metal-organic compounds
Poly[(acetonitrile-κN)-μ3-thiocyanato-κ3N:S:S-μ2-thiocyanato-κ2N:S-cadmium]
aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth Strasse 2, D-24098 Kiel, Germany
*Correspondence e-mail: treinert@ac.uni-kiel.de
The 2(CH3CN)]n, consists of one CdII cation, two thiocyanate anions and one acetonitrile ligand, all in general positions. The CdII cation is coordinated by three N atoms of two thiocyanate anions and one acetonitrile ligand, as well as three S atoms of symmetry-related thiocyanate anions within a slightly distorted octahedral coordination environment. The CdII cations are linked by μ-1,3(N,S) and μ-1,1,3(S,S,N) thiocyanate anions into layers that are located in the ab plane.
of the title compound, [Cd(NCS)Related literature
For related structures, see: Wöhlert et al. (2011). For background to transition metal thiocyanate coordination polymers and their magnetic properties, see: Boeckmann et al. (2010, 2011).
Experimental
Crystal data
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Data collection: X-AREA (Stoe & Cie, 2008); cell X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS92 (Sheldrick, 2008); program(s) used to refine structure: SHELXL92 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010).
Supporting information
https://doi.org/10.1107/S1600536813015870/zl2553sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813015870/zl2553Isup2.hkl
The title compound was obtained accidently during the reaction of 68.6 mg Cd(NCS)2 (0.30 mmol) with 11.1 µL 4-tert-butylpyridine (0.08 mmol) in 1.0 ml acetonitrile at RT in a closed 3 ml snap cap vial. After several months colourless blocks of the title compound were obtained.
The H atoms were positioned with idealized geometry, allowed to rotate but not to tip and were refined isotropic with Uiso(H) = 1.5 Ueq(C) of the parent atom using a riding model with C—H = 0.98 Å.
The
of the title compound was performed as part of a project on the synthesis of new coordination polymers based on transition metal and the investigations on their magnetic properties (Boeckmann et al. (2010, 2011)). Within this project, we have reacted cadmium(II)thiocyanate with 4-tert-butylpyridine in acetonitrile, which resulted in the formation of crystals of the title compound by accident. In the the Cd cations are surrounded by three N atoms of two N-bonded µ-1,3-briding thiocyanato anions and one acetonitril ligand as well as three S atoms of three S-bonded µ-1,1,3-bridging thiocyanato anions in a slightly distorted octahedral geometry (Fig. 1 and Tab. 1). The Cd···N distances range from 2.2544 (28) Å to 2.3396 (28) Å, the Cd···S distances from 2.6254 (9) Å to 2.8781 (8) Å (Table 1). The Cd cations are linked into dimeric units by pairs of µ-1,3-briding thiocyanato anions that are further connected into chains by single µ-1,3-briding anionic ligands. These chains are further connected by pairs of µ-1,1,3-bridging thiocyanato anions into layers which are parallel to the crystallographic a-b-plane.For related structures, see: Wöhlert et al. (2011). For background to transition metal thiocyanate coordination polymers and their magnetic properties, see: Boeckmann et al. (2010, 2011).
Data collection: X-AREA (Stoe & Cie, 2008); cell
X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS92 (Sheldrick, 2008); program(s) used to refine structure: SHELXL92 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).[Cd(NCS)2(C2H3N)] | F(000) = 1024 |
Mr = 269.61 | Dx = 2.131 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 22741 reflections |
a = 13.0939 (7) Å | θ = 1.9–28.2° |
b = 8.9752 (5) Å | µ = 3.02 mm−1 |
c = 14.2986 (11) Å | T = 200 K |
V = 1680.38 (18) Å3 | Block, colourless |
Z = 8 | 0.10 × 0.09 × 0.05 mm |
STOE IPDS-1 diffractometer | 2022 independent reflections |
Radiation source: fine-focus sealed tube | 1943 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
Phi scans | θmax = 28.1°, θmin = 3.1° |
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008) | h = −17→17 |
Tmin = 0.447, Tmax = 0.799 | k = −11→11 |
22741 measured reflections | l = −18→18 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.090 | w = 1/[σ2(Fo2) + (0.0511P)2 + 2.768P] where P = (Fo2 + 2Fc2)/3 |
S = 1.17 | (Δ/σ)max = 0.001 |
2022 reflections | Δρmax = 1.09 e Å−3 |
93 parameters | Δρmin = −0.89 e Å−3 |
0 restraints | Extinction correction: SHELXL92 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0100 (7) |
[Cd(NCS)2(C2H3N)] | V = 1680.38 (18) Å3 |
Mr = 269.61 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 13.0939 (7) Å | µ = 3.02 mm−1 |
b = 8.9752 (5) Å | T = 200 K |
c = 14.2986 (11) Å | 0.10 × 0.09 × 0.05 mm |
STOE IPDS-1 diffractometer | 2022 independent reflections |
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008) | 1943 reflections with I > 2σ(I) |
Tmin = 0.447, Tmax = 0.799 | Rint = 0.043 |
22741 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.17 | Δρmax = 1.09 e Å−3 |
2022 reflections | Δρmin = −0.89 e Å−3 |
93 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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. |
x | y | z | Uiso*/Ueq | ||
Cd1 | 0.580143 (17) | 0.70475 (2) | 0.516796 (17) | 0.02222 (14) | |
N1 | 0.7434 (3) | 0.7780 (4) | 0.4831 (2) | 0.0369 (8) | |
C1 | 0.8127 (2) | 0.8423 (4) | 0.4550 (2) | 0.0248 (6) | |
S1 | 0.91085 (5) | 0.93385 (8) | 0.40941 (5) | 0.02174 (19) | |
N2 | 0.5499 (3) | 0.9136 (3) | 0.5999 (2) | 0.0360 (7) | |
C2 | 0.5257 (2) | 1.0352 (3) | 0.6171 (2) | 0.0264 (6) | |
S2 | 0.49199 (8) | 1.20580 (8) | 0.64506 (6) | 0.0318 (2) | |
N11 | 0.6540 (2) | 0.5645 (3) | 0.6370 (2) | 0.0298 (6) | |
C11 | 0.6836 (2) | 0.4805 (4) | 0.6898 (2) | 0.0271 (6) | |
C12 | 0.7197 (4) | 0.3726 (5) | 0.7579 (3) | 0.0470 (10) | |
H12A | 0.6824 | 0.2789 | 0.7500 | 0.070* | |
H12B | 0.7083 | 0.4113 | 0.8211 | 0.070* | |
H12C | 0.7929 | 0.3550 | 0.7484 | 0.070* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.01867 (18) | 0.01728 (18) | 0.03070 (19) | −0.00145 (7) | −0.00221 (7) | 0.00423 (7) |
N1 | 0.0250 (16) | 0.0377 (19) | 0.048 (2) | −0.0124 (13) | 0.0000 (13) | −0.0006 (13) |
C1 | 0.0195 (13) | 0.0244 (14) | 0.0305 (14) | −0.0026 (12) | −0.0042 (11) | −0.0042 (12) |
S1 | 0.0181 (3) | 0.0197 (4) | 0.0274 (4) | −0.0017 (2) | −0.0021 (2) | 0.0012 (3) |
N2 | 0.0481 (18) | 0.0210 (13) | 0.0388 (15) | 0.0052 (12) | −0.0079 (14) | −0.0011 (12) |
C2 | 0.0282 (14) | 0.0249 (14) | 0.0260 (13) | −0.0030 (12) | −0.0053 (11) | 0.0051 (11) |
S2 | 0.0458 (5) | 0.0209 (4) | 0.0285 (4) | 0.0052 (3) | −0.0061 (3) | −0.0017 (3) |
N11 | 0.0296 (13) | 0.0277 (13) | 0.0322 (13) | 0.0014 (11) | −0.0037 (11) | 0.0020 (11) |
C11 | 0.0276 (14) | 0.0254 (14) | 0.0283 (14) | −0.0016 (12) | −0.0055 (12) | −0.0017 (12) |
C12 | 0.053 (2) | 0.039 (2) | 0.049 (2) | −0.0052 (17) | −0.0246 (19) | 0.0138 (17) |
Cd1—N2 | 2.254 (3) | S1—Cd1v | 2.8780 (8) |
Cd1—N1 | 2.287 (4) | N2—C2 | 1.163 (4) |
Cd1—N11 | 2.340 (3) | C2—S2 | 1.643 (3) |
Cd1—S2i | 2.6253 (9) | S2—Cd1i | 2.6253 (9) |
Cd1—S1ii | 2.7522 (8) | N11—C11 | 1.135 (4) |
Cd1—S1iii | 2.8780 (8) | C11—C12 | 1.452 (5) |
N1—C1 | 1.148 (5) | C12—H12A | 0.9800 |
C1—S1 | 1.659 (3) | C12—H12B | 0.9800 |
S1—Cd1iv | 2.7523 (8) | C12—H12C | 0.9800 |
N2—Cd1—N1 | 92.08 (13) | N1—C1—S1 | 177.3 (3) |
N2—Cd1—N11 | 97.64 (11) | C1—S1—Cd1iv | 104.43 (11) |
N1—Cd1—N11 | 85.58 (11) | C1—S1—Cd1v | 103.92 (11) |
N2—Cd1—S2i | 98.45 (8) | Cd1iv—S1—Cd1v | 98.29 (2) |
N1—Cd1—S2i | 93.60 (9) | C2—N2—Cd1 | 160.0 (3) |
N11—Cd1—S2i | 163.90 (7) | N2—C2—S2 | 178.1 (3) |
N2—Cd1—S1ii | 91.84 (9) | C2—S2—Cd1i | 99.62 (11) |
N1—Cd1—S1ii | 164.41 (9) | C11—N11—Cd1 | 170.7 (3) |
N11—Cd1—S1ii | 78.95 (7) | N11—C11—C12 | 179.1 (4) |
S2i—Cd1—S1ii | 100.74 (3) | C11—C12—H12A | 109.5 |
N2—Cd1—S1iii | 172.22 (9) | C11—C12—H12B | 109.5 |
N1—Cd1—S1iii | 95.29 (9) | H12A—C12—H12B | 109.5 |
N11—Cd1—S1iii | 85.43 (7) | C11—C12—H12C | 109.5 |
S2i—Cd1—S1iii | 78.63 (2) | H12A—C12—H12C | 109.5 |
S1ii—Cd1—S1iii | 81.71 (2) | H12B—C12—H12C | 109.5 |
C1—N1—Cd1 | 163.1 (3) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1/2, −y+3/2, −z+1; (iii) −x+3/2, y−1/2, z; (iv) x+1/2, −y+3/2, −z+1; (v) −x+3/2, y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | [Cd(NCS)2(C2H3N)] |
Mr | 269.61 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 200 |
a, b, c (Å) | 13.0939 (7), 8.9752 (5), 14.2986 (11) |
V (Å3) | 1680.38 (18) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 3.02 |
Crystal size (mm) | 0.10 × 0.09 × 0.05 |
Data collection | |
Diffractometer | STOE IPDS1 |
Absorption correction | Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008) |
Tmin, Tmax | 0.447, 0.799 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22741, 2022, 1943 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.662 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.090, 1.17 |
No. of reflections | 2022 |
No. of parameters | 93 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.09, −0.89 |
Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS92 (Sheldrick, 2008), SHELXL92 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011), SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).
Cd1—N2 | 2.254 (3) | Cd1—S1iii | 2.8780 (8) |
Cd1—N1 | 2.287 (4) | S1—Cd1iv | 2.7523 (8) |
Cd1—N11 | 2.340 (3) | S1—Cd1v | 2.8780 (8) |
Cd1—S2i | 2.6253 (9) | S2—Cd1i | 2.6253 (9) |
Cd1—S1ii | 2.7522 (8) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1/2, −y+3/2, −z+1; (iii) −x+3/2, y−1/2, z; (iv) x+1/2, −y+3/2, −z+1; (v) −x+3/2, y+1/2, z. |
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 the opportunity to use his experimental facility.
References
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The structure determination of the title compound was performed as part of a project on the synthesis of new coordination polymers based on transition metal thiocyanates and the investigations on their magnetic properties (Boeckmann et al. (2010, 2011)). Within this project, we have reacted cadmium(II)thiocyanate with 4-tert-butylpyridine in acetonitrile, which resulted in the formation of crystals of the title compound by accident. In the crystal structure the Cd cations are surrounded by three N atoms of two N-bonded µ-1,3-briding thiocyanato anions and one acetonitril ligand as well as three S atoms of three S-bonded µ-1,1,3-bridging thiocyanato anions in a slightly distorted octahedral geometry (Fig. 1 and Tab. 1). The Cd···N distances range from 2.2544 (28) Å to 2.3396 (28) Å, the Cd···S distances from 2.6254 (9) Å to 2.8781 (8) Å (Table 1). The Cd cations are linked into dimeric units by pairs of µ-1,3-briding thiocyanato anions that are further connected into chains by single µ-1,3-briding anionic ligands. These chains are further connected by pairs of µ-1,1,3-bridging thiocyanato anions into layers which are parallel to the crystallographic a-b-plane.