Bis[4-(4-methoxy­phen­yl)-4H-1,2,4-triazole-κN 1]bis­(thio­cyanato-κN)zinc(II)

Ya Zuo

doi:10.1107/S1600536808008325

. 2008 Apr 2;64(Pt 5):m609. doi: 10.1107/S1600536808008325

Bis[4-(4-methoxyphenyl)-4H-1,2,4-triazole-κN ¹]bis(thiocyanato-κN)zinc(II)

Ya Zuo ^a,^*

PMCID: PMC2961330 PMID: 21202168

Abstract

In the title complex, [Zn(NCS)₂(C₉H₉N₃O)₂], the Zn^II ion is coordinated by two N atoms from the NCS⁻ anions and two N atoms from two 4-(4-methoxyphenyl)-4H-1,2,4-triazole ligands in a slightly distorted tetrahedral geometry. Three intermolecular weak hydrogen-bonding contacts of the types C—H⋯N, C—H⋯S and C—H⋯O are observed in the crystal structure.

Related literature

For related literature, see: Han et al. (2006 ▶); Ling & Zhang (2007 ▶); Thomann et al. (1994 ▶); Yin et al. (2007 ▶); Zhao et al. (2002 ▶); Zhou et al. (2007 ▶).

Experimental

Crystal data

[Zn(NCS)₂(C₉H₉N₃O)₂]
M _r = 531.91
Monoclinic,
a = 7.812 (3) Å
b = 17.111 (6) Å
c = 18.201 (6) Å
β = 99.726 (6)°
V = 2398.0 (15) Å³
Z = 4
Mo Kα radiation
μ = 1.23 mm⁻¹
T = 293 (2) K
0.16 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.700, T _max = 0.884
13731 measured reflections
4932 independent reflections
2127 reflections with I > 2σ(I)
R _int = 0.121

Refinement

R[F ² > 2σ(F ²)] = 0.067
wR(F ²) = 0.158
S = 0.97
4932 reflections
300 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1999 ▶); 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/S1600536808008325/si2077sup1.cif

e-64-0m609-sup1.cif^{(21.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808008325/si2077Isup2.hkl

e-64-0m609-Isup2.hkl^{(241.6KB, hkl)}

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

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

Zn1—N8	1.923 (6)
Zn1—N7	1.970 (6)
Zn1—N1	2.005 (5)
Zn1—N4	2.009 (5)

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N8—Zn1—N7	112.9 (2)
N8—Zn1—N1	112.1 (2)
N7—Zn1—N1	108.5 (2)
N8—Zn1—N4	116.4 (2)
N7—Zn1—N4	103.8 (2)
N1—Zn1—N4	102.2 (2)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N5ⁱ	0.93	2.51	3.438 (8)	177
C7—H7⋯S1ⁱⁱ	0.93	2.86	3.735 (6)	158
C10—H10⋯O1ⁱⁱⁱ	0.93	2.42	3.265 (8)	151

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

supplementary crystallographic information

Comment

The organic ligands, 1,2,4-triazole and its derivatives continue to attract considerable attention due to the luminescent, magnetic, and electronic properties of their complexes and the potential application in material science (Yin et al., 2007; Zhou, et al., 2007; Han et al., 2006). On the other hand, 1,2,4-triazole and its derivatives combine the coordination geometry of both pyrazole and imidazole with regard to the arrangement and coordination of their three heteroatoms. Compared with the chelating to the metal centers with the nitrogen atom in the 1,2-positions (Thomann et al., 1994), it is familiar that the nitrogen atom serve as the solo coordinated atom (Ling & Zhang, 2007). In order to explore furthur the coordination chemistry of the 4-(4-methoxyphenyl)-4H-1,2,4-triazole system (hereafter abbreviated as L), the title complex was synthesized.

The coordination geometry of the Zn^II ion is a slightly distorted tetrahedron, in which each Zn^II ion is coordinated to two nitrogen atoms from the NCS^- anions and two nitrogen atoms from two ligands L. (Fig. 1). The separations of Zn—N range from 1.923 (6) to 2.009 (5)Å (Table 1), which is close to the corresponding distances in the 4-coordinated Zn compound (2.050 (4)Å and 2.023 (4) Å) reported previously (Han et al., 2006), while the average distance of Zn—N is 2.162 (2)Å in the 6-coordinated (Ling & Zhang, 2007) and 2.065 (2)Å in the 5-coordinated (Yin et al., 2007) compounds, respectively. The bond angles around Zn^II ions vary between 102.2 (2)° and 116.4 (2)°. The central Zn^II ion, is coordinated with the L ligands in the 1-position, which is the common coordination mode (Ling & Zhang, 2007) of 1,2,4-Triazole and its derivatives, differently from that in the 1,2-position (Thomann et al., 1994). As the important structural parameters, the dihedral angles between the triazole and phenyl rings of the two L ligands are distinct, that of C1—N3—C3—C8 is equal to 39.2 (9)°, while the value of C10—N6—C12—C17 is 93.8 (8)°. With regard to the two trans thiocyanato NCS^- anions, the group is almost linear with an N7—C19—S1 angle of 178.8 (8)° and N8—C20—S2 angle of 178.1 (7)°. The connection between Zn atoms and NCS groups are bent with a C20—N8—Zn1 angle of 168.1 (6)°, and a C19—N7—Zn1 angle of 160.9 (6)° (Zhao et al., 2002). Three intermoleular hydrogen bonding contacts of the type C—H···N, C—H···S and C—H···O are observed in the title structure (Table 2).

Experimental

The compound was synthesized under hydrothermal conditions. A mixture of L (L=4-(1,2,4-triazol)-1-methoxy-benzene) (0.3 mmol, 0.045 g), ZnSO₄˙7H₂O (0.1 mmol, 0.029 g), KSCN (0.2 mmol, 0.019 g) and water (10 mL) was placed in a 25 mL acid digestion bomb and heated at 160° for two days, then equably cooled to room temperature for three days. After washed by 5 ml water for twice, colorless block crystals of the title compound were obtained.