Crystal structure of poly[[μ-4-(hy­droxy­meth­yl)pyridine-κ2 N:O][4-(hy­droxy­meth­yl)pyridine-κN](μ-thio­cyanato-κ2 N:S)(thio­cyanato-κN)cadmium]

Julia Werner; Inke Jess; Christian Näther

doi:10.1107/S2056989015008890

. 2015 May 13;71(Pt 6):m129–m130. doi: 10.1107/S2056989015008890

Crystal structure of poly[[μ-4-(hydroxymethyl)pyridine-κ² N:O][4-(hydroxymethyl)pyridine-κN](μ-thiocyanato-κ² N:S)(thiocyanato-κN)cadmium]

Julia Werner ^a,^*, Inke Jess ^a, Christian Näther ^a

PMCID: PMC4459314 PMID: 26090166

Abstract

The crystal structure of the title compound, [Cd(NCS)₂(C₆H₇NO)₂]_n is made up of Cd²⁺ cations that are coordinated by three thiocyanate ligands and three 4-(hydroxymethyl)pyridine ligands within distorted N₄OS octahedra. The asymmetric unit consists of one Cd²⁺ cation, two thiocyanate anions and two 4-(hydroxymethyl)pyridine ligands in general positions. Two Cd²⁺ cations are linked by two μ-1,3 N- and S-bonding thioycanate anions into dimers which are further linked into branched chains along [100] by two μ-1,6 N- and O-bonding 4-(hydroxymethyl)pyridine ligands. One additional N-bonded 4-(hydroxymethyl)pyridine ligand and one additional N-bonded thiocyanate anion are only terminally bonded to the metal cation. Interchain O—H⋯S hydrogen bonds between the hydroxy H atoms and one of the thiocyanate S atoms connect the chains into a three-dimensional network.

Keywords: crystal structure, coordination polymer, cadmium, octahedral coordination, hydrogen bonding

Related literature

For similar structures with thiocyanate anions in bridging coordination to cadmium, see: Banerjee et al. (2005 ▸); Tahli et al. (2011 ▸). graphic file with name e-71-0m129-scheme1.jpg

Experimental

Crystal data

[Cd(NCS)₂(C₆H₇NO)₂]
M _r = 446.81
Monoclinic,
a = 10.9124 (3) Å
b = 20.3261 (6) Å
c = 7.9722 (2) Å
β = 105.965 (2)°
V = 1700.08 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.54 mm⁻¹
T = 200 K
0.47 × 0.33 × 0.20 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED 32; Stoe, 2008 ▸) T _min = 0.526, T _max = 0.672
25370 measured reflections
3597 independent reflections
3259 reflections with I > 2σ(I)
R _int = 0.063

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.058
S = 1.12
3597 reflections
245 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Data collection: X-AREA (Stoe, 2008 ▸); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ▸); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▸) and DIAMOND (Brandenburg, 1999 ▸); software used to prepare material for publication: publCIF (Westrip, 2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015008890/wm5156sup1.cif

e-71-0m129-sup1.cif^{(856.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015008890/wm5156Isup2.hkl

e-71-0m129-Isup2.hkl^{(287.1KB, hkl)}

Click here for additional data file.^{(724.5KB, tif)}

x y z x y z . DOI: 10.1107/S2056989015008890/wm5156fig1.tif

Part of the crystal structure of the title compound with labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) −x + 2, −y + 1, −z + 1.]

Click here for additional data file.^{(1.3MB, tif)}

. DOI: 10.1107/S2056989015008890/wm5156fig2.tif

Crystal structure of the title compound in a view approximately along [001]. Intermolecular O—H⋯S hydrogen bonding is shown as dashed lines; the disordered pyridine rings are omitted for clarity.

CCDC reference: 1063786

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O11H11OS1ⁱ	0.84	2.49	3.330(2)	174
O21H21OS1ⁱⁱ	0.84	2.42	3.2410(18)	164

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

Acknowledgments

We gratefully acknowledge financial support by the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

supplementary crystallographic information

S1. Synthesis and crystallization

CdSO₄·3/8H₂O was purchased from Merck and 4-(hydroxymethyl)pyridine and Ba(NCS)₂·3H₂O were purchased from Alfa Aesar. Cd(NCS)₂ was synthesized by stirring 17.5 g (57.0 mmol) Ba(NCS)₂·3H₂O and 14.6 g (57.0 mmol) CdSO₄·3/8H₂O in 300 ml water at RT for three hours. The white residue of BaSO₄ was filtered off and dried at 353 K. The homogeneity of the product was checked by X-ray powder diffraction and elemental analysis. The title compound was prepared by the reaction of 34.3 mg (0.15 mmol) Cd(NCS)₂ and 32.7 mg (0.30 mmol) 4-(hydroxymethyl)pyridine in 1.5 ml methanol at RT. After one week suitable crystals of the title compound were obtained.

S2. Refinement

The carbon-bound hydrogen atoms were positioned with idealized geometry and were refined with U_iso(H) = 1.2U_eq(C) using a riding model with C—H = 0.95 Å for aromatic and C—H = 0.99 Å for methylene H atoms. The oxygen-bound hydrogen atoms were located in a difference map. For the non-coordinating hydroxyl group the H atom was positioned with idealized geometry allowed to rotate but not to tip, and for the coordinating hydroxyl group its bond length was set to an ideal value of 0.84 Å. Finally, these H atoms were refined with U_iso(H) = 1.5U_eq(O) using a riding model. The pyridine ring of one of the 4-(hydroxymethyl)pyridine ligands is disordered and was refined using a split model in two orientations with an occupancy ratio of 0.46:0.54.