Bis(3-methyl­pyridine-κN)bis­(thio­cyanato-κN)zinc

Boeckmann, J.; Näther, C.

doi:10.1107/S1600536811024561

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page m994

doi:10.1107/S1600536811024561

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Bis(3-methylpyridine-κN)bis(thiocyanato-κN)zinc

Jan Boeckmann ^a ^* and Christian Näther ^a

^aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth Strasse 2, D-24098 Kiel, Germany
^*Correspondence e-mail: jboeckmann@ac.uni-kiel.de

(Received 15 June 2011; accepted 22 June 2011; online 30 June 2011)

The asymmetric unit of the title compound, [Zn(NCS)₂(C₆H₇N)₂], consists of one Zn²⁺ cation and two thiocyanate anions, all situated on special positions with site symmetry .m., and one 3-methylpyridine ligand. The zinc cation is coordinated by four N atoms of two terminal N-bonded thiocyanate anions and of two symmetry-related 3-methylpyridine co-ligands, defining a slightly distorted tetrahedral coordination polyhedron.

Related literature

For background to the magnetic properties of Co(II) thio- or selenocyanate coordination polymers, see: Boeckmann & Näther (2010 , 2011 ); Wöhlert et al. (2011 ). For isostructural and related compounds with different N-donor co-ligands and thio- or selenocyanate ligands, see: Bhosekar et al. (2010 ); Boeckmann et al. (2011a ,b ,c ); Taniguchi et al. (1987 ); Wu (2004 ); Zhu et al. (2008 ).

Experimental

Crystal data

[Zn(NCS)₂(C₆H₇N)₂]
M_r = 367.78
Orthorhombic, P n m a
a = 8.1510 (4) Å
b = 13.7382 (5) Å
c = 15.0111 (6) Å
V = 1680.94 (12) Å³
Z = 4
Mo Kα radiation
μ = 1.71 mm⁻¹
T = 293 K
0.13 × 0.11 × 0.08 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008) T_min = 0.789, T_max = 0.863
23123 measured reflections
2366 independent reflections
1918 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.122
S = 1.14
2366 reflections
107 parameters
H-atom parameters constrained
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Zn1—N1	1.928 (4)
Zn1—N2	1.942 (4)
Zn1—N11	2.026 (2)

N1—Zn1—N2	119.51 (18)
N1—Zn1—N11	108.39 (8)
N2—Zn1—N11	106.32 (9)
N11ⁱ—Zn1—N11	107.34 (12)
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z]$ .

Data collection: X-AREA (Stoe & Cie, 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811024561/wm2500sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811024561/wm2500Isup2.hkl

checkCIF report

Comment top

Recently, we have reported about the directed synthesis of one-dimensional and two-dimensional transition metal(II) thio- and selenocyanate coordination polymers with neutral N-donor co-ligands that were obtained by thermal decomposition reactions. The compounds with Co(II) are of special interest because several of them show a slow relaxation of the magnetization which is a rare and very interesting magnetic phenomenon (Boeckmann & Näther, 2010; Boeckmann & Näther, 2011; Wöhlert et al., 2011)). Following this synthetic procedure, powders of low crystallinity are frequently obtained and therefore their structures are difficult to elucidate. Structure determinations of these compounds are of special importance because in the case of coordination polymers containing cobalt(II), both octahedral and tetrahedral coordination polyhedra can occur in these structures. In this context we found out that diamagnetic zinc and cadmium compounds can easily be crystallized in solution and are very often isotypic to their paramagnetic analogues (Bhosekar et al., 2010; Boeckmann et al., 2011a; Boeckmann et al., 2011b; Boeckmann et al., 2011c; Taniguchi et al., 1987; Wu, 2004; Zhu, 2008). The structures of the paramagnetic counterparts can then simply be refined applying the Rietveld method. This is the reason why we have determined the crystal structure of the diamagnetic title compound, [bis(thiocyanato-κN)-bis(3-methylpyridine-κN)zinc].

In the crystal structure the zinc cations (site symmetry .m.) are bonded to four nitrogen atoms of two terminal thiocyanate anions (site symmetry .m.) and to two symmetry-related terminal 3-methylpyridine co-ligands within a slightly distorted tetrahedral coordination polyhedron (Fig. 1 and Tab.1). The discrete complexes are oppositely oriented into columns which spread along the crystallographic b axis (Fig. 2). These columns are further arranged in parallel along the crystallographic a and c axes into a three-dimensional packing.

Related literature top

For background to the magnetic properties of Co(II) thio- or selenocyanate coordination polymers, see: Boeckmann & Näther (2010, 2011); Wöhlert et al. (2011). For isostructural and related compounds with different N-donor co-ligands and thio- or selenocyanate ligands, see: Bhosekar et al. (2010); Boeckmann et al. (2011a,b,c); Taniguchi et al. (1987); Wu (2004); Zhu et al. (2008).

Experimental top

The title compound was prepared by the reaction of 90.0 mg Zn(NCS)₂ (0.50 mmol) and 97.3 µL 3-methylpyridine (1.00 mmol) in 1.50 ml water at RT in a closed 3 ml snap cap vial. After three days colourless block like crystals of the title compound were obtained.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. : Molecular structure of the title compound, showing the coordination around Zn²⁺, with labelling and displacement ellipsoids drawn at the 30% probability level. [Symmetry codes: i = x, -y + 1/2, z.]
	Fig. 2. : Packing diagram of the title compound with view along the crystallographic a axis (aqua = zinc; yellow = sulfur; blue = nitrogen; grey = carbon; light-grey = hydrogen).

Bis(3-methylpyridine-κN)bis(thiocyanato-κN)zinc top

Crystal data top

[Zn(NCS)₂(C₆H₇N)₂]	F(000) = 752
M_r = 367.78	D_x = 1.453 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 16444 reflections
a = 8.1510 (4) Å	θ = 2.0–29.3°
b = 13.7382 (5) Å	µ = 1.71 mm⁻¹
c = 15.0111 (6) Å	T = 293 K
V = 1680.94 (12) Å³	Block, colourless
Z = 4	0.13 × 0.11 × 0.08 mm

Data collection top

Stoe IPDS-2 diffractometer	2366 independent reflections
Radiation source: fine-focus sealed tube	1918 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ω scans	θ_max = 29.3°, θ_min = 2.0°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −11→11
T_min = 0.789, T_max = 0.863	k = −16→18
23123 measured reflections	l = −20→20

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0581P)² + 0.3791P] where P = (F_o² + 2F_c²)/3
2366 reflections	(Δ/σ)_max < 0.001
107 parameters	Δρ_max = 0.66 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

[Zn(NCS)₂(C₆H₇N)₂]	V = 1680.94 (12) Å³
M_r = 367.78	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 8.1510 (4) Å	µ = 1.71 mm⁻¹
b = 13.7382 (5) Å	T = 293 K
c = 15.0111 (6) Å	0.13 × 0.11 × 0.08 mm

Data collection top

Stoe IPDS-2 diffractometer	2366 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	1918 reflections with I > 2σ(I)
T_min = 0.789, T_max = 0.863	R_int = 0.048
23123 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.122	H-atom parameters constrained
S = 1.14	Δρ_max = 0.66 e Å⁻³
2366 reflections	Δρ_min = −0.39 e Å⁻³
107 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	0.48061 (6)	0.7500	0.49255 (3)	0.05827 (17)
N1	0.4523 (5)	0.7500	0.3651 (2)	0.0754 (10)
C1	0.4513 (5)	0.7500	0.2879 (3)	0.0606 (9)
S1	0.44866 (18)	0.7500	0.18058 (7)	0.0784 (3)
N2	0.2888 (5)	0.7500	0.5693 (3)	0.0792 (10)
C2	0.1682 (5)	0.7500	0.6084 (3)	0.0663 (10)
S2	−0.00054 (18)	0.7500	0.66536 (11)	0.1021 (5)
N11	0.6137 (3)	0.63122 (14)	0.52674 (13)	0.0549 (5)
C11	0.6306 (3)	0.60498 (19)	0.61208 (16)	0.0608 (6)
H11	0.5791	0.6426	0.6554	0.073*
C12	0.7202 (4)	0.5254 (2)	0.63937 (19)	0.0662 (7)
C13	0.7916 (4)	0.4695 (2)	0.5739 (2)	0.0737 (8)
H13	0.8499	0.4138	0.5892	0.088*
C14	0.7771 (5)	0.4958 (2)	0.4859 (2)	0.0760 (9)
H14	0.8267	0.4588	0.4415	0.091*
C15	0.6884 (4)	0.57729 (19)	0.46463 (17)	0.0642 (7)
H15	0.6800	0.5957	0.4052	0.077*
C16	0.7368 (5)	0.5021 (3)	0.7369 (2)	0.0953 (12)
H16A	0.7898	0.5553	0.7668	0.143*
H16B	0.8014	0.4441	0.7440	0.143*
H16C	0.6300	0.4920	0.7622	0.143*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0690 (3)	0.0527 (2)	0.0531 (2)	0.000	−0.00324 (18)	0.000
N1	0.089 (3)	0.078 (2)	0.0592 (18)	0.000	−0.0136 (17)	0.000
C1	0.066 (2)	0.0520 (18)	0.064 (2)	0.000	−0.0087 (16)	0.000
S1	0.1032 (9)	0.0745 (7)	0.0574 (5)	0.000	−0.0054 (5)	0.000
N2	0.082 (3)	0.063 (2)	0.092 (2)	0.000	0.019 (2)	0.000
C2	0.076 (3)	0.0442 (17)	0.078 (2)	0.000	−0.001 (2)	0.000
S2	0.0739 (8)	0.1173 (12)	0.1150 (12)	0.000	0.0199 (7)	0.000
N11	0.0666 (12)	0.0479 (10)	0.0501 (10)	−0.0036 (9)	−0.0028 (8)	0.0000 (8)
C11	0.0740 (16)	0.0564 (14)	0.0519 (12)	−0.0030 (13)	−0.0015 (11)	0.0003 (10)
C12	0.0725 (17)	0.0607 (14)	0.0655 (14)	−0.0130 (14)	−0.0139 (13)	0.0114 (12)
C13	0.0741 (19)	0.0554 (14)	0.092 (2)	0.0031 (14)	−0.0095 (16)	0.0072 (14)
C14	0.090 (2)	0.0624 (16)	0.075 (2)	0.0102 (15)	0.0062 (15)	−0.0107 (13)
C15	0.0795 (18)	0.0575 (14)	0.0557 (13)	−0.0010 (13)	0.0019 (12)	−0.0029 (11)
C16	0.113 (3)	0.099 (3)	0.074 (2)	−0.004 (2)	−0.020 (2)	0.0275 (17)

Geometric parameters (Å, º) top

Zn1—N1	1.928 (4)	C11—H11	0.9300
Zn1—N2	1.942 (4)	C12—C13	1.377 (5)
Zn1—N11ⁱ	2.026 (2)	C12—C16	1.505 (4)
Zn1—N11	2.026 (2)	C13—C14	1.374 (4)
N1—C1	1.158 (5)	C13—H13	0.9300
C1—S1	1.611 (4)	C14—C15	1.371 (4)
N2—C2	1.145 (5)	C14—H14	0.9300
C2—S2	1.619 (5)	C15—H15	0.9300
N11—C15	1.338 (3)	C16—H16A	0.9600
N11—C11	1.338 (3)	C16—H16B	0.9600
C11—C12	1.377 (4)	C16—H16C	0.9600

N1—Zn1—N2	119.51 (18)	C13—C12—C16	122.6 (3)
N1—Zn1—N11ⁱ	108.39 (9)	C11—C12—C16	120.4 (3)
N2—Zn1—N11ⁱ	106.32 (9)	C14—C13—C12	120.2 (3)
N1—Zn1—N11	108.39 (8)	C14—C13—H13	119.9
N2—Zn1—N11	106.32 (9)	C12—C13—H13	119.9
N11ⁱ—Zn1—N11	107.34 (12)	C15—C14—C13	118.9 (3)
C1—N1—Zn1	173.6 (4)	C15—C14—H14	120.5
N1—C1—S1	179.7 (4)	C13—C14—H14	120.5
C2—N2—Zn1	174.5 (4)	N11—C15—C14	122.0 (3)
N2—C2—S2	179.0 (4)	N11—C15—H15	119.0
C15—N11—C11	118.1 (2)	C14—C15—H15	119.0
C15—N11—Zn1	120.90 (17)	C12—C16—H16A	109.5
C11—N11—Zn1	120.99 (17)	C12—C16—H16B	109.5
N11—C11—C12	123.6 (3)	H16A—C16—H16B	109.5
N11—C11—H11	118.2	C12—C16—H16C	109.5
C12—C11—H11	118.2	H16A—C16—H16C	109.5
C13—C12—C11	117.0 (3)	H16B—C16—H16C	109.5

Symmetry code: (i) x, −y+3/2, z.

Experimental details

Crystal data
Chemical formula	[Zn(NCS)₂(C₆H₇N)₂]
M_r	367.78
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	293
a, b, c (Å)	8.1510 (4), 13.7382 (5), 15.0111 (6)
V (Å³)	1680.94 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.71
Crystal size (mm)	0.13 × 0.11 × 0.08

Data collection
Diffractometer	Stoe IPDS2 diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)
T_min, T_max	0.789, 0.863
No. of measured, independent and observed [I > 2σ(I)] reflections	23123, 2366, 1918
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.688

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.122, 1.14
No. of reflections	2366
No. of parameters	107
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.66, −0.39

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

Selected geometric parameters (Å, º) top

Zn1—N1	1.928 (4)	Zn1—N11	2.026 (2)
Zn1—N2	1.942 (4)

N1—Zn1—N2	119.51 (18)	N2—Zn1—N11	106.32 (9)
N1—Zn1—N11	108.39 (8)	N11ⁱ—Zn1—N11	107.34 (12)

Symmetry code: (i) x, −y+3/2, z.

Acknowledgements

We gratefully acknowledge financial support by the DFG (project number NA 720/3–1) and the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for the opportunity to use his experimental facilities. Special thanks go to Inke Jess for her support in single-crystal measurements.

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