catena-Poly[[[bis­(thio­cyanato-κN)zinc]bis­[μ-1,3,5-tris­(1H-1,2,4-triazol-1-yl­meth­yl)benzene-κ2 N 4:N 4′]] mono­hydrate]

Qing-Xia Li; Xian-Ju Shi; Lai-Cheng Chen

doi:10.1107/S1600536812039256

. 2012 Sep 26;68(Pt 10):m1299. doi: 10.1107/S1600536812039256

catena-Poly[[[bis(thiocyanato-κN)zinc]bis[μ-1,3,5-tris(1H-1,2,4-triazol-1-ylmethyl)benzene-κ² N ⁴:N ^4′]] monohydrate]

Qing-Xia Li ^a, Xian-Ju Shi ^a,^*, Lai-Cheng Chen ^a

PMCID: PMC3470170 PMID: 23125614

Abstract

In the title complex, {[Zn(NCS)₂(C₁₅H₁₅N₉)₂]·H₂O}_n, the Zn^II ion is located on an inversion centre and is six-coordinated in a distorted octahedral geometry, coordinated by N atoms from four bridging 1,3,5-tris(1,2,4-triazol-1-ylmethyl)benzene (ttmb) ligands and two terminal SCN⁻ counter-anions. Two of the three triazol groups in each ttmb ligand link the Zn^II atoms, forming a looped-chain structure along [0-11]. The lattice water molecule shows half-occupancy due to disorder around an inversion centre.

Related literature

For background to the use of flexible tripodal compounds in the design and construction of compounds with metal-organic framework structures, see: Moon et al. (2006 ▶); Xu et al. (2009 ▶). For similar structures, see: Yin et al. (2009 ▶); Shi et al. (2011 ▶).

Experimental

Crystal data

[Zn(NCS)₂(C₁₅H₁₅N₉)₂]·H₂O
M _r = 842.27
Triclinic,
a = 8.5766 (17) Å
b = 9.5036 (19) Å
c = 11.723 (2) Å
α = 80.01 (3)°
β = 85.40 (3)°
γ = 89.55 (3)°
V = 938.0 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.83 mm⁻¹
T = 293 K
0.20 × 0.18 × 0.16 mm

Data collection

Rigaku Saturn724 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2006 ▶) T _min = 0.852, T _max = 0.879
11566 measured reflections
4444 independent reflections
3972 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.108
S = 1.05
4444 reflections
265 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2006 ▶); cell refinement: CrystalClear (Rigaku/MSC, 2006 ▶); data reduction: CrystalClear (Rigaku/MSC, 2006 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalStructure (Rigaku/MSC, 2006 ▶); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2006 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812039256/ds2211sup1.cif

e-68-m1299-sup1.cif^{(18.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812039256/ds2211Isup2.hkl

e-68-m1299-Isup2.hkl^{(217.7KB, hkl)}

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

Acknowledgments

This work was supported financially by the National Natural Science Foundation (No. 20971110) and the program for the construction of Puyang Key Laboratory.

supplementary crystallographic information

Comment

Flexible tripodal compounds are known to be the versatile structural constructors in the rational design and construction of novel metal-organic frameworks (MOFs), in respect that its three potential coordination groups can bend and rotate freely to satisfy various coordination preferences and facilitate the formation of various complexes with diverse structures and properties (Moon et al., 2006; Xu et al., 2009). Therefore, the prospect of exploring the influential principles of tripodal compounds on the resulting framework structures provides an impetus for further researches on tripodal compounds. We were thus engaged in the synthesis of a flexible tripodal N-heterocyclic compound 1,3,5-tris(1,2,4-triazol-1-ylmethyl)-benzene (ttmb) (Yin et al., 2009; Shi et al., 2011), and employed it as a ligand to construct a new complex {[Zn(SCN)₂(ttmb)₂].H₂O}_n. In the title complex, Zn^II ion is six-coordinated in a distorted octahedral geometry, coordinated by N2, N2A, N8 and N8A from four ttmb ligands, and N1, N1A from two terminal counter-anion SCN^- (Fig. 1). In ttmb, the center of one triazol ring lies inside the benzene plane with the dihedral angle of 89.4 °, and the other two triazol rings lie in the opposite orientation outside the plane to form an infrequent trans conformation. Two of the three triazol groups in each ttmb link the Zn^II centers together to form an one-dimensional looped-chain structure (Fig. 2), in which the Zn^II ions are collinear with the adjacent Zn···Zn distance of 13.8 Å.

Experimental

A reaction mixture of ZnSO₄.7H₂O (29 mg, 0.1 mmol), 1,3,5-tris(1,2,4-triazol-1-ylmethyl)-benzene (ttmb) (32.1 mg, 0.1 mmol), KSCN (19.4 mg, 0.2 mmol), and 10 ml water was sealed in a Teflon-lined stainless steel vessel, which was heated at 130 °C for 72 h, and then cooled to room temperature, obtaining colorless crystals of the title complex. Yield (based on Zn): 31%.