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

Werner, J.; Neumann, T.; Jess, I.; Näther, C.

doi:10.1107/S160053681402039X

metal-organic compounds

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Volume 70| Part 10| October 2014| Pages m355-m356

doi:10.1107/S160053681402039X

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

Julia Werner,^a ^* Tristan Neumann,^a Inke Jess ^a and Christian Näther ^a

^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.

Keywords: crystal structure; zinc complex; thiocyanate; tetrahedral coordination; hydrogen bonding.

CCDC reference: 1021253

1. Related literature

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 ).

2. Experimental

2.1. Crystal data

[Zn(NCS)₂(C₁₂H₁₀ClN)₂]
M_r = 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 ) T_min = 0.879, T_max = 0.906
8309 measured reflections
2570 independent reflections
1773 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.68 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Data collection: X-AREA (Stoe, 2008); cell refinement: X-AREA; data reduction: X-AREA; 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 ).

Supporting information

CCDC reference: 1021253

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681402039X/wm5054sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681402039X/wm5054Isup2.hkl

checkCIF report

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 U_iso(H) = 1.2 U_eq(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

	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.]
	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
M_r = 588.85	F(000) = 1200
Monoclinic, C2/c	D_x = 1.489 Mg m⁻³
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 29.094 (3) Å	θ = 1.4–26.0°
b = 4.9911 (3) Å	µ = 1.32 mm⁻¹
c = 18.312 (2) Å	T = 150 K
β = 98.867 (8)°	Needle, colourless
V = 2627.3 (4) Å³	0.12 × 0.08 × 0.07 mm

Data collection top

Stoe IPDS-2 diffractometer	2570 independent reflections
Radiation source: fine-focus sealed tube	1773 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.077
ω scans	θ_max = 26.0°, θ_min = 1.4°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2008)	h = −35→35
T_min = 0.879, T_max = 0.906	k = −6→6
8309 measured reflections	l = −22→21

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.148	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0577P)² + 3.849P] where P = (F_o² + 2F_c²)/3
2570 reflections	(Δ/σ)_max < 0.001
159 parameters	Δρ_max = 0.68 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

[Zn(NCS)₂(C₁₂H₁₀ClN)₂]	V = 2627.3 (4) Å³
M_r = 588.85	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 29.094 (3) Å	µ = 1.32 mm⁻¹
b = 4.9911 (3) Å	T = 150 K
c = 18.312 (2) Å	0.12 × 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)
T_min = 0.879, T_max = 0.906	R_int = 0.077
8309 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.148	H-atom parameters constrained
S = 1.08	Δρ_max = 0.68 e Å⁻³
2570 reflections	Δρ_min = −0.46 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Zn1	0.0000	−0.30960 (18)	0.2500	0.0536 (3)
N1	0.03121 (14)	−0.4936 (9)	0.3362 (3)	0.0632 (11)
C1	0.04787 (16)	−0.6043 (11)	0.3893 (3)	0.0564 (12)
S1	0.07036 (5)	−0.7701 (3)	0.46152 (9)	0.0767 (5)
N11	0.04855 (12)	−0.0763 (8)	0.2133 (2)	0.0482 (9)
C11	0.04345 (16)	0.0091 (10)	0.1431 (3)	0.0547 (12)
H11	0.0185	−0.0612	0.1088	0.066*
C12	0.07260 (16)	0.1938 (10)	0.1181 (3)	0.0552 (11)
H12	0.0671	0.2525	0.0682	0.066*
C13	0.11000 (16)	0.2929 (10)	0.1667 (3)	0.0551 (12)
C14	0.11577 (16)	0.2014 (12)	0.2384 (3)	0.0591 (13)
H14	0.1411	0.2640	0.2731	0.071*
C15	0.08515 (16)	0.0205 (10)	0.2597 (3)	0.0561 (12)
H15	0.0899	−0.0395	0.3096	0.067*
C16	0.14365 (18)	0.4920 (11)	0.1412 (3)	0.0654 (14)
H16A	0.1505	0.6354	0.1786	0.078*
H16B	0.1289	0.5759	0.0944	0.078*
C17	0.18905 (16)	0.3592 (11)	0.1292 (3)	0.0600 (14)
C18	0.18905 (17)	0.1565 (13)	0.0792 (3)	0.0688 (15)
H18	0.1603	0.0952	0.0529	0.083*
C19	0.22994 (19)	0.0380 (15)	0.0660 (4)	0.0815 (18)
H19	0.2292	−0.1021	0.0307	0.098*
C20	0.27132 (18)	0.1235 (16)	0.1039 (4)	0.0776 (18)
C21	0.2727 (2)	0.3210 (18)	0.1536 (4)	0.093 (2)
H21	0.3017	0.3783	0.1800	0.112*
C22	0.2313 (2)	0.4443 (15)	0.1669 (4)	0.0854 (19)
H22	0.2324	0.5859	0.2018	0.103*
Cl1	0.32321 (5)	−0.0187 (5)	0.08551 (11)	0.1091 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0483 (4)	0.0500 (5)	0.0615 (5)	0.000	0.0050 (3)	0.000
N1	0.058 (2)	0.057 (3)	0.074 (3)	0.006 (2)	0.008 (2)	0.004 (2)
C1	0.051 (2)	0.055 (3)	0.061 (3)	−0.003 (2)	0.003 (2)	−0.007 (3)
S1	0.0709 (8)	0.0855 (12)	0.0657 (9)	−0.0042 (7)	−0.0148 (7)	0.0094 (8)
N11	0.0429 (18)	0.050 (2)	0.050 (2)	0.0061 (17)	0.0016 (16)	−0.0037 (19)
C11	0.048 (2)	0.053 (3)	0.059 (3)	0.001 (2)	−0.004 (2)	−0.002 (2)
C12	0.053 (2)	0.051 (3)	0.058 (3)	−0.001 (2)	−0.004 (2)	0.004 (3)
C13	0.051 (2)	0.041 (3)	0.071 (3)	0.005 (2)	0.001 (2)	−0.006 (3)
C14	0.052 (2)	0.063 (3)	0.059 (3)	−0.002 (2)	−0.004 (2)	−0.007 (3)
C15	0.055 (3)	0.058 (3)	0.053 (3)	0.001 (2)	0.004 (2)	−0.005 (2)
C16	0.064 (3)	0.048 (3)	0.081 (4)	−0.007 (2)	0.003 (3)	−0.002 (3)
C17	0.050 (3)	0.061 (4)	0.066 (3)	−0.011 (2)	−0.003 (2)	0.014 (3)
C18	0.049 (3)	0.076 (4)	0.078 (4)	−0.008 (3)	−0.001 (2)	0.001 (3)
C19	0.061 (3)	0.103 (5)	0.080 (4)	0.009 (3)	0.008 (3)	0.000 (4)
C20	0.050 (3)	0.110 (5)	0.069 (4)	0.004 (3)	−0.001 (3)	0.027 (4)
C21	0.051 (3)	0.132 (6)	0.089 (5)	−0.024 (4)	−0.012 (3)	0.034 (5)
C22	0.066 (3)	0.091 (5)	0.093 (5)	−0.017 (3)	−0.006 (3)	−0.003 (4)
Cl1	0.0565 (8)	0.168 (2)	0.1023 (13)	0.0255 (10)	0.0118 (8)	0.0551 (14)

Geometric parameters (Å, º) top

Zn1—N1ⁱ	1.928 (5)	C15—H15	0.9500
Zn1—N1	1.928 (5)	C16—C17	1.524 (7)
Zn1—N11	2.024 (4)	C16—H16A	0.9900
Zn1—N11ⁱ	2.024 (4)	C16—H16B	0.9900
N1—C1	1.157 (6)	C17—C18	1.363 (8)
C1—S1	1.611 (6)	C17—C22	1.380 (7)
N11—C11	1.342 (6)	C18—C19	1.383 (8)
N11—C15	1.346 (6)	C18—H18	0.9500
C11—C12	1.377 (7)	C19—C20	1.363 (8)
C11—H11	0.9500	C19—H19	0.9500
C12—C13	1.386 (7)	C20—C21	1.338 (10)
C12—H12	0.9500	C20—Cl1	1.747 (6)
C13—C14	1.375 (7)	C21—C22	1.408 (10)
C13—C16	1.518 (7)	C21—H21	0.9500
C14—C15	1.367 (7)	C22—H22	0.9500
C14—H14	0.9500

N1ⁱ—Zn1—N1	123.1 (3)	C14—C15—H15	118.6
N1ⁱ—Zn1—N11	105.49 (17)	C13—C16—C17	112.0 (4)
N1—Zn1—N11	106.33 (16)	C13—C16—H16A	109.2
N1ⁱ—Zn1—N11ⁱ	106.32 (16)	C17—C16—H16A	109.2
N1—Zn1—N11ⁱ	105.49 (17)	C13—C16—H16B	109.2
N11—Zn1—N11ⁱ	109.7 (2)	C17—C16—H16B	109.2
C1—N1—Zn1	176.6 (4)	H16A—C16—H16B	107.9
N1—C1—S1	177.6 (5)	C18—C17—C22	118.2 (5)
C11—N11—C15	116.9 (4)	C18—C17—C16	120.6 (4)
C11—N11—Zn1	121.4 (3)	C22—C17—C16	121.2 (6)
C15—N11—Zn1	121.4 (3)	C17—C18—C19	121.6 (5)
N11—C11—C12	123.2 (4)	C17—C18—H18	119.2
N11—C11—H11	118.4	C19—C18—H18	119.2
C12—C11—H11	118.4	C20—C19—C18	119.5 (7)
C11—C12—C13	119.3 (5)	C20—C19—H19	120.2
C11—C12—H12	120.4	C18—C19—H19	120.2
C13—C12—H12	120.4	C21—C20—C19	120.6 (6)
C14—C13—C12	117.5 (5)	C21—C20—Cl1	119.6 (5)
C14—C13—C16	121.5 (5)	C19—C20—Cl1	119.7 (6)
C12—C13—C16	121.0 (5)	C20—C21—C22	120.2 (6)
C15—C14—C13	120.3 (5)	C20—C21—H21	119.9
C15—C14—H14	119.9	C22—C21—H21	119.9
C13—C14—H14	119.9	C17—C22—C21	119.9 (7)
N11—C15—C14	122.9 (5)	C17—C22—H22	120.1
N11—C15—H15	118.6	C21—C22—H22	120.1

Symmetry code: (i) −x, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Zn(NCS)₂(C₁₂H₁₀ClN)₂]
M_r	588.85
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	29.094 (3), 4.9911 (3), 18.312 (2)
β (°)	98.867 (8)
V (Å³)	2627.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.32
Crystal size (mm)	0.12 × 0.08 × 0.07

Data collection
Diffractometer	Stoe IPDS2 diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe, 2008)
T_min, T_max	0.879, 0.906
No. of measured, independent and observed [I > 2σ(I)] reflections	8309, 2570, 1773
R_int	0.077
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.148, 1.08
No. of reflections	2570
No. of parameters	159
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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

Brandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Fettouhi, 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
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. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhu, 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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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 10| October 2014| Pages m355-m356

doi:10.1107/S160053681402039X

Open

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Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
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		CIF
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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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