Crystal structure of catena-poly[[bis(N-acethylthiomorpholine-κS)copper(I)]-μ-iodido]

In the title compound, the CuI atom is coordinated by two S atoms and two I atoms in a distorted tetrahedral mode.


Chemical context
Synthesis, structures and luminescence properties of copper(I) complexes involving CuI and thioethers as co-ligands have been studied extensively Knorr et al., 2010;Henline et al., 2014). The tendency of copper(I) iodide to form aggregates often leads to short Cu-Cu bonds and intriguing diversities in the respective crystal structures (Peng et al., 2010), comprising of [CuI] n chains with split stair motifs (Moreno et al., 1995;Blake et al., 1999;Cariati et al., 2002;Nä ther et al., 2003;Thé bault et al., 2006), zigzag chains (Munakata et al., 1997) or helical chains (Munakata et al., 1997;Kang & Anson, 1995). Most of these structures include aromatic nitrogen donor co-ligands. In this context we have studied the interaction of N-acetylthiomorpholine with CuI to investigate the coordination behaviour of the copper(I) atom with the S donor atom of the N-acetylthiomorpholine coligand, because both are soft atoms in the sense of the HSAB concept. Although a number of copper(I) complexes with thioether ligands are known Henline et al., 2014), to the best of our knowledge, a [CuI] n chain structure has not been reported until now. Herein, we report a copper(I) coordination polymer with a zigzag chain [CuI] n , resulting from the reaction of CuI with N-acetylthiomorpholine (L).

Structural commentary
The asymmetric unit of the title compound, [CuI(L) 2 ] n , comprises of a copper(I) iodide moiety and two N-acetylthiomorpholine co-ligands (L A and L B ) and is shown in Fig. 1. The Cu I atom has a slightly distorted tetrahedral environment ( Table 1). The two thiomorpholine rings have the stable chair conformation (Kang et al., 2015). The dihedral angles between acetyl CCO and thiomorpholine CNC planes are 3.9 (4) and 6.6 (2) for L A and L B , respectively. The I atoms link neighboring Cu I atoms in a 2 -bridging mode into polymeric zigzag chains extending parallel to [010] (Fig. 2).

Supramolecular features
As shown in Fig. 3, C10-H10AÁ Á Á O1 hydrogen bonds (yellow dashed lines) between the thiomorpholine ring of L B and the carbonyl oxygen atoms of L A result in a layered network parallel to (101). Additional C12-H12BÁ Á ÁO2 hydrogen bonds between methyl groups of L B ligands and carbonyl oxygen atoms of neighbouring L B ligands (red dashed lines) form cyclic centrosymmetric dimers of Nacetylthiomorpholines. The combination of the [CuI] n chains and the two types of hydrogen-bonding interactions with additional C-HÁ Á ÁO interactions (Table 2) leads to a threedimensional network.

Synthesis and crystallization
Preparation of N-acetylthiomorpholine (L) Thiomorpholine (1.03 g, 0.010 mol) and triethylamine (1.03 g, 0.010 mol) in chloroform (20 mL) were placed in a one-neck round-bottomed flask and kept at 273 K. Then, acetic anhydride (1.02 g, 0.010 mol) was added dropwise. The reactant mixture was stirred for approximately one day. The The asymmetric unit of the title compound, shown with displacement ellipsoids drawn at the 50% probability level. H atom are shown as small spheres of arbitrary radius. Table 1 Selected geometric parameters (Å , ).

catena-poly[[Bis(N-acethylthiomorpholine-κS)copper(I)]-µ-iodido]
Crystal data Special details 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.