catena-Poly[[bis­[[bis­(3-amino­prop­yl)amine-κ3 N,N′,N′′](thio­cyanato-κN)cadmium]-μ4-sulfato-κ4 O,O:O′,O′] methanol hemisolvate]

Jan Boeckmann; Christian Näther

doi:10.1107/S1600536811031163

. 2011 Aug 6;67(Pt 9):m1201–m1202. doi: 10.1107/S1600536811031163

catena-Poly[[bis[[bis(3-aminopropyl)amine-κ³ N,N′,N′′](thiocyanato-κN)cadmium]-μ₄-sulfato-κ⁴ O,O:O′,O′] methanol hemisolvate]

Jan Boeckmann ^a,^*, Christian Näther ^a

PMCID: PMC3200697 PMID: 22058845

Abstract

The asymmetric unit of the title compound, {[Cd₂(NCS)₂(SO₄)(C₆H₁₇N₃)₂]·0.5CH₃OH}_n, consists of two Cd²⁺ cations, two thiocyanate and one sulfate anion, two bis(3-aminopropyl)amine co-ligands and one methanol molecule with half-occupancy. Each Cd²⁺ cation is coordinated by four N atoms of one terminal N-bonded thiocyanate anion and one bis(3-aminopropyl)amine co-ligand, and by two O atoms of two symmetry-related sulfate anions, defining a slightly distorted octahedral coordination polyhedron. Each two Cd²⁺ cations are connected into dimers, which are located on centres of inversion and which are further μ-1,1:3,3-bridged via the sulfate anions into polymeric zigzag chains along the a axis.

Related literature

For background information about thermal decomposition reactions and the resulting intermediates, see: Boeckmann & Näther (2010 ▶, 2011 ▶); Boeckmann et al. (2011 ▶); Wöhlert et al. (2011 ▶); Wriedt et al. (2009a ▶,b ▶); Wriedt & Näther (2010 ▶).

Experimental

Crystal data

[Cd₂(NCS)₂(SO₄)(C₆H₁₇N₃)₂]·0.5CH₄O
M _r = 715.49
Triclinic,
a = 10.6648 (9) Å
b = 12.4441 (12) Å
c = 12.9240 (12) Å
α = 61.359 (10)°
β = 69.064 (10)°
γ = 68.772 (10)°
V = 1367.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.82 mm⁻¹
T = 200 K
0.18 × 0.13 × 0.09 mm

Data collection

STOE IPDS-1 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ▶) T _min = 0.746, T _max = 0.841
12730 measured reflections
5736 independent reflections
4365 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.113
S = 1.07
5736 reflections
301 parameters
H-atom parameters constrained
Δρ_max = 1.07 e Å⁻³
Δρ_min = −0.87 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 in SHELXTL (Sheldrick, 2008 ▶) and DIAMOND (Brandenburg, 2011 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811031163/bt5596sup1.cif

e-67-m1201-sup1.cif^{(22.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811031163/bt5596Isup2.hkl

e-67-m1201-Isup2.hkl^{(280.8KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cd1—N11	2.248 (4)
Cd1—N13	2.250 (5)
Cd1—N1	2.347 (5)
Cd1—N12	2.351 (5)
Cd1—O1ⁱ	2.388 (3)
Cd1—O1	2.619 (3)
Cd2—N23	2.247 (5)
Cd2—N21	2.250 (5)
Cd2—N2	2.283 (6)
Cd2—N22	2.374 (4)
Cd2—O3	2.386 (3)
Cd2—O3ⁱⁱ	2.676 (4)

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

We gratefully acknowledge financial support by the DFG (project number NA 720/3–1) and the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities. Special thanks go to Inke Jess for her support of the single-crystal measurements.

supplementary crystallographic information

Comment

Recently, we reported about the thermal decomposition reaction as a tool for the selective synthesis of one-dimensional and two-dimensional coordination compounds [Boeckmann & Näther (2010); Boeckmann & Näther (2011); Boeckmann et al. (2011); Wöhlert et al. (2011); Wriedt et al. (2009a,b); Wriedt & Näther (2010)]. In this approach precursors based on paramagnetic transition metal thio- and selenocyanates and bidentate and monodentate N-donor co-ligands are heated leading to a stepwise loss of the neutral co-ligands and the formation of higher condensed networks with modified magnetic exchange interactions. Unfortunately, structure determination of the ligand-deficient intermediates is very often difficult to achieve because most of them can only prepared by thermal decomposition which leads to powders of very poor crystallinity. This problem can be overcome by preparing similar compounds based on cadmium(II) thio- and selenocyanates, which can easily be crystallized from solution and which are very often isotypic to their paramagnetic counterparts. In this case the structures of the paramagnetic intermediates can simply be determined using the Rietveld method. In this connection, we tried to prepare a ligand-deficient intermediate on the basis of Cd(NCS)₂ and the tridentate co-ligand bis(3-aminopropyl)amine. Surprisingly a mixed anionic chain structure was obtained which was characterized by single crystal X-ray diffraction.

In the crystal structure of the title compound the cadmium(II) cations are coordinated by four nitrogen atoms of one terminal N-bonded thiocyanato anion, one tridentate co-ligand bis(3-aminopropyl)amine and two oxygen atoms of two symmetry related sulfate anions within a slightly distorted octahedral coordination geometry (Fig.1 and Tab.1). One of the Cd-O distances to Cd2 of 2.676 (4) Å is slightly elongated. These octahedra are bridged via the sulfur oxygen atoms into dimeric Cd²⁺ units that are located on centers of inversion. These units are further connected into zigzag chains that elongate in the direction of the crystallographic a axis (Fig.2).

Experimental

The title compound was prepared by the reaction of 128.2 mg CdSO₄^.8/3H₂O (0.50 mmol), 153.8 mg Ba(NCS)₂^.3H₂O (0.50 mmol) and 35.2 µL bis(3-aminopropyl)amine (0.25 mmol) in 1.50 ml methanol at RT in a closed 3 ml snap cap vial. After two days colourless blocks of the title compound were obtained.