catena-Poly[[bis­(3-acetyl­pyridine-κN)cadmium]-di-μ-seleno­cyanato-κ2N:Se;κ2Se:N]

Werner, J.; Boeckmann, J.; Jess, I.; Näther, C.

doi:10.1107/S1600536812018375

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page m704

doi:10.1107/S1600536812018375

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catena-Poly[[bis(3-acetylpyridine-κN)cadmium]-di-μ-selenocyanato-κ²N:Se;κ²Se:N]

Julia Werner,^a ^* Jan Boeckmann,^a Inke Jess ^a and Christian Näther ^a

^aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth-Strasse 2, 24118 Kiel, Germany
^*Correspondence e-mail: jwerner@ac.uni-kiel.de

(Received 23 April 2012; accepted 24 April 2012; online 28 April 2012)

In the crystal structure of the title compound, [Cd(NCSe)₂(C₇H₇NO)₂]_n, the Cd²⁺ cation is coordinated by two 3-acetylpyridine ligands and four μ-1,3-bridging selenocyanate anions within a slightly distorted CdN₄Se₂ octahedron. The asymmetric units consists of one Cd²⁺ cation, which is situated on a center of inversion, as well as one selenocyanate anion and one 3-acetylpyridine ligand in general positions. The metal cations are μ-1,3-bridged via the selenocyanate anions into chains along the a axis.

Related literature

For general background information including details on thermal decomposition reactions and magnetic properties of the precursor and μ-1,3 bridging compounds, see: Näther & Greve (2003 ); Boeckmann & Näther (2010 , 2011 ); Wöhlert et al. (2011 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

[Cd(NCSe)₂(C₇H₇NO)₂]
M_r = 564.63
Monoclinic, P 2₁ /c
a = 5.9447 (3) Å
b = 18.7233 (10) Å
c = 8.7548 (5) Å
β = 94.020 (4)°
V = 972.05 (9) Å³
Z = 2
Mo Kα radiation
μ = 4.88 mm⁻¹
T = 293 K
0.16 × 0.07 × 0.02 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ) T_min = 0.667, T_max = 0.902
17180 measured reflections
2458 independent reflections
2256 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.061
S = 1.13
2458 reflections
117 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.47 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 (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011 ); software used to prepare material for publication: publCIF (Westrip, 2010).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812018375/bt5897sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812018375/bt5897Isup2.hkl

checkCIF report

Comment top

The title compound was prepared within a project on the synthesis and the magnetic properties of paramagnetic transition metal thio- and selenocyanato coordination polymers in which the metal cations are µ-1,3 bridged by the anionic ligands (Näther & Greve, 2003, Boeckmann & Näther, 2010, 2011 and Wöhlert et al., 2011). In this context, also the corresponding compounds based on diamagnetic cadmium are of interest, because they are structural analogs of the paramagnetic compounds. In the course of systematic investigations crystals of the title compound were prepared and characterized by single crystal X-ray diffraction.

In the crystal structure of the title compound, the cadmium(II) cations each are coordinated by two nitrogen atoms of two terminal N-bonded 3-acetylpyridine and two nitrogen and two selenium atoms of µ-1,3 bridging selenocyanato anions (Fig. 1). The coordination polyhedron of the Cd cations can be described as a slightly distorted octahedra with the Cd cation located on a centre of inversion.

The Cd²⁺ cations are µ-1,3 bridged by selenocyanato anions into chains, which elongate in the direction of the crystallographic a axis (Fig. 2). The Cd···Cd intrachain distance amounts to 5.9447 (3) Å and the shortest interchain Cd···Cd distance amounts to 8.7548 (5) Å. It must be noted that according to a search in the CCDC database (ConQuest Ver.1.14.2012) (Allen, 2002) coordination compounds based on metal selenocyanates and 3-acetylpyridine are unknown.

Related literature top

For general background information including details on thermal decomposition reactions and magnetic properties of the precurser and µ-1,3 bridging compounds, see: Näther & Greve (2003); Boeckmann & Näther (2010, 2011); Wöhlert et al. (2011). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

Potassium selenocyanate and 3-acetylpyridine were purchased from Alfa Aesar, Cd(NO₃)₂.4H₂O were obtained from Merck. The title compound was prepared by the reaction of 77.1 mg Cd(NO₃)₂.4H₂O (0.25 mmol), 64.8 mg KSeCN (0.45 mmol) and 109 µL 3-acetylpyridine (1.00 mmol) in 1.5 mL H₂O at RT in a closed 3 ml snap cap vial. After several days colourless needles of the title compound were obtained.

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: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: 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 code: i = -x,-y+1,-z, ii = x-1, y, z, iii = -x+1, -y+1, -z
	Fig. 2. : Crystal structure of the title compound with view of the chains that elongate in the direction of the crystallographic a axis.

catena-Poly[[bis(3-acetylpyridine-κN)cadmium]-di-µ- selenocyanato-κ²N:Se;κ²Se:N] top

Crystal data top

[Cd(NCSe)₂(C₇H₇NO)₂]	F(000) = 540
M_r = 564.63	D_x = 1.929 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 17180 reflections
a = 5.9447 (3) Å	θ = 2.2–28.6°
b = 18.7233 (10) Å	µ = 4.88 mm⁻¹
c = 8.7548 (5) Å	T = 293 K
β = 94.020 (4)°	Needle, colourless
V = 972.05 (9) Å³	0.16 × 0.07 × 0.02 mm
Z = 2

Data collection top

Stoe IPDS-2 diffractometer	2458 independent reflections
Radiation source: fine-focus sealed tube	2256 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
ω scans	θ_max = 28.6°, θ_min = 2.2°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −7→7
T_min = 0.667, T_max = 0.902	k = −25→25
17180 measured reflections	l = −11→11

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)] = 0.031	H-atom parameters constrained
wR(F²) = 0.061	w = 1/[σ²(F_o²) + (0.0164P)² + 1.1235P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max = 0.001
2458 reflections	Δρ_max = 0.47 e Å⁻³
117 parameters	Δρ_min = −0.47 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0074 (5)

Crystal data top

[Cd(NCSe)₂(C₇H₇NO)₂]	V = 972.05 (9) Å³
M_r = 564.63	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.9447 (3) Å	µ = 4.88 mm⁻¹
b = 18.7233 (10) Å	T = 293 K
c = 8.7548 (5) Å	0.16 × 0.07 × 0.02 mm
β = 94.020 (4)°

Data collection top

Stoe IPDS-2 diffractometer	2458 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	2256 reflections with I > 2σ(I)
T_min = 0.667, T_max = 0.902	R_int = 0.045
17180 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.061	H-atom parameters constrained
S = 1.13	Δρ_max = 0.47 e Å⁻³
2458 reflections	Δρ_min = −0.47 e Å⁻³
117 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cd1	0.0000	0.5000	0.0000	0.03766 (9)
N1	0.3333 (4)	0.44388 (15)	0.0928 (3)	0.0478 (6)
C1	0.5139 (4)	0.43756 (15)	0.1480 (3)	0.0377 (6)
Se1	0.79466 (5)	0.429324 (18)	0.23721 (4)	0.04545 (11)
N11	0.0930 (4)	0.60142 (13)	0.1566 (3)	0.0422 (5)
O11	0.5790 (6)	0.72219 (18)	0.5227 (4)	0.1005 (13)
C11	0.2729 (5)	0.60423 (17)	0.2585 (3)	0.0430 (6)
H11	0.3604	0.5633	0.2736	0.052*
C12	0.3348 (5)	0.66449 (16)	0.3420 (4)	0.0442 (7)
C13	0.2032 (6)	0.72501 (18)	0.3206 (5)	0.0592 (9)
H13	0.2402	0.7666	0.3746	0.071*
C14	0.0168 (7)	0.72283 (19)	0.2183 (5)	0.0675 (11)
H14	−0.0757	0.7626	0.2034	0.081*
C15	−0.0302 (6)	0.66083 (17)	0.1387 (4)	0.0533 (8)
H15	−0.1548	0.6602	0.0683	0.064*
C16	0.5372 (6)	0.6672 (2)	0.4547 (4)	0.0570 (9)
C17	0.6815 (6)	0.6032 (2)	0.4794 (4)	0.0632 (10)
H17A	0.8070	0.6144	0.5503	0.095*
H17B	0.7360	0.5884	0.3837	0.095*
H17C	0.5951	0.5653	0.5202	0.095*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.02405 (13)	0.04299 (16)	0.04447 (17)	−0.00160 (10)	−0.00794 (10)	−0.00268 (12)
N1	0.0285 (11)	0.0554 (15)	0.0583 (17)	0.0002 (10)	−0.0059 (11)	0.0068 (12)
C1	0.0305 (13)	0.0398 (14)	0.0425 (15)	0.0013 (10)	0.0002 (11)	0.0028 (11)
Se1	0.02761 (14)	0.0576 (2)	0.04962 (19)	0.00067 (12)	−0.00791 (11)	0.01084 (14)
N11	0.0365 (12)	0.0447 (13)	0.0439 (14)	−0.0023 (10)	−0.0074 (10)	0.0003 (10)
O11	0.088 (2)	0.082 (2)	0.123 (3)	0.0018 (18)	−0.053 (2)	−0.043 (2)
C11	0.0372 (14)	0.0447 (15)	0.0457 (16)	−0.0003 (12)	−0.0075 (12)	−0.0022 (12)
C12	0.0418 (15)	0.0442 (15)	0.0453 (16)	−0.0047 (12)	−0.0064 (12)	−0.0030 (12)
C13	0.067 (2)	0.0412 (17)	0.066 (2)	−0.0009 (15)	−0.0177 (18)	−0.0074 (15)
C14	0.074 (2)	0.0444 (18)	0.079 (3)	0.0125 (17)	−0.029 (2)	−0.0031 (17)
C15	0.0510 (18)	0.0498 (18)	0.056 (2)	−0.0003 (14)	−0.0182 (15)	0.0033 (14)
C16	0.0466 (18)	0.061 (2)	0.062 (2)	−0.0043 (15)	−0.0136 (15)	−0.0132 (16)
C17	0.0481 (19)	0.080 (3)	0.058 (2)	0.0041 (18)	−0.0163 (16)	−0.0063 (19)

Geometric parameters (Å, º) top

Cd1—N1ⁱ	2.337 (2)	C11—H11	0.9300
Cd1—N1	2.337 (2)	C12—C13	1.382 (5)
Cd1—N11	2.384 (2)	C12—C16	1.502 (4)
Cd1—N11ⁱ	2.384 (2)	C13—C14	1.376 (5)
Cd1—Se1ⁱⁱ	2.8124 (3)	C13—H13	0.9300
Cd1—Se1ⁱⁱⁱ	2.8124 (3)	C14—C15	1.373 (5)
N1—C1	1.152 (4)	C14—H14	0.9300
C1—Se1	1.799 (3)	C15—H15	0.9300
Se1—Cd1^iv	2.8124 (3)	C16—C17	1.481 (5)
N11—C15	1.335 (4)	C17—H17A	0.9600
N11—C11	1.345 (3)	C17—H17B	0.9600
O11—C16	1.206 (4)	C17—H17C	0.9600
C11—C12	1.380 (4)

N1ⁱ—Cd1—N1	180.00 (12)	C12—C11—H11	118.2
N1ⁱ—Cd1—N11	89.92 (9)	C11—C12—C13	118.1 (3)
N1—Cd1—N11	90.08 (9)	C11—C12—C16	123.2 (3)
N1ⁱ—Cd1—N11ⁱ	90.08 (9)	C13—C12—C16	118.7 (3)
N1—Cd1—N11ⁱ	89.92 (9)	C14—C13—C12	119.1 (3)
N11—Cd1—N11ⁱ	180.0	C14—C13—H13	120.5
N1ⁱ—Cd1—Se1ⁱⁱ	86.16 (7)	C12—C13—H13	120.5
N1—Cd1—Se1ⁱⁱ	93.84 (7)	C15—C14—C13	118.8 (3)
N11—Cd1—Se1ⁱⁱ	87.41 (6)	C15—C14—H14	120.6
N11ⁱ—Cd1—Se1ⁱⁱ	92.59 (6)	C13—C14—H14	120.6
N1ⁱ—Cd1—Se1ⁱⁱⁱ	93.84 (7)	N11—C15—C14	123.7 (3)
N1—Cd1—Se1ⁱⁱⁱ	86.16 (7)	N11—C15—H15	118.2
N11—Cd1—Se1ⁱⁱⁱ	92.59 (6)	C14—C15—H15	118.2
N11ⁱ—Cd1—Se1ⁱⁱⁱ	87.41 (6)	O11—C16—C17	121.4 (3)
Se1ⁱⁱ—Cd1—Se1ⁱⁱⁱ	180.0	O11—C16—C12	118.8 (3)
C1—N1—Cd1	159.1 (3)	C17—C16—C12	119.8 (3)
N1—C1—Se1	178.7 (3)	C16—C17—H17A	109.5
C1—Se1—Cd1^iv	94.39 (9)	C16—C17—H17B	109.5
C15—N11—C11	116.7 (3)	H17A—C17—H17B	109.5
C15—N11—Cd1	119.5 (2)	C16—C17—H17C	109.5
C11—N11—Cd1	123.7 (2)	H17A—C17—H17C	109.5
N11—C11—C12	123.6 (3)	H17B—C17—H17C	109.5
N11—C11—H11	118.2

Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z; (iii) x−1, y, z; (iv) x+1, y, z.

Experimental details

Crystal data
Chemical formula	[Cd(NCSe)₂(C₇H₇NO)₂]
M_r	564.63
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	5.9447 (3), 18.7233 (10), 8.7548 (5)
β (°)	94.020 (4)
V (Å³)	972.05 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.88
Crystal size (mm)	0.16 × 0.07 × 0.02

Data collection
Diffractometer	Stoe IPDS2 diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)
T_min, T_max	0.667, 0.902
No. of measured, independent and observed [I > 2σ(I)] reflections	17180, 2458, 2256
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.674

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.061, 1.13
No. of reflections	2458
No. of parameters	117
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.47

Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011), publCIF (Westrip, 2010).

Acknowledgements

We gratefully acknowledge financial support by the DFG (project No. NA 720/3–1) and the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Boeckmann, J. & Näther, C. (2010). Dalton Trans. 39, 11019-11026. Web of Science CSD CrossRef CAS PubMed Google Scholar
Boeckmann, J. & Näther, C. (2011). Chem. Commun. 47, 7104–7106. Web of Science CSD CrossRef CAS Google Scholar
Brandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Näther, C. & Greve, J. (2003). J. Solid State Chem., 176, 259–265. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wöhlert, S., Boeckmann, J., Wriedt, M. & Näther, C. (2011). Angew. Chem. Int. Ed. 50, 6920-6923. Google Scholar

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