Structural, spectroscopic and theoretical studies of dimethylphenyl betaine complex with two molecules of 2,6-dichloro-4-nitro-phenol.

The 1:2 complex (1) of dimethylphenyl betaine (DMPB) with two molecules of 2,6-dichloro-4-nitro-phenol (DCNP) was prepared and characterized by X-ray diffraction, B3LYP/6-311++G(d,p) and B3LYP-D3/6-311++G(d,p)calculations, FTIR and NMR spectroscopies. The crystal is monoclinic, space group P21/c with Z=4. The protons at the oxygen atoms of phenols are bonded to each oxygen atoms of the DMPB carboxylate group by two nonequivalent H-bonds with the OH⋯O distances of 2.473(5) and 2.688(4)Å. Both H-bonds in the optimized structures 2 (in vacuum), 3 (in DMSO solution) and dispersion-correlated functional (D3) 4 (in vacuum) are comparable and are slightly shorter than O(6)H(O6)⋯O(2) in the crystal. The FTIR spectrum of 1 shows a broad absorption in the 3400-2000cm(-1) region corresponding to a longer hydrogen bond and a broad absorption in the 1800-500cm(-1) region caused by the shorter H-bond. The relations between the experimental (13)C and (1)H chemical shifts (δexp) of the investigated compound 1 in DMSO solution and GIAO/B3LYP/6-311++G(d,p) magnetic isotropic shielding constants (σcalc) obtained by using the screening solvation model (COSMO) for 3 are linear and reproduce well the experimental chemical shifts described by the equation: δexp=a+b σcalc.

Spectroscopic, structural and theoretical investigation of bis(4-trimethylammoniumbenzoate) hydroiodide hydrate.

The structure of bis(4-trimethylammoniumbenzoate) hydroiodide hydrate 1 has been studied by X-ray diffraction, B3LYP/6-311G(d,p) calculations, FTIR, Raman and NMR spectroscopic techniques. The crystal is polar in monoclinic space group Cc. Two 4-trimethylammoniumbenzoate moieties are joined by a short and asymmetric hydrogen bond of 2.45(2) Å. Water molecules are gradually released from the structure, causing shifts in the position of iodine anions, which induces their disorder. The water molecule interacts with 4-trimethylammoniumbenzoate moiety and iodide anion via two O(3)-H(1)⋯O(1) and O(3)-H(2)⋯I(1) hydrogen bonds of lengths 2.70(3) and 3.51(1) Å. Hydrogen bonds in theoretically predicted structures of 2 and 3 (in vacuum), and 4, 5 (in DMSO) optimized by the B3LYP/6-311G(d,p) approach are slightly longer than in crystal 1. The FTIR spectrum of 1 shows a broad and intense absorption in the 1500-400 cm(-1) region, typical of short hydrogen bonds assigned to the νas(OHO)+γ(OHO) vibrations. The correlations between the experimental (13)C and (1)H chemical shifts (δexp) of the investigated compound in DMSO and the GIAO/B3LYP/6-311G(d,p) magnetic isotropic shielding constants (σcalc) calculated by using the screening solvation model (COSMO) are linear, δexp=a+b σcalc, and they well reproduce the experimental chemical shifts.

Conformational richness and multiple Z' in salt co-crystal of N-methylpiperidine betaine with N-methylpiperidine betaine hexafluorosilicate.

The co-crystal structure of N-methylpiperidine betaine with N-methylpiperidine betaine hexafluorosilicate represents an unusual case of a salt co-crystal with a high Z' value (3), unexpected conformational variability, and with nearly 50% of its contents disordered. The betaine units from the salt and co-crystal formers are paired into several homoconjugated dimers via very short, linear O(-)...H(+)...O(-) bridges. These hydrogen bonds are the dominating interactions in the co-crystal structure, in variance with the simple hexafluorosilicate salt, which has a structure governed by COOH...F hydrogen bonds. The SiF(2-)(6) anion in the co-crystal structure has only C-H...F interactions with the betaine units. The zwitterion:cation:anion stoichiometry is 3:3:1.5. Some of the betaine units display disorder, but each case is different. One of the SiF(2-)(6) anions is ordered while possessing exact crystallographic symmetry. The other one is disordered in a general position. In addition, there are three water molecules in the crystal structure. One is fully ordered, one has an H atom disordered in two positions and the third one occupies two alternative positions with unequal populations.