Crystal and molecular structure of N-methyl-bis(2-hydroxyethyl)ammonium (4-chlorphenylsulfonyl)acetate

Article abstract of DOI:10.1134/S0022476613010289

By X-ray diffraction the crystal and molecular structure of N-methyl-bis(2-hydroxyethyl)ammonium (4-chlorphenylsulfonyl)acetate 4-ClC ₆H₄SO₂CH₂COO ^-·CH₃N⁺H(CH₂CH

Full text of DOI:10.1134/S0022476613010289

Journal of Structural Chemistry. Vol. 54, No. 1, pp. 182-185, 2013
Original Russian Text Copyright © 2013 by M. G. Voronkov, V. S. Fundamenskii, S. N. Adamovich,
È. A. Zel’bst, A. A. Kashaev, V. A. Brouskov, R. G. Mirskov, A. N. Mirskova
CRYSTAL AND MOLECULAR STRUCTURE
OF N-METHYL-Bis(2-HYDROXYETHYL)AMMONIUM
(4-CHLORPHENYLSULFONYL)ACETATE
1
M. G. Voronkov, V. S. Fundamenskii, S. N. Adamovich,
2
1
©
3
È. A. Zel’bst, A. A. Kashaev, V. A. Brouskov,
1
2
DOI: 10.1134/S0022476613010289
1
R. G. Mirskov, and A. N. Mirskova
1
By X-ray diffraction the crystal and molecular structure of N-methyl-bis(2-hydroxyethyl)ammonium (4-
– +
chlorphenylsulfonyl)acetate 4-ClC H SO CH COO ⋅CH N H(CH CH OH) synthesized by the interaction of (4-
6
4
2
2
3
2
2
2
chlorphenylsulfonyl)acetic acid with N-methyl-bis(2-hydroxyethyl)amine is studied.
Keywords: (4-chlorphenylsulfonyl)acetic acid, N-methyl-bis(2-hydroxyethyl)amine, ionic liquid, molecular
structure, single crystal X-ray diffraction study.
During the study of biologically active derivatives of arylheteroacetic acids ArYCH COOH (Y = O, S, SO ) [1-9],
2 2
–
the crystal and molecular structure of tris(2-hydroxyethyl)ammonium (4-chlorphenylsulfonyl)acetate 4-ClC H SCH COO
6 4 2
+
N H(CH CH OH) (I), having the structure of protatrane [10], was determined. In furtherance of this research, we have
2
2
3
synthesized its analogue (4-chlorophenylsulfonyl)acetate N-methyl-bis(2-hydroxyethyl)ammonium–quasi-protatrane (II) and
determined its crystal and molecular structure by X-ray diffraction (XRD).
Experimental. II was obtained by the interaction of (4-chlorophenylsulfonyl)acetic acid with N-methyl-bis(2-
hydroxyethyl)amine with a yield of 98%:
– +
4-ClC H SO CH COOH + CH N(CH CH OH) → 4-ClC H SO CH COO ⋅CH N H(CH СH OH) (II).
6
4
2
2
3
2
2
2
6
4
2
2
3
2
2
2
Compound II (colorless powder with T of 76°C) consists of the protonated amine cation and the acid anion, which
m
is typical of the structure of ionic liquids. As of now, solid substances with T ≤ 100°C are also classified as ionic liquids
m
–1
[11]. IR (ν, cm ): 1360, 1585 (COO ), 1139, 1315 (SO ), 3160 (OH). H NMR (δ, ppm, CD OD, HMDS): 7.94-7.58 (q, 4H,
–
1
2
3
13
С H ), 3.85 (t, 4H, OСH ), 3.30 (t, 4H, NCH ), 2.95 (s, 3H, NСH ); С NMR: 168.06 (С=O), 140.99-130.24 (С H ), 64.10
6
4
2
2
3
6
4
15
(SO СH ), 58.96 (OСH ), 56.68 (NСH ), 41.82 (NСH ); N NMR (relative to СH NO ): –340.43. Starting N-methyl-bis(2-
2
2
2
2
3
3
2
15
+
hydroxyethyl)amine: –354.00, Δδ = 14 ppm. Weak-field shift of N indicates the protonation of the nitrogen atom: N H [12].
The single crystals were produced by recrystallization of II from methanol (20°C). The samples suitable for X-ray
diffraction experiment were selected by photo diffraction. Single crystals of compound II were examined at 296 K on a
Bruker APEX-II autodiffractometer with CCD (50 kV, 35 mA, MoK radiation, graphite monochromator, multilayer optics).
α
The structure of II was solved by a direct method and refined by full-matrix LSM in the anisotropic approximation for non-
hydrogen atoms using the SIR-2008 software. Sites of hydrogen atoms, which could be calculated, were refined in the
isotropic approximation using the rigid-body model. Sites of the other hydrogen atoms were determined from the Fourier
1
2
A. E. Favorsky Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk. Saint-Petersburg
3
Technological University. East Siberian State Academy of Education, Irkutsk; zelbst@rambler.ru. Translated from Zhurnal
Strukturnoi Khimii, Vol. 54, No. 1, pp. 188-191, January-February, 2013. Original article submitted February 9, 2012.
182
0022-4766/13/5401-0182

Fig. 1. Anion A and cation K of compound II.
TABLE 1. Main Crystallographic Characteristics of Compound II and the Details of Structure Solution and Refinement
Chemical formula
Molecular weight
Crystal symmetry
Space group
C H O N Cl S
13 20 6 1 1 1
353.85
Triclinic
P-1
a, b, c, Å
7.422(4), 7.616(4), 14.567(8)
85.44(4), 83.52(4), 89.07(4)
α, β, γ, deg
3
V, Å
815.6(8)
2
Z
3
Density, g/cm
1.441
372
F(000)
40.0
ϑ
max
/deg
Number of measured/independent reflections
4002/1331(F > 3σ )
F
R , wR , GOOF
1 2
0.0469, 0.0437, 1.114
difference maps and were not further refined. The CIF files containing full information on the structure of II were deposited
with CCDC, No. 863881 (www.ccdc.cam.ac.uk/data_request/cif). The crystallographic characteristics and the details of
structure solution and refinement are listed in Table 1.
Results and discussion. The independent part of the unit cell of quasi-protatrane II contains 2 4-
– +
ClC H SO CH COO anions (A and A′) and 2 СH N (CH CH OH) cations (K and K′), Fig. 1. In the A and A′ anions, the
6
4
2
2
3
2
2
2
lengths of Cl–C bonds (1.741(9) Å and 1.738(6) Å) are the same and are in good fit with the average Cl–C(aryl) bond length
(1.737(4) Å) [13]. This interatomic distance is almost the same as in the anion of protatrane I being 1.746(5) Å [10]. The
chlorine atom is in the benzene ring plane in both independent anions. In the A anion, the sulfur atom is out of this plane by
0.16 Å, and in A′ only by 0.063 Å. The of C(aryl)–S bond length is the same (1.770(9) Å) in both anions.
The coordination polyhedron of the sulfur atom represents a somewhat distorted tetrahedron with typical bond
angles (103-112°) and lengths of S–CH (1.72 Å) and S–O (1.42 Å) bonds. The lengths of S–O bonds are the same in both
2
anions, and the OSO angles are different and are 117.7° and 121.0°, apparently due to packing features.
–
The COO groups have the identical geometry in both anions. The lengths of С–O bonds are the same in A and A′:
C17–O8 1.24(2) Å, C17–O10 1.235(10) Å in A and C15–O11 1.242(20) Å, C15–O12 1.237(15) Å in A′, and the O=C–O
angles have similar values of 126.5° and 128.8°. Similar proportions of these parameters were observed in the anion of
–
protatrane I, which evidences negative charge delocalization in the COO group [10].
183

Fig. 2. Packing of anions A and cations K in the crystal
of II, the (010) direction.
The K and K′ cations in II have the identical structure. As opposed to protatrane I, in the cation of II the CH group
3
substitutes for one of two hydroxyethyl moieties CH CH OH. The coordination polyhedra of the N1 and N2 atoms in the
2 2
cations is a tetrahedron with vertices C14, C26, С28 and the LP of the nitrogen atom for N1, and in the K′ cation the vertices
of the coordination tetrahedron are occupied by three carbon atoms (C13, С25, C27) and one hydrogen atom H37 appeared
on a difference electron-density map. From the O1 atom belonging to the K′ cation the N1 atom is at a distance of 2.809 Å,
which is somewhat shorter than the sum of the van der Waals radii of these atoms [14].
There are no substantial differences in the geometry of K and K′ cations in II: the lengths of N–C bonds are similar
(1.490-1.494 Å), С–C (1.49-1.52 Å), С–O (1.41-1.42 Å); the bond angles of the N and C atoms are tetrahedral. The geometric
parameters of the cation in I [10] and neutral molecule of triethanolamine [15] are close to that of II. As in the triethanolamine
molecule in free and protonated forms, in the K and K′ cations two oxyethyl groups are turned in one direction.
In the K and K′ cations, the nitrogen atoms deviate by the same value ΔN (0.40 Å and 0.46 Å respectively) from the
planes drawn through the carbon atoms bonded to the nitrogen atom. These planes in the crystal are almost parallel, and the
angle between them is 3.5°. The same or similar value of ΔN have all known protatranes; in I ΔN = 0.44 Å.
Low symmetry (space group Р1) makes it possible to describe the molecular packing in the crystal of II as infinite
ribbons of alternating anions (A and A′) and cations (K and K′). Hydrogen bonds between the cation OH groups and the
anion COO groups link the cations and anions into ion pairs filling the crystal space (Fig. 2). This structure is stabilized by
electrostatic interaction between the electronegative oxygen atoms and the positively charged nitrogen atom N1 on the
neighboring cation.
Intramolecular H…O are equal or larger in the K′ cation than the normal van der Waals value of 2.45 Å, just as non-
bonded N…O are somewhat larger than or equal to the sum of their radii 2.78 Å [14], their values being 3.096 Å and 2.940 Å
in the K cation and 2.77 Å and 2.89 Å in the K′ cation. Perhaps, methyl substitution for one of the hydroxyethyl groups
makes the cation geometry looser, while the interionic hydrogen bonds strengthen the packing in the crystal of II (Fig. 2).
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