Synthesis, crystal structure, infrared spectroscopy and Hirshfeld surface analysis of cis-(thiocyanato-κN)(1,4,8,11-tetraazacyclotetradecane-κN 4)chromium(III)(μ-1,3-thiocyanato-κN,S)trichloridozincate

The crystal structure of cis-[Cr(NCS)(cyclam)(mu-NCS)ZnCl3] (cyclam = 1,4,8,11-tetraazacyclotetradecane, C10H24N4) was determined using synchrotron radiation at 100 K. The chromium(III) ion is coordinated by four N atoms of cyclam and two N-bonded NCS groups in a cis arrangement, displaying a distorted octahedral geometry while the coordination sphere of the zinc(II) ion is bonded by three Cl ions and one S atom from bridged thiocyanate group with a slightly distorted tetrahedral environment. One thiocyanato group N6-C12-S2 forms a mu-1,3-NCS bridge between Cr and Zn ions. The Cr-N(cyclam) bond lengths are in the range of 2.076(2) to 2.086(2) angstrom while mean Cr-N(NCS) and Zn-S(SCN) bond lengths are 1.997(2) and 2.3819(16) angstrom. The [Cr(NCS)(2)(cyclam)](+) moiety in the complex adopts the cis-V configuration. The crystal structure is stabilized by intermolecular hydrogen bonds involving the cyclam N-H or C-H groups as donors and Cl ions of the ZnCl3(SCN) unit or S atoms of NCS groups as acceptors. Hirshfeld surface analysis indicated that the H center dot center dot center dot Cl/Cl center dot center dot center dot H (36.1%), H center dot center dot center dot H (24.8%), H center dot center dot center dot S/S center dot center dot center dot H (23.8%) and H center dot center dot center dot C/C center dot center dot center dot H (5.2%) interactions contributed most importantly to the crystal packing. Infrared (IR) spectroscopic properties were also described.

Automated summary

The crystal structure of cis-[Cr(NCS)(cyclam)(mu-NCS)ZnCl3] was determined, showing a distorted octahedral geometry for the chromium(III) ion coordinated by cyclam and NCS groups, and a slightly distorted tetrahedral environment for the zinc(II) ion coordinated by Cl ions and a bridged thiocyanate group. The crystal packing is stabilized by intermolecular hydrogen bonds, with H···Cl/Cl···H, H···H, H···S/S···H, and H···C/C···H interactions playing important roles.