research communications
κN1)bis(thiocyanato-κN)zinc
of bis(isonicotinamide-aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth Strasse 2, D-24118 Kiel, Germany
*Correspondence e-mail: t.neumann@ac.uni-kiel.de
The 2(C6H6N2O)2], consists of one Zn2+ cation located on a twofold rotation axis, as well as of one thiocyanate anion and one neutral isonicotinamide ligand, both occupying general positions. The Zn2+ cation is tetrahedrally coordinated into a discrete complex by the N atoms of two symmetry-related thiocyanate anions and by the pyridine N atoms of two isonicotinamide ligands. The complexes are linked by intermolecular C—H⋯O and N—H⋯O, and weak intermolecular N—H⋯S hydrogen-bonding interactions into a three-dimensional network.
of the title complex, [Zn(SCN)Keywords: crystal structure; discrete complex; zinc thiocyanate; isonicotinamide; hydrogen bonding.
CCDC reference: 1483379
1. Chemical context
The synthesis of magnetic materials is still a major field in coordination chemistry (Liu et al., 2006). For their construction, paramagnetic cations can be linked by small anionic ligands such as thiocyanate anions to enable a magnetic exchange between the cations (Palion-Gazda et al., 2015; Banerjee et al., 2005). In this context we have reported on a number of coordination polymers with thiocyanato ligands that show different magnetic phenomena, including a slow relaxation of the magnetization which is indicative of single-chain magnetism (Werner et al., 2014; 2015a,b,c). In several cases, such phases can only be prepared by thermal decomposition of suitable precursor compounds (Näther et al., 2013), leading to microcrystalline powders for which a straightforward determination is difficult. In order to avoid this scenario, compounds of the same composition based on cadmium or zinc can be prepared in the form of single crystals. In many cases, such zinc and cadmium compounds are isotypic to the paramagnetic analogues, and the structure of the latter can then easily be refined by the (Wöhlert et al., 2013). It should be mentioned that the structures of cadmium compounds are useful as prototypes for transition metal compounds with octahedral coordination spheres, whereas the structures of zinc compounds are useful prototypes for compounds with tetrahedral coordination spheres for the transition metal. The thermal decomposition of cobalt complexes is an example of the latter. In the course of our systematic investigation in this regard, we became interested in isonicotinamide as a co-ligand to be reacted with Zn(SCN)2. The synthesis and of the resulting compound, [Zn(NCS)2(C6H6N2O)2], are reported here.
2. Structural commentary
The 2+ cation, one thiocyanate anion and one neutral isonicotinamide ligand. The thiocyanate anion and the isonicotinamide ligand are located on general positions whereas the Zn2+ cation is located on a twofold rotation axis. The Zn2+ cation is tetrahedrally coordinated by two terminal N-bonded thiocyanato ligands and by two isonicotinamide ligands through their pyridine N atoms into a discrete complex (Fig. 1). As expected, the Zn—N bond length involving the thiocyanate anion (N1) is significantly shorter than that to the pyridine N atom (N11) of the neutral ligand (Table 1). The angular distortion of the ZnN4 tetrahedron is noticeable, with N—Zn—N angles ranging from 104.32 (13) to 123.6 (2)°.
of the title compound consists of one Zn
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3. Supramolecular features
In the c axis and are linked by intermolecular N—H⋯O hydrogen bonding between one of the two amide H atoms and the amide O atom of a neighboring complex (Fig. 2 and Table 2). There is a further weak contact between one aromatic H atom of the pyridine ring and the carbonyl O atom of a neighboring complex (Table 2). The second H atom of the NH2 group is involved in intermolecular N—H⋯S hydrogen bonding to the S atoms of the anionic ligand. In this way a three-dimensional hydrogen-bonded network is formed.
the discrete complexes are stacked along the4. Database survey
To the best of our knowledge, there are only five coordination polymers with isonicotinamide and thiocyanate anions deposited in the Cambridge Structure Database (Version 5.37, last update 2015; Groom et al., 2016). This includes two clathrate-structures of Ni compounds with μ-1,3-bridging thiocyanate anions and with 9,10-anthraquinone and pyrene as solvate molecules (Sekiya et al., 2009). Furthermore, a one-dimensional μ-1,3-thiocyanate-bridged cadmium compound with 9,10-dichloroanthracene as clathrate molecule (Sekiya & Nishikiori, 2005) as well as a three-dimensional network of Cd with μ-1,3-bridging thiocyanate anions (Yang et al., 2001) are known. Finally, a compound consisting of CuII–NCS sheets has been reported (Đaković et al., 2010).
5. Synthesis and crystallization
Ba(NCS)2·3H2O, ZnSO4·H2O and isonicotinamide were purchased from Alfa Aesar. Zn(NCS)2 was synthesized by stirring 3.076 g Ba(NCS)2·3H2O (10 mmol) with 1.795 g ZnSO4·H2O (10 mmol) in 350 ml water. The white residue was filtered off and the filtrate was dried using a rotary evaporator. The homogenity was checked by X-ray powder diffraction and elemental analysis. Crystals of the title compound suitable for single crystal X-Ray diffraction were obtained by the reaction of 27.2 mg Zn(NCS)2 (0.15 mmol) with 36.64 mg isonicotinamide (0.3 mmol) in methylcyanide (1.5 ml) within a few days.
6. Refinement
Crystal data, data collection and structure . C- and N-bound H atoms were located in a difference Fourier map but were positioned with idealized geometry. They were refined with Uiso(H) = 1.2Ueq(C, N) using a riding model with C—H = 0.95 Å for aromatic and N—H = 0.88 Å for the amide H atoms. The was determined and is in agreement with the selected setting [Flack x parameter: 0.005 (19) by classical fit to all intensities (Flack, 1983) and −0.005 (8) from 819 selected quotients (Parsons et al., 2013)].
details are summarized in Table 3Supporting information
CCDC reference: 1483379
https://doi.org/10.1107/S2056989016008963/wm5297sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016008963/wm5297Isup2.hkl
Data collection: X-AREA (Stoe, 2008); cell
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: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).[Zn(NCS)2(C6H6N2O)2] | Dx = 1.534 Mg m−3 |
Mr = 425.79 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Fdd2 | Cell parameters from 15683 reflections |
a = 19.1926 (9) Å | θ = 4.2–56.2° |
b = 36.3044 (12) Å | µ = 1.58 mm−1 |
c = 5.2930 (2) Å | T = 200 K |
V = 3688.0 (3) Å3 | Block, colorless |
Z = 8 | 0.20 × 0.16 × 0.11 mm |
F(000) = 1728 |
Stoe IPDS-2 diffractometer | 2012 reflections with I > 2σ(I) |
ω scans | Rint = 0.035 |
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2008) | θmax = 28.1°, θmin = 2.2° |
Tmin = 0.595, Tmax = 0.742 | h = −25→25 |
15338 measured reflections | k = −47→47 |
2132 independent reflections | l = −6→6 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.031 | w = 1/[σ2(Fo2) + (0.0282P)2 + 4.6943P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.067 | (Δ/σ)max < 0.001 |
S = 1.13 | Δρmax = 0.24 e Å−3 |
2132 reflections | Δρmin = −0.27 e Å−3 |
114 parameters | Absolute structure: Flack x determined using 819 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013). |
1 restraint | Absolute structure parameter: −0.005 (8) |
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. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.5000 | 0.5000 | 0.00134 (10) | 0.04197 (15) | |
N1 | 0.41911 (18) | 0.48143 (9) | −0.1702 (7) | 0.0562 (8) | |
C1 | 0.3688 (2) | 0.46990 (10) | −0.2648 (9) | 0.0514 (9) | |
S1 | 0.29987 (6) | 0.45456 (4) | −0.4003 (3) | 0.0802 (4) | |
N11 | 0.46205 (13) | 0.53943 (7) | 0.2367 (6) | 0.0399 (6) | |
C11 | 0.39419 (17) | 0.54254 (10) | 0.2958 (8) | 0.0465 (9) | |
H11 | 0.3616 | 0.5266 | 0.2164 | 0.056* | |
C12 | 0.37026 (17) | 0.56804 (10) | 0.4673 (8) | 0.0466 (8) | |
H12 | 0.3219 | 0.5697 | 0.5036 | 0.056* | |
C13 | 0.41714 (16) | 0.59132 (9) | 0.5870 (7) | 0.0373 (7) | |
C14 | 0.48690 (15) | 0.58811 (9) | 0.5240 (9) | 0.0438 (8) | |
H14 | 0.5205 | 0.6037 | 0.6011 | 0.053* | |
C15 | 0.50720 (17) | 0.56217 (10) | 0.3489 (7) | 0.0428 (8) | |
H15 | 0.5552 | 0.5604 | 0.3063 | 0.051* | |
C16 | 0.39066 (16) | 0.61924 (9) | 0.7711 (8) | 0.0429 (7) | |
N12 | 0.43541 (15) | 0.63295 (9) | 0.9372 (6) | 0.0486 (8) | |
H12A | 0.4215 | 0.6495 | 1.0479 | 0.058* | |
H12B | 0.4791 | 0.6255 | 0.9367 | 0.058* | |
O11 | 0.32905 (12) | 0.62889 (8) | 0.7653 (7) | 0.0590 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0442 (3) | 0.0394 (2) | 0.0424 (3) | 0.0020 (3) | 0.000 | 0.000 |
N1 | 0.059 (2) | 0.0546 (19) | 0.055 (2) | 0.0028 (16) | −0.0093 (16) | −0.0096 (15) |
C1 | 0.056 (2) | 0.0481 (18) | 0.050 (2) | 0.0044 (16) | 0.0007 (19) | −0.011 (2) |
S1 | 0.0496 (6) | 0.0997 (10) | 0.0914 (10) | −0.0051 (6) | −0.0034 (6) | −0.0432 (8) |
N11 | 0.0374 (13) | 0.0388 (13) | 0.0434 (16) | 0.0011 (10) | −0.0010 (13) | −0.0002 (13) |
C11 | 0.0353 (16) | 0.0455 (17) | 0.059 (3) | −0.0030 (14) | −0.0043 (16) | −0.0088 (17) |
C12 | 0.0311 (15) | 0.0500 (17) | 0.059 (2) | −0.0009 (13) | −0.0041 (15) | −0.0082 (18) |
C13 | 0.0330 (15) | 0.0381 (15) | 0.0408 (17) | 0.0017 (12) | −0.0052 (13) | 0.0017 (13) |
C14 | 0.0296 (16) | 0.0491 (16) | 0.053 (2) | −0.0052 (12) | −0.0021 (17) | −0.0081 (19) |
C15 | 0.0341 (16) | 0.0471 (18) | 0.047 (2) | −0.0004 (13) | −0.0007 (15) | −0.0036 (15) |
C16 | 0.0327 (14) | 0.0492 (17) | 0.0467 (19) | 0.0021 (12) | −0.0048 (15) | −0.0069 (17) |
N12 | 0.0349 (14) | 0.0582 (18) | 0.053 (2) | 0.0051 (13) | −0.0076 (13) | −0.0151 (15) |
O11 | 0.0322 (12) | 0.0719 (17) | 0.0728 (19) | 0.0104 (11) | −0.0097 (14) | −0.0258 (18) |
Zn1—N1i | 1.921 (3) | C12—H12 | 0.9500 |
Zn1—N1 | 1.921 (3) | C13—C14 | 1.385 (4) |
Zn1—N11 | 2.033 (3) | C13—C16 | 1.495 (5) |
Zn1—N11i | 2.033 (3) | C14—C15 | 1.378 (5) |
N1—C1 | 1.165 (5) | C14—H14 | 0.9500 |
C1—S1 | 1.605 (4) | C15—H15 | 0.9500 |
N11—C15 | 1.336 (4) | C16—O11 | 1.233 (4) |
N11—C11 | 1.344 (4) | C16—N12 | 1.326 (5) |
C11—C12 | 1.376 (5) | N12—H12A | 0.8800 |
C11—H11 | 0.9500 | N12—H12B | 0.8800 |
C12—C13 | 1.387 (5) | ||
N1i—Zn1—N1 | 123.6 (2) | C13—C12—H12 | 120.2 |
N1i—Zn1—N11 | 109.39 (13) | C14—C13—C12 | 117.8 (3) |
N1—Zn1—N11 | 104.32 (13) | C14—C13—C16 | 122.9 (3) |
N1i—Zn1—N11i | 104.32 (13) | C12—C13—C16 | 119.3 (3) |
N1—Zn1—N11i | 109.40 (13) | C15—C14—C13 | 119.5 (3) |
N11—Zn1—N11i | 104.42 (17) | C15—C14—H14 | 120.2 |
C1—N1—Zn1 | 177.2 (4) | C13—C14—H14 | 120.2 |
N1—C1—S1 | 178.8 (5) | N11—C15—C14 | 122.6 (3) |
C15—N11—C11 | 118.2 (3) | N11—C15—H15 | 118.7 |
C15—N11—Zn1 | 118.4 (2) | C14—C15—H15 | 118.7 |
C11—N11—Zn1 | 123.3 (2) | O11—C16—N12 | 122.1 (4) |
N11—C11—C12 | 122.3 (3) | O11—C16—C13 | 120.1 (3) |
N11—C11—H11 | 118.9 | N12—C16—C13 | 117.8 (3) |
C12—C11—H11 | 118.9 | C16—N12—H12A | 120.0 |
C11—C12—C13 | 119.7 (3) | C16—N12—H12B | 120.0 |
C11—C12—H12 | 120.2 | H12A—N12—H12B | 120.0 |
Symmetry code: (i) −x+1, −y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···O11ii | 0.95 | 2.54 | 3.365 (6) | 145 |
N12—H12A···S1iii | 0.88 | 2.62 | 3.407 (3) | 150 |
N12—H12B···O11ii | 0.88 | 1.97 | 2.821 (4) | 162 |
Symmetry codes: (ii) x+1/4, −y+5/4, z+1/4; (iii) −x+3/4, y+1/4, z+7/4. |
Acknowledgements
This project was supported by the Deutsche Forschungsgemeinschaft (Project No. NA 720/5–1) and the State of Schleswig-Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.
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