TY - JOUR

T1 - L-Cysteine Oxalates with Dimeric and Trimeric Cations

AU - Ghazaryan, V. V.

AU - Giester, G.

AU - Minkov, V. S.

AU - Boldyreva, E. V.

AU - Petrosyan, A. M.

N1 - This work was supported by the RA MES State Committee of Science and Russian Foundation for Basic Research (RF) in the frames of the joint research projects SCS 15RF-007 and RFBR 15-53-05023. This work was supported also in part by a research grant matsc-3822 from the Armenian National Science and Education Fund (ANSEF) based in New York, USA.

PY - 2024

Y1 - 2024

N2 - Abstract: Single crystals of two new compounds, (L-CysH⋯L-Cys)(HC2O4) (I) and (L-CysH⋯L-Cys⋯L-CysH)(HC2O4)2·0.5H2O (II), were obtained. Crystal structures were solved and refined using single-crystal X-ray diffraction, and compared with the previously known orthorhombic and monoclinic modifications of the simple salt (L-CysH)(HC2O4). Compound I crystallizes in the triclinic crystal system (space group P1, Z = 2) and contains (L-CysH⋯L-Cys) dimeric cations with very short O⋯O interatomic distance of 2.434(2) Å. Hydrogen oxalate anions form head-to-tail type chains with very short hydrogen bonds, characterized by O⋯O distances of 2.422(2) Å and 2.417(3) Å. The crystal lattice of II is monoclinic with the space group C2, Z = 4. It contains a new type of cation, that has never been observed before for cysteine salts, i.e. trimeric (L-CysH⋯L-Cys⋯L-CysH) cation. Protonated L-cysteinium cations are connected to the zwitterionic L-cysteine moiety through the same oxygen atom of the carboxylate group via hydrogen bonds, with O···O distances of 2.6410(18) Å and 2.4888(19) Å. Similar to the structure I, the hydrogen oxalate anions form head-to-tail type chains linked by short hydrogen bonds with O⋯O distances of 2.4369(17) Å and 2.4330(17) Å, respectively. The crystals were characterized by IR and Raman spectroscopy. The batches obtained on crystallization were also characterized by X-ray powder diffraction, in order to check the phase purity of all the sample.

AB - Abstract: Single crystals of two new compounds, (L-CysH⋯L-Cys)(HC2O4) (I) and (L-CysH⋯L-Cys⋯L-CysH)(HC2O4)2·0.5H2O (II), were obtained. Crystal structures were solved and refined using single-crystal X-ray diffraction, and compared with the previously known orthorhombic and monoclinic modifications of the simple salt (L-CysH)(HC2O4). Compound I crystallizes in the triclinic crystal system (space group P1, Z = 2) and contains (L-CysH⋯L-Cys) dimeric cations with very short O⋯O interatomic distance of 2.434(2) Å. Hydrogen oxalate anions form head-to-tail type chains with very short hydrogen bonds, characterized by O⋯O distances of 2.422(2) Å and 2.417(3) Å. The crystal lattice of II is monoclinic with the space group C2, Z = 4. It contains a new type of cation, that has never been observed before for cysteine salts, i.e. trimeric (L-CysH⋯L-Cys⋯L-CysH) cation. Protonated L-cysteinium cations are connected to the zwitterionic L-cysteine moiety through the same oxygen atom of the carboxylate group via hydrogen bonds, with O···O distances of 2.6410(18) Å and 2.4888(19) Å. Similar to the structure I, the hydrogen oxalate anions form head-to-tail type chains linked by short hydrogen bonds with O⋯O distances of 2.4369(17) Å and 2.4330(17) Å, respectively. The crystals were characterized by IR and Raman spectroscopy. The batches obtained on crystallization were also characterized by X-ray powder diffraction, in order to check the phase purity of all the sample.

KW - crystal structure

KW - dimeric cations

KW - oxalates

KW - salts of L-cysteine

KW - trimeric cations

KW - very strong hydrogen bonds

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85209823761&origin=inward&txGid=236e88b3e7e89101f5b3e83d701dce1f

UR - https://www.mendeley.com/catalogue/a8089e95-4cc5-3730-a2c6-7e84d408b72e/

U2 - 10.1134/S0022476624100172

DO - 10.1134/S0022476624100172

M3 - Article

VL - 65

SP - 2088

EP - 2100

JO - Journal of Structural Chemistry

JF - Journal of Structural Chemistry

SN - 0022-4766

IS - 10

ER -