The crystal structure of hexamethylenediammonium bis(thiosaccharinate) dihydrate, [H3N-(CH2)6-NH3](tsac) 2 · 2 H2O (tsac = C7H4NO 2S2, the anion of thiosaccharin), was determined by single-crystal X-ray diffraction. It crystallizes in the monoclinic space group P21/a with Z = 4. The thiosaccharinate moiety is planar and shows small but significant modifications in the bonding of the thioamide functional group as compared with the protonated neutral molecule. The ionic crystal is further stabilized by an extensive H-bonding network, which links the anions and cations into an infinite three-dimensional supramolecular assembly. The FTIR spectrum of the compound is briefly discussed in comparison with those of the neutral constituent molecules.Centro de Química InorgánicaInstituto de Física La Plat

Barán, Enrique José

Piro, Oscar Enrique

Zinczuk, Juan

Zeitschrift für Naturforschung B

English

El Servicio de Difusión de la Creación Intelectual

A New Supramolecular Assembly Obtained by Reaction Between 
Thiosaccharin and Hexamethylenediamine
Enrique J. Barana, Oscar E. Pirob, and Juan Zinczukc
a Centro de Química Inorgánica (CEQUINOR. CONICET/UNLP). Facultad de Ciencias Exactas.
Universidad Nacional de La Plata. C. Correo 962. 1900 La Plata. Argentina
h Departamento de Física and Instituto IFLP (CONICET). Facultad de Ciencias Exactas.
Universidad Nacional de La Plata. 1900 La Plata. Argentina
c Instituto de Química Orgánica de Síntesis (IQUIOS/CONICET. UNR). Facultad de Ciencias 
Bioquímicas y Farmacéuticas. Universidad Nacional de Rosario. 2000 Rosario. Argentina
Reprint requests to Dr. E. J. Baran. E-mail: baran@quimica.unlp.edu.ar
Z. Naturforsch, 2007. 62b, 1530- 1534; received June 1. 2007
The crystal structure of hexamethylenediammonium bis( thio saccharinate) dihydrate.
[H3N-(CH2 )6-NH3](tsac)2 • 2 I LO (tsac = C7H4NO2S2. the anion of thio saccharin), was determined 
by single-crystal X-ray diffraction. It crystallizes in the monoclinic space group P2\!a with Z = 4. 
The thio saccharinate moiety is planar and shows small but significant modifications in the bonding of 
the thioamide functional group as compared with the protonated neutral molecule. The ionic crystal 
is further stabilized by an extensive H-bonding network, which links the anions and cations into an 
infinite three-dimensional supramolecular assembly. The FTIR spectrum of the compound is briefly 
discussed in comparison with those of the neutral constituent molecules.
Key words: Hexamethylenediammonium Bis( thio saccharinate) Dihydrate. Crystallographic Data. 
Supramolecular Adduct. IR Spectra
Introduction
In the last years we have synthesized and character­
ized a number of metallic complexes of thiosaccharin 
(for a recent review cf. [1]), and have now initiated a 
search to verify the possible formation of supramolec­
ular adducts between thiosaccharin and some simple 
organic amines. In this paper, we present the first com­
pound of this type, hexamethylenediammonium bis 
(thiosaccharinate) dihydrate, generated by interaction 
of thiosaccharin with hexamethylenediamine (1,6-hex- 
anediamine).
Results and Discussion
Crystal and molecular structure
An ORTEP [2] drawing of the structure is pre­
sented in Fig. 1. Selected bond lengths and angles are 
shown in Table 1. As expected, the thiosaccharinate 
C7II4NO2S2 molecular skeletons are nearly planar 
(r. m. s. distance of atoms from least-squares planes 
less than 0.0194 A). A comparison with the structure 
of the neutral thiosaccharin (tsac) molecule [3] shows 
that the major bonding changes in the charged moi-
[H3N-(CH2)6-NH3](tsac)2 • 2 H2O showing the labeling of 
the non-H atoms and their displacement ellipsoids at the 
30 % probability level.
ety occur at the thioamide functional group, as also 
predicted by a previous quantum chemical study [4], 
In fact, upon deprotonation, the excess nitrogen elec-
0932-0776 / 07 / 1200-1530 $ 06.00 © 2007 Verlag der Zeitschrift für Naturforschung, Tübingen • http://znaturforsch.com
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E. J. Baran et al. ■ Thiosaccharin and Hexamethylenediamine 1531
Table 1. Selected interatomic bond lengths (A) and angles (°) 
in [NH3-(CH2 )6-NH3](tsac)2 • 2 I E(L
S(ll)-C(ll) 1.681(4) N(l)-C(ll) 1.326(5)
S(12)—0(11) 1.430(3) N(3)-C(l) 1.488(5)
S(12)—0(12) 1.435(3) N(4)-C(6) 1.478(6)
S(12)-N(l) 1.632(4) C(l)-C(2) 1.500(5)
S(12)—C(17) 1.752(4) C(3)-C(4) 1.505(5)
S(21)—C(21) 1.676(4) C(5)-C(6) 1.506(5)
S(22)-C(27) 1.742(5) C(ll)-C(12) 1.479(5)
C(12)-C(17) 1.394(5) C(22)-C(27) 1.394(5)
O(ll)-S(12)-O(12) 115.6(2) N(4)-C(6)-C(5) 111.6(4)
0(11 )—S(12)—N(l) 110.0(2) N(l)-C(ll)-C(12) 114.0(4)
0(12)—S(12)—N(l) 110.1(2) N(l)-C(ll)-S(ll) 123.8(3)
0(11)—S(12)—C(17) 111.9(2) C(12)-C(ll)-S(ll) 122.1(3)
0(12)—S(12)—C(17) 111.0(2) N(3)-C(l)-C(2) 110.3(3)
N(l)—S(12)—C(17) 96.6(2) C(l)-C(2)-C(3) 113.2(3)
C(ll)-N(l)-S(12) 111.4(3) C(4)-C(3)-C(2) 112.7(3)
Fig. 2. Crystal packing of |H3N-(CH2)6-NH3|(tsacj2 • 
2 H2O as viewed down the b axis (Platon [9]). The crystal 
a axis is along the vertical. For clarity, only hydrogen atoms 
involved in H-bonding are shown. H bonds are indicated by 
dashed lines. Sulfur atoms are denoted by larger shaded cir­
cles. while oxygen and nitrogen atoms are indicated by the 
smaller black discs.
tron mainly contributes to a delocalized N-C-S bond­
ing. This is shown by the shortening observed in both 
N-C bonds (from 1.384 Â in neutral tsac to 1.326(5) 
and 1.327(5) Â in the two anions present in the inves­
tigated adduct) and the lengthening of the C-S bonds 
(from 1.622 Â in tsac to 1.681(4) and 1.676(4) Â in the 
present compound). In contrast, no significant changes 
are observed for the C( 12)-C( 17) and C(22)-C(27) and 
the sulfonyl S-O bond lengths comparing the neutral 
and charged molecules. On the other hand, the bond 
lengths and angles in the title compound agree well 
with those reported for the sodium, potassium, ammo­
nium and bis(triphenylphosphinium) thiosaccharinate 
salts [5-8].
The crystal is further stabilized by the exten­
sive 3-D net of hydrogen bonds shown in the PLA­
TON [9] plot (Fig. 2). The H-bonding structure in­
volves both hexamethylenediammonium NH3 groups 
as donors, and as acceptors the exocyclic sulfur atom 
of one thiosaccharinate [¿(N3-• -S21) = 3.210 A and 
Z (N3-H- • -S21) = 161.4°], the sulfonyl oxygen atoms 
of neighboring thiosaccharinate ions [the strongest 
with ¿(N3---O22) = 2.937 A and Z (N3 - O22) = 
159.0°] and the water oxygen atoms [the strongest 
with ¿(N4- -Olw) = 2.813 A and Z (N4-H- -Olw) = 
161.2°]. This latter water molecule, in turn, acts as 
donor in a pair of H bonds, one with the other exo­
cyclic S atom [¿(Olw- • - Sil) = 3.230 A and Z (Olw- 
H- •-Sil) = 158.1°], the other with the imino N atom 
(Nl) of one thiosaccharinate anion [¿(Olw---N1) = 
2.835 A and Z (Olw-H- • -Nl) = 168.4°]. Further de­
tails of the crystal H-bonding are presented in Table 2.
In the case of the recently described adduct of sac­
charin, [H3N-(CH2)6-NH3](sac)2 (space group PZyJc, 
Z = 4), the extended hydrogen bonding system also in­
volves all six NH3 hydrogen atoms as donors as well 
as the six O atoms belonging to the two saccharinate 
anions as acceptors [10].
Infrared spectra
The assignment of some of the most characteris­
tic IR bands of the investigated compound is shown 
in Table 3. For comparative purposes we have also 
measured the spectrum of the free amine, and known 
data for the thiosaccharin molecule are also included 
[11,12], Standard references [13,14] were usedin the 
analysis and assignment of the spectra. Some aspects 
of the proposed assignments are commented as fol­
lows:
• In the case of the free amine a relative broad band 
is observed in the high-frequency range and only one 
of the two expected N-H stretching bands of the NH2 
groups could be observed. The same behavior was ob­
served for the v(NH3+) vibrations in the case of the 
salt.
• The characteristic defonnational bands of the pri­
mary amine groups are absent in the salt, instead of 
which those of the ammonium groups (R-NH3+) are 
observed.
• The stretching vibrations of the water molecules 
generate a very broad and ill-defined band, centered 
at about 3490 cm-1, pointing to a participation in hy­
drogen bridges of medium length [15]. The respective 
bending motion causes only a very weak shoulder at
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1532 E. J. Baran et al. ■ Thiosaccharin and Hexamethylenediamine
D-H d (D-H) d (H—A) DHA d (D—A) A Symm. operation Table 2. Hydrogen bonds of
N3-H3A 0.890 2.089 158.98 2.937 022 [2 - v, 2 - y, 2 - d [H3N-(CH2)6-NH3](tsac)2 •
N3-H3B 0.890 2.344 161.40 3.201 S21 2H2O (in A. angles in degrees).
N3-H3C 0.890 2.183 142.97 2.942 021 [2-.v, 1-y, 2-d
N3-H3C 0.890 2.376 132.99 3.053 022 [a- 1/2, 3/2 —y, d
N4-H4A 0.890 1.956 161.17 2.813 Olw [3/2-a, 1/2 + y, 1 —d
N4-H4B 0.890 2.070 150.53 2.878 O2w [1/2+ a, 3/2-y, d
N4-H4B 0.890 2.501 118.34 3.027 012
N4-H4C 0.890 2.254 158.95 3.101 Oil [2 - A', 1 - y, 1 - d
Olw-Hll 0.860 1.987 168.39 2.835 N1 [3/2-a, 1/2 + y, 1-d
O1W-H12 0.859 2.417 158.13 3.230 Sil [a - 1/2, 1/2-y, d
Thiosaccharin H2N-(CH2)6-NH2 [H3N-(CH2)6-NH3]
(tsac)2 -2 H2O
Assignment Table 3. Assignment of some of 
the most characteristic IR bands
3490 s, br v(O-H) H2O of [H3N-(CH2)6-NH3](tsac)2 •
3338 vs v(N-H) 2 H2O, H2N-(CH2)6-NH2, and
3232 sh, 3149 vs Vas(NH3+) thio saccharin3.
2943 s 2927 s Vas(CH2)
2860 s 2866 s Vs(CHa)
1637 s
1630 sh
<5(NH2)sciss.
<5(H2O)
a vs: very strong; s: strong; 
m: medium; w: weak; sh: shoul­
der; br: broad.1587 vs 5as(NH3+)
1506 vs 5s(NH3+)
1455 s 1452 s 1456 vs v(CC), <5(CH2)sciss.
1376 vs 1348 vs, 1321 s Vas(SO2)
1247 m 1234 vs v(NC), v(CC)
1156 vs 1115 vs, 1068 m vs(SO2), <5(CCC)
1144 m 1142 vs v(CC)
1061 m 1047 w v(CN)
1039 s
823 s, 796 s
1011 vs v(CS), v(CC) 
<5(NH2) out of plane
817 vs, 700 vw 785 m, 700 w v(NS), <5(CCC)
733 m, 712 s 756 s, 742 m p(CH2)
1630 cm 1, at the higher energy side of the very strong 
<5as(NH3+) band located at 1587 cm-1.
• Some of the characteristic v(CC), <5(CCC) and 
CH2 bands could also be unambiguously identified. 
Interestingly, the dl2 -rocking mode shows the typ­
ical splitting [19] in both, the free amine and the 
adduct.
• Three of the most typical thiosaccharinate bands, 
i. e. the two SO2 stretchings, and the v(CS) mode are 
clearly displaced to lower energies in [H3N-(CH2)6- 
NH3](tsac)2 • 2 H2O in comparison to their position in 
free thiosaccharin, surely as a consequence of its ion­
ization [4] and involvement in hydrogen bonding, as 
commented above. Besides, both the vas(SO2) and the 
vs(SO2) vibrations appear as a singly split absorption 
band. On the other hand, the v(NC) and v(NS) bands 
of thiosaccharin are displaced to lower frequencies in 
the salt.
• The v(CN) vibration of the amine is also affected 
by the salt formation as are also some of the character­
istic vibrations of the CH2 groups.
To conclude, this brief spectroscopic analysis is 
clearly compatible and consistent with the structural 
characteristics of the compound and reflects nicely its 
peculiarities.
Experimental Section
Synthesis of the adduct
Thiosaccharin (1,2-benzisothiazol-3(2H)-thione-1.1 -di­
oxide) was obtained by heating of a mixture of 0.1 mol of 
saccharin (Aldrich. 99 %) and 0.11 mol of P2S5 (Merck) un­
der an N2 atmosphere, according to the procedure described 
by Meadow and Cavagnol [16], The reaction product was 
extracted with benzene and the crude orange-yellow product 
was recrystallized from benzene. Its purity was confirmed 
by the melting point (181-182 :C) and by IR and Raman 
spectra [11],
The adduct was obtained by addition of 1.0 mmol of 
hexamethylenediamine to an aqueous solution (15 mL) 
containing 2.0 mmol of thiosaccharin. The mixture was 
heated with stirring for 10 min at 80 :C. The resulting 
solution was filtered, and the filtrate was slowly evaporated
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E. J. Baran et al. ■ Thiosaccharin and Hexamethylenediamine 1533
Table 4. Crystal data and details of the structure refinement 
of [H3N-(CH2 )6-NH3](tsac)2 • 2 H2O.
Formula C2oH3oN406S4
Formula weight 550.72
Crystal system monoclinic
Space group P2i/a (Nr. 14)
a, A 16.385(2)
b,k 7.927(1)
c, A 20.280(1)
jB, deg 93.95(1)
V (A3) 2627.8(5)
Dc (g-cn-T3) 1.392
Z 4
F(000) 1160
0 Range for data collection 2.18-67.99°
Index ranges hkl -19 <h <0;
-1 <k<9;
—24<l< 24
Reflections collected 5473
Independent reflections 4515
R(int) 0.050
Observed reflections [7 > 2<r(I)] 3371
Data/restraints/parameters 4515/3/323
Goodness-of-fit on F1 2 345 1.036
Rl/wR2[I > 2o(I)] 0.0671/0.1807
Rl/wR2 (all data) 0.086/0.211
Largest diff. peak and hole, e 0.80/-0.39
[1] E. I. Baran. V. T. Yilmaz. Coord. Chem. Rev. 2006. 250. 
1980-1999.
[2] C. K. lohnson. Ortep-II. A Fortran Thermal-Ellipsoid 
Plot Program. Report ORNL-5318. Oak Ridge Na­
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at r. t. The obtained yellow microcrystalline product was 
recrystallized twice from methanol, and after the slow evap­
oration of the solvent a few. very small crystals adequate 
for crystallographic studies could be selected under the 
microscope.
Crystal structure determination
Measurements were performed at 296(2) K. with an 
Enraf-Nonius CAD-4 diffractometer employing graphite 
monochromated (TiA'(/ radiation (A = 1.54184 A). A color­
less prismatic crystal of dimensions 0.31 x 0.17 x 0.08 mm 
was used. Crystal data, collection procedures and refine­
ment results are summarized in Table 4. The thiosacchari­
nate and hexamethylenediammonium hydrogen atoms were 
located in calculated positions and refined with the riding 
model. The H positions of the H3N-(CH2)2-NH3 terminal 
ammonium groups were optimized by treating them as rigid 
groups which were allowed to rotate during the refinement 
around the corresponding N-C bonds. As a result, both NH3 
groups converged to staggered conformations. The H atoms 
of one water molecule were located in a difference Fourier 
map and refined isotropically with O-H and H- • • H distances 
restrained to target values of 0.86( 1) and 1.36( 1) Á. respec­
tively. The other water molecule showed positional disorder 
and therefore its H atoms could not be determined reliably to 
be included in the final molecular model.
Intensity data were corrected for Lorentz and polariza­
tion effects as well as for absorption (Platon [9]). The 
unit cell dimensions were obtained by least-squares re­
finement of the angular settings for 23 reflections in the 
range 16.54 < 0 < 41.21°. Programs used were Cad4 [17], 
Xcad-4 [18], and Shelxs-97 [19] for data reduction and 
correction and structure solution and Shelxl-97 [20] for 
structure refinement.
CCDC 653328 contains the supplementary crystallo­
graphic data for this paper. These data can be obtained free 
of charge from The Cambridge Crystallographic Data Centre 
via www. cede.cam. ac.uk/data_request/cif.
Spectroscopic measurements
The infrared spectra of the compound as well as that of 
free hexamethylenediamine were recorded in the spectral 
range between 4000 and 400 cm on a FTIR Bruker IFS 
66 spectrophotometer, using the KBr pellet technique.
Acknowledgemen ts
This work has been supported by the Consejo Nacional 
de Investigaciones Científicas y Técnicas de la República 
Argentina (CONICET) and the Universidad Nacional de La 
Plata (UNLP). The authors are members of the Research Ca­
reer from CONICET.
[6] M. Penavic. O. Grupce. G. lovanovski. Acta Crystal- 
logr. 1991. C47. 1821-1823
[7] E. I. Baran. O. E. Piro. I. Zinczuk. Z. Anorg. Allg. 
Chem. 2006. 632. 437 - 440.
[8] M. Dennehey. O. V. Quinzani. S.D. Mandolesi. 
I. Guida. G. A. Echeverría. O. E. Piro. Monatsh. Chem.. 
in press.
[9] A. L. Spek. Platon. A Multipurpose Crystallographic 
Tool. University of Utrecht. Utrecht (The Netherlands) 
1998.
[10] Z. L. Wang. L. H. Wei. M. X. Li. I. Y. Niu. Acta Crys- 
tallogr. 2006. E62. 01314-01316.
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1534 E. J. Baran et al. ■ Thiosaccharin and Hexamethylenediamine
[11] E. J. Baran. J. Zinczuk. J. Raman Spectr. 2006. 37. 
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E. E. Castellano. Monatsh. Chem. 2001. 132. 77)- 
787.
[13] D. Lin-Vien. N.B. Colthup. W.G. Fateley. J.G. Gras- 
selli. Infrared and Raman Characteristic Frequencies 
of Organic Molecules. Academic Press. San Diego. 
1991.
[14] B. Smith. Infrared Spectral Interpretation. CRC Press. 
Boca Raton. 1999.
[15] H. Siebert. Anwendungen der Schwingungsspek­
troskopie in der Anorganischen Chemie. Springer. 
Berlin. 1966.
[16] J. R. Meadow. J. C. Cavagnol. J. Org. Chem. 1951. 16. 
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[17] Cad4 Express Software. Enraf-Nonius. Delft (The 
Netherlands) 1994.
[18] K. Harms. S. Wocadlo. Xcad-4. Program for Process­
ing CAD-4 Diffractometer Data. University of Mar­
burg. Marburg (Germany) 1995.
[19] G. M. Sheldrick. Shelxs-97. Program for the Solution 
of Crystal Structures. University of Gottingen. Gottin­
gen (Germany) 1997.
[20] G. M. Sheldrick. Shelxl-97. Program for the Refine­
ment of Crystal Structures. University of Gottingen. 
Gottingen (Germany) 1997.
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A new supramolecular assembly obtained by reaction between thiosaccharin and hexamethylenediamine

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A new supramolecular assembly obtained by reaction between thiosaccharin and hexamethylenediamine

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