The crystal structures of heptamethylenediammonium bis(saccharinate) monohydrate, [H3N-(CH2)7-NH3J(sac) 2-H2O(1) and octamethylenediammonium bis(saccharinate) hemihydrate, [H3N-(CH2)8-NH3J(sac) 2-0.5H2O(2), were determined by single-crystal X-ray diffraction methods. Compound 1 crystallizes in the triclinic space group PI with 2 molecules per unit cell, and 2 in the mono-clinic space group P2 1/a with Z = 4. The saccharinate moiety is planar in both compounds presenting bonding characteristics comparable to those found in other saccharinate salts. The ionic crystals are fürther stabilized by an extensive H-bonding network, which links the anions and cations into an infinite three-dimensional supramolecular assembly. The FTIR spectra of the adducts are briefly discussed in comparison with those of the constituent molecules.Facultad de Ciencias ExactasCentro de Química Inorgánic

Barán, Enrique José

Castellano, Eduardo Ernesto

Parajón Costa, Beatriz S.

Piro, Oscar Enrique

Zeitschrift für Naturforschung B

English

SEDICI - Repositorio de la UNLP

Two New Supramolecular Assemblies Obtained by Reaction Between 
Saccharin and Long-chain Diamines
Eduardo E. Castellano®, Oscar E. Pirob, Beatriz S. Parajón-Costac, and Enrique J. Baranc
a Instituto de Física de Sao Carlos. Universidade de Sao Paulo. 13560 Sao Carlos (SP). Brazil
h Departamento de Física and Instituto IFLP (CONICET). Facultad de Ciencias Exactas. Universidad 
Nacional de La Plata. 1900 La Plata. Argentina
c Centro de Química Inorgánica (CEQUINOR. CONICET/UNLP). Facultad de Ciencias Exactas.
Universidad Nacional de La Plata. C. Correo 962. 1900 La Plata. Argentina
Reprint requests to Dr. E. I. Baran. E-mail: baran@quimica.unlp.edu.ar
Z. Naturforsch, 2009. 64b, 1041 - 1045; received May 22. 2009
The crystal structures of heptamethylenediammonium bis(saccharinate) monohydrate. [H3N- 
(CEEri-NEyisach-EEO (1) and octamethylenediammonium bis(saccharinate) hemihydrate. [H3N- 
(CH2)8-NH3](sac)2-0.5H2O (2). were determined by single-crystal X-ray diffraction methods. Com­
pound 1 crystallizes in the triclinic space group Pl with 2 molecules per unit cell, and 2 in the mono­
clinic space group P2\Ja with Z = 4. The saccharinate moiety is planar in both compounds presenting 
bonding characteristics comparable to those found in other saccharinate salts. The ionic crystals are 
further stabilized by an extensive H-bonding network, which links the anions and cations into an 
infinite three-dimensional supramolecular assembly. The FTIR spectra of the adducts are briefly dis­
cussed in comparison with those of the constituent molecules.
Key words: Heptamethylenediammonium Bis (saccharinate) Monohydrate. Octamethylenediammo­
nium Bis(saccharinate) Hemihydrate. Crystal Structures. Supramolecular Adducts.
IR Spectra
Introduction
During the last years a number of interesting 
supramolecular structures of organic salts containing 
saccharin and different organic bases have been pre­
pared and characterized [1-6], and we have extended 
these studies to some related species generated from 
thiosaccharin instead of saccharin [7,8]. With the only 
exception of 1,6-hexanediamine [1,7], in all the struc­
tures reported so far relatively small organic bases 
were always present. To explore the possibility of sim­
ilar supramolecular assemblies with longer-chain di­
amines, we have prepared and characterized two new 
systems of this type containing 1,7-heptanediamine 
and 1,8-octanediamine, and the results are reported 
here.
Results and Discussion
Crystal and molecular structures
Fig. 1 shows an Ortep-3 [9] drawing of the struc­
ture of [H3N-(CH2)7-NH3](sac)2 H2O (1). Selected 
bond lengths and angles are shown in Table 1.
As expected, both (>,114(C OtSCLN saccharinate 
anions are planar (r. m. s. deviation of atoms from 
the corresponding least-squares plane are less than 
0.01 A). They are nearly perpendicular to each other 
[dihedral angle = 93.09(5)°], with the [HtN-iCHgh- 
NH3]2+ cation lying along the comer defined by the 
saccharinate planes. By translation along the crystallo­
graphic a and b axes an electrically neutral slab parallel 
to the ab plane with a wine cellar-like structure is gen­
erated, where the cellar walls are defined by the sac­
charinate anions and the stored bottles by the cations. 
The slab is further stabilized at its surfaces by NIL • • • 
N(sac) and N-H- • • O(sulfoxide) bonds between the en­
closed cations and their surrounding saccharinate an­
ions. Neighboring slabs along the c axes, in turn, are 
linked to each other through NH3 • • • O(carb), NH3 • • • O 
(sulf) and bridging N11 ? ■ • Ow-H- • N(sac) and (sac)- 
N- • • H-Ow-H- • O(sulf) bonds. Fig. 2 presents an OR- 
tep-3 [9] drawing of these interactions. Further de­
tails of the H-bonding network are provided in the de­
posited material.
An ORTEP-3 [9] drawing of the structure of [H3N- 
(CH2)s-NH3](sac)2 0.5H2O (2) is shown in Fig. 3
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1042 E. E. Castellano et al. ■ Two New Supramolecular Assemblies
Table 1. Selected bond lengths (A) and angles (deg) in 
[H3N-(CH2)7-NH3](sac)2-H2b (1).
Table 2. Selected bond lengths (A) and angles (deg) in 
[H3N-(CH2 )8-NH3](sac)2-0.5H2O (2).
Nd)—Cd) 1.490(3) C(15)-C(16) 1.379(4) N(l)-C(l) 1.489(4) C(15)-C(16) 1.389(6)
N(2)-C(7) 1.476(4) C(25)-C(26) 1.376(4) N(2)-C(8) 1.478(5) C(25)-C(26) 1.378(6)
C(l)-C(2) 1.510(3) C(16)-C(17) 1.382(3) C(l)-C(2) 1.502(5) C(16)-C(17) 1.379(5)
C(4)-C(5) 1.520(4) O(1W)-H(1W) 0.826(19) C(3)-C(4) 1.520(5) C(26)-C(27) 1.383(5)
C(6)-C(7) 1.498(4) O(1W)-H(2W) 0.83(2) C(7)-C(8) 1.551(7) C(24)-C(25) 1.366(6)
S(l)—0(13) 1.438(2) S(2)—0(23) 1.439(2) S(l)—0(13) 1.446(2) S(2)—0(23) 1.443(3)
S(l)—0(12) 1.439(2) S(2)—0(22) 1.445(2) S(l)—0(12) 1.436(2) S(2)—0(22) 1.437(3)
S(l)-N(ll) 1.608(2) S(2)-N(21) 1.589(2) Sd)-N(ll) 1.595(3) S(2)-N(21) 1.612(3)
S(l)-C(17) 1.759(2) S(2)-C(27) 1.761(2) S(l)-C(17) 1.764(3) S(2)-C(27) 1.764(3)
C(ll)-O(ll) 1.179(3) C(21)-O(21) 1.237(3) Cdl)-O(ll) 1.244(4) C(21)-O(21) 1.246(4)
Cdl)-N(ll) 1.388(3) C(21)-N(21) 1.355(3) Cdl)-N(ll) 1.348(4) C(21)-N(21) 1.340(5)
C(ll)-C(12) 1.528(3) C(21)-C(22) 1.504(3) C(ll)-C(12) 1.500(4) C(21)-C(22) 1.493(4)
C(12)-C(17) 1.372(3) C(22)-C(27) 1.376(4) C(12)-C(17) 1.379(5) C(22)-C(27) 1.378(5)
C(12)-C(13) 1.380(4) C(22)-C(23) 1.386(3) C(12)-C(13) 1.381(5) C(22)-C(23) 1.379(5)
N(l)-C(l)-C(2) 111.0(2) N(2)-C(7)-C(6) 113.7(3) N(l)-C(l)-C(2) 111.4(3) N(2)-C(8)-C(7) 112.1(4)
C(l)-C(2)-C(3) 112.6(2) C(7)-C(6)-C(5) 115.5(3) C(l)-C(2)-C(3) 111.9(3) C(8)-C(7)-C(6) 122.0(7)
0(13)—S(l)—0(12) 114.14(14) O(23)-S(2)-O(22) 112.14(11) 0(13)—S(l)—0(12) 112.48(15) O(23)-S(2)-O(22) 113.53(18)
O(ll)-C(ll)-N(l 1) 125.7(2) O(21)-C(21)-N(21) 123.8(2) 0(1 l)-C(ll)-Ndl) 123.5(3) O(21)-C(21)-N(21) 124.8(3)
S(l)-N(ll)-C(ll) 113.46(17) S(2)-N(21)-C(21) 111.48(17) Sd)-N(ll)-Cdl) 111.0(2) S(2)-N(21)-C(21) 111.5(2)
C(13)-C(12)-C(ll) 127.3(2) C(23)-C(22)-C(21) 129.9(2) C(13)-C(12)-C(ll) 129.7(3) C(23)-C(22)-C(21) 128.3(3)
H(W)-O(W)-H(W) 96(5) C(26)-C(27)-S(2) 129.7(2) C(16)-C(17)-S(l) 130.2(3) C(26)-C(27)-S(2) 131.3(3)
Fig. 1. Molecular structure of [H3N-(CH2)7-NH3](sac)2- 
FEO (1) in the crystal showing the labeling of the non-H 
atoms (displacement ellipsoids at the 30 % probability level).
and selected bond lengths and angles are shown in 
Table 2.
As for [H3N-(CH2)7-NH3](sac)2 H2O (1), both sac- 
charinate anions are planar (r. m. s. deviation of atoms 
from the least-squares plane less than 0.018 A) and 
present a similar supramolecular arrangement around 
the longer [H3N-(CH2)s-NH3]2+ cation. In fact, the 
two saccharinate planes now subtend an angle of 
100.89(7)° with each other and bind the cation which 
extends along the edge defined by the planes. The 
syimnetry of the crystal lattice gives rise to neutral
Fig. 2. Molecular packing of [H3N-(CH2)7-NH3](sac)2-H2O 
(1) in the crystal. Sulfur, oxygen and nitrogen atoms are in­
dicated by hatched ellipsoids and carbon atoms by crossed 
ones. Hydrogen bonds are denoted by dashed lines.
slabs parallel to the crystallographic ab plane which 
stack along the c axes, with the cellar-like structure 
described for 1. As for this salt, each slab is fur­
ther stabilized at its surfaces by NH3 - N(sac) and 
NH3-• O(sulf) bonds between the enclosed cations 
and their surrounding saccharinate anions. Neighbor­
ing slabs along the c axes, in turn, are linked to each 
other through NH3 • • • O(carb) and NH3 • • • O(sulf) inter­
actions. Further details of the H-bonding network are 
provided in the deposited material.
Finally, a comparison of bond lengths and an­
gles of the two described adducts with those found
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E. E. Castellano et al. ■ Two New Supramolecular Assemblies 1043
NaSac-FEO NH2(CH2)7NH2 NH2(CH2)8NH2 1 2 Assignment Table 3. Assignment of some
3320 s 3353 m Vas(NH2) of the most characteristic IR
3270 sh Vs(NH2) bands of saccharinate in the
3202 vs 3170 vs v(NH3+) sodium salt, of the two free
2927 s 2924 s 2935 s 2933 s Vas(CH2) amines and of the two new
2856 m 2853 m 2860 m 2863 m Vs(CH2) adducts 1 and 2 (band positions
2039 m 2054 m see text in ciTi 1 ).a
1642 vs 1629 vs 1632 vs v(C=O)
1590 s 1585 s 1581 s v(C-C) + <wnh3+) a vs, very strong; s, strong; m,
1577 vs 1580 vs 5Sciss(NH2) medium; w, weak; sh, shoulder.
1460 m 1463 m 1462 m v(C-C)
1336 m 1334 m 1335 m Vs(CNS)
1258 vs 1260 vs 1259 vs Vas(SO2)
1150 vs 1146 vs 1141 vs vs(SO2)
1085 w 1044 m 1052 s 1051 s V (CN)amine
970 s 980 w r(CH)
950 m 956 s 943 m Vas(CNS)
794 w 796 m 798 w S (CO)
821 w 818 m <5wagg(NH2)
677 m 681 m 680 m <5(CCC)
610 m 604 s 606 s <5(SO2)
486 m 481 w t(NH3+)
Fig. 3. Molecular structure of [H3N-(CH2)8-NH3](sac)2- 
O.5H2O (2) in the crystal showing the labeling of the non-H 
atoms (displacement ellipsoids at the 30 % probability level).
in some ionic saccharinates, for example NaCCvIU 
NO3S)-2/3H2O [10], Mg(C7H4NO3S)2-7H2O [10] or 
K2Na(C7H4NO3S)3 H2O [11], shows very similar val­
ues for all of them. A further comparison with data 
of free saccharin [12] shows in all cases the expected 
shortening of the C-N and S-N bonds upon deproto­
nation [13], whereas the C-O and S-O bonds are less 
affected than expected.
Infrared spectra
We have measured the FTIR spectra of the two new 
adducts as well as those of the two free diamines em­
ployed in their synthesis. The assignment of some of 
the most characteristic bands of these molecules was 
performed with the aid of standard references [14,15]. 
In Table 3 we compare the most characteristic IR bands 
of the adducts, the diamines and the saccharinate in its 
sodium salt [16].
As it can be appreciated, the typical v(C=O) 
stretching vibration of the saccharinate anion is 
slightly displaced to lower frequencies upon adduct 
formation, surely due to the involvement of this group 
in hydrogen bonding. The stretching vibrations of the 
SO2 groups are less affected, although the vs(SO2) 
mode shows a definite displacement to lower frequen­
cies. Skeletal saccharinate bands are practically not af­
fected.
As expected, most of the typical amine NH2 vibra­
tions are replaced by NH3+ vibrations in the adducts. 
Interestingly, a combination band, which is typical and 
often appears in the case of aimnine salts [14], could 
be clearly identified as a medium intensity band at 
2039 cm (adduct 1) and 2054 cm (adduct 2).
Experimental Section
Synthesis of the adducts
All reagents were commercially available (saccharin and 
diamines from Aldrich, solvents from Merck) and were used 
as purchased. The adducts were obtained by addition of 
1.0 mmol of the respective diamine to a methanolic solu­
tion (30 mL) containing 2.0 mmol of saccharin. The mix­
tures were heated with stirring for 15 min at 40 :C. The re-
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1044 E. E. Castellano et al. ■ Two New Supramolecular Assemblies
Table 4. Crystal and structure refinement data of 
[H3N-(CH2)7-NH3](sac)2-H2O (1) and |HiN-(CH2ix-
NH3](sac)2-0.5H2O (2).
1 2
Formula C2iH3oN407S2 C22H3iN4O6 5S2
Formula weight 514.61 519.63
Crystal system triclinic monoclinic
Space group Pl P2fa
a, À 7.9404(4) 16.5660(5)
b,A 8.2119(5) 8.0522(3)
c, A 18.8831(7) 19.5757(6)
a, deg 98.036(3) 90
P, deg 92.324(3) 106.107(2)
y, deg 92.821(2) 90
v, Â3 1216.32(11) 2508.75(14)
Dc, g cm ’ 1.405 1.376
Z 2 4
F(000), e 544 1100
0 range data collection, deg 2.51-25.93 2.49 - 26.00
Index ranges hkl -9 < h < 8 -20 < h < 20
—9<k< 10 -9 < A < 7
-23 < / < 23 -24 < / < 22
Reflections coll. / indep. 10513 /4694 16663 / 4912
^int 0.0600 0.0655
Observ. reflect. |/ > 2<r(/)] 3482 3423
Data / restraints/ ref. param. 4694/2/315 4912/0/316
Final 7?1 / w/?2 |/ > 2<r(I)] 0.0488/0.1179 0.0651 /0.1702
Final 7?1 / v/R2 (all data) 0.0745 /0.1305 0.0996/0.1952
Goodness-of-fit on F2 1.041 1.034
Apan (max / min), e A '5 0.38/-0.51 1.26/-0.88
suiting solutions were filtered, and the filtrates were slowly 
evaporated at r. t. After a few days an abundant quantity of 
crystalline material precipitated from the solution. Similar 
assays performed under the same conditions with 1.9-non- 
anediamine. and using a variety of solvents and solvent mix­
tures. were unsuccessful as it was impossible to isolate single 
crystals adequate for structural work from the solid precipi­
tates.
Crystal structure determination
X-Ray diffraction data were collected on an Enraf-Nonius 
Kappa-CCD diffractometer at 293(2) K with graphite - 
monochromatized MoA'(/ (A = 0.71073 A) radiation. Col­
orless crystals of dimensions 0.19x0.12x0.08 mm3 (1) 
and 0.25 x 0.18 x 0.08 mm3 (2) were used in the experi­
ments. Crystal data and refinement results are summarized 
in Table 4. The final unit cell parameters were based on all 
reflections. Data collections were made using the program 
Collect [17]; integration and scaling of the reflections 
were performed with the EIKL Denzo-Scalepack system 
of programs [18], Absorption corrections were deemed un­
necessary. The structures were solved by Direct Methods 
with Shelxs-97 [19], and the molecular model was refined 
by full-matrix least-squares on F2 by means of Shelxl- 
97 [20], All hydrogen atoms were stereochemically posi­
tioned and refined with the riding model, except the water 
hydrogens, which in the case of compound 1 were found in 
a difference map and refined restrained to a target O-EI dis­
tance of 0.82(2) A. In the case of compound 2 a disordered 
water molecule was modeled with an occupation factor of 
0.5; its H atoms could not be located in the final difference 
map and were not included in the model. Besides, the di­
ammonium cation in this same compound shows some de­
gree of disorder at carbon atom C7 as indicated by a peak 
of 1.26 e A ' in the final difference map. However, though 
attempts to model the disorder setting C7 in two different po­
sitions did improve the Fl factor slightly, it did not produce 
a significantly better stereochemistry of this moiety, and the 
procedure was therefore discarded. As a consequence of this 
disorder, interatomic distances involving C7 are somewhat 
dubious.
CCDC 736974 (1) andCCDC 736975 (2) contain the sup­
plementary crystallographic data. These data can be obtained 
free of charge from The Cambridge Crystallographic Data 
Centre via www.ccdc.cam.ac.uk/data_request/cif.
Spectroscopic measurements
The infrared spectra of the two compounds, as well as 
those of the respective free diamines, were recorded in the 
spectral range between 4000 and 400 cm on a FTIR- 
Bruker-EQUINOX-55 instrument, using KBr pellets.
Acknowledgement
This work has been supported by CONICET (Argentina). 
UNLP (Argentina) and FAPESP (Brazil). OEP. BSPC and 
EJB are members of the Research Career from CONICET.
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Two new supramolecular assemblies obtained by reaction between saccharin and long-chain diamines

Servicio de Difusión de la Creación Intelectual

Two New Supramolecular Assemblies Obtained by Reaction Between Saccharin and Long-chain DiaminesEduardo E. Castellano®, Oscar E. Pirob, Beatriz S. Parajón-Costac, and Enrique J. Baranca Instituto de Física de Sao Carlos. Universidade de Sao Paulo. 13560 Sao Carlos (SP). Brazilh Departamento de Física and Instituto IFLP (CONICET). Facultad de Ciencias Exactas. Universidad Nacional de La Plata. 1900 La Plata. Argentinac Centro de Química Inorgánica (CEQUINOR. CONICET/UNLP). Facultad de Ciencias Exactas.Universidad Nacional de La Plata. C. Correo 962. 1900 La Plata. ArgentinaReprint requests to Dr. E. I. Baran. E-mail: baran@quimica.unlp.edu.arZ. Naturforsch, 2009. 64b, 1041 - 1045; received May 22. 2009The crystal structures of heptamethylenediammonium bis(saccharinate) monohydrate. [H3N- (CEEri-NEyisach-EEO (1) and octamethylenediammonium bis(saccharinate) hemihydrate. [H3N- (CH2)8-NH3](sac)2-0.5H2O (2). were determined by single-crystal X-ray diffraction methods. Com­pound 1 crystallizes in the triclinic space group Pl with 2 molecules per unit cell, and 2 in the mono­clinic space group P2\Ja with Z = 4. The saccharinate moiety is planar in both compounds presenting bonding characteristics comparable to those found in other saccharinate salts. The ionic crystals are further stabilized by an extensive H-bonding network, which links the anions and cations into an infinite three-dimensional supramolecular assembly. The FTIR spectra of the adducts are briefly dis­cussed in comparison with those of the constituent molecules.Key words: Heptamethylenediammonium Bis (saccharinate) Monohydrate. Octamethylenediammo­nium Bis(saccharinate) Hemihydrate. Crystal Structures. Supramolecular Adducts.IR SpectraIntroductionDuring the last years a number of interesting supramolecular structures of organic salts containing saccharin and different organic bases have been pre­pared and characterized [1-6], and we have extended these studies to some related species generated from thiosaccharin instead of saccharin [7,8]. With the only exception of 1,6-hexanediamine [1,7], in all the struc­tures reported so far relatively small organic bases were always present. To explore the possibility of sim­ilar supramolecular assemblies with longer-chain di­amines, we have prepared and characterized two new systems of this type containing 1,7-heptanediamine and 1,8-octanediamine, and the results are reported here.Results and DiscussionCrystal and molecular structuresFig. 1 shows an Ortep-3 [9] drawing of the struc­ture of [H3N-(CH2)7-NH3](sac)2 H2O (1). Selected bond lengths and angles are shown in Table 1.As expected, both (>,114(C OtSCLN saccharinate anions are planar (r. m. s. deviation of atoms from the corresponding least-squares plane are less than 0.01 A). They are nearly perpendicular to each other [dihedral angle = 93.09(5)°], with the [HtN-iCHgh- NH3]2+ cation lying along the comer defined by the saccharinate planes. By translation along the crystallo­graphic a and b axes an electrically neutral slab parallel to the ab plane with a wine cellar-like structure is gen­erated, where the cellar walls are defined by the sac­charinate anions and the stored bottles by the cations. The slab is further stabilized at its surfaces by NIL • • • N(sac) and N-H- • • O(sulfoxide) bonds between the en­closed cations and their surrounding saccharinate an­ions. Neighboring slabs along the c axes, in turn, are linked to each other through NH3 • • • O(carb), NH3 • • • O (sulf) and bridging N11 ? ■ • Ow-H- • N(sac) and (sac)- N- • • H-Ow-H- • O(sulf) bonds. Fig. 2 presents an OR- tep-3 [9] drawing of these interactions. Further de­tails of the H-bonding network are provided in the de­posited material.An ORTEP-3 [9] drawing of the structure of [H3N- (CH2)s-NH3](sac)2 0.5H2O (2) is shown in Fig. 30932-0776 / 09 / 0900-1041 $ 06.00 © 2009 Verlag der Zeitschrift für Naturforschung, Tübingen • http://znaturforsch.comUnauthenticatedDownload Date | 8/23/19 11:44 PM1042 E. E. Castellano et al. ■ Two New Supramolecular AssembliesTable 1. Selected bond lengths (A) and angles (deg) in [H3N-(CH2)7-NH3](sac)2-H2b (1).Table 2. Selected bond lengths (A) and angles (deg) in [H3N-(CH2 )8-NH3](sac)2-0.5H2O (2).Nd)—Cd) 1.490(3) C(15)-C(16) 1.379(4) N(l)-C(l) 1.489(4) C(15)-C(16) 1.389(6)N(2)-C(7) 1.476(4) C(25)-C(26) 1.376(4) N(2)-C(8) 1.478(5) C(25)-C(26) 1.378(6)C(l)-C(2) 1.510(3) C(16)-C(17) 1.382(3) C(l)-C(2) 1.502(5) C(16)-C(17) 1.379(5)C(4)-C(5) 1.520(4) O(1W)-H(1W) 0.826(19) C(3)-C(4) 1.520(5) C(26)-C(27) 1.383(5)C(6)-C(7) 1.498(4) O(1W)-H(2W) 0.83(2) C(7)-C(8) 1.551(7) C(24)-C(25) 1.366(6)S(l)—0(13) 1.438(2) S(2)—0(23) 1.439(2) S(l)—0(13) 1.446(2) S(2)—0(23) 1.443(3)S(l)—0(12) 1.439(2) S(2)—0(22) 1.445(2) S(l)—0(12) 1.436(2) S(2)—0(22) 1.437(3)S(l)-N(ll) 1.608(2) S(2)-N(21) 1.589(2) Sd)-N(ll) 1.595(3) S(2)-N(21) 1.612(3)S(l)-C(17) 1.759(2) S(2)-C(27) 1.761(2) S(l)-C(17) 1.764(3) S(2)-C(27) 1.764(3)C(ll)-O(ll) 1.179(3) C(21)-O(21) 1.237(3) Cdl)-O(ll) 1.244(4) C(21)-O(21) 1.246(4)Cdl)-N(ll) 1.388(3) C(21)-N(21) 1.355(3) Cdl)-N(ll) 1.348(4) C(21)-N(21) 1.340(5)C(ll)-C(12) 1.528(3) C(21)-C(22) 1.504(3) C(ll)-C(12) 1.500(4) C(21)-C(22) 1.493(4)C(12)-C(17) 1.372(3) C(22)-C(27) 1.376(4) C(12)-C(17) 1.379(5) C(22)-C(27) 1.378(5)C(12)-C(13) 1.380(4) C(22)-C(23) 1.386(3) C(12)-C(13) 1.381(5) C(22)-C(23) 1.379(5)N(l)-C(l)-C(2) 111.0(2) N(2)-C(7)-C(6) 113.7(3) N(l)-C(l)-C(2) 111.4(3) N(2)-C(8)-C(7) 112.1(4)C(l)-C(2)-C(3) 112.6(2) C(7)-C(6)-C(5) 115.5(3) C(l)-C(2)-C(3) 111.9(3) C(8)-C(7)-C(6) 122.0(7)0(13)—S(l)—0(12) 114.14(14) O(23)-S(2)-O(22) 112.14(11) 0(13)—S(l)—0(12) 112.48(15) O(23)-S(2)-O(22) 113.53(18)O(ll)-C(ll)-N(l 1) 125.7(2) O(21)-C(21)-N(21) 123.8(2) 0(1 l)-C(ll)-Ndl) 123.5(3) O(21)-C(21)-N(21) 124.8(3)S(l)-N(ll)-C(ll) 113.46(17) S(2)-N(21)-C(21) 111.48(17) Sd)-N(ll)-Cdl) 111.0(2) S(2)-N(21)-C(21) 111.5(2)C(13)-C(12)-C(ll) 127.3(2) C(23)-C(22)-C(21) 129.9(2) C(13)-C(12)-C(ll) 129.7(3) C(23)-C(22)-C(21) 128.3(3)H(W)-O(W)-H(W) 96(5) C(26)-C(27)-S(2) 129.7(2) C(16)-C(17)-S(l) 130.2(3) C(26)-C(27)-S(2) 131.3(3)Fig. 1. Molecular structure of [H3N-(CH2)7-NH3](sac)2- FEO (1) in the crystal showing the labeling of the non-H atoms (displacement ellipsoids at the 30 % probability level).and selected bond lengths and angles are shown in Table 2.As for [H3N-(CH2)7-NH3](sac)2 H2O (1), both sac- charinate anions are planar (r. m. s. deviation of atoms from the least-squares plane less than 0.018 A) and present a similar supramolecular arrangement around the longer [H3N-(CH2)s-NH3]2+ cation. In fact, the two saccharinate planes now subtend an angle of 100.89(7)° with each other and bind the cation which extends along the edge defined by the planes. The syimnetry of the crystal lattice gives rise to neutralFig. 2. Molecular packing of [H3N-(CH2)7-NH3](sac)2-H2O (1) in the crystal. Sulfur, oxygen and nitrogen atoms are in­dicated by hatched ellipsoids and carbon atoms by crossed ones. Hydrogen bonds are denoted by dashed lines.slabs parallel to the crystallographic ab plane which stack along the c axes, with the cellar-like structure described for 1. As for this salt, each slab is fur­ther stabilized at its surfaces by NH3 - N(sac) and NH3-• O(sulf) bonds between the enclosed cations and their surrounding saccharinate anions. Neighbor­ing slabs along the c axes, in turn, are linked to each other through NH3 • • • O(carb) and NH3 • • • O(sulf) inter­actions. Further details of the H-bonding network are provided in the deposited material.Finally, a comparison of bond lengths and an­gles of the two described adducts with those foundUnauthenticatedDownload Date | 8/23/19 11:44 PME. E. Castellano et al. ■ Two New Supramolecular Assemblies 1043NaSac-FEO NH2(CH2)7NH2 NH2(CH2)8NH2 1 2 Assignment Table 3. Assignment of some3320 s 3353 m Vas(NH2) of the most characteristic IR3270 sh Vs(NH2) bands of saccharinate in the3202 vs 3170 vs v(NH3+) sodium salt, of the two free2927 s 2924 s 2935 s 2933 s Vas(CH2) amines and of the two new2856 m 2853 m 2860 m 2863 m Vs(CH2) adducts 1 and 2 (band positions2039 m 2054 m see text in ciTi 1 ).a1642 vs 1629 vs 1632 vs v(C=O)1590 s 1585 s 1581 s v(C-C) + <wnh3+) a vs, very strong; s, strong; m,1577 vs 1580 vs 5Sciss(NH2) medium; w, weak; sh, shoulder.1460 m 1463 m 1462 m v(C-C)1336 m 1334 m 1335 m Vs(CNS)1258 vs 1260 vs 1259 vs Vas(SO2)1150 vs 1146 vs 1141 vs vs(SO2)1085 w 1044 m 1052 s 1051 s V (CN)amine970 s 980 w r(CH)950 m 956 s 943 m Vas(CNS)794 w 796 m 798 w S (CO)821 w 818 m <5wagg(NH2)677 m 681 m 680 m <5(CCC)610 m 604 s 606 s <5(SO2)486 m 481 w t(NH3+)Fig. 3. Molecular structure of [H3N-(CH2)8-NH3](sac)2- O.5H2O (2) in the crystal showing the labeling of the non-H atoms (displacement ellipsoids at the 30 % probability level).in some ionic saccharinates, for example NaCCvIU NO3S)-2/3H2O [10], Mg(C7H4NO3S)2-7H2O [10] or K2Na(C7H4NO3S)3 H2O [11], shows very similar val­ues for all of them. A further comparison with data of free saccharin [12] shows in all cases the expected shortening of the C-N and S-N bonds upon deproto­nation [13], whereas the C-O and S-O bonds are less affected than expected.Infrared spectraWe have measured the FTIR spectra of the two new adducts as well as those of the two free diamines em­ployed in their synthesis. The assignment of some of the most characteristic bands of these molecules was performed with the aid of standard references [14,15]. In Table 3 we compare the most characteristic IR bands of the adducts, the diamines and the saccharinate in its sodium salt [16].As it can be appreciated, the typical v(C=O) stretching vibration of the saccharinate anion is slightly displaced to lower frequencies upon adduct formation, surely due to the involvement of this group in hydrogen bonding. The stretching vibrations of the SO2 groups are less affected, although the vs(SO2) mode shows a definite displacement to lower frequen­cies. Skeletal saccharinate bands are practically not af­fected.As expected, most of the typical amine NH2 vibra­tions are replaced by NH3+ vibrations in the adducts. Interestingly, a combination band, which is typical and often appears in the case of aimnine salts [14], could be clearly identified as a medium intensity band at 2039 cm (adduct 1) and 2054 cm (adduct 2).Experimental SectionSynthesis of the adductsAll reagents were commercially available (saccharin and diamines from Aldrich, solvents from Merck) and were used as purchased. The adducts were obtained by addition of 1.0 mmol of the respective diamine to a methanolic solu­tion (30 mL) containing 2.0 mmol of saccharin. The mix­tures were heated with stirring for 15 min at 40 :C. The re-UnauthenticatedDownload Date | 8/23/19 11:44 PM1044 E. E. Castellano et al. ■ Two New Supramolecular AssembliesTable 4. Crystal and structure refinement data of [H3N-(CH2)7-NH3](sac)2-H2O (1) and |HiN-(CH2ix-NH3](sac)2-0.5H2O (2).1 2Formula C2iH3oN407S2 C22H3iN4O6 5S2Formula weight 514.61 519.63Crystal system triclinic monoclinicSpace group Pl P2faa, À 7.9404(4) 16.5660(5)b,A 8.2119(5) 8.0522(3)c, A 18.8831(7) 19.5757(6)a, deg 98.036(3) 90P, deg 92.324(3) 106.107(2)y, deg 92.821(2) 90v, Â3 1216.32(11) 2508.75(14)Dc, g cm ’ 1.405 1.376Z 2 4F(000), e 544 11000 range data collection, deg 2.51-25.93 2.49 - 26.00Index ranges hkl -9 < h < 8 -20 < h < 20—9<k< 10 -9 < A < 7-23 < / < 23 -24 < / < 22Reflections coll. / indep. 10513 /4694 16663 / 4912^int 0.0600 0.0655Observ. reflect. |/ > 2<r(/)] 3482 3423Data / restraints/ ref. param. 4694/2/315 4912/0/316Final 7?1 / w/?2 |/ > 2<r(I)] 0.0488/0.1179 0.0651 /0.1702Final 7?1 / v/R2 (all data) 0.0745 /0.1305 0.0996/0.1952Goodness-of-fit on F2 1.041 1.034Apan (max / min), e A '5 0.38/-0.51 1.26/-0.88suiting solutions were filtered, and the filtrates were slowly evaporated at r. t. After a few days an abundant quantity of crystalline material precipitated from the solution. Similar assays performed under the same conditions with 1.9-non- anediamine. and using a variety of solvents and solvent mix­tures. were unsuccessful as it was impossible to isolate single crystals adequate for structural work from the solid precipi­tates.Crystal structure determinationX-Ray diffraction data were collected on an Enraf-Nonius Kappa-CCD diffractometer at 293(2) K with graphite - monochromatized MoA'(/ (A = 0.71073 A) radiation. Col­orless crystals of dimensions 0.19x0.12x0.08 mm3 (1) and 0.25 x 0.18 x 0.08 mm3 (2) were used in the experi­ments. Crystal data and refinement results are summarized in Table 4. The final unit cell parameters were based on all reflections. Data collections were made using the program Collect [17]; integration and scaling of the reflections were performed with the EIKL Denzo-Scalepack system of programs [18], Absorption corrections were deemed un­necessary. The structures were solved by Direct Methods with Shelxs-97 [19], and the molecular model was refined by full-matrix least-squares on F2 by means of Shelxl- 97 [20], All hydrogen atoms were stereochemically posi­tioned and refined with the riding model, except the water hydrogens, which in the case of compound 1 were found in a difference map and refined restrained to a target O-EI dis­tance of 0.82(2) A. In the case of compound 2 a disordered water molecule was modeled with an occupation factor of 0.5; its H atoms could not be located in the final difference map and were not included in the model. Besides, the di­ammonium cation in this same compound shows some de­gree of disorder at carbon atom C7 as indicated by a peak of 1.26 e A ' in the final difference map. However, though attempts to model the disorder setting C7 in two different po­sitions did improve the Fl factor slightly, it did not produce a significantly better stereochemistry of this moiety, and the procedure was therefore discarded. As a consequence of this disorder, interatomic distances involving C7 are somewhat dubious.CCDC 736974 (1) andCCDC 736975 (2) contain the sup­plementary crystallographic data. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.Spectroscopic measurementsThe infrared spectra of the two compounds, as well as those of the respective free diamines, were recorded in the spectral range between 4000 and 400 cm on a FTIR- Bruker-EQUINOX-55 instrument, using KBr pellets.AcknowledgementThis work has been supported by CONICET (Argentina). UNLP (Argentina) and FAPESP (Brazil). OEP. BSPC and EJB are members of the Research Career from CONICET.[1] Z. L. Wang. L. H. Wei. M. X. Li. I. Y. Niu. Acta Crys- tallogr. 2006. E62. 01314-01316.[2] Z. L. Wang. L. H. Wei. M. X. Li. I. P. Wang. Acta Crys- tallogr. 2006. E62. 0I8OO-0I8OI.[3] Z. L. Wang. M. X. Li. L. H. Wei. I. P. Wang. Acta Crys- tallogr. 2006. E62. o2127-o2128.[4] Z. L. Wang. M. X. Li. L. H. Wei. I. P. Wang. Acta Crys- tallogr. 2006. E62. o2171 -o2172.[5] R. Banerjee. B. K. Saha. G. R. Desiraju. Acta Crystal- logr. 2006. C62. o346-o349.[6] Z. L. Wang. M. X. Li. L. H. Wei. I. P. Wang. Acta Crys- tallogr. 2006. E62. o2274-o2275.[7] E. I. Baran. O. E. Piro. I. Zinczuk. Z. Naturforsch.2007. 62b. 1530-1534.[8] O. E. Piro. I. Zinczuk. E. I. Baran. Z. Naturforsch.2008. 63 b. 877-879.UnauthenticatedDownload Date | 8/23/19 11:44 PME. E. Castellano et al. ■ Two New Supramolecular Assemblies 1045[9] C.K. Johnson. M. N. Burnett. Ortep-3. Rep. ORNL- 6895. Oak Ridge National Laboratory. Oak Ridge. T. N (USA) 1996. Windows version: L. J. Farrugia. Univer­sity of Glasgow. Glasgow. Scotland (U. K.) 1999. See also: L. J. Farrugia. J. Appi. Crystallogr. 1997. 30. 565.[10] G. Jovanovski. B. Kamenar. Cryst. Struct. Comm.1982.11. 247-255.[11] K.M.A. Malik. S.Z. Haider. M. A. Hossan. M.B. Hursthouse. Acta Crystallogr. 1984. C40. 1696- 1698.[12] J. L. Wardell. J. N. Low. Ch. Glidewell. Acta Crystal­logr. 2005. E61. O1944-O1946.[13] P. Naumov. G. Jovanosvski. Struct. Chem. 2000. 11. 19-33.[14] D. Lin-Vien. N.B. Colthup. W.G. Fateley. J.G. Gras­selli. The Handbook of Infrared and Raman Charac­teristic Frequencies of Organic Molecules. Academic Press. Boston. 1991.[15] B. Smith. Infrared Spectral Interpretation. CRC Press. Boca Raton. 1999.[16] O. V. Quinzani. S. Tarulli. O. E. Piro. E. J. Baran. E. E. Castellano. Z. Naturforsch. 1997. 52b. 183- 187.[17] Collect. Nonius KappaCCD Software. Nonius BV. Delft (The Netherlands) 2000.[18] HKL Denzo. Scalepack. Z. Otwinowski. W. Mi­nor. in Methods in Enzymology. Vol. 276. Macromolec­ular Crystallography. Part A (Eds.: C.W. Carter Jr.. R. M. Sweet). Academic Press. New York. 1997. pp. 307-326.[19] G. M. Sheldrick. Shelxs-97. Program for the Solution of Crystal Structures. University of Gottingen. Gottin­gen (Germany) 1997.[20] G. M. Sheldrick. Shelxl-97. Program for the Refine­ment of Crystal Structures. University of Gottingen. Gottingen (Germany) 1997. See also: G. M. Sheldrick. Acta Crystallogr. 2008. A64. 112- 122.UnauthenticatedDownload Date | 8/23/19 11:44 PM

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Two new supramolecular assemblies obtained by reaction between saccharin and long-chain diamines

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