2W2···Cl1 and O1W—H1W1—Cl1 interactions (Table 1) link the molecules into a three-dimensional network.

Experimental

To an ethanolic solution (10.0 ml) of copper(II) chloride dihydrate (0.1708 g, 1 mmol), an ethanolic solution (10.0 ml) of DL-threonine (0.1191 g, 1 mmol) was added. After a few minutes, an ethanolic solution (20.0 ml) of 1,10-phenanthroline (0.1982 g, 1 mmol) was added dropwise to the mixture solution. The pH of the resulting solution was then adjusted to pH 8 by adding a few drops of NaOH aqueous solution. The blue solution was filtered and left to evaporate slowly at room temperature. Blue blocky single crystals of the title compound suitable for X-ray diffraction were obtained after a few days.