X-ray powder diffraction, solid-state NMR and dispersion-corrected DFT calculations to investigate the solid state structure of 2-ammonio-5-chloro-4-methylbenzenesulfonate

Bekö, Sándor L.; Thoms, Silke D.; Brüning, Jürgen; Alig, Edith; Streek, Jacco van de; Lakatos, Andrea; Glaubitz, Clemens; Schmidt, Martin

doi:10.1524/zkri.2010.1259

Cited by 16 publications

(12 citation statements)

References 17 publications

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“…2-Ammonio-5-chloro-4-methylbenzenesulfonate, C 7 H 8 ClN-O 3 S, (Ia), is an intermediate in the synthesis of lake red azo pigments. The present structure determination from singlecrystal data confirms the results of a previous powder diffraction determination [Bekö, Thoms, Brü ning, Alig, van de Streek, Lakatos, Glaubitz & Schmidt (2010). Z.…”

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confidence: 90%

2-Ammonio-5-chloro-4-methylbenzenesulfonate, its 1-methyl-2-pyrrolidone and dimethyl sulfoxide monosolvates and a corrected structure of 2,2′-(1,4-phenylene)di(4,5-dihydroimidazolium) bis(4-aminobenzenesulfonate) dihydrate

2012

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2-Ammonio-5-chloro-4-methylbenzenesulfonate, C(7)H(8)ClNO(3)S, (Ia), is an intermediate in the synthesis of lake red azo pigments. The present structure determination from single-crystal data confirms the results of a previous powder diffraction determination [Bekö, Thoms, Brüning, Alig, van de Streek, Lakatos, Glaubitz & Schmidt (2010). Z. Kristallogr. 225, 382-387]. The zwitterionic tautomeric form is confirmed. During a polymorph screening, two additional pseudopolymorphs were obtained, viz. 2-ammonio-5-chloro-4-methylbenzenesulfonate 1-methyl-2-pyrrolidone monosolvate, C(7)H(8)ClNO(3)S·C(5)H(9)NO, (Ib), and 2-ammonio-5-chloro-4-methylbenzenesulfonate dimethyl sulfoxide monosolvate, C(7)H(8)ClNO(3)S·C(2)H(6)OS, (Ic). The molecules of (Ib) have crystallographic m symmetry. The 1-methyl-2-pyrrolidone solvent molecule has an envelope conformation and is disordered around the mirror plane. The structure shows hydrogen-bonded ladders of molecules [graph-set notation C(2)(2)(6)R(2)(2)(12)] in the [010] direction. The benzene groups of adjacent ladders are also stacked in this direction. A different type of hydrogen-bonded ladder [graph-set notation C(6)R(2)(2)(4)R(4)(4)(12)] occurs in (Ic). In (Ia), (Ib) and (Ic), the molecules correspond to the zwitterionic tautomer. The structure of the cocrystal of 4-aminobenzenesulfonic acid with 1,4-bis(4,5-dihydroimidazol-2-yl)benzene [Shang, Ren, Wang, Lu & Yang (2009). Acta Cryst. E65, o2221-o2222] is corrected; it actually contains 4-aminobenzenesulfonate anions and 2,2'-(1,4-phenylene)di(dihydroimidazolium) dications, i.e. 2,2'-(1,4-phenylene)di(4,5-dihydroimidazolium) bis(4-aminobenzenesulfonate) dihydrate, C(12)H(16)N(4)(2+)·2C(6)H(6)NO(3)S(-)·2H(2)O. Hence, all known structures of aminobenzenesulfonic acid complexes contain ionic or zwitterionic molecules; there is no known structure with a neutral aminobenzenesulfonic acid molecule.

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confidence: 90%

2-Ammonio-5-chloro-4-methylbenzenesulfonate, its 1-methyl-2-pyrrolidone and dimethyl sulfoxide monosolvates and a corrected structure of 2,2′-(1,4-phenylene)di(4,5-dihydroimidazolium) bis(4-aminobenzenesulfonate) dihydrate

2012

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“…However, such a refinement is not possible with laboratory X-ray powder data of a compound with only moderate crystallinity. Therefore we applied a procedure which describes the tautomeric state with only one parameter [6]. For each molecule two sets of hydrogen atom positions were defined: One set for the -NH 3 + group of the zwitterionic tautomer, the other one for the -NH 2 and -SO 3 H groups of the neutral tautomer.…”

Section: Determination Of the Tautomeric State From X-ray Powder Datamentioning

confidence: 99%

“…In 2010 we investigated the crystal structure and the tautomeric state of 2 using X-ray powder diffraction (XRPD), IR and solid-state NMR spectroscopy. All methods revealed the zwitterionic tautomer of 2 [6,7]. In 1985 solid-state NMR investigations indicated that 2-aminobenzenesulfonic acid ( Figure 1, R 1 = R 2 = H) and 2-amino-5-methylbenzenesulfonic acid (R 1 = H, R 2 = CH 3 ) are zwitterionic, but the data on 2-amino-5-nitrobenzenesulfonic acid (R 1 = H, R 2 = NO 2 ) were interpreted as an indication for the neutral amine tautomer in solid state [8].…”

Section: Introductionmentioning

confidence: 97%

Determination of crystal structures and tautomeric states of 2-ammoniobenzenesulfonates by laboratory X-ray powder diffraction

Bekö

Czech

Neumann³

et al. 2015

Zeitschrift Für Kristallographie - Crystalline Materials

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The crystal structures of 4-chloro-5-methyl-2-ammoniobenzenesulfonate and of the corresponding derivatives 4,5-dimethyl-and 4,5-dichloro-2-ammoniobenzenesulfonates have been determined from laboratory X-ray powder diffraction data. The tautomeric state of all three compounds could also be unequivocally determined from laboratory data, using careful Rietveld refinements. The tautomeric state was confirmed by IR spectroscopy. The compounds are neither isostructural to each other nor to the 5-chloro-4-methyl derivate, despite the similar size of the chloro and methyl substituents. The influence of the chloro and methyl substituents on the packing and on the thermal stability is demonstrated. All crystal structures were confirmed by dispersion-corrected DFT calculations. For the 4-chloro-5-methyl and the 4,5-dichloro derivatives the DFT calculations indicated that the observed polymorph should not be the thermodynamical one. However, no other polymorphs could be found in experimental polymorph screening, even using seeding with the corresponding isostructural phases. Obviously the DFT methods need further improvements.

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“…H-atom positions are generally difficult to determine by X-ray powder diffraction, although there have been cases when they have been determined successfully (Schmidt et al, 2011), even from laboratory powder data (Bekö et al, 2010). H-atom positions are generally difficult to determine by X-ray powder diffraction, although there have been cases when they have been determined successfully (Schmidt et al, 2011), even from laboratory powder data (Bekö et al, 2010).…”

Section: Commentmentioning

confidence: 99%

Nimustine hydrochloride: the first crystal structure determination of a 2-chloroethyl-N-nitrosourea hydrochloride derivative by X-ray powder diffraction and solid-state NMR

et al. 2012

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Nimustine hydrochloride [systematic name: 4-amino-5-({[N-(2-chloroethyl)-N-nitrosocarbamoyl]amino}methyl)-2-methylpyrimidin-1-ium chloride], C(9)H(14)ClN(6)O(2)(+)·Cl(-), is a prodrug of CENU (chloroethylnitrosourea) and is used as a cytostatic agent in cancer therapy. Its crystal structure was determined from laboratory X-ray powder diffraction data. The protonation at an N atom of the pyrimidine ring was established by solid-state NMR spectroscopy.

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X-ray powder diffraction, solid-state NMR and dispersion-corrected DFT calculations to investigate the solid state structure of 2-ammonio-5-chloro-4-methylbenzenesulfonate

Cited by 16 publications

References 17 publications

2-Ammonio-5-chloro-4-methylbenzenesulfonate, its 1-methyl-2-pyrrolidone and dimethyl sulfoxide monosolvates and a corrected structure of 2,2′-(1,4-phenylene)di(4,5-dihydroimidazolium) bis(4-aminobenzenesulfonate) dihydrate

2-Ammonio-5-chloro-4-methylbenzenesulfonate, its 1-methyl-2-pyrrolidone and dimethyl sulfoxide monosolvates and a corrected structure of 2,2′-(1,4-phenylene)di(4,5-dihydroimidazolium) bis(4-aminobenzenesulfonate) dihydrate

Determination of crystal structures and tautomeric states of 2-ammoniobenzenesulfonates by laboratory X-ray powder diffraction

Nimustine hydrochloride: the first crystal structure determination of a 2-chloroethyl-N-nitrosourea hydrochloride derivative by X-ray powder diffraction and solid-state NMR

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