Poly[(aceto­nitrile-κN)-μ3-thio­cyanato-κ3N:S:S-μ2-thio­cyanato-κ2N:S-cadmium]

Reinert, T.; Jess, I.; Näther, C.

doi:10.1107/S1600536813015870

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 7| July 2013| Page m398

https://doi.org/10.1107/S1600536813015870

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Poly[(acetonitrile-κN)-μ₃-thiocyanato-κ³N:S:S-μ₂-thiocyanato-κ²N:S-cadmium]

Thorben Reinert,^a ^* Inke Jess ^a and Christian Näther ^a

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

(Received 5 June 2013; accepted 7 June 2013; online 15 June 2013)

The asymmetric unit of the title compound, [Cd(NCS)₂(CH₃CN)]_n, consists of one Cd^II cation, two thiocyanate anions and one acetonitrile ligand, all in general positions. The Cd^II 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 Cd^II 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.

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

[Cd(NCS)₂(C₂H₃N)]
M_r = 269.61
Orthorhombic, P b c a
a = 13.0939 (7) Å
b = 8.9752 (5) Å
c = 14.2986 (11) Å
V = 1680.38 (18) Å³
Z = 8
Mo Kα radiation
μ = 3.02 mm⁻¹
T = 200 K
0.10 × 0.09 × 0.05 mm

Data collection

STOE IPDS-1 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ) T_min = 0.447, T_max = 0.799
22741 measured reflections
2022 independent reflections
1943 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.090
S = 1.17
2022 reflections
93 parameters
H-atom parameters constrained
Δρ_max = 1.09 e Å⁻³
Δρ_min = −0.89 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—N2	2.254 (3)
Cd1—N1	2.287 (4)
Cd1—N11	2.340 (3)
Cd1—S2ⁱ	2.6253 (9)
Cd1—S1ⁱⁱ	2.7522 (8)
Cd1—S1ⁱⁱⁱ	2.8780 (8)
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813015870/zl2553sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813015870/zl2553Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Structure description top

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).

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: 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).

Figures top

	Fig. 1. : Crystal structure of the title compound with labelling and displacement ellipsoids drawn at the 50% probability level. 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.
	Fig. 2. : Crystal structure of the title compound with view along the crystallographic c-axis.

Poly[(acetonitrile-κN)-µ₃-thiocyanato-κ³N:S:S-µ₂-thiocyanato-κ²N:S-cadmium] top

Crystal data top

[Cd(NCS)₂(C₂H₃N)]	F(000) = 1024
M_r = 269.61	D_x = 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

Data collection top

STOE IPDS-1 diffractometer	2022 independent reflections
Radiation source: fine-focus sealed tube	1943 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
Phi scans	θ_max = 28.1°, θ_min = 3.1°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −17→17
T_min = 0.447, T_max = 0.799	k = −11→11
22741 measured reflections	l = −18→18

Refinement top

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(F_o²) + (0.0511P)² + 2.768P] where P = (F_o² + 2F_c²)/3
S = 1.17	(Δ/σ)_max = 0.001
2022 reflections	Δρ_max = 1.09 e Å⁻³
93 parameters	Δρ_min = −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)

Crystal data top

[Cd(NCS)₂(C₂H₃N)]	V = 1680.38 (18) Å³
M_r = 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

Data collection top

STOE IPDS-1 diffractometer	2022 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	1943 reflections with I > 2σ(I)
T_min = 0.447, T_max = 0.799	R_int = 0.043
22741 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.17	Δρ_max = 1.09 e Å⁻³
2022 reflections	Δρ_min = −0.89 e Å⁻³
93 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

Cd1—N2	2.254 (3)	S1—Cd1^v	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—Cd1^iv	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—Cd1^iv	104.43 (11)
N1—Cd1—N11	85.58 (11)	C1—S1—Cd1^v	103.92 (11)
N2—Cd1—S2ⁱ	98.45 (8)	Cd1^iv—S1—Cd1^v	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)]
M_r	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)
T_min, T_max	0.447, 0.799
No. of measured, independent and observed [I > 2σ(I)] reflections	22741, 2022, 1943
R_int	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
Δρ_max, Δρ_min (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).

Selected bond lengths (Å) top

Cd1—N2	2.254 (3)	Cd1—S1ⁱⁱⁱ	2.8780 (8)
Cd1—N1	2.287 (4)	S1—Cd1^iv	2.7523 (8)
Cd1—N11	2.340 (3)	S1—Cd1^v	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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