Poly[(aceto­nitrile-κN)-μ₃-thio­cyanato-κ³ N:S:S-μ₂-thio­cyanato-κ² N:S-cadmium]

Abstract

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,

• a = 13.0939 (7) Å

• b = 8.9752 (5) Å

• c = 14.2986 (11) Å

• V = 1680.38 (18) ų

• 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[F ² > 2σ(F ²)] = 0.033

• wR(F ²) = 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

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 ▶).

Supplementary Material

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

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) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

The H atoms were positioned with idealized geometry, allowed to rotate but not to tip and were refined isotropic with U_iso(H) = 1.5 U_eq(C) of the parent atom using a riding model with C—H = 0.98 Å.

Figures

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.

Crystal data

[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

Data collection

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

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)

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	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)

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.