Synthesis, crystal structures and non-bonded S···S contacts with OH···O/OH···S hydrogen bonds in isomeric hydroxyphenyl-1,3-dithianes

Article abstract of DOI:10.1080/17415993.2012.762919

The synthesis of isomeric hydroxyphenyl-1,3-dithianes and the role of sulfur in them to generate different engineered solids based on non-bonded O···S contacts and OH···S hydrogen bonds are presented. With an increasing number of OH groups and dithiane ri

Full text of DOI:10.1080/17415993.2012.762919

This article was downloaded by: [University of Connecticut]
On: 12 April 2015, At: 10:28
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Journal of Sulfur Chemistry
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gsrp20
Synthesis, crystal structures and non-
bonded S···S contacts with O‒H···O/
O‒H···S hydrogen bonds in isomeric
hydroxyphenyl-1,3-dithianes
Mrityunjoy Datta a , Allen D. Hunter b & Matthias Zeller b
a Department of Chemistry , University of Kalyani , Kalyani,
Nadia , West Bengal , 741235 , India
b STaRBURSTT-Cyberdiffraction Consortium @ YSU & Department
of Chemistry , Youngstown State University , 1 University Plaza,
Youngstown , OH , 44555-3663 , USA
Published online: 13 Feb 2013.
To cite this article: Mrityunjoy Datta , Allen D. Hunter & Matthias Zeller (2013) Synthesis,
crystal structures and non-bonded S···S contacts with O‒H···O/O‒H···S hydrogen bonds
in isomeric hydroxyphenyl-1,3-dithianes, Journal of Sulfur Chemistry, 34:5, 502-511, DOI:
10.1080/17415993.2012.762919
To link to this article: http://dx.doi.org/10.1080/17415993.2012.762919
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &

Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions

Journal of Sulfur Chemistry, 2013
Vol. 34, No. 5, 502–511, http://dx.doi.org/10.1080/17415993.2012.762919
Synthesis, crystal structures and non-bonded S· · ·S contacts
−
−
with O H· · ·O/O H· · ·S hydrogen bonds in isomeric
hydroxyphenyl-1,3-dithianes
Mrityunjoy Dattaa*†, Allen D. Hunterb and Matthias Zellerb
aDepartment of Chemistry, University of Kalyani, Kalyani, Nadia, West Bengal 741235, India;
bSTaRBURSTT-Cyberdiffraction Consortium @ YSU & Department of Chemistry, Youngstown State
University, 1 University Plaza, Youngstown, OH 44555-3663, USA
(Received 7 November 2012; final version received 27 December 2012)
The synthesis of isomeric hydroxyphenyl-1,3-dithianes and the role of sulfur in them to generate different
−
engineered solids based on non-bonded O· · ·S contacts and O H· · ·S hydrogen bonds are presented.
−
With an increasing number of OH groups and dithiane rings (e.g. 2, 3), the role of O H· · ·S interactions
−
−
becomes less prominent and the strong O H· · ·O hydrogen bonds along with C H· · ·π and π–π stacking
interactions dominate the packing arrangement of the hydroxyphenyl-1,3-dithianes.
A
S
S
A
S
S
S
S
D
OH
A
OH
OH
S
D
OH
A
S
OH
1
2
3
hydrogen-bond sites (A= acceptor, D = donor)
Keywords: hydroxyphenyl-1,3-dithianes; crystal structures; hydrogen bond; non-bonded contacts;
synthesis
1. Introduction
Understanding and harnessing non-covalent interactions are of contemporary interest in biology,
chemistry and material science (1–6), and the use of hydrogen bond motifs for designing and
*Corresponding author. Email: mdattap@rediffmail.com
†Present address: State Forensic Sience Laboratory, Government of West Bengal, 37/1/2 Belgachia Road, Kolkata –
700037, India
© 2013 Taylor & Francis

Journal of Sulfur Chemistry 503
exploiting crystal structures has been widely used in crystal engineering (7, 8). Both classical
−
−
−
(N H· · ·X and O H· · ·X; X = O, N) and weak hydrogen bonds (C H· · ·X; X = O, N) play
a significant role in the formation of supramolecular assemblies of a wide range of molecular
architechtures (9–12). In this aspect, the use of sulfur atoms for controlling the packing of organic
crystal structures seemsto bein contrastto nitrogen, oxygen, etc. muchlesscommonplace(13, 14).
This may be due, perhaps, to its infrequent occurrence in organic crystals, but also due to its
relatively low electronegativity, and thus the much weaker hydrogen bonds is able to form, which
makes sulfur atoms a less obvious choice as a means for controlling the molecular architecture
of crystalline compounds.
We reported the use of sulfur of dithiane rings in isomeric hydroxyphenyl-1,3-dithianes to gen-
−
erate different engineered solids based on non-bonded O· · ·S contacts and O H· · ·S hydrogen
bonds (15). In continuation of this work, we describe in this paper how the systematic vari-
ation of the number of phenolic hydroxyl groups and dithiane rings influences the hydrogen
bonding interactions and packing of the molecules in the solid state. In this context, we report the
synthesis and hydrogen bonding schemes of the three hydroxyphenyl-1,3-dithianes 1 (16), 2 and 3
(Scheme 1).
A
S
S
A
S
S
S
S
D
OH
A
OH
OH
S
D
OH
A
S
OH
1
2
3
Scheme 1. Hydrogen-bond sites (A = acceptor, D = donor).
2. Results and discussion
We reported earlier in our publication (15) that contacts in crystals between divalent sulfur and
other atoms X can be divided into two general types, depending on the nature of the second atom
as described by Rosenfield et al. (17). The two types are distinguished by the direction of the
− −
S· · ·X vector relative to the C S C plane (Figure 1). Electrophiles tend to approach from above
and below the plane, approximately along the directions corresponding to the electron lone pairs
of an S atom. These are denoted as Type I contacts. In contrast, nucleophiles tend to approach
− −
−
within the C S C plane, close to the posterior extensions of the S C bonds. These are shown
as Type II contacts and are interpreted as interactions between the nucleophile and σ∗ orbitals of
−
S C bonds. A comprehensive database study by Allen et al. (18) has demonstrated that divalent
− −
sulfur, particularly as part of a C S C unit, is a poor but adequate acceptor for conventional
−
−
hydrogen bond donors such as O H and N H. We previously reported the crystal structures of
three isomeric hydroxyphenyl-1,3-dithianes, ortho-, meta- and para-HO C6H4 C4H7S2, where
−
−
−
both non-bonded O· · ·S contacts and O H· · ·S hydrogen bonds play an important role in the
packing within their crystals (15).

504 M. Datta et al.
Figure 1. Geometry of non-bonded S· · ·X contacts for divalent sulfur.
2.1. Crystal structure of 1
Among the three dithiane compounds 1–3, the ortho isomer 1 (16) adopts a chair conformation
−
expected for a six-membered saturated ring and its disposition about the central C C bond
−
joining the dithiane and phenyl rings is such that one C S bond lies approximately perpendicular
to the plane of the phenyl ring (Figure S1). This structural aspect allows for the formation of an
−
intramolecular C H · · · O hydrogen bond between the slightly acidic carbon atom of the dithiane
group and the oxygen atom O1 of the hydroxyl moiety. In the network, the phenolic OH group
−
is also involved in an intermolecular O H · · · S hydrogen bond (Table 1), linking the molecules
into chains along the crystallographic b-direction (Figure S2). The geometry at the S acceptor is
consistent with the expected Type I approach. The chains propagate with approximate 120◦ turns,
imposed by the relative rotations of the phenyl and dithiane rings within the molecules themselves
(Figure S2). Adjacent chains are arranged to form sheets in the ab plane (Figure S3) involving
both the dithiane and phenyl rings. In the packing, no S· · ·S or S· · ·O contacts are observed.
2.2. Crystal structure of 2
With more than one OH group in the ring along with one and two dithiane rings (2, 3), respec-
tively, the packing arrangement possibilities are becoming more diverse. Similar to compound
1, the dithiane ring in 2 adopts the expected chair conformation (Figure 2(a)) and exhibits an
−
intramolecular C H· · ·O hydrogen bond between the slightly acidic carbon atom C7 of the
dithiane group and the oxygen atom O1 of the neighboring hydroxyl moiety. In 2, however, the
−
hydrogen bonding is not limited to O H· · ·S interactions, but there is also a strong intermolecular
−
hydrogen bond formed between the hydroxyl group O2 H2 para to the dithiane group and the
oxygen O1 of a neighboring molecule (Figure 2(b)). The para hydroxyl group is also hydrogen
bonded to the sulfur atom S2 of a nearer dithiane group consistent with Type I as described
by Rosenfield et al. The hydrogen bonding interactions are completed by a strong hydrogen
−
bond between O1 H1 and O2. In addition, a hydrogen atom of one of the dithiane methylene
groups points toward the centroid of the adjacent phenyl ring, forming a relatively short contact
◦
−
(H10B· · ·centroid = 2.72 Å, C10 H10B· · ·centroid = 133 ) that might be described as a com-
−
plementary C H· · ·π interaction. This interaction occurs on one side of the phenyl ring, the other
side is π-stacked with another phenyl ring. The π-stacking and hydrogen bonds observed in 2 and
−
especially the strong interaction between O2 H2 and O1 do not allow for an effective packing,
but large voids filled with water molecules are found in the unit cell, forming channels parallel to

Journal of Sulfur Chemistry 505
Table 1. Crystallographic data for 2 and 3.
Compound 2
Compound 3
Empirical formula
Moiety formula
Formula weight
Temperature
C10 H12 O3.39 S2
C10 H12 O2 S2, O1.39
250.32
C14 H18 S4 O2
346.52
100(2) K
100(2) K
Wavelength
0.71073Å
0.71073Å
Crystal system
Space group
Monoclinic
C2/c
Monoclinic
P21/c
Unit cell dimensions
a = 28.3902(17)Å,
b = 11.2221(7)Å,
c = 7.3345(4)Å, α = 90◦,
β = 96.9960(10)◦, γ = 90◦
2319.4(2)Å3
a = 12.8728(6)Å,
b = 11.3313(5)Å,
c = 10.9195(5)Å, α = 90◦,
β = 93.9350(10)◦, γ = 90◦
1589.02(13)Å3
4
Volume
Z
Density (calculated)
Absorption coefficient
F(000)
8
1.434 Mg/m3
1.448 Mg/m3
0.447 mm−1
0.595 mm−1
728
1048
Crystal size
Crystal shape
Color
θ range for data collection
Limiting indices
0.42 × 0.36 × 0.25 mm
0.42 × 0.35 × 0.30 mm
Block
Block
Yellow
Colorless
1.45–28.27◦
1.59–28.27◦
−37 ≤ h ≤ 37, −14 ≤ k ≤ 14,
−17 ≤ h ≤ 17, −15 ≤ k ≤ 15,
−14 ≤ l ≤ 14
16,089
−9 ≤ l ≤ 9
Reflections collected
11,628
Independent reflections
Completeness to θ = 28.27◦
Absorption correction
Max. and min. transmission
Refinement method
2875 (R(int) = 0.0188)a
3926 (R(int) = 0.0161)
99.9%
99.7%
Multi-scan
Multi-scan
0.890 and 0.675
Full matrix least squares on F2
2875/25/151a
1.102a
0.840 and 0.721
Full matrix least squares on F2
3926/0/253
Data/restraints/parameters
Goodness of fit on F2
1.044
Final R indices [I > 2σ(I)]
R indices (all data)
Largest diff. peak and hole
R1 = 0.0411, wR2 = 0.1325a
R1 = 0.0424, wR2 = 0.1341a
1.155 and −0.272e × Å−3a
R1 = 0.0248, wR2 = 0.0674
R1 = 0.0253, wR2 = 0.0678
0.440 and −0.214e × Å−3
Notes: aRefinement values after application of the Squeeze procedure to correct for electron density associated with disordered water
molecules: R(int): 0.0176; data/restraints/parameters: 2875/0/129; goodness of fit: 1.095; final R indices [I > 2σ(I)]: R1 = 0.0337,
wR2 = 0.0871; R indices (all data): R1 = 0.0353, wR2 = 0.0882; largest diff. peak and hole: 0.423 and −0.254e × Å−3
.
the c-axis of about 16% of the total unit cell volume (2 × 8%) (Figure 3). The water molecules are
encapsulated by a layer of dithiane molecules thus not allowing for effective hydrogen bonding
with the phenolic OH groups. It is worthy to be mentioned that sulfur-based compounds with
different structural features show inclusion capabilities. In this regard, recently Alshahateet et al.
(19) nicely described the inclusion phenomena of some sulfur-containing diquinoline host. How-
ever, in the present case, water molecules are severely disordered – they seem to be not forming
hydrogen bonds with any of the sulfur atoms – and have been omitted from the structural model
(see experimental details). The crucial factor for the kind of packing observed in 2 seems to be
−
the ability to form a strong hydrogen bond between O2 H2 and O1 in combination with the
−
−
π-stacking of the aromatic rings. The intramolecular C H· · ·O and the intermolecular O H· · ·S
contacts, which are in common for 1 and 2, seem to be of less importance. The hydrogen bonding
data for 2 are shown in Table 2.
2.3. Crystal structure of 3
−
With an additional dithiane ring, ortho to the other OH group, compound 3 crystallizes in the
space group P21/c. Figure 4(a) shows an ORTEP (Oak Ridge Thermal Ellipsoid Plot Program)

506 M. Datta et al.
Figure 2. (a) ORTEP plot of 2 with 50% probability ellipsoids and (b) hydrogen bonding scheme of 2.
Figure 3. Packing diagram for 2 (hydrogen interactions are omitted for clarity) showing the channels along the c-axis
at x = 0.5.
Table 2. Hydrogen bond distances (Å) and angles (◦) for compound 2.
−
−
D
H· · ·A
d (D H)
d (H· · ·A)
d (D· · ·A)
<(DHA)
−
O(2) H(2)· · ·S(2)#2
0.84
0.84
0.84
1.00
2.44
2.65
1.93
2.27
3.2417 (13)
3.047 (2)
2.7040 (17)
2.7737 (20)
159.2
110.4
153.0
110.07
−
O(2) H(2)· · ·O(2)#3
−
O(1) H(1)· · ·O(2)#4
−
C(7) H(7)· · ·O(1)
Note: Symmetry transformations used to generate equivalent atoms: #1: −x + 1, y, −z + 3/2;
#2: −x + 1/2, −y + 1/2, −z; #3: −x + 1/2, −y + 1/2, −z − 1; #4 −x + 1/2, y + 1/2, −z −
1/2.

Journal of Sulfur Chemistry 507
plot with the atom-numbering scheme. Similar to both 1 and 2, the dithiane rings are in a chair
conformation and orientated in such a way as to allow for a hydrogen bond between the dithiane
−
C H groups and the neighboring phenol oxygen atom to be formed. Three significant hydrogen
−
bonding interactions are observed for 3 (Figure 4(b)): one strong O H· · ·O interaction and two
−
−
weaker O H · · · S interactions. The strong hydrogen bond is formed between O2 H2 as the
donor and O1 of a neighboring molecule as the acceptor. The two weaker interactions are between
−
O1 H1 as the donor and two of the four sulfur atoms (S2 and S4). O1 is thus both acceptor for
−
−
−
−
one O H· · ·O and donor for two O H· · ·S hydrogen bonds. The O1 H1· · ·S2 and O1 H1· · ·S4
interactions observed in the network are consistent withType I as described by Rosenfield et al. H1,
being hydrogen bonded to both S2 and S4, bridges the two S atoms in aY shape. This brings the two
dithiane rings into close contact so that there is a meaningful S· · ·S interaction between S2 and S4.
Similar to 2, a hydrogen atom of one of the dithiane methylene groups points toward the centroid
−
of the adjacent phenyl ring, forming a relatively short contact (C10 H10B· · ·centroid = 2.544 Å,
16◦). The other side of the phenyl ring is π-stacked with another aromatic ring. The hydrogen
bonding data related to structure 3 are represented in Table 3. Figure 5 represents the packing
view of the compound 3 where the weak non-covalent forces as indicated in Figure 4(b) play a
Figure 4. (a) ORTEP plot of 3 with 50% probability ellipsoids and (b) hydrogen bonding interaction scheme in 3.

508 M. Datta et al.
Table 3. Hydrogen bond distances (Å) and angles (◦) for compound 3.
−
−
D
H
d (D H)
d (H· · ·A)
d (D· · ·A)
<(DHA)
−
O(2) H(2)· · ·O(1)#1
0.775(19)
0.761(18)
0.761(18)
2.112 (19)
2.955 (17)
2.529 (18)
2.8521 (12)
3.3910 (9)
3.2718 (8)
159.8 (17)
119.1 (15)
165.6 (17)
−
O(1) H(1)· · ·S(2)#2
−
O(1) H(1)· · ·S(4)#3
Note: Symmetry transformations used to generate equivalent atoms: #1: x, −y + 3/2, z + 1/2;
#2: −x + 1, y − 1/2, −z + 1/2; #3: −x + 1, −y + 2, −z + 1.
Figure 5. Packing plot of compound 3.
decisive role. This packing plot is quite different from Figure 3 for compound 2. No hollow space
is filled in by water molecules.
3. Conclusions
−
−
Thus, the occurrence of O H· · ·S hydrogen bonds in 1, 2 and 3 in preference to O H· · ·O
hydrogen bonds appears at first sight to be at odds with the relative strengths and frequencies
of the two types of interaction. This, however, is not the relative strength of two interactions,
but rather the prospects for their occurrence within the constraints of an overall efficient packing
−
arrangement. In 2 and 3, with an increase in the number of dithiane rings, the OH groups lie
close to the long edges of the molecules and are brought by these packing arrangements into the
−
proximity of dithiane rings thus leading to O H· · ·S interactions.
Importantly, the orientation of the dithiane groups with respect to the aromatic ring is so that a
−
C H· · ·O interaction can be formed. This is consistent for all three compounds and seems to be a
−
favorable interaction. Extremely important are the strong O H· · ·O bonds. If they can form at all,
they are dominating the molecular packing. For 2, they force it into a packing arrangement with
large hydrophobic channels filled with water, which would usually be seen as quite unfavorable.

Journal of Sulfur Chemistry 509
−
Still, the O H· · ·O interactions seem to be able to make up energetically for the loss in favorable
interactions along these channels. π-Interactions and the π-stacking interactions also seem to
−
play an important role. O H· · ·S interactions, on the other hand, seem to have no large influence
on the packing.
4. Experimental
All commercially available chemicals were reagent grade and used without further purification.
1H NMR spectra were recorded using a Bruker 300 MHz spectrometer. IR spectra were recorded
as KBr pellets at 25◦C using a Perkin Elmer L120-00A spectrophotometer.
4.1. Synthesis
The hydroxyphenyl-1,3-dithianes 2 and 3 were obtained from the corresponding hydroxyben-
zaldehydes via dithiane protection of the aldehyde functionalities, according to the following
general procedure: to a solution of hydroxybenzaldehyde (18.7 mmol) in 1,3-propanedithiol
(30.9 mmol), boron trifluoride etherate (2 ml) was added with stirring at 0◦C for 5 h.After comple-
tion of the reaction, the mixture was poured onto a saturated aqueous solution of sodium hydrogen
carbonate (50 ml) and was extracted three times (3 × 50 ml) with ethyl acetate. The organic layer
was washed repeatedly with aqueous sodium hydrogen carbonate. Finally, the organic layer was
dried over anhydrous sodium sulfate. The solvent was removed from the filtrate under vacuum
and the product was isolated by column chromatography with chloroform as the eluent.
4.1.1. 2-(1,3-Dithian-2-yl)phenol 1
1
Mp 126◦C, yield 87%. H NMR (CDCl3, 300 MHz): 7.28 (m, 1H), 7.21 (m, 1H), 6.89 (d, 2H,
J = 6 Hz,), 6.35 (s, 1H), 5.41 (s, 1H), 3.12–3.03 (m, 4H), 2.94–2.90 (m, 2H), 2.21–2.17 (m, 1H),
2.00–1.87 (m, 1H). FT–IR (KBr) νmax (cm−1): 3319, 2950, 2893, 1604, 1592, 1499, 1455, 1421,
1408, 1349, 1270, 1250, 1236, 1196, 1183, 1153, 1087, 1040, 790, 758. Elemental analysis: C:
56.55, H: 5.67%. Calcd for C10H12OS2: C: 56.56, H: 5.69%.
4.1.2. 4-(1,3-Dithian-2-yl)-1,2-benzenediol 2
1
Mp 162–164◦C, yield 80%. H NMR (d6-DMSO, 300 MHz): 9.71 (s, 1H), 9.38 (s, 1H), 7.10
(d, 1H, J = 9 Hz), 6.27 (s, 1H), 6.22 (dd, 1H, J1 = 2.1 Hz, J2 = 2.1 Hz), 5.47 (s, 1H), 3.02
(t, 2H, J = 12 Hz), 2.83–2.78 (m, 2H), 2.09–2.05 (m, 1H), 1.72–1.60 (m, 1H). FT–IR (KBr) νmax
(cm−1): 3122, 1631, 1498, 1443, 1329, 1230, 1163, 1129.
4.1.3. 4,6-Di(1,3-dithian-2-yl)-1,3-benzenediol 3
Mp 232–234◦C, yield = 70%. 1H NMR (d6-DMSO, 300 MHz): 9.85 (s, 2H), 7.40 (s, 1H), 6.36
(s, 1H), 5.45 (s, 2H), 3.03 (t, 4H, J = 12 Hz), 2.84–2.79 (m, 4H), 2.10–2.06 (m, 2H), 1.76–1.63
(m, 2H). FT–IR (KBr) νmax (cm−1): 3407, 3253, 2923, 2890, 1614, 1519, 1431, 1421, 1362, 1274,
1190, 1175.

510 M. Datta et al.
4.2. X-ray crystallography
Diffraction data for 2 and 3 were collected on a Bruker AXS SMART APEX CCD diffractometer
at 100(2) K using the monochromatic Mo Kα radiation with omega scan technique. The unit cells
were determined using SMART and SAINT+. ((a) Bruker Advanced X-ray Solutions SMART
for WNT/2000 (Version 5.628), Bruker AXS Inc., Madison, Wisconsin, USA, 1997–2002 and (b)
Bruker Advanced X-ray Solutions SAINT (Version 6.45), Bruker AXS Inc., Madison, Wisconsin,
USA, 1997–2003.) The structure was solved by direct methods and refined by full matrix least
squares against F2 with all reflections using SHELXTL. (Bruker Advanced X-ray Solutions
SHELXTL (Version 6.10), Bruker AXS Inc., Madison, Wisconsin, USA, 2000.) Refinement of
an extinction coefficient was found to be insignificant. All non-hydrogen atoms were refined
anisotropically.
In the crystal structure of 2, channels parallel to the c-axis are filled with severely dynamically
disordered water molecules. The channels make up about 16% (2 × 8%) of the unit cell volume of
2. In a first approach, the disordered water molecules O3–O6 were refined as partially occupied and
−
the associated hydrogen atoms were omitted from the model. The oxygen atoms O3 O5 are close
to each other and their occupancies were constrained to sum up to 1.2 (to take the electron density
of the missing hydrogen atoms into account). Occupancy ratios refined to 0.51(3):0.48(1):0.25(3)
for O3, O4 and O5, respectively. O6 refined to have occupancy of 0.152(4). All water oxygen
atoms have been restrained to have the same anisotropic displacement parameters, which have
been kept isotropic within a standard deviation of 0.01. In a second approach, the electron density
associated with the disordered water molecules was corrected for using the Squeeze procedure
implemented in the program Platon for Windows (A.L. Spek, Delft, the Netherlands, 2003). R-
values and structure quality indicators improved significantly (see footnote in Table 1), indicating
the inadequacy of the disorder model used.
For 2, all hydrogen atoms were placed in calculated positions and were refined with an isotropic
−
−
displacement parameter 1.2 times (C H bonds) or 1.5 times (O H) that of the adjacent car-
bon atom. Hydrogen atoms of 3 were located in the difference density Fourier map and were
isotropically refined. Crystal data and experimental details for 2 and 3 are listed in Table 1.
5. Supporting information
Crystallographic data (excluding structure factors) for the structures reported in this paper have
been deposited with the Cambridge Crystallographic Data Centre as supplementary publication
CCDC 777286-777288. Copies of data can be obtained free of charge on application to the
Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax int. code +44 1223 336033,
email: deposit@ccdc.cam.ac.uk). In addition, the single-crystal X-ray figures for structure 1 are
presented.
Acknowledgements
We thank DST, New Delhi, India, for providing infrastructural support under DST FIST program. We also sincerely thank
Dr Kumaresh Ghosh, University of Kalyani, for his helpful suggestions to prepare this manuscript.
References
(1) MacDonald, J.C.; Whitesides, G.M. Chem. Rev. 1994, 94, 2383–2420.
(2) Desiraju, G.R. Crystal Engineering: Design of Organic Solids; Elsevier: Amsterdam, 1989.
(3) Sarma, R.J.; Baruah, J.B. CrystEngComm 2005, 7, 706–710.

Journal of Sulfur Chemistry 511
(4) Moulton, B.; Zaworotko, M.J. Chem. Rev. 2001, 101, 1629–1658.
(5) Ferey, G. Chem. Soc. Rev. 2008, 37, 191–214.
(6) Ferey, G. Dalton Trans. 2009, 4400–4415.
(7) Bond, A.D.; Jones, W. In Supramolecular Organization and Materials Design; Jones, W., Rao, C.N.R., Eds.;
Cambridge University Press: Cambridge, 2002.
(8) Desiraju, G.R. Acc. Chem. Res. 2002, 35, 565–573.
(9) Tellado, F.G.; Geib, S.J.; Goswami, S.; Hamilton, A.D. J. Am. Chem. Soc. 1991, 113, 9265–9269.
(10) Rebek, J., Jr. Angew. Chem., Int. Ed. Engl. 1990, 29, 245–255.
(11) Desiraju, G.R.; Steiner, T. The Weak Hydrogen Bond in Structural Chemistry and Biology; Oxford University Press:
New York, 1999.
(12) Vishweshwar, P.; Nangia, A.; Lynch, V.M. Cryst. Growth Des. 2003, 3, 783–790.
(13) Wheeler, K.A.; Harrington, B.; Zapp, M.; Casey, E. CrystEngComm 2003, 5, 337–342.
(14) Dale, S.H.; Elsegood, M.R.J.; Hemmings, M.; Wilkinson, A.L. CrystEngComm 2004, 6, 207–214.
(15) Ganguly, N.C.; Datta, M.; Ghosh, K.; Bond, A.D. CrystEngComm 2005, 7, 210–215.
(16) Usman, A.; Fun, H.-K.; Ganguly, N.C.; Datta, M.; Ghosh, K. Acta Cryst. 2003, E59, o773–o775.
(17) Rosenfield, R.E.; Parthasarathy, R., Jr.; Dunitz, J.D. J. Am. Chem. Soc. 1977, 99, 4860–4862.
(18) Allen, F.H.; Bird, C.M.; Rowland, R.S.; Raithby, P.R. Acta Cryst. 1997, B53, 696–701.
(19) Alshahateet, S.F.; Bishop, R.; Craig, D.C.; Scudder, M.L. Cryst. Growth Des. 2011, 11, 4474–4483.