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ISSN: 2056-9890
Volume 70| Part 10| October 2014| Pages m355-m356

Crystal structure of bis­­[4-(4-chloro­benz­yl)pyridine-κN]bis­­(thio­cyanato-κN)zinc

aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth-Strasse 2, 24118 Kiel, Germany
*Correspondence e-mail: jwerner@ac.uni-kiel.de

Edited by M. Weil, Vienna University of Technology, Austria (Received 30 August 2014; accepted 11 September 2014; online 27 September 2014)

In the crystal structure of the title compound, [Zn(NCS)2(C12H10ClN)2], the Zn2+ cation is N-coordinated by two terminally bonded thio­cyante anions and by two 4-(4-chloro­benz­yl)pyridine ligands within a slightly distorted tetra­hedron. The asymmetric unit consists of half of the discrete complex, the central Zn2+ cation of which is located on a twofold rotation axis. The discrete complexes are linked into layers via a weak inter­molecular hydrogen-bonding inter­action, with a H⋯Cl distance of 2.85 Å and a C—H⋯Cl angle of 151°. These layers extend parallel to the ab plane and are held together by dispersion forces only.

1. Related literature

For related crystal structures with thio­cyanate ligands and Zn2+ in a tetra­hedral coordination sphere, see: Fettouhi et al. (2002[Fettouhi, M., El Ali, B., El-Ghanam, A., Golhen, S., Ouahab, L., Daro, N. & Sutter, J.-P. (2002). Inorg. Chem. 41, 3705-3712.]); Kong et al. (2010[Kong, L., Li, W.-J., Li, X.-L., Geng, W.-Q., Hao, F.-Y., Wu, J.-Y., Zhou, H.-P., Yang, J.-X., Tian, Y.-P. & Jin, B.-K. (2010). Polyhedron, 29, 1575-1582.]); Zhu et al. (2008[Zhu, L. Y., Xu, D., Wang, X. Q. & Yu, G. (2008). J. Chem. Crystallogr. 38, 609-612.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • [Zn(NCS)2(C12H10ClN)2]

  • Mr = 588.85

  • Monoclinic, C 2/c

  • a = 29.094 (3) Å

  • b = 4.9911 (3) Å

  • c = 18.312 (2) Å

  • β = 98.867 (8)°

  • V = 2627.3 (4) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 1.32 mm−1

  • T = 150 K

  • 0.12 × 0.08 × 0.07 mm

2.2. Data collection

  • Stoe IPDS-2 diffractometer

  • Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2008[Stoe (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.]) Tmin = 0.879, Tmax = 0.906

  • 8309 measured reflections

  • 2570 independent reflections

  • 1773 reflections with I > 2σ(I)

  • Rint = 0.077

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.063

  • wR(F2) = 0.148

  • S = 1.08

  • 2570 reflections

  • 159 parameters

  • H-atom parameters constrained

  • Δρmax = 0.68 e Å−3

  • Δρmin = −0.46 e Å−3

Data collection: X-AREA (Stoe, 2008[Stoe (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: XP in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and DIAMOND (Brandenburg, 2011[Brandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Synthesis and crystallization top

ZnSO4·H2O was purchased from Merck and 4-(4-chloro­benzyl)­pyridine and Ba(NCS)2·3H2O were purchased from Alfa Aesar. Zn(NCS)2 was synthesized by stirring 17.5 g (57.00 mmol) Ba(NCS)2·3H2O and 10.23 g (57.00 mmol) ZnSO4·H2O in 300 mL water at RT for three hours. The white residue of BaSO4 was filtered off, and the solution was evaporated by heating. The homogeneity of the product was investigated by X-ray powder diffraction and elemental analysis. The title compound was prepared by the reaction of (0.6 mmol) 108.9 mg Zn(NCS)2 and (0.15 mmol) 105.5 µL 4-(4-chloro­benzyl)­pyridine in 1.5 mL aceto­nitrile at RT. After few days, colorless needle-like crystals of the title compound were obtained.

Refinement top

Hydrogen atoms were positioned with idealized geometry and were refined with Uiso(H) = 1.2 Ueq(C) using a riding model with C—H = 0.95 Å for aromatic and C—H = 0.99 Å for methyl­ene H atoms.

Related literature top

For related crystal structures with thiocyanate ligands and Zn2+ in a tetrahedral coordination sphere, see: Fettouhi et al. (2002); Kong et al. (2010); Zhu et al. (2008).

Computing details top

Data collection: X-AREA (Stoe, 2008); cell refinement: X-AREA (Stoe, 2008); data reduction: X-AREA (Stoe, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound with atom labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry code: i) -x, y, -z+1/2.]
[Figure 2] Fig. 2. Crystal structure of the title compound in a projection along the b axis.
Bis[4-(4-chlorobenzyl)pyridine-κN]bis(thiocyanato-κN)zinc top
Crystal data top
[Zn(NCS)2(C12H10ClN)2]Z = 4
Mr = 588.85F(000) = 1200
Monoclinic, C2/cDx = 1.489 Mg m3
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 29.094 (3) Åθ = 1.4–26.0°
b = 4.9911 (3) ŵ = 1.32 mm1
c = 18.312 (2) ÅT = 150 K
β = 98.867 (8)°Needle, colourless
V = 2627.3 (4) Å30.12 × 0.08 × 0.07 mm
Data collection top
Stoe IPDS-2
diffractometer
2570 independent reflections
Radiation source: fine-focus sealed tube1773 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.077
ω scansθmax = 26.0°, θmin = 1.4°
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe, 2008)
h = 3535
Tmin = 0.879, Tmax = 0.906k = 66
8309 measured reflectionsl = 2221
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.063Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.148H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0577P)2 + 3.849P]
where P = (Fo2 + 2Fc2)/3
2570 reflections(Δ/σ)max < 0.001
159 parametersΔρmax = 0.68 e Å3
0 restraintsΔρmin = 0.46 e Å3
Crystal data top
[Zn(NCS)2(C12H10ClN)2]V = 2627.3 (4) Å3
Mr = 588.85Z = 4
Monoclinic, C2/cMo Kα radiation
a = 29.094 (3) ŵ = 1.32 mm1
b = 4.9911 (3) ÅT = 150 K
c = 18.312 (2) Å0.12 × 0.08 × 0.07 mm
β = 98.867 (8)°
Data collection top
Stoe IPDS-2
diffractometer
2570 independent reflections
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe, 2008)
1773 reflections with I > 2σ(I)
Tmin = 0.879, Tmax = 0.906Rint = 0.077
8309 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0630 restraints
wR(F2) = 0.148H-atom parameters constrained
S = 1.08Δρmax = 0.68 e Å3
2570 reflectionsΔρmin = 0.46 e Å3
159 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.00000.30960 (18)0.25000.0536 (3)
N10.03121 (14)0.4936 (9)0.3362 (3)0.0632 (11)
C10.04787 (16)0.6043 (11)0.3893 (3)0.0564 (12)
S10.07036 (5)0.7701 (3)0.46152 (9)0.0767 (5)
N110.04855 (12)0.0763 (8)0.2133 (2)0.0482 (9)
C110.04345 (16)0.0091 (10)0.1431 (3)0.0547 (12)
H110.01850.06120.10880.066*
C120.07260 (16)0.1938 (10)0.1181 (3)0.0552 (11)
H120.06710.25250.06820.066*
C130.11000 (16)0.2929 (10)0.1667 (3)0.0551 (12)
C140.11577 (16)0.2014 (12)0.2384 (3)0.0591 (13)
H140.14110.26400.27310.071*
C150.08515 (16)0.0205 (10)0.2597 (3)0.0561 (12)
H150.08990.03950.30960.067*
C160.14365 (18)0.4920 (11)0.1412 (3)0.0654 (14)
H16A0.15050.63540.17860.078*
H16B0.12890.57590.09440.078*
C170.18905 (16)0.3592 (11)0.1292 (3)0.0600 (14)
C180.18905 (17)0.1565 (13)0.0792 (3)0.0688 (15)
H180.16030.09520.05290.083*
C190.22994 (19)0.0380 (15)0.0660 (4)0.0815 (18)
H190.22920.10210.03070.098*
C200.27132 (18)0.1235 (16)0.1039 (4)0.0776 (18)
C210.2727 (2)0.3210 (18)0.1536 (4)0.093 (2)
H210.30170.37830.18000.112*
C220.2313 (2)0.4443 (15)0.1669 (4)0.0854 (19)
H220.23240.58590.20180.103*
Cl10.32321 (5)0.0187 (5)0.08551 (11)0.1091 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0483 (4)0.0500 (5)0.0615 (5)0.0000.0050 (3)0.000
N10.058 (2)0.057 (3)0.074 (3)0.006 (2)0.008 (2)0.004 (2)
C10.051 (2)0.055 (3)0.061 (3)0.003 (2)0.003 (2)0.007 (3)
S10.0709 (8)0.0855 (12)0.0657 (9)0.0042 (7)0.0148 (7)0.0094 (8)
N110.0429 (18)0.050 (2)0.050 (2)0.0061 (17)0.0016 (16)0.0037 (19)
C110.048 (2)0.053 (3)0.059 (3)0.001 (2)0.004 (2)0.002 (2)
C120.053 (2)0.051 (3)0.058 (3)0.001 (2)0.004 (2)0.004 (3)
C130.051 (2)0.041 (3)0.071 (3)0.005 (2)0.001 (2)0.006 (3)
C140.052 (2)0.063 (3)0.059 (3)0.002 (2)0.004 (2)0.007 (3)
C150.055 (3)0.058 (3)0.053 (3)0.001 (2)0.004 (2)0.005 (2)
C160.064 (3)0.048 (3)0.081 (4)0.007 (2)0.003 (3)0.002 (3)
C170.050 (3)0.061 (4)0.066 (3)0.011 (2)0.003 (2)0.014 (3)
C180.049 (3)0.076 (4)0.078 (4)0.008 (3)0.001 (2)0.001 (3)
C190.061 (3)0.103 (5)0.080 (4)0.009 (3)0.008 (3)0.000 (4)
C200.050 (3)0.110 (5)0.069 (4)0.004 (3)0.001 (3)0.027 (4)
C210.051 (3)0.132 (6)0.089 (5)0.024 (4)0.012 (3)0.034 (5)
C220.066 (3)0.091 (5)0.093 (5)0.017 (3)0.006 (3)0.003 (4)
Cl10.0565 (8)0.168 (2)0.1023 (13)0.0255 (10)0.0118 (8)0.0551 (14)
Geometric parameters (Å, º) top
Zn1—N1i1.928 (5)C15—H150.9500
Zn1—N11.928 (5)C16—C171.524 (7)
Zn1—N112.024 (4)C16—H16A0.9900
Zn1—N11i2.024 (4)C16—H16B0.9900
N1—C11.157 (6)C17—C181.363 (8)
C1—S11.611 (6)C17—C221.380 (7)
N11—C111.342 (6)C18—C191.383 (8)
N11—C151.346 (6)C18—H180.9500
C11—C121.377 (7)C19—C201.363 (8)
C11—H110.9500C19—H190.9500
C12—C131.386 (7)C20—C211.338 (10)
C12—H120.9500C20—Cl11.747 (6)
C13—C141.375 (7)C21—C221.408 (10)
C13—C161.518 (7)C21—H210.9500
C14—C151.367 (7)C22—H220.9500
C14—H140.9500
N1i—Zn1—N1123.1 (3)C14—C15—H15118.6
N1i—Zn1—N11105.49 (17)C13—C16—C17112.0 (4)
N1—Zn1—N11106.33 (16)C13—C16—H16A109.2
N1i—Zn1—N11i106.32 (16)C17—C16—H16A109.2
N1—Zn1—N11i105.49 (17)C13—C16—H16B109.2
N11—Zn1—N11i109.7 (2)C17—C16—H16B109.2
C1—N1—Zn1176.6 (4)H16A—C16—H16B107.9
N1—C1—S1177.6 (5)C18—C17—C22118.2 (5)
C11—N11—C15116.9 (4)C18—C17—C16120.6 (4)
C11—N11—Zn1121.4 (3)C22—C17—C16121.2 (6)
C15—N11—Zn1121.4 (3)C17—C18—C19121.6 (5)
N11—C11—C12123.2 (4)C17—C18—H18119.2
N11—C11—H11118.4C19—C18—H18119.2
C12—C11—H11118.4C20—C19—C18119.5 (7)
C11—C12—C13119.3 (5)C20—C19—H19120.2
C11—C12—H12120.4C18—C19—H19120.2
C13—C12—H12120.4C21—C20—C19120.6 (6)
C14—C13—C12117.5 (5)C21—C20—Cl1119.6 (5)
C14—C13—C16121.5 (5)C19—C20—Cl1119.7 (6)
C12—C13—C16121.0 (5)C20—C21—C22120.2 (6)
C15—C14—C13120.3 (5)C20—C21—H21119.9
C15—C14—H14119.9C22—C21—H21119.9
C13—C14—H14119.9C17—C22—C21119.9 (7)
N11—C15—C14122.9 (5)C17—C22—H22120.1
N11—C15—H15118.6C21—C22—H22120.1
Symmetry code: (i) x, y, z+1/2.

Experimental details

Crystal data
Chemical formula[Zn(NCS)2(C12H10ClN)2]
Mr588.85
Crystal system, space groupMonoclinic, C2/c
Temperature (K)150
a, b, c (Å)29.094 (3), 4.9911 (3), 18.312 (2)
β (°) 98.867 (8)
V3)2627.3 (4)
Z4
Radiation typeMo Kα
µ (mm1)1.32
Crystal size (mm)0.12 × 0.08 × 0.07
Data collection
DiffractometerStoe IPDS2
diffractometer
Absorption correctionNumerical
(X-SHAPE and X-RED32; Stoe, 2008)
Tmin, Tmax0.879, 0.906
No. of measured, independent and
observed [I > 2σ(I)] reflections
8309, 2570, 1773
Rint0.077
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.063, 0.148, 1.08
No. of reflections2570
No. of parameters159
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.68, 0.46

Computer programs: X-AREA (Stoe, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011), publCIF (Westrip, 2010).

 

Acknowledgements

We gratefully acknowledge financial support by the DFG (project No. NA 720/5–1) and the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

References

First citationBrandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
First citationFettouhi, M., El Ali, B., El-Ghanam, A., Golhen, S., Ouahab, L., Daro, N. & Sutter, J.-P. (2002). Inorg. Chem. 41, 3705–3712.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationKong, L., Li, W.-J., Li, X.-L., Geng, W.-Q., Hao, F.-Y., Wu, J.-Y., Zhou, H.-P., Yang, J.-X., Tian, Y.-P. & Jin, B.-K. (2010). Polyhedron, 29, 1575–1582.  Web of Science CSD CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationStoe (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.  Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationZhu, L. Y., Xu, D., Wang, X. Q. & Yu, G. (2008). J. Chem. Crystallogr. 38, 609–612.  Web of Science CSD CrossRef CAS Google Scholar

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 10| October 2014| Pages m355-m356
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