Crystallographic study of self-organization in the solid state including quasi-aromatic pseudo-ring stacking interactions in 1-benzoyl-3-(3,4-dimethoxyphenyl)thiourea and 1-benzoyl-3-(2-hydroxypropyl)thiourea

Abstract

1-Benzoylthioureas contain both carbonyl and thiocarbonyl functional groups and are of interest for their biological activity, metal coordination ability and involvement in hydrogen-bond formation. Two novel 1-benzoylthiourea derivatives, namely 1-benzoyl-3-(3,4-dimethoxyphenyl)thiourea, CHNOS, (I), and 1-benzoyl-3-(2-hydroxypropyl)thiourea, CHNOS, (II), have been synthesized and characterized. Compound (I) crystallizes in the space group P-1, while (II) crystallizes in the space group P2/c. In both structures, intramolecular N-H...O hydrogen bonding is present. The resulting six-membered pseudo-rings are quasi-aromatic and, in each case, interact with phenyl rings via stacking-type interactions. C-H...O, C-H...S and C-H...π interactions are also present. In (I), there is one molecule in the asymmetric unit. Pairs of molecules are connected via two intermolecular N-H...S hydrogen bonds, forming centrosymmetric dimers. In (II), there are two symmetry-independent molecules that differ mainly in the relative orientations of the phenyl rings with respect to the thiourea cores. Additional strong hydrogen-bond donor and acceptor -OH groups participate in the formation of intermolecular N-H...O and O-H...S hydrogen bonds that join molecules into chains extending in the [001] direction.

Novel tetrahedral cobalt(ii) silanethiolates: structures and magnetism

“…The angles on Co(II) ion are in the range of 99.22(3)-128.000 (14) (Table S2, ESI †) signalizing some deviations from the ideal tetrahedron conrmed by geometric parameters s 4 ¼ 0.82 and s 0 4 ¼ 0:78. 23,24 However these deviations do not inuence on the Co-N and Co-S bond distances which are generally in agreement with those of the previously reported tetrahedral cobalt silanethiolates (Table S2, ESI †). [15][16][17][18][19][20][21] The spatial arrangement of all ligands around metallic center enables the formation of two intramolecular N ppd -H/O silanethiolate hydrogen bonds with Nbonded hydrogen atom of piperidine ring and (tBuO) 3 SiS À residues (Fig.…”

“…16,17,19,[25][26][27][28][29] Co(II) based angles in 2 vary from 102.31 (11) to 119.34(5) (Table S2, ESI †) indicating some distortions of tetrahedral geometry veri-ed by s 4 and s 0 4 (Table S4 †). 23,24 Nonetheless, the distortion are Scheme 1 Synthesized complexes 1-3.…”

S,O or S,N Coordination? Unraveling the Coordination Modes of Arenesulfonylthiourea Ligands

“…The NHC­(S)­NH unit is planar, with the NHEt moiety rotated such that the NH proton forms an intramolecular hydrogen bond with the oxygen atom of the sulfonyl group (NH···O = 2.08 Å), resulting in an E / Z -configuration of the molecule. Similar H bonds with distances ranging from 1.81 to 2.05 Å are often found in the solid-state structures of E / Z -configured 3-monosubstituted 1-acylthioureas . The two independent molecules in the asymmetric unit are joined together by intermolecular NH···S bonds between the thione sulfur atom and the NH proton adjacent to the sulfonyl group.…”

“…Similar H bonds with distances ranging from 1.81 to 2.05 Å are often found in the solid-state structures of E/Z-configured 3-monosubstituted 1-acylthioureas. 25 The two independent molecules in the asymmetric unit are joined together by intermolecular NH•••S bonds between the thione sulfur atom and the NH proton adjacent to the sulfonyl group. We subsequently examined the reaction of PhSO 2 NHC(S)-NHEt with Ni(OAc) 2 in MeOH, which resulted in rapid formation of X-ray-quality grayish plates.…”