Crystal structure of [2-({4-[2,6-bis(pyri­din-2-yl)pyri­din-4-yl]phenyl}(methyl)amino)­ethanol-κ3 N,N′,N′′]bis­(thio­cyan­ato-κN)zinc N,N-di­methyl­formamide monosolvate

Shi-Chao Wang; Rou-Chen Pan; Wan-Ying Song; Sheng-Li Li

doi:10.1107/S1600536814019527

. 2014 Sep 6;70(Pt 10):m347–m348. doi: 10.1107/S1600536814019527

Crystal structure of [2-({4-[2,6-bis(pyridin-2-yl)pyridin-4-yl]phenyl}(methyl)amino)ethanol-κ³ N,N′,N′′]bis(thiocyanato-κN)zinc N,N-dimethylformamide monosolvate

Shi-Chao Wang ^a, Rou-Chen Pan ^a, Wan-Ying Song ^a, Sheng-Li Li ^a,^*

PMCID: PMC4257219 PMID: 25484674

Abstract

In the title compound, [Zn(NCS)₂(C₂₄H₂₂N₄O)]·C₃H₇NO, the Zn^II cation is N,N′,N′′-chelated by one 2-({4-[2,6-bis(pyridin-2-yl)pyridin-4-yl]phenyl}(methyl)amino)ethanol ligand and coordinated by two thiocyanate anions in a distorted N₅ trigonal–bipyramidal geometry. In the molecule, the three pyridine rings are approximately coplanar [maximum deviation = 0.026 (5) Å], and the mean plane of the three pyridine rings is twisted to the benzene ring with a small dihedral angle of 5.9 (2)°. In the crystal, complex molecules are linked by weak C—H⋯O hydrogen bonds into supramolecular chains propagated along [110]; π–π stacking is observed between adjacent chains [centroid–centroid distance = 3.678 (4) Å]. The dimethylformamide solvent molecules are linked with the complex chains via weak C—H⋯O hydrogen bonds.

Keywords: crystal structure, zinc complex, thiocyanate ligand, hydrogen bonding, π–π stacking

Related literature

For the crystal structures of related Zn^II thiocyanate complexes, see: Nie et al. (2014 ▶); Kharat et al. (2012 ▶); Eryazici et al. (2008 ▶). graphic file with name e-70-0m347-scheme1.jpg

Experimental

Crystal data

[Zn(NCS)₂(C₂₄H₂₂N₄O)]·C₃H₇NO
M _r = 637.08
Triclinic,
a = 9.565 (5) Å
b = 12.969 (5) Å
c = 13.652 (5) Å
α = 115.656 (5)°
β = 94.646 (5)°
γ = 91.621 (5)°
V = 1517.7 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.99 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.757, T _max = 0.827
10881 measured reflections
5293 independent reflections
3729 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.060
wR(F ²) = 0.174
S = 0.99
5293 reflections
373 parameters
H-atom parameters constrained
Δρ_max = 0.87 e Å⁻³
Δρ_min = −0.72 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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.

Supplementary Material

Crystal structure: contains datablock(s) I, Global. DOI: 10.1107/S1600536814019527/xu5817sup1.cif

e-70-0m347-sup1.cif^{(27.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814019527/xu5817Isup2.hkl

e-70-0m347-Isup2.hkl^{(290.2KB, hkl)}

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S1600536814019527/xu5817fig1.tif

The molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted.

Click here for additional data file.^{(965.6KB, tif)}

. DOI: 10.1107/S1600536814019527/xu5817fig2.tif

The one-dimensional chain structure of the title compound, Hydrogen atoms are omitted for clarity.

Click here for additional data file.^{(1.1MB, tif)}

. DOI: 10.1107/S1600536814019527/xu5817fig3.tif

The two-dimensional networks of the title compound, Hydrogen atoms are omitted for clarity.

CCDC reference: 1020385

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Zn1—N2	2.051 (4)
Zn1—N3	2.163 (4)
Zn1—N4	2.224 (4)
Zn1—N5	1.953 (5)
Zn1—N6	1.969 (4)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O2ⁱ	0.93	2.54	3.457 (8)	170
C14—H14⋯O2ⁱ	0.93	2.54	3.470 (7)	177
C16—H16⋯O2ⁱ	0.93	2.43	3.356 (9)	178
C24—H24⋯O1ⁱⁱ	0.93	2.58	3.488 (13)	164

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

Acknowledgments

This work was supported by Anhui Provincial Natural Science Foundation (grant No. 1308085MB24) and the Educational Commission of Anhui Province of China (grant No. KJ2012A025).

supplementary crystallographic information

S1. Comment

Zinc complexes with terpyridine derivatives are currently attracting attention for their interesting molecular topologies and crystal packing motifs, as well as the fact that they may be designed with specific applications in bioinorganic chemistry and material (Nie et al., 2014; Kharat et al., 2012). In turn, countless Zn terpyridine complexes have been surveyed and their crystals were demonstrated. However, the crystal of Zn(SCN)₂ terpyridine complexes are rarely mentioned (Eryazici et al., 2008). In this paper, we report the crystal structure of the terpyridine- Zinc complex. The molecular structure with the numbering scheme is shown in Fig. 1, the Zn^II is coordinated by three N atoms from terpyridine ligand and two thiocyanate anions in a highly distorted square-pyramidal trigonal bipyramidal geometry. Bond distances and angles around the Zn^II center are in the range 1.954 (5)–2.224 (4) Å and 74.93 (14)–124.48 (17)°, respectively. The dihedral angle between pyridine ring and phenyl ring is 6.24°, which can ascribe to the existence of the dimethylformamide molecule that restricts the rotation of single bonds and increase molecule planarity by C— H···O interactions. The one-dimensional chains are assembled by C24—H24···O1 (2.583 Å) hydrogen bond between adjacent complex molecules (Fig.2). In addition, two-dimensional networks formed by multiply C—H···S hydrogen bonds. The distances of C6—H6··· S2, C21—H21···S2 and C17—H17···S2 are nearly the same, which are 2.970 Å, 2.952 Å and 2.964 Å, respectively (Fig.3).

S2. Experimental

To a solution of Zn(SCN)₂ (0.18 g, 1 mmol) in freshly distilled ethanol (50 ml), was added N-methyl-N-(4-(2,6-di(pyridin-2-yl)pyridin-4-yl)phenyl)amino)ethanol (0.38 g, 1 mmol). The mixture was refluxed for 4 h. Then resulted orange suspension was filtered, washed with ethanol and dried in vacuo. Subsequent diffusion of diethyl ether into the concentrated dimethylformamide solution gave complex as air-stable orange crystals.