Tartaric acid and its O-acyl derivatives. 7. Crystal structure of O-p-anisoyl-D-tartaric acid and its dimethylammonium salt trihydrate

Article abstract of DOI:10.1134/S0022476613010228

Monoacylated derivatives O-p-anisoyl-d-tartaric acid and its N,N-dimethylammonium salt are synthesized by the partial hydrolysis of O,O′-di-p-anisoyl-d-tartaric acid. Crystal and molecular structures of both compounds have been determined and analyzed. In

Full text of DOI:10.1134/S0022476613010228

Journal of Structural Chemistry. Vol. 54, No. 1, pp. 155-158, 2013
Original Russian Text Copyright © 2013 by G. Wesela-Bauman, T. Boinski, P. Dominiak,
H. Hajmowicz, L. Synoradzki, M. Wierzbicki, B. Woliński, K. Woźniak, K. Zawada
TARTARIC ACID AND ITS O-ACYL DERIVATIVES.
7. CRYSTAL STRUCTURE OF O-p-ANISOYL-D-TARTARIC
ACID AND ITS DIMETHYLAMMONIUM SALT TRIHYDRATE
1,2
G. Wesela-Bauman, T. Boinski, P. Dominiak,
1
2
©
1 1
H. Hajmowicz, L. Synoradzki, M. Wierzbicki,
1
DOI: 10.1134/S0022476613010228
1 2
B. Woliński, K. Woźniak, and K. Zawada
1
Monoacylated derivatives O-p-anisoyl-D-tartaric acid and its N,N-dimethylammonium salt are synthesized
by the partial hydrolysis of O,O′-di-p-anisoyl-D-tartaric acid. Crystal and molecular structures of both
compounds have been determined and analyzed. In both of them, some strong and moderate strength [O–
H…O] hydrogen bonds exist between the carboxylic units. The intermolecular hydrogen bonds link the
adjacent fragments forming infinite one-dimensional chains parallel to the X-axis.
Keywords: tartaric acids, acyl derivatives, anisoyl.
INTRODUCTION
Tartaric acid acyl derivatives have wide applications in the chemical and pharmaceutical industry [1-3].
Monoacyltartaric acid derivatives are applied as ligands in chiral (acyloxy) boranes (CAB) [4-6], catalysts for Diels-Alder
[5, 7] and asymmetric aldol condensation [1, 8] reactions. The aim of this work is to obtain O-p-anisoyl-D-tartaric acid (B)
using the method based on partial hydrolysis and to confirm the structures of pure O-p-anisoyl-D-tartaric acid (B) and its salt
(A) by the X-ray structural analysis. This contribution continues our research focused on the determination and analysis of
the crystal structures of tartaric acid derivatives [9].
EXPERIMENTAL
Optical rotation was determined with Polarimetr PolAAr 32. Elemental analysis was carried out with Perkin Elmer
1
PE II CHNS/O. H NMR spectra were measured on Merkury 400 MHz in (D )DMSO; chemical shifts δ are in ppm relative
6
to SiMe . The IR spectrum (KBr pellet) was recorded on Specord M80. Single crystal X-ray measurements for A and B were
4
performed on a Kuma KM4CCD k-axis diffractometer with graphite-monochromated MoK radiation (λ = 0.71073 Å). Only
α
ω scans were taken into account. The multi-scan absorption correction was used. The solution and refinement were made using
the SHELX package [10]. Most important crystal parameters and structural details are included in Table 1. In the A structure, C-
type alert from checkcif stands for the disordered acidic H-atom ADPs. CCDC 803688 & 803689 contains the supplementary
crystallographic data (CIF files) for this paper (for compounds A and B respectively). They can be obtained
free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif or from the authors.
1
Laboratory of Technological Processes, Faculty of Chemistry, Warsaw University of Technology, Warszawa,
2
Poland. Department of Chemistry, University of Warsaw, Warszawa, Poland; grzegorz.wesela@chem.uw.edu.pl. The text
was submitted by the authors in English. Zhurnal Strukturnoi Khimii, Vol. 54, No. 1, pp. 162-165, January-February, 2013.
Original article submitted September 9, 2011.
0022-4766/13/5401-0155
155

TABLE 1. Selected Crystal Data and Refinement Details for A and B
Experimental details
A
B
+ –
[C H N] [C H O ] [3H O]
Chemical formula
C H O
12 12 8
2
8
12 11
8
2
M
r
383.35
284.22
Crystal system, space group
Cell parameters: a, b, c, Å
α, β, γ, deg
Orthorombic, P2 2 2
1 1
Monoclinic, P2
1
1
7.4917(6), 8.0304(5), 30.8271(19)
90.000, 90.000, 90.000
1854.6(2)
7.7087(3), 5.6236(2), 14.9159(6)
90.000, 94.043(3), 90.000
645.00(4)
3
V, Å
Z
4
2
–3
1.373
1.463
d , mg⋅cm
x
Crystal form, colour
Crystal size, mm
Needle, colourless
0.11×0.15×0.46
0.9471, 0.9870
17289, 4434, 3637
Block, colourless
0.20×0.36×0.49
0.9410, 0.9753
5814, 2356, 2327
T
min
, T
max
No. of measured, independent, and
observed reflections (I > 2σ(I))
R
0.0279
28.64
0.0063
28.21
int
Θ
max
Range of h, k, l
–10≤ h ≤10, –7 ≤ k ≤10, –41 ≤ l ≤ 41
–10 ≤ h ≤ 10, –7 ≤ k ≤ 6, –18 ≤ l ≤ 19
2
R[F > 2σ(F )], wR(F ), GOOF
2
2
0.0268, 0.0570, 1.002
2618
0.0214, 0.0573, 1.079
1626
No. of reflections
No. of parameters
327
194
–3
0.220, –0.164
803688
0.290, –0.142
803689
Δρ , Δρ , e/Å
max min
CCDC No.
Scheme 1. Synthesis of O-p-anisoyl-D-tartaric acid N,N-dimethylammonium salt trihydrate (A) and pure O-p-
anisoyl-D-tartaric acid (B)
RESULTS AND DISCUSSION
The synthesis of A and B is outlined in Scheme 1. The hydrolysis of O,O′-di-p-anisoyl-D-tartaric acid was carried
out in the presence of DMF as an antifoaming agent, and unexpectedly, due to the parallel hydrolysis of DMF, resulted in the
formation of O-p-anisoyl-D-tartaric acid N,N-dimethyl-ammonium salt trihydrate (A), M.p. 154-156°C. Elemental analysis
calcd. for C H NO : C 43.7%, H 6.5%, N 3.7%), found: C 43.9%, H 6.6%, N 3.6%. 1H NMR ((D )DMSO) δ: 2.440 (s,
14 25
11
6
6H, HN(CH ) ), 3.818 (s, 3H, OCH ), 4.312 (d, J = 4 Hz, 1H, C(OH)HCOOH), 5.256 (d, J = 4 Hz, 1H C(OOCAr)HCOOH),
3 2 3
7.029 (d, J = 8.8 Hz, 2H, o-C H ), 7.918 (d, J = 8.8 Hz 2H, m-C H ). Pure O-p-anisoyl-D-tartaric acid (B) was obtained after
6 4 6 4
156

Fig. 1. Anisotropic displacement parameters (ADPs) and atom labeling in O-p-anisoyl-D-tartaric acid
dimethylammonium salt trihydrate (a) and pure O-p-anisoyl-D-tartaric acid (b).
the acidification of A with hydrochloric acid. M.p. 191.3-195.2°C, [α] = +9.41 c = 1 MeOH. Elemental analysis calcd. for
C H O : C 50.7%, H 4.2%, found: C 50.62%, H 4.24%. 1H NMR ((D )-DMSO) δ: 3.834 (s, 3H, OCH ), 4.643 (d,
11 12
8
6
3
J = 2,4 Hz, 1H, C(OH)HCOOH), 5.418 (d, J = 2,8 Hz, 1H C(OOCAr)HCOOH), 7.063 (q, J = 4,8 Hz, 2H, o-C H ), 7.985 (q,
6 4
–1
–1
–1
–1
–1
–1
–1
–1
J = 4,8 Hz 2H, m-C H ). IR (KBr) 3305 cm , 1758 cm , 1700 cm , 1608 cm , 1512 cm , 1461 cm , 1393 cm , 1283 cm ,
6
4
–1
–1
–1
–1
–1
–1
–1
–1
–1
–1
–1
1218 cm , 1168 cm , 1137 cm , 1104 cm , 1060 cm , 1020 cm , 924 cm , 848 cm , 768 cm , 700 cm , 665 cm ,
–1 –1
583 cm , 508 cm . Crystals of A and B were obtained by evaporation from an aqueous solution.
X-ray structural analysis of A. Dimethylammonium trihydrate salt of O-p-anisoyl-D-tartaric acid crystallises in the
orthorhombic P2 2 2 space group with one O-p-anisoyl-D-tartaric anion, three water molecules, and one protonated N,N-
1
1 1
dimethylamine moiety in the independent part of the unit cell (Fig. 1). The acid molecules are linked by a strong O(8)–
H(4)…O(4) hydrogen bond containing a disordered H-atom position occupied with the occupancy ratio ca. 0.6:0.4. The D–
H…A angles are 174.1(5)° and 177.0(7)°, and the D…A distance is 2.445(1) Å (Fig. 2). Intermolecular hydrogen bonds link
the adjacent units together, thus forming infinite one-dimensional chains parallel to the X-axis. The aromatic fragments of the
acid moieties interact by weak C(4)–H(4)…O(2), and C(7)–H(7)…C(8) (methoxy group) interactions parallel to the Y-axis of
the crystal system.
The acid moieties interact by C(6)–H(6)…O(4) interactions parallel to the Z-axis with the aromatic rings located on
different neighbouring planes. Each chain of hydrogen bonds is additionally stabilized by N(1)–H(1A)…O(5) and N(1)–
H(1B)…O(6) hydrogen bonds with the D…A distances and D–H…A angles of 2.806(2) Å, 2.794(2) Å, 162.3(1)°, 160.1(2)°
respectively. Chains formed by the acid molecules are parallel onetoanother, and they are bound by hydrogen bonds with
water molecules.
X-ray structural analysis of B. Pure O-p-anisoyl-D-tartaric acid crystallises in the monoclinic space group P2
1
with one acid molecule in the asymmetric part of the unit cell. The molecular structure of the acid moiety is shown in Fig. 1.
The acidic fragments form chains bound by moderately strong O(1)–H(1)…O(5) hydrogen bonds. The D–H…A angle is
161.9(2)° and the D…A distance is 2.70(1) Å (Fig. 2).
157

Fig. 2. (a) Strong hydrogen bonds existing between the acid moieties
in the crystal structure of A, (b) moderate hydrogen bond in the acid B
crystal structure.
The acid molecules maintain the same type of packing as in the structure of A.
They form infinite one-dimensional chains of molecules parallel to the X-axis.
CONCLUSIONS
The presented report shows the synthesis of O-p-anisoyl-D-tartaric acid N,N-dimethylammonium salt trihydrate (A)
and pure O-p-anisoyl-D-tartaric acid (B). Details of the crystallographic structures of A and B have been presented.
Krzysztof Woźniak thanks the Foundation for Polish Science for the support within the Program “Mistrz”. Grzegorz
Wesela-Bauman thanks the Foundation for Polish Science for the support within the Program “International Ph.D. Projects”.
This work was supported by the Warsaw University of Technology.
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