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

Abstract

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,

• a = 8.1510 (4) Å

• b = 13.7382 (5) Å

• c = 15.0111 (6) Å

• V = 1680.94 (12) ų

• 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[F ² > 2σ(F ²)] = 0.050

• wR(F ²) = 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

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.

Supplementary Material

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

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) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

All H atoms were discernible in difference maps but were positioned with idealized geometry and were refined isotropically with U_eq(H) = 1.2U_eq(C) for aromatic H atoms and with U_eq(H) = 1.5U_eq(C) for aliphatic H atoms of the parent atom using a riding model with C—H = 0.93 Å (aromatic) and with C—H = 0.96 Å (aliphatic).

Figures

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).

Crystal data

[Zn(NCS)2(C6H7N)2]	F(000) = 752
Mr = 367.78	Dx = 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

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

Refinement

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(Fo2) + (0.0581P)2 + 0.3791P] where P = (Fo2 + 2Fc2)/3
2366 reflections	(Δ/σ)max < 0.001
107 parameters	Δρmax = 0.66 e Å−3
0 restraints	Δρmin = −0.39 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) x, −y+3/2, z.